1 Classical Glass Technology

Michael Cable

Division of Ceramics, Glasses and Polymers, School of Materials, University of Sheffield,

Sheffield, U.K.

List of Symbols and Abbreviations 3

1.1 The Historical Development of Glass Technology 6
1.1.1 Introduction 6
1.1.2 The Beginnings of Glass Technology 6
1.1.3 The Eighteenth Century 8
1.1.4 The Nineteenth Century 11
1.1.5 The Twentieth Century 13
1.2 Choice of Glass Compositions 18
1.2.1 Properties Important to the User 18
1.2.2 Properties Important to the Glass Maker 20
1.2.3 Choice of Glass Composition 21
1.2.4 Composition-Property Relations 22
1.2.5 Models for Composition-Property Relations 23
1.2.5.1 The Viscosity-Temperature Relation 24
1.2.5.2 Liquidus Temperature 25
1.2.5.3 Specific Heat 26
1.2.5.4 Thermal Conductivity 26
1.2.5.5 Summary 29
1.2.6 The Modern Approach to Choice of Glass Composition 29
1.2.7 Choice of Raw Materials 32
1.3 The Melting of Glasses 32
1.3.1 Introduction 32
1.3.2 Energy Requirements 33
1.3.2.1 Enthalpy of Reaction 33
1.3.2.2 Sensible Heat 34
1.3.3 Preparations 34
1.3.4 The Stages of Melting 35
1.3.4.1 Batch Heating 35
1.3.4.2 The Initial Melting Reactions 37
1.3.4.3 Refining 45
1.3.4.4 The Homogenizing of Glass Melts 53
1.3.4.5 Modern Furnaces 59
1.4 Glass Forming 62
1.4.1 Introduction 62
1.4.2 The Manufacture of Containers 64
Materials Science and Technology
Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
2 1 Classical Glass Technology

1.4.3 The Production of Lamp Bulb Envelopes 69

1.4.4 The Manufacture of Flat Glass 70
1.4.4.1 Introduction 70
1.4.4.2 Sheet Glass Processes 71
1.4.4.3 Float Glass 74
1.4.5 Rod and Tubing 78
1.4.5.1 The Danner Process 78
1.4.5.2 Vertical Drawing Processes 79
1.4.6 Glass Fibers 80
1.4.6.1 Introduction 80
1.4.6.2 The Physics of Fiber Drawing 80
1.4.6.3 The Technology of Fiber Production 81
1.4.6.4 Continuous Fibers 82
1.4.6.5 Non-Circular Rod Tube and Fiber 83
1.5 Polishing 83
1.5.1 Mechanical Polishing 83
1.5.2 Acid Polishing 84
1.6 References 85
 List of Symbols and Abbreviations 3

List of Symbols and Abbreviations

A amplitude of wave
A parameter in Vogel-Tammann-Fulcher equation
Ao initial amplitude of wave
a radius or semi-major axis of elliptical inclusion
a0 initial radius of sphere
a0 constant term in Eqs. (1-1), (1-2) and (1-4)
at coefficient for term i in Eqs. (1-1) and (1-2)
b coefficient in Eq. (1-43)
b semi-minor axis of elliptical inclusion
B parameter in Vogel-Tammann-Fulcher equation
B rate of production of bottles
Ca dissolved concentration in liquid at radius a
Cs concentration of gas inside bubble
C ro uniform dissolved concentration in liquid far from bubble
CEQ equilibrium concentration of silica in liquid in contact with silica grain
Ct concentration of dissolved silica in liquid at time t
C dimensionless concentration (0 < C < 1)
c specific heat
ct concentration of component i
Ac concentration difference driving dissolution
d equilibrium thickness of Float glass ribbon
D diffusivity
E dimensionless equilibrium shape of deformed inclusion
Ex approximate dimensionless equilibrium shape of deformed inclusion
E2 parameter used to define approximate dimensionless equilibrium shape of de-
formed inclusion
£* activation energy for viscous flow
Ft dimensionless dissolved concentration of gas i
F (a) net surface tension force over unit length
F(p) net force due to pressure over unit length
g gravitational acceleration
gt mole fraction of gas i in a bubble
G rate of shear
H enthalpy
h height of Float glass ribbon above surface of tin bath
h depth of glass melt
/ parameter describing initial behaviour of a multi-component bubble
kB Boltzmann constant
k constant in Eqs. (1-19), (1-20), (1-42) and (1-44)
/ linear dimension
L length of orifice
m number of components in system
M mass rate of flow through orifice
4 1 Classical Glass Technology

n number of degrees of freedom

n number of moles of a component
n refractive index
n number of terms in series
n number of bubbles of given size per unit volume of melt
N total number of bubbles per unit volume of melt
p pressure
p number of moles of silica in silicate liquid
Ap pressure difference or excess pressure due to surface tension
R gas constant
R dimensionless radius of sphere
R radius of atom or molecule
s natural strain
sa natural strain of a-axis for inclusion differing in viscosity from surrounding
liquid
5 aH natural strain of a-axis when inclusion h a s same viscosity as matrix
5 parameter defining eventual behaviour of multi-component bubble
T temperature
T{ interfacial temperature
t time
U velocity vector
V volume
w wall thickness
X value of a property
X mole fraction of a constituent
x diameter of bubble
y thickness of reaction product layer
z volume of product per unit volume of sphere
z number of moles of silica

a angle
a absorption coefficient
a mass fraction reacted
a thermal diffusivity
OL{ Ostwald solubility coefficient for gas i
P rate of growth parameter for sphere
y auxiliary parameter in Appen's property calculations
S concentration boundary layer thickness
X wavelength of electromagnetic radiation
X wavelength of wave on liquid
X thermal conductivity
X dimensionless viscosity parameter
Xo true thermal conductivity
XR apparent thermal conductivity due to radiant heat transfer
rj viscosity
 List of Symbols and Abbreviations

q> effective solubility of gas in liquid

q> auxiliary parameter in Appen's property calculations
0 temperature in °C
©0 temperature constant in Vogel-Tammann-Fulcher equation
9 angle
90 coefficient in Eq. (1-6)
Q mass density
a surface tension or interfacial energy
o Stefan-Boltzmann constant
\jj auxiliary parameter in Appen's property calculations
s eccentricity of ellipse
 1 Classical Glass Technology
1.1 The Historical Development
of Glass Technology
1.1.1 Introduction
Glass making is an extremely old tech-
nology, the history of which has often been
recounted, see for example Douglas and
Frank (1972), but is constantly in need of
revision as archaeological evidence keeps
advancing our understanding of various
aspects and throwing up new puzzles. Here
we consider only how the general advance
of science and the evolution of glass mak-
ing have interacted with each other. Few
events earlier than the middle of the seven-
teenth century deserve detailed discussion;
until that time chemistry and physics were
too primitive to be able to assist develop-
ment of high temperature processes like
glass or ceramic manufacture or iron mak-
ing. But before proceeding it is salutary to
remind ourselves of the brilliant technical
achievements occasionally produced in
distant ages: first, skill in glass melting
such as the Wilsford bead (Guido et al.,
1984) and the sealing-wax red glass from
Nimrud (Cable and Smedley, 1987 b) and
the glass of the Lycurgus cup (Brill, 1965)
required; second, virtuosity in after work-
ing of the cold glass such as the Roman
diatreta ware (Wiedman, 1954), the Port-
land or Barberini vase, and the modelling
of the Lycurgus cup. These remind us that
technological advance has often come
about by intuition and intelligent trial and
error experimentation rather than by ap-
plying scientific methods or knowledge.
Even in recent times advances in scientific
understanding have often been stimulated
by technical advances rather than the con-
verse.
Several notable cornerstones of modern
science depended on the availability of
glass apparatus and from mediaeval times
onwards glass was the pre-eminent choice
of alchemists and chemists for their appa-
ratus. Even if borosilicate glass for labora-
tory apparatus (Pyrex) is a twentieth cen-
tury invention, the relatively fragile glass
apparatus then available was essential to
many laboratory operations in earlier
times. One of the events having an obvious
claim to mark the beginning of modern
science was Galileo's work on the motion
of the planets which would have been im-
possible without astronomical telescopes
needing glass lenses. Isaac Newton's pio-
neering work in optics, begun in 1666, also
required prisms, lenses and mirrors. Other
basic investigations which required glass
apparatus were the classic investigations of
the properties of gases (Boyle's law and
Charles's law), thermometry, barometry
and the development of microscopes.
1.1.2 The Beginnings of Glass Technology
The earliest written records of glass
making are some famous clay tablets, dat-
ing from around 650 BC, from the library
of Assur-bani-pal, see Douglas and Frank
(1972), but these are incompletely under-
stood because we have no dictionary to
explain the technical terms. Many cen-
turies passed before written accounts of
glass making contained any useful insight
besides recipes to be followed by rote.
The earliest development in glass mak-
ing of which we have a reasonably docu-
mented description seems to be the inven-
tion of glass of lead by Ravenscroft around
1673-1676 (Moody, 1988, 1989). From
very distant times it had been common to
make much European glass using sand and
an alkali flux obtained from plant ash. By
mediaeval times it was known that leach-
ing the ash and purifying the alkali by
evaporation had several advantages in
melting the glass. Unfortunately this also
 1.1 The Historical Development of Glass Technology
made glass of simpler compositions richer
in alkali, to the serious detriment of chem-
ical durability. When Ravenscroft was
called their rescue the holders of the
monopoly on glass in England were in
danger of losing their privilege because of
customer dissatisfaction with the chemical
durability of their product. Ravenscroft
rescued them by developing a glass of lead
(not the same as modern English lead crys-
tal). This is the earliest work that we know
where an investigation was deliberately
made to find how to modify glass proper-
ties by adjusting composition. However,
this could not have been done by scientific
methods because chemistry was still on a
mystical basis and the techniques of analy-
sis needed did not exist. Some of the short-
comings of chemical knowledge of those
times are indicated by the many years that
Isaac Newton devoted to chemical studies
which had a negligible influence, unlike his
profound insights into gravitation and
light. His Optics (1704) was the first impor-
tant scientific book to be published in any
vernacular language rather than Latin. It
was not only directly concerned with the
properties of glass but also the first to ex-
pound the modern scientific method of
proposing hypotheses, devising experi-
ments to test them and reporting the re-
sults before theorizing further. It is inter-
esting to speculate how much further he
might have developed optics if he had been
able to experiment with glasses of dis-
tinctly different refractive indices and dis-
persions. The primitive state of glass tech-
nology may have let him down but led him
to invent the reflecting astronomical tele-
scope.
The most influential of all books on
glass was Antonio Neri's L'Arte Vetraria
which first appeared in AD 1612 and was
soon translated into both Latin and sev-
eral other vernacular languages (Turner,
1962), generally with a commentary by the
translator as exemplified by Merret's Art
of Glass (1662) and Kunckel's Glasmacher-
kunst (1679). Although these give much
useful information they are little more than
recipe books: insight into the reasons why
particular things should be done or
avoided is rare. The beginnings of a sound
glass science needed a better understand-
ing of both chemistry and physics. Devel-
opments in chemistry were needed to per-
mit the analysis of both glasses and raw
materials as well as to understand the dif-
ference between elements such as sodium
and potassium or calcium and magnesium.
Science lacked a proper understanding of
heat, which was thought of as some kind of
chemical element though, as knowledge
developed, it had to be treated as one with
a negative mass. As a result melting and
solidification and also glass formation
could not be understood. The only impor-
tant glass properties that could easily be
measured were density and refractive in-
dex.
This gives an unduly pessimistic a pic-
ture of what practitioners of the useful arts
could achieve. For example, in those days
glass makers did have some simple quality
control tools for their ash, probably de-
pending more on taste than anything else
because sodium and potassium salts have
different tastes as do carbonate, chloride,
sulphate and nitrate; there are published
comments such as "the bitterest is the best
for making glass". Assessment of silica was
a bigger problem and it was often assumed
that all whitish stones which would neither
dissolve in acid nor be affected by heat but
struck a spark with steel were chemically
equivalent and equally suitable for making
glass. The reasons for this situation are
clear: no other analytical tools were avail-
able. Another century was to pass before
much progress was possible with any of
 1 Classical Glass Technology

these crucial factors. Given what we now

know about the sensitivity of glass proper-
ties to changes in composition, it some-
times seems amazing that any good quality
glass was regularly made. Few glass mak-
ers can have enjoyed placid lives, a situa-
tion possibly not very different from today.
The other main problems were associ-
ated with furnaces. First there was the
problem of what to build them from, se-
condly, how to attain sufficiently high tem-
peratures and, thirdly, how to measure and
control temperature; even at the end of the
last century it was normal to speak of de-
grees of heat when talking about high tem-
perature processes. It was realised at an
early stage that drying the wood used as
fuel had important advantages; the net
calorific value of wood decreases almost
linearly with moisture content and be-
comes zero at about 70% H 2 O, so that air
dried wood still containing around 20%
moisture is much inferior to that which has
been thoroughly dried. It is also clear that
in those times glasses were regularly made
which needed melting temperatures much Figure 1-1. The traditional southern European bee-
above the 1200°C which used to be as- hive type of furnace; from Agricola. The wood fire
sumed to be the maximum melting temper- was central at ground level and charged through the
ature attainable (Cable and Smedley, opening shown; the exhaust gases passed over the
pots and out of the working holes. Straight sided pots
1987 a). The introduction of coal as the
were more common than the vases shown.
main fuel required significant changes in
the design of furnaces to allow for its differ-
ent combustion characteristics but this was Techniques of glass melting and forming
done, as so often, by trial and error without processes remained virtually unchanged
real scientific insight. from the practices of several preceding cen-
Up to those times two types of furnace turies.
had been developed (Newton, 1985). One
was the southern European 'beehive' type
1.1.3 The Eighteenth Century
exemplified by the famous woodcuts in
Agricola's book, Fig. 1-1 (Hoover and Several branches of chemistry and
Hoover, 1912). The other from northern physics made very rapid advances towards
Europe was a rectangular chamber fre- the end of the eighteenth century. Some of
quently built with four smaller furnace the essential physical properties of gases
chambers as wings on the corners, the plan were already known; Boyle's law was
looking like a butterfly, see Fig. 1-2. demonstrated in 1660 but Charles's law
 1.1 The Historical Development of Glass Technology
0 5m
Figure 1-2. A northern European wood fired furnace
showing the four small wing furnaces. Vertical section
through the middle and plan view just above the level
of the siege. Two fires were made, one at each end of
the hearth. After Bosc D'Antic and other French
not until 1787. The experiments that were
needed for these investigations would have
been impossible without glass apparatus.
A clear appreciation and separation of the
chemical and physical aspects of heat and
combustion came much later. Physicists
had the evidence to abandon phlogiston to-
wards the end of the 18th century but a
considerably longer time elapsed before all
chemists also came to a modern view of
heat. There were, however, some notable
publications about glass making in the
second half of the century. The glass
making sections of the great Diderot and
D'Alembert Encyclopedic (1765 -1772)
contain more than a hundred beautifully
drawn and engraved plates, which are well
known, as well as very detailed descrip-
tions of the processes, which are unjustly
neglected. The text of the Diderot and
D'Alembert Encyclopedic gives the most
detailed account of glass making practices
ever published and makes clear that much
skill and experience was involved but very
little science. The plates were republished
with a significantly different and obviously
more modern text in the Encyclopedic
Methodique (1791).
Figures 1-3 and 1-4 show examples of
these plates which illustrate the two long
established methods of making window
glass, the crown process and the cylinder
process. The crown process used a large
gather formed like a shallow bowl which
was transferred to a punty then reheated
and spun by hand so that centrifugal force
made it open up into an almost flat circular
disk with excellent fire polished surfaces;
the main disadvantages of crown glass
were the thickened central bullion where
the punty was attached and the fact that
the disk was always somewhat saucer
shaped. The glass, when homogeneous,
was nevertheless of uniform thickness, gen-
erally in the range 1 to 2.5 mm (Cable and
Swan, 1988).
Cylinder glass was made by blowing a
cylinder, cutting off the ends, cracking it
longitudinally, then reheating it and open-
ing out the cylinder into a flat sheet in a
separate furnace. This operation required
the use of a kind of wooden rake to open
out the cylinder. The effect of this tool on
the glass and of contact with the slab on
which it lay always produced slightly rip-
pled surfaces, although the sheet could be
quite flat overall. Cylinder glass could
provide considerably larger panes than
10 1 Classical Glass Technology
Figure 1-3. Reheating and spinning the gather in
making crown glass: from the Diderot Encyclopedia.
crown. Crown glass could make good but
slightly convex or concave mirrors but cyl-
inder glass was rarely good enough to
make looking glasses.
The Collected Works of Paul Bosc D'An-
tic (1780) cover a range of subjects but
glass making is the major part. In a fasci-
nating introduction and a lengthy essay
written in 1760 which is supplemented (in
the established way) by additional com-
mentaries written in 1780, he writes for the
first time about glass making in the mod-
ern way referring, where possible, to the
latest scientific literature. However, D'An-
tic was a man of complex personality and
some influence at the court of Louis XVI
(as physician to the King) but of dubious
practical achievement because he was dis-
Tig.z
Figure 1-4. Steps in making cylinder glass; from the
Diderot Encyclopedia.
missed from his position as Director at
Saint Gobain in 1761 after only two years
in that post. A clash of personalities may
have contributed to D'Antic's downfall.
His vivid style of writing suggests that he
may have been vain and opinionated, a
view clearly shared by Delaunay Des-
landes, his deputy and successor as Direc-
tor, who may not be an entirely impartial
witness but whose distinguished 31 years in
that post demonstrates his own technical
 1.1 The Historical Development of Glass Technology
expertise and tends to lend credence to his
strictures on D'Antic (Barton, 1989).
1.1.4 The Nineteenth Century
Enormous advances were made during
the last century. The title of most eminent
glass technologist of all time should proba-
bly be awarded to Joseph Fraunhofer
(1787-1826) who as a more or less self ed-
ucated orphan was in 1806, at the age of 19,
employed at the Optical Institute in Bene-
diktbeuern, where he assisted the elderly
Guinand in developing the stirring of glass
melts to produce optical glasses capable of
making good achromatic doublets. Fraun-
hofer soon supplanted Guinand and spent
the whole of his regrettably short career in
this post, making his enormous contribu-
tions to astronomical optics, especially
spectral analysis and diffraction, whilst en-
gaged in the manufacture of astronomical
telescopes. Although none of the telescopes
made by Fraunhofer himself still exists,
one made to the same design by his imme-
diate successors is still to be seen at the
Harvard College Observatory.
One of Fraunhofer's (1817) published
papers shows that he had developed a test
for the chemical durability of glasses using
sulphuric acid and also implies that he was
the discoverer of the mixed alkali effect,
that is to say recognizing that a mixture of
alkalis often gives properties quite different
from what one would have predicted from
measuring properties of glasses containing
only each alkali alone. Although chemistry
was advancing rapidly, Fraunhofer would
have been hindered by lack of pure materi-
als and inability to analyse them or his
glasses. These problems were rather less
severe for Michael Faraday, the most cre-
ative of all scientists to have spent some of
his time working as glass technologist, who
had better resources close to hand.
11
Faraday (1791-1867) was asked by the
Board of Longitude and the Royal Society
to find how to make good quality optical
glasses to enable better instruments to be
made and worked on this project from
1825 to 1830 when, having had reasonable
success and not seeing how to make much
further progress, he asked to be released to
continue his work with electricity. Faraday
(1830) described his methods but his work
failed to have any practical impact on glass
manufacture, largely because the system of
controlling glass making, to ensure that the
taxes were paid, and the way in which taxes
were levied made experimentation by glass
makers too difficult and expensive for most
of them to contemplate. The small scale of
his operations may also have failed to im-
press glass makers (Cable and Smedley,
1989).
William Vernon Harcourt (1789-1871)
was an important pioneer about whose
work we know too little. Vernon Harcourt
was a Church of England clergyman who
was influential in founding first the York-
shire Philosophical Society (his father was
Archbishop of York at the time) and then
the British Association for the Advancement
of Science; the early history of the latter has
been recounted by Morrell and Thackray
(1981). During much of his long life he
spent a great deal of time in making un-
usual glasses using a hydrogen furnace that
he had invented (Vernon Harcourt 1844).
His interest was to extend the range of op-
tical properties available to allow better
optical instruments to be made, latterly in
conjunction with Prof. Stokes who under-
took the optical measurements (Stokes,
1871). He used at least 29 elements in his
glasses and was the first person ever to use
at least 13 of them in glasses, see Fig. 1-5.
He produced good samples of titanate, bo-
rate and phosphate glasses. Unfortunately
his work, like Faraday's, led to no practical
12 1 Classical Glass Technology
Li Be
Na Mg
K Ca Ti V Cr Mn Fe- Co Ni Cu
Sr Mo
Ba W Au
U
applications. The punitive tax on glass had
been abolished in 1845 so that was not the
reason in this instance. Perhaps glass mak-
ers were unwilling to take seriously the re-
sults of such small scale laboratory experi-
ments by an amateur or to consider using
such unusual ingredients.
The real beginnings of glass technology
had to wait for the arrival on the scene of
Abbe and Schott who began the first really
fruitful investigations of property-compo-
sition relations in 1881, again with the in-
tention of improving optical instruments,
initially microscopes. Their success owed
much to the collaboration of Carl Zeiss
and his son Roderich in developing meth-
ods of large scale high quality lens manu-
facture which were soon also applied to
the production of photographic lenses:
Schott and Zeiss remain influential names
today. The results of their pioneering in-
vestigations were described in detail by
Hovestadt (1900) and an English transla-
tion by Everett (1902) soon appeared.
The basic engineering industries devel-
oped rapidly during the nineteenth cen-
tury, making possible advances in many
other fields which required the large scale
production of components and machines
or high standards of accuracy; the develop-
ment of electrical machines playing an es-
pecially important part. It is an interesting
B 0 F
Al Si P S
Figure 1-5. Periodic table
of the elements showing
Zn As
those used in his glasses by
Vernon Harcourt. Those
Cd Sn Sb which he was the first to
use are marked by a bold
TI Pb Bi outline; the others shown
had previously been used
II in glasses.
coincidence that the Siemens Brothers had
important roles in both electrical machin-
ery and in glass melting.
The tank furnace, which made possible
continuous large scale production of
molten glass, and machines for mechanized
production of containers and flat glass
were inventions crucial to the glass indus-
try which together revolutionized it. The
earliest patent for a regenerative glass melt-
ing furnace appears to have been granted
to Robert Stirling in 1816 but this patent
was never published, or exploited. Never-
theless it seems that Wilhelm Siemens
knew of this work (Maurer and Bischoff,
1930). Attempts to make glass melting con-
tinuous had begun as early as 1840 when
Joseph Crosfield obtained a patent for a
reverberatory furnace in which batch was
placed on an inclined surface and ran
down into a pot as it melted. Chance
Brothers in Smethwick obtained a patent
for a tank about this time but, even if tried,
there is no record of it being successful.
The regenerative tank furnace was
brought to success by two of the Siemens
Brothers, of whom there were five,
Friedrich, Hans, Karl, Werner, and Wil-
helm, who between them worked in Eng-
land and Russia as well as Germany but
remained in regular contact. Friedrich had
worked on regenerative furnaces in Eng-
 1.1 The Historical Development of Glass Technology
land in 1857 and, jointly with Wilhelm, ob-
tained an English patent for a regenerative
system of firing a gas furnace in 1861. The
regenerator as a means of heat recovery
brought both higher temperatures and bet-
ter fuel economy. The first successful glass
tank was built by Friedrich in Dresden in
1867; on examining its plans one is sur-
prised to see how little the main features
changed during the ensuing years. The use
of the tank for melting glass then spread
rapidly. At about the same time Friedrich
also devised a three compartment pot
which allowed continuous melting and
working on a smaller scale but it was never
successfully exploited. A fascinating his-
tory of these developments has been writ-
ten by Stein (1958).
The introduction of iron mold was an
important step forward in the glass indus-
try. Magoun obtained an American patent
for their use in 1847 and their usage was
soon accepted. The first major develop-
ment in mechanization occurred in United
States where the machine pressing of glass
made great progress between about 1820
and 1860. Soon after this the possibilities of
the press and blow process for hollow ware
were seen. In 1865 Gillinder of Pittsburgh
was granted a patent for a combined press
plunger and blow pipe with which he could
press the top of a water jug and then blow
the body. Following this line of thought
Arbogast in 1881 developed the pressing of
the neck and parison of a bottle in one
mold followed by its transfer to another
mold for blowing to the final shape, which
he patented in 1882. This reversal of the
traditional way of making containers in
which the mouth was the last part to be
shaped and hence called the finish was cru-
cial to the subsequent development of all
mechanized processes. The first blow and
blow machine for containers was invented
by Ashley, in England, in 1886. Although
13
Owens began work on bottle manufacture
around 1898, his major work took place in
the early years of the present century, so his
story will be taken up later.
1.1.5 The Twentieth Century
In the early years of the century the pos-
sibility of solids reacting together was be-
coming widely recognized and some of the
earliest systems studied were of interest to
glass makers. For example, Cobb (1910)
published some studies of reactions involv-
ing sodium carbonate, calcium carbonate,
and alumina with silica. Gustav Tammann
(1861-1938) did much to develop scientific
studies of glasses, including melting reac-
tions, over an extended period. One of the
most notable pioneers was W. E. S. Turner
(1881-1963) who, at the beginning of the
first World War, was already an ambitious
university physical chemist. The early
stages of the war showed him how badly
the British glass industry needed scientific
advice and research for which it had been
relying on Germany and this led to him
found the Society of Glass Technology in
1915 and the Department of Glass Tech-
nology at Sheffield University a year later.
This was the first University Department
to have glass technology as its special field
of teaching and research. For forty years
from its foundation the department was
organized and financed in a way very un-
usual for those times but probably now
widely thought very commendable, relying
heavily on funding coming directly from
the glass industry and being run by a joint
University-Industry committee.
The first successful attempt to produce
an approximate theory to describe the
kinetics of solid state reactions was by
Jander (1927) who used data for systems
including carbonates and silica to support
his theory. This developed an interest in
14 1 Classical Glass Technology
studies of glass making reactions among
chemists as well as glass technologists.
Science saw rapid advances in all fields.
More and more elements became readily
available and could be incorporated into
glasses to investigate their possible uses.
Correspondingly ever wider ranges of ap-
plications have called for novel glasses
with properties not previously known or
studied. Important novel families of glasses
have been developed: these include inor-
ganic non-oxide glasses such as the chalco-
genides sharing many general structural
similarities with oxides; quite unexpected
inorganic systems of which the halide, es-
pecially fluoride, glasses are the most nota-
ble; metallic glasses and organic glasses,
the last of which are no longer given only
grudging recognition by glass scientists.
All of these are discussed in later chapters
of this volume.
One of the most significant develop-
ments for glass technology was the Griffith
(1920) theory for the strength of brittle ma-
terials which proposed that surface flaws
were the controlling factor (see Sec. 13.3).
Griffith himself tested his theory on glass
bulbs deliberately scratched with a dia-
mond. This at once aroused interest in the
strength of glasses and provided a sound
theoretical underpinning for previously ill
defined and poorly understood studies of
glass strength. It thus had an enormous
beneficial influence on such work and on
attempts to improve the practical strength
of glasses. A notable practical result was
the elegant demonstration by Thomas
(1960) that strength is not necessarily de-
pendent on sample size.
The X-ray diffraction analysis of crystal
structures was a particularly exciting field
which had an enormous impact on glass
science in the first quarter of the century.
The most influential event in glass science
was probably Zachariasen's (1932) publi-
cation of his random network hypothesis of
oxide glass structures (see Sec. 5.1.1). This
derived from early studies of crystal struc-
tures by X-ray diffraction which had led
Zachariasen consider how one could build
up extended structures in which all bond-
ing requirements were met and nearest
neighbor coordination maintained with-
out imposing the exact long range order
that a crystal demands. Although this is a
static geometrical model of glass structures
it has remained useful and fruitful to the
present time, although it is now generally
thought that models based on rates of
cooling required to avoid crystallization
are more universally valid (Turnbull and
Cohen, 1960); however, they do not yield
such a rich harvest of ideas about composi-
tion-property relations. The next most ex-
citing development in structural studies
probably was the ability to use high magni-
fication electron microscopy to examine
sub-liquidus phase separation after about
1960.
Developments in technology also saw
enormous strides in many fields, some con-
sidered to be in the realms of fantasy, if
thought about at all in earlier times. An
interest in lighting, initially for purely eco-
nomic reasons, had led Count Rumford to
invent photometry two hundred years ago
(Brown, 1979) and twentieth century devel-
opments in lighting again called for major
improvements by glass technologists, for
example, in glasses for sealing to wire leads
and others resistant to sodium vapour,
then more recently glasses suitable for the
envelopes of quartz-halogen lamps. An in-
teresting review of the development of
lamp manufacture in Germany has re-
cently been published by Tober (1990 a, b).
Radio equipment made rather different de-
mands for the development of glasses and
television demanded consideration of X-
ray absorption, the improvement of glass
 1.1 The Historical Development of Glass Technology
homogeneity and development of high
quality pressing for large face plates. Solid
state electronics and microelectronics have
had yet other requirements, mainly for
electrical and mechanical properties. Some
of the ways in which glasses played a part
in these advances have been recorded in an
impressive history of one of Britain's most
successful industrial research laboratories,
the General Electric Company's Hirst Re-
search Centre, by Clayton and Algar
(1989). The vast expansion of architectural
uses and automobile manufacture put flat
glass production under great stress and
must have played an important part in the
decisions to invest very large sums in the
development of the Float glass process.
The industry's major developments were
in flat glass manufacture, automatic pro-
duction processes for containers and lamp
bulbs, and the development of fibers for
insulation and for textiles. The first im-
provement in flat glass production was the
Sieverts process which mechanized the
blowing of hand gathered cylinders and
somewhat increased their size but the Lub-
bers process of 1903 was more important.
This mechanized the blowing of large
cylinders, up to about 12 m long and 0.6 to
0.8 m in diameter, but these still had to be
split then opened up in a flattening furnace.
This increased the size of sheets that could
be made and the scale of production but
not the quality. Better flatness had to await
the success of drawing flat sheet directly
from the melt. Patents for sheet glass pro-
cesses date back to the 1850s but then had
no chance of success. Fourcault, who had
obtained a Belgian patent for a sheet draw-
ing process in 1902, was the first to succeed
but did not manage to produce continu-
ously drawn sheet glass until 1916, during
the First World War. Colburn obtained a
United States patent in 1903 and a French
one in 1905 but likewise did not achieve
15
success until the Libbey Owens company
was established in 1916.
The 1920s saw advances in other meth-
ods of drawing flat glass and in polished
plate manufacture. The Pittsburgh sheet
process was first operated in the United
States in 1928 and brought to Europe in
1930. The Pilkington continuous process
for grinding both sides of the cast plate
ribbon at the same time was a notable
engineering achievement of the 1930s.
However, the most important large scale
development was the invention of the
Float process in the 1950s which made the
very expensive plate process redundant. By
a remarkable coincidence the Float pro-
cess was being worked on simultaneously
by both Ford in the United States and
Pilkington in Britain but Pilkington sub-
mitted their patent applications only a few
months before Ford and thus won the race
which neither of them had consciously been
running. Some of the problems encoun-
tered and solved by Pilkington Brothers in
making the process work have been de-
scribed by Pilkington (1969).
Considerably quicker success attended
the inventors of machines for making bot-
tles. Michael J. Owens joined E. D. Libbey
when Libbey moved his bottle factory from
Boston, Massachusetts, and reopened in
Toledo, Ohio, in 1888. By 1894 Owens had
developed a paste mold machine which
could make lamp chimneys and he began
work on a bottle making machine in 1898.
By 1903 Owens had produced a successful
six arm rotary machine which differed
from most others in the way in which it was
supplied with glass. Semiautomatic ma-
chines which had to be supplied with gobs
by a skilled gatherer already existed and
persisted until about 1960. Owens solved
the gathering problem by using his parison
mold for this purpose. The parison mold
dipped into a pool of relatively fluid glass
16 1 Classical Glass Technology
and was filled by suction; a second mold
was then used for blowing, just as in the
press and blow process. Further models
followed and by 1920 improved and very
effective machines which used six, ten, fif-
teen, and twenty sets of molds had been
been put on the market. However, the
Owens machine had important disadvan-
tages, some technical and some commer-
cial. The major technical problem (which
was never solved) was the cut-off scar on
the base of the container where the hot
glass had been severed by a knife as the
parison mold was lifted from the pool of
glass. The Owens machine was very large
and this was a disadvantage. Apart from its
actual physical dimensions and weight,
hence heavy power consumption (despite
its continuous rotation), it also required
large number of sets of molds for every
article made. It was therefore suitable for
long runs producing millions of one type of
container but much less suited to produc-
ing a range of different products on a less
ambitious scale. Commercial disadvan-
tages included the high initial cost, the
strict licensing arrangements and the
heavy royalty payments required. Many
smaller manufacturers therefore were not
willing to use the Owens machine. This
stimulated work on feeder fed blow and
blow machines.
The glass industry has been very fortu-
nate in its engineering pioneers. The
Owens machine was brought almost to
perfection by about 1920: it then remained
almost unchanged but was an important
bottle producer until about 1960 when it
was supplanted by machines supplied by
gob feeders; the most successful of these
likewise established its main features at an
early stage.
The most important advance needed by
container manufacture was the successful
development of forehearths and gob feed-
ers capable of supplying accurately made
gobs of good quality glass to the forming
machines. This was necessary for any other
type of machine to compete with the
Owens. The Homer Brooke feeder was first
used in 1903 but was not very successful
because it used a cup to collect the glass
from a steady stream and thermal homoge-
neity was impossible to maintain. The cru-
cial advance here was made in 1922 by
Karl Peiler, a Massachusetts Institute of
Technology graduate, when he introduced
the first of the modern type of Hartford
feeder which used a reciprocating vertical
plunger and surrounding tube to control
the flow of glass and produce separate gobs
one at a time from the orifice. This made
possible the successful development of
gob-fed machines for container manufac-
ture and took away from the Owens ma-
chine the one major advantage that it had
enjoyed since its invention.
Containers are now almost universally
made by the Individual Section, or IS, ma-
chine which was invented in 1925 by Henry
Ingle of the Hartford Empire Company.
Nearly all previous machines had been
conceived as using molds on a circular
table which rotated, at first only intermit-
tently, to execute the necessary sequence of
operations. Most machines, other than the
Owens, used two tables, one for parisons
and one for blow molds. The major novel-
ties of the IS machine were to have molds
which are stationary, apart from opening
and closing, only the neck ring holding the
glass being moved, which greatly de-
creased essential operating power con-
sumption, and to make each section essen-
tially independent of the others, which
allowed interruption of part of the ma-
chine, for example to change a mold, with-
out having to stop the whole operation, a
feature unique to the IS. Although numer-
ous improvements have been made to con-
 1.1 The Historical Development of Glass Technology
trol methods and mechanisms in recent
years, for example the development of the
narrow mouth press and blow process for
containers in addition to the original blow
and blow and wide mouth press and blow
methods, the IS remains identifiably the
original machine and the most efficient yet
widely exploited. None of the numerous
alternative machines developed in the last
sixty years has long survived direct compe-
tition with the IS, one of the important
reasons being that having the molds sta-
tionary, except for opening and closing, al-
lows much more efficient mold cooling to
be installed. The Heye company in Ger-
many has developed a machine of great
technical promise but it has yet to become
a major competitor of the IS.
Although processes were needed for the
large scale manufacture of rod and tube,
which had long been drawn by hand, their
development did not need the same imagi-
native leap to entirely new methods as had
containers. The Danner process, developed
in 1912, is remarkably like the traditional
hand made process with glass being con-
tinuously fed onto the outer surface of an
inclined rotating mandrel from which it is
drawn off. The Philips process is similar
but draws the glass from inside a hollow
mandrel. Corning developed both upward
and downward drawing processes and the
Velio process is also a downward drawing
one.
The large scale production of glass fiber
for insulation and for textiles was another
important twentieth century development.
One of the puzzling facts of the early days
of glass technology was the high strength
of fine fibers and this must have influenced
attempts to exploit them. Reaumur, who
attempted to convert bottles to glass ce-
ramic about 270 years ago, also realized
that sufficiently fine glass fibers would be
capable of being woven. Some novelty fab-
17
rics of the nineteenth century used glass
fibers interwoven with silk. The evolution
of a separate branch of the industry
devoted to fibers dates from the 1930s
when the Owens-Corning company was
established and has ever since been the
leader in this field.
Other important advances which have
received little public attention include high
quality dimensionally accurate pressing for
television screen face plates, car headlight
lenses and some optical components. The
development of small tank furnaces, partly
lined with platinum and using platinum
stirrers, for the continuous production of
very homogeneous optical glass also
played a vital part in satisfying the needs of
the optical industries.
Optical instruments benefited from vig-
orous research into expanding the ranges
of combinations of optical properties avail-
able in glasses. During the last twenty
years this has been matched by advances in
lens design resulting from use of comput-
ers. Previously lens design and the evalua-
tion of aberrations depended on extremely
tedious manual ray tracing for every mod-
ification envisaged. Computer ray tracing
so accelerated the evaluation of lens de-
signs that major improvements in perfor-
mance have been realized in the recent
past.
A number of notable developments have
come from the Corning research laborato-
ries, the earliest being Pyrex borosilicate
glass for laboratory ware and other pur-
poses needing good thermal shock resis-
tance or chemical durability. Some years
later the Corning ribbon machine made
possible the very large scale production of
lamp bulb envelopes and Corning also de-
veloped a process for spinning television
tube components. On a more scientific
level the Corning laboratories saw the in-
vention of optical wave guides (also devel-
18 1 Classical Glass Technology
oped by the STL laboratories in England);
photosensitive glasses, the exploitation of
which by S. D. Stookey and his colleagues
led to glass ceramics (see McMillan, 1979)
(see Vol. 11, Chap. 4 of this series); pho-
tochromic glasses and more recently poly-
chromatic glass which can have multi-
coloured images developed in it. Another
Corning success was the exploitation of
phase separation in borosilicate glasses to
make Vycor which is produced by making
and forming an easily melted alkali boro-
silicate glass then heat treating it to cause
phase separation. After that it is leached in
acid to leave a microporous skeleton of
almost pure silica which can be fired again
to densify it. This makes possible the man-
ufacture of some articles very difficult to
form when working directly with pure sil-
ica. It also provides microporous struc-
tures for other applications.
The last two decades have seen the need
for glasses with much smaller transmission
losses than previously imagined to be feasi-
ble, for use in optical communication
systems and this has been one of the most
fruitful research and development fields
(see Chap. 15). This has led to the develop-
ment of halide glasses made in systems
never before considered capable of pro-
ducing glasses or worth investigation (see
Chap. 8). Subsequent developments have
led to studies of other possible optical
communication devices including optical
switches and amplifiers; this has encour-
aged detailed studies of glasses with non-
linear optical properties (see Chap. 12).
Glasses are usually good electrical insu-
lators but can be made with a very wide
range of electrical properties including
semi-conduction and fast ion conduction.
The most exciting discovery of the past few
years in the ceramic field has been 'high
temperature' superconductors, meaning
those which superconduct at liquid nitro-
gen temperatures. This property depends
on a particular type of crystal structure
and there is no sign that glasses can show
such behavior. However, it has been shown
that such superconductors can be made as
glasses and then converted to the crys-
talline superconducting form by the usual
glass-ceramic techniques (Zeng et al., 1989).
Where this can be done it is much simpler
than the usual ceramic techniques of prep-
aration.
1.2 Choice of Glass Compositions
Choosing a glass composition is a more
complicated exercise than may at first ap-
pear. One must first establish the proper-
ties important to the final user, next con-
sider those properties important to the
glass maker, then achieve a balance be-
tween these and lastly determine what
choice of batch materials will produce ei-
ther the best quality or, perhaps, the cheap-
est glass meeting the quality requirements.
Table 1-1 gives some examples of the range
of compositions used for various purposes.
1.2.1 Properties Important to the User
Many glass properties vary fairly
smoothly with composition across a con-
siderable range. The user of a glass for any
particular purpose therefore wishes to
choose the glass which will be the best for
his application. This requires decisions
about the most important properties and a
search for the glass coming closest to the
desired values. Which properties are im-
portant depends very much on the appli-
cation. From a designer's point of view,
strength would nearly always be the first to
be considered. However, because the prac-
tical strength of glasses is determined more
by surface flaws than anything else,
 1.2 Choice of Glass Compositions 19

Table 1-1. Typical glass compositions (wt.%).

Type of glass Na 2 O K2O CaO MgO ZnO BaO PbO A12O3 B 2 O 3 SiO2 Other

Containers
Mid 19th C bottle 4.7 0.9 20.5 5.4 0 0 0 4.4 0 62.5 Fe 2 O 3
Mid 20th C bottle 14.5 0.3 9.9 0.3 0 0 0 1.0 0 73.7 SO3
Late 20th C bottle 13.5 0.4 11.0 1.5 0 0 0 1.0 0 72.3 SO 3
Pharmaceutical
Ampoule 9.0 3.0 0 0 0 6.5 0 9.0 8.0 64.5
Ampoule 12.8 0 3.9 1.1 2.3 0 0 8.1 1.4 70.2
Flat glass
Float (UK) 13.0 0.6 8.4 3.9 0 0 0 1.0 0 72.6 SO 3 ,Fe 2 O 3
Fourcault sheet 12.3 0.7 8.8 3.6 0 0 0 1.8 0 72.1 SO 3 , Fe 2 O 3
Lead crystal
English 5.1 7.2 0 0 0 0 30.0 1.0 0 56.5
European 1.0 14.9 0 0 0 0 24.0 0.1 0 60.0
Laboratory ware
Pyrex 4.1 0.5 0.3 0.2 0 0 0 2.2 11.9 80.8
Kavalier 7.6 7.7 7.4 0.3 0 0 0 0.6 0 76.4
Vycor
As melted 6.6 0 0 0 0 0 0 3.5 26.9 62.7
After leaching 0.2 0 0 0 0 0 0 0.8 4.0 95.0
Sealing glasses
Molybdenum 4.8 0.7 0.9 0 0 4.6 0 4.8 8.4 75.5
Tungsten 4.0 1.8 0 0 0 0 0 2.0 16.9 75.3
Fibers
E glass 0.5 - 19.0 3.5 0 0 0 15.0 7.0 55.0 F2
Textile 1.0 0 18.0 4.5 0 0 0 14.6 7.4 54.3
Mineral wool 3.5 1.1 10.4 10.3 0 0 0 13.5 0 45.6 15.5Fe 2 O 3
C glass 8.5 0 14.0 3.0 0 0 0 4.0 5.0 65.0
Incandescent lamp
Envelope 16.3 1.0 5.5 3.4 0 2.0 0 1.4 0 70.3
Pinch 12.9 0.9 0.4 0 0 0 22.6 0.5 0 61.8
Pinch 5.1 7.2 0 0 0 0 30.0 1.0 0 56.5
Sodium vapor lamp
Inner coating 14.0 0 6.0 0 0 0 0 24.0 48.0 8.0
Inner coating 6.5 0 10.0 0 0 0 0 23.7 37.0 22.6
Inner coating 0 0 5.0 0 0 10.0 0 32.5 24.0 0 28.5 P 2 O 5
Outer casing 15.0 1.0 6.4 3.7 0 2.3 0 1.5 0.5 69.1

Totals may be less than 100% because of rounding off or omission of some minor constituents (e.g. refining agents
or decolorizers).

strength can generally be taken to be The next most important property,

weakly dependent on composition and
omitted from the specification. So far as
strength is concerned commercial glasses
can usually be considered as being either
pure silica or "the rest" and only two sets
of strength data need be considered.
which may not always come immediately
to mind, often is resistance to corrosion.
Good glasses are generally stable, already
being oxides, but can be leached by water
or other chemicals, something which is
only rarely desirable. Chemical durability
20 1 Classical Glass Technology

is strongly dependent on composition, es-
pecially alkali and alumina contents, and
thus should always be included. Next we
come to the properties essential for the
specific application. These may include re-
fractive index, electrical resistivity, thermal
expansion, transparency to or absorption
of radiation, softening temperature, and so
on. These properties fall into two classes,
those for which a specific value is needed,
like refractive index in an optical glass or
thermal expansion for a sealing glass, and
those that need to be better than some par-
ticular limit, like chemical durability or
thermal expansion when thermal shock re-
sistance is important.
1.2.2 Properties Important
to the Glass Maker
Apart from the criteria set by the final
user, several properties are very important
to the glass manufacturer. The viscosity-
temperature characteristic is crucially im-
portant to efficient forming; Fig. 1-6 shows
1 1 I i |\
-\
\ batch but partly by control of furnace at-
AA \
\2
10 \3
some typical viscosity curves for different
types of glasses and shows that a wide
range of working temperatures can be re-
quired. Also the liquidus temperature must
be below the temperature at which the melt
must be held to begin forming operations.
The actual devitrification characteristics
may be less important but it can be useful
to know whether crystal growth may be
rapid if it does occur. The glass manufac-
turer also wants to have a glass as easy as
possible to melt, refine, and homogenize
but these factors are not capable of being
specified in terms of standard properties.
Some glasses contain significant propor-
tions of elements which can exist in more
than one valence state and these may need
their oxidation states to be controlled. The
most familiar example is the decolorizing
of glass in which iron is oxidized, as far as
possible, to the ferric state which gives a
paler tint than the same concentration of
iron reduced to ferrous. On the other hand,
to make a heat absorbing glass one would
wish to reduce the iron to ferrous which
has a broad absorption peak in the near
infrared. Control of oxidation is generally
1 1 1 1 | 1 1 1 1
achieved largely by the selection of oxidiz-
\ 1 ing or reducing materials added to the
\ mosphere. In small scale laboratory melt-
\ • :

ing oxidation can be controlled by bring-

ing the melt to equilibrium with a specific
- y
A \ ^ :

atmosphere but this is not necessary and

5 would be difficult to achieve in large scale

k manufacture.
The batch materials can considerably in-
fluence ease of melting, degree of segrega-
tion during melting, volatilization losses,
1 I 1 i I I 1 I i i i i i i refining, and homogeneity of the glass.
500 1000 1500 2000
Temperature in °C
Both control of oxidation and overall melt-
ing performance can also be affected by
Figure 1-6. Viscosity-temperature relations for some
common types of glasses. 1) vitreous silica, 2) a glass minor constituents, that is to say cations or
for fibers, 3) a container glass, 4) sodium disilicate, anions added at levels usually below 1%,
5) lead crystal. which control oxidation through mutual
 1.2 Choice of Glass Compositions 21

interactions or have beneficial effects on possible to keep the same thermal expan-
melting, refining, and homogeneity. The in- sion but adjust composition to match one
teractions between iron and arsenic, anti- more property. With a four component
mony or cerium can play an important glass three properties can be matched, and
part in decolorizing. Sulfate is the most so on, see Fig. 1-7. Looked at formally it
commonly used refining agent: arsenic is may be seen that trying to match a partic-
often efficient but now rarely used because ular set of n properties requires n degrees of
of legal controls on its use and halides can freedom or, since every composition must
be effective. The glass maker will usually add up to 100%, n + 1 components.
expect to be allowed to modify slightly the If the number of constraints exceeds the
user's composition specification to opti- degrees of freedom it is impossible to sat-
mize these factors. isfy all the desired requirements. In that
case it will be necessary to accept a com-
promise. Choice of a glass composition
1.2.3 Choice of Glass Composition
used to rely heavily on the glass technolo-
Taking account of all the properties re- gist's experience and intuition, requiring
ferred to above can easily produce a list of first the selection of a composition, then
ten or more factors important to either the checking its properties, then making an-
user or the glass maker. Finding a glass to other guess and repeating the process until
satisfy all these requirements may not be the desired result was obtained: this could
easy. However, the task is easier if only be a tedious process. Any exercise of this
some of the properties need to have specific
values and the others need only to be
within some given limit. The number of
constraints to be met is the most important
reason for the complexity of most commer-
cial glasses many of which contain at least
six major constituents: soda, potash, lime,
magnesia, alumina, and silica. It is in fact
gratifying that so many different glasses
can be made without requiring a much
longer list of constituents although most of
the elements have some specific use. The
most commonly used other oxides include
Li 2 O, ZnO, B 2 O 3 , BaO, and PbO.
If one tries to select a glass from a binary
system only two degrees of freedom are
available: 1) which particular system to
choose (e.g. Na 2 O-SiO 2 , K 2 O-SiO 2 or
Li 2 O-SiO 2 ) and 2) the specific composi-
tion. The composition may be chosen so Figure 1-7. Property value surfaces for two different
properties (Y and Z) in a four component system
that one property, such as thermal expan-
(A-B-C-D). All compositions along the line XX
sion coefficient, has the desired value but have the same values of Yand Z; a third property can
all other properties are then already fixed. also be matched by choosing a particular composi-
If a third component is added it becomes tion along this line.
22 1 Classical Glass Technology

kind is made much easier if models exist to
describe the relations between properties
and composition. This can clearly greatly
reduce the number of steps needed and the
necessity for numerous trial melts and
measurement their properties.
1.2.4 Composition-Property Relations
Most research on composition-prop-
erty relations has been restricted to sys-
tems with no more than three components.
The major exceptions have been when an
investigation was undertaken with the in-
tention of producing a model for predict-
ing properties from composition. Several
factors have influenced this; the most im-
portant are the scientist's normal wish to
work with as simple a system as is worth
investigating and the difficulty of repre-
senting data for more than three compo-
nents in a two dimensional diagram, as
illustrated just above. The latter was a
very serious problem before the ability of
computers to work in multi-dimensional
space was exploited. This is clearly seen in
the invaluable comprehensive collection of
composition-property data assembled in
six volumes by Mazurin and his colleagues
(1973-1981), which is limited to three com-
ponents. Some of the problems of dealing
with more complex glasses can be appreci-
ated by consulting books such as Volf
(1961) where much insight into the reasons
for the complexity of several types of glass
may be obtained but information on the
specific effects of various individual com-
ponents helpful in designing a new glass
may be sparse.
One of the most familiar examples of
developing new compositions to solve
manufacturing problems is sheet glass. The
upward drawing of sheet glass was first
brought into production by Fourcault dur-
ing the first World War. Because of the
inherent instability of drawing a flat sheet,
these processes have very strict require-
ments for viscosity in the drawing chamber
and the rate of cooling of the sheet. As a
result the soda-lime glasses originally used
had to be held very close to their liquidus
temperatures and were subject to devitrifi-
cation. This remained a serious problem
for some years. Eventually it was discov-
ered that partial replacement of lime by
magnesia greatly alleviated the problem by
somewhat lowering liquidus but also giv-
ing much slower crystal growth. The clas-
sic work on the subject is by Swift (1947),
see Fig. 1-8. Ever since then flat glass com-
positions have contained about 8% CaO
and 3.5% MgO.
Another important problem concerned
the glass used in electric lamp bulbs
through which the wires carrying the cur-
rent are sealed. This glass must have suit-
able thermal expansion for sealing to the
wires, appropriate softening point and
1000
Temperature in °C
Figure 1-8. Devitrification characteristics of flat glass
compositions with 0, 2, and 4% MgO. Full lines are
for devitrite and dashed ones for cristobalite; after
Swift (1947).

good electrical resistivity up to at least nor-
mal lamp operating temperatures. The sec-
ond requirement implies a glass of fairly
high soda content but this clashes with the
third. Using a lead glass similar in compo-
sition to English lead crystal met those re-
quirements and far more glass of this type
is today used in lamps than for making
decorative products.
1.2.5 Models for Composition-Property
Relations
Most experimental work has obviously
led to data allowing the prediction of prop-
erties from the composition. Fortunately
simple additive equations are quite suc-
cessful for several important properties
over the range of compositions most often
used. Much effort was devoted to such
work by a number of pioneer glass technol-
ogists; one of the oldest such investigations
being that of Winkelmann and Schott
(1894). Such models are entirely empirical
and often of unknown accuracy and lim-
ited validity. Properties for which there are
widely accepted models of this kind in-
clude thermal expansion, room tempera-
ture density, refractive index, Young mod-
ulus, Poisson ratio, dielectric constant,
surface tension, specific heat, and thermal
conductivity. One of the most attractive
features of Scholze's (1977) well known
book is the inclusion of a considerable
number of these models and some com-
parisons of their predictions and ranges of
validity.
The classic models nearly all assume
that a property is a simple linear function
of composition and capable of calculation
from an equation of the type
X = Zaici (1-1)
or
= a0 a, ct (1-2)
1.2 Choice of Glass Compositions 23
where X is the property value, a{ coeffi-
cients for each constituent and c{ the con-
centration of each constituent present.
Concentrations are often expressed as
weight percentages, which are generally
the most convenient to use: in principle
molar percentages ought to be better, espe-
cially when oxides of very different molar
masses are concerned but, with linear ap-
proximations, the accuracy is not always
improved by converting to moles. Some-
times, because m components give only
m — 1 degrees of freedom, compositions are
expressed by the ratios of the other con-
stituents to the silica content when Eq.
(1-2) must be used; the coefficient a0 then
represents the notional property value for
pure silica. If the regression analysis fitted
the data very closely there would be no
point in using more than the necessary
number of coefficients; that is to say m — \.
Sometimes, when the fit is acceptable but
clearly not perfect, using m coefficients and
having one more degree of freedom in the
curve fitting exercise can yield a slightly
better result.
Before computers were available, pro-
cessing the data and obtaining the best set
of coefficients was a very tedious task and
this clearly made the evaluation of com-
plex models too daunting a task for most
investigators. Occasionally the inverse of
the property was found to give a better
correlation but few other refinements were
widely tried.
It is unfortunate that present under-
standing of the structures of glasses still
does not provide a more scientific basis for
dealing with accurate composition-prop-
erty relationships. The most important ad-
vances of recent years have been in the
more sophisticated models and methods of
analysis made possible by the development
of computer hardware and software. One
of the earliest useful attempts to work from
24 1 Classical Glass Technology
a rather sounder base was the work of
Huggins and Sun (1943) who used molar
volumes rather than simple factors for den-
sity itself. Huggins used his approach for
optical constants as well as density. The
following sections discuss some of the par-
ticular properties of greatest interest to
glass technologists and illustrate some of
the difficulties that can arise.
1.2.5.1 The Viscosity-Temperature
Relation
It should be no surprise to find that vis-
cosity has received more attention than
most other properties. One of the first at-
tempts to produce a simple useful method
was that of Okhotin (1954) whose work is
discussed by Braginskii (1973).
One of the most notable exercises has
been the work of Lakatos et al. (1972-
1981). They made their own set of very
careful viscosity measurements on a set of
carefully selected glasses and then analysed
the results. This work was initially in-
tended only to cover a fairly narrow range
of compositions close to those used for
containers and flat glass (Lakatos et al.,
1972 a) but experience has shown that it
can be extrapolated considerably outside
the original field with reasonable accuracy.
Their particular success was to find that
the constants A, B, and <90 in the Vogel-
Tamman-Fulcher equation for viscosity
logrj = -A + B/(0-0o) (1-3) cates excellent agreement at highest tem-
can be well represented by simply additive
terms for each of the oxides present. Thus
for a glass with m components and hence
m — 1 degrees of freedom,
: = 1 to m - j (1-4)
(1-5)
(1-6)
Their original measurements and analysis
were restricted to a range of compositions
including soda, potash, lime, magnesia,
alumina, and silica but were later extend-
ed to include small proportions of sev-
eral other oxides. In separate exercises
they also dealt with lead crystal glasses
(Lakatos et al., 1977, 1978, 1979) and
glasses for insulating fibers (Lakatos et al.,
1981).
Geologists are interested in the viscosi-
ties of silicates, though not to the precision
wanted by glass technologists; two inter-
esting papers on the estimation of viscosity
in systems of geological interest have been
published but, so far as is known, no one
has compared their predictions with those
already discussed. Bottinga and Weill
(1972) reviewed viscosity data for a wide
range of compositions and pointed out the
considerable scatter when plotted as In 77
versus mole fraction silica (XSiO2) but
chose best fit straight lines for several seg-
ments with boundaries at XSiO2 = 0.35,
0.45, 0.55, 0.65, 0.75, and 0.81. They then
used a simple linear additive relation to
estimate In 77 at 50 °C intervals from 1200
to 1700°C for each of these ranges for
11 oxides (SiO2, TiO 2 , FeO, MnO, MgO,
CaO, SrO, BaO, Li 2 O, Na 2 O, and K 2 O);
alumina was dealt with in terms of six alu-
minate compounds of Na, K, Mg, Ca, Ba,
and Mn (e.g. MgAl2O4). They include a
reasonably detailed comparison of their
predictions with reported data; this indi-
peratures and growing discrepancies at
lower temperatures, as might be expected.
They report that 77% of their results lay
within +0.25 In rj units and 99% within
±0.75 units.
Shaw (1972) based his work partly on
Bottinga and Weill but used a different ap-
proach to temperature dependence which,
according to the examples that are quoted,

gives a somewhat better fit than Bottinga
and Weill. Natural logarithm of viscosity is
again assumed to be a simple sum of the
contributions by each oxide but tempera-
ture dependence is assumed to be of simple
Arrhenius form,
lnrj = \nrio + E*/T (1-7)
and the activation energy £* also de-
scribed by a simple additive relation for the
mole fraction of each oxide multiplied by
an appropriate coefficient obtained from
calculations made for each pseudobinary
silicate system. This assumption about the
form of the viscosity-temperature curve
means that extrapolation to lower temper-
atures and much higher viscosities cannot
be relied on. The apparent activation en-
ergy for viscous flow in a typical soda-lime-
silica glass increases by a factor of about
2.5 between 1400 °C and 600 °C, so this is a
considerable weakness in seeking to use
Shaw's model at lower temperatures.
It is possible that either of these methods
may give as good or better results, at high
temperatures, than the models usually
used for compositions outside the range
usually used by the glass industry, but glass
technologists are often more interested in
lower temperatures and higher viscosities
than are dealt with by these models.
1.2.5.2 Liquidus Temperature
Liquidus temperature is the one impor-
tant property for which difficulties must be
expected to arise. Liquidus shows sharp
minima as well as inflexions and maxima
across sections of most systems and multi-
ple linear regression analysis might not be
expected to succeed. That is certainly the
conclusion reached on examining the at-
tempt of Lakatos et al. (1974, 1976 a) to
calculate liquidus by simple linear regres-
sion; his model fits quite well data used to
1.2 Choice of Glass Compositions 25
obtain the factors but gives large errors for
many other compositions, as might be ex-
pected when his range of compositions was
narrow. One possible solution to that
problem is to divide the system into differ-
ent regions and treat each one separately.
Doing this in terms of primary phase fields
as suggested by Babcock (1977) has obvi-
ous merit for liquidus temperature. The au-
thor has confirmed that this method gives
liquidus temperatures in the soda-lime-
alumina-silica system (Silverman, 1939) to
within + 8 °C for most of the compositions
used in the original analysis; the largest
discrepancy being 18 °C.
Simply as an exercise in curve fitting,
dividing any curve into short segments is
likely to allow it to be acceptably described
by a series of straight lines. However, nar-
rowing the composition field for which a
given model is evaluated, which will im-
prove accuracy within that field, is likely to
incur larger errors on extrapolating be-
yond its limits. This is certainly true when
a complex curve is modelled by several sep-
arate segments.
The possibility of improving liquidus
temperature predictions has recently been
investigated by Backman et al. (1990). This
work attempted to predict liquidus tem-
peratures in the soda-lime-silica system
using thermodynamically based models as
well as empirical regression analysis and
also measured the liquidus temperatures of
50 complex glasses with 10 components. In
planning the work it was expected that it
might be possible to derive coefficients for
each of the minor constituents which
would give reasonable values of the liq-
uidus of these complex glasses by estimat-
ing the change from its value for the pure
soda-lime base glass. In fact a multiple
regression analysis for the whole body of
data proved the best of the models exam-
ined, partly because accurate thermody-
26 1 Classical Glass Technology
namic modelling is not possible even for
the basic soda-lime-silica system because
some of the essential data are lacking. Yet
this best model still give errors of a hun-
dred degrees or so for some compositions.
When one considers how many experi-
ments are needed to establish even a fairly
straightforward ternary phase diagram, it
would have been a surprise if data for only
fifty complex glasses had produced a suffi-
ciently refined model.
1.2.5.3 Specific Heat
Specific heat is often needed by workers
concerned with melting or forming pro-
cesses. Because it is difficult to measure
temperatures during forming, determining
the total heat content of the glass after
dropping it into a calorimeter is often the
only measurement easily made. If a good
model for specific heat is available the av-
erage temperature of the glass is readily
calculated from such data.
Specific heat varies with temperature,
the rate of increase falling off as tempera-
ture rises; it is zero at OK and approaches
an asymptotic limit of about 3 R per atom
(R being the gas constant) at very high
temperatures. It is therefore important to
specify whether the value at a particular
temperature or the average over a wide
temperature interval is needed. For the
purpose just mentioned the latter is re-
quired and is also the information ob-
tained directly from the classic kind of ex-
periment in which a sample at a known
temperature is dropped into a calorimeter.
The first simple model was published by
Sharp and Ginther (1951) and then some-
what improved by Moore and Sharp
(1958) who still assumed that all glasses
show the same temperature dependence.
However, examination of the reliable data
available shows that to be a rather crude
approximation which works reasonably
well only because so many glasses fall in a
rather narrow range of compositions. A
better model has recently been proposed
by Richet (1987); this allows the tempera-
ture dependence to differ for each oxide.
However, his analysis covers temperatures
only up to about 950 °C and thus may not
be as accurate at the temperatures used for
glass forming operations as might be
hoped.
1.2.5.4 Thermal Conductivity
Heat transfer is a vital part of glass melt-
ing and glass forming operations as well as
annealing and thermal toughening. The
thermal conductivity is thus frequently re-
quired. Unfortunately it is one of the most
difficult properties to evaluate. The true
thermal conductivity is fairly easy to mea-
sure near room temperature and factors for
calculating it from glass composition have
been published by Russ (1928) and Rat-
cliffe (1963). Scholze (1977) discusses these
and shows that, at least for the examples
that he examines, Russ's rather more com-
plex calculation gives the better agreement
with experiment.
An important complication is the partial
transparent of most glasses to thermal ra-
diation. Any element inside a body of glass
at sufficiently high temperature can both
transmit and partially absorb radiation. If
the glass is at steady state any element
which absorbs radiation must also re-emit
as much as it absorbs and this step by step
process across the whole body could trans-
mit large heat fluxes even in a material of
zero true conductivity. The two limits of
this process are 1) the absorption coeffi-
cient is so low that a negligible fraction of
the radiation is absorbed by the body or 2)
the absorption coefficient is so high that
the depth of penetration of the radiation is

negligible. In the former case the methods
usually used for radiant transfer across
empty space may be used; in the latter the
problem is properly treated as simple con-
duction but most glasses fall in the inter-
mediate range.
The infrared transmission of most glasses
varies very significantly with wavelength
over the range important for radiant heat
transfer, which may be estimated by Wien's
law, according to which any particular po-
sition on the normalized black body radi-
ant energy versus wavelength (A) distribu-
tion curve is defined by
XT=k{ (1-8)
the value of k{ depending on the point on
the spectrum. The following three values
will suffice to make the points needed for
our present purpose;
Maximum intensity: k{ = 2898 (in jimK)
90% at longer wavelengths k{ = 2\95
90% at shorter wavelengths k{ = 9375
Most colourless silicate glasses transmit
well from about 350 nm to about 4.5 \im.
This means that the maximum intensity of
black body radiation falls within the range
over which a glass transmits at tempera-
tures from 370 °C to 8000 °C and a signifi-
cant fraction of the radiation may be trans-
mitted by a silicate glass at any tempera-
ture above 215°C. Clearly the role of radi-
ant transfer will be important in many pro-
cesses with glasses. Fortunately the diffi-
culties of dealing with radiation by using
quite different mathematical arguments
from those used for conduction can often
be avoided by inserting an effective conduc-
tivity into the usual conduction equations.
This effective conductivity is defined by
X = X0 (1-9)
where Xo is the true conductivity and XR is
the radiation conductivity.
1.2 Choice of Glass Compositions 27
This concept was first put forward by
Schuster (1903) who showed that, for a par-
allel beam of radiation travelling through a
partially transparent grey body, the net
heat flux density due to the emission and
reabsorption of radiation could be written
= (8n2aT3/a)dT/dx (1-10)
which by analogy with conduction gives
XR = Sn2aT3/a (1-11)
where n is the refractive index of the
medium, a the Stefan-Boltzmann constant
and a the absorption coefficient of the ma-
terial (see Chap. 12). Making this calcula-
tion for radiation in three dimensions gives
XR = 16n2aT3/3a (1-12)
It is thus assumed that the total heat flux
will be given by the sum of the contribu-
tions of true conduction and radiation so
that the calculations can be made as if the
process is one of conduction only but the
conductivity to be used is as defined by
Eqs. (1-9) and (1-12).
One difficulty immediately arises over
the evaluation of XR; coloring agents and
impurities such as iron make a strongly
dependent on wavelength for many glasses
so that evaluation of the best value to rep-
resent the equivalent grey body may not be
easy. As the absorption spectrum can be
quite strongly influenced by temperature of
the glass, merely measuring the room tem-
perature absorption spectrum is not suffi-
cient in many cases.
When radiation is important the effec-
tive conductivity becomes steeply tempera-
ture dependent above about 600 °C and it
may be more than an order of magnitude
greater than the true conductivity at
1200°C. The increase with temperature is
often less than the T 3 term indicates be-
cause of the changes in a and it may show
inflexions, see Fig. 1-9.
28 1 Classical Glass Technology
Temperature in °C
Figure 1-9. Typical effective thermal conductivities of
colourless flint and green container glasses compared
with the true conductivity over a range of tempera-
tures. After Genzel (1953).
A further complication arises when the
optical thickness of the glass is considered.
Whatever the actual thickness of the glass,
the validity of using radiation conductivity
depends on the optical thickness a x. If the
optical thickness is less than about 0.1 ra-
diant transfer plays a small enough role
to be ignored: if it is greater than about
a x = 3, there is a central region not direct-
ly influenced by conditions at the bound-
aries and heat transfer in the central part of
the glass may be dealt with using the calcu-
lated radiation conductivity and ignoring
boundary effects. However, if the optical
thickness lies between these limits the effec-
tive conductivity becomes a function of the
actual dimensions of the glass body, the
conditions at the boundaries and the rate
of heating or cooling. As Schuster demon-
strated, temperature gradients near any
boundary at which transparency to radia-
tion changes always deviate from those
found in the bulk of the body: in a material
of zero true conductivity there would be a
discontinuity in temperature which true
conduction smooths out in practice. Fig-
ure 1-10 shows some predictions of steady
state temperature distributions in thick
bodies of glass made by Walther et al.
(1953). As a result effective conductivity is
not easily estimated for many real situa-
tions, especially in bodies of intermediate
thickness. Radiation does, however, play a
vital and relatively straightforward role in
the transfer of heat in the molten glass in-
side a melting tank and a negligible role in
a typical glass no more than a few millime-
tres thick being rapidly cooled or heated.
One of the most authoritative reviews of
these matters is by Gardon (1961) and
Table 1-2 gives a selection of thermal con-
ductivities for sheet glass taken from Gar-
don's review; it can be seen how much ge-
ometry and cooling rate influence the
values even at a temperature where radia-
tion is just beginning to be important.
1500
1400
Q.
1200 -
0.2 0.4 0.6 0.8 1.0
Depth in m
Figure 1-10. Predicted temperature distributions in a
bath of glass with black body radiation from gas
above and black body refractories at the bottom. The
values of the absorption coefficient a in m" 1 are
shown on the curves: after Walther et al. (1953).
 1.2 Choice of Glass Compositions 29

Table 1-2. Thermal conductivity of flat glass at 600 °C puter models in designing new glass com-
according to conditions of measurement or process. positions. Existing models do, however,
Conditions Effective conduc- give valuable assistance in providing useful
tivity <(Win- 1 ^ 1 ) approximations which should generally
need little further experimentation to reach
Measured in steady state: a suitable final composition. Turkdogan
4.5 mm wall of cylinder 0.84
6 mm slab 1.59
(1983) deals extensively with slags as well
9 mm wall of cylinder 1.63 as glasses and provides a useful addition to
18 mm wall of cylinder 2.30 the sources of data usually consulted by
25 mm thick slab 1.67-2.09 glass researchers. Tables 1-3 and 1-4 give
50 mm thick slab 2.59 a selection of factors often used for the pre-
Measured by periodic flow: diction of glass properties using simple ad-
83 mm radius cylinder 3.47
ditive relations; however, these are of un-
Theoretical estimates:
True conductivity 0.837
specified accuracy and limited ranges of
Radiation conductivity in thick body 5.19 validity so readers are recommended to
Best values for use in calculations: consult the original sources or Scholze
Slow cooling of 6 mm slab 1.34 (1977) before using them.
Thermal toughening of 6 mm slab 1.00

1.2.6 The Modern Approach to Choice

1.2.5.5 Summary
The various examples given in the last
few sections show that the development of
improved property-composition models is
not just a matter of improved statistical
analysis of the data. Since most, but not all,
properties of glasses vary smoothly, even if
rapidly, with composition it will often be
possible to represent properties within lim-
ited areas by linear regressions. However,
higher order terms often become necessary
as the composition field is broadened.
Also, as Lakatos et al. (1975) showed in
their work on chemical durability, higher
order terms are sometimes necessary even
for quite restricted ranges of compositions.
Another problem with entirely empirical
models is that coefficients obtained for one
particular set of data are valid only for that
particular analysis.
Much more work is needed on proper-
ties like liquidus, chemical durability, elec-
trical conductivity, and specific heat before
it will be possible to rely entirely on com-
of Glass Composition
Basically two things are needed to make
the design of glass compositions easier.
One is the development of better multi-
dimensional computer models for more
properties and wider ranges of composi-
tions. The other is to approach the prob-
lem from the converse of the traditional
direction, that is to specify the properties
and then deduce the composition, or range
of compositions, coming closest to meeting
that specification. Huff and Call (1973) out-
lined the possibilities of developing proce-
dures for computing compositions from
specifications of properties by using op-
timization techniques. Westerlund et al.
(1983) have published a more detailed
account of procedures for this purpose
provided that the required composition-
property models exist and giving the mod-
els that they used. A typical application of
this program would specify six points on
the viscosity-temperature curve, thermal
expansion, Young modulus, Poisson ratio,
chemical durability, density and refractive
30 1 Classical Glass Technology

Table 1-3. Appen's factors for calculating density, refractive index, thermal expansion coefficient, Young modulus
and surface tension for multi-component glasses.

Property Density Refractive Thermal Young Surface

index expansion Modulus tension

Equation (1-1) (1-1) (1-1) (1-1) (1-1)

Unit of Cj mol% mol% mol% mol% mol%

Li 2 O 11.0 1.695 27.0 8.0 450

Na 2 O 20.2 1.590 39.5 5.95 295
K2O 34.1 1.575 46.5 4.1
MgO 12.5 1.610 6.0 9.2 520
CaO 14.4 1.730 13.0 11.15 510
ZnO 14.5 1.710 5.0 6.0 450
SrO 18 1.770 16.0 9.65 490
BaO 22.0 1.880 20 6.25 470
PbO 20.0 to 23.6 2.5 to 2.35 13.0 to 19 4.3
A12O3 40.4 1.520 -3.0 11.4 580
B2O3 18.4 to 34.0 1.47 to 1.710 -5.0 to 0.0 1.0 to 18.0
SiO 2 26.1 to 27.25 1.458 to 1.475 0.5 to 3.8 6.5 to 7.1 290

Sources: Appen (1949, 1954, 1956), Appen et al. (1961)

Calculation of values of variable factors

Density in g cm'3
Silica: c (SiO2) < 67, a (SiO2) = 26.1: c (SiO2) > 67, a(SiO2) = 23.75 + 0.035 c(SiO2).
Boric oxide: calculate cp = QT c(R 2 O) + E C ( R O ) - C ( A 1 2 O 3 ) ) / C ( B 2 O 3 ) then select a(B 2 O 3 ) according to the
following:
c (SiO2) 44 to 64; 0.33 < cp < 1, a (B 2 O 3 ) = 24.7 + 3.1/cp; l<cp<4,a (B2O3) = 30.8 - 3.1 cp;
cp>4, a(B 2 O 3 ) = 18.5.
c(SiO 2 ) 71 to 80: 0.333 <cp< 0.5, a(B 2 O 3 ) = 24.7 + 3.1/cp; 0.5<q><l9 a(B2O3) = 15.4 + 7.8/<p;
l<<p<1.6, a(B2O3) = 31.0-7.$ cp; <p>1.6, a(B 2 O 3 ) = 18.5.
Lead oxide: calculate y = c (SiO2) + c (B 2 O 3 ) + c (A12O3) then select as follows:
50 < y < 80, a (PbO) = 14.0 + 0.12 y; y > 80, a (PbO) = 23.6.

Refractive index
Silica: c (SiO2) < 67, a (SiO 2 ) = 1.475; c (SiO 2 ) > 67, a (SiO 2 ) = 1.5O85-O.OOO5 c (SiO 2 ).
Boric oxide: calculate cp as above then select as follows:
c(SiO2) 44 to 64: cp <0.333, a(B2O3) = 1.470; 0.333 <<p<l9a(B2O3) = 1.616-0.048/cp;
l < < p < 4 , a (B 2 O 3 ) = 1.518 + 0.048 cp; cp>4, a(B 2 O 3 ) = 1.710.
c(SiO 2 ) 71 to 80: cp < 0.333, a(B 2 O 3 ) = 1.470; 0.333 < cp < 0.5, a (B2O3) = 1.760-0.12/cp;
l<cp<1.6,a (B 2 O 3 ) = 1.518 4- 0.12 cp; cp > 1.6, a (B 2 O 3 ) = 1.710.
Lead oxide: calculate y as above then select as follows:
50 < y < 80, a (PbO) = 2.685-0.0067 y; y > 80, a (PbO) = 2.350.

Thermal expansion in 10~8 K'1 (20 to 400°C)

Silica: c(SiO 2 )<67, «(SiO2) = 3.8; c(SiO 2 )>67, c(SiO2) = 10.5-0.1 c(SiO2).
Boric oxide: calculate ij/ = {c (Na2O) + c (K2O) + c (BaO) - c (A12O3) + 0.7 (c (CaO) + c (SrO) + c (PbO)) +
+ 0.3 (c (Li2O) + c (MgO) + c (ZnO))} /c (B2O3) then a (B2O3) = -1.25 i// except for xfj > 4 when the value is
a(B 2 O 3 ) = -5.0.
Lead oxide: a (PbO) = 13.0 for a) alkali-free glasses, b) alkali lead silicate glasses with X C ( R 2O) < 3> c) other
glasses with E c (RO) + S c (RmOB)]/J] c (R2O) < 3; for other glasses not meeting conditions a) to c) it is
a (PbO) = 11.5 + 0.5 X c (R2O).
 1.2 Choice of Glass Compositions 31

Table 1-4. Factors for calculating viscosity and room temperature thermal conductivity.

Property Viscosity Thermal conductivity

Equation (1-2) (1-1)

Unit of c{ wt./wt SiO 2 wt.%

Author Lakatos et al. (1976 b) Iluss(1928)

A B To

Li 2 O -3.180 - 1 1 518 - 1 329 _

Na 2 O -1.620 - 6 601 50.0 10.70 0.3448
K2O 0.660 - 541 -236 13.40 0.3448
MgO 5.890 5 621 -212 4.55 0.2564
CaO 0.640 - 6 063 771 8.80 0.2564
ZnO 1.60 - 376.0 96.0 8.65 0.1695
BaO 0.260 - 2 103 109 11.85 0.1408
PbO -0.500 - 2 544 82.0 11.70 0.1000
A12O3 -0.870 1 521 140 6.25 0.3125
B2O3 -4.650 - 1 5 511 1203 3.70 0.4255
(B 2 O 3 ) 2 16.27 40 999 - 2 765 - —
SiO2 — __ — 3.00 0.4348
Constant (a0) 1.713 6 237.01 149.4 - -

Viscosity
The terms are summed to give the values of A, B and To to be put into the Vogel-Tammann-Fulcher equation,
log(?//dPa s) = —A-\-B/(0 — 0o); note that there are both first and second order terms for B 2 O 3 .

Thermal conductivity
First calculate the notional volume percentage of each oxide from f f = 100 ct vt/Y, ct vn then sum the vi (1/Af)
terms to obtain the reciprocal of the conductivity I/A'. To obtain the true room temperature conductivity
(Wm" 1 K) take the reciprocal of this (Xf) and multiply by 418.7.

Young Modulus in kbar

Silica: c (SiO2) < 67, a (SiO2) = 6.5; c (SiO2) > 67, a (SiO2) = 5.3 + 0.018 c (SiO2).
Boric oxide: calculate cp as above and select as follows:
<p<l, a(B2O3) = l + 14(p; l<<p<2, fl(B2O3) = 12 + 3 <p; <p > 2, a(B 2 O 3 ) = 18.

Surface tension in mNm~l (1300°C)

* These oxides can have very variable effects on surface tension in different glass melts, even the sign of the term
may change.
32 1 Classical Glass Technology
index. Weighting factors can be used to
emphasize the influence of the most impor-
tant properties.
Indeed Westerlund et al. (1983) have
taken the method two useful stages further.
The first is to work with batch materials,
not just glass composition; the second is to
include raw material prices, allowing opti-
mization of batch costs as suggested by
Kiessling and Dressel (1979).
1.2.7 Choice of Raw Materials
Selecting the cheapest batch is not al-
ways the best choice because choice of
batch can have very important effects on
melting and glass quality which are not
recognized by computer models. Neverthe-
less, the ability to examine the possibilities
of savings in cost of the batch is a very
useful tool and has been successfully ex-
ploited (Hatakka, 1986). As already indi-
cated, choice of raw materials can have sig-
nificant effects on ease of melting and glass
quality as well as costs. Even though the
commonest glasses use natural minerals
and the cheapest of manufactured chemi-
cals, the raw materials often cost more
than twice as much as the fuel used in melt-
ing. This is a tribute to the efforts of the
industry to achieve the most efficient use of
the fuel and shows that using the cheapest
raw materials is an attractive idea. How-
ever, this is not always the best choice. The
overall melting cost depends on ease of
melting and refining and the quality of the
glass, also on furnace life. Sometimes a
rather more expensive batch material
proves worthwhile because of its influence
on these other factors. West-Oram (1979)
gave an extensive and very informative re-
view of glass batch materials.
Choice of batch materials may also be
influenced by the need to control oxidation
of the melt. For this purpose the Batch
Redox Number is often useful. Manring
and Hopkins (1958) proposed that factors
for oxidizing or reducing power could be
assigned to each batch material and then
summed in the traditional way to obtain a
value that would describe the state of oxi-
dation of the melt produced. These factors
were based on a simple assumption about
the reducing action of carbon but modified
in the light of experience. The factors were
given and their use also illustrated by
Simpson and Myers (1978). The more re-
cent modification of this concept in terms
the chemical oxygen demand does not seem
to have important advantages.
Glass melting is discussed next. Here it is
sufficient to note that what is called melt-
ing is complex and it is not always easy to
predict what will produce the best result.
The possibilities of including accurate pre-
dictions about melting, refining, or homog-
enizing in a computer data base are at
present remote.
1.3 The Melting of Glasses
1.3.1 Introduction
It is important to recognize that glass
makers do not use the word melting in its
strict scientific sense; most glasses are
melted at temperatures below the melting
points of their major refractory constitu-
ent, most often silica. If a glass can be pro-
duced by normal melting that will nearly
always be the preferred method on
grounds of cost and scale of production:
when it will produce a satisfactory product
there is little reason to choose a more re-
stricted and expensive method. However,
alternatives to normal melting are very ac-
tive research topics at present.
Sol-gel and chemical vapour deposition
techniques have important parts to play in
high technology applications; these tech-

niques are usually expensive and limited to
small scale production, they are discussed
in the next chapter. It has often been said
that sol-gel methods can save energy in
the manufacture of refractory glasses, such
as pure silica, because considerably lower
temperatures are used and this is true when
the energy consumption of only the final
stage is considered. But when the energy
consumed in making the starting materials
for the sol-gel process is considered, that
method is seen overall to use a great deal
more energy and the prices of the raw ma-
terials demonstrate this.
Similar statements are sometimes made
about large scale electric melting. The effi-
ciency of using the energy supplied in a
well designed electric melting furnace
should be more than twice that achieved in
a good combustion heated furnace but the
efficiency of using the energy in a well de-
signed glass tank is considerably better
than that achieved in a fuel fired electricity
generating station. Therefore it is not gen-
erally more efficient to convert the thermal
energy of gas or oil to electricity before
using it. However, electric furnaces have
other advantages for certain purposes,
such as the melting of glasses containing
some important volatile constituents, or if
the electricity is produced hydroelectri-
cally. Determining the economics of large
scale glass production must consider all of
the relevant factors including capital and
running costs of the furnace. Electric fur-
naces are discussed in detail by Stanek
(1977).
1.3.2 Energy Requirements
Silicate glasses are usually melted at
temperatures of around 1400-1600°C and
forming operations need the melt to be
held at a certain viscosity, which usually
means temperatures of 1050-1200°C. Tak-
1.3 The Melting of Glasses 33
ing the raw materials at room temperature,
heating them to these high temperatures
but eventually cooling the glass produced
to room temperature uses a great deal of
heat much of which is apparently wasted.
The efficient use of this energy must thus be
examined. The energy required has two
basic components, the heat of reaction and
the sensible heat needed to raise the glass
to the maximum temperature used.
1.3.2.1 Enthalpy of Reaction
Accurate data for glass melting reactions
themselves are rare. It is therefore neces-
sary to treat the glass as a mixture of ap-
propriate compounds for which the basic
data are available and assume that the
heats of mixing of the silicate liquids are
zero. Heats of mixing are not in fact zero
but probably small enough for this proce-
dure to be acceptable. For a simple soda-
lime-silica batch comprising carbonates
one might use
Na 2 CO 3 + SiO2 -•
(1-13)
-+Na 2 SiO 3 + CO 2 T+2!iJ 1
Na 2 SiO 3 + SiO2 ->
->Na 2 Si 2 O 5 +zliJ 2 (1-14)
CaCO 3 -+CaO + CO2T (1-15)
CaO + SiO2 -• CaSiO3 + AH4 (1-16)
The overall enthalpy of melting is then ob-
tained by adding together the correct mole
fractions of these energies to make up the
correct glass compositions
(1-17)
AHM = nx AH1 + n2 AH2 + n3 AH3 + ...
The data usually used and the methods of
calculation employed are those given by
Kroger (1953) and Kroger et al. (1958).
34 1 Classical Glass Technology
1.3.2.2 Sensible Heat
Specific heat varies with temperature as
well as composition so it is important to
use the average over the proper tempera-
ture range. For glasses of the most com-
mon types the factors discussed in the pre-
vious section may be used. For many
glasses the average specific heat to raise to
melting temperature is close to l k J k g " 1
so that a rough estimate of the sensible
heat is easily made.
Calculations of this kind yield results
similar to those given in Table 1-5 and
some interesting observations arise from
these values. First, the sensible heat consid-
erably exceeds the enthalpy of reaction;
when the glass is to be cooled again to
room temperature this implies that energy
could be saved by using as low a melting
temperature as possible, for example, just
above the liquidus, but this is a false con-
clusion. Second, it seems that lead crystal
should be the easiest to melt of the glasses
mentioned and this is true but the labora-
tory ware borosilicate is by far the most
difficult to melt. Clearly the theoretical en-
ergy required for melting does not tell us
about the ease of melting the glass. Ease of
melting is determined by the kinetics of the
important reactions and the dissolution of
silica grains in essentially isothermal con-
ditions is generally the slowest of these.
Looking at the silica contents of these
Table 1-5. Theoretical heat required for glass melting
inkJkg-1.
Type Heat of Total heat to raise to:
reaction
1200°<C
Lead crystal 400 1830
Borosilicate 410 1820
Container 475 2125
Flat 700 2420
glasses gives us a much better idea of how
readily they melt; lead crystal has around
56wt.% SiO2 and Pyrex about 80wt.%
SiO2 whilst the others will have about
72wt.% SiO2.
Logic suggests that the use of raw mate-
rials which take part in exothermic glass-
forming reactions should be beneficial and
some ingenious ideas based on the use
caustic soda or soda-lime have been put
forward from time to time, for example by
Pugh (1968). Because of the exothermic re-
actions involving sodium hydroxide, it is
dangerous to cast soda-rich glasses or fu-
sions into water. However, the implied
smaller enthalpy of melting is no guarantee
of faster practical melting, quicker refining
or better homogeneity, as shown by Cable
and Siddiqui (1980). One of their findings
was that mixing NaOH and CaCO 3 allows
the reaction
2NaOH + CaCO 3 ->
-> Na 2 CO 3 + Ca(OH) 2 (1-18)
to proceed almost to completion before
any other begins. On the other hand, the
major contribution of the sensible heat
does mean that preheating of the batch can
bring appreciable savings if it can be
achieved. However, preheating must stop
below the temperature at which the batch
begins to react and form a sticky mass
which will clog any apparatus in which it is
reacting; this temperature can be below
500 °G
1.3.3 Preparations
In both laboratory and large scale glass
1500°C
making it is a serious mistake to neglect
batch preparation. The use of carefully pre-
2250 pared and homogeneous batch can have a
2250 great influence on the quality of the glass
2620 produced. It is not intended to discuss
2940
batch preparation and handling in detail

here, just to point out some of the impor-
tant factors. Glass batches usually contain
several, often seven or more, materials in a
wide range of relative proportions and,
perhaps, different particle sizes, which
makes their mixing difficult. When these
materials have a range of densities, shapes
and frictional properties, it is difficult to
achieve good mixing or, once attained, to
prevent segregation before the batch is
melted. Long mixing times, such as often
used in the ceramic industry, are rarely de-
sirable. There is ample evidence that the
quality of the batch put into the furnace
has an important influence on the quality
of the glass produced. Even if the batch is
well mixed some tendency to segregation
during melting is inevitable. Much thought
and experience goes into the design and
operation of a successful batch mixing,
transport and charging system on an in-
dustrial furnace. On a laboratory scale care
over accuracy of weighing out materials,
mixing and preventing segregation is
equally beneficial.
It can be claimed that the scientific prin-
ciples of mixing solids are reasonably well
understood and largely concern generating
random diffusive motion in an assembly of
particles. This can only occur when the
particles are already in motion caused by
stirring or tumbling the bulk of the mate-
rial. However, the theory is little help in
practice when particles having very differ-
ent properties are concerned. Different
sizes, shapes, and so on mean that different
particles always have some tendency to be-
have differently under the influence of
gravity. Hence the motion which is being
used to achieve mixing always has some
tendency to provoke segregation at the
same time. It is easy to mix glass batch too
long or to cause segregation by vibration
or free fall between mixing and charging
into the furnace. Deliberate addition of a
1.3 The Melting of Glasses 35
few percent of water can be very helpful in
retarding batch segregation. Papers by
Poole (1963) and Fletcher (1963), together
with several others in the same issue of
Glass Technology give some very useful in-
sight into these matters.
1.3.4 The Stages of Melting
Glass melting comprises a number of
rather complex stages in which different
physical and chemical phenomena pre-
dominate. It is therefore useful to consider
it in several stages but it must never be
forgotten that these overlap in time and
space and considerably influence each
other. Figure 1-11 shows the most useful
way of dividing the whole process; each of
these stages is considered in the sections
that follow.
1500 i -
Temperature
1000 -
Q
Dissolve
sand
| BAICH-hHLb
500 -
• /I Remove bubbles
~|SEED-FF
"Ij\ Homogenize
I
2 3
Time in h
Figure 1-11. Schematic diagram of the stages of glass
melting. Region (i) is where the batch has not yet
reached reaction temperature and (ii) shows the time
occupied by vigorous reaction.
1.3.4.1 Batch Heating
Melting reactions can be detected in
common silicate batches at about 400 °C
36 1 Classical Glass Technology
but usually are not sufficiently rapid to be
important until the temperature reaches
about 600 °C. Some subsidiary processes,
such as evaporation of moisture or the
melting of minor constituents with lower
melting points, may of course take place at
lower temperatures.
Glass batches are largely made from ma-
terials with poor thermal conductivities
and the question of how to heat the batch
deserves examination. This may be con-
firmed by taking a simple example. Sup-
pose that a furnace is producing 120 tonnes
of glass a day, which is equivalent to sup-
plying 100 kg of batch per minute, and that
the batch is charged as a continuous blan-
ket 4 m wide and 0.15 m thick which hence
must advance at a rate of 0.083 m min" x . If
this were a slab of solid material with both
of its surfaces suddenly heated to 1400 °C
the time for its centre to reach 600 °C by
simple conduction would, according to the
classic theory, be given by at/I2 = 0.33.
Here the half thickness / is 0.075 m and the
thermal diffusivity of the batch may be esti-
mated at about a = 2.8 x 10~7 m 2 s" 1 . The
time needed for all of the batch to begin to
react would thus be about HOmin during
which time the blanket would advance
9.2 m down the furnace and it might travel
as much as 20 m before melting was com-
plete. This is clearly a serious overestimate
of the length of furnace occupied by melt-
ing batch.
Several factors cause this serious error.
First, the thermal properties of the batch
vary with temperature, largely due to them
reacting; second, the batch blanket does
not remain of constant thickness as reac-
tion occurs; third, flow of liquid produced
by reaction and convection of hot gases
can both increase the rate of heat transfer.
Jack and Jacquest (1958) studied the impli-
cations of the simple constant property
model considered above and showed that
minimum melting length would be given
by a particular blanket thickness for a
given output.
Measurements by Ito et al. (1954) in a
layer of batch 150 mm thick charged on to
a melt in a pot 1 m in diameter found that
it took 60 min for all of the batch to reach
1000°C and thus react vigorously: our
simple model predicts that it should take
about 200 min for the centre to reach
1000 °C. Daniels (1973) found that the cen-
tre of a batch layer initially 40 mm thick
charged on to glass at 1400°C reached
1000 °C in 24 min. Comparing these two
observations suggests that the rule of time
proportional to square of thickness ex-
pected for simple conduction in a solid
does not apply to melting batch: if 24 min
were correct for 40 mm one would predict
340 min for 150 mm.
It is difficult to measure the thermal
properties of reacting batch but some use-
ful data were obtained by Kroger and
Eligehausen (1959) who measured the tem-
perature difference between the inner and
outer walls of an annular space filled with
batch when it was heated by a central axial
heating element. When operating at steady
state this is a standard method for deter-
mining conductivity; the energy input
gives the heat flux and the measured tem-
peratures allow the thermal conductivity
to be calculated. Several important bold
assumptions are made in applying exactly
the same simple analysis to reacting batch
but the data obtained are the best esti-
mates that we have. Figure 1-12 shows the
general trends found for measurements
made during both heating and cooling af-
ter the batch had been converted to glass.
The values for the latter are more influ-
enced by radiant transfer. It can be seen
that the apparent conductivity of batch
changes little until reaction begins but then
increases rapidly as temperature rises.

This brief discussion should have
demonstrated that, although rarely dis-
cussed in the literature, how to charge
batch into a large scale furnace to get the
most rapid melting and also minimum
melting segregation is a complex question
of considerable importance. Batch is a
good insulating material which greatly re-
stricts heat transfer into the melt below it
and thus to the under side of the batch
layer. Covering the whole of the melting
area with a uniform layer of batch may
give the thinnest batch layer, which by it-
self should accelerate melting, but seriously
restricts the melting of the bottom of the
batch layer unless a powerful convection
current of other energy source beneath the
batch layer provides the necessary heat in-
put. Optimizing the extent of cover of the
melting area by batch piles, logs or blanket
is a subtle matter. There is some discussion
of this topic in Trier (1984). Some electric
melting furnaces, for example the Gell
type, rely entirely on the insulating proper-
ties of the batch to prevent heat loss from
the top of the melt (Gell, 1956).
1.3.4.2 The Initial Melting Reactions
The rates at which the various materials
in a batch tend to react together depend on
temperatures as well as time. It is, of
course, essential for the reacting materials
to be in contact with each other and good
contact cannot be guaranteed until some
liquid has formed and is able to percolate
around the solid grains still present. If the
initial reactions occur in the solid state
their particle sizes and efficiency of mixing
must be important; reactions occurring at
a solid surface must depend on the surface
area available and thus on particle size.
Varying the particle size for a given rate of
heating can thus affect the extent to which
some of the possible reactions occur. The
1.3 The Melting of Glasses 37
200 400 600 800 1000 1200 1400
Temperature in °C
Figure 1-12. Estimates of the apparent thermal con-
ductivities of reacting batch during heating and of the
glass produced; after Kroger and Eligehausen (1957).
dependence of reaction rates on tempera-
ture also means that behavior can be mod-
ified by rate of heating. We have already
seen that different parts of a batch layer
cannot all be heated at the same rate, so
some complications may be expected for
that reason. As a result one cannot pro-
duce one reaction scheme which will al-
ways apply in a particular system and this
is the reason for some of the discrepancies
between the findings of different authors
who have studied similar batches but used
different methods or conditions. This is
easily illustrated for potash-red lead-sand
batches.
Figure 1-13 shows the average reaction
paths found for two somewhat different
compositions in this system. There is no
reason why the earliest reactions should
have been greatly influenced by the differ-
ence in final glass composition, yet the re-
sults shown suggest this. However, both
sets of results may be described fairly well
by assuming the following general scheme:
1) All the potash reacts to form a potas-
sium silicate.
2) This potassium silicate reacts with the
red lead.
38 1 Classical Glass Technology
Si0o
PbO
Figure 1-13. Average compositions of the liquid phase
during melting of lead crystal glass according to
Rosenkrands and Simmingskold (1962) and Bez-
borodov and Appen (1933). Idealized reaction se-
quences are shown dashed. The two investigations
used different experimental methods, see text.
3) The potassium lead silicate dissolves
the remaining silica to achieve the final
glass composition.
The important difference is in the com-
position of the potassium silicate first
formed. According to Rosenkrands and
Simmingskold (1962) it is the metasilicate,
K 2 SiO 3 , but Bezborodov et al. (1933)
found it to be the tetrasilicate, K 2 Si 4 O 9 ;
the difference is explained by the experi-
mental procedures used in the two cases.
Rosenkrands and Simmingskold took
small samples from a typical large pot melt
being made in normal conditions but
Bezborodov et al. used heat treatment of
laboratory samples in 100 °C steps from
200 °C to 1200°C, keeping the sample at
each temperature long enough for reaction
to have almost ceased. This clearly ex-
plains why their results show much more
silica reacted in the early stages than those
of Rosenkrands and Simmingskold. Both
sets of experiments agree about the main
points: reaction first produces whatever
product is most easily formed (a potassium
silicate) which then undergoes a further se-
quence of reactions, ending with the slow-
est step (dissolving residual silica). Melting
inevitably produces a range of composi-
tions which can differ greatly in composi-
tion, density and viscosity and thus may
easily segregate. Mixing these to make a
homogeneous glass can be difficult, espe-
cially if density and viscosity difference
have encouraged serious melting segrega-
tion.
Few books discuss glass melting reac-
tions; Bezborodov (1968) is a notable ex-
ception.
If one or more of the raw materials, early
liquid phases or the final melt has a strong
tendency to lose a component by evapora-
tion this can aggravate the difficulties of
producing a homogeneous melt. Alkalis,
sulphur, lead, boron and halogens are
amongst the most volatile constituents.
The kinetics of volatilization can be influ-
enced by several factors including diffusion
in the melt, transport in the gas phase and
reaction with the atmosphere, see Cable
(1978).
Laboratory Studies
The discussion above compared results
obtained in the laboratory with some typi-
cal of industrial practice. The former type
of experiment is convenient when it can be
employed but, as we shall see, does not
yield all the information that would be
helpful. However, direct experiment on an
industrial scale is difficult to organize and
control and also very expensive, especially
when the results are not directly beneficial.
There is therefore a role for both the appli-
cation of standard laboratory techniques
and for empirical melting studies: both are
needed to obtain the maximum insight that
can be expected. The most obviously useful
laboratory techniques are thermogravi-
metric analysis (at constant temperature),

differential thermogravimetry (with steadily
rising temperature) and differential ther-
mal analysis or its close analog differential
scanning calorimetry.
Thermogravimetry records only weight
changes and so can record decomposition
of carbonates, sulphates, nitrates and so on
but cannot identify the fraction of silica
reacted. Differential thermal analysis or
scanning calorimetry are more versatile be-
cause they record evolution or absorption
of energy, whatever its cause, but they like-
wise do no directly identify the process
concerned.
Constant temperature thermogravime-
try should be the simplest kind of experi-
ment to interpret and approximate theo-
retical models for solid state reactions in
two component systems are available.
Three are well known and widely used, the
Jander model, the Ginstling and Broun-
shtein model and the Valensi- Carter
model. Jander's (1927) equation was based
on a qualitatively correct analysis of diffu-
sion between two flat slabs of reacting
solids which maintain constant volume.
The important feature being that control
by diffusion would make the thickness y of
the flat layer of reaction product increase
as
y2 = kt (1-19)
If the spherical shell on an idealized parti-
cle of radius a0 is assumed to behave like a
flat slab and a is the mass fraction reacted,
this transforms into
[l-(l-a)ll3]2 = kt/a20 (1-20)
When examined quantitatively for a sphere
the equation becomes
/n)Dt/a2 (1-21)
where q> is the effective solubility; note that
it appears as cp2.
1.3 The Melting of Glasses 39
Ginstling and Brounshtein (1950) im-
proved this model to take the spherical
symmetry into account but their analysis
still ignores the motion of the boundary
and any change in volume of the system
and yields
l-(2/3)a-(l-a)2/3 = (1-22)
The Valensi-Carter (Valensi, 1935, 1936,
1950; Carter, 1961 a, b) model does allow
for a change of volume as well as spherical
or cylindrical symmetry. For spherical par-
ticles it gives
[1 + (z - 1 ) a] 2 / 3 + (z -1) (1 - a) 2/3 =
= z + 2(l-z)(pDt/a2 (1-23)
where z is the volume of product per unit
volume of the material in the sphere. The
limited validity of all these equations has
recently been examined by Cable and
Frade (1991) who conclude that they are
useful for seeing whether a reaction is diffu-
sion-controlled but not at all suitable for
estimating other parameters such as diffu-
sivity. No good models exist for multi-
component systems or for ones with liquid
present, where convection of that liquid is
very likely to affect the reaction.
Neither do any satisfactory theories ex-
ist for differential thermogravimetry. The
main use of this kind of experiment is to
indicate the temperature ranges where var-
ious reactions may be rapid and to amplify
the information available from differential
thermal analysis. In principle the area un-
der the peak of a differential thermal anal-
ysis trace gives the quantity of heat evolved
or absorbed. In practice it is extremely dif-
ficult to establish the base line with suffi-
cient accuracy to make quantitative evalu-
ation possible, largely because the thermal
properties of the material change whilst it
is reacting and the sample may also either
swell or shrink at the same time. It is easy
to show that better accuracy may be ex-
40 1 Classical Glass Technology
pected when a small sample is used and
modern sets of apparatus are therefore of-
ten designed for no more than 50 mg.
However, when one considers the size of
particle often used in glass batches and the
complexity of the mixtures concerned, it is
clear that obtaining an accurate and repro-
ducible result is by no means easy espe-
cially if it was intended to investigate the
effects of minor constituents. Very finely
divided powders must be used and one is
thus unable to study the known effect of
particle size on reaction kinetics with such
apparatus. The latest improvements in the
apparatus have not, in fact, helped workers
studying reactions in glass or ceramic sys-
tems.
One of the classic investigations of reac-
tions in the soda-silica system is the differ-
ential thermal analysis work of Wilburn
and Thomasson (1958, 1960). The second
part of this investigation was concerned
with the influence of minor additions on
sodium carbonate-silica reactions. These
workers necessarily used small samples
and finely divided materials which were
heated at 10 °C a minute. Their results for
the basic system indicate differences ac-
cording the particle size. Their main find-
ings were that an endothermic reaction can
begin around 550 °C, possibly influenced
by but not due to the quartz inversion at
573 °C; that there is an important exother-
mic reaction at about 700 °C and an endo-
thermic reaction at 780 °C. Glass was only
detected (by the presence of an annealing
peak) in samples heated to above 780 °C
which agreed with the formation of some
eutectic liquid. With coarser materials
(0.156-0.210 mm) the main loss of CO 2 oc-
curred at about 850 °C, the melting point of
sodium carbonate, thus suggesting only
limited solid state reaction in that case.
The second paper investigated the effects
of NaF, NaNO 3 , (NH 4 ) 2 SO 4 , and Na2SiF6
on Na 2 CO 3 -SiO 2 reactions. They found
that the main effects could be summarized
by putting each material into one of three
groups:
1) Production of a liquid at a lower tem-
perature by eutectic melting of the minor
addition with sodium carbonate (NaCl,
NaF, Na 2 SiF 6 );
2) Reaction between the minor compo-
nent and a major one producing a new
compound which might or might not assist
melting ((NH 4 ) 2 SO 4 , Na 2 SiF 6 );
3) the minor phase melting to form a
liquid at a lower temperature (NaNO3).
Other studies of this kind were reported
by Wilburn et al. (1965). Such work is evi-
dently very useful but far from sufficient to
reveal everything about glass making reac-
tions. Devising other experiments that will
reveal useful information is often a greater
challenge than making the experiment.
Cable and Martlew (1971, 1984, 1985,
1986) studied the corrosion of silica rods
by a variety of liquids, and found that
adding relatively small proportions of sil-
ica to molten sodium carbonate evolved
proportions of carbon dioxide equivalent
to the formation of the metasilicate,
Na 2 SiO 3 . The various results available
suggest the following kind of scheme as a
basic model but it does not always show
the exact sequence of reactions even in this
apparently simple system.
Na 2 CO 3 zSiO 2 (1-24)
Na 2 O SiO2 + CO 2 t + (z - l)SiO 2
N a 2 O S i O 2 + ( z - l ) S i O 2 -+
(1-25)
-» Na 2 O • 2 SiO2 + (z - 2) SiO2
Na 2 O • 2 SiO2 + (z - 2) SiO2 -> (i _26)
-> Na 2 O • n SiO2 + (z - n) SiO 2 , n « 2.5
Na 2 O • n SiO2 + (z - n) SiO2 ->
-• Na 2 O • p SiO2 + (z - p) SiO2 (1-27)

Na 2 O • p SiO2 + (z - p) SiO2
-• Na 2 O • z SiO2 (1-28)
The value of n in the above equations may
be the disilicate-silica eutectic composition
and p the composition of liquid in equilib-
rium with silica according to the phase di-
agram (see below). This range of liquids
differs considerably in density and viscos-
ity so that segregation under the influence
of gravity may easily occur. There may also
be a definite tendency for undissolved silica
to float to the surface of the melt. Of course
these reactions overlap in time and space
so that it may be very difficult to identify
them beyond the second step.
A recent study of melting reactions in 3 g
soda-lime-silica batches by Sheckler and
Dinger (1990) found a complex series of
reactions clearly sensitive to silica particle
size, when mixed with very fine soda and
limestone but, they, unfortunately, do not
specify their rate of heating which was
probably 10 °C per minute. The samples
were held for 5 minutes at each of seven
temperatures from 775 to 865 °C and
cooled for examination. Silica was the only
compound to persist throughout this range
but numerous others had a transient pres-
ence. For example, some double sodium
calcium carbonate was always formed yet
sodium disilicate was present only up to
790 °C and wollastonite occurred above
805 °C but only with the finest grade of
silica (< 53 |im) in both cases. On the other
hand, Na 2 O • 2CaO • 3SiO 2 formed to-
wards the top end of the temperature range
with all three grades of silica used. An in-
termediate carbonate, 5 CaO • SiO2 • CO 3 ,
was found for two grades of silica but not
the finest. The authors correctly conclude
that no existing model of melting can cor-
rectly predict the behavior to be found in
even a relatively simple three component
system. This behaviour depends on heating
1.3 The Melting of Glasses 41
rate (which cannot be uniform throughout
a typical volume of batch) as well as on
particle size.
Most batches contain more sand, usu-
ally the most refractory constituent, than
any other component and this must be dis-
solved by the liquid phase or phases. Dis-
solving the quartz which did not react dur-
ing the early vigorous reactions often
occupies the majority of the batch-free
time. The dissolution of residual silica is
normally controlled by diffusion in the
melt with equilibrium conditions at the sil-
ica-melt interface (Kreider and Cooper,
1967; Hlavac and Nademlynska, 1969).
Thus, even if the rest of the liquid were
homogeneous, this would produce inho-
mogeneities in the form of silica-rich haloes
around each sand grain, see the photo-
graphic demonstration of this by Jebsen-
Marwedel (1956) and by Cable and Bower
(1965). Figure 1-14 indicates what happens
in the simple binary soda-silica system.
Suppose that we choose to melt a glass
with 34% soda at 1400 °C. The phase
diagram shows that the liquid in contact
with the sand grains will contain 12.7%
Na 2 O and the concentration difference
driving dissolution will be equivalent to Ac
= 213% Na 2 O. Even when all the sand
grains have just disappeared the melt must
contain regions of compositions covering
at least the range from about 13 to 35%
Na 2 O. One useful way of minimizing the
problem of silica dissolution is to use sili-
cate minerals like feldspars or nepheline
syenite to decrease the proportion of silica
that must be supplied as quartz. This also
has the advantage of decreasing the
amounts of alkali that must be added as
the expensive carbonates. It is usually a
mistake to use oxides as raw materials sim-
ply to save the trouble of doing the neces-
sary batch calculations because many of
those that are stable (e.g. MgO, A12O3) are
42 1 Classical Glass Technology

I I I I I I I j One of the most notable contributions not

1600 - mentioned is that of Kroger who, with his
colleagues, made a detailed thermogravi-
metric study of reactions in soda-lime-sil-
AC _y ica batches between 1933 and 1957.
1400
Some of the problems encountered in
o
/ such work may be illustrated by a brief
/ examination of Kroger's work. Such exper-
1200 - iments reveal how quickly the carbonates
CD decompose but nothing directly about the
Q.
reaction of the silica or other refractory
I 1000 - oxides. The only theoretical models avail-
able to interpret the results were the admit-
\
tedly approximate equations derived for
800 V solid state reactions in binary systems
which are often acceptable up to about
I I I i | I
40 60 80 100
50% mass fraction reacted but not beyond
wt. % SiCL (Frade and Cable, 1991 a). These did not fit
Kroger's data which were for three compo-
Figure 1-14. The driving force for dissolution of resid-
ual sand grains in a binary melt with 34% soda when
nent mixtures and reaction in the presence
melted at 1400 °C, assuming equilibrium at the silica- of liquid but he found that the following
melt interface. equation generally yielded straight lines,

not at all reactive; materials that decom-
pose on heating together are much more
suitable.
The above example shows that further
mixing and diffusion beyond the batch-free
time will be essential to produce homoge-
neous glass. Unfortunately diffusivities are
low and mixing by diffusion alone will be
effective only over distances of fractions of
a millimetre even after many hours. Flow
can stretch and intermingle different layers
and considerably accelerate mixing; this is
discussed under homogenizing.
This brief discussion does scant justice
to the work of numerous other experi-
menters who have studied various aspects
of glass melting reactions but the processes
are so complex and our theoretical frame-
work for trying to understand them so in-
adequate that it is impossible to give an
informative brief summary of their work.
(1-29)
He showed that this equation is equivalent
to assuming
= k'l(yt) (1-30)
but did not further justify this model. How-
ever, quite a lot of results showed an inflex-
ion, and it may be very misleading to as-
sume that this indicates a change in the
reaction. This empirical analysis was how-
ever useful in demonstrating the tempera-
ture dependence of reaction rate and the
sudden increase in it as soon as eutectic
liquid has formed.
Estimating how much silica has reacted
is a difficult task. Some workers have at-
tempted to do this by measuring the size of
the differential thermal analysis peak due
to the quartz inversion but this is not easy
to make quantitative. Azm and Moore
(1953) used an X-ray diffraction method to
follow reactions in several soda-lime-silica

batches at temperatures between 900 and
1400°C, see Fig. 1-15 and confirmed that
initial reaction is rapid even at 900 °C but
at that temperature becomes extremely
slow once about half the silica has reacted.
Raising the temperature accelerates the ini-
tial reaction but, more important, increases
the proportion of silica which reacts
quickly. It is interesting to note that the
liquidus temperature of this glass is about
1040 °C and that its primary crystalline
phase is devitrite but it is near to the /J-wol-
lastonite border; when a considerable pro-
portion of silica has yet to dissolve it might
produce Na 2 O 2CaO • 3 SiO 2 . This does
not mean that it would be impossible to
react all the silica at temperatures below
1040 °C but such reaction would be accom-
panied by the formation of one or more of
these crystalline phases and such a reaction
would proceed only slowly. This doubtless
explains why the extent of reaction after
48 h was only about 57% at 900 °C and
78% at 1000°C but had risen steeply to
98% at 1100°C. From what we have al-
ready seen the course of reaction does not
involve just one simple step; not surpris-
ingly, Azm and Moore failed to find a sim-
ple model to describe the overall kinetics.
More insight was shown by Botvinkin
(1936) than some other workers when he
suggested that one might be able to de-
scribe the progress of reaction by a modi-
fied boundary layer model
da/dt=DAt(CEQ-Ct)/S (1-31)
where D is diffusivity, At the surface area of
silica available at time t, CEQ the equilib-
rium silica concentration at the relevant
temperature and Ct the actual concentra-
tion of silica in the liquid at time t. How-
ever, this still leaves some problems over
the value of CEQ for a complex glass and
determining At as well as severe complica-
tions in trying both to estimate Ct and to
1.3 The Melting of Glasses 43
1300°C 1200°C
10 20 30 40 50
Time in h
Figure 1-15. Variation of fraction of quartz reacted
with time in small melts of a sodium carbonate-cal-
cium carbonate-sand batch (11.2% Na 2 O, 10.0%
CaO) at different temperature; Azm and Moore
(1953).
predict the boundary layer thickness S. To-
day this remains a very difficult field in
which to make sound theoretical progress,
even for interpreting simple model experi-
ments like those of Cable and Martlew
(1971, 1984a, b, 1986).
Empirical Melting Studies
Because of the difficulties pointed out
above, there is a place for observations
made directly on glass melts. Whenever
complex phenomena can be observed, see-
ing what happens (or appears to happen)
can be a powerful stimulus to thought and
understanding. Relying only on instru-
ments which give strictly limited and pre-
determined information can be misleading.
Simple qualitative and quantitative experi-
ments involving batch melting thus have a
useful role to play. One of the most impor-
tant questions to be asked of any experi-
ment is how to scale up the results to pre-
dict what will happen on a large scale. This
44 1 Classical Glass Technology
is impossible with standard laboratory
methods of thermal analysis. It might be
possible if melting were studied on a range
of melt or batch charge sizes.
The experiment recognized as useful to
some degree by all glass makers is the
batch-free time. This is simply the time
needed to dissolve all of the original batch
ingredients, silica usually being the slowest
to dissolve completely. Because of the poor
heat transfer properties of batch, if for no
other reason, batch-free time must depend
on the size of the sample. Another factor
determined by the size of the sample is the
influence of the gases evolved during reac-
tion on the atmosphere in which melting
effectively occurs. In a reasonably large
sample the atmosphere is determined al-
most entirely by the gases given off by the
reactions. However, with a very small sam-
ple mixing of these gases with the sur-
rounding atmosphere may be so quick as
prevent this. Where the influence of atmo-
sphere is not important samples as small as
1 g may give useful information but, if the
atmosphere and oxidation of the melt do
matter, samples weighing less than about
50 g are not likely to give useful informa-
tion. One obvious problem with measure-
ments of batch-free time is the tendency for
segregation to occur and another the stick-
ing of some silica grains to the crucible
walls above the level of the melt or the
floating of some grains on the surface
around the meniscus. In both cases those
grains may take much longer to dissolve
than any others and they should be dis-
counted. Potts et al. (1944) used a slightly
inclined furnace and rotated the melt so
that grains near the meniscus were washed
down and stirred into the melt, thereby
decreasing the scatter of the batch-free
time measurements.
In one of the early classic investigations
Preston and Turner (1940) showed a simple
linear relation between sand grain size and
batch-free time which can be interpreted in
the following disarmingly simple but inex-
act way. Assume that the inverse of batch-
free time gives the average reaction rate
just as the total surface area of a given mass
of similar shaped particles is proportional
to the inverse of particle size; the observed
linear relation, with an intercept close to
what can be justified by the time to heat to
reaction temperature, can thus be taken to
mean that rate of reaction is proportional
to the surface area of silica available. This
seems to be an unexceptionable conclusion
but is not generally valid as shown by the
other classic series of experiments by Potts
(1939, 1941) and his colleagues at Owens
Illinois (Potts et al, 1944). They found that
batch-free time can go through a minimum
when particle sizes are varied, the mini-
mum being where all particle sizes are
matched, see Fig. 1-16.
The increase in batch-free time seen here
for very fine sand was not observed by
Preston and Turner because they used very
finely divided chemical reagent sodium
and calcium carbonates so that their silica
was always coarser than the other materi-
als.
That the increase in batch-free time for
very fine silica was largely due to segrega-
tion and inadequate contact between dif-
ferent types of particle is supported by re-
sults of Manring and Bauer (1964) whose
experiments with dry batches also showed
such a minimum but when water was
added, so that soda-rich solution could
coat all the sand grains, the minimum dis-
appeared and the finest sand again gave
the shortest batch-free time as shown in
Fig. 1-17.
Interesting experiments by Boffe and
Letocart (1962), who used graded sands,
showed that the real behavior is quite com-
plex. The average rate of the initial reac-
 1.3 The Melting of Glasses 45

! I I I I I tions must be approximately proportional

Sand to the surface area of silica available but
/
300 - - the final stage of dissolving the last few
/
silica grains must depend on the size of the
Lime largest grains, even if there are only a few
/ // of them. Hence batch-free time is not al-
200
ways a simple function of either surface
/ / Soda
/ area of silica or of average particle size, as
/ / •
shown in Fig. 1-18.
s Hot stage microscopy can be very infor-
Cd mative. Thus Manring et al. (1964) showed
CQ
100 - - that molten sodium carbonate can prefer
to wet cullet rather than sand grains and
this led them to make some suggestions
about how cullet should be charged into a
0 I I I I I I
furnace. In glass melting studies it is often
0 0.2 0.4 0.6 much more difficult to devise a useful ex-
Average particle grain size in mm periment than to carry out experiments by
Figure 1-16. The effect of varying one at a time the one of the standard but not very relevant
particle sizes of the three raw materials on the batch- laboratory methods.
free times of small melts of a soda-lime-silica glass at
1427 °C; after Potts et al. (1944).
1.3.4.3 Refining
A typical batch to produce 100 kg of
glass weighs about 120 kg and thus evolves
around 20 kg of combined gases during

sz
o
05
CQ

10 -

0 0.2 0.4 0.6

Average sand grain size in mm Specific surface in m 2 kg' 1

Figure 1-17. Comparison of batch-free times at
1482 °C of dry and moist batches of a soda-silica
glass (25.6% Na 2 O) when using different sand particle
sizes with a constant soda fraction (about 0.256 mm);
after Manring and Bauer (1964).
Figure 1-18. The relation between specific surface of
silica and batch-free time for melts made using graded
sands. The anomalous values near the middle of the
diagram are for sands containing small proportions of
large grains; after Boffe and Letocart (1962).
46 1 Classical Glass Technology
melting. The majority of this gas is car-
bon dioxide from carbonates which, at a
melting temperature of 1400 °C and 1 atm,
occupies nearly 1500 times as large a vol-
ume as the melt produced. It cannot be
surprising that vigorous gas evolution
during the early stages of melting some-
times causes a melt to boil over the pot
which contains it. Much of this gas is given
off at somewhat lower temperatures during
the course of the batch reactions and it
provides the majority of the atmosphere in
which the glass is produced. The presence
of oxidizing or reducing agents in the batch
can therefore have a considerable effect on
the degree of oxidation of the freshly made
melt. Much of the gas escapes easily by
forming large bubbles which coalesce and
quickly reach the surface where they burst.
However, when the vigorous reactions
have ceased the melt contains some resid-
ual dissolved gases, but may not be satu-
rated with them, and also a considerable
number of smaller bubbles some of which
cannot rise rapidly through the melt. Re-
fining is the elimination of these bubbles
which are only easy to study beyond the
batch-free time.
Many melts contain less than 1 vol.% of
bubbles at the batch-free time but the aver-
age size may be less than 1 mm and the
number sufficient to make the glass almost
opaque. Several factors influence the num-
ber of bubbles and their size distribution
but a fairly typical number at the batch-
free time would be 500 per mL, and the
size distribution would range from about
25 jam up to 1 mm diameter. These small
bubbles are called seed and normally rep-
resent a very tiny fraction of all those pro-
duced during melting. Bubbles bigger than
about 2 mm in diameter are called blisters.
The number and size distribution depend
on the type of glass, choice of batch materi-
als, refining agents used and size of sand
grains as well as melting temperature and
size of melt.
It is not easy to observe bubbles in a
melt at high temperature so the majority of
our information about refining is based on
measurements made on samples cooled to
room temperature. Such samples have to
be prepared with care if reliable informa-
tion is to be obtained from them. One of
the main problems concerns relaxation of
the glass during cooling. Near to melting
temperature the viscosity of the melt is
sufficiently low for a bubble to expand or
shrink to maintain equlibrium internal
pressure as temperature changes. Thus, as-
suming ideal behavior,
PiVJT1=p2V2/T2 (1-32)
or, if x is the diameter of the bubble,
Pixl/T1=p2xl/T2 (1-33)
The pressure in the melt outside the bubble
will be only slightly higher than the exter-
nal atmosphere pressure p0 because the hy-
drostatic head will be small, so Eq. (1-33)
may be written
•2a/pox2)xl/T2 (1-34)
Only if the bubbles are less than about
50 jim in diameter does surface tension a
have a measurable effect on their be-
havior. Many bubbles will therefore main-
tain equilibrium pressure and shrink ac-
cording to
x 2 /x 1 = (T2/T1)1>3 (1-35)
On cooling the melt will eventually be-
come too viscous for flow to occur and the
bubble becomes frozen into the effectively
solid glass. The size will now remain al-
most constant on further cooling but the
internal pressure will change according to
•2a/pox)/T2 (1-36)

The viscosity at which the glass becomes
effectively solid in this respect is near the
upper end of the annealing range and bub-
bles containing non-condensable gases
usually have internal pressures close to
0.30 atm at room temperature. Figure 1-19
shows the behavior expected of bubbles on
cooling provided there is no reaction of the
contents with the surrounding glass. This
question has recently been examined in de-
tail by Cable and Frade (1991).
If glass is cast then quenched below the
annealing range some bubbles can behave
in a startlingly different fashion. Consider a
sphere of glass 100 mm in diameter which
is rapidly cooled to room temperature and
which before cooling contained one tiny
bubble near its centre. The outer skin of the
sphere may become solid at about 500 °C
when the average temperature of the still
fluid interior is perhaps 750 °C. As the
sphere cools further the inner core is still
able to flow under stresses down to about
Pressure
1.0 -
400 800
Temperature in °C
Figure 1-19. Approximate changes in size and internal
pressure in a bubble in a body of glass which is being
cooled relatively slowly.
1.3 The Melting of Glasses 47
500 °C, by which stage it will have wanted
to contract by about an additional 4.6 mL
(taking the volume coefficient of thermal
expansion to be 3.5xl0~ 5 ). The glass is
close to incompressible so that the sphere
should be highly stressed, tensile in the cen-
tre and compressive on the outside, unless
now annealed. However, since it contains a
seed near the centre, the work needed to
expand this is much less than the stored
strain energy, so the bubble is expanded
and its internal pressure decreases as the
glass relaxes and much of the stress is re-
lieved. This is why Rupert's drops some-
times contain relatively large bubbles.
Only bubbles nearest the slowest cooling
part of the glass are expanded in this way.
Of course the real behavior is more com-
plex and the volume of the bubble perhaps
no more than a third of the volume esti-
mated.
The Role of Buoyancy in Refining
Rise to the surface is the most obvious
way in which seed might be removed once
the vigorous melting reactions have
stopped. Jebsen-Marwedel (1936) used
model calculations for a typical range of
bubble diameters, temperatures and vis-
cosities, to show that it was doubtful
whether this could be the only mechanism
at work.
Stokes's law is one of the classic exercises
in hydrodynamics and shows that the ter-
minal velocity Vs of an isolated solid sphere
of diameter x in a large body of liquid is
given by
Vs=(l/lS)(Ql-Q2)x2g/r1 (1-37)
where QX and Q2 are the densities of solid
1200
and liquid and g is gravitational accelera-
tion. Jebsen-Marwedel plotted a very clear
diagram showing how this velocity varied
with temperature and bubble diameter for
a typical viscosity-temperature relation.
48 1 Classical Glass Technology
Bastick (1956) took this argument one
step further by demonstrating that mea-
surements of how total number of bubbles
varied with time yielded a temperature de-
pendence steeper than that predicted by
allowing for the known changes in viscos-
ity of the melt and variation in size of a
bubble according to the perfect gas laws,
see Fig. 1-20. Note that Bastick extrapo-
lated his measured data back to a common
100 200 300 400
Time in min
Figure 1-20. Variation of rate of refining with temper-
ature according to Bastick (1956). The rate changes
more steeply with temperature than would be ex-
pected from the known dependence of viscosity.
intercept at zero time but, although this is
an interesting observation, it is an unwise
thing to rely on because the phenomena
occurring during the shortest times (batch
heating and gas-evolving reactions) are
clearly different from those occurring later.
Bastick used the slopes of the lines in his
figures to show that combining Eqs. (1-35)
and (1-37) would lead one to expect rate of
disappearance by rise to the surface to be
given by
= (im(Ql-Q2)x2g/t1 =
= kx(T)2/r,(T) (1-38)
Putting in the known variation of glass
melt viscosity rj1 and x(T) showed that k
was not a constant but increased as tem-
perature rose. A possible explanation is
that the refining agents present made bub-
bles expand more than expected, thus in-
creasing doubts about the role of rise. The
fact that the Rybczynski-Hadamard anal-
ysis for a fluid sphere shows the terminal
velocity (FB) of a fluid sphere of very low
viscosity in a liquid of much higher viscos-
ity to be given by
VB = (3/2) Vs= (1/12)(Q 1 -Q 2 )x 2 g/f 1 (1-39)
does not affect this argument. Hornyak
and Weinberg (1984) confirmed that bub-
bles in a glass melt obeyed Eq. (1-39).
Hearing Bastick describe these experi-
ments and his deductions from them led
Cable (1958) to make similar experiments
which then included measuring the size
distributions of the seed as well as their
total numbers in all samples. He reasoned
as follows. The spatial distribution bubbles
of particular size must be close to uniform
at some time soon after the vigorous reac-
tions have finished but before the batch-
free time. Bubble formation may not cease
until the melt is batch free but may be as-
sumed unimportant from this time on-
ward. If the melt is static all bubbles will
rise towards the surface at a rate given by
Eq. (1-39), so that the fraction disappeared
at any particular time will be in proportion
to the distance risen divided by the depth
of the melt h. If the number of bubbles of a
given size present per unit volume at the
assumed beginning of the process is n 0 , the
decay in number at longer times should be
n = no(l-k'x2t/h) (1-40)
k! being obtained from Eq. (1-39) with t
measured from the time when the random
spatial distribution existed.
When a range of sizes is present the total
number of bubbles should be obtained by
summing Eq. (1-40) for all sizes,
N=Yno-{k'lh)tY (1-41)
o o

As indicated the summation must be made
only for the sizes still remaining and cut off
at
c' = (*/W 2 (1-42)
Bubbles obeying such a law could easily
produce an exponential decay of total
number with time as the average size and
average rate of disappearance will both de-
crease with time.
However, analysis of the recorded data
shows the relation between n and t not to
be linear but closer to
log n = log n0 — b t (1-43)
Since d(logn)/dt = (l/n)(dn/dt% the pre-
dicted slope of such a graph should be
b = x2/[h/k-x2t] (1-44)
Figure 1-21 shows the predictions of this
equation for appropriate times together
with two sets of experimental data. It can
be seen that bubbles large enough to disap-
pear by rise and bursting do so but smaller
bubbles disappear faster than expected and
the discrepancy gets larger as the size be-
comes smaller; there is no indication that
rate of disappearance approaches zero for
x = 0 and rate of disappearance is, fortu-
nately, less sensitive to bubble size than
this theory indicates. Also note that the
general features of the behavior are very
similar for melts with and without refining
agents.
This model ignores convection of the
melt. Horizontal velocities would affect the
path followed by a bubble but not the time
taken to rise to the surface but vertical ve-
locities will affect time to rise and be able to
burst at the surface. The internal circula-
tion caused by thermal convection in a pot
or tank must therefore have some effect.
However, any flow system in a pot or
crucible must have as much downward
flow as upward and it is difficult to see how
1.3 The Melting of Glasses 49
C/)
c
o
0 0.1
Seed diameter in mm
Figure 1-21. Comparison of calculated rate of disap-
pearance at 1400 °C of seed by rise to the surface
(shaded area) and actual observations in small melts
of a soda-lime-silica glass: without (•) and with (•)
refining agent (0.50% As2O3); after Cable (1960).
thermal convection would accelerate the
removal of most bubbles. Another possible
mechanism is coalescence which is evi-
dently important whilst the vigorous early
reactions take place but is most unlikely to
occur in such viscous liquids when small
bubbles are on average a considerable
number of diameters apart.
Refining agents, that is minor con-
stituents added to the batch to accelerate
refining, have been known for a long time.
The most important are sulfates, arsenic
oxide, antimony oxide, and halides, espe-
cially chloride. Sulfate is the most used to-
day. If refining were governed by rise to the
surface they could only act by either affect-
ing the density and viscosity of the melt or
by making the bubbles bigger. At the levels
used (< 1%) their effects on the properties
50 1 Classical Glass Technology
of the melt are too small to accept that
explanation; the kind of analysis just de-
scribed allows for any effect of bubble size
and thus shows that refining agents affect
the rate of disappearance of bubbles of the
same size. Some other explanation must be
found.
The Role of Mass Transfer
Since large volumes of gas are evolved
during the melting reactions, most of
which happen before the reacting batch
has reached maximium temperature, the
melt may or may not be saturated with
gases and interaction between bubble and
gases dissolved in the melt may make bub-
bles either grow or dissolve. The former
would accelerate rise to the surface, assist-
ing larger bubbles most, and the latter
would make rise to the surface unneces-
sary. The first reliable evidence that mass
transfer does occur between bubble and
melt was reported by Appen and Polya-
kova (1938). These workers showed that
the composition of the gas in bubbles in
samples taken from a melt at different
times changes during the course of refining.
Bubbles from a melt without refining
agents were largely carbon dioxide, as
might be expected from the batch materi-
als, but changes occurred when a refining
agent had been added. At first the bubbles
were still rich in carbon dioxide but they
soon became rich in oxygen and later rich
in nitrogen. Appen and Polyakova had to
use primitive methods of gas analysis and
their results represented a considerable ex-
perimental feat. Slavyanskii (1957) re-
ported a larger body of similar data by
Russian workers also obtained by the same
methods.
Since about 1960 it has been possible to
analyse nanolitre and picolitre quantities
of gas by several techniques and numerous
workers have confirmed and extended
these early data for samples taken from
melts then analysed at room temperature,
see for example Cable and Naqvi (1975),
Cable etal. (1969) and Mulfinger (1974,
1976). The relation between the rate of
change of gas composition, the amount of
refining agent used and the change in refin-
ing behavior, see Cable and Naqvi (1975),
is very convincing qualitative evidence that
refining agents do act by mass transfer.
However, these data do not show whether
growth or dissolution is the crucial pro-
cess, or whether both are generally in-
volved. The conditions in which bubbles
are formed and in which refining occurs are
far from equilibrium and simple models as-
suming that conditions around the bubble
are at equilibrium may give seriously mis-
leading predictions.
Direct observation of bubbles during re-
fining would be the best way to determine
what happens but accurate observation in
conditions typical of refining is difficult al-
though several workers have measured
bubble behavior in model experiments.
The first notable experiments which
demonstrated that bubble growth or disso-
lution is possible were by Greene and
Gaffney (1959); Greene and Kitano (1959);
Greene and Lee (1965); Greene and Platts
(1969); Greene and Davis (1974). This
work confirmed that oxygen bubbles sub-
sequently formed and reheated in well re-
fined glass could shrink in the conditions
used. Also that equimolar proportions of
SO2 and O 2 could easily dissolve. These
experiments also showed that complete
dissolution of a bubble is much influenced
by low impurity levels in the initial gas or
by gases dissolved in the melt, some of
which will diffuse into the bubble in the
early stages. Solinov and Pankova (1965)
reported some data for bubble growth
which showed that adding arsenic retarded

bubble growth but these were not typical
refining bubbles. Nemec (1974, 1977a,b,
1980) has also published a considerable
body of data on bubble growth.
Cable and Haroon (1970) tried a differ-
ent experiment in freshly made melts, one
without and one with refining agent. They
injected a few relatively large bubbles of
carbon dioxide at 1200 °C, left the melts for
a few minutes, cooled and annealed them,
then recovered these bubbles, measured
them and also analysed their contents.
These bubbles had become enriched in ox-
ygen but also shrunk, more in the melt
containing the refining agent than in the
other, showing that the refining agent had
made transfer of CO 2 into the melt faster
than transfer of O 2 from the melt into the
bubble in those conditions.
Both growth and dissolution can clearly
occur in melts under different conditions,
one of the obvious factors being the tem-
perature dependence of gas solubilities in
the melt, most gases becoming more solu-
ble as temperature falls. However the melt
is not at equilibrium during the short pe-
riod of time which determines the condi-
tions for refining and the age of the melt
may affect behavior even at constant tem-
perature. The widely accepted picture is
that growth occurs at maximum melting
temperature but that resorption allows dis-
solution of residual bubbles on cooling
near the end of melting. This may often be
true but will not apply to isothermal labo-
ratory melts on which many studies have
been made.
Theoretical Models for Mass Transfer
Two approaches are possible and both
have some range of validity. The diffusion-
controlled change in size of a sphere is a
very difficult problem to solve even when
the spherical symmetry of the system is
1.3 The Melting of Glasses 51
maintained. As a result it is a considerable
challenge to deal with a bubble assumed to
be stationary in the melt and this is one
model. The other is to use standard
boundary layer approximations for a freely
rising bubble. The latter should apply for
relatively fluid melts and fairly large bub-
bles but must eventually fail for a dissolv-
ing bubble even if valid in its early stages.
The classic model for a stationary bub-
ble takes over the result of Carslaw and
Jaeger (1959) for heat transfer in a region
internally bounded by a bubble which has
a constant temperature on its surface. This
leads to
da/dt=D[(CO0-Ca)/Cs]-
-[I/a- (1-45)
where C^ is the assumed uniform concen-
tration of gas in the melt, Ca the value at
the surface of the bubble and C s the con-
centration of gas inside the bubble. This
equation is valid only for very low solubil-
ity and hence very slow change in bubble
size; it also assumes that the bubble con-
tains only one gas, which we know not to
be true. Even this equation is difficult to
integrate and both of the two not very sat-
isfactory approximations obtained by as-
suming either I/a g> l/(nD t)lj2,
a2 = a2 + 2D[(C^-Ca)/Cs]t (1-46)
or l/(7i D 0 1 / 2 M M
a = a0 + (2/T^2)D1/2 [(C*, - Ca)/Cs] t^2
have often been used; the latter can be cast
into the same form as Jander's Eq. (1-21).
The motion of the boundary changes the
area through which mass transfer can oc-
cur and also distorts the concentration
profile in the liquid around the bubble. A
change in composition of the bubble
means that concentrations of the various
gases at the surface of the bubble also
52 1 Classical Glass Technology
change with time; this further complicates
solution of a realistic model of the process.
Adding surface tension for small bubbles
and the fact that Sieverts' law rather than
Henry's law may be needed to describe
conditions at the interface for water va-
pour increases the complexities.
These complications mean that numeri-
cal methods must be used to obtain valid
results and this family of problems in diffu-
sion-controlled bubble growth and dis-
solution have been studied in detail by
Cable and Frade (1987a,b,c,d, 1988) for
both one component and multi-compo-
nent bubbles.
Growth of a one component bubble
from zero initial size must follow
R = 2p(Dt)1/2 (1-48)
as shown by Scriven (1959), where R is the
dimensionless radius and the growth rate
constant is a function of, but not in general
equal to, (CO0 — Ca)/Cs. This also repre-
sents the asymptotic behavior of a bubble
growing from finite initial size and most
bubbles closely follow this regime for
R > 5. Dissolving bubbles, on the other
hand, are always in a transient regime and
the only valid simple approximation for
one component dissolving bubbles applies
only for very low solubility and is
Ri = l-D[(C^-Ca)/Cs]t (1-49)
Over most of the range of values of solubil-
ity the form of JR (t) is sensitive to the values
of the parameters.
Multi-component bubbles can show sev-
eral interesting features. Bubbles which
continue to grow will always eventually
achieve a constant composition which can
be estimated from the properties of the
particular case. If the bubble initially had
this composition it would behave like a
one component bubble but one with any
other initial composition can show com-
plex transient behavior. It may, according
to the deviation from equilibrium bubble
composition, initially exhibit either shrink-
age or accelerated growth: it seems that
only one change in the sign of dR/dt is
possible with a given bubble but this is
difficult to demonstrate rigorously. Multi-
component bubbles which eventually dis-
solve can show either positive or negative
values of dR/dt at the beginning, for the
same reasons as with growing bubbles, but
do not generally tend to an asymptotic
constant composition because they cannot
achieve a pseudo-steady state. Although it
is difficult to predict the details of behavior
there are simple rules for deciding whether
the initial value of dR/dt will be positive or
negative and for deciding whether the bub-
ble will in the end grow or dissolve (Cable
and Frade, 1987 d).
If the dissolved concentration of each
gas i is defined in terms of Fi = (C — C (oo))J
C s , gt(0) is the mole fraction of each gas
initially in the bubble and oct is the Ostwald
solubility coefficient for that gas, the initial
sign of dR/dt will be the same as that of
I = I.(Fo.t-*igi(0)) (1-50)
whilst its final behavior is controlled by
S = ItFOti/ai (1-51)
If S is positive the bubble will grow, if S is
negative it will dissolve. The asymptotic
composition of a growing bubble could of-
ten be determined experimentally but the
solubilities, diffusivities and saturations of
each of the gases involved will rarely be
known with sufficient accuracy to make a
theoretical prediction. However, the bub-
ble must have the most mobile species
tending to diffuse into the bubble as its
major constituent. The observation that
seed eventually become rich in nitrogen to-
wards the end of refining cannot be attrib-

uted to bubble growth because nitrogen
normally behaves like an inert gas of low
solubility and diffusivity. Bubbles which
become rich in nitrogen late in their lives
must be dissolving, the other gases which
find it easier to diffuse out leaving the bub-
ble rich in nitrogen. This does not exclude
the possibility that other bubbles grew be-
cause those may have risen to the surface
and burst by that stage of refining. It is
interesting that Cable and Frade (1987d)
could not match the observed CO 2 ->O 2 ->
N 2 composition cycle or any plausible set
of values of solubilities, diffusivities and
dissolved concentrations.
The theory confirms the finding of
Greene and his students that a tiny impu-
rity content in the initial gas or a very small
residual content of other gases dissolved in
the melt can greatly retard complete disso-
lution of a bubble and shows that it is not
easy to tell which of these factors has af-
fected any particular bubble.
The standard boundary layer model for
freely rising bubbles was applied to bub-
bles in glass by Onorato et al. (1981), using
plausible model values for the properties of
the gases but there is again a lack of accu-
rate data for these parameters and also for
experimental data to which the model is
known to apply.
It is difficult to claim that our knowledge
of refining glass melts is qualitatively
clearly understood and only in need of
data for solubilities and diffusivities to re-
solve all the problems. Why, for example,
does it seem to be frequently true that too
little refining agent makes refining worse
and that too much also makes perfor-
mance fall off again? This appears to be
related to the rate of conversion from car-
bon dioxide to oxygen; with too little refin-
ing agent this is not observed to happen,
with too much it is retarded. The usually
accepted model, proposed by Otto Schott,
1.3 The Melting of Glasses 53
assumes a process such as
(1-52)
and that it tends to go further to the right
as temperature falls so that the melt is su-
persaturated at the maximum melting tem-
perature and less than saturated on cool-
ing to near working temperature. How-
ever, this does not explain why refining
agents function in isothermal melts. Nor
does it account for the more rapid transfer
of carbon dioxide out of the bubble than of
oxygen in observed by Cable and Haroon
(1970). Refining requires that the melt
around a bubble can rapidly absorb or de-
sorb a small amount of gas; this may not
necessarily require an increased equilib-
rium solubility, a transient kinetic effect
would suffice.
1.3.4.4 The Homogenizing of Glass Melts
The discussion of melting reactions has
made it clear that a range of liquids which
vary considerably in density, viscosity, re-
activity, volatility and other properties will
be formed at different stages of melting.
These must be mixed together to attain the
degree of homogeneity required of most
glasses. Differences in refractive index lead
to optical distortion and, as a result, opti-
cal glasses must have higher standards of
homogeneity than any other material
made on a large scale. Differences in ther-
mal expansion can cause considerable and
increasing internal stress as a glass cools
from the glass transition range which can
make inhomogeneous glasses very fragile
at room temperature and this implies high
standards of homogeneity in many glasses
where optical properties are not the most
important. Likewise not all properties are
simple additive functions of composition
so that accurate and reproducible mea-
surements of many properties need sam-
ples of good homogeneity.
54 1 Classical Glass Technology

Diffusive Mixing Table 1-6. Dimensionless times for the decay of con-
centration at the centre of inhomogeneities of thick-
In the end mass transfer working at an ness or diameter 2 /.
atomic level must make glass composition 2
Type of Time (Dt/l ) to decay to:
as uniform as can be achieved. Although inhomogeneity
the classic Stokes-Einstein relation be- OAAC0 0.05 AC0 0.01 AC0
tween viscosity and diffusivity
Isolated:
> = kBT/(6nrjR) (1-53) Slab 31.67 126.8 3185
Cylinder 2.37 4.87 24.87
applies only to liquids comprised of large Sphere 0.854 1.42 4.34
spherical molecules of radius JR, not to typ- Regular array:
ical glass melts, it is sufficient to show that Alternate layers 1.031 1.31 1.97
mass transfer diffusivities are very low in
glass melts even at melting temperatures.
Effective diffusivities for mass transfer are
try has a very significant effect; a point
strongly dependent on both composition
which is reinforced by imagining that the
and temperature; values will not often ex-
flat slab has been stretched and folded nu-
ceed 10~ 1 0 m 2 s~ 1 . Unaided diffusion will
merous times to make a laminar structure
require extremely long times to homoge-
with alternate layers of the two composi-
nize a viscous liquid.
tions. If these layers are assumed to be of
If an inhomogeneity could be repre-
equal thickness the dimensionless concen-
sented as a slab of thickness 2 /, with a
tration is given by
concentration of solute C o , immersed in a
large bulk of material with uniform con- (-i)n
centration C^, its centre concentration (1-57)
would decay with time according to
Dt
exp -
1/2
Jf2 cos 2/
-erf(//2(Dr) ) (1-54)
and the concentration on the centre line of
If it were a cylinder the radial diffusion a layer by
would proceed rather faster according to
C(0) = 1 - e x p ( - l2/(4Dt)) (1-55) C(0)=^
if it were a sphere the result would be Dt
exp (1-58)
12
C(0) = erf 1/2{Dt) ' - (2/^/n) (1/2 JDt) • Jl2
•exp(-/ 2 /(4£>£)) (1-56) This series converges rapidly for (Dt)/l2
>0.2; for short times the following is more
All of these involve the dimensionless time convenient, ,. ^_Q.
Dt/l2 which shows that real time is in-
versely proportional to diffusivity and di-
rectly proportional to square of size. Table
1 -6 shows the predicted times for the max-
imum concentration to decay to a tenth Figure 1-22 compares the rates of decay of
and a hundredth of its original value for the central concentrations in an isolated
these cases. It can be seen that the geome- layer and in one in a regular array: the

advantage of the latter is clear. The decay
of the latter is much quicker for two rea-
sons: 1) the maximum distance over which
diffusion must occur is greatly reduced and
2) stretching and folding that layer p times
to make one layer of thickness 2 / into a
series of layers each of thickness only 2 l/p
brings an extra advantage.
These relations make clear that there are
only three ways in which homogenizing by
diffusion can be accelerated: 1) by increas-
ing diffusivity by raising temperature, 2) by
decreasing duffusion distances and 3) by
decreasing the initial concentration differ-
ence which must be reduced. The first of
these can only be achieved by raising tem-
perature, which is only possible within
specific limits; the second is the most at-
tractive and achieved by stirring; the third
is very important but often forgotten in
general discussions; choice of batch mate-
rials and melting schedules can be very in-
fluential here. Preventing the development
of inhomogeneity is better than trying to
cure it afterwards.
1 10 102 10 3
2
Dimensionless time, Dt/I
Figure 1-22. Predicted decay by diffusion of the centre
concentration for a single slab of inhomogeneity of
thickness 2 / embedded in a melt and for a layer in a
regular array of alternate layers and glass matrix each
of the same thickness.
1.3 The Melting of Glasses
Convective Mixing
Glass melts are sufficiently viscous for
flow to nearly always be governed by vis-
cous drag and so in the laminar flow
regime. This is very convenient when wish-
ing to describe and calculate flow patterns
but the predictability of the flows implies
that the degree of randomness required for
good mixing is difficult to achieve. How-
ever, as is shown below, simple shear can
assist homogenizing of viscous liquids. It
can redistribute inhomogeneities on a large
scale by convective flow so that diffusion
distances are decreased and in doing so
individual inhomogeneities can be dis-
persed, stretched and made thinner. Three
cases need to be examined.
The Deformation
of Homogeneous Inclusions
A homogeneous inclusion is one which
is assumed to have the same viscosity as its
surroundings although differing in other
properties. Its deformation is thus a rela-
tively simple exercise in analysis of flow
patterns. The most useful model to con-
sider is steady laminar flow with a constant
velocity along a straight flow path but a
velocity gradient at right angles, such as
will occur in flow along a rectangular open
channel. The inhomogeneities that concern
us are generally much thinner than the
overall body of fluid and it is reasonable to
assume that the local velocity distribution
is represented by a straight line although,
in many cases, this will be part of a pa-
rabola. Consider a rectangular element of
length / lying at an angle a0 to the direction
of flow. Its two ends will be moving at
different velocities so that it is stretched out
and rotated, see Fig. 1-23.
This model has been evaluated by
several authors including Mohr (1960),
McKelvey (1962) and Cooper (1966a,b).
56 1 Classical Glass Technology

h cot a. Ght large amounts of shear may be required

merely to make these the same thickness as
they were to start with. However much
shear is applied there will always be a nar-
row range of angles for which matters will
be made worse but sufficient shear means
that these will occur infrequently.
Of course, with almost perfect laminar
flow, acceleration of the flow will attenuate
inhomogeneities in an easily predictable
way. The simplest way of achieving this is
to make the melt flow through a reduced
cross section, such as the throat of a fur-
Figure 1-23. The geometry of deformation by simple nace or the orifice of a gob feeder, when all
shear of a layer initially lying at an angle <x0 to the
velocity vector U.
the constituent parts of stream will be re-
duced in the same proportions as the cross
section of the whole flow. However, if the
The most important facts are that the lay- stream expands again, as on exit from the
ers are rotated to become almost parallel throat, little may have been achieved. Un-
to the direction of flow but that the rate of fortunately this is not likely to assist diffu-
stretching approaches zero as this occurs. sive mixing very much because of the short
For the two dimensional case where the
velocity vector U lies along the x axis and
dU/dx = 0 but dU/dy = G and the liquid
is assumed incompressible, this leads to
(1-60)
b _ 1
Yo ~ [1 + G t sin 2 a 0 + G2t2 sin2 a o ] 1 / 2
Note that only the product Gt, the total
shear, appears and neither of these vari-
ables is itself important. Some of the pre-
dictions of this equation are shown in
Fig. 1-24. The decrease in thickness with
amount of shear is roughly a double expo-
nential of G t for favorably oriented layers
and a factor of ten reduction in thickness is
easily achieved but a factor of a hundred is
hardly possible. If attenuation by a factor
0.01
of more than about twenty is required, it is 0 20 40
necessary to change the flow pattern and Total shear, Gt
the orientation of the layers relative to the
Figure 1-24. Predicted changes in layers of initial
velocity vector. Note particularly that thickness b0 by simple shear for a range of initial
some layers in a randomly oriented array orientations according to Eq. (1-60) which ignores dif-
will be compressed rather than attenuated; ferences in viscosity.
 1.3 The Melting of Glasses 57

residence time in the narrow part of the
system. The combined effects of shear and
reduction in cross section were discussed
by Rhiel (1976).
Deformation of Inhomogeneous Inclusions
Here this term means inclusions which
differ in viscosity from their surrounding
matrix. Most inclusions in glass will fall
into this category. A rigid inclusion would
not deform at all although it would rotate,
so intuition rightly suggests that a more
viscous inclusion should deform less than
one of low viscosity subject to the same
stresses. This problem can be elegantly
treated by a method devised by Eshelby
(1957, 1959) to deal with elastic inclusions
which he kindly demonstrated to the au-
thor in 1968. By this method a simple rela-
tion can be deduced to describe the differ-
ence in deformation of a homogeneous two
dimensional inclusion and an inhomoge-
neous one when both have been subjected
to the same (but unspecified) amount of
shear. Since deformation may be large it is
defined in terms of the natural strain 5
f d a
1
(1-61)
s= J—
a = In
flo
dimensional case and an incompressible
liquid, the minor axis of the inclusion must
decrease by the same factor as the major
axis increases. Figure 1-25 shows how vis-
cosity affects deformation according to this
model; it can be seen that an inclusion of
lower viscosity deforms rather more than a
homogeneous one but increasing viscosity
soon causes a considerable decrease in the
deformation. This analysis is best used in
two steps; the model in the previous sec-
tion is used to obtain an explicit relation
between shear and deformation for the ho-
mogeneous case and Eq. (1-63) used to de-
termine the difference in deformation be-
tween the homogeneous and inhomoge-
neous cases. One important inference to be
drawn from this is that any furnace will be
unable to deal with inclusions significantly
more viscous than those that usually oc-
cur; feasible changes in furnace operating
conditions are likely to have very little ef-
fect: only removing the source of the vis-
cous inclusions will cure the problem,
Three dimensional inclusions were stud-
ied by Bilby et al. (1975) and Howard and
Brierley (1976); the general features of
these are very similar to Eshelby's original
analysis.

The other parameter introduced is the rela- 1

fB ' J I -J I I •
1
1 1
'
tion between the two viscosities defined by ^° - — — . 20

w
x
* = (*1i-*iM)/tiM (1-62) 8 \ \ \ \
£ 0.1 -

where the subscripts refer to the inclusion o X X

in th

\2 ^
(i) and the matrix (M). The relation be- 0
\ \

wNX
S\
CD
O> \
tween the deformation of the inclusions in | 0.01 -
\ \

the two cases is given by 6 \ \

0.002 1 i l l 1 1 \k \ \ I i ^X i

s a +(A/2) tanhs a = : (1-63) 1 0.1 10" 2 10" 3 10~ 4

b/bQ for homogeneous case

where sa is the elongation of the longer axis
of, for example, the cross section of a long
cylinder being deformed at right angles to
its major axis, and saH is the deformation in
the homogeneous case (k = 0). For the two
Figure 1-25. Results of Eshelby's analysis of the differ-
ence in deformation of homogeneous and inhomoge-
neous (in the sense of viscosity) elliptical inclusions
subject to simple shear; values on the diagram are
viscosity ratios, see text.
58 1 Classical Glass Technology
Deformation Limited by Surface Tension
Both of the above models assume that
inclusions are, in principle, infinitely de-
formable and that only the total shear G t
affects the result. This is not true when an
interfacial tension exists, as is the case with
gas bubbles. Here there is a discontinuity
in pressure and normal stress at the inter-
face because of the additional pressure
which is given by
Ap = <r(l/a + l/b) (1-64)
where a is the surface or interfacial tension
and a and b are the principal radii of the
curved surface. When this term is not triv-
ial, because of the magnitude of a or the
small values of the radii, a sphere reaches
an equilibrium shape which depends on
the rate of shear and this equilibrium shape
may be more important than the rate at
which it is approached.
The classic analysis, limited to small de-
formations, was undertaken by Taylor
(1934) and led to
a-b
= E1 = (1-65)
a+b 16i?r
Since the second term can have values ly-
ing only between 1 and 1.1875, Taylor con-
sidered that the approximation
= GrjMa0/a (1-66)
would usually be satisfactory.
A number of other authors re-examined
this question within the last twenty years
and some published results are incorrect.
An analysis which gave the rate of defor-
mation as well as the equilibrium shape
was published by Cox (1969). Although
limited to small deformations this analysis,
involving spherical harmonics, is valid for
any value of viscosity ratio. If the equilib-
rium angle relative to the shear vector is
defined as cpa = n/4 + 0, the value of 9 is
given by
tan 2 6 = 19Griia0/{20&) (1-67)
This shows that the equilibrium rotation
increases with both rate of shear and vis-
cosity of the inclusion. The shape is defined
in terms of deviations from spherical shape
as
a/a o = l + ea and b/ao = l— eb (1-68)
which is related to the equilibrium values
by
(1-69)
£
E2 = ( e a " b)/(2 + sa + fib) «(e a - e b )/2
The equilibrium elongation of the longer
axis (a) is given by
E2 = E1cos2 6 (1-70)
Figure 1-26 shows some predictions based
on Cox's theory which confirm that a high
viscosity ratio, which makes the equilib-
rium angle soon approach 90° as rate of
shear increases, is associated a very limited
degree of deformation. A gas bubble thus is
the most sensitive indicator of the stress
around it as the glass melt solidified. Cox's
Rate of shear parameter, E
Figure 1-26. The dependence of equilibrium shape on
shear rate for elliptical inclusions where deformation
is limited by interfacial energy according to Cox's
model. The ratio of the major axes is plotted against
rate of shear expressed by E1 (Eq. (1-65)). The values
on the curves are viscosity ratios (inclusion/matrix).

theory shows the time dependence of shape
to be approximately a sine wave superim-
posed on an exponential.
Study of the shapes and orientations of
bubbles in glass is capable of yielding infor-
mation about the stress fields existing in
the glass as it became effectively solid
somewhat above annealing temperature.
However, one of the most obvious types of
such bubbles, namely the very long thin
bubbles sometimes found in drawn sheet
or rod and tube confirm their orientation
to be essentially parallel to the main stress
vector but their shapes are not elliptical,
the tips being too pointed. However, this
section is not in the plane of maximum
shear. An exact analysis of this case re-
mains to be undertaken.
1.3.4.5 Modern Furnaces
Glass making has evolved over a long
period, the most significant advances being
within the last century. Most glass is made
in tank furnaces which appear from the
outside to be merely large rectangular
chambers. In fact they must be very sophis-
ticated devices to meet the different needs
of melting, refining, and homogenizing.
Melting rates and requirements for refining
and homogeneity vary considerably with
the product and this leads to many appar-
ently small differences in design and con-
struction which nevertheless have impor-
tant effects on performance. The design of
a particular furnace can often be consid-
ered in two separate parts, the tank full of
molten glass and the combustion space,
with the only essential link between the
two being the exchange of heat. The overall
size of the melting end of the tank depends
on the glass quality needed, the properties
of the glass and the required output. Since
the energy is transmitted through the free
1.3 The Melting of Glasses 59
surface of the melt it is usual to estimate
the surface area of the tank in terms of
daily output per unit surface area, which
implicitly recognizes the energy input per
unit area from the combustion space. Val-
ues in the range 1.3 to 2.2 t m~ 2 d" 1 are
common.
The ratio of length to breadth (L/B) de-
pends on several factors, two of the most
important are 1) a length sufficient to es-
tablish the desired longitudinal tempera-
ture profile and thus the required internal
circulation of the melt and 2) the width
must be large enough to allow efficient
combustion of the fuel (in a crossfired tank)
but not so great as to threaten the stability
of the crown which is a free standing arch.
As a result small furnaces (about 20 m2)
often have L/B about 1.2 but larger fur-
naces have greater values of L/B, say 2.3
for a 90 m 2 furnace. The depth of the melt
should be such as to prevent the melt at the
bottom becoming to cool and thus too vis-
cous to flow easily, allow the required in-
ternal circulation but also avoid the bot-
tom refractories becoming too hot and
thus easily corroded. The depth must thus
take account of the transparency of the
melt to infrared radiation. Depths from
about 0.75 to 1.3 m are common but rarely
exceed 1.0 m for strongly infrared ab-
sorbing glasses. Most tanks have a throat,
a central passage at the bottom of the
chamber, between melting end and work-
ing end. This helps to prevent unmelted
batch or only partially melted glass being
carried into the working end and also al-
lows the melt to cool before entering the
forehearths which supply the forming ma-
chines. Because of the cooling of the melt
as it passes through the throat there is a
tendency for a return flow of denser glass
to develop from working end to melting
end. Sunken throat designs which control
this are often used. The tank may also in-
60 1 Classical Glass Technology

elude weirs or bubblers or supplementary

electrodes to control the flow of the melt
and, in the last case, also to increase energy
input and melting rate.
The combustion space must match the
length and width of the melting area but its
dimensions must allow the insertion of
ports for fuel (if gas is used) and combus-
tion air of a size and number sufficient to
supply the necessary energy and establish
the desired temperature distribution. Be-
cause there is a minimum effective flame
length for any particular type of fuel and
burner system small tanks often have a
horseshoe or U-shaped flame, the entry
and exit ports both being in the end wall of
the furnace where the batch is normally
charged. Such furnaces must have a dog
house to charge the batch at the side. These
factors are discussed by Trier (1984).
Figure 1-27 shows a schematic diagram
of a modern container glass tank and Fig.
1-28 a flat glass furnace. The main differ-
ences are in size and the absence of a bridge
wall and throat in the flat glass furnace in Figure 1-27. Layout of a typical gas fired modern tank
which it is necessary to develop a better furnace for container glass. Partially sectioned plan
internal circulation. view and vertical section across the melting chamber,
a) melting end, b) working end, c) throat, d) fore-
Energy distribution and hence tempera- hearths, e) combustion space, f) port neck, g) air re-
tures inside the tank are carefully con- generator, h) gas regenerator, i) crown.
trolled ro retain partly melted batch near
the dog house and to control the internal The electrical resistivity of glass is suffi-
circulation of the melt, which is complex. ciently low at high temperatures to pass an
The energy distribution is most easily con- electric current and heat the glass by the
trolled with cross fired tanks having sev- Joule effect. Heating by electricity avoids
eral pairs of ports along the side walls. The having to deal with very large volumes of
internal circulation plays a very important combustion gases and their possible prob-
part in mixing and homogenizing the glass. lems of controlling furnace emissions; it
Since perfect homogeneity is rarely attain- needs no regenerators or recuperators, al-
able, considerable effort goes into stretch- though batch gases are still produced. It
ing out inhomogeneities and aligning them also uses the energy input much more effi-
parallel to the direction of flow. Some of ciently inside the furnace but this does not
the important differences between furnaces necessarily make electric melting cheaper.
for container glass and flat glass are due to Many electric furnaces are very similar in
the higher standard needed in this respect general appearance to combustion fired
to minimize optical distortion in flat glass. ones because the requirements for melting,
 1.3 The Melting of Glasses 61

frvi fT^l ts^ IXN K ^ l ^ l k ^

IN.XWSN^XXX-'
^r^

i Kkuuvvvvuv^^vv.uT

QDDDDDD

_Q O Q O Q Q Q Q c
c
fl d
— ,

e
0 10 20 m
1 1 1

Figure 1-28. Layout of a modern gas fired Float glass furnace showing sections just above the surface of the melt,
vertical section along the center line and transverse section of the melting chamber, a) melting end, b) doghouse,
c) working end or conditioning chamber, d) Float bath, e) regenerators, f) combustion space, g) port.

refining and homogenizing remain the

same. The electrodes immersed in the glass
are usually of molybdenum but graphite
was used by some of the pioneers such as
Borel (1958). Electric furnaces are dis-
cussed at length by Stanek (1977) and by
Trier (1984). Electric furnaces are especially
useful for small scale melting and for the
melting of glasses which contain volatile
constituents such as fluorides. One inge-
nious furnace of this type is that due to
Gell (1956) which uses the very poor ther-
mal conductivity of the batch cover to ren-
der a crown unnecessary in normal opera-
tion, see Fig. 1-29. This can also trap and
recycle condensible volatiles evolved where
the melting reactions take place. Figure 1-29. Layout of a small 'cold top' electric glass
melting furnace using molybdenum plate electrodes
The complex internal flow of the melt set along the side walls. The insulation provided by
means that the residence time distribution the batch cover makes a crown unnecessary whilst
of glass inside the furnace is quite broad. operating normally.
62 1 Classical Glass Technology
This can be investigated experimentally
when changing from one glass composi-
tion to another, or by introducing a new
constituent as a tracer into the batch, and
monitoring its concentration in the output.
Such measurements show that some of the
new glass usually appears six to eight
hours after the batch was charged, the
maximum concentration often occurs after
20 to 30 hours but a few percent of the glass
is still inside the furnace after 150 to 200
hours. Understanding this behavior is very
important in furnaces where the color or
composition of the glass must be changed
from time to time. Furnace design and op-
eration probably owe more to accumu-
lated experience than scientifically based
analysis but some firms do now spend
large amounts on the study of models, es-
pecially for flow patterns in the melt.
The highest standards of homogeneity
are required of optical glasses which, for
about the last forty years, have been melted
in small special tank furnaces which are
partly lined with platinum and use me-
chanical stirring to achieve the attenuation
of inhomogeneities necessary to satisfy
quality standards. Given these conditions,
making optical glass does not require long
times and the average residence time for
optical glass may be no more than about
ten hours.
Good homogeneity is much more diffi-
cult to attain in pots than in tanks because
of the differences in flow within the melt.
Mechanical stirring must be used in pots
and crucibles if high standards are to be
achieved. The author and his students have
studied methods of measuring homogene-
ity (Cable and Bower, 1965; Cable and
Walters, 1980; Afghan and Cable, 1983;
Aylward et al., 1986) and made detailed
studies intended to devise simple stirrers
suitable for laboratory melts, see for exam-
ple Cable and Hakim (1973). Very detailed
model studies were made by Sadeghi (1980)
and these led to a very effective simple stir-
rer the performance of which in glass melts
has recently been investigated by Joanni
(1989); Joanni et al. (1989). These can make
optical quality glass of many compositions
on a very small scale, something that used
to be considered impossible.
Stirrers are sometimes used in full size
furnaces but represent a rather different
challenge because of the differences in ge-
ometry and throughput flow as well as the
very high cost of making and installing
them. Simple stirrers are quite often used in
forehearths where they may do more for
thermal than for chemical homogeneity.
1.4 Glass Forming
1.4.1 Introduction
Glass forming involves simultaneous
fluid flow and heat transfer. Flow normally
depends on the newtonian behavior of
glass melts, which means that velocity may
be assumed exactly proportional to the
stress applied. However, the rapid change
of temperature, and hence viscosity, as the
glass cools during forming as well as often
the complex geometry makes mathemati-
cal analysis of most glass forming opera-
tions a difficult task. The need to deal with
both flow and heat transfer makes resort to
numerical methods necessary for most
problems of interest. The equations to be
solved are usually easy to set up but prob-
lems often arise in setting realistic
boundary conditions, especially for heat
transfer, and in determining the effective
thermal conductivity.
In general flow occurs under quite low
stressses and glass making machinery
rarely needs to be massively built. In most
cases the removal of heat from the glass is

the slower and controlling process. The ini-
tial viscosity of the glass must be high
enough to prevent excessive flow under
gravity but not so great that high stresses
are needed to complete the shaping as the
glass cools. In the interests of efficiency the
glass must then be cooled to become essen-
tially solid as soon as possible after reach-
ing the required shape. Table 1-7 gives
some typical values of the viscosities at
which various processes occur but some of
these are rather crude estimates because so
many operations do not take place in
isothermal conditions.
Two important features of industrial
glass forming operations are that 1) it is
normal to complete the whole process
from raw materials to the finished product
in one continuous cycle of operations and
2) mechanized glass forming operations are
suited only to the production of large num-
bers of articles. The first of these arises
partly from the brittle nature, poor thermal
shock resistance of large pieces and other
typical properties of glasses, partly from
the fact that cooling and then reheating is
a very inefficient use of energy. Very few
large scale operators buy previously
melted glass and then re-process it; it is
however normal to remelt rejects produced
during manufacture and many large scale
producers also buy cullet (waste glass) to
add to their batches. The second arises
from the delicate non-equilibrium condi-
tions under which molds, for example,
must function for efficient processing.
Molds can be preheated before fitting to a
machine but cannot be brought before-
hand to the actual non-isothermal condi-
tions in which they operate efficiently.
Forming processes can be classified in
several different ways. Two of the more im-
portant aspects are: 1) whether a continu-
ous stream of glass is used (flat glass, tube,
fibers) or separate gobs formed (containers,
1.4 Glass Forming 63
Table 1-7. Approximate viscosity values for glass
forming operations in dPa s.
Operation logfa/dPas)
Melting 1.5 to 2.5
Seal glass to glass 3.5
Seal glass to metal 3.8
Forming gobs for containers 3.6 to 4.2
Drawing Fourcault sheet 4.0 to 4.4
Pressing 4.0 to 6.3
Surface of parison during forming 4.0 to 8.0
Glass at tip of Danner mandrel 5.5
Surface of bottle during blowing 5.7 to 10.0
Sinter glass powder to solid body 6.0
Littleton softening point 7.65
Sinter glass powder to porous body 8.0 to 8.8
Thick tube collapse under vacuum 11.0
Deform under gravity 11.3
Dilatometric softening point Mg 11.3 to 11.7
Lehr belt marks base of container 11.7
Annealing 12.0 to 14.0
Stress release occurs in a few seconds 12.8
Temperature for matching glass and
metal expansion curves for seals 14.0 to 14.5
Stress release too slow to be useful 14.6
television screens) and 2) whether or not
molds are used to shape the glass. Some
processes, like container manufacture, re-
quire that the temperatures in one place,
such as a particular point on a mold, keep
repeating a certain time-temperature cycle
whilst others, such as drawing tube or
forming flat glass, require the temperature
at a particular point to be as constant as
possible but temperatures vary rapidly
with position. In both instances the glass
itself changes temperature rapidly as it
flows during forming and the optimum
conditions can only be established whilst
the process is operating. Different types of
process have different preferred viscosity-
temperature relations. Even with today's
sophisticated controls it can take several
hours to optimize operating conditions af-
ter making a change, such as fitting a new
set of molds; frequent changes in operat-
64 1 Classical Glass Technology
ing conditions are thus very undesirable.
Glass manufacturers usually expect to
make very large numbers of individual ar-
ticles between changes in operating condi-
tions. Making quantities that represent
only a few hours production (which could
still mean more than 50000 containers) is
inefficient and expensive because of the
production lost during stoppages and the
rejects produced whilst achieving optimum
conditions.
1.4.2 The Manufacture of Containers
Forming by blowing in a split mold us-
ing compressed air permits complex shapes
to be made and this has long been the pre-
ferred method for making most containers.
The manufacture of containers by a skilled
workman manipulating a gather on a blow
pipe was practised for nearly two thousand
years and required a complex series of op-
erations to form a parison by rolling on a
marver, using gravity to stretch or com-
press the length of the parison and blowing
a little from time to time; the parison was
then put into the blow mold and blown to
the final shape. The pressure available
when blowing by mouth is very low and
too high a viscosity risks flow being very
slow and possibly not complete; automatic
machines use an effective pressure of only
about 2 atm. Forming the mouth followed
breaking the container off the blow pipe
and reheating the neck; this led to the
mouth being known as the finish.
One of the early successes of pioneers in
container production was to demonstrate
that the process could be done in two steps
using two body molds, a parison mold and
a final blow mold. Of course the mouth
now has to be formed first and held in a
neck ring whilst performing the other oper-
ations but it is still called the finish. Al-
though the whole process has many neces-
sary individual steps the essential seven
are: 1) form a gob and feed it to the parison
mold, 2) form the mouth or finish of the
container, 3) form the parison, 4) transfer
the parison to the blow mold, 5) blow the
container to its final form, 6) cool in the
blow mold until sufficiently rigid to keep
its shape and 7) open the mold and remove
the container. The container must then be
annealed.
The gob must be supplied in as near to
an isothermal a state as is possible and at
a viscosity sufficiently high to prevent too
rapid flow under gravity whilst still ready
to flow when blown. The viscosity for gob
formation depends on the particular pro-
cess and article being made but is usually
around log r\ = 3.7 to 4.2 (dPa s). Later
stages of the operations are less easy to
characterize in terms of viscosity because
the glass is being rapidly cooled and steep
gradients of both temperature and viscos-
ity exist within it; however the viscosity of
the surface layers must be the most impor-
tant value.
As mentioned in the historical review,
nearly all containers are now made on in-
dividual section (IS) machines. These are
made up by coupling a row of identical
sections which work independently of each
other, except that feeding the gobs to each
section in turn must clearly be coordi-
nated. A machine may have only four or
five sections but up to sixteen is known. All
the parison molds sit along one side of the
machine and all the blow molds along the
other. These molds open and close as re-
quired but are otherwise stationary. The
neck ring is swung vertically through 180°
to transfer the parison to the blow mold.
Figure 1-30 illustrates the steps in forming
a bottle on an IS machine. Many of the
details of construction of the IS and other
machines then widely used are discussed
by Giegerich and Trier (1964). Bollert et al.

/! S
Figure 1-30. Schematic diagram of the blow-blow op-
eration of the IS machine. The top row shows stages
in parison forming and the bottom row blowing in the
blow mold. In the center the neck ring is seen in the
position occupied during parison formation. The
parison is transferred to the blow mold by rotating
the arm through 180° (position shown dashed). 1) gob
entering mold, 2) blow down to ensure proper forma-
tion of neck, 3) blowing of parison complete, 4) pari-
son enclosed by blow mold, 5) blowing just begun,
6) mold opened for bottle to be removed.
(1987) more recently reviewed the evolu-
tion of the IS machine and some of its most
recent refinements.
The majority of containers have necks
which are relatively narrow compared with
their bodies so it is normal to drop the gob
into the inverted parison mold. Two differ-
1.4 Glass Forming 65
ent methods of forming the parison may
then be used, blow and blow or press and
blow. When first developed the press and
blow process was limited to wide mouthed
articles like jam jars but it is now used for
many narrow necked containers. If the
parison is made by the blow and blow pro-
cess the mold is at once covered by a blow
head and compressed air applied to ensure
that the mouth is properly formed; any
distortion of the sealing surface will often
make that container unusable. As soon as
the mouth has been formed the opening is
covered by a baffle plate and the parison
blown to fill its mold. Failure to blow at
least a small bubble as soon as possible
risks the glass around the plug forming the
inside of the mouth becoming too viscous
to be blown at all. In the press and blow
process a central metal plunger is used to
form the central cavity in the parison and
to ensure that the neck ring is properly
filled. This process has several advantages
which include being able to make the cen-
tral cavity an exact shape and some simpli-
fication of the steps needed to form the
parison. If the glass in the parison does not
have the desired wall thickness as well as
external contour, it may not give the re-
quired wall thickness distribution in the
final article.
Although the machine most widely used
for the manufacture of containers was de-
signed and brought into service many
years ago, recent years have seen impor-
tant improvements in it and in the contain-
ers produced. Reducing the weight of glass
in a given type of container has several
obvious advantages and such progress is
steadily continuing, as demonstrated by
Fig. 1-31 which shows how the weight of
the standard English one pint (568 mL) milk
bottle has changed over the recent past.
Once formed the parison is transferred
to the blow mold and blown in the same
66 1 Classical Glass Technology

600
gap between glass and mold, or the parison
may be deliberately left for a period en-
closed by the blow mold before beginning
500 - to blow. The mold surfaces are quite hot
and simply introducing the air gap de-
400 - creases heat transfer to the mold by a con-
O)
c siderable factor. Whilst it is reheating the
parison stretches under gravity and this
o 300 -
must not be permitted to go too far. Figure
1-32 shows typical examples of tempera-
ture profiles in a parison at different stages.
It is extremely difficult to study the flow
of the glass during parison formation. Di-
rect observation is impossible and it is nec-
essary to resort to computing by finite ele-
ment methods, solving for both heat
<1960 1965 1975 1985 1995
transfer and fluid flow, or to use physical
Year models. Interesting studies using model
Figure 1-31. Changes in the weight of the standard liquids were undertaken by Reinhardt
English 568 ml milk bottle over the years. The devel- (1965) and Schmid and Hertel (1968).
opment of the narrow mouth press and blow process
has been an important factor. By courtesy of PLM-
Redfearn Glass.
1000

way with both processes. On the IS ma-

chine the arm carrying the neck ring
swings vertically through 180° to carry the
parison to the blow mold which at once
closes around it. A very important stage of
foming the bottle or jar is reheating of the
surface of the glass once blowing of the
parison is finished. Reheat occurs when the
surface of the parison is no longer in close
contact with the metal mold and not hav-
ing heat extracted so rapidly. The steep
internal temperature gradient ensures that
heat continues to flow towards the surface;
as it is no longer being lost at the previous
rate this heat accumulates just below the
surface and the thin surface layer of the
glass which has been cooled most by con- 0.2 0.4 0.6 0.8 1.0
Fraction of wall thickness
tact with the mold gains in temperature
Figure 1-32. Typical temperature distributions in the
and becomes less viscous. To assist reheat- wall of a pressed parison at different stages of its
ing the parison mold may be opened a frac- formation: 1) just after beginning of pressing, 2) at the
tion to make sure that there is a small air beginning of reheat, 3) at the end of reheat.

Giegerich (1960) devised a simple
scheme for comparing the main stages of
the forming cycle on different machines
and published some data which indicate
why the IS machine has become so fa-
vored. The actual construction and opera-
tion of the Emhart IS, or any other ma-
chine, has innumerable complexities but it
is possible to give a simple outline of the
main features of the process by Giegerich's
method.
Figure 1-33 shows Giegerich's method
of analysis. A gob is dropped into the in-
verted parison mold at t = 0. All the opera-
tions necessary to form the mouth and
blow the parison are included in the pari-
son forming time £P, then the mold is
slightly opened to assist reheating for a
time tR which includes the time needed to
transfer the parison to the blow mold and
close that mold. A time tB is needed for
blowing in the blow mold, followed by a
cooling time tc before the mold is opened
and the container removed. The time be-
tween the delivery of successive gobs to the
same mold is tG and the total time needed
to make one article is tT. If the process were
operating as efficiently as possible the idle
time tY between removing one parison from
the parison mold and supplying the next
gob would be negligible and the total time
would be divided equally between parison
and blow molds. The idle or wasted time in
each cycle may therefore be defined as
tY=tG~\l2tT (1-71)
Although part of the time tG—(tP-\-tR) *S
needed to cool the parison mold it may be
considered wasted; so may most of the
cooling time tc for the blow mold as well as
the time that it is actually empty. When
times are measured in seconds, the actual
productivity in bottles per minute is,
B = 60/t G (1-72)
1.4 Glass Forming 67
Gob 1
Bottle 2
Figure 1-33. Schematic diagram of Giegerich's
method of analysing container machine operations,
see text.
whilst the ideal productivity would be
B max =120/t T (1-73)
Giegerich showed that tP increased more
or less linearly with gob weight and the
data for most machines fell very close to
the same line. When total time (tT) was
plotted against parison forming time (tP)
all machines again showed similar behav-
ior. However, the IS machine showed
shorter reheat times (tR) than any other
gob fed machine, although the suction fed
Owens machine was slightly better from
this point of view. However, when the var-
ious productivity figures were compared,
the IS machine clearly outperformed most
others and achieved about 80% of the
maximum possible value whilst some other
machines commonly used up to about 20
years ago worked at little more than half
the maximum value.
One of the most important aspects of
container manufacture is the heat transfer
between glass and metal mold. Perfect con-
tact between the two would assist rapid
heat transfer but implies that the glass ad-
heres to the mold which would be disas-
trous. However, the perfect contact model
68 1 Classical Glass Technology
is the one to start with. If two relatively
thick isothermal slabs of the same material
at temperatures TA and TB were brought
into perfect contact the interface tempera-
ture would be T{ = (TA + TB)/2. If the slabs
have different thermal properties the di-
mensionless interface temperature T*
should be given by
£BCB)] 1 / 2 (1-74)
Although not given a particular name in
English, the parameter XQC is called the
Temperaturleitzahl in German. When typi-
cal values for the properties of glass (A) and
cast iron (B) are taken and TA assumed to
be 1100°C and TB 550 °C, the calculated
value of T{ is found to be about 585 °C. It
is important that this should not exceed
the sticking temperature of the glass to the
mold material which is often about 600-
620 °C; such intimate contact would be
good for heat transfer but prevent removal
of the glass from the mold or, at least,
badly damage the surface of the glass. The
fact that the glass contracts as it cools
whilst the metal expands on heating helps
to prevent sticking. However it is found
on analysing glass-mold heat transfer that
the heat transfer coefficient at the interface
is strongly time dependent. This consider-
ably complicates attempts to calculate
temperatures and viscosities within the
glass during forming. Figure 1-34 shows
some data for the variation of glass to
mold heat transfer during pressing re-
ported by McGraw (1961). The mold sur-
face of course cannot be absolutely smooth
and clean, indeed it is usual practice to
apply mold dopes to the inner surfaces of
the mold to aid release of the glass and
improve surface finish; these may contain
graphite and oils which carbonize.
Trier (1955) reported some interesting
results of varying parison mold contact
1
0.4 0.8
Contact time in s
Figure 1-34. Variation glass-mold heat transfer coef-
ficient during a pressing operation according to mea-
surements by McGraw (1961).
times and total cycle times on a semi-auto-
matic machine without changing any other
parameters. These show that a proper bal-
ance must be maintained between heat re-
moved from the glass and heat removed
from the mold, see Fig. 1-35. Too short a
total cycle time makes the mold overheat
so that the glass sticks and too long a cycle
time makes the mold too cool so that the
glass is chilled and will not flow properly.
Too short a time in the parison mold leaves
the glass too fluid allowing it to distort too
much under gravity but too long a parison
forming time leaves it too viscous to be
blown in the blow mold. Current cycle
times on an IS machine would be consider-
ably shorter than those seen here.
The design of molds to ensure the de-
sired rates of heat extraction from different
parts and thus the temperature distribu-
tion over the inner surface is a complex
matter. One of the most obvious features is
that a considerable proportion of the heat
transferred from the glass is lost again from
the inner surface of the mold by forced
convection cooling whilst the mold is open
and empty. The inner surface temperature
 1.4 Glass Forming 69
16 I I I i I I
1.4.3 The Production
of Lamp Bulb Envelopes

Parison too
The manufacture of bulbs for incandes-
12 - viscous cent electric lamps is a very important
450°C

CD
r ~-~ — — -• branch of the glass industry. These differ
Sticks to / * 6 1 (re , from most other kinds of hollow ware in
mold /
o _ / having much thinner walls, usually some-
eg /•600°C
c
o
/ what less than 1 mm. These are made by a
o /
j /•450 rather different process which also uses a
/
610°C special machine. Thin walled articles of
435°C
y ^j
/ ^avy
surface this kind, including some drinking glasses
4 -
Parison are made using paste molds. A paste mold
- too fluid - is one which does much less damage to the
surface of the glass during manufacture.
I 1 i i 1 i

16 24 32 This is achieved by using a mold with a

Total cycle time in s relatively soft and porous lining which is
used saturated with water so that the glass
Figure 1-35. The effects of varying parison mold glass
contact time and total cycle time on parison forma- vaporizes the water when it is introduced
tion on a semi-automatic machine. Some mold sur- into the mold and the glass is prevented
face temperature readings are also shown. After Trier from coming into close contact with the
(1955). mold by a cushion of steam. This method
is restricted to thin walled articles because
of the limit on the heat that can be used in
evaporating the water. The molds are usu-
typically varies by about 80 °C during the ally relatively thin iron shells which are
whole cycle of operations. Drilling cooling lined with a carbon layer produced by ap-
passages in the wall of the mold, parallel to plying a layer of cork granules mixed with
the long axis of the container, is one of the additives which is carbonized before use.
ways in which the efficiency of the IS ma- The molds have a short life and the ware is
chine has been improved in recent years. normally rotated in the mold throughout
The only easy measurement of the heat blowing, partly to obtain as uniform and
extracted from the glass during forming is circular a section as possible also to avoid
to drop into a calorimeter 1) a gob, 2) a mold seams. Such bulbs are made at very
parison at transfer and 3) a just completed high rates of production on the Corning
bottle. If good specific heat data are avail- ribbon machine the main features of which
able these results can give the average tem- are shown in Fig. 1-36; the most notable
peratures of the whole article at each stage. features are the mounting of the blow
Data of Giegerich indicate that the heat heads and blow molds on two separate
loss during forming of a container on an IS bands like caterpillar tracks, one above the
machine was equivalent to a fall in average other, whilst the continuous ribbon of glass
temperature of about 320 to 400 °C with carrying the bulbs advances between them.
the loss during parison formation being
rather greater than during blowing, which
points out the necessity of reheating before
blowing the parison.
70 1 Classical Glass Technology

n u n n n n n n( (n n n n

J 1
n M

TOO
Figure 1-36. Schematic diagram of the Corning ribbon machine for making lamp bulbs. A stream of glass (a)
passes between two rollers (b) which shape it slightly; it then falls onto a band of metal plates (c) each with a
central hole through which the glass sags under gravity to begin parison formation. Blow heads (d) mounted on
the upper belt press against the upper surface of the glass ribbon and begin to blow at (e). The paste molds (f)
mounted on the lower belt close around the parison at (g) and the bulb then blown in the rotating mold. At (h)
the blow heads are lifted away and the blow molds open leaving the bulbs suspended from the ribbon from which
they are cracked off and collected at (i). The ribbon is then crushed and returned to be used as cullet.

1.4.4 The Manufacture of Flat Glass
1.4.4.1 Introduction
The requirements of buildings and vehi-
cles make flat glass production one of the
largest sections of the industry. As men-
tioned in the introduction, the crucial ad-
vances in flat glass manufacture occurred
during the present century: the first suc-
cessful processes for continuous drawing of
sheet coming into production between
about 1916 and 1930, to be followed by the
development of the Float process in the
fifties and sixties. Cast plate glass, made by
grinding and polishing thick cast plate, was
invented around AD 1680 but its large
scale manufacture was greatly improved
largely by Pilkington Brothers between
1920 and 1940; however, it has now been
entirely replaced by Float glass. Although
they are also now obsolescent it is worth
briefly outlining the important sheet draw-
ing processes which are still in use.
Whether drawn upwards or downwards
a stream of any liquid, even one of high
viscosity, is inherently unstable. Any at-
tempt to draw a thin sheet of viscous liq-
uid, for example using a knife blade dipped
into a pool, shows that it at once necks and
tends towards a circular section. Even a
circular jet will break up unless rapidly
cooled and made effectively solid. The
break up of a circular jet is a classic and
complex problem of hydrodynamics but
some useful analytical approximations ex-
ist. By taking the simplest useful approxi-
mations for the equations governing the
behavior of a circular jet Levich (1962) esti-
mated the time to break up (TB) for either
a low viscosity jet or a viscous jet. For a
viscous jet of radius a this is approximately
(1-75)

which means that if its velocity is U9 the
critical (break up) length is about
LB= 5 Ur]a/a (1-76)
High velocity, high viscosity and large di-
ameter will all help to increase this length.
It is clear that rapid increase in viscosity to
make the glass essentially solid (rj >1012
dPa s) within say a quarter of the initial
isothermal break up length will achieve
reasonable stability of the process. Such an
analysis done beforehand would have en-
couraged a pioneer of flat glass manufac-
ture to proceed but emphasizes that very
rapid cooling is necessary, something not
favored, from the heat transfer point of
view, by a large thickness. Because of its
shape, forming and preserving the desired
width and thickness of a sheet is a bigger
problem than controlling a circular jet.
Mathematical modelling of the drawing
of a sheet from a pool at first looks rela-
tively simple because it can be treated as a
two dimensional problem symmetrical
about the center line of the sheet. As the
glass is so much more viscous than the air
it can be assumed that shear stress and so
velocity gradient go to zero at the surfaces.
However, the positions of the surfaces
where these boundary conditions apply are
not known; indeed finding them is the
main purpose of the exercise. The foot of
the sheet could, for example, be assumed to
be of hyperbolic or exponential form but,
in practice, it may bulge into what is called
the onion just above the surface of the melt.
This therefore is a difficult problem to
solve properly even if the conditions are
assumed isothermal. When the heat trans-
fer and rapid change of viscosity with posi-
tion, which are essential features of the real
process, are introduced the difficulties are
considerably multiplied.
The need for rapid cooling, in conditions
where the effective conductivity is very lit-
1.4 Glass Forming 71
tle greater than the true conductivity of the
glass (largely because the sheet is usually of
small optical thickness), is one of the main
factors limiting the maximum thickness of
glass that can be produced. Thin sheet
must be drawn off at a higher speed and
thus subject to greater stresses so that the
danger of the sheet breaking is one of the
limitations on minimum thickness. How-
ever, the critical factors controlling com-
plex industrial processes are not always the
most obvious ones.
The most comprehensive description
and discussion of sheet glass manufactur-
ing processes is the book by Goerk (1966);
a useful review is given by Hynd (1984).
1.4.4.2 Sheet Glass Processes
The Fourcault Process
Fourcault (1862-1919), the first inven-
tor to make his process work, overcame
the major difficulties by inventing the debi-
teuse (a word not translated into English)
which is a kind of refractory clay boat
which floats in the glass. It has in its base
a slot of approximately elliptical shape,
through which the glass will flow up. This
rate of flow may be increased by pushing
the debiteuse down into melt. If this stream
is gripped and pulled up at the same vol-
ume rate of flow, without it being able to
wet and fill the inside of the debiteuse, a
sheet can be formed. Rectangular water
cooled iron boxes extending across the
whole width of the drawing chamber are
placed very near to the surfaces of the sheet
and not far above the top of the debiteuse
to cool the glass sufficiently quickly to con-
trol its tendencies to neck down and try to
form a circular jet or become unstable. The
outer edges will cool more quickly than the
rest so that the still deformable sheet is
held between two almost rigid side strips
from very close to the top of the debiteuse.
72 1 Classical Glass Technology

As soon as the surfaces of the sheet are

sufficiently cool it is gripped very lightly by
the first of a series of pairs of rollers (at
least 12), which used to be covered with
asbestos, and is drawn vertically upwards.
The height of the first pair of rollers above
the surface of the melt must have an impor-
tant influence on the stability of the pro-
cess. The minimum height of these depends
on the rate of cooling and the upward ve-
locity of the sheet.
The main disadvantage of the Fourcault
process is that the slot in the clay debiteuse
is subject to forced convection corrosion
and eventually threads of corrosion prod-
uct, which obviously lie on the surfaces of
the sheet, are drawn up and impair the
optical quality. Because of the large differ-
ence in refractive index between glass and
air, small surface imperfections cause the
maximum optical distortion and the paral-
lel lines that result are called piano or music
lines. As a result the debiteuse must be
changed at rather frequent intervals, often
around 60 days. Not surprisingly, the
waviness of the surfaces is usually least
near the center and wide strips from the
edges are sometimes cut off and discarded
when the best quality sheet is required.
Accurate control of temperatures is vital
in such a process and this means that con-
trol of the convection of the air in the
drawing chamber and in the vertical draw-
ing tower is important. The rate of cooling
in the middle part of the tower must be
controlled carefully to achieve a reason-
able degree of annealing before the glass is
cut into sheets at the top of the tower. Fig-
ure 1-37 shows the essential components of
the Fourcault system.
The glass sheet may be up to 3 m wide
but around 1.8 or 2.3 m is more common.
The range of thicknesses (or substance) that
can be produced is surprisingly large, from
about 0.6 to 14 mm, but the whole of the
>5
El
Figure 1-37. The essential components of the Four-
cault sheet drawing process. The upper diagram
shows a vertical section through the middle of the
drawing chamber, the lower one a plan view and
sections of the debiteuse (slightly larger scale). 1) De-
biteuse, 2) water cooling box, 3) push rod holding
debiteuse, 4) control for adjusting immersion of debi-
teuse, 5) drawing rollers.
potential range is not usually exploited and
a range from about 0.7 to 6 mm is more
typical. To exploit the whole range of
thicknesses requires that the width of the
slot in the debiteuse be varied. Drawing
speeds can vary from around 3.5 m min" 1
for thin glass to 0.2 m m m " 1 for thick
glass; surface distortion is difficult to avoid
with sheet near to the maximum thickness.
The height of the drawing tower rarely ex-
ceeds 6 m and this can mean that thick
glass is not well annealed. The main con-
trols over thickness being produced in a
given installation are 1) the temperature of
the drawing chamber, 2) the speed of draw-
ing, 3) the depth of immersion of the debi-
teuse and 4) the positions of the water cool-
ing boxes.

The Pittsburgh Process
The main difference in the Pittsburgh or
Pennvernon process is that the debiteuse is
replaced by a draw bar which is totally
immersed in the melt so that the corrosion
products eventually formed and drawn off
lie buried near the centre of the sheet and
do not cause the obvious defects seen on
the surfaces of Fourcault glass. The im-
mersed draw bar has its upper surface 60 to
80 mm below the surface of the glass and
helps to stabilize the foot of the sheet. The
shape has many variants; it sometimes has
a central slot in it through which chilled
glass from the just below the point of draw-
ing can sink, mix with the rest, and be re-
heated. Two different ways of quickly cool-
ing the edges have been used. The original
method is to have edge cooling cups or
forks about 250 mm in diameter and
100 mm deep, each with a radial slot from
edge to center, so that the cup encircles and
quickly chills the edge of the sheet very
close to the surface of the bath, thereby
making two almost rigid side strips. The
other is to use air cooled edge rolls, ribbed
or knurled, which actually grip the sheet
immediately above the surface of the bath
to form the two almost solid side strips,
which are driven upwards at a controlled
rate from this position. This method was
originally part of the Colburn process and
provides the closest control of the edges of
the sheet during drawing. Figure 1-38
shows a typical Pittsburgh drawing cham-
ber. Note that the actual drawing position
is more or less isolated from the rest of the
furnace chamber by the L-blocks. The
Pittsburgh process is otherwise very simi-
lar to the Fourcault.
Although capable of giving better sur-
face quality than the Fourcault process the
Pittsburgh process is not quite so versatile
in range of thickness and requires more
1.4 Glass Forming 73
Figure 1-38. Sketch of a Pittsburgh sheet drawing
chamber showing 1) the skimmer block, 2) the im-
mersed draw bar, 3) the edge rolls, 4) one of the water
coolers, 5) one L-block, 6) the lowest pair of drawing
rolls) and 7) the sheet of glass.
accurate control of temperatures and glass
level. The maximum width of the sheet (in-
cluding the edge strips) is about 3.05 m but
2.1 to 2.75 m is the common range. The
thickness of the sheet made by this process
is usually in the range 2.0 to 9.5 mm. Pro-
duction of thinner glass is difficult partly
because drawing speeds are generally
rather higher than for the Fourcault pro-
cess. The largest single sheets produced on
the cutting floor are 3.0 m long (for 6 mm
thickness) but a common size supplied to
customers is 1840 x 1220 mm.
The Libbey-Owens-Ford Process
The vertical drawing of sheet is rather
inconvenient from an engineering point of
view. The height of the tower should be
determined by rates of cooling need for
annealing but given the need to handle all
the glass at a considerable height above
ground level, is obviously fixed and partly
determined by engineering factors. Col-
burn, inventor of this process, who first
made it succeed and founded the Libbey-
Owens company in 1916, avoided this
74 1 Classical Glass Technology
problem by bending the sheet horizontally
over a polished air cooled metal roller just
before it became too viscous for this to be
done. The feasibility of doing so may have
been suggested by the opening and flatten-
ing of the cylinders long practised in the
hand and Lubbers processes. The roller is
about 0.2 m in diameter and approxi-
mately 0.7 m above the surface of the bath.
Colburn also introduced air cooled edge
rolls to control the stability of the point of
drawing and the width of the sheet by pro-
ducing two chilled strips along the edges of
the sheet. Figure 1-39 shows a schematic
diagram of a Libbey-Owens-Ford draw-
ing chamber. The total length of the hori-
zontal chamber can be much longer than
the maximum feasible height of a Four-
cault or Pittsburgh drawing tower and
may be as much as 60 m; this permits good
annealing of even the thickest sheet.
The Libbey-Owens-Ford process can
make glass up to about 3.5 m wide and is
capable of a wide range of thicknesses,
from about 0.6 mm to 25 mm, but 2 m
wide and 1.0 to 10.0 mm thick represents a
more typical range of production. Drawing
speeds are higher than for the other two
processes, about 2.5 m min" 1 for 2 mm
Figure 1-39. The layout of the Libbey-Owens sheet
drawing process. 1) the conditioning chamber of the
tank, 2) auxiliary burner, 3) the edge rolls, 4) water
cooling box to chill sheet, 5) the bending roll, 6) water
cooler.
and 0.7 m min 1 being typical. Lemaire
(1965) published some interesting studies
of temperature distributions and flow pat-
terns in a Libbey-Owens drawing cham-
ber.
Downward Drawing Processes
Several methods of drawing a stream
downwards have been developed in recent
years and are used to make much thinner
sheet than the other processes can easily
produce, such as that used for microscope
slides. The most obvious is analogous to
the Fourcault process with a stream of
glass being drawn down from a slot in a
platinum bushing but the surface quality is
not as good as with the Float process.
However, another method which avoids ir-
regularities that would be produced by
slight imperfections in the edges of the slot
has been developed by Corning Glass
Works. Molten glass is fed into one end of
a trough with an inclined base to give a
steadily decreasing depth; the upper edges
also deviate very slightly from the horizon-
tal. A proper combination of these geomet-
rical features can make the rate of overflow
the same along the whole length of the
trough. The two streams flowing down
each side meet at the central ridge along
the bottom of the trough and the resultant
sheet is gripped just below by edge rolls
and is then drawn away by other rollers
lower down. The melt in the trough has a
viscosity of about 4 x 104 dPa s and cool-
ers increase this to about 3 x 105 dPa s as it
leaves the ridge or root at the bottom of the
trough. Hynd (1984) gave some details of
this process and it is mentioned by Dum-
baugh et al. (1991).
1.4.4.3 Float Glass
In the past high quality flat glass for
mirrors, vehicle or shop windows and such

like had to be made by mechanically grind-
ing and polishing cast plate. Large scale
manufacture involved considerable engi-
neering difficulties and made the process
costly; a continuous plate glass line was
about 600 m long and used about 1.7 MW
of electrical energy solely for grinding the
glass. The development of the Float pro-
cess has rendered polished plate obsolete.
The idea of floating glass on a bath of
molten metal, for a variety of purposes,
some misconceived, can be traced back for
about a century but older inventors lacked
the insight and the sophisticated engineer-
ing skills needed to develop a successful
process. The physical basis of the modern
Float process is beautifully simple: a broad
stream of glass is allowed to spread out
and come to equilibrium whilst floating on
a bath of molten metal. It is then cooled
until almost rigid and lifted off. Both sur-
faces of the glass can have almost ideally
flat and smooth firepolished surfaces so
that grinding and polishing are unneces-
sary. A fascinating review of the evolution
of flat glass manufacture and the early de-
velopment of the Float process has been
given by Pilkington (1969) and another ac-
count is by Hynd (1984).
The Physical Principles of the Process
The metal must be denser than the glass,
which is not a problem: the other require-
ments are not so easily met. On consider-
ing the range of viscosities over which the
deformation of the glass can occur and be
controlled, it is clear that the metal must
have a melting point below 600 °C and a
boiling point above 1050°C. Both the
molten metal and the atmosphere above it
have very low viscosities compared with
the glass which will therefore spread out to
come to equilibrium under a balance be-
tween hydrostatic and surface tension
1.4 Glass Forming
forces, so long as the atmosphere and
molten metal are not vigorously disturbed.
The cross section of a continuous ribbon is
thus similar to a two dimensional sessile
drop which, if sufficiently wide, will have a
broad flat central region. Figure 1-40
shows the two factors which control the
thickness of the sheet. The balance of the
interfacial tensions gives a net force over
unit length of this section of
F(a) = ag + <jgm-Gm (1-77)
which is balanced by the forces due to the
hydrostatic pressures. If the thickness of
the sheet is d and its depth of immersion in
the molten metal bath (d — /*), Archimedes
principle requires that
Qgd = Qm(d-h) (1-78)
If one imagines that the left part of the
ribbon has been removed, as shown in the
Figure, it is necessary to apply forces to
keep the remaining part in equilibrium.
There are two contributions to this: 1) the
hydrostatic pressure in the glass which in-
creases linearly from x = 0 to d and 2) the
pressure in the molten metal which acts in
the opposite direction but only from x = h
to d. The net force due to these over a
section of unit length is
(1-79)
Figure 1-40. The forces controlling the equilibrium
thickness of Float glass, see text.
76 1 Classical Glass Technology
and equating F(o) with F(p) gives
i-am = {Qgd2l2-Qm{d-h)2l2)g
(1-80)
from which (d — h) can be eliminated
through Eq. (1-78). On rearrangement this
yields the equilibrium thickness d,
(1-81)
The other basic model is to calculate the
time needed for a surface irregularity to be
smoothed out. This may be determined by
considering the decay of a sine wave distur-
bance of the surface. Three different mech-
anisms could be involved, 1) viscous flow
due to gravity, 2) viscous flow due to sur-
face tension forces and 3) surface diffusion.
These would in turn predominate on de-
creasing scales with gravity controlling the
behavior of long waves and surface diffu-
sion only becoming controlling when the
wavelength approaches atomic scale.
The gravitational driving force is just the
difference in hydrostatic pressure due to
the amplitude (A) of the wave,
Ap=Agg (1-82)
Since the amplitude itself represents the
driving force, an exponential decay,
A=. (1-83)
may be expected. In a very viscous liquid
the constant k in Eq.(1-83) is QgX/(4nrj)
for control by gravity (Lamb, 1932). The
driving force for flow when surface tension
governs is the excess pressure due to curva-
ture of the surface which, for a surface
curved in only one plane, is Ap = a/a if a
is the radius of curvature. For a sine
wave this also leads to exponential decay
(Mullins, 1970)
A =A0Qxp( — (na/Xrj)t) (1-84)
Gravity thus causes rapid decay of long
waves but surface tension governs short
waves. The two processes have the same
rate of decay when
X2rit = 4n2a/Qg (1-85)
and waves of this critical wavelength are
the slowest to decay. For typical glass
properties Xcrit is about 23 mm and such a
wave decays to 1.5% of its initial ampli-
tude in 100 s if the viscosity is 104 dPa s.
Cassidy and Gjostein (1970) confirmed
that the decay of corrugations on glass of
wavelengths around 5 to 15 \xm was con-
trolled by surface tension and that more
complex profiles become simple sine waves
as they decay, experiment and theory
agreeing quite well. In practice it is found
that about one minute is needed at about
1050 °C (viscosity 104 dPa s) to achieve op-
tical quality flatness.
Chemistry of the Float Process
The molten metal must have a low vapor
pressure ( < 1 0 N m ~ 2 at 1050°C) other-
wise condensation towards the cool end of
the Float bath may be troublesome. Chem-
ical interaction between the molten metal
and the glass must be minimal. On examin-
ing the properties of all molten metals it is
found that only gallium, indium, and tin
satisfy these requirements (lead has too
high a vapor pressure) and that tin is best
in terms of vapor pressure and availability.
Tin has the highest boiling point, which is
above 2500 °C, and is the metal always
used. Pure tin easily reacts with the oxygen
in the air to form solid oxides but reacts
less with the glass. It is therefore necessary
to have a reducing atmosphere in the Float
bath; 97% N 2 , 3% H 2 is commonly used.
Very low levels of oxygen or sulfur impu-
rity in the tin are sufficient to cause prob-
lems due to formation of stannous oxide or

sulphide. If these compounds are formed
they can condense near the cool end of the
bath, be reduced to metal by the atmo-
sphere, and form specks of tin adhering to
the upper surface of the ribbon; because of
its higher solubility sulfur is the greater
problem. The glass itself contains a signifi-
cant proportion of sulfur, as sulfate added
to aid melting and refining, some dissolved
water and some variable valence elements,
chiefly iron, capable of being oxidized or
reduced to absorb or evolve oxygen. A very
delicate control of these factors is therefore
required. Sodium is the most reactive ma-
jor constituent of the glass and is also the
most mobile ion within it. It is thus likely
that reactions between sodium in the glass
and the tin bath will be the most significant
and some aspects of this have been dis-
cussed by Miiller et al. (1989).
Float Glass Technology
The overall layout of the process derives
from the continuous casting of plate glass.
A controlled stream of glass is delivered by
the melting furnace onto the molten tin
bath and drawn along it to the other end
where it is lifted off. The glass is fed onto
the molten tin at about 1050°C, allowed
to become flat, cooled until too viscous
to flow easily or be damaged (about
lO^dPas), then lifted off it at the other
end at about 600 °C.
The melting tank may be up to about
65 m long and l l m wide with the melt
about 1.3 m deep and capable of producing
as much as 6000 tonnes a week. Energy
consumption in the melting tank is now
around 5800 kJ kg" *. A smaller condition-
ing section approximately 9 m wide and
25 m long is attached to the end of the
melting tank; in it the glass is cooled and
brought to a uniform temperature suitable
for forming the stream which is fed onto
1.4 Glass Forming 77
the Float bath. The Float bath may be
about 5 m wide and 35 m long and the
molten tin needs to be only about 100 mm
deep. On leaving the Float bath the ribbon
passes through an annealing furnace. At
the end of the line the curved meniscus
regions are removed then the ribbon is cut
into whatever size sheets are required, tak-
ing into account any defects that have been
detected before cutting it.
One of the major problems of Float
glass development was the production of a
range of thicknesses. The natural equilib-
rium thickness of the ribbon is about
7 mm, which is very fortunate because the
largest market used to be for 1/4 in
(6.3 mm) polished plate. As was soon dis-
covered, nature tries to insist on achieving
this equilibrium thickness and attempts to
control thickness simply by drawing faster
have a greater effect on width than on
thickness. The first method of making thin-
ner glass was to allow the ribbon to spread
out to equilibrium width and cool it to a
viscosity of around 10 8 dPas (700 °C) at
which position the edges were gripped by
edge rolls; further downstream the ribbon
was reheated to around 106 dPa s (850 °C)
and stretched to the required thickness,
with some reduction in width, by adjusting
the rate of drawing. The roof of the Float
bath thus needs to be fitted with both elec-
tric heaters and cooling panels to permit
the adjustment of the longitudinal temper-
ature distribution. This method permits
glass of high quality to be produced at
thicknesses down to 3 mm. Subsequently
other methods were developed. At high
furnace loads the drag force of the tin can
be used to confine stretching largely to the
cooler end of the Float bath, where width
and thickness are decreased in the same
proportions, instead of acting only at the
hot end where thickness hardly changes.
Another variant uses several pairs of
78 1 Classical Glass Technology
driven toothed wheels along the length of
the Float bath to prevent excessive reduc-
tion in width; these wheels, which press on
the edges of only the upper surface of the
ribbon, are about 300 mm in diameter and
20 mm wide and mounted on long cooled
shafts. They are especially useful in pro-
ducing a wide ribbon at high loads.
Glass thicker than the natural equilib-
rium thickness is produced by using graph-
ite guides, which are not wetted by the
glass, to prevent lateral spreading. This al-
lows glass up to about 25 mm thick to be
produced.
Several types of process have been devel-
oped which permit coatings to be applied
to the ribbon in the cooler end of the Float
bath, or soon after its emergence from the
tin bath. The Electrofloat process uses an
electrolytic method to produce a surface
layer on the top of the ribbon inside the
Float bath by ion exchange. These pro-
cesses are especially useful in making glasses
with controlled heat transmission charac-
teristics. Some information about them is
given by Hynd (1984). Coatings are also
discussed by Kirkbride and Williams (1991).
1.4.5 Rod and Tubing
A circular jet is inherently unstable, as
pointed out in discussing flat glass manu-
facture, but drawing a circular rod or tube
has fewer problems than maintaining a flat
sheet. Rod and tube are made by very sim-
ilar methods and have been little analysed
in the literature, nor has their technology
been discussed in detail. Although upward
and downward drawing processes exist,
those in which the rod or tube is drawn off
sideways from the end of an inclined rotat-
ing mandrel are more widely used, rotation
being necessary to cancel the effect of grav-
ity. To make tubing it is necessary to have
a mandrel with a central hole and to blow
air down it at a pressure only slightly
greater than atmospheric. Rod is made in
the same way but without the central air
flow.
1.4.5.1 The Danner Process
The Danner process may be regarded as
the mechanization of hand drawing with a
steady stream of glass falling on to the ro-
tating blow pipe or mandrel at about
103 dPa s and running down to form a uni-
form layer then being drawn away from the
lower end at about 5 x 104 dPa s and car-
ried onto a horizontal series of rollers. The
refractory sleeve of the mandrel is about
800 mm long and around 200 mm diame-
ter; it is mounted on a heat resisting steel
shaft about 50 mm in diameter. The nose of
the mandrel may be of heat resistant steel,
especially for tubing, because it can be ma-
chined and maintained to greater dimen-
sional accuracy than a refractory nose. The
mandrel rotates at around 8 rpm and is
inclined at about 15° to the horizontal so
that the glass will flow towards the tip. The
tube is drawn away from the nose approx-
imately in line with the axis of the mandrel
and led onto a horizontal track about 50 m
long where it is supported by rollers, see
Fig. 1-41. Towards the end of the track,
when quite cool, the tube is lightly gripped
by two caterpillar driving belts which draw
it away at the desired rate. These driving
belts may be slightly angled across the line
of draw so that the tube is rotated in the
contrary sense to the rotation of the man-
drel. As a result of these twisting forces the
mass of glass just beyond the tip of the
mandrel may look remarkably asymmetri-
cal. The tube is cut into lengths just beyond
these driving belts. One of the few detailed
descriptions of the process is due to Sibilia
(1939) and an approximate theoretical
model was developed by Yamauchi (1977).

Figure 1-41. Schematic diagram of a Danner tube
drawing machine enclosed by a gas fired muffle cham-
ber.
Since tube drawing does not use a mold
control of both viscosity and the main
parameters of the process must be very
precise if accuracy of tube dimensions is
required. Bajorat and Weiss (1965) re-
ported data on some of the factors affecting
the dimensions of Danner tube; their most
detailed data being for tube of 37 mm OD
with a 0.9 mm thick wall being drawn at
25 m min ~1 with the mandrel rotating
at 8.1 rpm and an air pressure of 2.9
x 10 ~ 3 atm. The measurements concerned
both the magnitude and the frequency of
variations in air pressure, pipe rotation
and drawing speed. For example, air pres-
sure fluctuations of up to 4% lasting for 0.2
to 0.4 s had no measurable effect on tube
diameter but a variation persisting for 2 to
4 s had a clear effect. Douglas (1938)
showed that the rate of expansion of a long
tube under internal pressure can be calcu-
lated by analogy with the elastic strain of a
solid tube. If the tube is of external radius
a and wall thickness w its rate of expansion
under a pressure difference ZIP is given by
da/dt = a2AP/(4wrj) (1-86)
Bajorat and Weiss (1965) reported that a
1% change in diameter was caused by a
1.4 Glass Forming 79
1.6% change in pressure lasting for 2 s;
putting these values into the equation gives
a viscosity of 4.2 x 104 dPa s, which is close
to the viscosity of the glass at the tip of the
mandrel and confirms the reasonableness
of their findings. Variations in the rotation
of the mandrel can trap bubbles where the
stream of glass falls on to the mandrel and
may also lead to ovality of the tube.
The Philips process is very like the Dan-
ner but uses glass drawn from the inside of
a heat resistant steel mandrel and may thus
avoid contamination of the inside of the
tube by corrosion products, which must
eventually happen with the refractory
mandrel of the Danner process.
1.4.5.2 Vertical Drawing Processes
The upward or downward drawing pro-
cesses appear more straightforward but,
like vertically drawn sheet, suffer from pro-
ducing the tube or rod at a considerably
higher or lower level than that at which the
glass is melted, unless the tube is curved
round. The Koroljov process is based on
the Fourcault process with a central blow-
ing nozzle fitted below the centre of the
debiteuse and can produce tubing up to
175 mm diameter. The Schuller and Corn-
ing processes also function by drawing ver-
tically upwards from a refractory ring im-
mersed in a pool of glass with the tube
passing through a circular cooler just
above the pool from which the tube is
drawn; the Schuller method uses a circular
ring with holes which blow air down on to
the tube but the Corning process uses a
water cooler. The Velio process uses a
stream of glass which flows out of the bot-
tom of a forehearth orifice and is spread
out by a cone suspended on the end of a
hollow shaft through which air is blown;
the formed tube is gently curved round to
be drawn along a horizontal track. There is
80 1 Classical Glass Technology
also a Corning downward drawing process
in which the glass flows over the inner rim
of a circular channel and is pulled down-
wards. There is an inner concentric water
cooled truncated cone through the centre
of which air may be blown but this cone
acts chiefly as a cooler and is not in contact
with the glass at any time.
The literature on tube and rod drawing
is sparse; Giegerich and Trier (1964) report
most of what is available.
1.4.6 Glass Fibers
1.4.6.1 Introduction
Manufacture of fibers has been an im-
portant branch of the glass industry for
about sixty years but within the last decade
fibers of an entirely new kind have become
very important, namely those used for op-
tical communication systems. The first
fibers used for optical communication were
of very pure silica but these are incompat-
ible with most other glasses because of
their very low thermal expansion, unusu-
ally high softening point and very high vis-
cosity. Thus, apart from trying to develop
glasses with even better optical properties,
silica fibers were rather difficult to use in
some applications and most recent re-
search has been devoted to heavy metal
halide glasses (see Chap. 8). Such fibers are
made by specialized methods based on the
same principles as those used for other
fibers but differing in many details and are
not considered here. Some of the most in-
teresting aspects of glasses for optical fibers
have recently been discussed by Parker
(1989), and a full treatment will be found in
Chap. 15.
The more traditional kinds of fibers are
widely used for low density insulation, for
reinforcement of polymers, and in some
kinds of textiles. Such fibers have small di-
ameters, typically from 5 to 20 jim, and a
very high surface to volume ratio; as a re-
sult they need to be made from glasses of
better than average chemical durability.
The standard type of glass developed for
this purpose is called E-glass which means
a glass with specific properties rather than
a specified composition; a typical composi-
tion may include a little fluoride, see Table
1-1. This glass has a liquidus temperature
of about 1140°C and, because it has very
little alkali to act as a flux during melting,
needs melting temperatures of 1550 to
1600°C. Despite its low alkali content it is
not very resistant to attack by mineral
acids and C-glass was developed for the
improved acid durability needed for some
purposes; it has some alkali but about 10%
more silica than E-glass, see Table 1-1. The
two main products are continuous fibers
and staple or short curled lengths. The lat-
ter are mainly used for low density insulat-
ing mat which is bonded by spraying on an
organic binder. Continuous fibers may be
chopped into short lengths and also used
for mat but can be made into a large vari-
ety of rovings (untwisted bundles of fila-
ments) or yarn (twisted bundles of fila-
ments) and used in many different ways,
including being woven into cloth. A high
proportion of all the continuous fiber
made is used as reinforcing for polymer
composite materials.
1.4.6.2 The Physics of Fiber drawing
The simple criteria developed to de-
scribe the stability of a liquid jet intro-
duced when discussing the drawing of flat
glass are directly relevant here. It may be
recalled that a very viscous circular jet of
radius a leaving an orifice would break up
in a time of about
TB=5rja/a (1-87)

if a is the surface tension. A fairly typical
nozzle radius for fiber drawing would be
a = 0.5 mm and assuming a viscosity of
about 104 dPa s, a jet of that size would
break up in about 20 ms. However, the fi-
ber is drawn away at such a speed that its
radius is much decreased immediately be-
low the orifice and its radius is so small
that it cools and becomes rigid in less than
the critical time, without needing special
measures to achieve sufficiently rapid cool-
ing as is essential in producing flat glass.
The hydrodynamics of fiber drawing is
nevertheless very interesting.
In the conditions used in making glass
fibers it may be assumed that the flow
through the nozzle itself is governed by
Poiseuille's law, that is to say the mass rate
of flow M through an orifice of radius a
will be
nAPa4
M =Q (1-88)
SrjL
where AP is the pressure difference causing
flow (the hydrostatic head) and L the
length of the nozzle. Drawing the fiber
more quickly reduces its final diameter
without increasing the mass flow rate; it is
generally better to control the flow by hav-
ing a short relatively small diameter orifice
rather one a longer one of greater diame-
ter. The viscosity range used for fiber draw-
ing is quite narrow; if less than about
500 dPa s at the orifice the jet breaks up
into drops; if greater than about 1000dPas
the stresses become too high and breakage
is frequent.
Although drawing the fiber from the
nozzle might appear to be very simple it
shows some unexpected features. It is pos-
sible to observe four different profiles just
below the orifice in the range of conditions
that might be used for fiber drawing: 1) the
fiber diameter decreases steadily (approxi-
mately exponentially) with distance from
1.4 Glass Forming 81
the rim of the orifice, 2) the jet emerges as
a stream of the same diameter as the ori-
fice, 3) the stream of glass bulges out, rather
like the onion in Fourcault sheet drawing,
immediately below the orifice, or 4) a thin
fiber forms from a base distinctly smaller
than the size of the orifice. Burgman (1970)
investigated these and showed that they
could be related to Reynolds number.
Glicksman (1968) made calculations of the
rate of cooling of a fiber then used these
results to predict how fiber diameter would
change with distance from the orifice and
obtained good agreement between mea-
sured and predicted profiles.
1.4.6.3 The Technology of Fiber Production
Staple fibers may be produced directly
by several methods. One common method
uses two rows of platinum alloy nozzles in
the bottom of a forehearth which has adja-
cent downward pointing steam jets on each
side to accelerate and attenuate the fila-
ments. Because both glass and steam have
similar kinematic viscosities in these condi-
tions there is a major interaction between
the two flows and the turbulent flow of the
steam also curls the fibers and makes them
break into fairly short lengths. As the fibers
fall on to a collecting belt they are sprayed
with a binder to form mat suitable for insu-
lation. The fiber diameter is likely to vary
between about 5 and 30 jim.
The Hager-Rosengarth process uses cen-
trifugal forces produced by a thin stream of
glass falling on to the centre of a rotating
disk to produce fibers. The disk rotates at
3000-4000 rpm and produces fairly long
fibers (about 500 mm) of diameter around
20 jim which are carried away by a current
of air and often laid down to make a mat.
The TEL process is a rather similar one in
which a stream of glass falls into the center
of a shallow dish or spinner made of heat
82 1 Classical Glass Technology
resistant steel which has several thousand
apertures about 1 mm in diameter drilled
around its circumference. The spinner ro-
tates at about 3000 rpm and jets of glass fly
horizontally out of the apertures to meet
the combustion gases of a series of burners
set around the perimeter of the spinner and
pointing vertically downwards. The rela-
tively thick jets leaving the spinner are thus
reheated and further extruded to make the
final fibers about 6jnm in diameter and
about the same length as given by the
Hager process. These are collected in a
similar way. Some additional details of the
processes are given by Giegerich and Trier
(1964).
1.4.6.4 Continuous Fibers
The glass for manufacturing continuous
fibers is generally melted in a small tank at
about 1580°C and fed directly to the fiber
drawing heads but it may be formed into
19 mm diameter marbles which are then
fed directly into a separate drawing cham-
ber, thus separating melting from fiber pro-
duction. Although making marbles, cool-
ing to room temperature and reheating,
wastes a considerable amount of heat, the
remelting and drawing is easy to control
and is still the favored method for a few
types of fiber. Continuous fibers are made
by a process which relies on pulling the
fiber away from a nozzle and using the
velocity of drawing to attenuate the fiber to
the desired diameter. The crucial nozzle
dimensions are usually in the range of di-
ameter 1 to 2.5 mm and length of the cylin-
drical part which controls flow rate 3 to
6 mm. The velocity of drawing may be
more than 25 000 times the average veloc-
ity in the nozzle and the final fiber diameter
as little as 6 jum; drawing speeds may be as
high as 2500 mmin" 1 . Avoiding bubbles
or crystalline inclusions in the glass is
thus very important. The large reduction
in cross section also means that fibers are
sometimes drawn under stresses not far
short of the fracture stress and breakages
may occur.
The electrically heated platinum alloy
bushing from which the fibers are drawn
has several hundred nozzles (usually in
multiples of 200) spaced as close together
as convenient and is heated by the Joule
effect. Having to stop the drawing for any
reason, correct the defect and then restart
drawing is a tedious operation; avoidable
manufacturing defects are guarded against
very carefully. A bushing has a working life
of about 12 months and weighs 2 to 4 kg so
that replacing it is a major expense. The
drawing of a large number of fibers from a
bushing creates a considerable flow of the
air adjacent to the bushing and it is normal
to supply an appropriate flow of clean air
through inlets. The fibers are then sprayed
with water before being coated with size by
passing over a size applicator; this is often
a rotating cylinder partially immersed in a
bath of size. Next the fibers are gathered
together by passing over a gathering shoe
or wheel which may form one or several
strands of yarn. The gathering shoe needs
to be wetted to prevent the size adhering to
it. Finally the strand is wound on a suitable
core to make a cylindrical cake which is
then dried and is ready for the final user. To
make the strand easy to unwind it is
wound on as a helix traversing from end to
end of the bobbin.
One important function of the size is to
act as a surface lubricant to minimize dam-
age by glass to glass abrasion during draw-
ing and winding but it is very common for
it to be formulated to act as a keying agent
when the fiber is to be used in some kind of
polymer composite; many different types
of size exist for the latter use. The high
drawing velocities mean that problems can

sometimes arise over the rheological prop-
erties and wetting of the fiber by the size.
An expert and detailed account of continu-
ous fiber production is given by Loewen-
stein (1983).
1.4.6.5 Non-Circular Rod Tube and Fiber
Because glass flows as a perfectly new-
tonian liquid in most conditions it is possi-
ble to extrude preforms of many shapes
and preserve their cross section, except for
slight rounding off of sharp corners, pro-
vided that the extrusion is done at rela-
tively high viscosity and fairly high stresses
which minimize the effect of surface ten-
sion. The production of solid sections of a
variety of shapes, such as rectangular and
also hollow ones with internal ribs and
partitions, was reported by Humphrey
(1965). More recently Roeder and Egel-
Hess (1987) have described the continuous
extrusion of tubes with complex inner
cross sections.
1.5 Polishing
Most glass working operations are per-
formed with hot fluid glass but polishing is
the most important operation often neces-
sary on cold glass. The Float process has
made polishing unnecessary on large
pieces of flat glass but it is still needed for
high quality optical components and in
preparing small samples for many kinds of
laboratory measurements. Some glasses
may also be polished by chemical rather
than mechanical means but chemical pol-
ishing is not used when very accurate sur-
face profiles are required.
1.5.1 Mechanical Polishing
Mechanical polishing is a rather slow
and expensive process which consumes
1.5 Polishing 83
large amounts of mechanical energy. The
standard procedure is to wet grind the sur-
face using in succession several grades of a
suitable hard abrasive powder, each finer
than the last, until a very fine frosted gran-
ular texture free from any pits or scratches
left by the coarser grades is produced. The
rate of removal decreases as the particle
size and consequently chip size decrease.
The liquid used at this stage is nearly al-
ways water and iron wheels are generally
used. Large scale grinding of plate glass
used to use quartz, which is a little harder
than the glass but smaller scale operations
usually use silicon carbide. Diamond
wheels may be used for more rapid grind-
ing or when making curved surfaces of
specific radii but are much more costly.
Having obtained a sufficiently fine texture
the final stage of polishing uses a different
very finely divided polishing agent in a
similar way. Plate glass polishing used to
use iron oxide but small scale operations
frequently use specially prepared ceria on a
cloth or felt covered wheel which is damp
rather than wet. This eventually produces
the required smooth and shiny surface.
Polishing is an old art but one which is
incompletely understood. The early stages
of grinding to the necessary contour clearly
operate by pressing the particles of grind-
ing agent against the glass and breaking off
chips of glass. The surface is formed by
many small cracks which spread out and
join together but also penetrate into the
glass beneath. The use of several succes-
sively finer grades of abrasive is necessary
to minimize the depth affected by this dam-
age and thus avoid leaving sub-surface
damage below the polished surface. The
obvious simple physical model of polishing
is to assume that the glass always behaves
as an isotropic brittle material; using finer
and finer grades of grinding and polishing
agents is then assumed to produce essen-
84 1 Classical Glass Technology
tially similar surface texture on an ever
smaller scale until the scale of the rough-
ness is rather less than the wavelength of
light and no longer gives scattering at the
interface. Such a view has often been
put forward in the past, for example by
Newton in 1695 (see Thomson, 1922 and
Preston, 1921). However, we now know
that glass can flow on a small scale at room
temperature: diamond pyramid micro-in-
dentation tests can make permanent im-
pressions in glasses, as in metals, so the
possibility of some local flow cannot be
ignored. A theory of flow in polishing was
first elaborated by Beilby (1921) but has
found few adherents. Its most obvious de-
fect is that it attributes polishing entirely to
flow of the surface layer but all quantita-
tive studies show that polishing does re-
move material.
It is now widely agreed that some chem-
ical interaction between glass, polishing
agent and liquid medium must be consid-
ered. This view was shared by Preston
(1930) only a few years after his earlier
championing of the abrasion theory. How-
ever, no theory yet put forward seems to be
capable of explaining all the observations
made in glass polishing studies.
One of the most obvious pieces of evi-
dence for a chemical interaction is that pol-
ishing efficiency is clearly not determined
simply by particle size and hardness: most
of the effective polishing agents are oxides
of variable valence elements. The staining
of the surface that can occur during polish-
ing with iron oxide, chromium oxide, and
ceria is another interesting demonstration
of some chemical interaction. The liquid
medium also has a definite influence and
the pH of the medium can considerably
affect both rate of removal of material and
surface finish (Compton, 1989). One recent
attempt to interpret the polishing of glasses
is by Koucky and Matusek (1984) but, de-
spite its importance to the optical industry,
mechanical polishing of glass remains only
partially understood.
1.5.2 Acid Polishing
For many years it has been the practice
of the lead crystal industry to polish cut
(abraded) glass chemically by using hy-
drofluoric acid, the one readily available
reagent capable of easily dissolving silicate
glasses. It has also been known for a con-
siderable time that etching away the sur-
face layers of glass containing flaws which
weaken it can increase the strength (Proc-
tor, 1962). Such etching does not necessar-
ily produce a polished surface, especially
when the products of reaction are not re-
moved, and commercial etchants of this
type are often used for badging or other-
wise producing frosted surfaces. Ammo-
nium fluoride may be present in these mix-
tures.
In recent years there have been many
studies concerned with the safety of the
operation and the disposal of the residues
from the mixtures of hydrofluoric and sul-
furic acids normally used but few con-
cerned with details of the chemistry and
the influence of the acid on the glass, how-
ever, some of these matters were discussed
by Maskill and Ferguson (1950). A lengthy
discussion by Kausch (1973) gives exten-
sive descriptions of typical installations
and useful information about the construc-
tion of baths and accessories sufficiently
resistant to hydrofluoric and sulfuric acids
for industrial use. Vacek and Kopackova
(1977) concentrate more on some of the
chemical aspects of the process.
The essential step in the process may be
considered to be
2 H + + SiF62~ n)H 2 O (1-89)

When polishing glasses which contain lead
or barium with a medium using sulfuric
acid, the sulfates of these elements are also
precipitated because they are considerably
less soluble than the fluorides. Extraction
of other alkali and alkaline earth ions also
tends to neutralize the acid. It is thus neces-
sary to replenish both acids from time to
time as well as to dispose of the sludge
which is formed.
The low pH of the solution encourages
the process ^ ^
2 H + + SiF62~ -> H2SiF6 -> 2HF + SiF4
to proceed to the right and the evolution of
both HF and SiF4 as vapors is an impor-
tant health hazard which must be strictly
controlled.
The rate at which glasses are etched
by hydrofluoric acid based solutions is
strongly dependent on glass composition
and Loftier (1954, 1957, 1964) used this to
develop techniques for identifying various
types of cord and ream by examining in an
interferometer sections first polished and
then acid etched, different types of cord
giving different characteristic etching con-
tours. Cable and Hakim (1973) used this
technique to obtain a quantitative index of
homogeneity.
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2 Special Methods of Obtaining Glasses
and Amorphous Materials
Jerzy Zarzycki

Laboratory of Science of Vitreous Materials, University of Montpellier,

Montpellier, France

List of Symbols and Abbreviations 93

2.1 Introduction 94
2.1.1 Glasses and Amorphous Materials 94
2.1.2 The Concept of "New Glasses" 94
2.1.3 Different Routes to Non-Crystalline Solids 95
2.2 Melt Quenching Techniques 95
2.2.1 Unconventional Melting 95
2.2.2 Ultrafast Quenching 95
2.3 Vapor Quenching Techniques 98
2.3.1 Evaporation 98
2.3.2 Sputtering 98
2.3.3 Reactive Deposition 99
2.4 Solid-State Methods 100
2.4.1 Radiation Damage 100
2.4.2 Effects of Intense Shock Waves 100
2.4.3 Slow Mechanical Actions 101
2.4.4 Diffusion Effects 101
2.5 Electrochemical Methods - Anodic Oxidation 102
2.6 Pyrolysis 102
2.7 Solution Methods; "Sol-Gel" Processing of Glasses 102
2.7.1 Methods of Gel Formation 103
2.7.1.1 Gel Formation from Alkoxides 103
2.7.1.2 Gel Formation from Sols 105
2.7.1.3 Redispersion Methods 106
2.7.2 Aging Effects 107
2.7.3 Drying 107
2.7.3.1 The Role of Capillary Forces 108
2.7.3.2 Obtaining Monolithic Gels 108
2.7.3.3 Structural Aspects 110
2.7.4 Curing-Sintering 110
2.7.4.1 Viscous Flow Sintering Ill
2.7.4.2 Devitrification Kinetics - Use of TTT Diagrams Ill
2.7.5 Forming Processes 112
2.7.5.1 Bulk Glass 112
2.7.5.2 Thin Films 112
Materials Science and Technology
Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
92 2 Special Methods of Obtaining Glasses and Amorphous Materials

2.7.5.3 Fibers 113

2.7.5.4 Hollow Glass Microspheres 113
2.7.6 Advantages and Disadvantages of the Sol-Gel-Process 114
2.7.7 Future Trends 114
2.8 References 116
 List of Symbols and Abbreviations 93

List of Symbols and Abbreviations

c critical point
D fractal dimension
E Young's modulus
critical stress concentration coefficient
P pressure
r radius of the pore
reduced time
r fracture surface energy
7 specific surface energy
n viscosity
V Poisson's number
CVD chemical vapor deposition
DCCA drying control chemical additives
HSE hypercritical solvent evacuation
ICF inertial confinement fusion
NMR nuclear magnetic resonance
rf radio frequency
SAXS small angle X-ray scattering
TTT time-temperature-transformation
94 2 Special Methods of Obtaining Glasses and Amorphous Materials
2.1 Introduction
2.1.1 Glasses and Amorphous Materials
Glasses, in the current sense of the term,
are essentially non-crystalline materials
obtained by fusing together silica (sand)
with Na and Ca oxides (in the form of car-
bonates), which act as fluxes and lower the
processing temperature. The resulting melt
is cooled at a sufficient rate to avoid crys-
tallization and then shaped into different
forms: flat sheets, containers, fibers. This
classical glass technology was the object of
the preceding chapter.
The glass-making process has evolved
over the centuries and now represents a
heavy industry with a yearly production of
approximately 18 million tons for the Eu-
ropean Community and about the same
amount for the U.S.A. It is well known,
however, that substances other than silica
or silicates can exist in a non-crystalline
form. Tamman (1933) coined the concept
of the "glassy state of matter" to describe
this situation, and glasses are often simply
identified with non-crystalline materials.
This definition is obviously too wide, as it
encompasses materials which, though non-
crystalline, frankly have different proper-
ties (e.g., gels). Furthermore, quenching a
liquid is not the only way in which non-
crystalline solids can be obtained. It would
therefore seem more appropriate to reserve
the term of "glasses" only for those non-
crystalline solids which present the phe-
nomenon of "glass transition", whatever
their origin, and to call the remainder
amorphous materials (Zarzycki, 1982 a).
This classification however, has not yet
been universally adopted. The terms
"amorphous" and "non-crystalline" are of-
ten considered as synonymous; for in-
stance, Elliott (1990) defines glass as "an
amorphous solid which exhibits a glass
transition".
2.1.2 The Concept of "New Glasses"
Non-crystalline solids, glasses, and
amorphous materials alike now play an in-
creasingly important role in modern tech-
nology. Besides common glass, which is an
indispensable material in today's economy
in architecture, transport, lighting, condi-
tioning, etc., there is a whole set of glasses
and amorphous materials which enter into
more and more sophisticated applications
in optics, electronics, optoelectronics, bio-
technologies, etc. The concept of "new
glasses" emerged progressively and covers
materials other than classical glasses. The
Japanese experts consider the market for
these new materials to be of the order of
$ 1 billion in 1987 and estimate that it will
reach $ 17 billion by the beginning of the
21st century.
It should be noted that in many cases the
methods of producing these materials dif-
fer so profoundly form classical glass tech-
nology that their manufacture is being
taken over by firms not traditionally con-
cerned with glass but rather with electronic
equipment or chemistry. Most of these
glasses are high-tech materials and their
production is to be evaluated in tons rather
than in millions of tons as is the case of
classical glass.
The purpose of this chapter is to review
the various "unusual" ways of producing
glass and amorphous materials. Some of
these methods are of purely academic
value or are still in the laboratory stages,
while others have already gained industrial
importance. Previous reviews of this sub-
ject have been made by Secrist and
Mackenzie (1964) and Scherer and Schultz
(1983).
Particular attention will be paid here to
the obtention of glasses from precursors
using methods of soft chemistry which
have shown particularly rapid develop-
ment in recent years.

2.1.3 Different Routes
to Non-Crystalline Solids
To obtain a glass or an amorphous solid,
it is necessary either to retain at ambient
temperature the disordered state of a liquid
or gas, or, alternatively, to destroy (amor-
phize) the structure of a crystal. It is also
possible to produce the disordered struc-
ture directly by means of suitable chemical
reactions which may or may not be as-
sisted by external fields (electrical or chem-
ical potentials).
The following general types of methods
are at our disposal:
• melt quenching
• vapor quenching
• crystalline solid disordering (other than
melting)
• interdiffusion and sintering
• electrolysis
• pyrolysis
• reactions in solution
2.2 Melt Quenching Techniques
2.2.1 Unconventional Melting
The usual way of obtaining a glass is by
quenching a melt obtained by fusion of one
or several crystalline substances. When the
rate of the decrease in temperature is suffi-
cient to bypass crystallization, the disor-
dered state of the liquid is retained in the
solid state (see Chapters 3 and 4). In classi-
cal glass technology, where glass formers
such as SiO2 or B 2 O 3 are used, air quench-
ing is sufficient, and the composition of the
glasses is optimized to avoid the risk of
crystallization (devitrification).
For oxide glasses the melt can be ob-
tained in air, although control of the Re-
dox conditions may be necessary (see Chap-
ter 1). For chalcogenide glasses (see Chap-
ter 7) the exclusion of oxygen is essential,
2.2 Melt Quenching Techniques 95
which leads to melting in an atmosphere of
inert gas, often in sealed ampoules. Atmo-
spheric control is also necessary for metal-
lic glasses (see Chapter 9). For halide
glasses (see Chapter 8) the melt is obtained
by fluorination of corresponding oxides in
an atmosphere containing HF.
Melting under high pressure has seldom
been used in practice. It was applied by
Datta et al. (1964) under 1 kbar pressure to
produce K 2 CO 3 -MgCO 3 glasses, as well
as glasses combining Mn, Pb, or Ca car-
bonates. Operating under pressures of up
to 10 kbar, in an Ar, H 2 O, or CO 2 atmo-
sphere, Roy et al. (1964) produced glasses
containing unusually large amounts of dis-
solved gases (up to 25mol% H 2 O and
4mol% Ar).
While the quench in air is average, the
quench in a liquid (water, mercury, or liq-
uid nitrogen) is strong and may be used to
achieve higher cooling rates. The quench-
ing rate, however, is quickly limited in
practice (up to 10 2o C/s) by the formation
of an insulating vapor layer at the glass-liq-
uid interface (calefaction effect).
2.2.2 Ultrafast Quenching
To achieve higher cooling rates it is nec-
essary to use a contact with a solid of high
thermal conductivity, generally a metal
such as copper (see also Chapter 2 of Vol-
ume 15). The splat-cooling technique (Du-
wez etal., 1960) consists of projecting a
droplet of a melt by the action of a pressure
shock wave which propulses the sample
towards a curved Cu-plate (Fig. 2-1). The
glass is obtained in the form of thin flakes
of a few microns in thickness resulting from
high-speed conduction cooling (10 5 -10 9
°C/s). The quality of the contact between
the liquid and the solid substrate controls
the effective cooling rate, as shown by Ruhl
(1967).
96 2 Special Methods of Obtaining Glasses and Amorphous Materials

In another device, designed by Pietro-

kowsky (1963), a molten droplet is expelled
Pressurized from a crucible and smashed between two
He • I
metallic plates, one of which is electroni-
- High-pressure
chamber cally triggered via a photocell by the
droplet itself (Fig. 2-2). The advantage of
- Breakable this device is that it produces plates of uni-
mylar diaphragm
(~80um thick) form thickness devoid of holes as in
Duwez' device, but quenching speeds are
-Low-pressure somewhat lower (10 5o C/s). The calcula-
chamber
tion of limiting cooling speeds in splat
Ar
cooling was performed by Bletry (1973),
and recent devices using laser sources for
melting were developed by Krepski et al.
(1975) and Veltri et al. (1979).
-Furnace
-Molten sample The cooling of a molten droplet between
(~100mg) two rapidly rotating steel rollers was used
in crucible by Zarzycki and Naudin (1967) to produce
Molten jet Opening flakes of B 2 O 3 -PbO-Al 2 O 3 glasses for
unmixing kinetics studies (Fig. 2-3). Chen
and Miller (1970, 1976) developed a simi-
Copper reception
strip
lar device for obtaining metallic glasses,
which was also used by Suzuki and An-
thony (1974) to examine various binary
Figure 2-1. Duwez-type splat-cooling device (sche-
systems of refractory oxides, some of which
matic). formed glasses.
All the preceding devices produce small
samples suitable only for laboratory exam-
-Furnace ination of structure. The device of Chen
and Miller (1976) opened the way to mak-
ing continuous ribbons of metallic glasses,
by the use of a metallic (Cu-Be) wheel
spinning at 300-1800 rpm. A liquid stream
impinges on the inside of the wheel's torus-
like, convex surface. The quenched ribbon
slips out of the wheel under the action of
the centrifugal force. Ribbons 0.5 mm
wide, 20 jam thick, and up to 100 m in
length were produced.
The technique was further improved by
quenching the melt on the outside of the
spinning wheel (Fig. 2-4). The liquid is
Stationary Fast-moving
anvil hammer spread in the form of continuous film with
Figure 2-2. Hammer-and-anvil splat-cooling device quench rates of 1 0 6 - 1 0 8 K s " 1 . Modern
(schematic). devices enable ribbons up to several deci-
 2.2 Melt Quenching Techniques 97

J— Furnace C0 2 Laser \
(250 W)
Molten sample \
in crucible — Laser beam focussed
onto the tip of the sample
Spun-off
spherules
High-speed
v)
A Falling droplet (20000 rpm)
Rotating sample rod
Collecting —\
hopper \
Fast rotating \_ Steel collecting tray
steel rollers
Figure 2-5. Laser spin-melting device (schematic).

Splat
laser-film melting, whereby the beam of a
Figure 2-3. Rollers splat-cooling device (schematic).
CO 2 laser is used to scan the surface of a
specimen, producing a molten layer which
Gas pressure quickly solidifies in perfect contact with
the solid (not molten) substrate (United
Technologies Research Center, 1976).
In splat-cooling techniques one dimen-
sion (the thickness) of the splat or of the
Furnace ribbon is kept small in order to speed up
Crucible
the heat exchange. It is also possible to
subdivide the melt into droplets small
Liquid metal
enough to achieve a high cooling rate by
radiation. In the method of laser-spin melt-
ing (Topol et al., 1973) small droplets are
Quenched produced by spinning the target in the
glass ribbon form of a rod at 8000-30000 rpm. The ex-
tremity of the target is heated by a CO 2
laser (Fig. 2-5). Cooling rates for droplets
500 jim in thickness were estimated at
Fast rotating 4000 °C/s. Various refractory oxides and
wheel
their mixtures (A12O3, Ga 2 O 3 , La 2 O 3 ,
Figure 2-4. Melt-spinning device (schematic). Nb 2 O 3 , Ta 2 O 5 , etc.) were obtained in
partly non-crystalline form. Other experi-
ments were made in the preparation of
meters wide to be produced. More details glass-melting experiments in migrogravity
on this important industrial technique will conditions (Spacelab and Shuttle mis-
be given in Chapter 9 of this Volume. Re- sions).
views on splat cooling are to be found in
Anantharaman and Suryanarayana (1971),
Jones (1972), and Jones and Suryanara-
yana (1973). A variant of splat cooling is
98 2 Special Methods of Obtaining Glasses and Amorphous Materials
2.3 Vapor-Quenching Techniques
The formation of non-crystalline solids
may also be achieved by depositing one or
several components in the vapor state onto
a substrate. The vapor may be produced by
heating a suitable compound and de-
posited as such without further modifica-
tion (nonreactive deposition), or a chemi-
cal reaction may intervene (reactive de-
position).
These processes are typically used for
producing thin films for electronic and op-
tical applications. Reactive deposition,
however, may also be used to produce ei-
ther bulk glasses that are difficult to obtain
from the melt or hyperpure materials,
when are needed (e.g., blanks for optical
fibers).
2.3.1 Evaporation
The evaporation method consists of
emitting a vapor under vacuum and con-
densing it onto the specimen (Fig. 2-6). The
various techniques differ according to the
heating method employed to evaporate the
substance: electrical resistance heating,
electron beam heating, or high-frequency
heating. The operation takes place in a re-
Vacuum jar Sample at
controlled
temperature
-Shutter
Residual /N
atmosphere
(1CTA-10-7Torr)
\±l | Heated
evaporation
boats
I
To pumping
system
Figure 2-6. Thermal evaporator (schematic).
Vacuum jar
Solid to be
sputtered
(cathode)
Sputtered
atoms
Specimen to
be coated
(anode)
Figure 2-7. Sputtering coating device (schematic).
sidual atmosphere (10 4 - 1 0 7 Torr), and
the vapor pressure of the depositing mate-
rial is kept below 10 ~2 Torr. Single metals
can be readily evaporated in this way. For
multicomponent systems several separate
sources may be used or a metal alloy
rapidly evaporated using the "flash" tech-
nique. In the case of oxides, their dissocia-
tion (e.g., SiO formation in the case of
SiO2) may cause difficulties.
2.3.2 Sputtering
In the sputtering method the specimen to
be coated and the solid source are both
contained in a closed vessel in a low-pres-
sure gas atmosphere (generally Ar), Fig.
2-7). A high d.c. voltage of a few kilo volts
is used to produce a glow discharge, with
the specimen as anode and the source as
cathode. This discharge produces Ar +
ions, which after being driven toward the
cathode, eject (sputter) the atoms from the
cathode. Some of these atoms will con-
dense on the specimen forming a uniform,
generally non-crystalline film of a compo-
sition close to that of the source material.
(For the physics of sputtering, see Towns-
end et al., 1976.)

The method can be used to deposit both
elemental metals or alloys. It is widely used
in electronic and optical applications. In
glass technology continuous sputtering
devices are used to coat glass panes with
metal or oxide layers for applications in
architecture (light control). The industrial
devices use alternating voltages and mag-
netic fields (magnetron sputtering) to in-
crease the path of the ions and thus their
collision frequency, which results in a bet-
ter yield. A standard work on the deposi-
tion of thin films is that of Holland (1956).
2.3.3 Reactive Deposition
In reactive-deposition processes a chemi-
cal reaction is initiated in the gas phase
by supplying sufficient activation energy:
thermal, in the form of heat, or electrical, in
an rf glow discharge. Heterogeneous and
homogeneous processes must be distin-
guished. For example, SiO2 glass may be
produced by homogeneous or heteroge-
neous oxidation of SiCl4 vapor or by oxi-
dizing the surface of a silicon wafer.
In reactive sputtering, if the Ar gas con-
tains O 2 or N 2 , the resulting sputtered film
will be the oxide or nitride of the sputtered
cathode metal. With an Si cathode, SiO2 or
Si 3 N 4 films will be produced. Processes of
this kind are extremely important in the
electronics industry, where glass films are
used for encapsulating integrated circuits
and thin dielectric films as both active and
positive components. Using these tech-
niques, amorphous films can often be ob-
tained in systems where the obtention of
glasses by direct methods is impossible.
For general reviews on these applications
see Amick et al. (1977) and Pliskin et al.
(1967).
Chemical Vapor Deposition (CVD) in-
volves a heterogeneous reaction and depo-
sition from organometallic or metal halide
2.3 Vapor-Quenching Techniques 99
vapors at a heated solid substrate. For ex-
ample, gas mixtures such as SiH 4 , PH 3 ,
and O 2 , or SiCl4, POC1 3 , and O 2 passing
over a heated Si surface at temperatures
below 1000°C, SiO 2 -P 2 O 5 glass layers are
formed at a rate < 1 jim/min.
Most of the work done concerns SiO2,
Si 3 N 4 , SiO 2 -P 2 O 5 , SiO 2 -B 2 O 3 , and
A12O3 both for low-temperature CVD
(450 °C) or high-temperature CVD
(850 °C). Glow discharge plasmas (rf or mi-
crowave) allow for low-temperature opera-
tions (310 °C). This method was used to
prepare chalcogenide films and SiJCN}?Hz
films. For details see Kern and Rosier
(1977).
Thermally activated homogeneous oxi-
dation of mixtures of metal halide vapors is
performed to obtain large bulk glasses of
high purity and quality by vapor-deposi-
tion techniques. Metal halides (SiCl4,
GeCl 4 , TiCl 4 , BC13, POC13) are generally
used as starting compounds as are SiH4
and organometallics (e.g., (CH4)3B). At
temperatures above 1500°C, a homoge-
neous oxidation reaction predominates,
and without a catalyzing surface a finely
divided glass particulate material called
"soot" is obtained. The reaction
SiCl4 + O 2 -* SiO2 + 2Cl 2 (2-1)
is obtained by passing a mixture of SiCl4
and O 2 in a burner through a methane-
oxygen flame. The high specific surface of
the soot (^20m 2 /g) provides a strong
driving force for sintering (see Chapter 3).
When soot is collected on a target
heated at a sufficiently high temperature
( » 1800°C for SiO2), sintering and conver-
sion into solid bubble-free glass occur,
(Fig. 2-8). By this process very large glass
"boules" (over 500 kg) were obtained for
SiO 2 , either in pure form or with additions
(TiO2, A12O3, B 2 O 3 ); see Dalton and
Nordberg (1941) and Nordberg (1943).
100 2 Special Methods of Obtaining Glasses and Amorphous Materials
5iCl^+ 0 2 ( +Dopants)
— Burners
\l V
ik Soot-carrying flames
Y//////////////////<V77; Deposited SiO2 "boule"
Slowly rotating substrate
held at ~1800°C
Figure 2-8. Flame oxidation process for producing
bulk silica (schematic).
Lowering the soot deposition tempera-
ture to less than 1500°C helps to retain the
more volatile components (e.g., B 2 O 3 ); this
results in a porous silica body which can
then be sintered in a separate step at a
higher temperature (Schultz, 1975). Depo-
sition methods based on these principles
are used to prepare preforms for glass opti-
cal fibers. These important techniques will
be described in Chapter 16 of this Volume.
2.4 Solid-State Methods
Non-crystalline solids may be obtained
from crystals without passing through the
fusion stage. There are several other ways
of destroying a regular crystal lattice.
2.4.1 Radiation Damage
The collision of energetic particles with
the atoms of a crystal produces lattice de-
fects; the effect is cumulative and the pro-
cess may end in the formation of a non-
crystalline solid. Fast neutrons have a low
probability of collision, but each collision
produces a large number of defects;
charged particles have a higher probability
of collision but produce less displacements.
The transfer of the kinetic energy of the
particle to the neighboring atoms produces
"thermal spikes" of the order of several
thousand degrees Kelvin for 10 " 1 ° -10 " 1 1 s
which extend to regions of the order of 104
atoms and may produce local melting fol-
lowed by an ultrafast quench. Exposure of
various ceramic materials to neutron doses
of approximately 3xlO 2 0 neutrons/cm 2
renders these materials amorphous (Wul-
laert, 1964; see also Ch. 9, Sec. 9.2.5).
The classic work of Primak (1958) has
shown that on irradiation quartz and
cristobalite are progressively amorphized
and that their properties tend toward those
of vitreous SiO2. Radioactive materials,
e.g., complex uranium oxide minerals, be-
come rnetamictized, i.e., disordered by their
own radioactivity (Primak and Bohmann,
1962).
Ion implantation may be used to modify
the structure of superficial layers of materi-
als. Some results are presented in Chapters
6 and 9. As yet, amorphization by irradia-
tion effects has not been exploited in glass
technology, but ion implantation has re-
cently been used to modify oxide glass sur-
faces (Ch. 6).
2.4.2 Effects of Intense Shock Waves
Powerful pressure shock waves of sev-
eral hundred kilobars generated during ex-
plosions may produce amorphization of
crystals without their melting. The external
boundaries of the original crystal are con-
served and show the absence of flow, but
the crystalline lattice is destroyed. Such
glasses are called diaplectic or thetomor-
phic.
Impacts of meteorites produce such ma-
terials (Chao, 1967), and in particular, it
was discovered that the surface of the
moon is covered with glassy material. Re-
search on glasses linked with the lunar ex-
ploration (Apollo program) was destined
to determine whether these materials were

of volcanic origin or the result of continu-
ous meteorite bombardment (Pye et al.,
1984).
In the laboratory the first diaplectic
glasses were produced by De Carli and
Jamieson (1959) who amorphized silica
with shock waves at pressures exceed-
ing 350 kbar and Milton and De Carli
(1963) who obtained diaplectic plagioclase
(NaAlSi 3 O 8 -CaAl 2 Si 2 O 8 ) glass with pres-
sures up to 800 kbar. For a review, see
Stoffler (1972, 1974).
Shock waves are produced in the labora-
tory by explosions in which a projectile
(striking plate) is propelled at a specimen.
Upon impact with the specimen, a pressure
pulse of several hundred kilobars with a
duration of a few microseconds is pro-
duced (Fig. 2-9). Methods of calculating
pressures and temperatures thus generated
were given by Wackerle (1962) and Gib-
bons and Ahrens (1971). In natural events
(meteoritic impacts) much higher pressures
are expected, reaching several megabars.
This may induce partial or total fusion and
even vaporization of the sample.
Practical applications are as yet rare.
The firm Schott Glasswerk has obtained a
patent (Schott, 1968) for shock-produced
oxide glasses (B2O3-La2O3-ThO2-
Nb 2 O 3 -Ta 2 O 5 ) and fluoride glasses
(CaF 2 -SrF 2 -LaF 3 -AlF 3 -NaPO 3 ) with el-
evated refractive indices. The pressures
employed were 5-10 kbar. The preceding
oxide glasses cannot be obtained by con-
ventional melting, and the fluoride glass
has a refractive index superior to that of
glass obtained by melting.
Another use of shock waves which
should lead to important applications in
the field of metallic glasses is the explosive
compaction of metallic glass particles into
homogeneous cylinders or disks, first re-
ported by Cline and Hopper (1979). Such
bulk pieces cannot be obtained by sinter-
2.4 Solid-State Methods 101
Sample
Heavy
Explosion-
propelled steel
projectile block
Striker
plate
Figure 2-9. Shock-amorphization device (schematic).
ing without inducing crystallization,
whereas shock-wave treatment preserves
the amorphous character of the material.
Dynamic compaction of metallic glass
powders and ultrasonic welding of ribbons
is being developed in Japan (Makino,
1985). For more details, see Matsumoto
(1986), Negishi et al. (1985), Toda et al.
(1985), and Aoki et al. (1986).
2.4.3 Slow Mechanical Actions
The effects of shearing under prolonged
mechanical grinding of a crystal can pro-
gressively destroy the crystalline order and
lead to the formation of a non-crystalline
solid. Mechanical alloying processes are
used to prepare various metallic glasses
(see also Ch. 9, Sec. 9.2.7 and Vol. 15, Ch. 5,
Sec. 5.6.3).
2.4.4 Diffusion Effects
Interdiffusion effects can be employed to
produce non-crystalline materials. Using
multilayers formed of superposed crys-
talline metallic thin films, Johnson et al.
(1985) have examined the possibility of
producing amorphous interlayers when
pure metals characterized by a large nega-
tive heat of mixing are brought into con-
tact under suitable kinetic conditions. The
couples investigated were Au-La, Zr-Ni
and Hf-Ni.
Amorphous alloys can also be obtained
from intermetallic compounds by hydro-
gen absorption. Yeh et al. (1983) found this
102 2 Special Methods of Obtaining Glasses and Amorphous Materials
phenomenon for metastable Zr 3 Rh and
subsequently (Aoki et al., 1985, 1986) for
SmNi2 and GdCo 2 Laves phases. The phe-
nomenon is found in many Laves phases
consisting of transition metals and rare
earth metals such as CeFe 2 , CeCo 2 ,
CeNi 2 , YNi 2 , etc., even at room tempera-
ture under 5MPa hydrogen gas pressure
(Masumoto, 1986). The subject of interdif-
fusion amorphization will be treated in
greater detail in Chapter 9.
2.5 Electrochemical Methods -
Anodic Oxidation
Amorphous oxide layers can be grown
on the surface of a metal of semiconductor
by making it the anode in an electrolytic
cell in a variety of aqueous electrolytes
(Fig. 2-10). Al, Zr, Nb, and especially Ta
will oxidize when a current is passed
through the cell under sufficient over-
voltage, whereby a glass layer is formed
with a thickness of up to several thousand
angstroms (Young, 1961; Vermilyea, 1960).
Amorphous silica films can be grown on
Si substrate (Schmidt and Michel, 1957).
Doped silica films have been obtained by
Schmidt and Owen (1964) and Crosset and
Dieumegard (1973). Anodic oxidation of
D.C.
Power
supply
Sample to be
oxidized
Cathode - (Anode)
Electrolyte
Figure 2-10. Anodization cell (schematic).
GaAs (Hasegawa and O'Handley, 1979)
and of InAs, InSb, GaP, and GaAsP
(Schnable and Schmidt, 1976) have also
been obtained. The technique, however, is
not as widely used in the semiconductor
industry as thermal oxidation.
2.6 Pyrolysis
Pyrolysis is a method in which a suitable
compound (the precursor) is subjected to
controlled thermal decomposition, the
residue being the product to be synthe-
sized. Pyrolysis of organometallic precur-
sors is an established way of producing ad-
vanced ceramics, namely polycrystalline
SiC and Si 3 N 4 .
As far as non-crystalline materials are
concerned, pyrolysis is used in the synthe-
sis of glass-like carbons. These were first
obtained by pyrolysis of cellulose and then
of thermosetting resins. Phenol-aldehyde
resins were the starting materials for "vit-
reous carbon" (Cowlard and Lewis, 1967).
"Glassy carbon" was obtained from fur-
furyl-alcohol resin (Yamada and Sato,
1962) and "vitro-carbon" from acetone-
furfural resin. Carbon fibers were manufac-
tured by pyrolyzing spinned phenol resin
fibers (Kawamura and Jenkins, 1970). The
details of these processes will be discussed
in Chapter 10 of this Volume which also
contains references to numerous patents.
2.7 Solution Methods;
"Sol-Gel" Processing of Glasses
In polymer technology non-crystalline
or partly crystalline materials ("plastics")
are currently obtained in a direct way us-
ing methods of organic chemistry. This im-
portant theme is the subject of Volume 18,
"Processing of Polymers".
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
There exists, however, a large array set
of methods in which inorganic glasses may
be synthesized using methods of solution
chemistry. Sol-gel processes belong to this
last group of syntheses: they are based on
the possibility of forming the disordered
network of the glass, not directly at high
temperatures from a melt, but at low tem-
peratures from suitable compounds by
chemical polymerization in a liquid phase.
In this way a gel is first formed from which
glass may be obtained both by the succes-
sive elimination of the interstitial liquid
and by the collapse of the resulting solid
residue by sintering.
This "precursor-based" synthesis of
glasses, ceramics, and composites is cur-
rently one of the most rapidly progressing
fields of materials science and engineering.
The "sol-gel" method of preparing glasses
is being actively studied in leading labora-
tories all over the world, and in the last ten
years, the number of scientific publications
in this field has shown an exponential in-
crease.
Current research work in this field is to
be found in the Proceedings of the Inter-
national Workshops on Gels: Gottardi
(1982), Scholze (1984), Zarzycki (1986),
Sakka (1988), Aegerter (1990); the Interna-
tional Conferences on Ultrastructure Pro-
cessing: Hench and Ulrich (1984, 1986),
Mackenzie and Ulrich (1988), Uhlmann
and Ulrich (1990); as well as in the series of
symposia "Better Ceramics through
Chemistry": Brinker et al. (1964, 1986,
1988). For general reviews, see Sakka
(1982), Zarzycki (1984), Rabinovich (1985).
The recent books by Klein (1988), Aegerter
et al. (1989), and Brinker and Scherer
(1990) present different aspects of sol-gel
technology. The excellent treatise of Her
(1979) should be consulted for details on
silica sols and gels.
103
2,7.1 Methods of Gel Formation
The main steps of sol-gel processing are
summarized in Fig. 2-11. The different
variants developed depend on the way in
which the initial gel is obtained and on the
forming process. As silica is the essential
ingredient of most of the glasses prepared
by sol-gel methods, our description will be
centered on silica-based gels. There are
three ways of obtaining them: (1) Hydroly-
sis and polycondensation of organo-metal-
lic compounds (alkoxides) dissolved in alco-
hols in the presence of a limited amount of
water. (2) Destabilization of silica sols (e.g.,
Ludox ®), pure of containing other metal
ions added in the form of aqueous solu-
tions of salts. (3) Redispersion of fine dry
silica particles in a suitable liquid medium
by mechanical (shearing) action to form a
sol which gels spontaneously.
2.7.1.1 Gel Formation from Alkoxides
Metal alcoholates, also known as metal
alkoxides M(OR) n , where M is a metal
(e.g., Si) and R an alkyl group (e.g., CH 3 or
C 2 H 5 ), react with water and undergo hy-
drolysis and polycondensation reactions
which lead to the progressive formation of
a metal oxide. The overall reaction scheme
consists of at least two main steps:
(2-2)
3 (2-3)
The resulting metal oxide is produced
in the form of extremely small particles
( « 2 nm) which may link to form a gel.
In reality, the situation is more complex;
the reactions (Eqs. (2-2) and (2-3)) proceed
simultaneously and are generally incom-
plete. Hydrolysis may be achieved using a
smaller quantity of water than that re-
quired by stoichiometry, and a number of
radicals R remain unreacted. Polyconden-
104 2 Special Methods of Obtaining Glasses and Amorphous Materials

Liquid ingredients

Mixing
Reacting

Figure 2-11. Principle of sol-gel processing (from Zarzycki, 1987 a).

sation is incomplete and the final product Bradley et al. (1978) and Andrianov (1955).
corresponds rather to the formula Since alcoholates and water are immis-
cible, the reagents are dissolved in alcohol,
(MOyOH),(OR) z (2-4)
generally methyl- or ethylalcohol. The use
In cases where several different com- of a common solvent can be avoided, how-
pounds (e.g., M(OR)n, M'(OR)J are re- ever, by subjecting the alcoholate-water
acted, a complexation step may precede
reactions Eqs. (2-2) and (2-3).
Table 2-1. Alkoxides used in gel synthesis.
In this way complex networks involving
several different cations, (e.g., M, M') may M M(OR)n
be produced:
Si Si(OCH3)4
-M-O-M-O-M- (2-5) Si(OC 2 H 5 ) 4
Al Al(O-iso C 3 H 7 ) 3
The use of alkoxides of Si, B, Ti, Zr, etc., Al(O-sec C 4 H 9 ) 3
leads to the formation of complex gels Ti Ti(O-C 2 H 5 ) 4
composed of small particles which prefig- Ti(O-isoC 3 H 7 ) 4
Ti(O-C 4 H 9 ) 4
ure the network of corresponding oxide
Ti(O-C 5 H 7 ) 4
glasses. B B(OCH 3 ) 3
Table 2-1 gives a list of organometallic Ge Ge(O-C 2 H 5 ) 4
compounds most frequently used in the Zr Zr(O-iso C 3 H 7 ) 4
synthesis of glasses by this method. For Zr(O-C 4 H 9 ) 4
Y Y(O-C 2 H 5 ) 3
details on the synthesis of alkoxides and
Ca Ca(O-C 2 H 5 ) 2
chemistry involving these compounds see
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
mixture to ultrasound (Tarasevich, 1984).
The "sonogels" obtained in this way are
more dense due to the absence of the sol-
vent, and their structural properties are dif-
ferent from those of "classical" gels (Zar-
zycki, 1991).
The water necessary for hydrolysis can
be taken from the atmosphere (as in the
case of thin coatings) or more generally
added to the solution in a controlled
amount. Other cations may also be intro-
duced in the form of alcoholic or aqueous
solutions of salts (nitrates, acetates, etc.). A
carefully controlled amount of a catalyst,
either an acid (hydrochloric, nitric, or
acetic acid) or a base (ammonia, amines,
etc.), is added. The gelling time depends on
the pH, the temperature, the amount of
water, and the nature of the catalyst.
The structure of the gel depends very
much on the nature of the catalyst used:
acid catalysis leads to filamentous struc-
tures with a low degree of reticulation of
the - M - O - M - chains, while basic cataly-
sis produces more compact spheroidal par-
ticles with a higher internal degree of retic-
ulation.
2.7.1.2 Gel Formation from Sols
Most colloidal solutions of silica (silica
sols) are either prepared by chemical con-
densation methods, acidifying solutions of
Na silicates, K silicates, and NH 4 silicates,
or made from hydrolyzable products such
as SiCl4 or Si(OR)4, where R is an alkyl
group. The formation of silicic acid in
aqueous solutions is followed by polymer-
ization of monomers Si(OH)4 when its
concentration exceeds 100 ppm, which is
the limiting solubility in water at 25 °C.
The polymerization reaction is based on
the condensation of silanol groups with the
elimination of water. (2-6)
-Si-OH + H O - S i - -> - S i - O - S i - + H 2 O
105
Amorphous spheroidal groupings of about
1 to 2 nm are formed by a nucleation pro-
cess similar to what occurs in the forma-
tion of crystalline precipitates.
At low pH values, particle growth stops
once the size of 2-4 nm is reached. Above
pH 7, particle growth continues at room
temperature until particles of about 5 -
10 nm in diameter are formed, and then it
slows down. At higher temperatures parti-
cles are negatively charged, and they repel
each other. Growth continues without ag-
gregation, resulting in the formation of sta-
ble sols.
Commercial silica hydrosols (e.g., Lu-
dox®, Nalcoag®, Nyalcol ®, Snowtex®)
are stable sols with 20-50 wt.% SiO2.
They are made up of dense silica particles
with an average diameter of between 7 and
21 nm. The pH is between 9 and 11.
To obtain a gel from a stable sol, the sol
must be destabilized either by a tempera-
ture increase or by the addition of an elec-
trolyte. An increase in temperature reduces
the amount of intermicellar liquid by evap-
oration and increases thermal agitation,
which in turn induces collisions between
particles and their linking in chains by con-
densation of surface hydroxyls.
The sol-gel transition should be distin-
guished from a precipitation or floccula-
tion mechanism. In the latter mechanisms
separate aggregates are formed, whereas a
gelling involves a continuous three-dimen-
sional particle network that invades the to-
tal volume of the sol (Fig. 2-12).
By electrolyte addition the pH of the sol
may be modified in order to reduce the
electric repulsion between the particles (de-
pending on the zeta potential). This is ac-
complished by adding an acid to diminish
the pH to 5-6 to induce gel formation by
aggregation. This conversion of sol into gel
is progressive, the growing aggregates (mi-
crogel) gradually invading the whole vol-
106 2 Special Methods of Obtaining Glasses and Amorphous Materials

temperature, the gelling time may vary

from minutes to months.
Sol
2.7.1.3 Redispersion Methods
Fine dry silica particles such as the com-
mercial "fumed silica" Cab-O-Sil®, or
Aerosil® obtained by flame oxidation of
SiCl4, can be mechanically redispersed in
water using a shear blender. At pH 2-7, a
sol is formed which will gel in a few hours.
SiO2 particles form agglomerates which
are linked by hydrogen bonds. SiO2 disper-
sions in organic liquids such as chloroform
or n-decanol were also prepared; they can
Figure 2-12. Difference between gelling and precipita- be readily gelled by the action of amines or
tion of a sol (schematic). ammonia vapor. Not only pure silica but
also SiO 2 -GeO 2 particles, obtained by the
method of flame oxidation for mixtures of
ume originally occupied by the sol. When gaseous SiCl4, TiCl 4 , GeCl 4 , were success-
about half of the silica has entered the gel fully gelled (Rabinovich, 1985).
phase, a rapid increase in viscosity is noted
(Fig. 2-13).
The mechanism of interparticle bonding J i
leading to microgels and gels involves the
attachment of two neighboring silica parti-
cles via the formation of Si-O-Si bonds
(Eq. (2-6)). Colloidal particles will form gels 2 - o"
only if there are no active forces which
4>
would promote coagulation into aggre- D
o
gates with a higher silica concentration (S)
o A
than the original sol. Metal cations, espe- Q_ o
1 -
cially the polyvalent ones, may lead to pre-
c*
cipitation rather than gelling: This is en- TO A
o Aoo
countered with some multicomponent gels.
In that case at least one gelling constituent a
a ° A A*o
O _
(generally silica sol) is required. Other con- 0 -
A
D

A
Q D
A

stituents may be added in the form of solu- A

ble salts (nitrates, sulfates, etc.) or organo-
metallic compounds.
By adjusting the temperature, concen- -1 I

tration, and especially the pH of the result- 0.90 1.00

ing sol, a homogeneous solution is ob-
tained which may then be gelled in a con-
trolled way in order to avoid precipitation.
According to the composition, pH, and
T/Tfgel
Figure 2-13. Evolution of viscosity of various TMOS-
alcohol-water mixtures approaching the gelling point
as a function of the reduced time T/Tgel (from Mizuno
et al., 1985).
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses 107

2.7.2 Aging Effects

The freshly prepared "wet" gel consists
of a network of particles holding an inter-
stitial liquid - the solvent trapped during Neck formation
the gelling step is water in the case of hy- Figure 2-14. Strengthening of particle chains by depo-
drogels and mixtures of alcohols and water sition of silica at the necks due to differential solubil-
for the alcogels. The interstitial liquid still ity effect (from Zarzycki et al, 1982).
contains unreacted sol particles, which
progressively attach themselves to the net-
work.
Furthermore, there is a transport of
SiO2 from convex to concave parts due to
solubility effects which smooth the in- Secondary deposition
equalities between linked particles and con- Figure 2-15. Strengthening of chains during aging by
vert the chains into filaments (Fig. 2-14). secondary deposition of silica (from Zarzycki et al.,
Additional deposition of SiO2 from solu- 1982).
tion may further "nourish" and thus stiffen
the chains (Fig. 2-15). The syneresis effect
then sets in, whereby the network slowly
contracts and tends to progressively expel
106
the interstitial liquid in order to reduce the
internal interface. With time all these ef-
fects bring about a gradual increase in the
Young's modulus, E, of the wet gel (Fig. 105
2-16); the gel stiffens progressively, even if
evaporation of the interstitial liquid is pre-
vented.
u L H
Freshly gelled wet silica gel is an ex- Days

tremely fragile material, which behaves as Figure 2-16. Evolution of Young's modulus, E, as a
a brittle solid with conchoidal fracture. function of time for a Ludox gel (v: Poisson's number)
(from Zarzycki, 1988).
Gels prepared from Si alkoxides are pre-
dominantly elastic while those from col-
loidal solutions (Ludox®) show partly vis-
co-elastic or viscoplastic properties. Fig.
300
2-17 shows the critical stress concentration
coefficient Klc of some SiO2 gels, and Fig.
200
2-18 the corresponding fracture surface en-
ergy.
100

2.7.3 Drying 0 1 2 3 A 5
Days
The drying stage is necessary to free the Figure 2-17. Evolution of critical stress intensity fac-
solid network of the gel from the accompa- tor K1C as a function of time for a Ludox gel (from
nying interstitial liquid phase. Zarzycki, 1988).
108 2 Special Methods of Obtaining Glasses and Amorphous Materials
0.1 T(Nm"
-0.05
0 1 2 3 A 5 6
Days
Figure 2-18. Evolution of the fracture surface energy
as a function of time for a Ludox gel (from Zarzycki,
1988).
2.7.3.1 The Role of Capillary Forces
Elimination of the liquid phase leads to
dry gels, namely xerogels. When a "wet"
gel is dried, the following sequence of
events is generally observed on a macro-
scopic scale:
• progressive shrinkage and hardening
• stress-development
• fragmentation
The chief difficulty is encountered in the
preparation of bulk glass, where specimens
of gel without any cracks are required. This
problem, occurring in monolithic gels, was
recently the object of intensive research.
Cracking during the drying stage is the
result of non-uniform shrinkage of the dry-
ing body, a well-known phenomenon in
ceramic technology. The stresses arise not
only from the local differences in expan-
sion coefficients due to variable water con-
tent but primarily from the action of capil-
lary forces which become operative when
the pores start to empty and a liquid-air
interface is present in the form of menisci
distributed in the pores of the drying gel.
The magnitude of these forces is given by
Laplace's formula:
Ap = (2y cos9)/r (2-7)
The change in pressure Zip is proportional
to the specific surface energy y of the liq-
uid-air interface and inversely propor-
tional to the radius r of the pore; 6 is the
contact angle at the liquid-solid-air
boundary line. Considerable stresses may
be generated in this way: Ap = 7.3 xlO 7
Nm " 2 for a pore radius r = 2 nm filled with
water, assuming perfect wetting (Fig. 2-19).
Differential stresses due to adjacent
pores then induce breaking if the tensile
strength is exceeded. A detailed treatment
of drying, comprising the analysis of stress
redistribution due to interstitial liquid
transfers was recently proposed by Scherer
(1988).
2.7.3.2 Obtaining Monolithic Gels
In practice, a very long drying time is
necessary to preserve "monolithicity". This
may reach hundreds of hours even for
small specimens with surface areas of a few
square centimeters. Much effort has there-
fore been spent to find more economical
ways of drying gels and still preserving
their integrity.
All actions which tend to minimize the
capillary stress and increase the mechani-
cal resistance of the network should en-
hance the probability of keeping the gel
108r
Q_
a
o
10£
10° 101 102
Pore radius in nm
Figure 2-19. Capillary pressure Ap in a drying gel as
a function of pore-radius when the interstitial liquid is
(a) water (b) alcohol (after Zarzycki et al., 1982).
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
monolithic. The following measures are
possible:
• Strengthening the gel by reinforcement
(aging)
• Enlarging the pores
• Tending toward monodispersity of the
pores
• Reducing the surface tension of the liquid
• Making the surface hydrophobic
• Evacuating the solvent by freeze-drying
• Operating in hypercritical conditions
where the liquid-vapor interface vanishes
The last two methods are the most efficient
ways of eliminating the destructive action
of the surface tension of the liquid sup-
pressing the liquid-vapor interface.
Hypercritical solvent evacuation (HSE)
consists in treating the gel in an autoclave
in hypercritical conditions for the solvent. It
is directly applicable to alcogels produced
from alkoxides. Hydrogels cannot be di-
rectly treated in this way as under hyper-
critical conditions for water, silica is solu-
bilized. This has prompted the importance
of the alkoxide method. Redispersion
methods, on the other hand, permit the
obtention of wet gels with large pores by
a double redispersion treatment. These
pores facilitate solvent evacuation without
the danger of cracking in the gels
(Rabinovitch, 1985).
The HSE process is schematized in Fig.
2-20, which shows the equilibrium curve
between the liquid and the gas phase of the
solvent. In order to ensure the continuity
of the liquid-gas transition, the path of the
thermal treatment must not cross the equi-
librium curve. To circumvent the critical
point C, a path such as a, b, d, e may theo-
retically be used.
In practice this path is modified in the
following way: the open container which
contains the gel is placed inside an auto-
clave, and to obtain hypercritical condi-
tions, a given quantity of solvent (e.g.,
109
Temperature
Figure 2-20. Principle of hypercritical solvent evacua-
tion (from Zarzycki, 1984).
methanol) is added to the autoclave. The
autoclave is then closed and electrically
heated. When the critical temperature of
methanol is exceeded, slow decompression
followed by successive flushings with dry
argon eliminate the last traces of alcohol.
The autoclave is then cooled down and the
gel removed at ambient temperature (path
a,d,e). The gel, which contains air-filled
pores, is termed aerogel
A number of experiments has shown
that monolithicity depends on many vari-
ables:
• the speed of heating
• the proportion of the additional solvent
• the concentrations of organometallic
compounds and
• the water of hydrolysis
• the geometry of the sample and its size
• the previous aging of the gel
Monolithic samples can be obtained with
100% certainty when these variables are
optimized (Zarzycki, 1982).
The aerogels are hydrophobic due to
partial surface esterification and contain
an appreciable percentage of adsorbed or-
ganic radicals. Their mechanical resis-
tance, however, is sufficient for these radi-
cals to be eliminated by subsequent
110 2 Special Methods of Obtaining Glasses and Amorphous Materials
thermal treatment without loss of mono-
lithicity, and they can finally be converted
into a clear glass of excellent optical qual-
ity.
Aerogels can be made with an exceed-
ingly high porosity (close to 99%) and a
pore size of a few nanometers, which makes
them excellent thermal insulators. For sil-
ica aerogels thermal conductivity of the or-
der of 0.01 W m " 1 K " 1 has been demon-
strated. Their refraction index may be close
to 1, and they can be made translucent -
hence their application in Cerenkov radia-
tion detectors. (For these and other appli-
cations, see Fricke, 1986.)
Another method consists in adding a
suitable substance to the sol before gelling
that will influence the subsequent behavior
of the sol during drying. The most success-
ful of these drying control chemical addi-
tives (DCCA) is formamide (Hench, 1986).
Its effect seems to be a tendency toward the
formation of gels with smaller but more
uniform pores which favor drying in
monolithic form.
2.7.3.3 Structural Aspects
The gelling process, the structure of the
resulting wet gels, and that of the xero- and
aerogels have been the object of numerous
studies on various systems, the detailed de-
scription of which is outside the scope of
the present article. The use of small-angle
X-ray scattering (SAXS) combined with
spectroscopic methods (IR, Raman, NMR)
and electron microscopy has permitted the
various aggregation theories to be tested,
and the results of these methods have led to
structural models.
Gelling may be explained either using
Flory's theory, familiar in polymer chemis-
try, or by percolation theories, which are
more in favor with the physicists. The
structure of growing aggregates and of the
resulting gels may be described using frac-
tal concepts (Mandelbrot, 1983). A fractal
cluster has a structure which becomes in-
creasingly wispy as its dimensions increase.
In particular, its mass scales as r D , where r
is the radius of the cluster, and D the "frac-
tal dimension" which is smaller than three.
The fractal dimension D may be obtained
by a variety of methods. See, for example,
Zarzycki (1987 b) for a synthetic presenta-
tion.
2.7.4 Curing-Sintering
The final structure of the dry gel will
depend on the structure of the wet gel orig-
inally formed in solution; it is a contracted
or a distorted version of the latter. The
constituent particles are coated with resid-
ual OH groups which are partly eliminated
during the transition from a particulate
texture to a continuous solid. They may be
detected and analyzed by conventional in-
frared spectroscopic techniques.
To transform the particulate structure of
a dried gel into continuous glass, the ele-
mentary particles must fuse together, re-
sulting in progressive pore elimination.
This is achieved by heating the gel in order
to promote diffusion phenomena and vis-
cous flow. During this heat-treatment the
residual OH and OR groups will first tend
to be eliminated in the form of H 2 O and
ROH which is accompanied by an addi-
tional polymerization of the system:
(2-8)
- S i - O R + O H - S i - -> - S i - O - S i + ROH
The escape of residual products from
closed pores may constitute a problem; the
organic residues are finally carbonized at a
higher temperature which brings about a
coloration of the gel and leaves carbona-
ceous particles in the glass. It is therefore
important to favor the escape of residues
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
before complete closure of the pores, and
oxidation treatments are often necessary to
eliminate certain organic groups. For pure
SiO2 gels this oxidation treatment is car-
ried out at 300-400 °C. It is important to
define the heating schedule in each particu-
lar case in order to eliminate the unwanted
residues without impairing monolithicity
before the onset of viscous flow.
Occluded OH groups and H 2 O may
cause bloating on heating at high tempera-
tures - even if the specimen has remained
monolithic up to this stage. Residual OH
groups may be eliminated by chlorination
treatments if very low OH levels are re-
quired in the final glass (e.g., for optical
fibers applications). On the other hand, oc-
cluded water may be used in foaming pro-
cesses, e.g., in blowing gel particles into
microspheres (see Sec. 2.7.5.4).
2.7.4.1 Viscous Flow Sintering
Densification is essentially a sintering
process by which the pores of a dry gel are
eliminated, and the initially opaque mate-
rial progressively converted into clear bulk
glass. After elimination of residues, the
driving force in this process is supplied by
the surface energy of the porous gel. This
tends to reduce the interface, thus eliminat-
ing the pores, the collapse being governed,
in the case of glasses, by Newtonian viscous
flow. Extra pressure, as in hot-pressing
techniques, may be applied externally to
speed up the process (Decottignies et al.,
1978). The theoretica aspects of sintering
are presented in Chapter 3 of this Volume.
2.7.4.2 Devitrification Kinetics -
Use of TTT Diagrams
During densification the gel will tend to
crystallize (devitrify) at the same time. The
successful conversion of gel into glass
therefore depends on a competition be-
111
tween phenomena which lead to densifica-
tion and those which promote crystalliza-
tion.
The TTT (time-temperature-transfor-
mation) diagrams are a convenient way of
studying the problem of devitrification ver-
sus compaction in order to define the ap-
propriate thermal treatment (Zarzycki,
1982 b). The TTT diagrams show the time
ty required to obtain a determined crystal-
lized fraction y as a function of the temper-
ature T. Treating y as a parameter, a set of
Cy curves is obtained which represent the
kinetic behavior of the system. In particu-
lar, if y0 corresponds to the smallest crys-
tallized fraction detectable by analytical
techniques, the curve Cyo represents a fron-
tier not to be crossed during a thermal-
treatment schedule if crystallization is to
be avoided (generally y0 = 10 ~6 is adopted,
see Chapter 3).
The relative positions of the thermal-
treatment path during densification and
the Cyo curve of the gel determine the pos-
sibility of obtaining glassy or crystallized
materials at the end of the compaction pro-
gram. For example, (Fig. 2-21) if there is no
danger of devitrification using path (a) for
Time
Figure 2-21. Use of TTT diagrams for determining
sintering heat treatment without crystallization (from
Zarzycki, 1982 b. Reprinted by permission of the
American Ceramic Society).
112 2 Special Methods of Obtaining Glasses and Amorphous Materials
a gel corresponding to Cl9 this will no
longer be true for the curve of C 2 , the same
path would lead to crystallized material.
The solution would then be either to
shorten the sintering time, e. g., by applying
a suitable external pressure (path (b)), or to
increase the temperature for a short time
using the technique of "flash-pressing"
(path (c)).
In the case of gels the position of the
curves C strongly depends on the impuri-
ties of the material and, in the first instance,
of water content which influences the vis-
cosity, as well as the surface energy of the
material.
2.7.5 Forming Processes
In the classical process, the resulting
melt is generally immediately formed into
the desired end products: sheet glass, hol-
low ware, or fibers. In sol-gel technology
the various forming operations have to oc-
cur before or during the gelling stage (e.g.,
molding an object, forming a thin coating,
or spinning a fiber); the drying-curing and
sintering stages simply consolidate the
original shape produced at low tempera-
tures (Fig. 2-11).
The nature of the processes during
gelling and subsequent drying, which are of
a diffusional nature, favors, however, those
configurations in which at least one of the
dimensions is small: Thin films, fibers, and
small particles (or shells) are current exam-
ples, and it is significant that the first estab-
lished industrial applications of the sol-gel
route were precisely in the field of thin coat-
ings.
2.7.5.1 Bulk Glass
It is possible to produce bulk pieces of
glass if cracking of gels during drying is
avoided. This problem of obtaining mono-
lithic gels has been extensively studied in
recent years - hypercritical solvent evacua-
tion and drying chemical control additives
(DCCA) have proved effective against
cracking.
In the laboratory, pure SiO2 glasses, as
well as those combining SiO2 with other
oxides (e.g., B 2 O 3 , TiO 2 , GeO 2 , P 2 O 5 ,
ZrO 2 , etc.) were successfully prepared.
Glasses containing oxides of alkali and al-
kaline-metals sometimes prove more diffi-
cult to obtain because of the tendency of
gels to devitrify during the sintering stages.
The difficulty linked with monolithicity
can be avoided if hot-pressing techniques
are used to compact gels in a granular
form; this, however, limits the size of the
specimens. In industrial practice the early
attempt in 1970 by Owens-Illinois (USA)
at commercializing bulk gel-made glass
was discontinued because of the high cost.
However, the manufacture of sizeable glass
pieces of pure SiO2 for optical applications
has been reported (Hench, 1986).
Advanced glasses for optical-fiber pre-
forms (SiO2 doped by GeO 2 , P 2 O 5 , or
B 2 O 5 ) have been successfully made, but
the corresponding industrial applications
have not yet followed.
2.7.5.2 Thin Films
At the present time, the main industrial
applications recognized for sol-gel meth-
ods are in the production of thin glass coat-
ings by Schott Glass (FRG). They use the
alkoxide method to modify the spectral
transmission of flat glass for architectural
applications (Schroeder, 1969; Dislich,
1971, 1988).
In the method of dip coating (Fig. 2-22),
a sheet of glass is first immersed in a tank
containing a dilute solution of suitable alk-
oxide precursors and then slowly with-
drawn at a constant rate. This leaves a su-
perficial film of equal thickness which is
then reacted with water vapor from the
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
surrounding atmosphere to induce hydrol-
ysis and polymerization. The glass is then
dried and baked in an oven at ^500°C;
successive layers of several hundred
angstroms may be applied up to a total
thickness of « 3000 A, Thicker films tend
to craze or peel away.
Other methods consist in applying an
even initial liquid film by spinning (e.g., for
optical components of circular shape) or
spraying. Solar reflective TiO 2 coatings
containing Pd or Au are manufactured by
these methods. Antireflective coatings,
contrast-enhancing coatings and protec-
tive coatings for optical surfaces against
laser damage as well as electrically conduc-
tive layers have also been produced in this
manner (Mukherjee and Lowdermilk,
1982; Dislich, 1988; Pettit et al., 1988).
An interesting application of thicker sol-
gel films of about one micron, which may
be superficially patterned by pressing, is
reported for the production of supports for
recording disks for audio-visual purposes
(Fig. 2-23), (Tohge et al, 1988).
7"~5OO°C
Glass -
sheet
Film -=
H20
Vap.
ROH
Vap.
a b
Figure 2-22. Thin-film deposition by dip-coating pro-
cess (schematic).
113
W////////////////M*--Gel film
(a)
<=—Glass substrate
^-Stamper
(b)
\
Electric furnace
(c)
////A
Wn^BnfIIh7fIIhTfIJhTfIJhWI\<-Glass film with
fine pattern
(d)
Figure 2-23. Patterning process of gel coatings (from
Tohge et al., 1988).
2.7.5.3 Fibers
Continuous glass fibers may be pro-
duced by sol-gel methods. On approaching
gelling point, the solution is drawn into a
gel fiber, which is then converted into glass
by heating. The composition of the starting
solution must be carefully adjusted to ren-
der it spinnable. In general low water con-
tent for hydrolysis and an acid catalyst are
thus required. The cross section of the
fibers prepared in this way may not be cir-
cular. The process requires strict viscosity
control. Pure SiO2 fibers as well as those of
SiO 2 -Al 2 O 3 , SiO 2 -ZrO 2 , SiO 2 -ZrO 2 -
Na 2 O and SiC^-A^C^-I^C^ systems
have been prepared (Sakka, 1988 b; Sow-
man, 1988; La Course, 1988).
2.7.5.4 Hollow Glass Microspheres
Hollow glass microspheres are used as
c fillers in plastic resins or paints and also in
a more sophisticated version as targets for
inertial confinement fusion (ICF) in ther-
114 2 Special Methods of Obtaining Glasses and Amorphous Materials
monuclear fusion research. They are pro-
duced from gels which are first dried, then
crushed and sieved. The resulting powder
is subsequently fed into an electrical verti-
cal drop tower furnace where the gel parti-
cles, falling freely, are blown and vitrified
into spherical shells by residual gas con-
tained in the gel. Shells of up to 1000 jim
with uniform wall thickness of 0.4-20 Jim
were produced for ICF experiments
(Downs et al, 1988).
2.7.6 Advantages and Disadvantages
of the Sol-Gel Process
As the sintering operation is carried out
at temperatures much lower than those re-
quired for the melting of glass-forming
components - practically in the vicinity of
the transition temperature - the process is
particularly attractive for the production
of those glasses which require high melting
temperatures (e. g., SiO2 glass can be made
at 1200 °C instead of at 2000 °C).
The second important characteristic of
the process is that final homogeneity is di-
rectly obtained in solution on a molecular
scale. This can be compared to the diffi-
culties of obtaining homogeneous glasses
in the classical way, particularly when one
of the components is more volatile or when
the resulting melts possess a high viscosity
which hinders efficient mixing of the con-
stituents. In some cases it is then necessary
to remelt the original batch several times
to reach the necessary compositional uni-
formity. This in turn increases the likeli-
hood of contamination from crucible walls,
particularly at high temperatures, or dur-
ing repeated crushing procedures.
In the sol-gel route the wet gel may, in
principle, be obtained with a degree of pu-
rity which depends only on the starting
ingredients. The degree of purity of the fi-
nal glass will depend on the sintering pro-
cess, which is performed at lower tempera-
tures, and thereby reduces the risk of
contamination.
A substantially lower elaboration tem-
perature, excellent homogeneity obtained
directly, and a high degree of purity are the
main advantages attributable to the sol-gel
process. Is this enough to make the process
competitive with the classical glass-melting
practice?
The lower elaboration temperature,
from which energy saving might be ex-
pected, is largely offset by the high cost of
the initial ingredients necessary for making
the gel. In addition, organometallic precur-
sors are not always available at present for
the more exotic cations that might be re-
quired in some cases, and the initial formu-
lation of the solution leading to a proper
gel (without flocculation) can be a very dif-
ficult task indeed.
The subsequent treatment of the gel, the
drying-curing and sintering stages, are also
more complicated and time-consuming in
practice than the direct melting and fining
involved in classical glass processing. Fur-
thermore, they are specific to a given com-
position and the process has to be "tai-
lored" for each new glass, which requires a
complete preliminary study in each case.
It seems therefore that the sol-gel pro-
cess can only be competitive in areas of
advanced technology (high-tech areas),
and that neither window nor bottle glass
will ever be made industrially in this way.
2.7.7 Future Trends
What really differentiates the sol-gel
route from the classic igneous route is es-
sentially the fact that an inorganic gel is a
two-phase system where each of the two
phases can be influenced separately by the
preparative methods.
 2.7 Solution Methods; "Sol-Gel" Processing of Glasses
In the classical method of obtaining
glasses, the structural disorder is produced
by progressive breakdown at high temper-
ature of different crystalline components,
and the resulting melt is a collection of
more or less polymerized anions and frac-
tions of chains with interdispersed accom-
panying cations. For a given melt the dis-
tribution of these entities depends es-
sentially on the equilibrium conditions in
the melt, i.e., on the temperature and atmo-
sphere of the furnace which controls the
oxidation-reduction changes. This high-
temperature situation is preserved during
quench, and the polyanionic distribution
reflects the equilibrium conditions in the
melt. Apart from systems which undergo
phase separation (either in the liquid or
sub-liquidus), the quenched melt is a one-
phase system with frozen-in local composi-
tional fluctuations. The equilibrium condi-
tions cannot be influenced to a great extent
except by initial compositional changes.
On the other hand, if we consider the
processes which lead to the constitution of
a gel, the various steps by which the disor-
Interstitial
liquid Backbone
Solvent
exchange Hypercritical
^ drying
Aerogel
Reaction
— Drying
Dry gel
115
dered network is built up are essentially
chemical polymerization, polycondensa-
tion, cross-linking, etc., processes familiar
in polymer chemistry. In this way elemen-
tary particles, filaments, etc., are produced
which progressively link up to produce
first a colloidal solution - a sol - and then
a gel, when these elements unite into a
reticulated network spanning the volume
offered. A gel is essentially a system consti-
tuted of two phases: a solid backbone im-
mersed in an interstitial liquid. The two
phases are intimately mixed on a very fine
scale.
It is possible to change the nature of this
second phase by various operations (Fig.
2-24). In the drying process the liquid was
simply replaced by a gas-solvent vapor and
air leading to aerogels.
Using exchange processes, one liquid
may be substituted for another; e.g., water
may be replaced by alcohol to enable hy-
percritical treatment of aquagels. Foreign
reactants may be diffused into gels via the
interstitial liquid whereby chemical reac-
tions, precipitation, etc., may be produced
Figure 2-24. Examples of
exchange methods com-
bined with sol-gel process-
-Sintering • ing to obtain composite
materials (from Zarzycki,
1987 a).
116 2 Special Methods of Obtaining Glasses and Amorphous Materials
within the second phase or also within the
backbone if this is done during gel forma-
tion.
Infiltration of foreign substances into
dry gels permits the air pockets (pores) to
be filled, e.g., by colored or index matching
substances. In this way a whole range of
glass composites may be obtained on a
very fine scale, depending on the backbone
configuration. The range of the scale may
descend to a few nanometers, hence the
name nanocornposites, which was proposed
for this class of materials (Roy et al., 1984,
1986).
For example, gels containing suitable
dyes may be prepared for advanced nonlin-
ear optical applications. On the other
hand, the preparation of gels with a com-
plex backbone combining inorganic and
organic systems, opens up new and unlim-
ited possibilities of synthesis of hybrid
amorphous materials, which are interme-
diate between pure inorganic glasses and
organic polymers. This is the field of "or-
ganically modified silicates" (Ormosils),
which has barely begun to be explored
(Schmidt, 1985).
Attempts to apply the sol-gel techniques
to obtain chalcogenide glasses are reported
where the inherent heterogeneity of melt-
obtained glasses could be improved, or
new systems produced. Halide gels are also
being investigated initially and thus com-
pletely new sol-gel systems are likely to be
explored in the near future.
2.8 References
Aegerter, M.A. (Ed.) (1990), 5 th Intern. Workshop
"Glasses and Ceramics from Gels" Rio de Janeiro,
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3 Glass Formation and Relaxation
George W. Scherer

E.I. DuPont de Nemours & Co.,Wilmington, DE, U.S.A.

List of Symbols and Abbreviations 121

3.1 Introduction 124
3.2 Glass Formation from the Melt 124
3.2.1 Nucleation of Crystals 125
3.2.1.1 Homogeneous Nucleation 125
3.2.1.2 Heterogeneous Nucleation 126
3.2.2 Crystal Growth 127
3.2.2.1 Interface Control 127
3.2.2.2 Diffusion Control 128
3.2.3 Kinetics of Glass Formation 129
3.2.3.1 Critical Cooling Rate 130
3.2.3.2 Nonisothermal Analyses 131
3.2.3.3 Simplified Model 132
3.2.3.4 Heterogeneous and Transient Nucleation 133
3.2.3.5 Factors Favoring Glass Formation 134
3.3 Sintering and Crystallization 134
3.3.1 Sintering 134
3.3.2 Competition Between Sintering and Crystallization 136
3.4 The Glass Transition 137
3.4.1 Phenomenology 138
3.4.1.1 Cooling Rate Dependence of Tg 138
3.4.1.2 Fictive Temperature 139
3.4.1.3 Hysteresis 141
3.4.1.4 Nonlinearity 141
3.4.1.5 Nonexponential Relaxation Function 142
3.4.2 Thermodynamic Aspects 144
3.4.3 Theories of Relaxation 146
3.4.3.1 Rheological Models 146
3.4.3.2 Kinetic Models 148
3.4.3.3 Relaxation Models 150
3.4.4 Phenomenological Models 151
3.4.4.1 Tool's Equation 151
3.4.4.2 Narayanaswamy's Theory 153
3.5 Viscoelasticity 155
3.5.1 Elasticity, Stress Relaxation, and Creep 156
3.5.1.1 Elasticity 156
Materials Science and Technology
Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
120 3 Glass Formation and Relaxation

3.5.1.2 Creep and Stress Relaxation 157

3.5.1.3 Viscosity 159
3.5.2 Temperature Dependence 160
3.5.2.1 Equilibrium Liquid 160
3.5.2.2 Nonequilibrium Liquid 162
3.5.3 Calculation of Thermal Stresses 163
3.5.3.1 Glass-to-Metal Seals 164
3.5.3.2 Tempering 166
3.5.3.3 Annealing 169
3.6 References 171
 List of Symbols and Abbreviations 121

List of Symbols and Abbreviations

A constant
a coefficient, radius
a (T) shift function
B constant
b coefficient
cp isobaric heat capacity
D transport coefficient
d dimension of space
Dc kinetic coefficient for transport across interface
DL lattice diffuson coefficient
E Young modulus
AE activation energy
en embryo containing n monomers
/ interface site factor
/(0) function of 0
g {v) function of v
G shear modulus
Ag free energy change
AgD activation barrier for transport
Agn free energy of formation of an embryo of n monomers
Agv free energy difference between unit volumes of crystal and liquid
Gd delayed elastic strain
H enthalpy
h Planck constant
h(T) function of T
h magnetic field
hf molar heat of fusion
Iv rate of homogeneous nucleation
Jt shear compliance or creep compliance
J2 dilatational compliance
K bulk modulus
K (T) function of temperature
kB Boltzmann constant
kn rate constants for the addition and removal of a monomer
Kp constant
/ thickness of seal
Ltj phenomenological transport coefficients
mt number of neighbors in "up" position
Mp relaxation function of property p
n number of pores per unit volume of liquid phase
n stiffness ratio
n* number of embryos larger than r*
N1 number of monomers remaining in the liquid phase
122 3 Glass Formation and Relaxation

Avogadro number
"d refractive index of a liquid in equilibrium at Tx
number of embryos with n monomers
nv number of molecules of nucleating phase per unit volume
P pressure
q cooling rate
heating rate
r distance vector
biaxial relaxation function
r, r* radius, critical radius
Re critical cooling rate
R
s
ideal gas constant
s interfacial area
sc configurational entropy
s
f entropy of fusion
T temperature
t time
TiV fictive temperature for volume V
% fictive temperature
glass transition temperature
TK Kauzmann temperature
TL liquidus temperature
time corresponding with the "nose" method
Tn temperature corresponding with the "nose" method
Tr reduced temperature
TR room temperature
Ts setting temperature
TK temperature of crossover experiment
u growth rate
V volume
V volume fraction
vm molar volume
w width of seal
wk weighting factors
W* thermodynamic barrier to nucleation
w,w0 relaxation rate, primary relaxation rate
X nonlinearity parameter
x, y, z stress axes
z number of molecules
Z 1 ? —Z N set of order parameters

a thermal expansion coefficient

P exponent with a value between 0 and 1
y constant near unity
interfacial energy (solid/liquid; liquid/vapor)
 List of Symbols and Abbreviations 123

5 height of hierarchical energy barriers

s volumetric strain
rj viscosity
9 contact angle between crystal a n d nucleating heterogeneity
x isothermal compressibility
X j u m p distance size of the diffusing species
Aji potential barrier per molecule hindering rearrangement
v vibration frequency, Poisson ratio
FITP Prigogine-Defay ratio
Q relative density, density of sites
o hydrostatic (or dilatational) stress
G{ spin state
T duration of period of transient nucleation
T relaxation time
TU uniaxial relaxation time
0X (t\ <P2 (t) functions
CD attempt frequency
co (r) energy transfer rate
coc characteristic time
AG Adam-Gibbs
CRS cooperatively rearranging subsystem
KWW Kohlrausch-Wiliam- Watts
PFT partial fictive temperatures
SR structural relaxation
TRS thermorheologically simple
TTT time-temperature-transformation
VE viscoelasticity
VFT Vogel-Fulcher-Tamman
124 3 Glass Formation and Relaxation
3.1 Introduction
When a liquid is cooled below the liq-
uidus temperature (TL) it enters a state of
metastable equilibrium. If the thermody-
namic barrier to nucleation can be over-
come, a crystal of the equilibrium phase is
formed and the volume of the system de-
creases discontinuously, as shown in Fig.
3-1. In Section 3.2 we briefly review the
theory of nucleation and growth, and es-
tablish the parameters that control the de-
gree of crystallization during cooling. The
goal is to predict the critical cooling rate,
which is the minimum cooling rate that
prevents the formation of a detectable de-
gree of crystallinity.
Of course, as indicated in the preceding
chapter, glasses are formed in many ways
other than cooling from the melt. In Sec-
tion 3.3 we examine the problem of form-
Equilibrium liquid
Metastable liquid
Glass transition
£ Glass
Crystal
Figure 3-1. Volume change during cooling of a liquid.
If nucleation of crystals occurs easily, the volume de-
creases discontinuously at the liquidus temperature,
TL. Otherwise, the liquid remains in metastable equi-
librium until reaching the glass transition tempera-
ture, where structural rearrangement is kinetically ar-
rested. Further contraction results from the decreas-
ing amplitude of vibration of the atoms around fixed
positions (as in the crystal), so the slopes are similar
for the glass and crystal.
ing a glass object by sintering of a powder
compact or gel. The degree of crystalliza-
tion that occurs during sintering is rela-
tively insensitive to thermal history, but
does depend strongly on pore size and ap-
plied pressure.
If nucleation does not occur, the liquid
remains in metastable equilibrium below
TL and continues to contract at the high
rate corresponding to the thermal contrac-
tion coefficient of the equilibrium liquid. At
lower temperatures the atomic mobility of
the liquid decreases, and eventually the
atoms become trapped in fixed positions.
This occurs over a range of temperature
called the glass transition region, which is
discussed at length in Section 3.4. The glass
transition temperature (Tg) is generally de-
fined as the point of intersection of lines
extrapolated from the glass and metastable
liquid ranges (see Fig. 3-1). In the glass
transition range, the properties of the liq-
uid vary with time at a rate that is readily
detected by human observers. This has im-
portant implications for stress develop-
ment during cooling (especially for glass-
containing composites), because the vis-
cosity that controls the rate of stress relax-
ation is a function of time as well as tem-
perature. This problem is discussed in Sec-
tion 3.5.
3.2 Glass Formation from the Melt
A glass is typically formed by homoge-
nizing the components in the liquid state at
a temperature well above TL, then cooling
below Tg. The cooling rate must be great
enough so that no significant quantity of
crystals can form. The critical rate depends
on the kinetics of nucleation and growth,
so we begin by discussing the standard the-
ories for those processes.

3.2.1 Nucleation of Crystals
3.2.1.1 Homogeneous Nucleation
The barrier to nucleation arises from the
interfacial energy (ySL) between the crystal
and liquid phases. The free energy change
(Ag) on growing a spherical crystal to
a radius r is given by (Uhlmann and
Chalmers, 1965; Christian, 1975):
Ag=-(4n/3)r3Agv (3-1)
where Agv is the difference in free energy
between unit volumes of the crystal and
liquid. Since energy is expended to form
the interface, the high surface-to-volume
ratio of small crystals inhibits their growth.
The break-even point occurs at the critical
radius (r*), where
dAg
= 0 (3-2)
dr
Crystals with radii smaller than r* are
called embryos, and they tend to shrink
because dAg/dr>0 when r<r*; larger
crystals are called nuclei, and they grow
spontaneously because for them dAg/dr
< 0. The critical radius is found by substi-
tuting Eq.(3-1) into (3-2):
r* = 2ysL/Agv (3-3)
The interfacial energy can be related to the
molar heat of fusion, Ahf, by (Turnbull,
1964)
" - ' "U, (3-4)
where NA is Avogadro's number and Vm is
the molar volume. The free energy change
can be approximated by (Hoffman, 1958)
Agv*Ah(Tr(l-Tt)/Vm (3-5)
where Tr is the reduced temperature, Tr =
T/7J. As we shall see, the maximum nu-
cleation rate occurs in the range 0.5 < Tr
<0.7, so when Eqs.(3-4) and (3-5) are sub-
3.2 Glass Formation from the Melt 125
stituted into Eq,(3-3), the critical radius is
found to be
r*^4{VJNA)^ (3-6)
which is just 4 formula units for the crystal-
lizing compound, so r * ^ l nm. However,
at small undercooling (TL—T), the liquid
and crystal are in equilibrium, so Agv = 0
and the radius of the critical nucleus is in-
finite; thus, homogeneous nucleation (where
crystals form directly from the liquid) only
becomes favorable at large undercoolings.
Growth of embryos is assumed to occur
by reactions of the type
K '" (3 ?)
"
where en is an embryo containing n
"monomers" (e.g., formula units) and the
kn are constants for the addition and re-
moval of a monomer. If equilibrium were
established, the number of embryos with n
monomers (Nn) would be
Nn=NlQxp(-Agn/kBT) (3-8)
where Nt is the number of monomers re-
maining in the liquid phase and Agn is the
free energy of formation of an embryo of n
monomers. However, there is no equilib-
rium, because embryos larger than the crit-
ical size (ft* monomers, or radius r*) grow
rapidly and are removed from the system.
Instead, a steady state develops, where the
rate of the forward reaction in Eq. (3-7) be-
comes independent of time and n. The nu-
cleation rate increases during the transient
period (of length T) while the steady-state
distribution of embryos is developing. The
t Thompson and Spaepen (1979) find that Hoff-
man's approximation is appropriate for materials
with a large change in cp at TL, but it does not work
well for metals; they recommend replacing the factor
of Tx with 2 Tr/(1 + Tt). Takahashi and Yoshio (1973)
also find that Eq. (3-5) is not accurate for alkali disil-
icates; better results are obtained by neglecting the
factor of T .
126 3 Glass Formation and Relaxation
kinetics of transient nucleation are very well
described by the theory due to Kashchiev
(1969), a fact that has been verified by ex-
periment (James, 1974) and by computer
simulations (Kelton et al, 1983).
Substituting Eq.(3-6) into Eq.(3-1) we
find the free energy of the critical nucleus,
which is the thermodynamic barrier to nu-
cleation:
Ag{r*) = W* =
"5 A (3.9)
The rate of formation of critical nuclei, or
rate of homogeneous nucleation (Iv) is given
by (James, 1985; Zanotto and James, 1985)
;n v vexp
where nv is the number of molecules or
formula units of nucleating phase per unit
volume, v is a vibration frequency, v&
kBT/h, where k is Boltzmann's constant
and h is Planck's constant; AgD is the acti-
vation barrier for transport across the nu-
cleus/liquid interface, and W* is the ther-
modynamic barrier to nucleation defined
in Eq. (3-9). It is conventionally assumed
that transport at the interface is related to
a diffusion coefficient,
D = v X1 exp ( - AgD/kB T) (3-11)
where X is a jump distance, of the order of
atomic dimensions. It is further assumed
that D can be related to the viscosity (rj) by
the Stokes-Einstein equation
kBT
D= (3-12)
so that
W*
exp - (3-13)
The validity of Eq. (3-13) has been exten-
sively investigated. James (1985) gives an
excellent account of this work. Rowlands
and James (1979) concluded from a study
of nucleation in lithium disilicate glasses
that the temperature dependence of the nu-
cleation rate was well represented by the
theory, except at very large undercoolings,
but the magnitude of the measured rate
was 20 orders of magnitude larger than
predicted! Later it was shown (Zanotto
and James, 1985) that the temperature de-
pendence was indeed predicted correctly
by Eq. (3-13), if viscosity values and nucle-
ation rates were measured in the same
glass; however, the magnitude of Iv was
still grossly in error. Finally, James (1985)
showed that the magnitude could also be
brought into agreement by allowing for a
weak (and physically reasonable) tempera-
ture dependence in y^.
3.2.1.2 Heterogeneous Nucleation
In most real systems, crystals result from
heterogeneous nucleation, where foreign
material provides a surface that facilitates
the formation of a critical nucleus. As indi-
cated in Fig. 3-2, a nucleating agent (such
as laboratory dirt, which is largely com-
posed of aluminosilicates) is effective if it
provides a low-energy interface with the
crystal. In that case the energy invested to
form the nucleus is smaller and the rate of
t Weinberg and Zanotto (1989 a) argue that the use
of the Stokes-Einstein equation, Eq. (3-12), is unjusti-
fied. Based on the very successful theory of Kash-
chiev (1969), they propose that the temperature-
dependence of the transient time x gives a better rep-
resentation of the kinetics of transport at the crystal/
liquid interface. Using measured values of x and Iv,
they find that the predicted and measured values of
the nucleation rate are not in agreement at large un-
dercoolings. However, Kelton et al. (1983) found in
their computer simulations that the temperature de-
pendence of the transient time was not the same as for
transport at the interface, and the difference was in
the right direction to account for the results reported
by Weinberg and Zanotto, so the standard theory is
probably correct after all, even with the use of the
Stokes- Einstein approximation.

Unfavorable
yr > yY
sv SL
Crystal:
Liquid i
Vapor •
Figure 3-2. Schematic illustration of homogeneous
and heterogeneous nucleation; 6 is the contact angle
between the crystal and the nucleating heterogeneity.
nucleation is faster. For a nucleus in the
form of a spherical cap growing on a
flat substrate, the barrier to heterogeneous
nucleation is given by (Uhlmann and
Chalmers, 1965)
where
/ (0) = (2 + cos 6) (1 - cos 0)2/4
and 6 is the contact angle between the crys-
tal and the nucleating heterogeneity, as il-
lustrated in Fig. 3-2. The function f(6\
shown in Fig. 3-3, substantially reduces the
barrier to nucleation when the contact an-
gle is small (<90°). This allows nucleation
to occur at relatively small undercoolings,
where homogeneous nucleation is improb-
able.
Heterogeneities are responsible for the
appearance of crystals at small undercool-
ings, and for the occurrence of crystalliza-
tion originating at the surface of a body of
glass. As illustrated in Fig. 3-2, a free sur-
face is an unfavorable site for homoge-
neous nucleation, because of the high en-
ergy of the solid/vapor interface. However,
3.2 Glass Formation from the Melt 127
contamination by particles is most likely to
occur at the surface, and these heterogenei-
ties can be potent nucleating agents.
3.2.2 Crystal Growth
3.2.2.1 Interface Control
The standard theory for crystal growth
is discussed in several good reviews (Jack-
son etal., 1967; Uhlmann, 1969, 1972 a).
When growth is controlled by attachment
of atoms to the interface, the growth rate
(u) can be written
where Dc is the kinetic coefficient govern-
ing the rate of transport at the crystal/liq-
uid interface, / is the interface site factor
(i.e., the fraction of sites on the interface to
which an atom can attach), and the quan-
tity in brackets is the thermodynamic fac-
tor determining the probability that an
(3-14) atom on the crystal surface will remain
there, rather than jumping back into the
liquid; Vm is the molar volume, .Rg is the
ideal gas constant, and Agv is the same free
(3-15)
energy that appears in Eq. (3-1). The coeffi-
cient Dc is generally identified with D in
0 20 40 60 80 100 120
e
Figure 3-3. Function f(0), defined in Eq. (3-15),
causes drastic reduction in barrier to nucleation when
contact angle 6 is small.
128 3 Glass Formation and Relaxation
Eq.(3-ll) and approximated using the
Stokes-Einstein equation, as in Eq.(3-12).
A material with an entropy of fusion
(Asf=Ahf/TL) less than 2Rg is expected to
develop a rough liquid/crystal interface
(Jackson et al, 1967), so the interface site
factor will be near unity. In such cases, for
small undercoolings Eq. (3-16) reduces to
Dc\ (As,
RgT
(3-17)
where the second equality follows from
Eq. (3-5). If the entropy of fusion is > 4 Rg,
the crystal/liquid interface is smooth, and
attachment is relatively difficult. If growth
occurs at the ledge of a screw dislocation,
then / increases in proportion to the un-
dercooling:
(3-18)
If growth advances by formation of disk-
shaped nuclei on the smooth interface, the
growth rate has the form
B
where A and B are constants (Hillig, 1966).
3.2.2.2 Diffusion Control
In many systems, growth is not con-
trolled by attachment kinetics. In rapidly
crystallizing materials, such as metals,
growth may be limited by the rate of trans-
port of the heat of fusion away from the
interface. In multicomponent systems
(which includes most oxides of commercial
or geological significance), the limiting step
may be diffusion of solute. The rejected
heat or solute builds up at the interface and
decreases the driving force for crystalliza-
tion (viz., the undercooling); growth will
stop unless it diffuses away. As growth pro-
ceeds, the rejected layer increases in thick-
ness, so that diffusion must occur over
greater and greater distances; conse-
quently, the growth rate decreases with
time according to
uocr112 (3-20)
Once a diffusion layer forms, as indi-
cated in Fig. 3-4, any perturbation that
forms on the interface enters a region
where the undercooling is greater, so it
grows faster. This situation is called consti-
tutional supercooling (Chalmers, 1964), and
it accounts for the instability of smooth
interfaces in systems crystallizing under
diffusion control. Such systems typically
exhibit dendritic ("tree-like") or spherulitic
morphologies; the latter consists of den-
TL-T greater
at
tip of bump
a)
b)
c)
Figure 3-4. Schematic illustration of diffusion-limited
growth. Solute accumulating at the crystal/liquid in-
terface reduces the driving force (TL—T) for growth;
a perturbation on the interface enters a region with a
greater undercooling, so it grows faster, leading to
breakdown of the planar interface. The same phe-
nomenon occurs when heat, rather than solute, is the
diffusing species.

dritic needles with a common point of
origin. An important feature of dendritic
growth is that the growth rate is constant,
rather than obeying Eq. (3-20). The reason
is that the tip of the dendrite continually
moves into "uncontaminated" liquid, so
that diffusion occurs through a layer whose
thickness is constant, rather than increas-
ing (Christian, 1975).
3.2.3 Kinetics of Glass Formation
A variety of schemes have been pro-
posed to account for the ability of certain
compositions to form glasses; many are
discussed in reviews by Uhlmann and Yin-
non (1983) and Gutzow et al. (1985). Rules
based on the ratios of the sizes of the
atoms, the strengths of the bonds, or other
structural features seem to work for certain
groups of materials, but always fail for oth-
ers. Such approaches are logically unsatis-
factory, because glass formation is a kinetic
phenomenon: even silica will crystallize if
cooled too slowly, and water will vitrify if
cooled fast enough. The answer to whether
a given material is a glass former is not
"yes" or "no". The answer is always "yes, in
principle", because any liquid will form a
glass if it is cooled rapidly enough.
Dietzel and Wickert (1956) identified the
quality of a glass-former by the reciprocal
of its maximum crystallization rate. This
would be reasonable if the nucleation be-
havior of various liquids were comparable,
but it is not. The growth rate is not related
to the interfacial energy that controls the
nucleation barrier, so a liquid that crystal-
lizes easily might be hard to nucleate.
Turnbull (1969) suggested that the condi-
tion for glass formation should be the ab-
sence of any nucleation:
v\lvdt<l (3-21)
3.2 Glass Formation from the Melt 129
i i i i i
1 -
0.8 ~
A • *
'•
I p (max) u(max) / •
0.6 -
0.4 -
0.2
;
/ \ '' \
o - \
0.5 0.6 0.7 0.8 0.9 1.1
T/Tr
Figure 3-5. Rates of nucleation and crystal growth in
SiO2, calculated from standard theory, using parame-
ters given by MacFarlane (1982).
where V is the volume of the sample. This
is a rigorous definition, certainly, as it en-
sures that a material that is called a glass is
truly free of any crystallinity. However,
when this proposal was investigated by
Vreeswijk et al. (1974) their calculations
predicted that SiO2 would have to be
cooled 1010 times faster than GeO 2 to form
a glass, and that As 2 O 3 would have to be
quenched at 10 7o C/s. These results are
clearly inconsistent with experimental evi-
dence. The reason for the failure of this
approach is indicated in Fig. 3-5: for many
materials, the temperature ranges where
the nucleation and growth rates are signif-
icant do not overlap. It may be virtually
impossible to avoid forming a nucleus, but
those nuclei that do form may not be able
to grow to any meaningful «i™ 1"
^ Note that the situation is quite different on cooling
and reheating. During cooling, the concentration of
critical nuclei is near zero as the liquid passes through
the temperature of the maximum growth rate. How-
ever, once it has been cooled through the range where
the nucleation rate is high, many nuclei are available
to grow during reheating.
130 3 Glass Formation and Relaxation
3.2.3.1 Critical Cooling Rate
The most comprehensive method of pre-
dicting glass formation was introduced by
Uhlmann (1972 b). The idea is to construct
a time-temperature-transformation (TTT)
curve as in Fig. 3-6: the curve defines the
time required at any temperature to pro-
duce a particular volume fraction of crys-
tallization, v. Uhlmann chose a fraction of
v = 10" 6, on the basis that it represents the
limit of detectability of crystallinity by cur-
rent techniques; the results are not sensi-
tive to this choice of v, as we shall see. Thus,
a glass is implicitly defined as a material
that contains an insignificant quantity of
crystal. The TTT curve is used to calculate
the critical cooling rate (Rc\ which is the
minimum rate that results in a glassy prod-
uct (i.e., one having a crystalline content
< v). There is no clear-cut separation be-
tween glass-formers and non-glass-form-
ers; instead, the glass-forming tendency of
a liquid is quantified in terms of Rc.
r
« log t
Figure 3-6. Schematic illustration of a TTT curve. The
abscissa indicates the time required at each tempera-
ture to produce a volume fraction of crystals of v. The
critical cooling rate (Rc) is the minimum rate that
avoids crossing the curve. The "nose" of the curve, at
time tn and temperature Tn, corresponds to the fastest
rate of transformation. The nose method uses the
approximation JRC «(TL — Tn)/tn, where TL is the liq-
uidus temperature.
The TTT curve is calculated using the
Johnson-Mehl-Avrami theory (Christian,
1975), which relates v to the rates of nucle-
ation (Iv) and growth (u):
(3-22)
4 71
> = 1 — exp I — J/Jjudr df
Under isothermal conditions, when Iv and
u are constant, this reduces to
(3-23)
v = l — exp lv u i
or, when v is small, to
v& —. (3-24)
This expression can be modified (Christian,
1975) to account for those cases when the
growth rate is not constant (e.g., under dif-
fusion control, when u oc t~1/2) or is aniso-
tropic (e.g., when crystals grow in the form
of needles or plates). It must also be modi-
fied when heterogeneous or transient nu-
cleation are important; these situations are
discussed below.
The TTT curve can be constructed using
Eq. (3-24), together with measured or cal-
culated values for Iv and u. The curve then
represents isothermal crystallization, but
we are interested in crystallization during
constant cooling. A conservative estimate
of the critical cooling rate is obtained by
the "nose method":
K*(TL-Tn)/tn (3-25)
where Tn and tn are the temperature and
time corresponding to the nose of the TTT
curve (see Fig. 3-6). The nose of the curve
represents the fastest rate of transforma-
tion of liquid into crystal, and Eq. (3-25)
gives the cooling rate that would be re-
quired if that crystallization rate applied
over the whole temperature range from TL
to Tn. The values of Rc found in this way,
 3.2 Glass Formation from the Melt 131

using measured values for u, rj, and W*9 are

generally in order-of-magnitude agreement
with experiment (Uhlmann and Yinnon,
1983). Similar agreement has been ob-
tained by other workers (e.g., Davies, 1976;
Ramachandrarao et al., 1977; Tanner and
Ray, 1979; Vil'kovskii, 1988) who used this
approach to calculate Rc for metallic glass-
formers.
3.2.3.2 Nonisothermal Analyses
An improved estimate of Rc can be ob-
b)
tained by taking proper account of the
I ~
transformation rate at each temperature 1500
during a constant cooling treatment,
rather than using the nose method. U00
A simple way of adapting an isothermal
TTT diagram to describe constant cooling £ 1300

is an averaging method suggested by

Grange and Kiefer (1941): it is assumed
that on cooling through a small tempera-
ture interval from T± at time t1to T2 at time
t2, the amount of crystallization is equal to
that produced isothermally at temperature
(T1 + T2)/2 in a time period of
Onorato and Uhlmann (1976) adapted this
method to calculate curves appropriate for
cooling at a constant (dT/dt = constant)
or logarithmic (dT/d (In t) = constant) rate,
with the results shown in Fig. 3-7. The de-
scending curves in Fig. 3-7 a represent con-
stant cooling rates, and the one that barely
misses the nose of the curve corresponds
to Rc. When the constant cooling rate is
taken into account, a smaller value of Rc is
found, as expected, but the difference is
typically less than a factor often. Note that
Rc is relatively insensitive to the assumed
value of v: a change o f ~ 5 x l 0 5 i n i ; causes
a change by a factor of ~20 in Rc. Fig.
3-7 b shows that a logarithmic cooling rate
(encountered in the cooling of many large
bodies) produces a curve that falls between
the isothermal TTT and the constant rate
curve.
•1200
1100
1000
t2-tv
Figure 3-7. a) Isothermal TTT for v = 10" 6 and con-
stant-rate cooling curves for v = 10" 6 and v =0.5-0.9;
calculated for lunar glass 79155 (multicomponent sil-
icate); b) Isothermal TTT and nonisothermal curves
assuming constant (continuous) or logarithmic cool-
ing rates, all for v =0.01; calculated for lunar glass
15286. From Uhlmann and Yinnon (1983).
A more rigorous nonisothermal analy-
sis, suggested by Hopper et al. (1974), al-
lows prediction of the distribution of crys-
tal sizes following a given cooling treat-
ment, or inference of the cooling rate from
measurement of the size distribution. For
the calculation of Rc it reduces to Eq. (3-22).
A simpler method was suggested by Mac-
Farlane (1982), based on the concept of
additivity. This means that the rate of
transformation depends on the current
state of the system (i.e., v and T), and not
132 3 Glass Formation and Relaxation
on the thermal history. Then it can be
shown (Cahn, 1956) that
(3-26)
where h and g are functions only of T and
v9 respectively. MacFarlane (1982) noted
that Eq.(3-24) can be written in the form
(3-27)
Then, when additivity is valid, for a cooling
rate ofq = dT/dt = constant, Eq. (3-27) be-
comes /^ ~QX
(3-Z5)
- 0I At' Y
K(T(t'))J)
f dT
'Y
which is readily evaluated. However, as
Cahn (1956) explained, Eq.(3-26) is not
generally valid when both Iv and u are tem-
perature-dependent, so it cannot describe
concurrent homogeneous nucleation and
growth. However, it is valid when growth
occurs from a constant number of nuclei,
as might happen when heterogeneous nu-
cleation dominates. (It is also valid when Iv
and u have identical temperature depen-
dences, Iv oc w, but no example of this cir-
cumstance is known or expected. See Fig.
3-5, for an example of typical temperature
dependence.) Weinberg and Zanotto
(1989 b) compared the prediction of Eqs.
(3-22) and (3-28) and found that the predic-
tions of v were very different when homo-
geneous nucleation was assumed. How-
ever, since Rc depends on t?1/4, an error of
103 in v causes less than an order of magni-
tude error in Rc.
3.2.3.3 Simplified Model
Actually, it is easier to measure Rc di-
rectly than to obtain all the data necessary
to calculate it, even using the nose method.
Therefore, Uhlmann et al. (1979) have de-
veloped various simplified methods to pre-
dict JRC from limited data. One method is to
calculate tn from Eq. (3-24), using Eq. (3-16)
for u and Eq. (3-13) for Iv; Agv is approxi-
mated using Eq. (3-5), and the transport
coefficients are approximated using the
Stokes-Einstein equation, Eq. (3-12). Fur-
ther, based on experience with a wide
range of materials, it is recognized that the
temperature of the nose occurs near
r n *0.77T L (3-29)
With these approximations, Eqs. (3-24)
and (3-25) lead to (Uhlmann and Yinnon,
1983)
RCK ^-exp(-0.212b)-
(3-30)
where a = 0.04 J/cm 3 K, rjn is the viscos-
ity at 0.77 TL, and b is related to the nucle-
ation barrier at a reduced temperature of
T=0.8:
b= (3-31)
0.8fe B T L
The cooling rates calculated from Eq. (3-30)
were found to be in order-of-magnitude
agreement with experiment, so the results
were almost as good as when the more
rigorous analysis was used. Of course, it is
essential to make a good choice for the
value of b, because a 15-20% change in b
results in a 10-fold change in Rc.
The performance of the simplified analy-
sis is surprisingly good, considering that it
assumes that nucleation occurs homoge-
neously and that crystal growth is inter-
face-controlled. The presence of hetero-
geneous nucleation changes only the mag-
nitude of the nucleation barrier, not the
form of the equations, but it does have a
profound effect on the transformation rate,

as we shall see. The reproducibility of ex-
perimental measures of Rc indicates that
heterogeneous nucleation is minimal or
that the samples are contaminated in a
consistent way.
In many of the systems studied, growth
is certainly diffusion-controlled, so the im-
plication (Uhlmann and Yinnon, 1983) is
that Eq. (3-16) is reasonably accurate in
predicting the rate of dendritic growth in
the vicinity of Tn. This would certainly not
be expected a priori. However, it is worth
noting that Magill et al. (1973) have shown
that the crystal growth rates for a variety
of organic glass formers can be collapsed
onto a single master curve by plotting
u(T)/u(Tmax) versus (T-TJ/(TL-TJ,
where Tmax is the temperature of the maxi-
mum growth rate and T^ is a parameter
(which may be related to the glass tran-
sition temperature). Moreover, Dearnley
(1983) has shown that growth rate data for
a variety of minerals (basalts, plagioclase,
and diopside) can be described by the same
curve. The organic systems probably grow
under interface control, but the latter al-
most certainly exhibit diffusion control;
nevertheless, in spite of a range of several
hundred degrees in TL, all of these materi-
als show similar temperature dependence
for w.
3.2.3.4 Heterogeneous
and Transient Nucleation
The effect of heterogeneous nucleation
on the TTT curve has been examined by
Onorato and Uhlmann (1976) and by Yin-
non and Uhlmann (1981). The latter study
used Eqs. (3-13) and (3-14) to calculate the
effect of heterogeneities with various con-
tact angles, 9. The TTT diagrams were con-
structed using Eq. (3-22) together with
measured crystal growth rates for anor-
thite (CaO • A12O3 • 2SiO 2 ) and the or-
3.2 Glass Formation from the Melt 133
320
310 0.95
0.90
0.85
Homogeneous,
0.80
nucleation
only
250
-U -3 - 1 0 1 2
Log t (mini
Figure 3-8. Continuous cooling curves for homo-
geneous 4- bulk heterogeneous nucleation in o-ter-
phenyl with contact angles as indicated, as well as for
homogeneous nucleation only. Curves calculated
from Eq. (3-22). From Uhlmann and Yinnon (1983).
ganic glass-former o-terphenyl. As shown
in Fig. 3-8, heterogeneities with #<100°
cause drastic reductions in the critical
cooling rate, because they allow nucleation
in the temperature range where crystal
growth is rapid. When heterogeneities with
a range of contact angles are present, those
with the smallest 6 are depleted first during
cooling and those with larger 9 become
more important at greater undercoolings.
Uhlmann (1972 b) concluded that tran-
sient effects in nucleation would have a
negligible effect on the calculation of Rc,
because the transient period (of duration T)
is generally short compared to (TL — Tn)/
Rc. Gutzow et al. (1985) used the theory of
Kashchiev (1969) for transient nucleation
to modifiy Eq. (3-24). For isotropic isother-
mal growth, they obtained
3v
(3-32)
The transient effects were found to be im-
portant when very potent heterogeneous
nuclei were present, in which case high crit-
ical cooling rate were required. Kelton and
Greer (1986) used a numerical method to
simulate cluster growth directly, rather than
134 3 Glass Formation and Relaxation
using the Johnson-Mehl-Avrami analysis.
They found that transient nucleation effects
were insignificant for lithium disilicate,
which is a good glass-former (Rc « 3.8 K/s),
and were minor for (Au 85 Cu 15 ) 77 Si 9 Ge 14 ,
which is a relatively poor glass former
(Rc«104 K/s). However, for Au 81 Si 19 , cal-
culations including transient nucleation ef-
fects gave R c ^ 1 0 5 K / s , while steady-state
calculations gave Rc « 2.4 x 107 K/s. Thus,
when the critical cooling rate is high, tran-
sient effects become important, and ignor-
ing them leads to a very pessimistic esti-
mate of Rc. (See also Vol. 15, Chap. 9, Sec.
9.3.3.)
3.2.3.5 Factors Favoring Glass Formation
Kinetic analyses suggest that the follow-
ing factors are most important in reducing
the critical cooling rate (Uhlmann and
Yinnon, 1983):
1) High viscosity at the melting point or
liquidus temperature (as is characteristic of
silicate liquids) or a viscosity that rises
rapidly with undercooling (as in organic
glass-formers), since Iv and u are both in-
versely related to rj.
2) A high value of Tg/TL, since glass for-
mation requires cooling from TL to Tg (this
is clearly closely related to factor 1).
3) No heterogeneous nucleation.
4) A high barrier to homogeneous nucle-
ation.
5) A large difference in composition be-
tween the crystal and liquid, since this
makes crystal growth difficult. This condi-
tion, along with a small ratio of Tg to TL, is
often met at eutectic compositions. Metal-
lic glasses are most often found near eutec-
tics.
6) Asymmetric molecules (as in o-ter-
phenyl) that inhibit crystal growth.
(See also Vol. 15, Chap. 9, Sees. 9.3.2 and
9.3.3.)
3.3 Sintering and Crystallization
As explained in Chapter 2, glasses are
formed in many ways other than cooling
from the melt. One method that has
achieved considerable importance in re-
cent years is sol-gel processing, where wet-
chemical techniques are used to prepare an
inorganic gel that is sintered to obtain a
dense ceramic (Brinker and Scherer, 1990).
In this section we discuss the factors that
determine whether the sintered product
crystallizes or remains glassy. This prob-
lem is closely related to that considered in
the previous section, except that the glassy
state is approached from below during
heating of the gel, rather than from above,
as during quenching of a melt.
3.3.1 Sintering
A porous glass contains an excess energy
equal to yLV S, where yLV is the liquid/va-
por interfacial energy and S is the interfa-
cial area. If the body is heated to a temper-
ature at which the atoms have sufficient
mobility, this energy provides a driving
force for densification. The reduction of
porosity through viscous flow or diffusion
driven by surface energy is called sintering.
This process is used to produce a variety of
glassy objects, as described by Rabinovich
(1985). In sol-gel processing, the surface
area of the body is so enormous (typically
300-1000 m 2 /g) that the driving force is
sufficient to permit sintering at very low
temperatures. This raises the possibility of
producing glasses that tend to crystallize
or phase separate when prepared from the
melt. For example, Yamane and Kojima
(1981) made clear glasses in the strontium
silicate system; since these compositions
fall within a stable immiscibility region ex-
tending above 2000 °C, such glasses are vir-
tually impossible to prepare by melting.
 3.3 Sintering and Crystallization 135

On the other hand, sodium silicate glasses (Scherer, 1984 b)

that are readily prepared by melting can-
not be sintered, because crystallization of
the porous gel is too rapid (Prassas and
Hench, 1984).
In glassy materials, sintering occurs by
viscous flow. The kinetics of the process
were first modeled by Frenkel (1945), who
suggested that the energy gained by reduc-
tion in surface area must be equal to the
energy dissipated in viscous flow. A variety
of models have been developed based on
that principle, differing principally in the
geometry assumed for the pores (Macken-
zie and Shuttleworth, 1949; Scherer, 1977).
These models and their application to gels
have been recently reviewed (Scherer,
1987; Brinker and Scherer, 1990). The pre-
diction of these models, which is remark-
able insensitive to the geometrical assump-
tions, is that the densification rate is given boundary or through the lattice. Surface
approximately by
,1/3
de
0.3 < Q < 0.9 (3-33)
dt
where Q is the relative density of the porous cesses do not cause densification.
body (i.e., the volume fraction of porosity
= 1 — Q) and rj is the viscosity. The geomet- proposed to describe the kinetics of sinter-
ric parameter, n, is the number of pores per
unit volume of the liquid phase; for a body
composed of spherical particles of radius a,
there is roughly one pore per particle, so
(3-34)
4na3
Sintering of crystalline materials is more
complicated, because transport can occur
simultaneously by diffusion through the
crystal lattice, along grain boundaries, or
across the surface of the particles, or by
evaporation and condensation. As indi-
cated in Fig. 3-9, there is a grain boundary
at the point of contact (called a neck) be-
tween sintering crystalline particles, be-
cause the crystal planes do not generally
align. Densification occurs when the cen-
ters of the particles move toward one an-
other, and this requires that material be
removed from the grain boundary and
transported to the pore. This can be
achieved only by diffusion along the grain
diffusion and evaporation/condensation
reduce the surface area by moving material
to the neck (a process called coarsening),
but as indicated in Fig. 3-10, these pro-
A large number of models have been
ing when diffusion follows one or more
paths, and Ashby (1974) has developed
"maps" that indicate which process domi-
nates in a given range of temperature. For

Path 2: Lattice diffusion

Path 5:
Lattice diffusion
Figure 3-9. Schematic illustration
Path 3: Path 1: of sintering of crystalline particles
Evaporation Surface Diffusion showing possible paths for trans-
port of matter. For densification
Path 4: to occur, atoms must be removed
Boundary diffusion from the grain boundary (dashed
line) at the plane of contact (neck)
between the particles.
136 3 Glass Formation and Relaxation
Densification Coarsening
Figure 3-10. Densification results when atoms move
from the grain boundary to the pore. Coarsening oc-
curs when atoms move from the surface of the particle
toward the neck; the centers of the particles do not
move toward one another.
our purposes, it is sufficient to consider a
widely used model for densification pro-
duced by diffusion from the grain
boundary through the lattice (Coble, 1961).
The densification rate is given by
336 DL-
(3-35)
dt
where a is the radius of the particle, D L , is
the lattice diffusion coefficient, y sv is the
solid/vapor interfacial energy, and X is the
size of the diffusing species. To compare the
sintering rates permitted by viscous flow
and diffusion, we use the Stokes-Einstein
equation, Eq. (3-12), to replace DL with the
viscosity, rj. Then, assuming that the sur-
face energies are similar, Eqs. (3-33) to
(3-35) lead to
2 flow can occur. This generally means that
dg
(3-36)
dt diffusion dt flow
This indicates that sintering of crystalline
materials is slower than sintering of glass,
unless the particles are a few times larger
than a molecule. Clearly, then, it is advan-
tageous to densify a porous body before it
crystallizes, if that is possible. A practical
application of this principle is the demon-
stration by Thomas (1974) that dense glass
ceramics can be made from amorphous
aerogels, but only if the amount of crystal-
lization during sintering is less than 5-10
vol%. To find a thermal treatment that will
produce densification of a glass without
excessive crystallization, it is necessary to
combine the TTT diagram discussed in the
previous section with information about
the kinetics of viscous sintering.
3.3.2 Competition Between Sintering
and Crystallization
From Eqs. (3-33) and (3-34) it can be
seen that the time to achieve densification
by viscous sintering is approximately
TS * 1.6arj/yLY (3-37)
Knowing rj (T) one can calculate the sinter-
ing time for a given particle size and plot it
together with a TTT curve, as in Fig. 3-11.
If the sintering curve does not cross the
TTT curve, the sample can be sintered be-
fore it crystallizes. This variant on the TTT
diagram was proposed by Uhlmann et al.
(1975), who were interested in inferring the
thermal history of a sample from examina-
tion of its microstructure. It is also useful if
one seeks a sintering treatment that will be
complete before significant crystallization
occurs.
Whereas a melt must be quenched to
obtain a glass, a porous glass or gel must
be heated to a temperature where viscous
the sample must pass through the tempera-
ture range where the nucleation rate is
greatest, and the presence of abundant nu-
clei facilitates the crystallization that we
seek to avoid. In fact most gels sinter in the
vicinity of the glass transition temperature
(Brinker and Scherer, 1990), where nucle-
ation may be rapid; fortunately, growth in
that temperature range is generally slow.
Glass powders sinter at higher tempera-

U00
Breccias with crystallinities
between 1% and 90%
1300
Completely crystalline
breccias
6 8
log10 t (s)
tures (because the particle size, a, in
Eq.(3-37) is larger), so they may have a
significant growth rate as well as a high
content of nuclei. The general guideline is
that the particle size should be as small as
possible, so that sintering can proceed at a
temperature where the crystal growth rate
is small. Of course, one should avoid het-
erogeneous nuclei, but even these are not
important if the temperature is kept low
enough. If the crystallization rate is fast
even at temperatures too low for sintering,
the densification rate can be accelerated by
applying pressure (with a piston, for in-
stance). However, to be effective, the ap-
plied pressure must be comparable to the
capillary pressure, 2yLY/a, that drives sin-
tering; for gels, this is on the order of 10-
100 MPa.
In gels, the viscosity may be much lower
than in a melted glass with the same oxide
content, because gels tend to have high
concentrations of hydroxyl (~ 0.1-0.3%
OH). Therefore, the viscosity of a gel can
be varied by low-temperature treatments
that reduce the OH content, and one might
expect this to have an impact on the ease of
3.4 The Glass Transition 137
Figure 3-11. Curve indicating sin-
tering time (SINTERS) combined
with isothermal TTT curves for
various volume fractions of crys-
tallization for a lunar glass. A
breccia is a rock containing sharp
fragments embedded in a fine-
grained matrix. The objective of
this study (Uhlmann et al., 1975)
was to infer the thermal history of
the sample from the degree of
crystallinity and extent of sinter-
ing.
sintering without crystallization. Zarzycki
(1982) considered the question and con-
cluded that chemical impurities that
change rj will have the same effect on the
rate of sintering and crystallization, since
both processes are proportional to t/rj.
Zarzycki found some evidence that OH
could affect the barrier to homogeneous
nucleation (probably by reducing ySL), but
the differences in crystallinity among the
silica gels he examined was attributed to
heterogeneous nucleation.
3.4 The Glass Transition
We have seen that a liquid can be cooled
below the liquidus temperature if the rates
of nucleation and growth are small
enough. At moderate undercoolings the
liquid is in metastable equilibrium, which
means that physical properties such as
specific volume, V9 are functions of temper-
ature (T) and pressure (P), independent of
time. Following small changes in state
(caused, for example, by sudden heating or
138 3 Glass Formation and Relaxation

cooling) the properties of the liquid gradu- final subsection we discuss that theory and
ally approach their equilibrium t values. its application to such practical problems
The time-dependent variation in physical as tempering, annealing, and fabrication of
properties as the liquid approaches equi- glass-to-metal seals.
librium is called structural relaxation or
physical aging. The glass transition is a re- 3.4.1 Phenomenology
gion of temperature (corresponding to a
The glass transition is characterized by a
viscosity of t] ^ l O ^ - l O 1 3 Pas) in which
change in the temperature dependence of
the rate of relaxation is slow enough to be
properties such as volume (V) and en-
readily detectable by human observers.
thalpy (H) during cooling. As illustrated in
The process of structural relaxation is
Fig. 3-12, the volumetric thermal expansion
nonlinear and nonexponential, and this
coefficient (av = d In V/dT) and isobaric
gives rise to a rich phenomenology that is
heat capacity (cp = dH/dT) decrease near
described in the next subsection. The same
Tg from a high value characteristic of the
behavior is found in every class of liquid,
equilibrium liquid (avl9 cpl) to a small value
including network oxides (e.g., soda-lime-
characteristic of solid glass (ayg, cpg). In the
silicates), fluorides (e.g., the heavy metal
glass, the atoms are frozen into fixed posi-
fluorides being considered for optical tele-
tions, and the properties change only be-
communications), salts (e.g., 0.4Ca(NO3)2 •
cause the temperature affects the ampli-
•O.6KNO3), molecular liquids (e.g., o-ter-
tude of vibration of the atoms around
phenyl), polymers (e. g., polycarbonate),
those positions. Stronger temperature de-
and metals (e.g., Si 15 5 Cu 6 Pd 7 8 5 ). More
pendence is found in the liquid, because the
detailed discussions of relaxation in glass-
atoms are free to diffuse, so changes in tem-
forming liquids are presented in the books
perature can produce different atomic con-
Relaxation in Viscous Liquids and Glasses
figurations in addition to changes in vibra-
(Brawer, 1985) and Relaxation in Glasses
tional amplitude. As the temperature is
and Composites (Scherer, 1986 b). After a
lowered toward Tg, the mobility of the
brief look at the thermodynamic implica-
atoms decreases and relaxation times (T) on
tions of the glass transition, we review a
the order of seconds or minutes are re-
variety of theories that attempt to explain
quired for the liquid to achieve the equilib-
the kinetics of relaxation based on different
rium configuration. If the temperature is
views of the microscopic nature of the re-
dropping at the rate of a few degrees per
laxation processes. The most powerful tool
minute, it is evident that the structure will
for prediction of the kinetics of relaxation
not be able to remain in equilibrium; the
is a theory proposed by Narayanaswamy
liquid will be trapped in a configuration
(1971) that makes no assumption about the
characteristic of a temperature near Tg.
microscopic processes of relaxation. In the
3.4.1.1 Cooling Rate Dependence of Tg
"f In the remainder of this chapter we are exclusively
concerned with relaxation processes that occur below The higher the cooling rate (q = dT/dt),
the liquidus. When we refer to the equilibrium state of
a liquid it is understood to mean the metastable equi- the higher the glass transition temperature,
librium state of the undercooled liquid. Of course, as indicated in Fig. 3-12. This is easy to
large excursions in T or P can result in transforma- understand if the process of cooling is re-
tion to the true equilibrium structure - the crystal -
by nucleation and growth, but we exclude such cases garded as a sequence of temperature jumps
from consideration. of size A T followed by isothermal holds of

(B) slow cool and
heat at rate I a I
1
B
pg
Temperature
length At=AT/q. The liquid remains in
equilibrium as long as At is much longer
than the relaxation time, which is propor-
tional to the viscosity (Rekhson et al., 1971;
Mazurin, 1977):
xp = t1/Kp (3-38)
where Kp is a constant and xp is the relax-
ation time for the property p that is being
measured; for the relaxation of volume in
oxides, Kp » 2.5 x 109 Pa. At high tempera-
tures, T <At, but near Tg, % &At, so relax-
ation of one temperature step is not com-
plete before the next step is taken, and the
structure drifts farther and farther out of
equilibrium as cooling continues. The
greater the cooling rate, the less time is
available for relaxation of each step; since
At is smaller, the transition (zp &At) occurs
at a higher temperature. This idea has been
3.4 The Glass Transition 139
Figure 3-12. Change in property p
(illustrated for specific volume V
and enthalpy if) during cooling of
a glass-forming liquid. As the
cooling rate (q) increases, so does
the glass transition temperature
(Tg). Lower part of plot shows
slope of curves in upper plot:
oc = d(\nV)/dT and cp = dH/dT;
subscripts / and g refer to proper-
vg
ties of equilibrium liquid and
glass, respectively.
quantified by Copper (1985), who identifies
the glass transition with the temperature
where
1
(3-39)
dT dT
Expressions that are more useful for quan-
titative predictions of Tg (q) are discussed in
Section 3.4.4.2.
3.4.1.2 Fictive Temperature
A convenient way of characterizing the
structure of the nonequilibrium liquid is by
the value of the fictive temperature (Tf),
which is defined in Fig. 3-13. The continu-
ous curve represents the change in prop-
erty p during constant cooling of a glass-
forming liquid, until it reaches temperature
7\ at time t0. If a line is drawn from the
140 3 Glass Formation and Relaxation
Constant cooling rate
Quench
a.
t
Tt Tf(tn)Tf(t0)
Temperature
Figure 3-13. The fictive temperature (Tf) is found by
extrapolating a line with the glassy slope from any
point on the nonequilibrium curve to its point of
intersection with the curve of the equilibrium liquid.
The continuous curve shows the path of property p
during constant cooling, arriving at temperature Tx at
time t0; if a line with the glassy slope is extrapolated
from temperature Tx, the fictive temperature is found
to be Tf (t0). If a sample were equilibrated at temper-
ature T{ (t0) and then quenched to Tlt it would have
the same value of p as the continuously cooled sam-
ple. During an isothermal hold at Tx, property p re-
laxes toward its equilibrium value, and T{ relaxes to-
ward T,.
nonequilibrium curve with the slope dp/dT
characteristic of the glass (i.e., the "glassy
slope"), it intersects the extrapolated equi-
librium curve at the fictive temperature,
Tt (t0). If another sample were equilibrated
at temperature Tf (t0), then quenched to Tx,
p for that sample would change along a
line with the glassy slope, so the quenched
sample would have the same value of p as
the continuously cooled sample. Since the
structure of the sample is assumed to be
unchanged during the quench, the implica-
tion is that the structure of the continu-
ously cooled sample is the same as that of
a liquid in equilibrium at Tf.
As we shall see, this is not strictly true:
two samples with the same value of p do
not necessarily have the same structure.
However, the fictive temperature is a sim-
Figure 3-14. At high temperatures the liquid is in
equilibrium and Tf = T, but on cooling into the glass
transition region p lies above its equilibrium value
and correspondingly Tf lags behind T. In the glassy
state, T{ reaches a constant minimum value, which is
called Tg.
ple and useful measure of the structural
state of the glass. If the sample is held
isothermally at 7\, p relaxes toward its
equilibrium value, which lies on the ex-
trapolation of the equilibrium curve (heavy
dashed line in Fig. 3-13). The fictive tem-
perature decreases to Tf (tx) at time t1, and
eventually becomes equal to Tx when the
sample reaches equilibrium.
The relationship between Tf and Tg is
illustrated in Fig. 3-14. In the equilibrium
liquid, the fictive temperature is equal to
the actual temperature, but as the liquid is
cooled into the glass transition region T{
decreases more slowly than T. By the time
the liquid has frozen into the glassy state,
Tf has reached the lowest possible value
(for that cooling rate), and that value is
called 71.
 3.4 The Glass Transition 141

3.4.1.3 Hysteresis ically in Fig. 3-16, If a liquid in equilib-

rium at temperature T± is instantaneously
Fig. 3-12 indicates that the properties of
cooled to T2, property p changes immedi-
a glass exhibit hysteresis during reheating
ately because of the reduced vibrational
through the glass transition range. At first
amplitude of the atoms; thus, dp/dT has
the reheating curve bends toward the equi-
the value characteristic of the glass. During
librium curve, as we might expect, but then
an isothermal hold at T2, there is a further
it crosses that curve and approaches equi-
change in p with time as the configuration
librium from below. Low atomic mobility
approaches equilibrium. In terms of the fic-
prevents the structure from reaching equi-
tive temperature, we could say that the
librium until the temperature is raised
sample arrives at T2 with Tf = T1, and re-
above Tg; then relaxation is rapid and the
laxes until Tf = T2. A similar experiment
slope of the reheating curve is actually
can be performed by suddenly heating a
greater than that of the equilibrium curve.
liquid to T2 after equilibrating at T3. Struc-
As shown in the lower portion of Fig. 3-12,
tural relaxation is slower in this case, be-
the sudden approach to equilibrium causes
cause the sample arrives at T2 with a struc-
an overshoot in cp (or <xv) on reheating. If
ture characteristic of the lower tempera-
the heating rate is much faster than the
ture (Tf = T3). Therefore, the atoms have
preceding cooling rate, the overshoot is
less mobility than those in the sample
particularly dramatic. On the other hand,
quenched from Tt, which arrives at T2 with
if the reheating rate is relatively slow, there
a structure characteristic of the higher tem-
is plenty of time for relaxation during heat-
perature. This is an illustration of the non-
ing, so p(T) bends strongly toward the
linearity of structural relaxation: the rate
equilibrium curve. As shown in Fig. 3-15,
of relaxation depends on the size and direc-
this causes an undershoot in dp/dT below
tion of the temperature jump, because TP
Tg, and relatively little overshoot.
depends on the structure of the liquid. The
phenomenon is clearly illustrated in the
3.4.1.4 Nonlinearity data of Hara and Suetoshi (1955) for the
The kinetics of structural relaxation are relaxation of the density of window glass
most clearly revealed in experiments using following jumps of 30 °C from above and
temperature jumps, as shown schemat- below (see Fig. 3-17). If the temperature

Figure 3-15. Hysteresis in

j \ + qh (fast) dp/dT, where p is a prop-
erty of the glass-forming
liquid and T is tempera-
ture; if p is enthalpy, then
this plot represents the
heat capacity, cp. The over-
dT shoot on reheating is
greater when the heating
rate (qh) is greater than the
preceding cooling rate (qc).
qh (fast) »\q \» qh (slow) If qh<\qc\ there is rela-
q (slow) tively little overshoot, but
there is an undershoot be-
low 71.
142 3 Glass Formation and Relaxation

Glassy
slope
\ yf

bo Equilibrium \/
slope \ )h—
"eqm
Pro erty p

/T
OH

I
Temperature Time
Figure 3-16. Approach to equilibrium following instantaneous jump to temperature T2 following equilibration
at Tx or T3. During the jump (left side of figure), the change in property p reflects changes in the vibrational
amplitude of atoms in fixed positions; time-dependent changes at temperature T2 (right side of figure) result from
relaxation of the atomic configuration.

2.504
ation function of property p (Narayana-
swamy, 1971):
l~p(oo,T)
Mp = (3-40)

Structural relaxation in nonexponential,

which means that Mp cannot be accurately
represented by an equation of the form

2.492
200 : exp(-- (3-41)

Figure 3-17. Change in density with time at 530 °C for where t is the time following a jump to
soda-lime-silicate glass previously equilibrated at temperature T. Empirically, the relaxation
560 °C (•) and 500 °C (o). The temperature jump is function can be represented by a sum of
30 °C for both samples, but the sample quenched from
exponential terms,
the higher temperature relaxes faster. Data of Hara
and Suetoshi (1955). t
Mp = (3-42)

jump is very small, then the configura-
tional change is also small, and the relax-
ation appears linear; however, nonlinear-
ity is clearly seen for oxide glasses fol-
lowing jumps as small as 7°C (Rekhson
and Mazurin, 1974).
3.4.1.5 Nonexponential Relaxation
Function
The shapes of the curves in Fig. 3-17 or
the right side of Fig. 3-16 define the relax-
where the xk are independent relaxation
times and the wk are weighting factors, or
by the stretched exponential,
Mp = exp - (3-43)
where the exponent /? has a value between
0 and 1; a smaller value of /? corresponds to
a broader distribution of relaxation times.
(As written, the preceding equations apply
only to linear relaxation; for temperature

jumps of more than a few degrees, it is
necessary to take account of the time de-
pendence of rp by replacing t/zp with j dt/
xp. This is discussed in Section 3.4.4.)
Eq. (3-43) was originally used by Kohl-
rausch (1847) to describe creep of metals
under mechanical stress, and later was ap-
plied for modeling of creep and stress re-
laxation in oxides by DeBast and Gilard
(1963, 1965). Williams and Watts (1970)
found it useful for describing dielectric re-
laxation. It is now often called the Kohl-
rausch-William-Watts of KWW function
and, as we shall see, it emerges from a wide
variety of theoretical models of the glass
transition. If it is approximated by a sum of
exponential terms, as in Eq. (3-42),
exp
Hi k= l
p expl- (3-44)
the distribution of weighting factors varies
with the exponent /? as shown in Fig. 3-18.
To describe structural relaxation, typical
values of /? are in the range of 0.6 to 0.8
(Mazurin, 1977), whereas /?^0.5 for stress
relaxation (Rekhson and Ginzburg, 1976).
Although the KWW function has some
theoretical support, it does not provide a
perfect description of the relaxation func-
tion when the data cover several orders of
magnitude in t/xp, either for stress relax-
ation (Kurkjian, 1963), or structural relax-
ation (Scherer, 1986 a).
The nonexponential character of struc-
tural relaxation is most clearly illustrated
in a crossover experiment of the type
shown in Fig. 3-19. The sample is
quenched from temperature 7\ to T2 and
held there until the refractive index reaches
nd = a, which is the index of a liquid in
equilibrium at temperature Tx; thus, the
fictive temperature for the sample is now
Tf = Tx. Then the sample is immediately
transferred to a furnace at temperature Tx
and nd is measured as a function of time
3.4 The Glass Transition 143
0.6
-o.i
10' l(f 10°
l (x /T
°Sio p *>
Figure 3-18. Distribution of relaxation times obtained
when the KWW function is represented by sum of
exponential terms, as in Eq. (3-44); ft = 1 corresponds
to a single relaxation time. As p decreases the distri-
bution broadens, but always remains skewed to short
times.
(Fig. 3-19b). Since a -1.51493 is the equi-
librium index at that temperature we
would expect nd to remain constant, but it
clearly decreases (apparently moving away
from equilibrium) before relaxing toward
the equilibrium value. As noted by Ritland
(1954), this demonstrates that a glass with
a fictive temperature of Tf = Tx does not
necessarily have the same structure as a
liquid at equilibrium at Tx.
Macedo and Napolitano (1967) con-
cluded that the relaxation process must
consist of at least two processes that relax
exponentially: a fast process with relax-
ation time rf and a slow process with relax-
ation time TS. During the hold at T2, the
fast process relaxes almost to equilibrium
(C) while the slow process barely rises
above B, but the average of the two pro-
duces an index of a. When the sample is
exposed to Tx9 the fast process effectively
experiences a downward quench from
equilibrium at T2, while the slow process is
effectively up-quenched. The dashed lines
in Fig. 3-19 b represent the paths of these
two processes during the isothermal hold
at Tx9 and the solid curve shows their aver-
144 3 Glass Formation and Relaxation

a) *d

T
2

C C
\

i
a i \— 4 m a

B ( \ .i.
••-
TEMPERATURE TIME (t)

b) 1.51600
1
Fast component
75 - 1.51493 + .00103 exp( - tl 7.77)
i ^ ^

50 -
Figure 3-19. Scheme of crossover
t experiment used by Macedo and
25 _ i
*
Napolitano (1967). a) Sample
Z quenched from temperature T± to
O 1.51500 nd = a T2 shows instantaneous increase
P 1.51493 in refractive index from A to B,
followed by relaxation toward
1.51475 -
equilibrium at C; a is index of liq-
w uid at equilibrium at Tx. When in-
Pi
+' \ Average Calculated
50 --
** Curve
dex reaches a, sample is trans-
ferred to furnace at Tx and change
t
25 .
in index with time is followed,
b) Refractive index (sodium d-line)
^pp S/ow component versus time at Tx (o); solid curve
1.51400 -
4
1.51493 - 0.0111 exp (- tl 64.4) is average of two dashed curves
t with relaxation times of rf = 7.77
1.51375 and TS = 64.4 minutes.
0 30 60 90 120 150 180

TIME (MINUTES)

age (assuming that each process con- 3.4.2 Thermodynamic Aspects

tributes equally to the refractive index).
Note that both processes approach di- Fig. 3-20 illustrates a phenomenon that
rectly toward equilibrium, but their aver- is called the Kauzmann paradox. Kauz-
age value moves away and then returns. If mann (1948) noted that the configuration
the relaxation process were simply expo- entropy (Sc)-of the equilibrium liquid de-
nential, the index could not move away creases so strongly with temperature that it
from equilibrium. would fall below the entropy of the cor-

Equilibrium
liquid
s which freezes the configurational
d entropy. This apparent coinci-
responding crystal if extrapolated below
temperature TK. This unacceptable situa-
tion is prevented by the glass transition,
which freezes the configuration and "locks
in" Sc at a value characteristic of the equi-
librium liquid at Tg. What is disturbing is
that the thermodynamic catastrophe is ap-
parently prevented by the coincidental in-
tervention of a kinetic phenomenon - the
glass transition. Moreover, the interval be-
tween the Kauzmann temperature (TK) and
Tg is often quite small, even at moderate
cooling rates (Angell, 1988), so one could
imagine cooling at such a slow rate that Tg
would drop below TK. Kauzmann (1948)
suggested that crystallization would always
occur before TK, but that does not seem to
be true in every case (Angell et al., 1986).
Various theories propose that the reduc-
tion in Sc is arrested by thermodynamic
phase transitions of first order (Grest and
Cohen, 1981) or second order (Gibbs and
DiMarzio, 1958), while Stillinger (1988) ar-
gues plausibly that no phase transition is
likely. The existence of a phase transition
must be regarded as an open question, but
it is clear that an adequate theory of the
glass transition must provide a resolution
for this paradox.
3.4 The Glass Transition 145
Figure 3-20. The configurational
entropy of the equilibrium liquid
is dropping so fast that the en-
tropy would fall below that of the
crystal at temperatures < TK. This
thermodynamic catastrophe is
averted by the glass transition,
dence (i.e., a kinetic escape from a
thermodynamic problem) is called
the Kauzmann paradox.
Davies and Jones (1953) considered the
thermodynamic implications of having a
single order parameter, such as Tf, that de-
termines the state of a glass. They showed
that the Prigogine-Defay ratio,
must have a value of unity if only a single
order parameter exists. In Eq. (3-45), Acp is
the difference in heat capacity between the
equilibrium liquid and the glass, and Ax
and A a are the corresponding differences in
isothermal compressibility and volumetric
thermal expansion coefficient, respectively;
Vm is the molar volume. Data collected by
Moynihan and Lesikar (1981) indicate that
nTP has a value of ~ 2-5 for a variety of
glass-forming liquids, so none can be char-
acterized by a single order parameter.
Gupta (1988 a) suggested that the fictive
pressure could be used as a second order
parameter. Irreversible thermodynamics
can be used to develop a theory of relax-
ation based on the existence of an arbitrary
number of order parameters (Moynihan
and Gupta, 1978; Berg and Cooper, 1978).
These models (discussed in Section 3.4.3.2)
lead to a relaxation function in the form of
146 3 Glass Formation and Relaxation
a sum of exponential terms, so they can be
made to agree with experimental observa-
tions; unfortunately, the theory offers no
clue as to the nature of the order parame-
ters, nor the temperature dependence of
the relaxation times.
3.4.3 Theories of Relaxation
A wide variety of theories of relaxation
have been developed based on distinct mi-
croscopic models, and only a few of the
more important ones are presented here.
This material is drawn from a more exten-
sive review by Scherer (1990). It is conve-
nient to categorize theories of relaxation as
rheological models, which predict the tem-
perature-dependence of the relaxation time
(zp), kinetic models, which describe the form
of the relaxation function (Mp), and relax-
ation models, which endeavor to explain
both. The principal features that a com-
plete theory must explain are nonlinearity
(i.e., dependence of xp on structure) and
nonexponentiality. The latter property is
well described by the KWW equation,
Eq. (3-43), and there is now an astounding
number of models based on different phys-
ical principles that lead to that expression.
Theorists have exploited two means of ob-
taining nonexponential relaxation: requir-
ing cooperative relaxation or invoking
heterogeneity (distributions of density or
energy, or randomly situated acceptor/do-
nor sites). In real glasses, both these factors
are likely to be important, particularly
near Tg, and a few theories have attempted
to embrace both. Phenomenological models,
which make no assumptions about the
molecular-scale processes involved in re-
laxation, are discussed in detail in Section
3.4.4.
3.4.3.1 Rheological Models
As indicated by Eq. (3-38), the relaxation
time is proportional to the viscosity, so
models for xp are equivalent to models for
rj. That is why the term "rheological" is
used to describe theories that account for
the temperature dependence of xp. One of
the most famous of these is the free volume
theory developed by Cohen and Turnbull
(1959, 1961, 1970). The idea is that flow
occurs by movement of molecules into
voids of a size greater than some critical
size. That is, the molecules rattle around in
the cage created by the surrounding
molecules, until density fluctuations create
a hole large enough to jump into. The free
volume (v{) is somewhat vaguely defined,
but it represents roughly the space not oc-
cupied by the core volumes (v0) of the
molecules. According to this model the vis-
cosity can be written as (Scherer, 1984 a)
(3-46)
TJ(a,-a )dr
g
where y is a constant (close to unity), Tfv is
the fictive temperature for the volume, To is
the temperature where v{ = 0, and oq and ocg
are the expansion coefficients for the liquid
and glass, respectively. The free volume de-
pends on the actual atomic configuration,
rather than the equilibrium configuration,
so v{ is written in terms of the fictive tem-
perature, rather than the actual tempera-
ture. At equilibrium (T{ = T), if al — ocg is
constant, Eq. (3-46) reduces to the empiri-
cal Vogel-Fulcher-Tamman (VFT) equa-
tion:
(3-47)
T-Tn

where rj0, A, and To are constants. The
VFT equation is the most successful 3-pa-
rameter expression for describing r\ (T).
In a liquid out of equilibrium, it is clear
that Eq. (3-46) can account for nonlinear-
ity, since it implies that TP = TP(T{). How-
ever, it fails to explain experiments of the
sort represented in Fig. 3-21. In addition to
measuring the equilibrium viscosity, Ma-
zurin et al. (1979, 1981) have measured the
isostructural viscosity: the sample is equili-
brated at a high viscosity, then quenched
to a slightly lower temperature where the
viscosity can be measured before a signifi-
cant amount of relaxation occurs; thus,
they obtain the temperature dependence of
rj when Tf is constant. The measurements
made on a variety of oxide glasses indicate
that the isostructural viscosity obeys the
Arrhenius equation,
AE
(3-48)
where Rg is the ideal gas constant and AE is
an activation energy. The equilibrium vis-
cosity obeys the VFT equation, Eq. (3-47),
and the concave form of that curve corre-
sponds to an apparent activation energy,
AEA(T% that increases as the temperature
decreases. Typically, the isostructural acti-
vation energy is about half of AEA(Tf).
Note that Eq. (3-46) indicates that rj is con-
stant when Tf is constant, so it cannot ac-
count for the isostructural data. The free
volume model also fails to predict the
change in Tg with applied pressure (Gold-
stein, 1963; Angell and Sichina, 1976). Re-
cent developments of the free volume the-
ory that correct some of these defects are
discussed in the section on relaxation mod-
els.
An entirely different picture of viscous
flow, developed by Adam and Gibbs
(1965), traces its motivation back to Kauz-
mann (1948). Gibbs and DiMarzio (1958)
3.4 The Glass Transition 147
17
NBS 710
16 ISOSTRUCTURAL /
Tf =522X1
15
14
1 13
o
11
10
10 12 13 14 15
io4/r(K)
Figure 3-21. Viscosity of soda-lime-silicate glass NBS
710 under equilibrium (Tf = T) and isostructural
(T{ = constant) conditions measured by Mazurin et al.
(1979). Isostructural data obtained by equilibrating at
very high viscosity (10 135 Pa s) then quenching and
measuring f]{T) before significant structural relax-
ation could occur. Curves calculated using Adam-
Gibbs model for viscosity (Scherer, 1984 a).
presented a statistical mechanical theory
that predicted a second order phase transi-
tion at the Kauzmann temperature TK to
an ideal glass with configurational entropy
(Sc) equal to zero, thus avoiding the ther-
modynamic catastrophe. This transition
cannot be observed in practice, because TK
lies below Tg, so the laboratory glass tran-
sition is merely a kinetic manifestation of
an unattainable thermodynamic transi-
tion. Adam and Gibbs (AG) argued that
the increase in viscosity as T-> Tg could be
attributed to the loss of configurations
available to the liquid. Their model is
based on the idea that relaxation requires
cooperative rearrangement of a group of z
molecules. As the temperature drops and
148 3 Glass Formation and Relaxation
the liquid becomes denser, movement of
one molecule disturbs an increasingly large
number of its neighbors; i.e., z increases as
T decreases. AG assumed that the barrier
to rearrangement increased in proportion
to z (AE = z A\x, where zl^u is the potential
barrier per molecule hindering rearrange-
ment), and determined the temperature de-
pendence of z in terms of S c . Their result is
, = T0 exp (3-49)
where S* is the configurational entropy of
the smallest cooperatively rearranging sub-
system (CRS); it is generally assumed that
the latter must contain 2 configurations, so
S?^/c B ln2.
Eq. (3-39) has several appealing features.
First, it provides an escape from the Kauz-
mann paradox: even if there is no phase
transition, Sc can never fall below zero, be-
cause xp diverges as that point is ap-
proached; thus, even in an infinitely long
experiment, Sc = 0 can only be approached
asymptotically. In fact, to avoid the para-
dox it seems inevitable that either there is
a phase transition or the relaxation time is
a function of S" 1 , or both. Second, it is
clear how the relaxation time (or viscosity)
depends on the fictive temperature, since
we can write (Howell et al., 1974; Scherer,
1984 a)
fH
Ac
(3-50)
1
TV
where Acp = cpl — cpg; we have assumed
that Sc(TK) = 0 and that the configura-
tional entropy is governed by the fictive
temperature of the enthalpy, H. At equilib-
rium we can approximate (Angell and
Sichina, 1976) Acp ^const/7; so that Eqs.
(3-49) and (3-50) lead to the VFT equation,
Eq.(3-47), with To identified with TK. This
is consistent with the observation that the
value of To found empirically is often close
to the Kauzmann temperature (i.e., the
temperature where Sc extrapolates to zero).
If TfH is constant, then so is S c , and Eqs.
(3-38) and (3-49) yield Arrhenius behavior
for the isostructural viscosity. In fact, the
curves shown in Fig. 3-21 for both the
equilibrium and isostructural viscosity
were calculated from the AG equation.
In addition to its ability to reproduce the
form of rj (T), the AG equation is much
more successful than the free volume
model at predicting the effect of pressure
on Tg (Goldstein, 1963; Angell and Sichina,
1976). Gupta (1987) has shown that it is
also in qualitative accord with the observa-
tion that some liquids decrease in viscosity
when subjected to compressive pressure
(Sharma et al., 1979; Mysen et al., 1980;
Angell etal., 1982).
3.4.3.2 Kinetic Models
The order parameter model begins with
the assumption that the free energy (g) de-
pends on a set of order parameters (Zl9Z2,
... Zjy), in addition to T and P (Moynihan
and Gupta, 1978; Berg and Cooper, 1978).
The parameters Z- are not identfied with
specific physical characteristics, such as
free volume. According to the principles of
nonequilibrium thermodynamics, the rate
of relaxation may be written as
(3 51)
dAZt "
At j k
where we have defined the affinities
At = —dg/dZt, as well as AZi=Zi—Zie
(where Zie is the equilibrium value of Zt)
and atj = —dAJdZj. The constants L(j are
phenomenological transport coefficients,
equivalent to relaxation frequencies \/xk.
Eq. (3-51) leads to the following relaxation
function for the response of property p to a
change in variable x:
(3-52)

This approach leads to some important
conclusions about the nature of these re-
laxation functions; for example, MVT =
MHP 7^ MVP. That is, the relaxation of the
volume in response to a change in temper-
ature is different from its response to a
change in pressure, but is equivalent to the
response of the enthalpy to a change in
pressure. A particularly interesting version
of the order parameter model, introduced
by Gupta (1988 b), is based on the idea that
the free energy of the system is related to
the spatial gradients in the order parame-
ters. For a single parameter this leads to a
relaxation equation of the form
where T 0 and D are constants. Eq. (3-53)
leads to a continuous distribution of relax-
ation times for Z. This theme recurs in
many of the models discussed below: inho-
mogeneity in the structure of the liquid
gives rise to nonexponential relaxation.
A group of models based on the formal-
ism of chemical reactions is discussed in an
excellent review by Blumen et al. (1986).
One class of model involves direct transfer
of energy from a donor to an acceptor site.
If the sites are uniformly distributed, relax-
ation is found to occur by a simple expo-
nential decay; however, if randomness is
introduced into the structure through an
inhomogeneous distribution of sites, the
decay becomes nonexponential. Let the en-
ergy transfer rate w (r) depend on the dis-
tance r between donor and acceptor; ne-
glecting back-transfer, the probability of
decay of the donor at rD to an acceptor at
rA is
~rD)] (3-54)
and this leads to a relaxation function of
the form
M.(t,r D ) = ] 'jlf{t,rA,rD)y\ (3-55)
3.4 The Glass Transition 149
where g^ is the probability of having j ac-
ceptors at one site. For isotropic multipo-
lar interactions, the transfer rate is given by
w(r) = a lVs (3-56)
When this is used in Eq. (3-55), the relax-
ation function reduces to the KWW func-
tion, Eq. (3-43), with ft = d/s (where d is
the dimension of space) and xp = aj
[VdpQr(l-d/s)]s/d, where Vd is the vol-
ume of the unit sphere in d dimensions, p is
the concentration of acceptor sites, Q is the
density of sites, and F is the gamma func-
tion. If the sites are assumed to be distrib-
uted on fractals, the fractal dimension (df)
replaces d in the preceding results.
Another type of model assumes that
donors or acceptors make random walks
on a lattice and react instantly on meeting
(Blumen et al., 1986). This produces simple
exponential relaxation in 3 dimensions,
but the KWW function if the random walk
is performed on a fractal. Thus, the nonex-
ponential relaxation results in this case
from geometric randomness. Alternatively,
the randomness can be introduced by al-
lowing a distribution of waiting times be-
fore each step of the random walk, and this
also leads to nonexponential relaxation. In
hierarchical models, a diffusing particle
must surmount a series of barriers of
height 5; given an excitation AE=j5, the
particle can move among j levels. The ran-
domness introduced through the energy
levels leads to nonexponential relaxation
at low temperatures, but at high tempera-
tures where the particle can move freely
among the levels, the relaxation reverts to
simple exponential decay. This is consis-
tent with the relaxation behavior of real
liquids.
Ngai et al. (1986) have developed a cou-
pling model They assume that the system
consists of primary species with a relax-
ation rate Wo that controls the initial re-
150 3 Glass Formation and Relaxation
sponse to an impulse. After a characteristic
time (co ~ 1 ), coupling between the primary
species modifies the relaxation rate,
W{T,t):
<3 57)
^•"-V/KO"-. «:»i - figurations, rather than 2, as is often as-
The relaxation function is found from
dM p_ _
= -W(T,t)Mp (3-58)
dt
which leads to Eq. (3-43) with xp = \fia>l~p/
W0]1/fi. An example of the process envi-
sioned in this model is the relaxation of a
polymer, where the coupling comes from
entanglement of chains, which interferes
with the movement of a single chain only
after an initial lag (Ngai et al., 1988). This
model makes no assertions about the tem-
perature or structure dependence of the re-
laxation process. It has been applied to the
analysis of structural relaxation by making
additional assumptions about those fac-
tors (Rendell et al., 1987), but Rekhson
(1987) has challenged those assumptions.
3.4.3.3 Relaxation Models
Nonlinear, nonexponential relaxation
kinetics follow simply from the require-
ment that relaxation involve cooperative
movement. This is consistent with the
qualitative similarity seen in the relaxation
kinetics of every class of liquid. That is,
such behavior cannot be dependent on the
details of bonding or structure, but must
follow from some general phenomenon. A
particularly nice example of this idea is the
facilitated Ising model studied by Fred-
rickson and Brawer (1986) and Fredrick-
son (1986). Consider a set of Ising spins on
a square lattice that are subjected to a
magnetic field (h) that tends to make the
spins flip down. A spin is allowed to flip
only if two of its nearest neighbors are
"up", so the rearrangement is cooperative.
To establish a connection with real glasses,
the up and down spins could be imagined
to represent regions of high and low den-
sity, respectively. As shown in Fig. 3-22, the
smallest CRS in this model contains 4 con-
sumed in application of the AG model. The
rate (Wt) at which a spin at site i flips from
state ai to — o{ [where ot can be + 1 (up) or
- 1 (down)] is
where co is an attempt frequency and mt is
the number of neighbors in the "up" posi-
tion. Monte Carlo simulations of this
model indicate that it relaxes according to
Eq. (3-43), with /? decreasing slightly with
temperature. The relaxation time obeys
the the AG equation, Eq.(3-49) [the con-
figurational entropy is known exactly for
this model]. The latter result requires a
high degree of cooperativity: Fredrickson
(1988) has extended this model to three di-
mensions, allowing a spin to flip when n
neighbors are "up", and finds that the AG
equation applies when n = 3, but not when
n = 2. The beauty of the facilitated Ising
model is that it assumes only a simple form
of cooperativity, yet it reproduces the es-
sential features of relaxation in viscous
liquids.
\i
Figure 3-22. Smallest cooperatively rearranging sub-
system (CRS) in the 2-spin facilitated Ising model has
4 configurations, since spins a and b can both flip.

Brawer (1984) has developed a much
more specific model of relaxation that as-
sumes that a local region of the liquid must
be excited to a transition state with high
energy and low density before that region
can relax to a higher density. In this model,
the size of the CRS is assumed to be inde-
pendent of temperature. The most difficult
problem in analyzing such a model is ac-
counting for the overlap of the regions.
Suppose the CRS has a radius of 10 atoms:
then any single atom lies within ~ 103 such
regions centered on different neighboring
atoms, and it may participate in a rear-
rangement with any of those regions. This
problem was ignored in the derivation of
the AG equation. Brawer avoids it by lim-
iting consideration to the earliest stage of
relaxation (i.e., 1 — Mp<^ 1), when relatively
few regions have transformed and the effect
of overlap is negligible. The existence of
density (or energy) fluctuations in the fluid
produces a distribution of relaxation times,
because the regions in a higher state of
excitation relax first. The relaxation is non-
linear, because the distribution of energies
depends on the temperature history. Thus,
the model has all of the right features.
Cohen and Grest (1979) and Grest and
Cohen (1981) have developed a version of
free volume theory that involves percola-
tion of "liquid-like cells" (for a lucid discus-
sion of percolation, and its connection to
this theory, see Zallen (1983)). An atom vi-
brates in a cage in a solid-like manner un-
less the cage contains a sufficient amount
of volume (v > vc\ in which case it is called
liquid-like; free volume (vi = v — vc) is freely
exchanged between liquid-like cells. Diffu-
sion requires that vi exceed the molecular
volume (vm); a cluster in which v{ >vm is
liquid, rather than liquid-like. As the
amount of free volume increases, the num-
ber of liquid-like cells increases to the point
that a contiguous network (i.e., a percola-
3.4 The Glass Transition 151
tion cluster) appears, which gives macro-
scopic fluidity to the material. The free en-
ergy of the system is written explicitly in
terms of the communal entropy, which is the
contribution to the entropy resulting from
the freedom of atoms in liquid-like cells to
move within liquid clusters (i.e., it repre-
sents the accessible configurations of the
system). The communal entropy biases the
distribution of free volume so as to increase
the number of liquid-like cells and sup-
press solid-like cells. This leads to a discon-
tinuous change in the probability (px) of
liquid-like cells as the temperature is re-
duced, which corresponds to a first order
phase transition. The viscosity of the sys-
tem is still given by Eq. (3-46), but an ex-
plicit expression for v{ is obtained that has
a sufficiently complicated temperature de-
pendence (involving 3 parameters) to ac-
count fully for actual viscosity data. Since
the viscosity depends only on vf, this
model still does not account for the
isostructural viscosity.
The above mentioned model was ex-
tended (Grest and Cohen, 1980) to account
for structural relaxation by using Eq. (3-40)
with p = Pi and xp given by Eq. (3-46); this
allows for nonlinear exponential relax-
ation. Nonexponential behavior was ob-
tained by assuming (Cohen and Grest,
1984) that each cluster relaxes indepen-
dently at a rate proportional to its surface-
to-volume ratio (since relaxation involves
diffusion of volume across the boundary of
the liquid-like regions). This leads to a re-
laxation function in the form of Eq. (3-43).
3.4.4 Phenomenological Models
3.4.4.1 Tool's Equation
Phenomenological models (discussed in
detail by Scherer, 1986 b) have been devel-
oped that permit accurate calculation of
the changes in properties of liquids during
152 3 Glass Formation and Relaxation

arbitrary thermal cycles. Great success has

been obtained in the use of these models to
predict stresses in composites, such as
glass-to-metal seals, and in annealing and
tempering of glass, as explained in Section
3.5. The first important step in the develop-
ment of these models was taken by Tool
(1945, 1946), who proposed, by analogy to p(T2,t)
viscoelastic stress relaxation, that struc-
tural relaxation of property p should obey
pe(T)-p(T,t)
(3-60)
dt
where pe(T) = p(T,oo) is the equilibrium
value of the property at temperature T.
Consider the relaxation following an in- i2 if it
stantaneous jump from temperature 7\ to Temperature
T2. It is clear from Fig. 3-23 that the cur-
rent value of p can be written as Figure 3-23. Relaxation of property p following jump
from temperature Tx to T2; pe is the equilibrium value,
a} and ocg are the values of dp/dT in the liquid and
glassy states, respectively. The sample arrives at T2 at
a g (T 2 -T f (0) (3-61 a) time t = 0 and relaxes toward p(T 2 , oo) = pe(T2).

(3-61 b)
so Ritland (1954) showed that Eqs. (3-63)
(3-62) and (3-64) can be used to predict the effect
of cooling rate on Tg. The glass transition
temperature corresponding to cooling
With Eqs. (3-61 b) and (3-62), Eq. (3-60) can
rates q± and q2 can be shown to be related
be written in the form known as Tool's
by
equation:
(3-65)
1
(3-63) In
dt
Tool's most important contribution was or
the suggestion that the effect of structure dTa
(3-66)
be incorporated by writing the relaxation d\n\q\
time as Thus Tg increases logarithmically with the
, = T0 exp(-A1T-A2Tf) (3-64) cooling rate, a result that was experimen-
tally verified by Ritland (1954).
Although this formula lacks theoretical The principal weakness of Tool's theory
justification, it was found to be quite effec- is that it uses only a single parameter, Tf, to
tive in accounting for the nonlinearity of represent the state of the glass. Ritland
relaxation. (1956) was the first to perform a crossover

experiment of the type shown in Fig. 3-19,
and he did it to demonstrate that the struc-
ture is dependent on thermal history, so
that glasses with a given value of property
p (and hence a given Tf) are not struc-
turally identical. The problem was clearly
recognized, but was not resolved for an-
other 15 years.
3.4.4.2 Narayanaswamy's Theory
A major stride was taken by Nara-
yanaswamy (1971) who generalized Tool's
theory by allowing for a distribution of re-
laxation times. (An essentially identical
model was later proposed independently
by Kovacs et al., 1979.) He obtained the
following expression for the fictive temper-
ature:
(3-67)
0
where £ is the reduced time defined by
(3-68)
T
0 p
and xr is the value of i p at some reference
temperature. If the relaxation function is
represented by a single relaxation time, as
in Eq. (3-41), it can be shown (Scherer,
1986b) that Eq.(3-67) reduces to Tool's
equation, Eq. (3-63). Narayanaswamy
wrote the relaxation time in terms of the
Arrhenius equation as
xAE (l-x)AEl
,= T0 exp (3-69)
where x, the nonlinearity parameter, divides
the temperature dependence between the
temperature and fictive temperature. This
gives a better representation of the temper-
ature dependence off/ or TP than Eq. (3-64),
but still it is useful only over a limited
range of temperature (typically ~100°C
for a silicate glass). A function with the
3.4 The Glass Transition 153
form of the VFT equation, Eq.(3-47), is
needed to represent a wider temperature
interval.
If the relaxation function Mp is repre-
sented by Eq. (3-42), then the fictive tem-
perature can be decomposed into "partial
fictive temperatures" (PFT) (Rekhson,
1986; Scherer, 1986b)
Tf= f> f c T f f c (3-70)
where each of the Tfk relaxes in a simple
exponential manner with relaxation time
ik (i.e., they individually obey Tool's equa-
tion). This is formally equivalent to the or-
der parameter model described in Section
3.4.3.2, with each PFT representing an or-
der parameter. When there is more than
one, the Prigogine-Defay ratio, Eq. (3-45),
will be greater than unity, as is found ex-
perimentally. Rekhson (1986) has shown
how the crossover experiment can be un-
derstood in terms of the independent relax-
ation of the PFT. The measured property
value reflects the average Tf, but the ther-
mal history of the sample determines the
distribution of PFT, and many different
distributions can yield the same average.
The two relaxation processes indicated in
Fig. 3-19 b correspond to two partial fictive
temperatures.
Narayanaswamy's theory has been ex-
tensively tested [see e.g., Moynihan et al.
(1976 b), Mazurin (1977), and Scherer
(1986 b)] on many types of liquids, and it
displays all of the necessary features. Non-
exponentiality follows from use of Eqs.
(3-42) or (3-43) to represent the relaxation
function. The KWW function (introduced
in this context by Moynihan et al., 1976 a)
has been most useful, typically with 0.6 <
</?<0.8. Nonlinearity is expressed using
Eq. (3-69) with 0.4 < x < 0.6. The curves in
Fig. 3-17 were calculated in this way
(Scherer, 1986 a). A particularly striking ex-
154 3 Glass Formation and Relaxation

575
540
494

420
(a) 0 40 80 120 240 280 320
t (min)

4 8 12 16 20

78
(b) 0 40 80 120 160 200
t (min)

100

90

Figure 3-24. Calculated curves and

80 measured values (points) for change
in length of specimen of soda-lime-
silicate glass (Tg = 524 °C): a) ther-
mal history; b) isothermal holds at
70 494 °C (curve 1, lower time scale)
and 540 °C (curve 2, upper time
scale); c) entire thermal cycle. From
Mazurin et al. (1975).
(c) 400 450 500 550

ample of the success of this theory is pre- Experiments including temperature

sented in Fig. 3-24: part a shows the ther-
mal cycle, including cooling, reheating, and
isothermal holds; part b shows the relax-
ation during the holds; part c shows the
dilatometer curve for the entire cycle. The
calculated curves in parts b and c are in
excellent agreement with the data.
jumps, crossover, and continuous cooling
can all be modelled quantitatively in this
way, unless the range of temperatures ex-
amined is too broad. The origin of this
limitation is not certain, but the most likely
causes are (1) changes in the distribution of
relaxation times (or, equivalently, changes

in the exponent /? in the KWW equation)
with temperature, and (2) the narrow range
of applicability of the Arrhenius equation,
Eq. (3-69). The first problem has been ad-
dressed by several models (Mazurin and
Startsev, 1981; Scherer, 1986 a) but that
seems to be less important than using a
correct form for the relaxation time. A par-
ticularly effective modification (Scherer,
1984 a) is to represent xp by the Adam-
Gibbs equation, using Eqs. (3-49) and (3-50).
If, following Hodge (1987), we adopt the
approximation J C p ^ c o n s t / T suggested
by Angell and Sichina (1976), the relax-
ation time has the form
,=?0exp (3-71)
T(l-T K /T f )
At equilibrium, when T{ = % Eq. (3-71) has
the form of the VFT equation, Eq. (3-47),
with To identified with the Kauzmann tem-
perature, TK, so it can correctly represent
the shape of the equilibrium curve. Under
isostructural conditions (Tf = constant),
Eq.(3-71) has the form of the Arrhenius
equation, Eq. (3-48), in keeping with exper-
imental observations (see Fig. 3-21). In ad-
dition, Eq. (3-71) offers a theoretical foun-
dation for the incorporation of the fictive
temperature into rp9 and provides an ex-
pression for the nonlinearity parameter, x,
(Hodge, 1987):
: = 1-T K /T f (3-72)
As noted by Howell et al. (1974), the AG
equation is unique in that the parameters
that control the shape of the equilibrium
curve also dictate the slope of the isostruc-
tural curve. Hodge (1987) has found that
incorporating the AG equation into Nara-
yanaswamy's model gives a better fit than
Eq. (3-69) to the enthalpy relaxation of
polymers annealed far below Tg. In other
cases (Scherer, 1984 a, 1986 a; Opalka,
1987; Crichton and Moynihan, 1988) the
3.5 Viscoelasticity 155
fit is equally good with Eq. (3-49) or (3-69),
but the AG equation yields parameters
that have physically reasonable values
(e.g., pre-exponential factors with the cor-
rect order of magnitude). This version of
the theory also provides an excellent de-
scription of the nonlinear relaxation be-
havior of the facilitated Ising model (Fred-
rickson and Brawer, 1986).
Moynihan et al. (1974, 1976 b) showed
that Eqs. (3.67) to (3-69) lead to an expres-
sion analogous to Eq. (3-66) for the depen-
dence of T on cooling rate, q:
dln(l/T g )
(3-73)
AE
Again, the shift in Tg with q depends on the
temperature dependence of the equilibrium
viscosity. Based on numerical evaluation
of Eq. (3-67) with xp given by the Adam-
Gibbs equation, Scherer (1984 a) con-
cluded that the shift could be written in the
general form
dln(T.)
iL — (3-74)
Narayanaswamy (1988) has presented a
rigorous analysis of the implications of
Eq. (3-67) for the shift of Tg with q. The
expressions derived by Ritland (1954) and
Moynihan et al. (1974, 1976 b) were shown
to be exact, regardless of the form of the
relaxation function. Narayanaswamy finds
that Eq. (3-74) is not exact, although it is
numerically accurate.
3.5 Viscoelasticity
The theory of viscoelasticity is presented
in several texts, so only the essential ele-
ments are reviewed here. A mathematically
rigorous treatment of viscoelasticity (VE) is
given by Christensen (1982). A more read-
able discussion, with the emphasis on or-
156 3 Glass Formation and Relaxation

2e

a) c)

Figure 3-25. Modes of deformation of a unit cube: a) pure shear causes change of shape without change of
volume; b) triaxial stress causes change of volume and, if the normal stresses are not all equal, change of shape;
c) under uniaxial stress, the Poisson effect causes a strain in the directions normal to the applied stress, ex = —vaz.

ganic polymers, is provided by Ferry stress is applied, as in Fig. 3-25 b, there is a

(1961). Scherer (1986b) presents the theory volumetric strain (e) given by
of VE, and shows how it can be combined
AV
with Narayanaswamy's theory of struc- (3-76)
tural relaxation (1971) to calculate thermal
stresses. This section is based on that book. which is related to the hydrostatic (or di-
latational) stress (a) by
3.5.1 Elasticity, Stress Relaxation
and Creep (3-77)

3.5.1.1 Elasticity where

The mathematical relation between
stress and strain is called a constitutive
equation. For an isotropic elastic material,
such as glass, the constitutive equation re-
quires only two parameters: the shear mod-
ulus (G) and bulk modulus (X), or Young's
modulus (E) and Poissorfs ratio (v). A pure
shear stress (Fig. 3-25 a) causes a change in
shape without any change in volume, and
the strain is related to the stress by
azx = 2Gszx
The subscripts on atj and e^- indicate that
axis i is normal to the plane on which the
stress acts, and the stress acts in the direc-
tion of axis j ; for shear, i # j . When triaxial
(3-78)
By definition, tensile stresses are positive;
pressure (P) obeys the opposite sign con-
vention, and is defined by
P=-(crx + ay + oz)/3 (3-79)
If the stresses (ax, oy,oz) are not all equal,
there is a change in shape as well as vol-
ume. For example, when the stress is uni-
axial (Fig. 3-25 c), the stress and strain are
related by
(3-75)
az = Esz (3-80)
In this case the stress can be shown to be
2/3 shear and 1/3 dilatation. The axial
compression causes the cube to expand in
 3.5 Viscoelasticity 157

the x and y directions; this is called the

Poisson effect, and the strains are related
by
8x = 8y = -V8z (3-81)

For a general state of stress, the elastic con-

stitutive equations can be written as (Ti-
moshenko and Goodier, 1970)
a)
1
(3-82 a) Figure 3-26. Mechanical models of viscoelastic relax-
~E ation: a) the Maxwell element consists of a spring,
1 corresponding to the elastic shear modulus G, and a
(3-82 b) dashpot (representing a piston moving through oil),
corresponding to the shear viscosity \\\ b) dilatational
relaxation is most simply represented by a spring,
(3-82 c) corresponding to the elastic bulk modulus K, in series
with a Voigt element, which consists of a spring in
The constitutive parameters are interre- parallel with a dashpot; the spring in the Voigt ele-
ment limits the amount of volumetric contraction.
lated as follows:

(3-83 a) and the dashpot contributes the viscous

3(l-2v) flow. The compliance of this element is
E (3-83 b) given by
2(1
. , 1 t
9KG IT (3-85)
E= (3-83 c)
3K + G
If the viscosity is infinite (a fair approxima-
3K-2G (3-83 d) tion to the glassy state), the response is
v = 2(2K + G) purely elastic (J1 = 1/2G); but if the viscos-
ity is low, the elastic strain is negligible
3.5.1.2 Creep and Stress Relaxation compared to the viscous strain. From Eqs.
(3-84) and (3-85) it is clear that the viscous
Stress causes flow of a viscoelastic (VE) strain is comparable to the elastic strain
material, so the constitutive parameters when t = z, where T is the Maxwell relax-
are functions of time. For instance, when a ation time,
constant shear stress is applied, the shear
strain is (3-86)
6» = <f«A(t) (3-84) If the Maxwell element is subjected to a
constant strain, the stress relaxes accord-
where J1 is the shear compliance; the re-
ing to
sponse of a VE material to a constant
stress is called creep, so J t is also called the tfz* = G«GiW (3-87)
creep compliance. The simplest model for
where the shear relaxation function is given
viscoelastic behavior is the Maxwell ele-
by
ment shown in Fig. 3-26 a. The spring pro-
vides the instantaneous elastic response G1(t) = 2Ge-«t (3-88)
158 3 Glass Formation and Relaxation
At the instant that the strain is imposed,
G1 (0) = 2 G, so Eqs. (3-87) and (3-88) indi-
cate that the initial stress is the same as
that in the purely elastic material, Eq.
(3-75); the stress then decreases to zero as
the sample flows in the direction of the
applied stress.
A VE material also relaxes under a
purely hydrostatic load, but the volume
cannot change very much, so the stress
generally cannot relax to zero. When a
constant hydrostatic stress is applied, the
volumetric strain is given by
\ = aJ2(t) (3-89)
where J 2 (0 *s the dilatational compliance.
The simplest mechanical model represent-
ing dilatational relaxation is shown in Fig.
3-26 b. The compliance of this model is
1
(3-90)
3KD
where the dilatational relaxation time is
given by
xD = rjD/3KD (3-91)
Note that the viscosity that controls vol-
ume relaxation is not necessarily the same
as the shear viscosity; experimental evi-
dence indicates that rjD is several times
larger than r\, but has the same tempera-
ture dependence.
These simple mechanical models faith-
fully represent the essential features of VE
response, but the behavior of actual mate-
rials is more complex in detail. The shear
relaxation function of oxide glasses must
be represented by a distribution of relax-
ation times (which could be represented by
a group of Maxwell elements in parallel),
N
( t
} E wk exp - (3-92)
or the KWW function,
G1(t) = 2 G e x p \ - l - (3-93)
DeBast and Gilard (1963) showed that
Eq. (3-93) gave a very good representation
of the relaxation behavior of a soda-lime-
silicate glass, and Rekhson and Ginzburg
(1976) showed stress relaxation in a wide
variety of glasses could be described by
Eq. (3-93) with /? = 0.5. This is only a good
approximation, however, and very precise
data cannot be adequately fit by Eq. (3-93).
For example, Kurkjian's data (1963) for
shear relaxation in a soda-lime-silicate
glass require Eq. (3-92) with N = 6.
The shear compliance of an oxide glass
is given by
where 4>l (t) is a function that can be repre-
sented by a sum of exponential terms or
the KWW function; thus, ^ ( 0 ) = ! and
0i (0 -~* 0 at t -> oo. Even when Gt and cj)1 (t)
are both given by the same functional
form, the relaxation times for relaxation
and creep are not related in a simple way.
The most convenient way to calculate G±
from Jx, or vice versa, is to use the Laplace
transform (Scherer, 1986 b). The second
term in Eq. (3-94) describes the delayed
elastic strain and Gd is the delayed elastic
shear modulus.
The three contributions to the shear
strain can be understood schematically as
follows. When the stress is first imposed,
the instantaneous elastic response results
from bond stretching with no change in the
configuration of the molecules; the delayed
elastic response results from gradual dis-
entanglement of chains or clusters of mole-
cules; viscous flow occurs as those struc-
tural elements slide past one another.

When the stress is removed, the bonds
immediately snap back to their natural
length, so the elastic strain is recovered in-
stantly. The delayed elastic strain is also
completely recovered as the structure re-
turns to its equilibrium configuration; this
requires about the same period of time as
the strain took to develop. The viscous
strain does not recover.
The dilatational compliance of an oxide
can be written as
z w 4>Z2V{t)] (3-95)
3K 3K D L " /J
where 4>2 (t) is a function that can be repre-
sented by a sum of exponential terms or the
KWW function. Corsaro (1976 a) showed
that the dilatational relaxation of B 2 O 3
could be described by using the KWW
function for (j)2 (t) with j8 = 0.60. The final
strain was about three times greater than
the instantaneous elastic strain, J2(ty/
j 2 (oo) = 0.30. He further showed (Corsaro,
1976 b) that, because of the nonexponential
nature of the relaxation, the crossover ef-
fect (discussed in Section 3.4.1.5) could be
produced by subjecting a sample to a series
of pressure jumps.
Since the dilatational modulus relaxes to
a substantial fraction (typically ~ l / 3 ) of
its original value, while the shear modulus
goes to zero, it is not surprising that the
relaxation of uniaxial or biaxial stresses is
dominated by the shear behavior. For ex-
ample, for a material whose shear response
is given by Eq. (3-88) and which exhibits no
dilatational relaxation at all (J 2 = 1/3K),
the response to a constant uniaxial strain &z
is (Scherer and Rekhson, 1982 a)
-t/Tu (3-96)
Thus, shear deformation allows the uniax-
ial stress to relax to zero even though the
stress is partially hydrostatic. The uniaxial
relaxation time, TU , exceeds the shear relax-
3.5 Viscoelasticity 159
ation time only by a factor of 3/2 (1 + v) «
1.2. For purposes of stress analysis, the di-
latational relaxation can be entirely ig-
nored, unless the sample is triaxially con-
strained, in which case shear deformation
is inhibited.
3.5.1.3 Viscosity
It can be shown that the shear viscosity
is related to the shear relaxation function
by
(3-97)
where x is an average relaxation time. If Gx
is given by Eq. (3-92)
(3-98)
k =1
and if Gx is given by Eq. (3-93) (DeBast and
Gilard, 1963),
(3-99)
where F is the gamma function. Compar-
ing Eqs. (3-86) and (3-97) we see that the
Maxwell relaxation time is the average re-
laxation time for the glass. Indeed, experi-
mental studies confirm that the viscosity
obtained from direct measurements (i.e., in
creep experiments) agrees with the values
found by integrating stress relaxation data,
according to Eq. (3-97). Comparing Eqs.
(3-38) and (3-97) we see that the structural
relaxation time and the stress relaxation
time are proportional to one another, but
experiment (Rekhson, 1975) indicates that
Kp is about an order of magnitude smaller
than G, so stress relaxation is a much faster
process. This is what makes it possible to
measure the isostructural viscosity (Ma-
zurin et al., 1979): a measurable amount of
creep occurs before structural relaxation
produces a significant change in 7^.
160 3 Glass Formation and Relaxation
From Eqs. (3-84) and (3-94) it can seen
that the shear strain rate in a creep experi-
ment approaches the limit
(3-100)
If the applied stress is uniaxial (as is typi-
cally the case) rather than pure shear, the
corresponding relation is
(3-101)
At 3rj
Thus, the viscosity can be measured from
the slope of a plot of strain versus time; it
is only necessary to wait until the delayed
elastic strain is fully developed. Oxide liq-
uids exhibit Newtonian viscosity, which
means that the viscosity does not depend
on the magnitude of the stress that is ap-
plied. This also means that the relaxation
time governing stress relaxation and creep
is independent of the applied stress, so ox-
ides are linearly viscoelastic. This is in con-
trast to the nature of structural relaxation
in the same materials: the rate of structural
relaxation depends on the size and direc-
tion of the temperature jump; the stress
relaxation rate is the same for tensile or
compressive stresses.
Actually, this is only approximately
true: if the stress is large enough to affect
the structure of the liquid significantly,
nonlinear effects appear. However, the
stresses required to produce nonlinearity
are large: for a soda-lime-silicate glass it
can be shown (Scherer, 1986 b) that a pres-
sure of 12MPa is thermodynamically
equivalent to a temperature change of 1 °C.
Nonlinearity is evident following tempera-
ture jumps of ~ 5 °C, so the same should
be expected under applied pressures
>60MPa. Indeed, Simmons et al. (1982)
found non-Newtonian behavior under ten-
sile stresses of that magnitude. Li and
Uhlmann (1970) showed that alkali silicate
glasses exhibited non-Newtonian behavior
under shear stresses exceeding ~ 100 MPa.
In both cases, the viscosity decreased by an
order of magnitude or more. This is consis-
tent with molecular dynamics calculations
which indicate that catastrophic changes
in the structure of liquids occur under high
stresses: the atoms arrange into layers that
slide relatively easily. Particularly interest-
ing effects are observed under purely hy-
drostatic loads. It is expected (intuitively,
and particularly where the free volume
model applies) that hydrostatic compres-
sion will increase the viscosity.
However, Sharma et al. (1979) found
that the viscosity of GeO 2 decreases under
high compressive loads. It is known
(Mysen et al., 1980) that network silicates
exhibit this behavior when the average sili-
con atom has less than one nonbridging
bond. Thus, highly modified networks,
such as Na 2 O • SiO2 (with two nonbridg-
ing bonds per Si), show "normal" behavior
(viz., rj increasing with pressure), but ger-
mania (with no nonbridging bonds) does
not. This experimental result is supported
by molecular dynamics calculations (An-
gell et al, 1982).
3.5.2 Temperature Dependence
The rates of relaxation and creep are
strongly temperature-dependent. We first
examine how the VE response varies in
isothermal experiments at various temper-
atures, when the liquid remains in thermo-
dynamic equilibrium during the experi-
ment. Then we consider cases in which
structural relaxation and stress relaxation
occur simultaneously.
3.5.2.1 Equilibrium Liquid
Since the relaxation time is proportional
to the viscosity, the rate of stress relaxation
increases rapidly with temperature. For ex-
 3.5 Viscoelasticity 161

ample, if a constant shear strain is applied
to a glass, the shear relaxation function
varies with temperature as shown in Fig.
3-27. If the data are plotted against log £, as
in Fig. 3-27 b, curves for different tempera-
tures are identical in shape, but shifted
along the abscissa. The distance, which we
shall call log [#(71)], between points A and
B is the same as that between points D and
E. If the data for temperature 7\ are plot-
ted against log t + log [a (T±)] = log [t a {T±)]9
they coincide with the data for temperature
T2. Similarly, if we call the (negative) dis-
tance between points C and B log[a(T 3 )],
and plot the data for T3 against log [t a (T3)],
those data coincide with the other sets. In
this way the shift function, a(T\ can be
used to create a single master curve from
all the data. This is possible for any materi-
als whose relaxation function retains the
same shape at all temperatures when plot-
ted against \ogt. A material that exhibits
this behavior is said to be thermorheologi-
cally simple (TRS).
In terms of Eq. (3-92), TRS behavior is
obtained when all of the relaxation times
have the same temperature dependence
(xk oc t] for all h) and the weighting factors

0.8

a) 25

0.8 -

0.6 -

2G
0.4 -
Figure 3-27. Shear stress relax-
ation function of thermorheologi-
0.2 - cally simple material at several
temperatures: a) relaxation rate
increases with temperature;
0 1 i i b) when plotted versus log t, the
b) 0.001 0.01 0.1 1 10 100 curves have the same shape, but
log t are shifted along the abscissa.
162 3 Glass Formation and Relaxation
are constant [w k ^w k (T)]t. If the relax-
ation function is represented by Eq. (3-93),
TRS requires that the exponent /? be inde-
pendent of temperature. In either case, the
shift function represents the temperature
dependence of the average relaxation time,
(3-102)
where, Tr is the reference temperature, the
temperature of the data set onto which all
of the others are shifted. In relaxation stud-
ies it is conventional to introduce the re-
duced time,
(3-103)
When T= TT, then £ = t; in general, £ is the
time that would be required at Tr to relax
to the same extent that occurs in time t at
temperature T.
Thermorheological simplicity was first
noted by Leaderman (1943) in a study of
organic polymers, and has been widely ob-
served in oxides (see discussion in Scherer,
1986 b). It must be recognized that TRS is
only approximately true: the distribution
of relaxation times seems to become nar-
rower at temperatures well above Tg. How-
ever, for oxides, TRS provides an excellent
approximation at least within + 50°C of
Tg, and this proves to be very helpful in
analysis of thermal stresses, as we shall see
in Section 3.5.3.
3.5.2.2 Nonequilibrium Liquid
Hopkins (1958) pointed out that non-
isothermal stress relaxation in a TRS mate-
t In principle, each of the relaxation times could have
different temperature dependence and the weighting
factors could change in such a way that the relaxation
function retains the same shape. This seems improba-
ble.
rial could analyzed by writing the reduced
time in the form
At1
= \a[T(t')]dt' (3-104)
o
and replacing t with I; in the stress relax-
ation functions. During an isothermal test,
£/T (Tr) = t/z; if T= Tr, then £ = t. This is
an inescapable consequence of TRS of
equilibrium liquids; however, it is not obvi-
ous that TRS will hold if the changing tem-
perature causes the liquid to drift out of
equilibrium. That is, the form of the relax-
ation function might change under non-
equilibrium conditions. This proposition
was tested in an ingenious experiment by
DeBast and Gilard (1963), in which they
measured structural relaxation and uniax-
ial stress relaxation simultaneously on the
same sample. The equilibrium relaxation
was found to obey
a At)
MO) -<-($] (3-105)
with /? = 0.54. Nonequilibrium experi-
ments were performed by equilibrating the
sample at T1? then changing the tempera-
ture (by ~30°C) to T2 and simultaneously
applying a load. Using measured values of
rj (t) and assuming TU OC rj, they could pre-
dict the course of relaxation using
The calculated curves were found to be in
excellent agreement with the relaxation
function measured following the tempera-
ture jump. A similar study Rekhson et al.
(1977) included changing loads as well as
changing temperature; using measured
values for rj (t% they obtained excellent
agreement between calculated and mea-
sured creep strains. Thus, TRS does apply
in nonequilibrium situations.
 3.5 Viscoelasticity 163

3.5.3 Calculation of Thermal Stresses
Thermal stresses are of great importance
in many applications of glasses, and the
magnitudes of those stresses are dependent
on both structural and stress relaxation.
We briefly review the analysis of stresses
caused by thermal expansion mismatch in
composites, such as glass-to-metal seals,
and the stresses that arise during rapid
cooling of a liquid as it transforms into a
glass. The origin of thermal stresses is il-
lustrated in Fig. 3-28. Let layers A and B
represent glass and metal components
of a composite that shrink by different
amounts when cooled by AT. The strains
efA and efB are the free strains that occur
if the materials are not bonded together;
for example, if aA is the linear thermal ex-
pansion coefficient of A, then efA = ocA A T.
When the layers are bonded together, then
cooled, they are obliged to contract by the
same amount, so the true strain, £A = £B, is
a weighted average of the free strains. In
this case, the true strain exceeds the free
strain in layer A, so it is forced into com-
pression, while layer B is stretched into
tension. This type of thermal stress results
from thermal expansion mismatch between
dissimilar layers, and is common in com-
posites.
Another type of thermal stress results
from temperature gradients within a com-
positionally uniform material; then layers
A and B are the same material, but their
free strains are different because each is
cooled (or heated) by a different amount.
This type of stress develops during rapid
cooling of a liquid; it is exploited to
strengthen glass objects by creating com-
pressive stresses at the surface in a pro-
cess called tempering (see Sec. 13.5.1). Such
stresses are relieved by heat treatments
near Tg, a process called annealing that al-
lows VE relaxation; mismatch stresses can-
not be removed by annealing, because new
stresses develop on cooling from the an-
nealing temperature.

Free Strain True Strain

A A A
£
fB

L L L L L L
a a a a a a
y y y y y y
e e e e e e
r r r r r r

A B A B A B

Initial Cooled Joined

Figure 3-28. Stress caused by mismatch in thermal expansion: when layers A and B are cooled, they tend to
contract by different amounts. The free strains, s{A and siB, are proportional to the thermal expansion coefficients
of the layers. When the layers are joined, as in a composite, the true strain is the same in each, and is a weighted
average of the free strains.
164 3 Glass Formation and Relaxation
3.5.3.1 Glass-to-Metal Seals
As a simple example of mismatch
stresses in composites, we consider the
sandwich seal shown in Fig. 3-29. To calcu-
late the stress we begin with the elastic con-
stitutive equations, modified to allow for
the free strain. These equations have the
form (Timoshenko and Goodier, 1970)
1
(3-107)
where the subscript i is G and M in the
glass and metal layers, respectively. The
symmetry of the problem requires that
ax = oy, and sx = 8y; since there is no con-
straint perpendicular to the faces of the
plates, az = 0. The force on the edge of each
plate is axi 11 w, and the net force across the
composite must be zero, so we require
^G'GW + ^MIMW = 0 (3-108)
The result is that the stress in the glass in
the plane of the plate is
J (^G-^ (3-109)
where
KG = (3-110)
and n is a weighting factor called the stiff-
ness ratio, given by
lr
n= (3-111)
EM
Thus, the stress depends on the difference
between the free strains in the layers. The
free strain is calculated from the setting
temper amre (Ts), the temperature below
which the glass behaves elastically, to
room temperature (TR). Typically such a
composite is joined at a high temperature,
where the glass layer flows readily, and
W2
Figure 3-29. Planar composite called a sandwich seal
consists of a plate of glass between two plates of metal
(or conversely); total thickness of glass and metal lay-
ers is /M and / G , respectively, and width of seal is w.
stresses develop as the temperature enters
the glass transition range. Choosing an ap-
propriate value for Ts is something of an
art, because the transition from liquid to
elastic behavior does not happen suddenly
at a given temperature, but develops con-
tinuously over a range of temperature. This
problem does not arise in the VE analysis
that we consider next.
A rigorous calculation of the stresses in
the sandwich seal can be obtained by start-
ing with the VE constitutive equations, but
they are complicated functions of time.
Fortunately, for TRS materials the VE
equations take on a simple form after ap-
plication of the Laplace transform, and
problems of thermal expansion mismatch
can be solved in a straightforward way
(discussed in detail in Scherer, 1986 b). If
the uniaxial stress relaxation function for
the glass is assumed to be given by Eq.
(3-96), then Eq. (3-109) is replaced by
(Scherer and Rekhson, 1982 b)
TR r t(TR) dr/-i
J
xG — KoJexp - 1 f-
•(a G -oc M )dT (3-112)
This differs from Eq. (3-109) in that the free
strain is calculated from the temperature

To where cooling starts, and the transition
from liquid to glassy behavior is controlled
by the relaxation time T G , given by
*G=WT4
T
" . , (3-H3)
[Calculations using a more realistic relax-
ation function for the glass lead to expres-
sions more complicated than Eq. (3-112),
but the average relaxation time for the
composite is still given by Eq. (3-113).] The
relaxation time for the composite depends
on the stiffness ratio (a fact first recognized
and explained by Rekhson and Mazurin,
1977) for the following reason. Suppose the
sandwich consists of a very thin glass layer
and thick metal layer, so that n is small. As
the composite cools and the glass begins to
stiffen, the larger metal component exerts a
high stress on the glass, and forces it to
flow, so the stress relaxes quickly. When n
is small the glass cannot resist flowing un-
der the force exerted by the metal until the
viscosity becomes very high. On the other
hand, if the glass layer is much thicker than
the metal (n is large), the metal cannot exert
much stress on the glass; then the glass
15 r-
10 20 30 40
lGl I seals, the elastic layer is
3.5 Viscoelasticity 165
barely flows at all, and the stress relaxes
slowly. This means that the effective setting
temperature for the composite depends on
ft, with Ts being lower when n is small,
Rekhson (1979) (with experimental as-
sistance from V. Ginzburg) studied the
stresses in a series of sandwich seals made
of the same materials, but with different
stiffness ratios, and obtained the remark-
able results shown in Fig. 3-30. Whereas
the elastic solution predicts that the stress
in the glass rises as the glass layer becomes
thinner (because the elastic layer forces it
to deform more), the data show the oppo-
site trend. The reason is that the stiffness
ratio controls the temperature at which the
glass stops flowing, so the setting tempera-
ture changes with n. The elastic analysis
provides no way to predict the magnitude
of this effect, so the stresses are calculated
assuming that Ts is independent of n. By
taking account of both structural relax-
ation and viscoelasticity, Rekhson (1979)
was able to predict the trend in stress with
stiffness ratio (see curve 1 in Fig. 3-30).
This result shows the importance of ac-
counting for viscoelastic behavior in ther-
mal stress analyses involving glass.
Figure 3-30. Stress in sand-
wich seal (<JXG) at room
temperature versus thick-
ness ratio of glass and elas-
tic layers (lG/lM), according
to experiment (circles) and
elastic solution, Eq. (3-109)
(curve 2). Curve 1 is calcu-
lated taking account of
both structural relaxation
60 and viscosity. In these
alumina. From Rekhson
(1979).
166 3 Glass Formation and Relaxation

10

Figure 3-31. Stress in sandwich seal (GXG) at room temperature versus stiffness ratio, n. VE analysis assuming
single relaxation time, Eq. (3-112), yields curve 1; assuming three relaxation times (a good approximation to the
measured relaxation function) yields curve 2. Both curves allow for structural relaxation in calculation of
expansion coefficient and relaxation time, and agree with measured stresses (circles). Curve 3 calculated from VE
analysis assuming three relaxation times, but ignoring structural relaxation.

When the VE analysis is used (Scherer
and Rekhson, 1982 b; Scherer, 1986 b), the
stresses are correctly predicted, as indi-
cated in Fig. 3-31. Curves 1 and 2 represent
VE calculations in which the uniaxial re-
laxation function of the glass is represented
by one or three exponential terms, respec-
tively, and they both give good agreement
with the measured stresses. Both curves
were calculated using Narayanaswamy's
(1971) theory to account for the effects of
structural relaxation on the thermal ex-
pansion coefficient and relaxation time.
Curve 3 is obtained from the three-term
relaxation function, but ignoring structural
relaxation, and it is seriously in error.
These results demonstrate two important
facts: 1) it is essential to allow for the VE
behavior of the glass to predict thermal
stresses with accuracy, but it is acceptable
to use a simplified expression for the relax-
ation function of the glass; 2) the VE anal-
ysis will be accurate only if proper account
is taken of structural relaxation.
3.5.3.2 Tempering
Tempering is a quenching treatment used
to impart strength to a glass by creating
high compressive stresses at the surface
of the body (see Sec. 13.5.1). We include a
brief discussion of tempering here, because
the magnitude of the residual stress is con-
trolled by viscoelastic and structural relax-
ation. The process is discussed in an ex-
cellent review by Gardon (1980). The re-
sidual stress distribution in a tempered
plate is approximately parabolic, with ten-
sion <rm at the midplane and compression
<JS « — 2 am at the surface; a tempered plate
of commercial window glass typically has a
surface compression of GS& —100 MPa.
 3.5 Viscoelasticity 167

The stored elastic energy in a tempered
plate is also beneficial in the event of frac-
ture, since it causes fragmentation into
roughly cubic pieces, rather than the blade-
like pieces created when an untempered
plate breaks.
Consider a plate of elastic material being
quenched from a high temperature by air
jets directed at its faces; as indicated in Fig.
3-32, a parabolic temperature distribution
develops. The origin of the stresses can be
understood from Fig. 3-28: B is the cooler
surface layer and A is the hotter interior of
the plate; the surface is stretched into ten-
sion, because the interior will not let it con-
tract freely. As the plate cools, the interior
and exterior both approach room temper-
ature (7^), so the differential strain disap-
pears and the stresses fade away. In a vis-
coelastic plate, if the initial temperature is
high enough, stress relaxation is so fast
that the temperature distribution becomes
established without creating any signifi-
cant stresses. However, as the plate cools it
becomes glassy, so that we have a stress-
free elastic plate containing a temperature
gradient (see Fig, 3-32 b, curve (2)), Sup-
pose that the surface is at temperature
Ts<Tg when the midplane is at Tg. As the
plate approaches room temperature, the
midplane contracts by an amount aG
(Tg — TR\ which is greater than the contrac-
tion aG(Ts— 7^) of the cooler exterior.
Therefore, the exterior is driven into com-
pression as the temperature equilibrates.
If the starting temperature is not high
enough to allow instantaneous relaxation
of stresses, some tension will arise at the
surface when cooling starts, as in the elastic
case, and this will reduce the residual com-

L:
(D and©
CD a n d ©
\ Tension
Compression

a) Elastic plate b) Viscoelastic plate

Figure 3-32. Stress distribution during quenching of a plate of (a) elastic or (b) viscoelastic material. The stress,
GZ (x), in the elastic plate is proportional to the parabolic temperature gradient, T(x), which is already parabolic
by the time the surface has cooled to temperature Tx; az disappears when the plate reaches room temperature,
TR (curve ®). In the viscoelastic plate, the stresses relax rapidly at high temperatures, so the temperature
distribution is established without creating any corresponding stress (curves © and (J)). However, as the plate
cools it solidifies; then as temperature becomes uniform at TR, the midplane contracts more than the surface,
resulting in residual compression (curve (3)).
168 3 Glass Formation and Relaxation

pression; in extreme cases, the transient'

5 (Annealed glass)
tension can cause fracture during cooling. 2.5U -
This effect is indicated in Fig. 3-33: the
maximum tempering is achieved only
when the starting temperature exceeds ^
o 2.512

~ 650 °C, where stress relaxation is too fast o

to allow significant transient stresses. If the a>

starting temperature is <550°C, the plate Q. 2.510L ._

behaves like the elastic material in Fig. U)
c
3-32, and no residual stress is obtained. <D
a
The preceding discussion ignored the in- 2.508 -- 2
\ \
fluence of structural relaxation during
quenching. In fact, the difference in cooling Density N N "Stress-Free" \
rate between the interior and surface of the 2.506 as temperecT density p2 J
P\
plate causes a gradient in fictive tempera- i i i i i i i i
0.5 0.5
X/X n

3000 -0.73 cm-

Heat transfer coefficient Figure 3-34. Density distributions in tempered glass
cal/cm 2 °Csec
2500
shown by heavy curves, average densities by thin hor-
izontal lines. Numbers identify specimens in order of
S increasing temper: 5, 4, 3, 1, 2; no. 1 represents com-
5 2000 mercial "full temper". Gardon (1978).

Ok

I 1500

ture, as well as true temperature. The mag-

1000
500
(natural convection)
500 600 700
Initial Temperature T'
Figure 3-33. Degree of temper is a photoelastic mea-
sure of the tension at the midplane of a plate. In this
study by Gardon (1965, 1980) it is shown to increase
with quenching rate (characterized by the heat trans-
fer coefficient), which increases the temperature gradi-
ent in the plate. If the starting temperature To is
> 650 °C, the parabolic temperature gradient is estab-
lished without significant stress, and the maximum
tempering stress is achieved; no tempering is possible
if T 0 <550°C, because the plate is elastic. Solid sym-
bols represent samples that cracked because of tran-
sient tensile stresses at the surface.
nitude of this effect is shown in Fig. 3-34: in
the tempered plate, measurements of re-
fractive index indicate that the density is
high near the surface, but when the plate is
broken into fragments to relieve the stress,
the opposite trend appears. In the unbro-
800
ken plate, the compressive stresses raise the
density of the surface, but when the stresses
are removed, the gradient in fictive temper-
ature is revealed; the higher Tf produced by
faster cooling at the surface corresponds to
a lower density.
Many models have been developed to
predict the development of tempering
stresses, and these are reviewed by Gardon
(1980). The first to correctly incorporate
viscoelastic effects was an analysis by Lee
et al. (1965), which assumed TRS behavior

in the glass. The result was
o-z(x,t) = 3 j
o
(3-114)
S f
7[sz(x,t')-aT(x,t )]df
where R (£) is a biaxial relaxation function,
the VE analogue of the quantity Ej
3 (1 — v). This is similar to the expressions
for stress in composites given in Section
3.5.3.1, except that the reduced time is a
function of position as well as time. The
stress relaxes more quickly where the tem-
perature is higher, and, since the stresses
through the plate must balance, relaxation
transfers the stress to the cooler layers.
Thus, the stress that develops in any one
layer is related to the stress development in
all of the others, and the calculation is
complicated. Narayanaswamy and Gar-
don (1969) compared the VE analysis, Eq.
(3-114), to experimentally determined
stresses, and found that it could success-
fully predict the transient stresses. Good
predictions of the final stress were obtained
only if the initial temperature was high, but
in that case most of the stress comes from
temperature equalization. Complete agree-
ment with experiment was obtained only
when Narayanaswamy (1978) included the
effect of structural relaxation on the ther-
mal expansion coefficient and stress relax-
ation time. As shown in Fig. 3-35, the stress
is seriously underestimated if volume re-
laxation is ignored; neglecting the effect of
structural relaxation on the viscosity is less
important. This is similar to the compari-
son of curves 2 and 3 in Fig. 3-31, where
accurate calculation of the stress in a com-
posite was shown to require consideration
of structural relaxation.
For geometries more complicated than a
plate, analytical solutions such as Eq.
(3-114) are generally not available. Fortu-
3.5 Viscoelasticity 169
500 600 700 800
Initial glass temperature 7^ (°C)
Figure 3-35. Effect of structural relaxation (SR) of
density and viscosity (or stress relaxation time) on
tempering stress calculated from viscoelastic model:
without SR (dashed curve A); with SR (solid curve);
structure dependence of viscosity suppressed (o,
curve B); structure dependence of density suppressed
(n, curve C). From Narayanaswamy (1978).
nately, finite element methods are now
available that allow for both structural re-
laxation (using Narayanaswamy's theory)
and viscoelasticity (see discussion in Sche-
rer, 1986 b). Burke (1981) has applied finite
element analysis to the problem of temper-
ing, and obtained results in good agree-
ment with the analytical result; the surface
compression was found to be 89% greater
when structural relaxation was incorpo-
rated in the calculation.
3.5.3.3 Annealing
Annealing is a process of controlled cool-
ing that allows reduction of residual ther-
mal stresses. For example, suppose a tem-
pered plate is held near Tg until Tf (x) = Tg
throughout the plate, so that the specific
volume has its equilibrium value every-
where. If the plate is then cooled slowly
enough so that no significant temperature
gradients develop, the essentially elastic
plate will arrive at room temperature with
no residual stress. This is particularly im-
portant for optical glasses, because resid-
170 3 Glass Formation and Relaxation
400
T(°C)
1 2 3
Time t (h)
ual stresses cause birefringence and inho-
mogeneity in refractive index. The effect of
a given heat treatment can be calculated
using the phenomenological theory devel-
opment by Narayanaswamy (1971), and he
discusses this application in a very good
review (1986). In the case of a plate, the
availability of an analytical solution allows
the use of variational methods to calculate
the optimal cooling schedule for annealing,
providing the minimum stress for a given
processing time (Narayanaswamy, 1981).
Particularly interesting effects occur
during annealing of composites, because
the glass contracts during structural relax-
ation, but the elastic component does not.
Therefore, structural relaxation causes the
mismatch stress to rise, and VE relaxation
Figure 3-36. Stress development
during (a) cooling (3°C/min) and
500 600
(b) annealing (4 h) of glass-to-
alumina sandwich seal using iso-
thermal holds at (1) 500 °C and
(2) 460 °C; inset shows strain ver-
sus temperature. Symbols are
measured stresses; curves were
calculated from VE analysis
(Rekhson, 1979; see also Scherer
and Rekhson, 1982 b).
concurrently tends to reduce the stress.
The results of this competition are illus-
trated in Fig. 3-36 by Rekhson's (1979)
data for a glass-to-alumina sandwich seal.
If the hold temperature is not far below Tg,
the volume change during structural relax-
ation is not large and is completed quickly,
and the rate of stress relaxation is relatively
rapid, so the stress decreases substantially
during the anneal (Fig. 3-36 a). At lower
hold temperatures the glass is so far from
equilibrium that the volume change accu-
mulates throughout the hold, and the slow
VE relaxation cannot eliminate the result-
ing stress; therefore, the net effect of the
annealing treatment is an increase in ten-
sion (Fig. 3-36 b). If the hold were main-
tained long enough, the stress would pass

through a maximum at 460 °C (when struc-
tural relaxation was complete), and the
stress would eventually relax to zero. In
some cases, the stress developed during
low-temperature annealing can cause frac-
ture of composites. However, judicious use
of annealing allows the stress in the com-
posite to be adjusted either upward or
downward.
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Rekhson, S.M. (1986), J. Non-Cryst. Solids 84, 68-
85.
Rekhson, S.M. (1987), J. Non-Cryst. Solids 95/96,
131-148.
Rekhson, S. M., Ginzburg, V. A. (1976), Sov. J. Glass
Phys. Chem. 2, 422-428 (Engl. transl.).
Rekhson, S. M., Mazurin, O. V. (1974), J. Am. Ceram.
Soc. 57, 327-328.
Rekhson, S.M., Mazurin, O. V. (1977), Glass Tech-
nol. 18, 7-14.
Rekhson, S.M., Bulaeva, A.V, Mazurin, O.V.
(1971), Sov. J. Inorg. Mater 7, 622-623 (Engl.
transl.).
Rekhson, S. M., Gonchukova, N. O., Chernousov,
M. A. (1977), Proc. Xlth Int. Cong. Glass, Prague,
Vol.1, 329-338.
Rendell, R. W, Ngai, K. L., Fong, G. R., Aklonis, J. J.
(1987), Macromolecules 20, 1070-1083.
Ritland, H.N. (1954), J. Am. Ceram. Soc. 37, 370-
378.
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406.
Rowlands, E.G., James, P.F. (1979), Phys. Chem.
Glasses 20, 1-8.

Scherer, G.W. (1977), /. Am. Ceram. Soc. 60, 236-
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Scherer, G.W. (1984a), /. Am. Ceram. Soc. 67, 504-
511.
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Scherer, G. W (1986 b). Relaxation in Glass and Com-
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3.6 References 173
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General Reading
Glass transition: Brawer, S.A. (1985), Relaxation
in Viscous Liquids and Glasses. Columbus, OH:
American Ceramics Society.
Sintering and crystallization of gels: Drinker, C.J,
Scherer, G.W (1990), Sol-Gel Science. New York:
Academic Press; Chap. 11.
Theory of nucleation and growth: Christian, J.W
(1975), The Theory of Transformations in Metals
and Alloys, Part I. New York: Pergamon Press.
Tempering: Gardon, R. (1980), Glass: Science and
Technology, Vol. 5: Elasticity and Strength in
Glasses. New York: Academic Press; pp. 145-216.
Annealing: Narayanaswamy, O.S. (1986), Glass: Sci-
ence and Technology, Vol. 3: Viscosity and Relax-
ation. New York: Academic Press: pp. 275-318.
Viscoelasticity, glass-to-metal seals: Scherer, G.W
(1986 b), Relaxation in Glass and Composites.
New York: Wiley.
Kinetics of glass formation: Uhlmann, D. R , Yinnon,
H. (1983), Glass: Science and Technology, Vol. I:
Glass-Forming Systems. New York: Academic
Press; pp. 1-47.
4 Models for the Structure of Amorphous Solids
Philip H. Gaskell

Cavendish Laboratory, University of Cambridge, Cambridge, U.K.

List of Symbols and Abbreviations 178

4.1 Introduction 180
4.1.1 Rationale 180
4.1.2 Background 181
4.1.3 Liquids, Crystals, Glasses, Quasicrystals and "Amorphous" Solids 182
4.1.4 Types of Order 183
4.1.5 Outline 185
4.2 Conceptual Models 186
4.2.1 Randomness as the Paradigm 186
4.2.1.1 Dense Random-Packed Hard Sphere Models 187
4.2.1.2 Random Networks 188
4.2.2 Crystallographic Order as the Paradigm 188
4.2.2.1 Simple Microcrystallite Models 189
4.2.2.2 "Quasi-Crystalline" Models 190
4.2.2.3 "Paracrystalline" Models 190
4.2.3 Non-Crystallographic Order as the Paradigm 191
4.2.3.1 "Curved-Space" Models 192
4.2.3.2 Polytetrahedral Models 193
4.2.4 Constrained Disorder as the Paradigm. Stereo-Chemically Defined Models 193
4.2.4.1 Similarity to Random Networks 196
4.2.4.2 Similarity to Paracrystalline Models 196
4.2.4.3 Local Order as a Consequence of Medium-Range Order 196
4.2.4.4 Stereo-Chemically Defined Models for Close-Packed Oxides
and Amorphous Metals Involving Medium Range Structure-Forming
Operations 198
4.3 Experimental Structural Techniques 199
4.3.1 Neutron Scattering Techniques - Static Structural Methods 199
4.3.2 X-Ray Scattering 201
4.3.3 Effects of Disorder on Scattering Data 202
4.3.3.1 "Termination" Smearing 202
4.3.4 Polyatomic Solids 203
4.3.4.1 Total Distribution Functions and Structure Factors 203
4.3.5 Extraction of Partial Structure Factors 204
4.3.5.1 Combination of the Results of X-Ray, Neutron and Electron Scattering . . 204
4.3.5.2 Neutron Scattering with Isotopic Substitution 205
Materials Science and Technology
Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
176 4 Models for the Structure of Amorphous Solids

4.3.5.3 "Difference" Methods 205

4.3.5.4 X-Ray Absorption Spectroscopy 206
4.3.5.5 X-Ray Anomalous Scattering 208
4.3.6 Vibrational Spectroscopy 208
4.3.7 High Resolution Transmission Electron Microscopy 210
4.3.8 Nuclear Magnetic Resonance 212
4.4 Modelling Techniques 214
4.4.1 Construction of Atomic Models for Amorphous Solids 214
4.4.1.1 Physical Models 215
4.4.2 Molecular Dynamics 215
4.4.3 Potential Energy Functions 217
4.4.4 Energy Minimisation 219
4.4.5 Monte Carlo Calculations 219
4.4.6 Validation of the Model: Calculation of Microscopic
and Macroscopic Properties 220
4.4.6.1 Bond Length Distributions 221
4.4.7 Calculation of Dynamical Properties 223
4.5 Elemental Tetrahedral Semiconductors 223
4.5.1 Amorphous Ge and Si 224
4.5.1.1 Local Structure - Diffraction Data 224
4.5.1.2 Local Structure - Complementary Techniques. Medium-Range Structure . 227
4.5.2 Amorphous Carbon 229
4.5.2.1 Static Properties 229
4.5.2.2 Excitations 231
4.5.3 Network Models - Static Properties 233
4.5.4 Models for Amorphous Carbon 236
4.6 Amorphous Silica 238
4.6.1 Experimental Situation 238
4.6.2 Local Structure 239
4.6.2.1 Diffraction Data 239
4.6.2.2 Complementary Techniques 239
4.6.3 Medium-Range Structure 240
4.6.4 Random Network Models 241
4.6.5 Ordered Models 244
4.6.5.1 Quasi-Crystalline Models 244
4.6.5.2 Microparacrystalline Models 244
4.6.6 Simulation of Dynamical Properties 245
4.6.7 Molecular Dynamics Models 247
4.6.8 Monte Carlo Simulations 248
4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates 250
4.7.1 Apologia 250
4.7.2 Local Structure Around "Network Modifiers" in Oxide Glasses 251
4.7.2.1 Diffraction and EXAFS Data 251
4.7.2.2 Complementary Techniques 256
 4 Models for the Structure of Amorphous Solids 177

4.7.3 Medium-Range Structure Centred on "Network-Modifiers"

in Oxide Glasses 257
4.7.3.1 Diffraction Data 257
4.7.3.2 Complementary Techniques 259
4.7.4 Speciation 259
4.7.4.1 Borates 259
4.7.4.2 Silicates 260
4.7.5 Network Models 264
4.7.6 Molecular Dynamics 265
4.7.7 Microcrystallite Models 266
4.7.8 Stereo-Chemically Defined Models 267
4.8 Concluding Remarks 269
4.8.1 Information Content 270
4.8.2 Microscopic and Macroscopic Properties 271
4.8.3 Structural Models - Present and Future 273
4.9 Acknowledgements 274
4.10 References 274
178 4 Models for the Structure of Amorphous Solids

List of Symbols and Abbreviations

b neutron scattering length

ca concentration of atomic species a
dhkl distance between crystal planes with Miller indices hkl
n-D rc-dimensional
E energy
/ (Q) atomic scattering factor
F (Q) reduced interference function
g (r) pair distribution function
g (co) vibrational density of states function
G (r) reduced radial distribution function
i (Q) interference function
/ intensity, nuclear spin
J (r) radial distribution function
k photon or photoelectron wave vector
kB Boltzmann constant
M (Q) modification function
na atomic fraction of species a
N coordination number, number of atoms
Nc number of constraints
NF number of degrees of freedom
N (r) running coordination number
Nj coordination number of j ' t h atomic shell
P*p{r) P a i f correlation function between atomic species a and /?
P* (r), P*fi (x) peak shape function
q phonon scattering vector
Q scattering vector, modulus Q
Qn number of bridging oxygens (n) (around Si in this case)
rap interatomic distance between atoms of species a and /?
<rf> mean bond length of i'th shell
Rj radius o f / t h shell of atoms
S (Q) structure factor
Tg glass transition temperature
7^ melting temperature
(u{ > mean square displacement of atomic species i
W{ ( 0 Debye-Waller factor for atomic species i
Wap weighting factor for atoms of species a and p
za electronic charge on atoms of species a
Z atomic number
5 phase shift
e dielectric function; e l 9 s2 are real and imaginary parts
X (k) /c-dependent normalised EXAFS signal
<P potential energy
 List of Symbols and Abbreviations 179

X wavelength
A photoelectron mean free path
Q(r) atomic (number) density
Qo average atomic (number) density
a (a) standard deviation of a
9 scattering angle (conventionally 2 6)
CO frequency
CRN continuous random network
CTF contrast transfer function
DRP dense random packed (model)
EELS electron energy loss fine structure
ESR electron spin resonance
EXAFS extended X-ray absorption fine structure
fee face centred cubic
hep hexagonal close packed
HRTEM high resolution transmission electron microscopy
IR infra-red
MASNMR magic angle spinning NMR
MC Monte Carlo
MD molecular dynamics
NMR nuclear magnetic resonance
PE potential energy
ppm parts per million
PT polytetrahedral
RDF radial distribution function
SCD stereo-chemically defined
TEM transmission electron microscopy
TM-m transition metal-metalloid
TMS tetramethyl silane
XAFS X-ray absorption fine structure
XANES X-ray absorption near edge spectroscopy
XAS X-ray absorption spectroscopy
180 4 Models for the Structure of Amorphous Solids
4.1 Introduction
4.1.1 Rationale
Knowledge of the structure of a material
is central to any adequate understanding
of its properties. For most classes of solids,
for gases, many polymers - including bio-
logical macromolecules - such knowledge
exists and there is a well-established link
between structure at the atomic level
and macroscopic properties. Liquids and
glasses can be excluded from this state-
ment. The structure of most glasses is not
even understood in simple qualitative, con-
ceptual terms. With the added complica-
tions of thermal motion, liquids present
even more intractable difficulties.
Reasons for this state of affairs are not
difficult to find. Translational periodicity
implies enormous simplification of the
experimental, theoretical and conceptual
problems. Experimentally, the phase-relat-
ed response of atoms in identical unit cells
to the stimulus of electromagnetic radia-
tion, for example, results in strong signals
of high information content, in energy-
or reciprocal-space. Theoretical models
based on the small cluster of atoms com-
prising the unit cell are readily constructed
and optimised to fit experiment. And the
conceptual problem hardly exists; experi-
ment provides many or most of the neces-
sary clues. Glasses, on the other hand,
have aperiodic structures and at some level
are isotropic. Experimental data are there-
fore extensively averaged - scrambled, in-
deed - so that the signal is weak with low
information content. Much of the symme-
try information is lost. Theoretically, mod-
elling loses its rigour: approximations are
inevitable, computations become unwieldy
because of the large (strictly infinite) size
of the models and are constrained not only
by limited experimental information but
also by computational uncertainties.
The conceptual problem is perhaps the
most unsettling. Many macroscopic prop-
erties become intelligible simply by recog-
nising the essential microscopic behaviour
at a qualitative level. Sharp lines in the
vibrational spectrum of a crystal can be
seen as the phase-related response of
equivalent atoms in all unit cells. But how
does one explain, to oneself or to a student,
the residual effects associated with (crys-
tal) momentum in an amorphous solid to
which the concept is strictly inapplicable,
since there is no unit cell; or, ionic migra-
tion, that in the crystal can be thought of
in terms of defect-controlled mechanisms,
when the glass is "all one big defect"?
It is therefore relatively easy to argue
that the art of modelling the structure of
amorphous solids is central to any under-
standing of their macroscopic properties.
Certainly, further progress in the develop-
ment of this extensive family of socially-
important materials depends on it. A rep-
resentative atomic model, with accurate in-
teratomic forces, allows us to simulate na-
ture. It then becomes possible to compute
physical and chemical behaviour ranging
from straightforward properties such as
the density, through to electronic, optical
and magnetic characteristics. Dynamic
events can be followed on the computer
including processes that occur on time
scales that are impossible to achieve in the
laboratory. New materials can be ex-
plored, computationally, by formation at
quench rates that would not easily be at-
tainable to practice.
Techniques for producing and exploring
atomic models have grown to represent a
major area of computational science. Not
principally for the reasons advanced in the
previous paragraph - those attractions are
largely for the future - but as a response to
the experimental problem of translating
incomplete, inadequate structural data in-

to meaningful models. For the reasons dis-
cussed above, structural information avail-
able from an experiment on an amorphous
solid is minute compared to that routinely
acquired from an experiment on a crys-
talline powder. In 1983 it seemed "fairly
safe to assume that no single experimental
structural technique, nor perhaps any
combination, will in the near future
provide a sufficiently large bank of infor-
mation that we can 'solve' the structure (of
a glass) in the sense that the structures of
crystals have been solved" (Gaskell, 1983).
This statement may be more arguable now
but the need to combine structural data
from many techniques, or from a number
of related techniques and several materials
remains. And the task of combining that
information is made easier by cross-refer-
ence and adaptation of models that try to
represent that data - and is only complete
when all of the information is encapsulated
in an acceptable model. It is to this area
that modelling has been attracted in the
past, and has proved its worth. The speed
with which computational power is now
becoming accessible to the average experi-
mentalist, as well as to the theoretician,
implies that this movement will accelerate
in the future. Indeed, user-friendly atomic
modelling systems must become the essen-
tial tool of the experimental scientist or
technologist working on materials in fu-
ture years.
This increase in available computational
power exerts a new pressure - to develop
adequate models that are consistent with
experiment, rather than simplified, ide-
alised models whose principal merit is the
ease of programming.
The challenge of this chapter is to set out
the ground rules, to present the knowledge
that has been established and that which
needs to be gained. The approach is delib-
erately experimentally biased. Although
4.1 Introduction 181
the mechanics of computer generation of
models, for example, must form part of
this chapter, the major thrust is to depict
what experiments - including computer
experiments - can tell us, where they are
defective and how we need to make them
more sophisticated. Secondly, it will be im-
portant to pare down the concepts and,
not only to deconstruct, but also to recon-
struct the bones of new approaches.
4.1.2 Background
We begin by restating those characteris-
tics of the glassy or amorphous states of
matter that relate directly to structural
questions; either by informing those ques-
tions or because the characteristics them-
selves require structural interpretations.
By definition, glasses are non-crystalline
solids. Conventionally, we regard the
glassy state as that persisting below a char-
acteristic glass temperature, Tg9 at which
the material becomes metastable both with
respect to the global thermodynamic
ground state corresponding to the crystal
and to the local equilibrium represented by
the supercooled liquid. Separating the
glass from the super-cooled liquid is a so-
called "glass transition" that has resem-
blance to a thermodynamic second order
transition but, operationally, can be re-
garded as a departure from equilibrium
imposed by the increased viscosity of the
melt. The transition thus has some charac-
teristics related to the time-dependence of
"structural relaxations" including well-
known hysteresis effects in differential
scanning calorimetry signals, for instance.
Apart from unsettled questions concerning
the dynamical interaction responsible for
the glass transition, the continuous nature
of the transition has implications for struc-
ture. In contrast to the essential disconti-
nuity that lies at the heart of the change of
182 4 Models for the Structure of Amorphous Solids
state from the liquid to the crystalline solid
- expressed through the appearance of a
nucleus and extension of the crystal/liquid
interface, discontinuous changes in energy,
volume etc. marking the thermodynamic
first order transformation - there is no ev-
idence for any change of state during the
glass transition. The structure of the glass
and that of the liquid - whatever they may
be - have essential similarities.
Glass formation may be seen as a pro-
cess in which crystallization is avoided - a
feature that has been stressed by Turnbull
(1969). Glasses are formed when the disor-
dered structure characteristic of the liquid
is preserved from temperatures above TM,
where the disordered state is thermody-
namically stable, to temperatures below Tg
where the disordered, glassy state is kineti-
cally stable. Crystallization, involving dif-
fusional motion of atoms is, like all such
transport processes, "frozen out" below
T%. The tendency of the material to crystal-
lize or devitrify has important structural
implications, of course. In a real sense this
is the obvious reference point for micro-
crystallite models for glasses, and yet there
is still the need to reconcile this approach
with structural changes that are implicit in
the nucleation of a crystal.
A further instability relates to the ten-
dency of many multicomponent glasses to
"phase separate". Microphase immiscibili-
ty is characteristic of many simple liquids
and is well understood in that context in
thermodynamic terms. Again, the transi-
tion from a single phase liquid at high tem-
peratures to a multiphase immiscible liq-
uid mixture as the temperature is reduced,
can be seen as a progressive increase in the
relative importance of energetic (ordering)
parameters rather than entropic terms.
Operationally, the boundaries of immisci-
bility have been defined in composition-
temperature-time space although a satis-
fying explanation in atomistic terms is
still awaited. The implications of immisci-
bility for structural studies are two-fold.
Firstly, there is the experimental problem -
that single phase glasses exist only over
limited composition ranges, so that the
experimentalist finds it difficult to explore
many otherwise interesting compositions.
Secondly, the obvious tendency of some
glasses to become unmixed on a scale of
micrometres implies - like the crystal-
lization transition - the possibility of sepa-
ration into two or more phases at an atom-
ic level. "Granularity" at this level is thus
by no means foreign, as judged by the be-
haviour of glasses in macroscopic terms.
4.1.3 Liquids, Crystals, Glasses,
Quasicrystals and "Amorphous" Solids
The brief survey of the characteristic
properties of glasses shows them to be in-
termediate between the ordered crystalline
state on the one hand and the essentially
disordered, time-dependent structure of
liquids on the other. Glasses can be
thought of as being liquids with diffusional
atomic motion subtracted. Studies of the
structure of glasses - although of intrinsic
value - gain added importance as an entree
into the more difficult studies on liquids.
Not only are glasses necessarily more or-
dered than the corresponding melt, by
virtue of a reduction in diffusive motion,
vibrational motion is also suppressed as a
result of lower measurement temperatures.
Structural data therefore suffers less ther-
mal broadening.
Quasicrystals may provide another link.
Several metallic alloys form quasicrys-
talline and glassy phases so that the rela-
tionships between them are currently a
matter for considerable interest and specu-
lation. Both phases require special prepa-
ration conditions - rapid quenching for in-

stance - to avoid formation of stable or
metastable crystalline phases. Both phases
are clearly defective. Both may be related
to an underlying structural principle - pos-
sibly the same structural principle.
Sharing the same structural diagnostics
- lack of order and metastability - are a
whole family of "amorphous solids" typi-
fied by evaporated films of, say, Si, Se,
H 2 O, and amorphous metals. These may
or may not be, strictly, glasses under the
above definition. Films deposited from the
vapour phase or by atom by atom deposi-
tion do not necessarily relate at all to other
condensed states of matter except that of
the crystal. Structurally, deposited films
range from those that may have more re-
semblance to a loose aggregate of
molecules such as certain oxides or sul-
phides of As or P, or they may form giant
frameworks entirely analogous to the net-
work glasses.
It has become customary to distinguish
amorphous solids from "true" glasses by
the presence or otherwise of a glass transi-
tion, rather than by any exclusively struc-
tural characteristic. Amorphous solids may
thus defined by the absence of changes in
the heat content near Tg9 although, in
practice, such changes may be masked by
crystallization.
4.1.4 Types of Order
By definition and from experience,
glasses are disordered on some length
scale. Experiment shows, however, that
the vast majority of glasses have recognis-
able order over a length scale correspond-
ing to first neighbour distances. How
should the order in a structure be speci-
fied? Firstly, we recognise that if a com-
plete set of atomic coordinates were, by
magic, available to use, we would find this
unhelpful - as anyone who has modelled
4.1 Introduction 183
even a 1000-atom cluster knows. Structur-
al information is required in the form of
distribution functions, local symmetry, a
geometrical description, orientational rela-
tionships, distribution of chemical species
- features, in fact, that are most useful in
discussing the structure of a crystal with a
large unit cell.
We consider the following facets of a
structural description.
Positional, or geometrical, order. As-
suming that a local arrangement of atoms
can be identified - a coordination polyhe-
dron and a central atom - we can specify
the extent of order through the mean, (rt >,
and standard deviation, a(r£), (and higher
moments if necessary) of bond length,
bond angle distributions and the number
of neighbours - the coordination number.
An ordered arrangement implies a narrow
distribution of first neighbour distances
and, ideally, an identifiable coordination
number, Nc - rather than a continuous in-
crease in N(r) with increasing r.
Comparison with a compositionally-
equivalent crystalline phase may show
some correspondence between values for
crystals and glasses and this can be taken
as further evidence for ordering - although
not necessarily for a crystallographic mod-
el of ordering.
If the parameters for higher order neigh-
bour shells can be extracted - and usually
they can, with more difficulty, to second
neighbours - then <r 2 ) and a(r 2 ) again
give a measure of order. Additionally, if
the ratio of <r2> and <rx> corresponds to
the geometry of say, a tetrahedral unit,
then the symmetry of the local unit of
structure can be specified, indirectly.
Symmetry information can be obtained
more directly through measurements of
the infra-red or Raman spectra, X-ray ab-
sorption near edge structure, NMR etc.
and clearly represents an important struc-
184 4 Models for the Structure of Amorphous Solids
tural parameter. In many cases, symmetry
information alone can be used to decide
between alternative models with different
local symmetries.
In previous paragraphs it has been con-
venient to discuss structural parameters in
terms of a length scale that is implicit in the
word "local structure". This can be taken
to mean the structural characteristics of
the immediate environment of a given
atomic species out to perhaps second
neighbours. The upper limit is arbitrary
but since it is usually only possible to ana-
lyse experimental correlation functions
without recourse to models, out to second
neighbours, then it has a certain aptness.
At the other extreme of the length scale,
glasses are clearly geometrically disor-
dered and as experiment suggests a limit of
about 1.5 to 2.0 nm to be the shortest dis-
tance at which deviations from random-
ness can be seen, then this marks the lower
limit of what is often termed the long-range
structure. There still remain deviations
from a structureless solid but such devia-
tions are confined to compositional inho-
mogeneities occurring on a length scale of
about 2 to 200 nm. From second neigh-
bour distances at 0.4-0.5 nm to 1.5 nm -
between the limits for local and long range
structure - comes the "intermediate range"
structure or "medium-range" structure.
(Often the terms medium-range structure
and medium-range order are used inter-
changeably, but since the latter, clearly,
implies order it seems better to use the
more neutral term, structure.) Medium
range structure is less easy to define in
terms of geometry or symmetry, so that
topology generally provides a specification.
In amorphous tetrahedral semiconductors,
for instance, the network topology ex-
pressed as the relative proportions of n-
membered rings, represents one of the few
ways of clearly distinguishing competing
models.
Compositional ordering represents a fur-
ther structural characteristic. For a poly-
atomic solid, this may be relevant on all
length scales: local (compositional) order-
ing in an amorphous Co-P alloy represents
the distinction between models in which
Co atoms preferentially cluster around P
and alternatives in which Co-Co and P-P
pairs are preferred, or in which the distri-
bution is random - determined only by the
relative numbers of each type of atom and
their relative atomic radii. Compositional
ordering, at local and medium-range struc-
tural levels, is also important as in certain
polyatomic oxide glasses, and in Si: H "al-
loys". In crystalline lithium silicates, for
example, the silicon-oxygen anions have
formal charges that vary with the concen-
tration of Li. Considering the mixture of
oxides (Li 2 O) x (SiO 2 )i- x ; the composition
with x = 0 corresponds to a structure in
which all four oxygens are "bridging" that
is, they are linked to two silicons. In NMR
terminology this is usually specified by the
notation Q4 representing four bridging
atoms around the tetrahedral (Quaternary)
atoms. As x increases, so does the number
of non-bridging oxygens so that the frac-
tion of Q4 atoms decreases with corre-
sponding increases in Qn (n<4). The vari-
ous silicate "species" are shown in Fig. 4-1
for random and compositionally-ordered
silicate glasses. In a random model, all spe-
cies are expected to be present in propor-
tions governed by the average composi-
tion, energy and temperature etc. Experi-
ment, especially NMR measurements, al-
lows some definition of the relative pro-
portions of each species so that anionic
"speciation" becomes an important struc-
tural characteristic. We can thus specify
the extent to which a given composition
leans towards competitive models in which
the majority of species present corresponds
to that of the compositionally-equivalent
crystalline phase.

Figure 4-1. Various silicate species Q" in silicate
glasses (schematic), a) Elementary g 3 tetrahedron
with 3 bridging and 1 non-bridging oxygens, b) Ex-
ample of isolated and paired non-bridging oxygens,
c) Compositionally ordered glass, d) Random net-
work.
Compositional ordering is also evident
in the long-range structure of polyatomic
glasses. As with other liquids, complete
miscibility of several components is only
conditionally possible. For reasons that
are not always obvious in structural terms,
the thermodynamically stable state of a
glass in the liquid or super-cooled liquid
states may be multi-phase rather than sin-
gle phase. The boundaries in composition-
temperature-time space are understood in
terms of well-established (thermodynamic)
parameters. Experimentally, the multi-
phase nature of a particular glass becomes
obvious as a separation into two or more
distinct liquid-like phases on a length scale
of a few tens of nanometres upwards.
(Complete separation into two immiscible
liquids can occur - stable immiscibility -
when the two-liquid state is preferred at
temperatures above TM, but metastable
4.1 Introduction 185
immiscibility, corresponding to TM<T<
jTg, is more usually a complication since
phase separation may then only be obvi-
ous on a microscopic scale.
4.1.5 Outline
As a direct result of the limited amount
of experimental data obtainable for all
amorphous solids and glasses, it becomes
necessary to extract all the information ob-
tainable from a given technique or, prefer-
ably from a combination of complemen-
tary techniques. In order to interpret the
data it is crucial to express it in terms of
candidate models, then to compare models
and experimental data and try to achieve
agreement to the limits of accuracy, both of
experiment and the simulation technique.
Unless comparison is made at this level of
detail, then the results can be disappoint-
ing and even misleading. Models of many
different types can be made to agree with
the general features of structural data if the
only data available is the total correlation
function with a relatively low information
content. On the other hand, experimental
data of the highest information content
currently available - partial pair correla-
tion functions - have not yet been mod-
elled to the accuracy of experiment and of
computation.
An account of models for the structure
of glasses must include, therefore, a critical
analysis of the results of particular tech-
niques, and a synthesis of results from oth-
er techniques or from other related materi-
als.
The strategy for this chapter is to begin
(Sec. 4.2) with a discussion of the various
conceptual models for amorphous solids
starting with extreme models based on ran-
domness on the one hand and crystal-like
order on the other. We then pass to models
that are ordered but without underlying
186 4 Models for the Structure of Amorphous Solids
crystallographic order as the rationale.
These are the so-called icosahedral, or
curved-space models related, perhaps, to
quasicrystallinity. We also try to express in
words what is implied in other hybrid
models that are less easy to describe: those
based on twinning, or on constrained ran-
domness, or stereochemically-constrained
models.
Section 4.3 discusses some of the experi-
mental structural techniques in outline and
presents a summary of the formal defini-
tion of structural parameters. Emphasis is
placed not so much on the details of the
techniques but on the results that are ob-
tainable and their value in providing useful
experimental data. Other chapters in this
series provide the essential background.
Section 4.4 considers how models can be
made and tested either by computer simu-
lation techniques such as Monte Carlo or
Molecular Dynamics algorithms that ex-
hibit little or no bias towards a particular
model. We also consider models that are
based on crystals - either as a convenient
starting point or as the result of "intu-
ition" and those within which certain
structure-forming rules are embedded
which restrict the range of possible out-
comes. We then examine how these models
may be validated by comparison with ex-
perimental data and the corrections neces-
sary to allow accurate comparisons.
Sections 4.5 to 4.7 is where all the above
- which is essentially preamble - is tested
against reality. Three case histories are giv-
en of structural campaigns. Examples are
selected to allow conclusions to be drawn
about the nature of the amorphous state in
materials such as a-Si, through silica, to
the relatively complex polyatomic silicates
and similar oxide glasses.
The final section attempts to bring to-
gether what has been learned and com-
pares this with what can and should be
known, with some suggestions for new ap-
proaches.
Structures of metallic glasses are treated
in Vol. 1, Chap. 4, those of chalcogenide
glasses in Chap. 7 of this volume. Struc-
tural relaxation is fully treated in Chap. 3,
and the special case of structural relax-
ation in metallic glasses in Chap. 9 of this
volume. The diffraction concepts used here
are treated in depth in Vol. 2, Chap. 8.
4.2 Conceptual Models
The plain experimental facts that glasses
and amorphous solids are metastable with
respect to crystals, that glasses and amor-
phous solids can be produced by rapid
quenching from the melt or vapour, natu-
rally tend to condition our views on struc-
ture. Glasses may be considered to be an
approach to the crystalline state or as a
departure from the liquid state. Extreme
models for the structure of glasses - micro-
crystallite models or random packing
models - encapsulate these two preconcep-
tions. Even if only as a framework for dis-
cussion it is useful to try to classify models
in terms of the paradigms or patterns they
can be said to represent.
4.2.1 Randomness as the Paradigm
Experiment immediately dispels any no-
tion that glasses or amorphous solids can
be represented as some kind of completely
chaotic "frozen atomic gas". Nearest
neighbour distances only rarely show sig-
nificant departures from values expected
for crystals or those obtainable from tables
of appropriate atomic radii. This would be
expected on the basis of macroscopic prop-
erties: densities and enthalpies, for exam-
ple, differ by only a few percent from val-
ues appropriate to crystals, so that a signif-

icant number of broken or extensively
strained primary bonds is not expected.
All random models for glasses start with
atoms in contact in the case of DRP mod-
els or with essentially fully interconnected
local polyhedral units for random net-
works. In both cases the first neighbour
bond lengths are constrained.
4.2.1.1 Dense Random-Packed Hard
Sphere Models
Pioneering experiments by Bernal (1964)
on the structure of monoatomic liquids
have proved to be immensely influential in
directing subsequent research on the struc-
tures of dense-packed alloys, amorphous
halides and, by extension, oxides. Bernal's
early experiments moulding ball bearings
packed into rubber bladders, which were
then kneaded and set in black paint, have
since been replaced by computer simula-
tion and 3-D graphics. Although the detail
has changed, the basic concepts persist.
Bernal showed that non-crystalline aggre-
gates could be produced by constraining
the exterior surface to an irregular con-
tour. The interatomic arrangement could
then be analysed in terms of five deltahe-
dra, "canonical polyhedra" (Fig. 4-2), with
a strong preference for tetrahedra and half
octahedra.
(i)
Figure 4-2. Polyhedra formed by packing of equal spheres: i) tetrahedron, ii) octahedron, iii) trigonal prism
capped with three half octahedra, iv) Archimedean antiprism capped with two half octahedra, v) tetragonal
dodecahedron. After Bernal (1960).
4.2 Conceptual Models 187
Later computer modelling by Finney
(1970) refined the figures for the relative
proportion of each polyhedral type, but
with the introduction of soft interaction
potentials by Finney and Wallace (1981) in
an energy minimization routine, the pro-
portions of large polyhedra dropped sig-
nificantly. The only major contributions
remaining were from tetrahedral and half
octahedral interstices.
The influence of the DRP model can be
gauged by the degree to which its salient
features were retained in the modifications
required to include new knowledge. An ex-
ample is the extension of DRP mono-
atomic models to include additional ele-
ments. Models were proposed and tested
in which atoms of two or more species
were assigned randomly to sites in a
monoatomic hard sphere structure. An al-
ternative (Polk, 1972), designed for transi-
tion metal-metalloid glasses, incorporates
the smaller metalloid in the large Bernal
holes (Archimedean antiprisms or trigonal
prisms). Recently, similar DRP structures
have been simulated by sequential addi-
tion to a seed, using spheres of two sizes
and realistic potential functions.
Models of this type can, in principle, be
constructed with polyatomic units of any
shape and size. In practice, only rarely
have attempts been made to construct
188 4 Models for the Structure of Amorphous Solids
models of randomly packed molecules, for
example.
4.2.1.2 Random Networks
Closely allied to DRP models are ran-
dom networks. Indeed the two are mutual-
ly interconvertible, by suitable decoration
of a DRP model, say. The rationale here is
that if a local structural unit can be defined
- such as a silicon tetrahedron in amor-
phous silicon - then the random network is
created by connecting such units with no
rules other than on each addition of a unit
to the existing cluster, their relative orien-
tations shall be unconstrained. Additional
restrictions, such as reduction of the num-
ber of "dangling" bonds to some arbitrary
fraction, choice of ring statistics, or the
inclusion of constraints relating to mini-
mum strain energy or to a specified densi-
ty, may be added at a later stage.
Models of this type are very flexible in
that the constrained unit can be considered
to be as large as experimental data re-
quires. That is, if it is clear that a local
structural unit can be defined, random
connection of these units then provides a
realistic non-crystalline model - even if the
size of the "local" structural unit is similar
to that of a unit cell. Most, if not all, suc-
cessful models could be considered to fall
within this class. By common usage,
though, the term has come to mean a ran-
dom grouping of n-atom "molecular"
units with n in the range 1 to 10.
The term "random network" is inextri-
cably linked with Zachariasen (1932) who
proposed "that the atomic arrangement in
glass is characterized by an extended three-
dimensional network which lacks symme-
try and periodicity" (Fig. 4-3 a). This mod-
el gained support as a result of Warren's
work on silica by X-ray diffraction (War-
ren et al., 1936) and the essential features
of the Warren-Zachariasen model persist
today. Variations in the composition are
easily incorporated as a random addition
of species other than Q4 with associated
alkali or alkaline earth cations, Fig. 4-3 b.
That any random network can extend
indefinitely to form a "continuous" ran-
dom network, CRN, does not appear to
have been proved. Phillips (1979) has sug-
gested that continuity may be only condi-
tionally possible - the key parameter being
the relation between the number of me-
chanical degrees of freedom per atom, 7VF,
and the relevant number of constraints,
Nc. By defining constraints to mean the
forces acting on an atom from its neigh-
bours - given by the number of indepen-
dent terms in a valence force field, Phillips
suggests that Nc = NF represents the condi-
tion for "ideal" glass-forming composi-
tions. In the chalcogenides NC = NF for a
composition where the average number of
bonds per atom is 2.4 - corresponding to
As 2 S 3 . Amorphous Si, on the other hand,
is "over-constrained" and, Phillips argues,
cannot be represented by a CRN without
intrinsic defects. Some of the defects may
take the form of an extended medium-
range structure or interfaces in a granular
structure.
4.2.2 Crystallographic Order
as the Paradigm
Similarity between structural parame-
ters, such as the structure factor S(Q) or
the pair correlation function, for glasses
and compositionally-equivalent crystals is
a common circumstance. This provides
support for the notion that glasses can be
thought of as assemblies of microcrystals.
Strain introduced due to lattice mismatch
at grain boundaries, the presence of a dis-
ordered interfacial or matrix region, and
 4.2 Conceptual Models 189

a b
Figure 4-3. Schematic two-dimensional representation of the structure of a) SiO2 (only three bonds are shown);
b) a sodium silicate glass. The Na atom marked with an asterisk is isolated. Greaves' "Modified random
network", Fig. 4-63, does not include such atoms, see Sec. 4.7.5 (Zachariasen, 1932 and Warren et al, 1936).

defects such as dislocations, or stacking with experiment. Similarly, although the

faults can be assumed to give rise to depar-
tures from periodicity at distances smaller
than the average grain size.
4.2.2.1 Simple Microcrystallite Models
In an unqualified form, a microcrystal-
lite model for glasses rightly receives no
experimental support. Cargill's early work
on a possible model for amorphous Ni-P
alloys showed that a model based on 2 nm
regions with hexagonal close packing of Ni
atoms (which make the major contribution
to the X-ray scattering data) was inade-
quate to explain experimental data
(Cargill, 1970). Variations in stacking fault
density, dilatation and lattice symmetry
proved insufficient to reconcile models
clear impression gained from comparisons
of the rdfs of amorphous and crystalline
Ge is that the structure to second neigh-
bours is similar in both forms, beyond
that, there is virtually no recognizable
agreement. This is indicated by the almost
complete absence of the third peak in a-Ge
at about 0.47 nm, Fig. 4-4. Amorphous
and crystalline Ge are thus fundamentally
different and since the R 3 peak at 0.47 nm
is due to correlations across 6-fold rings,
its absence in the correlation function for
a-Ge might suggest a relative decrease in
the proportion of 6-fold rings in favour of
5-fold rings, in which three bond distances
are equivalent to those to second neigh-
bours. The structural differences may thus
relate to essential topological variations.
190 4 Models for the Structure of Amorphous Solids
10
Figure 4-4. Experimental radial distribution function,
J (r) = 4 n r2 Q (r), for a) crystalline Ge, b) a-Ge for two
specimens deposited at substrate temperature of
350 °C (upper) and 150°C (lower). After Temkin et al.
(1973).
4.2.2.2 "Quasi-Crystalline" Models
Some time before the term "quasicrys-
talline" acquired its present meaning,
models for glasses based on crystalline
polymorphs with variable "correlation
lengths" were investigated. An example is
the early work of Leadbetter and Wright
(1972); further, more recent, examples are
quoted in Sec. 4-6. The correlation func-
tion for the crystal, Gc (r), is multiplied by
some function, F(r), running from unity at
r = 0 to zero for r>L, where L is the corre-
lation length. Comparison with experi-
ment may be through the reciprocal space
function, F(Q) = Q(S(Q)-1) and F{Q)
calculated by the modified sine transform:
F ( 0 = ]Gc(r)F(r) sin (Qr)dr (4-1)
o
and
Here, Qc(r) is the r-dependent atom
number density and QC0 the average atom
density for the crystal. Typical values cho-
sen for L are about 1 nm.
Although quasi-crystalline models give
some agreement with experiment for the
structure of the local environment, dis-
crepancies are too large at higher values of
r for the method to be considered as any-
thing other than a first approximation.
The problems again seem to stem from dif-
ferences in topology rather than the de-
tailed form of F(r), or the choice of L.
4.2.2.3 "Paracrystalline" Models
Two authors, Hosemann et al. (1986)
and Phillips (1982), have employed the
term "paracrystalline" to describe their
models for amorphous solids. Both use
crystalline polymorphs as the basis for
simulation and both introduce specific fea-
tures that are essential ingredients for any
degree of success the models achieve.
The work of Hosemann and co-workers
is the more general and extensive. The
model is predicated on the observation
that if the disorder is expressed in terms of
interplanar distances, dhkU by
1/2
<d2hki>
-1 (4-2)
where N is the number of lattice planes,
then experimentally, the relation, N1/2 g =
a*, with a* = 0.15, holds to a good approx-

imation for a wide range of semi-ordered
materials.
Relations such as Eq. (4-2) define the
statistics of fluctuations in dhkl as a func-
tion of distance from an origin atom -
clearly correlations become more diffuse at
longer interatomic distances. This alone is
insufficient to provide agreement with ex-
periment and for the case of SiO2 consid-
ered in Sec. 4.6.4.1, a "microparacrystal"
with edge length of 1.25 nm is assumed,
with a relative twist of 22° between adja-
cent SiO4 tetrahedra introduced to fit ex-
periment.
Glasses have also been pictured as an
assembly of misoriented microcrystallites
in which random relative orientations and
the presence of several polymorphic micro-
crystalline phases represents the essential
ingredients inhibiting devitrification. Most
recently, this notion has been advanced by
Goodman (1983) as a "strained microcrys-
tallite model" - strain arising from the mis-
match between the various sublattices thus
giving rise to diffuse scattering.
Phillips - among others - rejects this no-
tion pointing out that a material such as
As 2 Se 3 , which is an excellent glassformer,
has only one known crystallographic
phase. Phillips' extensive series of papers
describe a variety of glasses, such as the
chalcogenides and oxides through to
amorphous solids such as a-Si and Ge. The
underlying rationale for such models fol-
lows from the precept that the relation be-
tween the number of constraints - imposed
by covalent bonds - and the number of
degrees of freedom, implies that certain
compositions are "ideal" for glass forma-
tion, others are not. Both under- and over-
constrained structures are poor glass form-
ers and lead to partially broken topologi-
cal order - to discrete boundaries between
amorphous aggregates and to broken
chemical order. In the chalcogenides, for
4.2 Conceptual Models 191
example, deviations from chemical order-
ing lead to chalcogen-chalcogen bonding
at the edges of GeS2 "rafts". In SiO 2 ,
Phillips argues that broken chemical order
arises from a tendency of oxygen to form
double bonds. In either case granular
rather than "continuous" models result.
Phillips' descriptions have the almost
unique distinction among crystallite mod-
els in that both the nature of the crystal-
lites and their intervening surfaces are pre-
scribed in detail.
4.2.3 Non-Crystallographic Order
as the Paradigm
The assumption that an ordering princi-
ple necessarily leads to periodic structures
clearly has exceptions. It is well known
that the lowest free energy configuration
for clusters containing small numbers of
atoms, involve arrangements based on te-
trahedral close-packing. Atoms, or larger
groups packed in this way contain symme-
try elements - five-fold rotation axes for
example - that are inconsistent with trans-
lational periodicity and therefore with a
crystal lattice. Fig. 4-5 shows examples of
some pentagonal structures produced by
progressively extending the principle of
packing tetrahedra. Hoare and Pal (1975)
have enumerated several families of non-
crystallographic clusters which can be
shown to be more stable than crystallo-
graphic structures containing the same
number of atoms. Icosahedral packing -
twelve atoms surrounding a central thir-
teenth, or twelve packed tetrahedra - is
particularly stable, so that icosahedral, or
incomplete icosahedral packing is a struc-
ture likely to be favoured in non-crystallo-
graphic packings.
Polytetrahedral packing is not space-fill-
ing though, so that infinite aperiodic struc-
tures are not possible in general. The angu-
192 4 Models for the Structure of Amorphous Solids
Figure 4-5. a, b) Non-crystallographic clusters pro-
duced by tetrahedral close packing; c) 55-atom
"Mackay icosahedron" (Mackay, 1952); d) Thirteen,
13-atom icosahedra bridged by octahedra producing
an icosahedron of icosahedra; e) 471-atom triaconta-
hedron produced from 23 interpenetrating 55-atom
Mackay icosahedra. After Barker (1977).
lar mismatch when five tetrahedra are
packed around a common 5-fold axis is
small (7.5°) but strain accumulates as a
tetrahedrally-packed cluster grows. Larger
structures thus contain considerable strain
energy and eventually become unstable
with respect to periodic structures and
probably with respect to a composite of
small aperiodic clusters in a "random"
matrix.
The "father" of icosahedral packing is
often taken to be F. C. Frank (1952) (al-
though he suggests that "countless genera-
tions of schoolboys may have proceeded
him"). He pointed out the relative energy
and volume savings involved. Subsequent-
ly, icosahedrality in randomly packed ar-
rays has become a key issue largly through
the work of Turnbull (1985), Sadoc and
Mosseri (1982), Sachdev and Nelson (1985)
and Yonezawa et al. (1987). The fact that
tetrahedral packing is relatively stable for
small numbers of atoms and the conflict
between local and long range ordering sug-
gests that local energy minimisation in the
liquid or glassy state will lead to intercon-
nected, partially icosahedral groups. Fur-
ther, that the barriers to crystallisation to-
pologically imposed by the organisation of
atoms at a local level - to form tetrahedra
and octahedra, for instance - will lead to
extended kinetic stability for the aperiodic
structure. Turnbull (1985) has argued
that the crystallisation process in glasses
is essentially discontinuous. Whereas mi-
crocrystallite models might be expected
to crystallise by progressive coarsening,
through atomic migration at grain bound-
aries, devitrification generally occurs by a
nucleation and growth mechanism. He
then extends the argument to suggest that
this provides evidence that the short range
order in glasses is essentially different
from that of the corresponding crystal,
and that icosahedral arrangements provide
that necessary difference. Yonezawa et al.
(1987) have simulated the structure of
Lennard-Jones or Stillinger-Weber mono-
atomic liquids as functions of temperature
and time. Calculations of the local symme-
try of nearest neighbour shells allow the
proportion of icosahedral clusters to be
recorded (as a movie) and show the devel-
opment and clustering of icosahedral re-
gions near the glass transition.
4.2.3.1 "Curved-Space" Models
An alternative to viewing aperiodic
packing in terms of the relative energies of
small groups of atoms is to consider poly-
tetrahedrality or icosahedrality as a space-
filling tiling of a suitable non-Euclidean
"curved-space". A planar triangulated
network requires a mean coordination
number of 6, local variations giving 5- or
7-fold coordination require curvature of
the two-dimensional plane into 3-D. Simi-
larly, perfectly periodic polytetrahedral
tilings that are impossible in 3-D can be
designed in a suitable space of higher di-

(a)
(c)
Figure 4-6. a) View of the central portion of a poly-
tope constructed by Sadoc and Mosseri (1982) show-
ing the first 13 vertices - with an icosahedral arrange-
ment, b) 20 new vertices (shaded) are added, forming
a dodecahedron, c) View of the polytope 'mapped'
back into 3-D space.
4.2 Conceptual Models 193
mension. Sadoc and Mosseri (1982) have
developed this theme in a number of influ-
ential papers. A 4-D "polytope" may be
constructed and can then be de-curved to
bring the model back into 3-D space.
Clearly, mapping back into Euclidean
space involves breaks in symmetry com-
parable with the tears in the skin of an
orange mapped from 3-D towards 2-D.
Defect regions separating the polytetrahe-
dral structures are thus an intrinsic proper-
ty of this type of model, Fig. 4-6.
4.2.3.2 Polytetrahedral Models
Models for network glasses based on the
above principle can also be constructed.
Thus if a tetrahedrally-bonded atom is
placed at the centre of each tetrahedron in
an icosahedron, the dual - a pentagonal
dodecahedron is formed. This is the basis
for several models of amorphous mate-
rials: for instance, Tilton (1957) and
Robinson's (1965) model for oxide glasses
and Grigorivici and Manaila's (1967,
1968) "amorphon" model for amorphous
tetrahedral semi-conductors. If the tetra-
hedra are decorated with sections of a dia-
mond cubic lattice, then polytetrahedral
structures, which combine amorphous
cluster and microcrystallite models can be
constructed, Fig. 4-7. To date, only the
properties of complete, symmetrical, poly-
tetrahedral structures have been examined
although there is clearly a need to model
the "connective tissue" which will not be
polytetrahedral.
4.2.4 Constrained Disorder
as the Paradigm. Stereo-Chemically
Defined Models
It is a common experimental fact that
many glasses contain structural elements
that are also characteristic of composition-
ally-equivalent crystals. What implications
194 4 Models for the Structure of Amorphous Solids
{110)
Figure 4-7. Decoration of a tetrahedron with a 14-
atom diamond cubic lattice. Packing of such tetra-
hedra give large non-crystallographic cluster models
for amorphous tetrahedral semiconductors (Gaskell,
1975).
does this have for structural models? The
answer is not obvious. The experimental
evidence, though, has prompted the devel-
opment of a diverse and ill-defined family
of structural models. In the most general
description this family overlaps the territo-
ry occupied by the random models yet also
extends into the province of the microcrys-
tallite and amorphous cluster models. In
many cases models have been generated
as essentially ad hoc responses to specific
structural data and the underlying general
ideas that link them to other similarly iso-
lated models have not been extracted. In
other cases the models can be satisfactorily
categorised under other headings - micro-
crystallite or random networks - and
broader parallels have not emerged. Here
we attempt to replace the specific solutions
with a more general category, one that in-
cludes most glasses and amorphous solids.
As mentioned above, the limited struc-
tural similarities between crystals and the
corresponding glasses represents the cen-
tral unifying theme. Models are based on
characteristic signatures of the structural
features observed experimentally in each
phase. The common feature may corre-
spond to the presence of a local structural
unit - a tetrahedron or octahedron - and
include the mode of interconnection. Fur-
ther analysis may then reveal similarities
extending into the medium-range of struc-
ture and indicating a more spatially exten-
sive structure-forming principle.
The principle underlying the notion of
constrained disorder as a model for the
amorphous phase is that similarities in
structure between a glass and a corre-
sponding crystalline phase are the result of
a set of, what can be termed, equivalent
structure-forming operations. In the case of
the glass, the operations are applied with-
out further constraint. For the crystal, ad-
ditional constraints are needed to generate
translational periodicity. Disorder is cen-
tral to the structure of the glass but now
only within limits: the structure-forming
operations - at the level of local or medi-
um-range order - limit the extent of disor-
der.
A simple example serves to illustrate the
argument. In almost all the crystalline
forms of SiO 2 , Si is tetrahedrally coordi-
nated and each SiO4 tetrahedron is vertex-
linked to its four neighbours. We take this
as an undisputed structure-forming princi-
ple for most crystalline polymorphs of sili-
ca and are not surprised to find experimen-
tal evidence for the same local structural
unit in a-SiO2. If there are no further rules
governing the structure, then vertex link-
ing with a random choice of oxygen bond
angle, complete connectivity (ideally),
leads to the familiar Zachariasen random
network model. We could go further and
 4.2 Conceptual Models 195

Figure 4-8. Formation of a chain by application of a) a structure-forming operation consisting of connecting

triangles at two vertices. For the triangle marked with an asterisk, the choice is between A, B, C, or D (viewed
from the local coordinates of the pair of triangles). In b) a random choice is made and the result is one of the
infinite set of translationally aperiodic chains. Formation of a periodic chain requires additional rules: in c) the
choice is constrained to "ABCD-ABCD" etc. (starting from the atom marked with an asterisk and working
upwards).

argue that this model for a-SiO2 is the em-
bodiment of the structure-forming princi-
ple in its purest or most idealised form since
no other rules have been used to generate
the structure. In order to generate a crys-
tal, however, the structure-forming princi-
ple is further constrained to apply in only
a limited sense - in one direction, say, to
ensure that atoms lie in straight lines. A
simple illustration, a 2-D packing of trian-
gles, is shown in Fig. 4-8.
A descriptive name for models of this
type is needed. The term "stereo-chemical-
ly defined" (SCD) model has some attrac-
tions. "Stereo-chemical" can be regarded
as short-hand for the set of "structure-
forming" operations that are central to the
model. The local structure, therefore, has
196 4 Models for the Structure of Amorphous Solids
been stereo-chemically defined and the
longer range structure becomes defined as a
result of stereo-chemical constraints.
4.2.4.1 Similarity to Random Networks
The principle of limited structural equiv-
alence of crystalline and amorphous
phases applied at different levels, can lead
to structures that are indistinguishable
from CRNs on the one hand or to micro-
crystallite models on the other. In the ex-
ample above, the only structure-forming
principle linking the crystalline to the
amorphous phase involves local structural
units, with all arrangements of these units
equally probable. The general result is a
random model: a random network (or ran-
dom coil for the example of Fig. 4-8). A
further example could be the network
models for a-Si generated by Wooten and
Weaire (1987) (see Sec. 4.5.3) in which the
topology of a diamond-cubic crystal was
progressively modified by switching bonds
until agreement was reached with experi-
mental data for a-Si. Again, the implicit
structure-forming operations are retained
as constraints - strictly fourfold, approxi-
mately tetrahedral bonding, no breaks in
connectivity, and these are also character-
istic of the crystal. Another example is the
"boroxol ring" model for a-B 2 O 3 where a
(medium-range) structural unit - the B 3 O 9
ring (Fig. 4-59 a) is connected randomly
through the oxygens to form a CRN.
4.2.4.2 Similarity to Paracrystalline
Models
Variations in the geometry of a crystal
without accompanying topological modifi-
cation lead to structures that are probably
best considered as paracrystalline models.
For example, Yasui et al. (1983) modelled
the structure of amorphous chain and
sheet silicates starting from the corre-
sponding crystalline lattices with modifica-
tion of the geometry of the chains, so that
the SiO3 chains were bent regularly in one
plane until agreement with experiment was
achieved (see Sec. 4.7.7). Clearly, in so do-
ing, none of the structure-forming princi-
ples characteristic of the crystal were vio-
lated.
4.2.4.3 Local Order as a Consequence
of Medium-Range Order
If the last two sections, describing the
structures of end members of the series
represented the entire picture, then there
would be no reason to introduce a new
category of SCD models. However, there
are glasses for which the structure-forming
principle relates to medium-range ordering
and which are describable in the same lan-
guage as the CRN and microcrystallite
models. Before discussing these, it is neces-
sary to introduce a connection between lo-
cal and medium range structure. Several
types of glasses exhibit local ordering sim-
ilar to that of a crystalline phase but any
explanation of the local order in either re-
lates to medium-range ordering.
Two illustrations serve to focus the dis-
cussion. Firstly, amorphous transition
metal - metalloid (TM-m) alloys appear to
be structurally similar to crystals in that
the immediate environment of metalloids
in the glass and crystal have similar nine-
fold coordination, trigonal symmetry and
narrow bond length distributions. Second-
ly, the local environments of several alkali
and alkaline earth cations in silicate glass-
es, mimic the local structure of the corre-
sponding crystals. At first sight, these facts
may seem unremarkable. Atoms like Si or
B have well-defined coordination spheres
in amorphous oxides: models incorporat-
ing well-defined coordination shells for B
in, say, a-Ni4B or Na in a-Na 2 Si 2 O 3

should thus present no additional difficul-
ty and random models for each should
work. Indeed, random models for TM-m
alloys have been built (Gaskell, 1979), and
these can be considered to be CRNs with a
trigonal prismatic BNi9 cluster as the local
structural unit. Also, Greaves (1985) has
proposed a "modified" CRN model in
which the alkali network "modifiers" ex-
hibit a preferred coordination, and exist in
defined regions of the structure, giving
random percolation channels intercalating
the silicon-oxygen "network" sub-struc-
ture.
The problem is to explain the structure-
forming principle - why do clusters like
BNi9 or NaO 5 exist? Well-defined tetrahe-
dral SiO4 units or triangular BO3 groups
can be said to "exist" as a result of the
strong, directional interatomic bonds. Al-
though it could be argued that B-Ni bonds
are strong too, there is no evidence for
nine-fold directional bonding. It is difficult
to see how this could be achieved as the
central B atom has no available d orbitals.
The case is even more compelling for alkali
and alkaline earth oxide glasses with weak,
ionic bonds to oxygen. In neither case can
isolated "molecular units" be contemplat-
ed. For both types of materials, local ge-
ometry and symmetry observed around B
in the closed-packed crystalline transition
metal borides and around Li, Na and Ca in
the close-packed regions of silicate crystals
is an essential consequence of an ordered
close-packing. In other words, local struc-
tural characteristics in these crystals derive
from particular medium-range packing
schemes in the crystal.
There are reasons to believe that this
conclusion extends to glasses also. For a-
TM-m alloys, the experimental evidence is
the most clear-cut and details have now
emerged - principally from neutron scat-
tering experiments with isotopic substitu-
4.2 Conceptual Models 197
tion (Lamparter et al., 1982) that the local
structure is well-defined, with nine-fold co-
ordination of the metalloid by the metal.
Evidence for a well-defined local structure
implies the presence of a degree of medium-
range ordering, of some sort. We cannot
say at the outset what the nature of the
medium-range ordering is, but that it ex-
ists. Models for amorphous TM-m alloys
were therefore constructed by Dubois,
Gaskell and Le Caer (1985) (see Sec.
4.2.4.4) which incorporated the medium-
range structural principles observed in the
crystal, to produce a SCD domain model
that satisfactorily reproduced the partial
distribution functions obtained by Lam-
parter and co-workers.
For the "network modifier" cations in
oxide glasses, similar arguments apply and
experimental evidence for medium-range
ordering is now emerging also and will be
considered in Sec. 4.7.
The point to stress here is that where
experimental evidence shows that atoms
in close-packed solids - or within close-
packed substructures - have a well-defined
local structure, then models for these
materials could contain a "medium-range
structure-forming principle" similar to that
responsible for the structure of the corre-
sponding crystal phase. More generally,
evidence for well-defined local structures
in materials where the local structural unit
has a high connectivity, require definitions
of the medium-range structure too.
These points may be rationalised by ac-
cepting that many crystal structures repre-
sent a compromise between the space and
coordination requirements of atoms in dif-
ferent sublattices. The result is that not all
structures that are topologically possible
do, in fact, exist as crystals: a point made
clearly by Dent-Glasser (1979) for silicates.
Constraints imposed by each of the con-
stituent sublattices in a silicate crystal, lim-
198 4 Models for the Structure of Amorphous Solids
it the range of existing crystals. Can we
assume that glasses, because they are non-
crystalline, avoid similar rules? The answer
is - almost certainly, No. Pauling's rules
on which the structure of crystals can be
classified are essentially arguments based
on considerations of local charge balanc-
ing, bond counting, valence, coordination
numbers, density and overall composition.
Clearly, none of these parameters is spe-
cific to the translationally-periodic solid:
all should relate to the amorphous state
too, so that Pauling's rules alone should
constrain amorphous structures. The
structure for the crystal is one successful
solution to the problem - one of the many
structures that could, hypothetically, exist,
that does. Investigations of structures for
an amorphous solid can use this as a sound
starting point - especially if a "structure-
forming" principles can be extracted from
the crystal and transferred to the glass.
4.2.4.4 Stereo-Chemically Defined Models
for Close-Packed Oxides and Amorphous
Metals Involving Medium-Range
Structure-Forming Operations
Several authors have produced random
models by modifying the topology of the
crystal at the level of the medium-range
structure. A recent example is the work of
Barenwald (1988) et al. who attempt to
model the structure of a chain phosphate,
Ba(PO 3 ) 2 by a Monte Carlo method. The
structure-forming operation preserved in
this work is the essentially parallel packing
of infinite, linear (PO3)W chains. PO 4
groups remain intact but the bond and tor-
sion angles are varied randomly to pro-
duce a fit to experiment.
A similar but more constrained SCD
model is that reported by Gaskell (1985 b)
for chain metasilicates, see Sec. 4.7.8. The
starting point was a Na or Li metasilicate
crystal in which oxygen atoms form a dis-
torted hexagonal close-packed (hep) sub-
lattice. Si, Li (or Na) occupy the tetra-
hedral interstices (highly distorted for
Na). Each (SiO3~)n chain is surrounded
by six M-0 chains (M = Na, Li). For the
glass, the hep oxygen sublattice was
preserved and the tetrahedral interstices
were populated with Si or M atoms to
form randomly-coiled, self-avoiding sili-
cate chains surrounded by M-O chains.
The resulting model thus preserves the
following structure-forming operations:
oxygen close-packing, semi-infinite, non-
branching chains, chemical ordering, "re-
pulsion" between Si atoms in adjacent
chains and "attraction" between Si and M-
containing chains. SiO4 tetrahedra are pre-
served, of course, with interconnections
through "bridging" oxygens. Randomness
while essential to the model, is applied only
after taking account of the "stereochemi-
cal" constraints imposed by the structure-
forming operations.
A final example comes from the work of
Dubois, Gaskell and Le Caer (1985) on
amorphous TM-m alloys. The apparently
complex structures observed in TM-alloys
can be considered as close-packed lattices
of TM atoms with twinning at the unit cell
level. Specifically, the cementite, Fe 3 C,
structure used here as a template for the
glass, is produced by inserting twinning
planes in every three {112} planes of the
hep structure. Capped trigonal prisms are
thus formed which are linked through
edges and vertices to form planes within
which boron atoms are accommodated.
These structure-forming operations are
preserved in a model for the glass in that
parallel twinning planes operate over a de-
fineable correlation length (1 to 2 nm). Be-
yond, lie other domains also generated by
twinning, but with planes lying in other
orientations. Topological continuity of the
 4.3 Experimental Structural Techniques
local structural units (trigonal prisms) and
the twinning planes is preserved by the in-
terface atoms too so that the ground state
of the model has no primary discontinuity
at domain boundaries. These constraints
lead to more detailed local restrictions on
the arrangement of structural units and to
a model that is topologically ordered (but
not geometrically ordered) on a length
scale of several nearest neighbour dis-
tances, but topologically and geometrical-
ly disordered beyond.
4.3 Experimental Structural
Techniques
In this section, a brief account is given of
the principal structural techniques used to
study amorphous solids. Details are given
in other volumes of this series. For com-
pleteness and to establish the basic formal-
ism, some repetition is inevitable. Particu-
lar emphasis is placed on the methods re-
quired to obtain structural data of high
information content.
Quantitative results are expressed in
terms of probability functions or distribu-
tion functions. We can define the probabil-
ity of finding an atom at a position r, in an
element of volume dr. This is a one-particle
distribution function. Similarly, we can de-
fine a more useful quantity - the probabil-
ity of finding two atoms simultaneously at
positions r1 and r 2 , thus defining a two
particle or pair distribution function. It is
more convenient to place the origin to co-
incide with one atom and work with inter-
atomic vectors, or for a homogeneous sys-
tem, interatomic distances. Then the prob-
ability of finding an atom in an element of
volume dV at a distance r from the origin
atom equals Qog(r)dV= Q(r)dV. Here,
g (r) is the pair distribution function, Q (r) is
the r-dependent atom density and Q0 the
199
average atom (number) density. For amor-
phous solids, since g(r) = Q(r)/Q0, the
function tends to unity at large values of r.
Although experimental information on
higher order distribution functions is diffi-
cult to obtain, we could define a triplet
distribution function in terms of the proba-
bility of finding atoms simultaneously at
r
i •> ri j r3 Setting the origin at a given atom
position allows a definition of the triplet
distribution function in terms of the prob-
ability of finding one atom at an inter-
atomic distance rt, a second at r2 with the
included angle being 6.
Often the terms distribution function
and correlation function are used inter-
changeably. Strictly, the pair correlation
function, h(r) = g{r)-\ so that this func-
tion tends to zero as r tends to infinity.
Cusack (1987) gives an excellent account
of the necessary formalism.
4.3.1 Neutron Scattering Techniques -
Static Structural Methods
Neutrons have zero charge and do not
interact with charges in the specimen, in
contrast to X-rays and electrons. Neutrons
interact with the (small) atomic nuclei and
this considerably simplifies any descrip-
tion of the scattering equations, since the
scattering mechanism is essentially inde-
pendent of the scattering angle, if inelastic
scattering is neglected.
For an isotropic liquid or glass, vectorial
information characteristic of a crystal is
averaged, so that the intensity is Q-depen-
dent but there is no other angular varia-
tion. In a typical (elastic) scattering mea-
surement, the intensity of a monochro-
matic beam of scattered neutrons is mea-
sured as a function of the scattering angle
- conventionally 2 9. Usually the result is
expressed in terms of the modulus of a
scattering vector, Q, \Q\ = Q = 4nsinO/A,
200 4 Models for the Structure of Amorphous Solids

where X is the incident neutron wave-

length.
The experimental scattered intensity os-
cillates around a background, I*xpi term
equal to the scattering from a structureless
medium of the same atomic density and
composition as the specimen - "self scat-
tering". Neglecting inelasticity effects,
7fxp = Nb2 where b is the neutron (coher-
ent) scattering length for the atoms of a Figure 4-9. Typical experimental neutron scattering
monoatomic solid and TV is the number of data showing the "self-scattering", Nb2, from a struc-
atoms in the neutron beam. Generally tureless medium containing the same number of
there is also a degree of incoherent scatter- atoms per unit volume as the specimen.
ing that is subtracted from the total scat-
tering to obtain the coherently-scattered
fraction. Oscillations around /fxp are due Each distance in the specimen thus exhibits
to constructive and destructive interfer- its signature in the form of a sine wave of
ence from neutron de Broglie waves scat- "period" AQ = 2n/rmn - short distances
tered from nearby nuclei and these oscilla- giving rise to long period fluctuations in
tions contain the structural signals, I(Q) Q-space and vice-versa (see Fig. 4-10).
(Fig. 4-9). Thus, The Debye equation, Eq. (4-5), is conve-
nient for simple calculations on molecular
groups with discrete interatomic distances.
= Nb2S(Q) (4-3 a) For a solid or a liquid it is preferable to
work with the atomic density, Q (r), defined
where S (Q) is the so-called structure factor as the number of atoms in a volume d3r, at
and contains all the structural information.
Often the same equation is re-expressed in
terms of the "interference function"
i(Q)=I(Q)/Nb2-l = (4-3 b)
It is useful to obtain, at the outset, a con-
ceptual grasp of what information S(Q)
contains. For an isotopic specimen, Debye
showed that the scattering from N particles
separated by a constant distance rmn is
Q /nm"
given by:
Figure 4-10. The reduced interference function, F(Q\
1 N for a monoatomic specimen. With a gaussian distri-
(4-4) bution, centered on R, the result is a damped sinu-
soidal wave of period 2n/R. The full line shows F(Q)
or, more simply, in terms of a "reduced for R1 = 0.246 nm, <r1 = 0.0074 nm, corresponding to
interference function", the first neighbour Ge-Ge distance. The dashed
curve corresponds to values typical of the second
peak in a-Ge: R2 — 0.305 nm, o2 = 0.026 nm. Note the
relatively rapid decay of the second-neighbour data
(4-5) which is only detectable for relatively small values
ivii of Q.
 4.3 Experimental Structural Techniques 201

distance r; so that the number of atoms in and

a spherical shell, radius r, thickness dr is:
= ^F(Q)smrQdQ (4-1 lb)
J(r) = 4nr2Qog(r)dr = 4nr2Q{r) (4-6 a)
where J(r) is the so-called radial distribu- (In other conventions, G (r) is replaced with
tion function (rdf). D (r) - the differential correlation function.)
A function t(r) is often used:
4.3.2 X-Ray Scattering
t (r) — 4 n r Q (r) or
X-rays interact with atoms of the speci-
T(r) = 4 n rb2 Q{T) (4-6 b) mens chiefly through their electrons. (A
It may be shown (Warren, 1969) that: term involving the nuclei is reduced by the
ratios of the masses of electrons and nu-
clei.) Since electron orbitals - particularly
Q the outer valence shells - have radii that
° (4-7)
are comparable to interatomic distances,
where Q0 is the average atom (number) interference terms arise from the "shape" of
density. the orbitals. Assuming spherical shells, the
Defining a "reduced" radial correlation effect is to replace the neutron scattering
function: lengths, b, in the above equations with an
\ = 4nr(Q(r)-Q0) (4-8) atomic scattering factor, f(Q% i.e. atomic
scattering factors are now g-dependent,
then, due to interference from waves scattered by
1 electrons within the shells. Such atomic
S(Q) = l+— fG(r)singrdr (4-9)
Qo scattering factors (or "form factors") are
or, tabulated in standard works. Thus the
scattered intensity is now related to a Q-de-
F(Q)= fG(r)sinQrdr (4-10)
pendent background, Fig. 4-11. With this
o
modification, the remaining equations in
The advantage of these forms of the De- Sec. 4.3.1 hold.
bye equation is that only deviations from
the average atomic density contribute to
F(Q). For liquids and glasses, the atomic
density, g(r\ approaches Q0 at large r so
that integration can be usually truncated
at r& 1.5 to 2.0 nm.
It is possible - and often desirable - to fit
structural data in the form of S (Q) or F (Q)
with computer data for a structural model
that gives G (r). However, the structural in-
formation is easier to visualise in real space
using the fourier (strictly sine) transform of
S (Q) or F (Q). We thus have two symmetri- u
cal transforms:
Figure 4-11. Typical X-ray scattering data, oscillating
F(Q)= jG(r)sinQrdr (4-1 la) around a Q-dependent atomic scattering factor, / (k).
0 (Here, k is used instead of Q.)
202 4 Models for the Structure of Amorphous Solids
For electron diffraction, interaction is
again with the electrons but the charge on
the nucleus now becomes important. If the
atomic scattering factors for electron and
X-ray scattering are fE(Q) and fx(Q) then:
^= 4n2(Z-fx(Q))/Q2 (4-12)
Electron scattering is much stronger (typi-
cally 104 larger) than X-ray scattering
which is in turn very much stronger than
neutron scattering. Thus very thin films are
necessary for electron diffraction com-
pared to specimens of 5 to 10 g for neutron
scattering.
4.3.3 Effects of Disorder
on Scattering Data
F(Q) for a monoatomic specimen with
all atoms at a constant distance, R, will be
an infinite sine wave. Non-crystalline
solids are characterised by a distribution of
local sites rather than a single environ-
ment, so that the distributions are broad-
ened. The corresponding F (Q) is a damped
sine function, Fig. 4-10.
For a peak shape in the form of a gaus-
sian i.e.
G(r)ozQxp(-(R-r)2/2(i2)
then,
exp(- (4-13)
F{Q)K
R the "true" real space function which would
For more general r-space distributions
with a number of peaks in r-space, the
transform of each is multiplied by
the corresponding "damping function"
exp(— Q2a2/2) and the contributions are
then summed. The result is a smearing of
F(Q) at high Q. The above is an example of
the convolution or folding theorem. G (r) in
this case is a convolution of a set of delta
functions with a gaussian. The transform,
F ( 0 , is a product of the transform of G (r)
and the transform of the gaussian broaden-
ing function, which is another gaussian -
given by the exponential term in Eq. (4-13).
Similarly, the transform of a product of
two functions is the convolution of the
fourier transforms of the two functions.
Broadening of the distribution of inter-
atomic distances arises partly from differ-
ences in the environment of each atom due
to disorder - the static broadening, as. In
addition, thermal motion leads to another
contribution, ath. For the j t h interatomic
distance the total effect is obtained by
addition in quadrature: (c^)2 = (asj)2 +
2
4.3.3.1 "Termination" Smearing
Since scattering measurements are lim-
ited to a scattering angle, 2 6max = n9 g max is
limited to 4 n/ 2, and for typical X-ray and
neutron wavelengths of 0.05 to 0.1 nm,
Qmax = 250 to 125 nm" 1 . Eq.(4-llb) in-
volved a transform of the scattering func-
tion F(Q) over an infinite Q range. The
effect of truncating the integral at Qmax is
equivalent to multiplying F (Q) with a mod-
ification function, M(Q), such that:
M(Q) =
M{Q) = \
Q < e max
From the convolution theorem, if G* (r) is
be obtained by transformation of F(Q)
with <2max=oo, then truncation of the
fourier transform of F (Q) at Qmax implies
that G* (r) is convoluted with a peak shape
function, P*(r) which is the cosine trans-
form of M(Q):
P* (r) = - J M (Q) cos (r Q) &Q (4-14)
71
0
(See for example Waser and Schomaker
(1953).)
 4.3 Experimental Structural Techniques
For M (Q) in the form of a step function,
the peak shape function is a SINC func-
tion, Fig. 4-12. Thus if G*(r) is considered
to be made up of a set of (5-functions, the
effect of multiplying of ^-function by P (r)
and then summing to obtain G (r) - which
amounts to a convolution of G*(r) with
P* (r) - is to broaden the features of G* (r)
and to introduce satellite "termination rip-
ples". The ripple may be suppressed, at the
expense of further broadening, by using
smooth modification functions. A number
are quoted in Fig. 4-12.
-40
Figure 4-12. Peak shape functions corresponding to a
fourier transform of reciprocal space data truncated
at Qmax by a modification function M (Q).
A. M(Q) = B.
with B = \oge(10/Q 2
max). C. M(fi) = l (Wright and
Leadbetter (1976)).
203
4,3,4 Polyatomic Solids
Scattering in polyatomic solids can be
treated using the Debye equation but the
terms involving the different atomic spe-
cies, a, /?, etc. must now be accounted. We
must now consider partial structure fac-
tors, Sap(Q), and partial pair correlation
functions Gap(r). For a solid containing m
atomic species, there are m(m + l)/2 inde-
pendent partial functions.
The number of atoms of type /? in a vol-
ume d 3 r at a distance r from an origin a is:
)= 4nr2Qap(r) (4-15)
The relative density can also be defined in
terms of the mean density of atoms of type
P,Q0(p) = npQ0 where np is the atomic frac-
tion of species /?. Thus:
9ap(r) = Qap(r)/npQ0 (4-16)
The partial reduced radial correlation
function is:
(4-17)
Eqs. (4-11) now become:
= \Gap{r) sin(Qr)dr (4-18a)
and
Gap (r)=-$FaP (Q) sin (r Q) dQ (4-18 b)
4.3.4.1 Total Distribution Functions
and Structure Factors
Partial distribution functions and struc-
ture factors give a detailed description of
the environment of each atomic species
and the information content is equivalent
to G (r) or S (Q) obtained for a monoatomic
solid. Experimental scattering measure-
204 4 Models for the Structure of Amorphous Solids
ments from polyatomic solids do not di-
rectly give the partial functions. The mea-
sured total structure factor, S(Q) is a
weighted sum of contributions from inde-
pendent pairs of atom types, a a, /?/?, a/?,
etc. Thus for a diatomic solid:
7 it becomes vital to extract partial structure
aeSaAQ) (4-19 a)
a fi
where WaP is a weighting factor,
nanfibab*
(4-19 b)
and b a , bp (or / a , /^ for X-rays) are the
scattering lengths for atomic species a, /?
and
The total structure factor is defined as:
S(0 = . ^ +1 (4-20)
N\(by\2
Again, the brackets, < >, refer to a compo-
m
2
sition average so that <b > = Z (**«&«)•
a=1
From iS (<2) the total reduced radial corre-
lation function, G(r) can be obtained as:
G(r) = I Z ^ G ^ ( r ) (4-21)
Since the weighting factors differ for X-ray
and neutron scattering, S (Q) and G (r) mea-
sured by X-rays will not be identical to that
measured using neutrons.
4.3.5 Extraction of Partial Structure
Factors
It will be obvious that averaging over
three partials for a diatomic solid leads to
a drastic reduction in the information con-
tent of a measurement. Peaks in one partial
tend to overlap with troughs of another, so
that the resulting destructive interference
leads to smooth total functions in cases
where the underlying partial functions are
strongly oscillatory.
Furthermore, partials with small weight-
ing factors are buried beneath the oscilla-
tions of strongly-weighted partials. For the
most informative structural measurements,
factors from total structure factors and
partial correlation functions from total
correlation functions.
Apart from a few simple solids like SiO2
where this can be done by inspection (see
Mozzi and Warren, 1969), it is necessary to
employ special techniques. We consider
five possibilities.
4.3.5.1 Combination of the Results
of X-Ray, Neutron and Electron Scattering
For a binary alloy, if three experiments
can be performed with three types of radia-
tion thus providing three sets of equations
of the form S (Q) = £ £ WaP Safi ( 0 , and if
a fi
values of Wafi are sufficiently different for
the three measurements, then the three
equations can be solved for the three un-
known quantities S aa , Safi9 Spp.
The atomic scattering factors depend on
the character of the probing radiation, as
mentioned earlier. Furthermore, although
X-ray and electron form factors increase
monotonically with atomic number Z, the
neutron scattering length, b, is determined
by two contributions - "potential scatter-
ing" which increases very slowly with Z,
and a "resonance scattering" term - that
oscillates, apparently haphazardly. It is
thus possible to choose systems for which
the X-ray and neutron weighting factors,
Wap9 are significantly different for the vari-
ous types of radiation.
Form factors for electrons are insuffi-
ciently different from those for X-rays for
electron diffraction to be of much use as a
third experiment (in addition to X-ray and
 4.3 Experimental Structural Techniques
5 6
r(A)
neutron scattering). For elements with a
magnetic moment, such as Co, the moment
may be oriented with a suitable external
magnetic field. The atomic scattering
length for polarised neutrons depends on
whether the atomic moment lies parallel or
anti-parallel to the neutron spin, so that for
Co-containing alloys, magnetic scattering
offers two experiments. A classic investiga-
tion of a-Co 4 P was performed in this way
by Sadoc and Dixmier (1976) using a com-
bination of X-ray scattering, polarised and
unpolarised neutron scattering to obtain
the three partial structure factors for the
alloy (Fig. 4-13).
43.5.2 Neutron Scattering
with Isotopic Substitution
Not only do neutron scattering lengths
vary sharply from element to element; they
also vary from isotope of the same element.
For example, Ni has isotopes in which b (in
units l(T 1 5 m) varies from - 8 . 7 (62Ni) to
14,4 (58Ni). Three experiments with three
isotopic mixtures of Ni in a binary alloy
205
Figure 4-13. Partial struc-
ture factors, Gij{f) for a-
Co 81 P 19 obtained by Sadoc
and Dixmier (1976).
10
thus allow extraction of partials from three
sets of neutron scattering data. In another
seminal measurement, Lamparter et al.
(1982) obtained the partials for a-Ni 81 B 19
using alloys of X1B with nat Ni, 62 Ni, and a
mixture of 62 Ni and 60 Ni giving a coherent
scattering length of zero. X-ray scattering
data was also collected for good measure.
The results are shown in Fig. 4-14.
4.3.5.3 "Difference" Methods
For compounds with more than two
atomic species, direct extraction of partials
would be impractical. For a triatomic ma-
terial, six independent measurements would
be required. However, it is still possible to
simplify the problem and to increase the
information content of measurements by
obtaining information on the environment
of a selected atomic species. This is done by
taking differences of the neutron intensities
scattered by two samples of the same mate-
rial, identical apart from the isotopic con-
centrations of one of the species, M, say.
Writing the normalised neutron scattering
206 4 Models for the Structure of Amorphous Solids
geometrical packing model
2.0 4.0 6.0 8.0 10.0
Figure4-14. Partial structure factors Gtj(r) for a-
Ni 81 B 19 obtained by Lamparter et al. (1982).
intensity per atom:
^' a a, B
(4-22)
The first term on the right hand side
contains g-independent "self scattering"
terms; the second, terms involving M such
as: b^ HM(SMM(Q) -1) and terms involving
pairs of atoms other than M. Only the
terms involving bM are affected by isotopic
substitution so that (apart from a differ-
ence of background levels) the difference
between two intensities for the two mea-
surements, A J ( 0 , contains only terms in-
volving correlations between M and other
species (including M) thus:
M (Q) = Const + A (SMM (Q) - 1 ) +
where
where bM and b'u are the neutron scattering
lengths of the two isotopes. The technique,
pioneered by Soper et al. (1977) in studies
of molten salts and aqueous solutions has
now been applied to many glasses (see Sec.
4.7).
4.3.5.4 X-Ray Absorption Spectroscopy
Each element has a characteristic ab-
sorption edge, corresponding to excitation
of a bound electron from a core shell to an
excited state above the conduction band
minimum. The energy involved lies in the
X-ray region and is specific for each ele-
ment. At energies, £, immediately above
the threshold, £ 0 , the absorption coeffi-
12
cient exhibits a series of oscillations ex-
tending up to 1 keV above the absorption
edge. After background subtraction and
suitable normalisation, the oscillatory part
of the signal, x (E), the X-ray absorption
fine structure (XAFS) contains structural
information on the environment of the ex-
cited atom.
Specifically, x (E) represents interference
between the photoelectron wave emitted
by the excited atom and waves back-scat-
tered from its neighbours. It thus has con-
siderable similarity to the interference
function in X-ray, electron and neutron dif-
fraction and provides similar structural in-
formation.
Similar effects occur after excitation with
fast electrons: scattering processes that in-
volve excitations from core states, appear
in the electron energy loss spectrum
(EELS) as saw-tooth peaks with an associ-
ated fine structure at higher energies. Such
transitions can be observed in an electron
microscope, for example, if the transmitted
electron beam is energy-analysed.
The fine structure in both types of spec-
tra can be roughly categorised as the rela-
tively sharp oscillations in the immediate
 4.3 Experimental Structural Techniques
vicinity of the "edge" and the gentler oscil-
lation of the extended XAFS. The former
involves strong scattering of low energy
photoelectrons for E — Eo «100 eV and the
latter region can be treated by a single scat-
tering approximation (Sayers et al., 1971).
Writing the latter approximation in
terms of the modulus of the photoelectron
wave vector, k2 = 2mQ(E—E0)/h2 then:
• exp ( - 2 o) k2) exp ( - 2 Rj/A (fc)) (4-24)
This expression is clearly more compli-
cated than the corresponding expression
for X-ray or neutron scattering (Eq. (4-5)).
However, the similarities become more ob-
vious on inspection. Rj is the distance from
the central atom to a shell of Nj neigh-
bours. Eq. (4-5) contains a term in sin QRj
whereas Eq. (4-24) has a similar term in
sin 2 kRj. Each, therefore, indicates that a
discrete peak in r-space at Rj gives rise to
sine wave oscillations in Q-space or k-
space, of period 2 n/Rj or n/Rj respectively.
(In XAFS, the interfering wave travels from
the central particle to its neighbours and
back again - a distance of 2 Rj.) Complica-
tions inherent in Eq. (4-24) involve a phase
shift term Sj(k% a 'Debye-Waller' term
exp (— 2 a? fc2) where Oj measures the
breadth of the r-space distribution, and a
term exp (— 2 Rj/A (k)) representing the de-
cay of the amplitude of the photoelectron
wave due to inelastic processes. A is a mea-
sure of the mean free path. The back scat-
tering factor, \fn(k)\9 corresponds to the
term f(Q) in X-ray scattering (the n indi-
cating 180° scattering).
As with X-ray or neutron scattering, it
may be preferable to convert Eq. (4-24)
from its Debye-like form into a version
that includes pair distribution functions,
207
3=n-l
,(*)_
kr2\fn(k)\
•exp(-2rM(fc)) (4-25)
Here, a corresponds to the excited ele-
ment of species a, and /? to neighbours of
other species which includes neighbouring
atoms of species a. The important point is
that in a triatomic alloy, say Xa involves
terms in P aa , Pafi, Pay but excludes other
terms not involving a. The structural infor-
mation is thus analogous to that obtain-
able from neutron scattering with isotopic
substitution of species a in the difference
mode, or to X-ray differential anomalous
scattering at the absorption edge of ele-
ment a.
The advantages, though, are that this
element-specific technique is much more
generally applicable since medium atomic
number elements can be examined by X-
ray absorption techniques and light ele-
ments by EELS without any requirement
for isotopes with contrasting scattering
properties. Moreover, a high maximum
value of reciprocal space or fc-space data
is routinely available - typically kmax =
200 nm x equivalent to g max = 400nm x
in neutron scattering.
There is a major disadvantage, however,
for disordered materials. If a peak in r-
space is broad - as they are in glasses for
second- and higher-neighbours, then the
Debye-Waller term tends to zero except for
the region below fc^40nm-1 - which is
also the region corresponding to strong
multiple scattering of low energy pho-
toelectrons and where single scattering
theory does not apply. The extended
XAFS spectrum thus offers little informa-
tion beyond the first peak in r-space and
even then is not sensitive to broad features
- shoulders or wings - that correspond to
higher frequency fourier components in re-
ciprocal space.
208 4 Models for the Structure of Amorphous Solids
One answer to this problem, of course,
would be to analyse the low energy region
where information on high neighbour cor-
relations is contained. The difficulty with
this approach is that there is no method for
inverting the data to obtain, directly, the
real-space distribution. One must proceed
by comparing experimental data with
computed low energy XAFS or EELS data
computed from trial structures. Although
some success has been achieved by this
method - for example work on a-Si dis-
cussed in section 5 - the accessible infor-
mation content is limited.
4.3.5.5 X-Ray Anomalous Scattering
In the vicinity of an absorption edge in the
X-ray spectrum of an element, the atomic
scattering factor, / , for that element be-
comes energy-dependent. Writing / in
terms of its real (f±) and imaginary (f2)
components: f=f0 +f1 + if2 - Here, f0 rep-
resents the contributions to the scattering
factor from all processes other than that
associated with the absorption.
The imaginary (absorptive) part shows a
step function change as the energy is in-
creased through the region of the absorp-
tion edge, whereas fx is small and negative
at energies below the edge, has a deep min-
imum at the position of the edge and then
rises progressively beyond that. By taking
scattering measurements at two incident
X-ray energies on either side of the absorp-
tion edge, preferably using a tunable X-ray
Synchrotron source, values of/ x can be
sufficiently different that subtraction of
the two scattering curves gives element-
specific information - as in the isotopic
substitution technique. Thus, A/(g) can
be written as a similar equation to Eq. 4-23
with weighting factors given by Ludwig et
al. (1987). In principle, further measure-
ments can be taken at the absorption edges
of other elements in the material.
The magnitude of the changes in ft can
be about 20 % but it has proved quite diffi-
cult to obtain good separation of the par-
tials in binary alloys due to a combination
of random and systematic errors. More-
over, the X-ray wavelength is determined
by the position of the absorption edge
which increases with atomic number, Z, so
that to obtain X-ray scattering with a rea-
sonably large Q range, the element of in-
terest should have a high atomic number.
On the other hand, there are none of the
problems associated with the low Q cut-off
that limit the usefulness of XAFS data.
Pioneering measurements on the struc-
ture of Ge-Se alloys were performed by
Fuoss et al. (1981) and more recent work
includes studies of a-Ni2Zr (de Lima et al.,
1988).
4.3.6 Vibrational Spectroscopy
The static structural properties consid-
ered above give one view of the properties
of an amorphous solid. Dynamical proper-
ties - the response of the solid to an excita-
tion, not only give additional information
on the static structure but also add new
information.
The simplest description of the vibra-
tional properties of a material is given by
the vibrational density of states function,
g(co); the number of vibrational modes
with frequencies between co + Aco. This
quantity is not directly measurable but ex-
perimental methods provide information
that can be related to g(co). However, for
amorphous solids - in contrast to crystals
- this transformation is by no means with-
out uncertainty. Lack of periodicity in an
amorphous solid has the important effect
that the (crystal) momentum selection rule
 4.3 Experimental Structural Techniques
appropriate to crystals is no longer strictly
valid. The infra-red absorption process
in a crystal is governed by laws of con-
servation of energy and momentum,
E(ko) = E(q); ko = q, where k0 and q are
the wavevectors of the incident photon
and the created phonon respectively, and a
selection rule restricting the modes to
those for which there is a net change in
the dipole moment. For isotropic solids,
k = \k\ = 2njX so that for the IR effect
with 2^10 jim, k is effectively zero on
the scale of the Brillouin zone boundary
( ^ l O n m " 1 ) and the IR spectrum there-
fore picks out the sub-set of modes in g (co)
for which £ = 0. In an amorphous solid
with no identifiable unit cell, k becomes a
poor quantum number so that all modes in
g(co) become potentially optically active.
Similar statements applies to the Raman
effect (although now it is the changes in
polarisability rather than the dipole mo-
ment that provides one of the selection
rules).
Thermal neutrons with energies similar
to vibrational quanta can also be scattered
inelastically that is with the creation or
destruction of one or more phonons. The
static structure factor, S(Q), discussed
above is thus replaced in a complete treat-
ment by S(Q, co) - the dynamical structure
factor. Certain nuclei - notably H - pos-
sess a spin, /, and since scattering of neu-
trons involves the properties of a com-
pound nucleus, neutron + nucleus, with
spin 7+1/2 or 7—1/2, the two states have
different scattering lengths so that scatter-
ing from such nuclei is only partially co-
herent. H has a particularly large incoher-
ent cross section and since incoherent scat-
tering involves addition of intensities of
scattered waves - the scattering intensity is
given by a sum over essentially indepen-
dent vibrating atoms. Thus the energy gain
(or loss) of neutron scattered by such pro-
209
cesses is directly related to g(co), i.e.
S(Q,co) = g(co)fN(Q,co)
where,
/N iQ,<o) = E ^ r <uf (a))> exp ( - 2 Wi (Q))
1 Mi
(4-26)
Here, bt and Mt are the incoherent scatter-
ing lengths and mass of the ith species;
<w? (co)} is the mean square displacement
of the ith atom averaged over phonon
modes near co and Wt(Q) = Q2 <u?>/6 is a
Debye-Waller factor.
Neutron incoherent scattering data
from any materials is useful because of the
close resemblance of the experimentally
measured spectrum to g (co) with few of the
problems associated with the transform
from, say, Raman data to g(cn).
Experimental data from Raman and IR
spectra has great value in structural studies
on amorphous solids. The symmetry-
based selection rule still operate so that
totally symmetric vibrations, for example,
that produce no change in dipole moment
but a change in polarisability are, to first
order, IR-inactive and Raman-active - as
in molecules. This is valuable information
therefore. Secondly, the high frequency vi-
brational bands, at least, associated with
the motion of atoms in local structural
units are only slightly shifted (and broad-
ened) compared to the crystal, that it is
trivial (and cheap) to distinguish between
tetrahedral and octahedral coordination
in, say, a-GeO 2 .
The problem for amorphous solids is
that in some materials - such as the amor-
phous semiconductors, the observed IR or
Raman spectrum does indeed mimic g (co)
whereas for many oxide glasses - notably
borates and phosphates - sharp bands are
observed that are unlikely to give any di-
rect representation of g(co).
210 4 Models for the Structure of Amorphous Solids
In a glass like SiO 2 , or an amorphous
semiconductor such as a-Si, the tetrahe-
drally-bonded atoms are extensively inter-
connected but without any simplifying pe-
riodicity. The vibrations of the atoms com-
prising the ensemble now depend on the
relative phase of all the other atoms -
nearest-neighbour atoms being most im-
portant. Since there is no unit cell, the con-
cept of a well-defined phase difference be-
tween equivalent atoms in adjacent unit
cells is inapplicable and the independent,
plane wave-like vibrational states no
longer exist. Modes are therefore strictly
hybrids of all others. We can still require
that selection rules operate but now strictly
over the total number of atoms in a macro-
scopic specimen. Progress has been made -
for example by Shuker and Gammon
(1970), Galeener and Sen (1978) and oth-
ers but the exact quantitative treatment de-
pends on calculations of the properties of
relatively large models.
4.3.7 High Resolution Transmission
Electron Microscopy
High resolution transmission electron
microscopy (HTREM) differs fundamen-
tally from the diffraction techniques dis-
cussed earlier. Diffraction of X-rays, neu-
trons or electrons involves interference be-
tween waves scattered from neighbouring
atoms as a result of phase and amplitude
differences: structural information is con-
veyed in the angular distribution of the
intensity of scattered waves but phase in-
formation is absent in the final signal. The
information content is significantly de-
graded therefore. HRTEM images are the
result of scattering of electron by atoms of
the specimen but amplitude and phase in-
formation is preserved - albeit with some
significant distortion introduced by the
electron optics.
For sufficiently thin specimens, the elec-
tron wave incident on the specimen is
weakly scattered and the wave function of
the emergent beam can be represented in
terms of an (almost) unchanged amplitude
but with the phase shifted by an amount
proportional to the specimen potential
projected onto a plane perpendicular to
the incident electron wave vector. This is
related to the projected electron density of
the specimen, so that the emergent wave
can be considered as a 2-D mapping of the
projected electron density of the specimen.
An optically faithful electron microscope
could thus give a magnified view of the
electron density on the scale of interatomic
distances, if this phase difference map were
to be translated into- an intensity, or con-
trast, difference in the image. This is
achieved in a "phase-contrast" image
which makes use of changes in phase intro-
duced by the imaging electron optics, in an
analogous manner to phase microscopy in
(light) optics. A microcrystalline specimen
can thus be imaged as a series of lattice
planes in which a suitably Bragg-oriented
microcrystallite generates a periodic fluc-
tuation of the phase of the scattered elec-
tron wave of period dhkl in a plane perpen-
dicular to the electron beam direction, z.
This phase grating is translated into a mag-
nified periodic fluctuation in the contrast
of the final image.
One of the major differences between
this structural information and that
derived from the angular distribution of
the scattered intensity is in the degree of
averaging involved. In an X-ray measure-
ment, the scattered information is a repre-
sentation of the sum of interatomic vectors
from about 1020 origin atoms. In a TEM
image, structural information relating to a
local region of the specimen is retained
within a corresponding local region of the
image. Consequently a cubic microcrystal-
 4.3 Experimental Structural Techniques 211

lite of, say, 4 nm edge length involves aver- Specimen periodicity (A)
aging over about 104 atoms. Moreover the 2010 6
1
U 3
1 1 1
2 1.5
i i • 1 i
image is a 2-D representation of a 3-D 1 -
a) "
object, rather than a one-dimensioned pic-

L/ v/ J X
/ • -

/
\ /
ture as in electron diffraction. /
/

C3 /

In practice, perfect transmission of T 0

/
\ /
V
structural information is not achievable \
\

and current high resolution images are sig- f

nificantly degraded maps of the electron
density of the specimen. The problems 31- b) J

arise from aberrations in the electron opti-

cal imaging system and from the diffi- A
culties inherent in unscrambling informa-
tion from a projection of the atomic densi-
2 -- \
ty over the thickness ( « 4 nm) of the spec-
imen. Abberations in the objective lens of s
\ ________ f-A V •,%
' \
/ \
i
\
\
\

/' J! / \ t<''
to _ _ /- * — V- —
the microscope limit faithful imaging to
_ _ _ _

/ \
\
waves scattered through angles, 9 to the \

optic axis that lie within "windows" where •

>

phase contrast is effective. Specifically, a i 1

so-called "contrast transfer function",
T(Q), can be defined in terms of 6 and
therefore Q, with the effect of an instru-
ment response function. This function can
be positive or negative (implying contrast
reversal) and good imaging corresponds to
a range in Q for which T(Q) has a relative-
ly large and constant value (see Fig. 4-15).
T(Q) for modern high resolution electron
microscopes is large at moderate angles,
corresponding to Bragg scattering from
lattice planes with Q in the range 5 to
30 nm" 1 and interplanar spacings of
about 1 to 0.2 nm. For Q values greater
than this, the CTF passes through zero
(with zero transmission of information,
therefore) and then becomes oscillatory
and this defines an effective resolution lim-
it. Effects of beam convergence, chromatic
aberration, incoherence etc. also limit the
resolution to about 0.15 nm.
The effects of the above are that a
HRTEM image is only a partial represen-
tation - and in many cases a "scrambled"
representation, at that - of the projected
Figure 4-15. a) Contrast transfer functions, T(Q), for
100 kV microscopes (dashed line) and 500 kV (full
line) corresponding to a generalised defocus value of
3 1/2 . b) Structure factors for a-Pd4Si taken from neu-
tron scattering data (full line) and X-ray data for a-Ge
(dashed line) (Gaskell et al., 1979).
specimen potential and electron density. In
terms of the interference function, i(Q),
high resolution images contain informa-
tion limited to the first peak in i{Q) for
amorphous semiconductors and only the
best microscopes have resolution extend-
ing to the first peak for amorphous metals,
which have smaller d-spacings. With mod-
ern high resolution microscopes, the prob-
lems are no longer severe for the majority
of amorphous solids with relatively large
d-spacings. However, much of the older
work in the literature needs to be treated
with caution due to neglect of the effects of
the aberrations in 100 keV microscopes
operated at or beyond their limits of reso-
lution.
212 4 Models for the Structure of Amorphous Solids
The second problem arises as a result of
the effects of projection. Since the electron
wave-function immediately after the speci-
men is a projection of the specimen poten-
tial over a column which is the thickness of
the specimen, it becomes impossible to dis-
tinguish atoms that are, say, nearest neigh-
bours, from those that appear to be at the
same projected distance but in fact lie at
the upper and lower edge of the foil and
are thus separated by about 4 nm in the z
direction. Moreover, ordered regions giv-
ing coherent Bragg diffraction, are unlike-
ly to be larger than 2 nm in size so that
there is at least as much material contrib-
uting information to the image which is
either ordered but not Bragg orientated, or
from a random matrix. The non-Bragg ori-
ented material therefore contributes noise
which significantly degrades the image.
In practice, there is a third problem due
to inelastic scattering which is especially
prominent at low scattering angles and can
submerge the coherently scattered electron
intensity and thus further degrade the im-
age.
As a result of these problems, HRTEM
has proved to be of only limited use in
establishing the short-range structure of
amorphous solids. It is important to recog-
nise, though, that when the technique is
used to complement diffraction studies,
the information gained concerns the medi-
um-range structure in the range 1 to 2 nm
where diffraction methods are relatively
powerless. Examples of the use of
HRTEM will be discussed in Sec. 4.5.
4.3.8 Nuclear Magnetic Resonance
In a strong applied magnetic field, Ho,
the degeneracy of nuclear spin states is re-
moved (Zeeman interaction). For nuclei
with spin, /, the difference between the en-
ergy levels is given by:
E(m) = yhmH0 (4-27)
where, y is the gyromagnetic ratio charac-
teristic of the nucleus and m is the magnetic
quantum number. Application of exciting
radiation results in a transitions between
states with quantum numbers that differ by
Am= ± 1, and the frequency at which this
transition occurs depends, through y, on
the excited nucleus. NMR is thus an ele-
ment-specific structural technique.
Sensitivity to the local environment of
the nucleus comes from electrons near the
nucleus which, by their motion, create
small magnetic fields that add vectorially
to // 0 , so modifying the local magnetic
field at the nucleus. The nucleus can be said
to be partially shielded from the external
field by the electron distribution of the
atom which, in turn, is determined by
bonding interactions with neighbouring
atoms. Since the electron distribution is, in
general, non-spherical, the interaction is
orientation-dependent, represented by a
shielding tensor, a; the isotropic compo-
nent being represented by the "trace" of the
tensor:
a{ = 1/3Tr(d) = 1/3(tT±1 +<r22 + <733) (4-28)
For a single crystal, the anisotropy in
this chemical shift interaction changes the
Zeeman frequency into a set of new fre-
quencies, the number being determined by
the local site symmetry. Thus two frequen-
cies are observed for a nucleus in an axially
symmetric site, three for orthorhombic
symmetry. NMR is therefore sensitive to
the symmetry of the local environment of
the absorbing nucleus. For polycrystalline
specimens and amorphous solids, in which
the local symmetry axes are randomly ori-
entated, the resulting NMR spectrum is a
sum of all the frequencies representing the
range of chemically-shifted resonant fre-
 4.3 Experimental Structural Techniques 213

a) Zeeman Chemical b)
shift anisotropy
-1/2 -
T Na 2 Si 2 0 5

1/2 <
i . | i r i T—y . , , , , , , , ,
-50 -100 -150 -200
Parts per million from TMS

c) d)

Na2Si205
Rotation axis
SSB CB
Flutes Magic angle
SSB
Sample rotor R.f. coil

Driving gas
1
I T
Stator
-50 -100 -150 -200
Parts per million from TMS
Figure 4-16. a) Energy levels for a nucleus such as 29Si with spin, 1 = 1/2 in an external magnetic field, HQ. The
nuclear Zeeman splitting and the effect of chemical shift anisotropy are shown, b) The broad "powder" line-shape
for sodium disilicate due to anisotropic chemical shielding, measured as the shift in parts per million (ppm) from
the corresponding line for tetramethyl silane (TMS). c) MASNMR spectrum of Na 2 Si 2 O 5 showing the splitting
of the spectrum into the resonance line (CB) at about 97 ppm and spinning side-bands, SSB. d) Magic angle
spinning (schematic) (Oldfield and Kirkpatrick, 1985).

quencies (and including other interactions
- nuclear dipole-dipole and nuclear
quadrupolar interactions, for nuclei with
/ > 1). The result is therefore a broad spec-
trum with structural information con-
tained in the shape of the distribution. In-
terpretation of such broad line spectra has
allowed the composition-dependence of
the various boron oxygen species to be
identified in alkali borate glasses (see Sec.
4.7.4.1).
In liquids, where rotational motion oc-
curs on a time-scale faster than the charac-
teristic time-scale of the NMR frequency,
the anisotropic interactions are averaged
out leading to very narrow peaks corre-
sponding to the frequency associated with
the isotropic part of the chemical shift in-
teraction, G{. For solids, similar effects can
be achieved by spinning the specimen at
a frequency, co, of the order of the peak
breadth (a few kHz) at an angle 6 to Ho.
This causes the anisotropic interactions to
be multiplied by a term 3 cos2 0 - 1 , which
equals zero for 0 = cos" 1 (3~ 1/2 ) = 54.74° -
the "magic angle".
The effect of magic angle spinning is to
cause the broad powder resonance, shown
for 29Si in Na 2 Si 2 O 5 in Fig. 4-16b to col-
lapse into an underlying frequency related
214 4 Models for the Structure of Amorphous Solids
to (ji? and spinning side-bands associated
with time-dependent terms in the various
interactions. The true resonance (CB), at
about 97 ppm in Fig. 4-16 c is independent
of the spinning speed, the side bands are
not. In favourable compounds, the lines
are sufficiently narrow in relation to the
frequency splitting associated with differ-
ent bonding arrangements around the ex-
cited atom, that the species present can be
quantitatively analysed (see Sec. 4.7.4.2
and an excellent review by Kirkpatrick et
al., 1986).
4.4 Modelling Techniques
In this section, a brief account is pre-
sented of computational methods for pro-
duction, refinement and testing of atomic
models for amorphous materials. Refer-
ences to the literature will suffice to direct
the reader to examples of the major com-
putational "experiments" and further de-
tails will emerge in Sees. 4.5 to 4.7. The
subject conveniently divides into three sec-
tions - construction of the model, refine-
ment and validation.
4.4.1 Construction of Atomic Models
for Amorphous Solids
Perhaps the most difficult - certainly the
most tedious - part of the modelling pro-
cess is finished when a structural idea has
been translated into a set of atomic coordi-
nates in a computer. Ideally, generation
also should be the preserve of the comput-
er but increasingly, as models become
more sophisticated, algorithms contain
some form of human guidance - either ac-
tually through a physical model or implic-
itly through the construction algorithm.
At the outset we should question the
need for atomic models. After all, most
structural information represents a one-di-
mensional average over 1020 or more
atomic centres and, possibly, over the envi-
ronment of several atomic species. What is
to be gained by an approximate fit to these
data by a model in the form of a finite
cluster of atoms?
Several answers to this question occur.
Firstly, once a 3-D model has been con-
structed that is compatible with X-ray dif-
fraction data, for instance, it is then pos-
sible to use the coordinates to calculate
other properties - elastic moduli, vibra-
tional spectra, optical properties - infor-
mation that is not contained in the X-ray
data and which would be difficult or im-
possible to calculate otherwise.
Secondly, it becomes possible to com-
pare the information contained in the re-
sults of two or more different types of ex-
periments by reference to an atomic model
that eventually can be adjusted to fit both
datasets. In this way the amount of struc-
tural information is multiplied.
Perhaps the most important factor is
that a 3-D atomic model allows a rather
complicated series of packing or connec-
tivity constraints to be incorporated into
the model - constraints that might be diffi-
cult or impossible to formulate otherwise.
The fact that atoms cannot occupy the
same region of space introduces con-
straints - involving rules that are not easily
expressed analytically. Space-filling ran-
dom structures encapsulate packing rules
expressed through topology rather than
geometry, and homotopy groups describe
the connectivity rather than space group
symmetry, as pointed out be Rivier and
Lissowski (1982), Rivier (1983). Similarly,
connectivity relationships in directionally-
bonded systems - especially the provision
of particular fractions of ra-membered
rings - can be incorporated in atomic mod-
els but, except for near neighbour correla-
tions, become too clumsy otherwise.

Finally, there is a sense that juggling
atoms in a computer comes close to the
processes that nature adopts to "choose" a
particular structure.
4.4.1.1 Physical Models
In the early history of the subject, al-
most every model was hand-built. Notable
pioneers were Bernal (1964), Scott (1960)
and Finney (1970). For network glasses,
probably the most influential random
model has been Bell and Dean's (1972)
"ball and stick" model for SiO 2 , although
Evans and King's (1966) work on the same
material has historical precedence. Coor-
dinates were established by metrology and
properties then calculated by "digital"
computation. Models of a similar kind for
amorphous tetrahedral semiconductors
were produced - notably by Polk (1971)
and for a-Si:H by Mosseri and Dixmier
(1981).
In later work, computer algorithms en-
ter at an earlier stage - physical models
were used to establish the topology in a
polytetrahedral model of a-Ge and to en-
sure close packing in models for amor-
phous TM-m alloys, the detailed coordi-
nates then being computed from the topol-
ogy of the physical model. The domain
model of Dubois et al. (1985) for these
amorphous alloys also started with a phys-
ical model. Until recently, there seemed lit-
tle alternative for structures of some com-
plexity but the advent of molecular graph-
ics packages now offers real prospects of
advance.
Many hand-built physical models are
clusters of no more than a few hundred
atoms so that a high proportion lie near
the surface. Apart from the problem of
excluding underbonded surface atoms in
subsequent calculations, near-surface
atoms have additional degrees of freedom
4.4 Modelling Techniques 215
not possessed by those comprising the inte-
rior. The problems of "imbedding" cluster
models have been reviewed by Finney
(1977). One alternative is to construct
models with periodic boundary condi-
tions. A rare example of a hand-built ran-
dom model with periodic boundary condi-
tions was the 61-atom cell constructed by
Henderson in (1974), and more recently by
Guttmann and Rahman (1988). Although
periodic models are routinely constructed
by Monte Carlo and Molecular Dynamics
algorithms, physical models with periodic
boundaries remain a rarity.
4.4.2 Molecular Dynamics
The subject has progressed some way
since the pioneering days of Alder and
Wainwright (1959). Typically, the proce-
dure involved construction of an initial
starting structure - a random collection of
atoms or a crystal structure - inside a peri-
odic cubic box. Atoms are allowed to
move under the action of an assumed po-
tential energy function and Newtonian
equations of motion are solved over time
slices of the order 10~ 14 to 10~ 15 s. (See,
for example, Soules (1990).) A typical ex-
ample of a recent investigation is that of
Vashishta et al. (1989 b) on a-GeSe2 in
which the authors assumed an effective
two-body potential involving a Coulomb
term, charge-dipole interactions and steric
repulsions. The motion of 648 atoms was
followed over time steps, Af = 5 x l O ~ 1 5 s
in a cubic box of side 2.75 nm, adjusted to
provide agreement with the experimental
density. The system was equilibrated at
1100 K for about 3 x 104 At and the prop-
erties average over a further 3.6 x 103 At
to provide structural properties for liquid
GeSe 2 . The glass is simulated by progres-
sively reducing the particle velocities over
about 3 x 104 steps (corresponding to a
216 4 Models for the Structure of Amorphous Solids

2
0

12 Ge-Se _

10
8 Figure 4-17. Partial pair
correlation functions,
r6 ga/?(r), for two simulations
i
of a-GeSe2 at 300 K using
4 a) a two-body potential;
b) a potential including
2
three-body terms. Coordi-
0 nation numbers are indi-
cated (Vashishta et al.
2 1989 b; Vashishta et al.,
0 1989 a).
0 4 8 12 0 4 8 12
a r(A)

quenching rate o f 5 x l 0 1 2 K s 1 )to values
corresponding to T<Tg and properties
measured again after thermalisation for
about 3-4 x 103 At. Static structural prop-
erties such as the partial pair distribution
function (Fig. 4-17 a) dynamical properties
and structure factor (Fig. 4-19 a) were cal-
culated.
An additional step of exploring a poten-
tial minimum near an initial configuration
has been reported by Stillinger and Weber
(1983, 1985). The configuration generated
by MD at any temperature is energy-min-
imised, using a steepest-descents algorithm
and the resultant "mapping" of the initial
configuration onto the nearby potential
minimum produces a pronounced en-
hancement of all the structural features,
Fig. 4-18 a, b. Apart from the obvious in-
terpretation that the configuration has

9 2

Figure 4-18. a) Pair correlation function, g, for a MD simulation of liquid Si at a reduced temperature, T* =
kBT/s = 0.0817 where s is proportional to the cohesive energy, b) The corresponding function obtained by
allowing the liquid configuration at T* =0.0677 to settle to an energy minimum giving the "inherent" pair
correlation function for liquid Si. The higher temperature structure for a liquid at T* = 0.1492 relaxes to
essentially the same configuration. Stillinger and Weber (1985).

been allowed to eliminate high energy un-
stable local bonding arrangements, Stil-
linger and Weber point out that mapping
of liquid MD configurations at various
temperatures leads to a relatively small set
of underlying (temperature-independent)
"inherent structures". That is, the temper-
ature-dependence of pair correlation func-
tions in simple liquids consists of varia-
tions in "vibrational" displacement away
from potential minima; not in substantial
shifts from region to region of configura-
tion space, corresponding to other groups
of potential energy minima.
This procedure, involving potential en-
ergy mapping and averaging over a num-
ber of local configurations belonging to
different potential energy minima, has
been used to effect in simulations of metal-
lic glasses by Hafner and co-workers (e.g.
Hafner, 1988).
4.4.3 Potential Energy Functions
Given adequate potential energy func-
tions, molecular dynamics simulations
could provide an entirely adequate de-
scription of the complexity of structure
generation and the transformations in-
volved in quenching from the melt. Many
MD calculations - particularly the early
ones - necessarily used simplified poten-
tials. Woodcock etal. (1976) employed a
Born-Mayer-Huggins potential:
b-
• exp (4-29)
L Q J
where za is the electronic charge on an
atom of species a, n is the number of outer
shell electrons, a is a distance parameter
characteristic of the ionic radius and b and
Q are constants. The function thus consists
4.4 Modelling Techniques 217
of a Coulombic (first term) and a repulsive
(hard sphere) term. The BMH potential
has been used extensively in MD simula-
tions for covalent solids with the long
range Coulomb term summed using
Ewald's method.
For amorphous semiconductors, a po-
tential proposed by Stillinger and Weber
(1985) has proved popular. This consists of
a mixture of two- and three-body terms:
(4-30)
where i is the index of one of N identical
atoms.
Neglecting the single particle potential
terms, V1(r), the interaction can be ex-
pressed in terms of the pair and triplet
functions, V2(r) and V3(r).
For Si, Stillinger and Weber introduce
the functions V2(r) and V3(r) in the form:
•exp[(r-a) '] \
V2(r) = 0 J r>a (4-31)
Where e is an energy unit and a is a cut-off
radius and r is a reduced radius.
V(ri9rj9rk) = s[h(rij9rik, 6jik) + ^2)
+ h(rji9rjk9 9ijk) + h(rki9rkj9 6ikj)]
Here 9jik is the angle at i between r>} and rk
and h is given by:
+ 7(rik-ay1] (cos 0jik +1/3) 2 (4-33)
for rij9rik< a, otherwise h = 0.
The effects of introducing three-body
terms in simulations of covalent systems
are pronounced. Most simulations of
amorphous elemental semiconductors, ox-
ides and chalcogenides are unrealistic in
218 4 Models for the Structure of Amorphous Solids

a) b)
i i i

» Expt. 108AK
2 —
~ Liquic T = 1070K "
— MD 1071 K

1 - A
w < o^-
a)
' ' I I I I I I 1 1 1

2 - Glass T=300K -
JL

1 _

t i . i . i .
8 12 16 20 12U 8
Q (A"1) Q (A"1)
Figure 4-19. Comparison of experimental and computed total neutron structure factors S(Q) for a-GeSe2.
Computer data was obtained using a) a two-body potential function and b) a Stillinger-Weber potential including
three-body terms (Vashishta et al. 1989 a, b).

that distortions are significantly greater pseudopotentials, see for example Hafner
than experiment: bond angle distributions (1980, 1986).
are generally much broader with a high Energy minimisation techniques applied
proportion of atoms with unexpected to elemental semiconductors and oxides
valence and ring sizes. Figs. 4-17 b and often assume a Keating potential (Keating,
4-19 b show the improved agreement be- 1966) that is computationally simpler than
tween computed and experimental static a valence potential. This consists of bond
structure factors for a-GeSe2 obtained by stretching and bending terms:
Vashishta et al. (1989) using three-body
terms of the Stillinger-Weber type com-
pared with pairwise functions of Vashishta 3a
etal. (1989).
For amorphous metals, the simplest po-
tential energy function is a Lennard-Jones 3($
>rik~r20 cos 90)2 (4-35)
function:

>.-=4eiy '•-Rfj) (4-34) where a and p are stretching and bending

where </>-t is the potential of the ith atom
and Rtj is a reduced distance; R(j =
2'1/6Rfj/riJ, where Rfj is the equilibrium
internuclear distance and ri-J is the actual
distance between atoms i and j .
Hafner, in an extended sequence of in-
vestigations on metallic alloys has calcu-
lated interatomic forces on the basis of
force constants, r0 and rtj are the equilibri-
um and actual internuclear distances be-
tween atoms / and j and 90 is the equilib-
rium angle jik. Lapiccirella et al. (1984)
have introduced a more sophisticated ver-
sion of the valence force-field - the Lipson-
Warshel PE function, in calculations of the
structure and properties of a-Si and a-Ge
(Tomassini et al., 1987).

Molecular dynamics simulations using
empirical potential energy functions have
the drawbacks noted above. A method for
removing this difficulty has been proposed
and applied by Car and Parrinello (1985)
and coworkers. In this approach, the inter-
atomic potential is derived from the elec-
tronic ground state of the system calculat-
ed with accurate density-functional tech-
niques. Specifically, the sets of atomic co-
ordinates and electronic wavefunctions of
the occupied states are both considered as
dynamical variables, governed by equa-
tions of motion for electron and nuclei.
The minimum energy state is obtained by
following the "motion", as the tempera-
ture is reduced, by a process described as
"Dynamical simulated annealing" to com-
pare with the "simulated annealing" meth-
od of Kirkpatrick et al. (1983) (using MC
formalism).
The method is effectively parameter-free
so that such ab-initio calculations can de-
scribe the "true" structure of an amor-
phous material given only the electronic
properties of its atoms. Applications to a-
Si and a-C are considered in Sec. 4.5.
4.4.4 Energy Minimisation
Models constructed by hand or by vari-
ous computer algorithms lack realism in
that bonds are strained, broken, or the co-
ordination numbers are unrealistic. By cal-
culating the potential energy - essentially
the elastic strain energy of the structure -
and the gradient, atoms can be moved in
directions that minimise the energy. After
a relatively small number of iterations the
model settles into the potential energy
minimum in the local region of configura-
tional space corresponding to the starting
structure: the model becomes "relaxed",
implying an increase in geometrical order.
4.4 Modelling Techniques 219
The extent of topological ordering de-
pends on the detailed algorithm.
The method embraces a number of min-
imisation algorithms. A popular and easy
method is the steepest-gradients method
which involves calculation of the energy
and the force on each atom. Each atom is
then moved either a distance proportional
to the force or to an estimated position of
minimum energy (Steinhardt et al., 1974).
Another method is the so-called "conju-
gate gradient" method which attempts to
find the minimum in configuration space
by searching in orthogonal directions at
each iteration.
Like MC calculations, the potential en-
ergy functions and derivatives are reason-
ably simple to compute so that with the
Keating potential energy function the
method is computationally cheap. Various
sophisticated potentials have been devised
for silicon, and carbon compounds and are
only marginally more difficult to deal with.
4.4.5 Monte Carlo Calculations
Models may also be generated and re-
fined using variations of the Metropolis
Monte Carlo method. An initial, essential-
ly arbitrary starting structure is chosen -
usually with periodic boundaries. An atom
is selected at random and given a random-
ly chosen displacement. The state of the
system, as characterised by the energy or
the fit to an experimental variable such as
the structure factor, is then tested. The
move is accepted if the goodness of fit is
improved, rejected if not. A variant is that
the move may be accepted according to
a Boltzmann probability, exp(— AE/kBT)
where AE is a measure of the goodness of
fit - the decrease in energy, say, and kBTis
a suitable scaling factor. Thus the al-
gorithm allows the system to explore con-
220 4 Models for the Structure of Amorphous Solids
figurations that initially may be unfa-
vourable, so that the procedure helps to
prevent the model becoming trapped in a
local minimum of configuration space.
The process is repeated until the fit to ex-
periment is judged to have converged.
The method has been used extensively
in constructing models for amorphous
metals, chalcogenides, amorphous semi-
conductors and oxides. It has the advan-
tage that a relatively large number of con-
figurations can be explored quickly and
cheaply in computer time. Moreover, it is
generally possible to use more realistic po-
tentials so that difficulties introduced by
pairwise potentials have not been so
prominent in MC as in MD simulations.
McGreevy and Putztai (1988) have revised
a method similar to that used by Ren-
ninger et al. (1974) in which the criterion
for guiding the approach of the MC com-
putation is the quality of the fit to experi-
mental scattering measurements alone.
The energy is not considered. The authors
point out that the amount of information
normally extracted from experimental dif-
fraction data is generally small and that a
fitting procedure offers a more detailed
idea of the real 3-D geometric structure.
The authors are clear that while it appears
that a 3-D structure has been extracted
from 1-D S(Q) or G(r) information, this is
strictly impossible and that the final struc-
ture is only one (of many, perhaps) that is
consistent with the data.
Evans (1990) has commented on the ap-
parent contradiction that higher order
functions such as the three-body distribu-
tion should be obtainable from structural
knowledge that contains no more than
pairwise information (see Sec. 4.3). Evans
points out that a simulation could succeed
for an amorphous solid for which the
atomic forces are describeable solely by a
pairwise potential. For materials with sig-
nificant three-body terms in the PE func-
tion, such as the covalently-bonded amor-
phous semiconductors, this need not be so.
Although the pair distribution function,
g(r), depends on three-body terms, this
dependence is insufficient to determine,
uniquely, any higher order correlations. If
two- and three-body terms are present in
the PE function then experimental g (r) and
triplet correlation functions would be nec-
essary.
4.4.6 Validation of the Model: Calculation
of Microscopic and Macroscopic Properties
Given a complete set of atomic coordi-
nates, it is then possible to calculate micro-
scopic properties such as G(r), S(Q), or
S(Q), even S(Q, co). With further assump-
tions, vibrational and electronic densities
of states functions can also be computed as
described below. Macroscopic physical
properties are also accessible - density, en-
thalpy of crystallisation, free energy, en-
tropy, elastic moduli, gas solubility, diffu-
sivity etc. These are often neglected or de-
emphasized when checking the validity of
a model, which is generally a mistake. It
comes as a surprise to find that a simple
property like density is sensitive to struc-
tural details that appear to evade compari-
sons with microscopic properties - particu-
larly when the latter are used in a qualita-
tive or semi-quantitative fashion. An accu-
rate fit to the experimental density should
be seen as an essential prerequisite for fur-
ther consideration of the model, and fail-
ure to agree should lead to its demise. Den-
sity values may be built into a simulation
as a constraint. When this is done, it fol-
lows from the foregoing that it is a rather
strong constraint.
The most useful properties are probably
G(r) and S{Q\ combined with density and
heat of crystallisation data. For reasons

discussed earlier, the information content
of partial pair correlation functions and
partial structure factors is so much greater
than that contained in the total functions,
that the former provide the most discrimi-
nating test of a structure model. For poly-
atomic materials, even models that are
radically different produce adequate fits to
S(Q) or G(r) - especially when experimen-
tal data is measured to low values of Q.
Only by examination of the detail of these
functions can differences be discriminated.
4.4.6.1 Bond Length Distributions
Successful models must reproduce the
details of each of the bond length distribu-
tions, that is, not only the interatomic dis-
tance corresponding to the peak and the
integrated area leading to the coordination
number, but the shape of the distribution
as expressed through higher moments:
standard deviation and (possibly) asym-
metry (kurtosis). Such parameters are im-
portant structurally and represent valuable
diagnostic information.
Microscopic parameters computed from
models and those derived by experiment
must be compared in detail, as indicated
above, and using equivalent data. Early
models were relatively crude and thus the
two data sets were compared only superfi-
cially without proper regard for equiva-
lence. However, the efforts of a number of
authors such as Wright and Leadbetter
(1976) have emphasized the proper treat-
ment.
A major problem arises from the fact
that experimental data are generally limit-
ed in reciprocal space. X-ray and neutron
diffraction S(Q) data are often limited to
values of Qmax in the region of 200 nm" 1
and whilst EXAFS data can routinely be
extended to higher values (as can X-ray
and neutron data with synchrotron and
4.4 Modelling Techniques 221
pulsed neutron sources), multiple scatter-
ing introduces low Q limitations also. The
result of terminating S(Q) at g max leads to
convolution of G{r) with a peak shape
function so that a ^-function in G(r) is
transformed into a broadened peak with
side lobes - so-called termination broaden-
ing and termination ripple (see Fig. 4-20).
Thus
a
^ |<ft>| 2 V y a *
is replaced with:
a p 0
(4-36)
where P*p(r-r') is a peak shape function
given by:
Pa%(x) =
M(Q)cos(Qx)dQ
(4-37)
E
GO
o
-0.2 1
Figure 4-20. Experimental difference distribution
function GCa (r) for a calcium silicate glass (bold line)
and a fit to the data to about 0.5 nm (upper dashed
line). The latter has been convoluted with a SINC
function to compare with experimental data. The un-
derlying (unconvoluted) sum of gaussian functions is
shown by the lower dashed line. This function has
more information, since the termination smearing is
absent but is only one of the possible fits to the exper-
imental data (Eckersley et al., 1988).
222 4 Models for the Structure of Amorphous Solids
Here M(Q) is a modification function
(see Sec. 4.3.3). For X-ray and neutron
diffraction this could be a step function,
M ( 0 = 1, for Q < Q m a x , and M(Q) = 0
thereafter, or some smoother function such
as the exponential function.
For neutron scattering where the atomic
scattering lengths are Q-independent, or
for X-ray scattering in those cases where
the ratios fa{Q)ffi(Q)/Kf>\2 are essential-
ly g-independent for all a and /?, then:
P«%(x) = c*°^2 TM(Q)cos(Qx)dQ
K\\U/\ o Q- and r-space since although they both
(4-38)
If M (Q) is a smooth function, it may be
possible to replace P*p (x) with a gaussian,
(2nr1/2exp(-x2/2a2) with a = l.6/Qmax
for approximate work.
For accurate comparison, a convolution
of the model G (r) is necessary before com-
parison is made with experimental real-
space data. Even analysis of the experimen-
tal data to obtain parameters such as the
first, second and higher coordination num-
bers and associated mean bond lengths
and G values requires care. Although the
coordination number can be obtained
approximately from an integral: jG aj3 (r)
n loss in accuracy. Since the result is obtain-
where r1? and r2 represent the "limits" of
the peak, such limits cannot be defined ac-
curately - especially if termination ripple is
present and peaks overlap. A better meth-
od involves fitting the experimental data
with a series of gaussian peaks (say) convo-
luted by P*p (x). Once this has been done,
the set of gaussians (unsmeared by the
peak shape function) is narrower and may
be more representative of the structure.
Thus where available, this function should
be quoted. An example is shown in Fig.
4-20 from recent investigations of Eckers-
ley et al. (1988) on a-CaSiO 3 .
Convolution by a peak shape function
and the resulting smearing thus represents
some degradation of the structural infor-
mation and efforts have been made to min-
imise the impact. One solution is to com-
pare computed and experimental data in
reciprocal space so that problems of termi-
nation broadening of the g-space data are
circumvented. However, unless the model
is large, with a radius greater than about
1.5 nm, truncation of the r-space data
leads to a convolution of computed recip-
rocal space data with another peak-shape
function. Ideally comparison of models
with experiments should be made in both
contain the same information, certain fea-
tures such as the first sharp diffraction
peak, may be more evident in one than the
other.
Konnert, Karle and coworkers and oth-
ers have attempted to devise methods to
reduce the impact of termination at Qmax.
Their treatment is based on the fact that if
Qmax is reasonably large - say 150 nm" 1
for oxide glasses - then only the first one or
two interatomic correlations are sufficient-
ly sharp in r-space to contribute to S(Q)
near Qmax. If the contribution from these
peaks to S(Q) is removed, then Qmax c a n
be set to infinity for the remainder with no
able only by fitting the experimental data
for the first few peaks, it represents a non-
unique solution and lacks some of the ob-
jectivity of the Fourier transform.
The choice of the fitting algorithm clear-
ly biases the results and a question arises as
to the most appropriate choice of function.
Recently, the claims of maximum entropy
techniques in this field have been enhanced
by several workers. If experimental data
is fitted by a procedure that maximises
the (information) entropy, then this set of
choices represents the least biased (maxi-
mally non-committal) choice. Wei (1986)
has shown that experimental neutron scat-
 4.5 Elemental Tetrahedral Semiconductors
tering data for a-Ni 64 B 36 (Cowlam et al.,
1984), analysed using a maximum entropy
technique provides more informative data
in real space than the fourier transform
technique (Fig. 4-21). This would be ex-
pected for most fitting algorithms - the
advantage of the Maximum Entropy tech-
nique is that it allows an objective (unbi-
ased) choice of one of the manifold of pos-
sible solutions that could fit experimental
data.
The use of ME techniques in extraction
of partial distribution functions in a
ternary Ag-Ge-Se alloy has been demon-
strated by Westwood and Georgopoulos
Figure 4-21. Reduced radial distribution function,
G (r) for 58 Ni 64 B 36 obtained from the neutron scatter-
ing data of Cowlam et al., 1984 by fourier transform
(FT) (a, c) and maximum entropy (ME) methods (c? d).
Km is the maximum value of 4 n sin djX in the dataset
(Wei et al., 1986).
223
(1989). In this case the data was from X-
ray anomalous scattering measurements at
two energies at each of the K-edges of all
the elements.
4.4.7 Calculation of Dynamical Properties
From the coordinates of an atomic
model and an assumed PE function, the
vibrational density of states function can
be calculated. Description of the various
computational techniques lies beyond the
scope of this review and a brief list of refer-
ences giving an entree into the subject must
suffice.
Vibrational frequencies are obtainable
directly in a MD simulation - see for ex-
ample Hockney and Eastwood (1981). A
popular and efficient method for calculat-
ing the phonon states of a cluster is the
"recursion method" reviewed in Heine et
al. (1980). A similar method is the "equa-
tion of motion" method (Beeman and Al-
ben, 1977).
Electron states can also be calculated by
the use of these techniques (Heine et al.,
1980).
4.5 Elemental Tetrahedral
Semiconductors
Of all amorphous solids, silicon and ger-
manium are perhaps the most extensively
investigated. Recently, interest has mount-
ed in a a third element - carbon - although
this is not strictly a tetrahedral material -
the extent of tetrahedral bonding is vari-
able and as yet, inadequately defined. The
three materials have important properties
- Si and Ge are semiconductors and, like
the crystalline elements, can be doped to
provide a range of useful electronic prop-
erties. Carbon, in its diamond-like form,
can be very hard and has useful properties
224 4 Models for the Structure of Amorphous Solids
as a damage-resistant coating and as a
dielectric. Each can be prepared as an alloy
with other elements - notably hydrogen.
Indeed, some contamination with H is dif-
ficult to avoid but, more importantly, de-
liberate alloying with H decreases the
number of energetic defects such as 'dan-
gling bonds' thus improving optical and
electronic properties.
In this section, we concentrate on the
structure of the essentially pure elements,
recognising that H may be an almost un-
avoidable impurity. A recent review by El-
liott (1989) extends the subject to alloys of
Si containing large amounts of H and oth-
er elements. With the exception of amor-
phous carbon, there is no paucity of good
experimental, data for amorphous semi-
conductors. The most complete data is for
a-Ge and, since there are strong qualitative
similarities between the results for all the
Group IV elements (and their alloys) we
concentrate on data for a-Ge and intro-
duce deviant behaviour as appropriate -
amorphous carbon being the most impor-
tant case.
4.5.1 Amorphous Ge and Si
4.5.1.1 Local Structure - Diffraction Data
X-ray data for several specimens of a-
Ge has been reported by Temkin et al.
(1974) (see Fig. 4-4) and Kinney (1976).
Neutron scattering data was obtained by
Etherington et al. (1982) from the speci-
men of evaporated Ge used by Kinney. A
small amount of H was observed (indirect-
ly). Results of this work are shown in
Fig. 4-22 as the experimentally-derived
correlation function f (r) and the authors'
best estimate of the true correlation func-
tions t(r). The latter function was obtained
by subtracting the contribution of the first
peak (in r-space) to the reciprocal space
data, Q(S(Q) — 1). This gives a reciprocal
Figure 4-22. Experimental correlation function (full
line) t'(r) = 4n rg{r) for a-Ge, together with Ether-
ington et al.'s (1962) estimate of the true correlation
function t(r) (dashed line) obtained as a fit to the
experimental scattering data.
space function that has effectively reached
an asymptotic value below Qmax, so that
fourier transformation is possible without
any truncation effects.
The overall tetrahedral nature of the
material is confirmed, with <rx> = 0.246
3 nm (0.2450 nm for c-Ge) although the
first shell coordination number, 3.68, is
less than the expected value. Second shell
coordination numbers depend on the as-
sumptions made in fitting the second peak
around 0.395 nm but a figure below the
value of 12 expected for a fully-coordinat-
ed network is likely. Deviation from four-
fold coordination is ascribed to broken
bonds associated with voids etc. A nota-
ble feature of the structure of a-Ge and
a-Si is the small disorder-induced broaden-
ing of the first neighbour distance. For
a-Ge, the static broadening parameter o\
amounts to 0.0074 nm. By contrast, the
static breadth of the second peak is much
larger, as2 = 0.026 nm, indicating that the
disorder chiefly introduces variations in
the bond angle of about a (6) = 10° from
the mean tetrahedral angle. Current data
 4.5 Elemental Tetrahedral Semiconductors
for a-Si is less accurate but results from
X-ray and electron diffraction techniques
on a-Si: H alloys suggest values of the first
coordination number less than four and
that the second coordination number is
less than 12. For instance, Schulke (1981)
finds <rx > = 0.2363 nm, <r 0 0 = 0.006 nm
and ^ = 3.4 + 0.1, JV2 = 11.4±0.1 for an
alloy containing about 33 at. % H. At-
tempts to extract partial structure factors
and correlation functions have been pre-
sented by Postol et al. (1980) and, more
recently, by Bellissent et al. (1985) using
H/D substitution in alloys containing
about 15 % H. Results are shown in Fig. 4-
23 and again indicate the lack of distortion
of the first shell and a broad second neigh-
bour peak.
2.34 A
10
Figure 4-23. Partial pair correlation function, g (r), for
a-Si: H obtained by H/D substitution (Bellissent et al.,
1985).
225
2.5
~~T~
2.0 a)
1.5
S 1.0
2 0.5
•2 0 'W
£2.5
o
I 2-°
«_
£ i.o
0.5
0
0 7 k 6
Radial coordinate (A)
Figure 4-24. a) Fourier transform of the EXAFS data,
k2 x (fc), for a-Ge: H from 30 < k < 140 nm " 1 . b) Simi-
lar transform for c-Ge (Bouldin et al., 1984).
Both a-Si, a-Ge and their hydrogen
alloys have been thoroughly studied by
EXAFS techniques. An example is the
work reported by Bouldin et al. (1984).
They measured the EXAFS spectrum for
specimens of a-Ge that were nominally
free of H and samples with around 5 -
6 at. % H. The fourier transform of the
resulting data for the pure material (Fig.
4-24) shows a sharp peak corresponding to
the first neighbour distance which is al-
most identical to that for c-Ge and the
coordination number is 4.0 to within a few
percent. In contrast to the data for crys-
talline germanium, Fig. 4-24 b, informa-
tion on second- and higher-neighbour
peaks is almost indistinguishable from the
noise in the transform as Fig. 4-24 a indi-
cates. This is the result of the limitation of
226 4 Models for the Structure of Amorphous Solids

the data analysis procedure to values of the

photoelectron wave-vector, k, greater than
about 30 nm" 1 , where the effects of multi-
ple scattering are not too large, as dis-
cussed in Sec. 4.3.5.5. The Debye-Waller
term, Qxp(-2a2k2) in Eq. (4-24) has
the values 0.24 at £ = 30 nm" 1 (with o2 =
0.028 nm deduced from Etherington et al.,
1982) and only 0.08 at £ = 40 nm" 1 where
the contribution of x(k) (weighted by a
smooth windowing function) is significant-
ly greater than zero. Information on sec-
ond and higher-neighbour peaks is thus
very difficult to obtain from the extended
spectrum. On the other hand, the presence
of the second-neighbour peak in the fou-
rier transform can be used as a diagnostic
test of partial crystallisation, as shown by
Evangelisti et al. (1981) and by Menelle
etal. (1986).
Nonetheless, a signal due to second
Figure 4-25. Multiple scattering contribution to the
neighbours is present in the experimental XAFS signal in a-Ge. Each contribution is labelled by
data and recent work by Mobilio, Filip- the number of atoms involved in the scattering event
poni and coworkers has shown some pro- and the degeneracy. Thus, #3A 12 represents a wave
gress in extracting this information. For emitted from the origin and scattered by two further
atoms. There are 12 such paths in a fully bonded
example, Mobilio and Filipponi (1987)
tetrahedral network (Filipponi et al., 1989).
show that a weak higher neighbour signal
can be extracted from accurate experimen-
tal x(k) data using the regularised least expected, but at the position of a third
squares fitting procedure proposed by Ba- neighbour in c-Si. Filipponi et al. show
banov et al. (1981). In this way they repro- that this is the result of destructive interfer-
duce the first and second peaks in g(r), ence between single scattering from second
extending to about 0.5 nm. In more recent neighbours and multiple scattering arising
work (Filipponi et al., 1989), the contribu- from paths involving two, three, etc. scat-
tion to the EXAFS signal of a-Si arising tering events, Fig. 4-25. An essential con-
from the first peak in g(r) is subtracted tribution to the signal comes, therefore,
from the experimental data and the residu- from paths involving a photoelectron wave
al signal can then be analysed in terms of emitted from an origin atom, which is then
single and multiple-scattering terms from scattered by a neighbour of that atom, to
higher neighbours, Fig. 4-25. In fact, the another neighbour and then back to the
residual signal cannot be satisfactorily origin atom, where it interferes with the
analysed unless multiple scattering is in- outgoing wave, resulting in a modulation
cluded. The r-space feature corresponding of the X-ray absorption coefficient.
to the difference signal occurs not at the The importance of this type of analysis
position of the second peak as would be is that in addition to functions like g(r),
 4.5 Elemental Tetrahedral Semiconductors
which represent the distribution of pairs of
atoms, an exact fit to the EXAFS data for
a-Si seems to require specification of triplet
correlation functions g(r1,r2,9). The lat-
ter function expresses the probability that
an atom lies at a distance rx from an origin
atom, another at r 2 , with an angle 9 be-
tween the vectors to the two atoms. Clear-
ly, this is data additional to that which can
be derived directly from an analysis in
terms of g (r), and this represents potential-
ly new and valuable structural informa-
tion. Another way of looking at this is to
recognise that triplet correlation functions
also relate to the local site symmetry,
which again is not available directly from
pair functions.
4.5.1.2 Local Structure - Complementary
Techniques. Medium-Range Structure
Infra-red and Raman spectra of a-Si and
a-Ge display the behaviour noted in Sec.
4.3.6, namely the broad double humped
100 200 300 0 100
Frequency (cm"1)
227
structure, Fig. 4-26, characteristic of the
vibrational density of states function, g (co)
and with little resemblance to the sharp
features seen in the IR or Raman spectra
of crystalline materials. This is the result of
the loss of translational symmetry which
removes the force of the crystal momen-
tum, k = 0, selection rule so that all modes
of g(co) become potentially optically active
(Sec. 4.3.6). In fact, the major features of
g (co) for amorphous tetrahedral semicon-
ductors are obtained by just broadening
the density of states function for the crys-
tal. Experimental g(co) data for a-Ge has
been reported by Maley et al. (1986); Ma-
ley and Lannin (1987) and for a-Si by
Kamitakahara et al. (1987). The former
also made detailed comparisons with the
Raman spectra of a-Ge, Fig. 4-26, which
shows the close relationship between the
Raman intensity and g(co) determined
from neutron inelastic scattering. Dynami-
cal structure factor data, S(Q,co) also ex-
ists for a-Ge (Maley et al. 1986) - Fig.
4-27.
Figure 4-26, Neutron in-
elastic scattering data (solid
lines) and a) depolarised,
c) polarised components of
the Raman spectra for a
"highly-ordered" specimen
of a-Ge (substrate tempera-
ture =150 °C): b) and d)
show similar data for a
more disordered specimen
prepared at a substrate
temperature of 5 °C (Maley
and Lannin, 1987).
200 300
228 4 Models for the Structure of Amorphous Solids
O.O
High resolution electron microscopic
examinations of a-Ge and a-Si have a long
history. The subject was particularly active
in the 1970's as a result of efforts to "see"
details of the structure of amorphous semi-
conductors directly. The presence of mi-
crocrystallites in a-Ge was claimed by
Rudee and Howie (1972) on the basis of
images produced by tilted-illumination
dark-field microscopy. The controversy
these early results generated lead to a de-
tailed analysis of the power - and limita-
tions - of high resolution electron micros-
copy as applied to amorphous solids (see
for example Cochran, 1973; Howie, 1978).
Subsequently, most experimental effort
has concentrated on studies using axial
bright-field microscopy - as discussed in
Sec. 4.3.7. Smith et al. (1981) made a care-
ful study of foils of amorphous C, Si and
Ge using a 120 kV microscope. They
showed that images of thick films
(«10 nm) presented no structurally signif-
icant features. That is, the image appeared
to be qualitatively identical to a secondary
image produced by randomising the phase,
while maintaining the intensity distribu-
tion (Krivanek et al., 1976). For thin foils
of thickness « 3 nm, the images did differ
from their phase-randomised counterparts
- graphitic planes are visible in the images
Figure 4-27. Two-dimen-
sional plot of the dynami-
cal structure factor, S (Q, E\
of a-Ge (Lannin, 1987).
of a-C, for example. Even thinner foils of
a-Ge ( « 2 nm) were examined by Saito
(1984). Crossed fringes were observed over
an area of about 2 nm 2 with a spacing of
0.3 nm corresponding to the {111} planes
of Ge. The image compared well with that
simulated for a 2 nm Ge crystal with cor-
rection for the aberrations introduced by
the microscope.
Ourmazd et al. (1985) and Phillips
(1987) re-awakened interest in the subject.
The former studied relatively thin (10 nm)
specimens of a-Si near the interface with a
crystalline Si wafer that had been cleaned
by ion milling to remove oxide or other
contamination before deposition of a-Si.
The specimen was examined with the elec-
tron beam parallel to the interface, so that
a cross-sectional view was obtained. Near
the interface, a number of ordered regions
resembling microcrystallites were observed
- as shown by the presence of crossed lat-
tice fringes with a spacing corresponding
to dltl for c-Si. The (photographic) images
were then converted into optical diffrac-
tograms - a standard technique being to
illuminate the photographic negative with
a laser beam. Diffraction patterns from re-
gions of about 5 nm in diameter were
found to be exhibit sharp Bragg spots.
Moreover, it was claimed that the spots
 4.5 Elemental Tetrahedral Semiconductors
were orientated and in registry with the
lattice planes of the substrate. Such fea-
tures were observed up to 50 nm from the
interface and the effect was termed the Ori-
entational Proximity Effect - reflecting the
suggestion that the submicrocrystallites in
a-Ge become quasi-epitaxially orientated
near the interface. In later work using a
microscope with superior resolution,
structurally significant features were ob-
served less easily in the image but were
nonetheless seen in the optical microdif-
fraction patterns. In this case, sharp "spot-
ty" optical diffraction patterns were ob-
served almost 8 nm from the substrate
(Phillips, 1987).
The picture that emerges from this work
is that a-Si - which is overconstrained ac-
cording to Phillips' (1979) criteria - cannot
form a continuous network and the strain
resulting from disorder is distributed local-
ly as grain boundaries. Within the grain,
the material adopts the more stable crys-
talline structure. The orientational prox-
imity effect allows the intrinsically granu-
lar microcrystalline structure of the mate-
rial to be more easily detected.
4.5.2 Amorphous Carbon
4.5.2.1 Static Properties
Amorphous carbon represents a classic
example for structural studies of local and
medium-range ordering in amorphous ma-
terials. As mentioned earlier, carbon is an
unusual element in that both trigonal, sp 2 ,
and tetrahedral, sp 3 , bonding is possible.
Moreover, the extent to which sp 2 atoms
form in clusters - as chains or "aromatic"
rings, either singly or fused to give planar
graphite-like sheets, and the extent to
which such sheets have a parallel orienta-
tion to give laminar structure of graphitic
islands - are questions to which there are
only partial answers. Since structure and
229
properties are strongly dependent func-
tions of deposition conditions, it is more
sensible to talk about a hierarchy of amor-
phous carbon structures. "Amorphous
carbon" is, in fact, a generic term for a
whole family of materials with diverse
structures and properties.
It is usual now to refer to carbon evapo-
rated from a carbon arc, say, at ambient
temperatures as (ordinary) amorphous
carbon: variations introduced by some
form of energetic deposition leading to
hard films and increased sp 3 content as
"diamond-like" carbon. In addition, hy-
drogen may be introduced - deliberately or
accidentally and this appears to make the
films harder and more "diamond-like". A
further form of non-crystalline carbon is
the so-called "glassy carbon". However, it
is clear that this material is extensively
graphitized with very obvious parallel lat-
tice fringes seen in electron microscopy -
the fringes having a spacing corresponding
to the {002} planes of graphite. Diffraction
data of Mildner and Carpenter (1982) con-
firms this.
Scattering data from a-C are very limit-
ed. Kakinoki et al. (1960) measured elec-
tron scattering from arc-evaporated car-
bon to <2max = 27Onm~1 and found a
C-C peak at 0.151 nm which lies be-
tween distances corresponding to diamond
(0.155 nm) and graphite (0.141 nm). The
data were interpreted in terms of a mixture
model consisting of 55 to 60% of the dia-
mond-like structure. Energy-filtered elec-
tron diffraction has been used by McKen-
zie et al. (1987), (see also Green et al.,
1989) to obtain G(r) for a number of spec-
imens of a-C and a-C: H. The specimens
were thin foils, and measurements were
made in an adapted electron microscope so
that very small specimen volumes contrib-
uted to the data. McKenzie et al. observed
values of the carbon bond angle ranging
230 4 Models for the Structure of Amorphous Solids
from 118 to 120° for glassy carbon and
a-C:H, to 115° for evaporated a-C. The
bond angle was found to be 110° for a
form of amorphous carbon prepared by
condensation from a plasma, generated by
a carbon arc, with magnetic filtering to
minimise contamination by graphite mi-
crocrystals produced as a result of the ac-
tion of the arc. This latter material they
refer to as "amorphous diamond".
A specimen of "amorphous diamond"
has been examined by neutron scattering
to
2max = 165 nm" 1 by Gaskell et al.
(1991). The specimen was very small
(^20-30 mg) so that intensities were diffi-
cult to normalise. However, data for G(r)
shown in Fig. 4-28 is very informative. The
first peak, <rx> = 0.153 nm; iV=4.0±0.5;
G± = 0.011 nm, indicates predominantly
sp 3 bonding. However, the slight shift of
the first peak from the position for crys-
talline diamond (0.1546 nm) could be the
result of a small amount of graphitic bond-
ing. The first peak has been modelled as a
weighted sum of two gaussian distribu-
tions with centres corresponding to the
bond lengths of graphite and diamond.
The proportion of "graphite-like" materi-
al appears to be 10-15 %. The second peak
position, 0.2517 nm, corresponds to tetra-
hedral bonding - the calculated C bond
Figure 4-28. Reduced radial distribution function,
G(r) for amorphous diamond-like carbon (Gaskell
etal., 1991b).
angle is 110 + 1°. The static breadth of
the second peak, a\ = 0.016 nm is much
smaller than values for Ge (0.026 nm) - a
reflection of the large bond bending force
constant in carbon. The major difficulty
with this work, apart from the problems
introduced by the miniscule sample mass,
is the uncertainty surrounding the extent
of H contamination. Estimates of the con-
centration of H from the magnitude of the
inelasticity correction, suggest 9 to 11 %
H. The amount bonded as C-H must be
less than this, otherwise the first coordina-
tion number would be significantly less
than the value of 4, but estimates of the
fraction of bonded H have proved to be
difficult. Taken at face value, though, there
can be little doubt that this material is
largely tetrahedral carbon and is analo-
gous therefore to a a-Si and a-Ge.
Honeybone et al. (1991) have also used
neutron scattering to examine a specimen
of amorphous carbon containing around
30% H. The films were produced from
an ion beam source using propane or
acetylene. Measurements to Qmax =
500 nm" 1 allowed good real space resolu-
tion of the first C-C peak at 0.14-
0.15 nm. This was found to be split into
two components, in the ratio 1:4, Fig.
4-29. The C-C coordination number was
So
Figure 4-29. G (r) for an amorphous C: H film pre-
pared from an ion-beam source using propane as a
precursor (Honeybone et al., 1991 a).
 4.5 Elemental Tetrahedral Semiconductors 231

2.5 + 1.0 compared to about 3.5 for a fully

connected sp 3 network - after making al-
lowance for the proportion of C-H bonds.
A second neighbour shell is observed be- a) /A \\
tween 0.23 to 0.27 nm with a coordination
\
number of 4.0 + 2.0. Strong C-H and
H - H features are seen and inelastic scat-
tering confirms the presence of H 2 mole- \ • • • • '
. . • • • '
/
\
cules in a high pressure state (Honeybone
e t a l , 1991a).
EXAFS and XANES spectra for a-C: H b)
!

A
have been studied by several workers. A
recent example is that by Comelli et al.
u
a
o
U)
/ \\\\
(1988). Near edge data shows a prominent >> : i
1 s -> 7i* transition which grows as the
DJ1H
j {..... "
film is annealed, indicating an increasing j j
sp 2 content. The EXAFS spectrum has >,
been analysed to give a C-C distance of
0.1445 nm - very close to that for graphite,
0.1421 nm. Moreover, this distance re-
in
c
03
:

! i

i i l\
i

A /

\ \.\
r'l
/

mains constant on annealing. It is suggest- c)

ed that the film consists of a two-phase
structure: a disordered graphite-like net-
work of even- and odd-membered C-C
rings and a random matrix consisting of
different types of C-C bonds but with
d) . !
/
/

\
/

chain-like units and defects in the form of j v.. .. /

' • • • • • . . . .

dangling bonds. The amount of the gra-

phitic material is estimated to be 60% in
the as-deposited film and to rise to over
90% on annealing at 1050 °C.
4.5.2.2 Excitations
Work by Berger et al. (1988) using elec-
tron energy loss spectroscopy showed the
presence of only a small amount of sp 2 -
bonded material in "amorphous dia-
mond" thin films. Graphite has a pro-
nounced peak at 6.2 eV (Fig. 4-30) corre-
sponding to transitions from the highest
filled valence band state to the lowest emp-
ty conduction band state (n*) and it is this
feature that is absent in crystalline dia-
mond and only barely detectable in
20 30
AE(eV)
Figure 4-30. Electron energy loss spectra for several
forms of amorphous carbon: a) diamond, b) "amor-
phous diamond", c) graphitised carbon, d) evaporated
a-C (Berger et al, 1988).
"amorphous diamond". Similar features
are seen at higher energies due to transi-
tion from core state, 1 s levels to the TC*
state, and the intensities of the ls->7c*
transition in amorphous diamond com-
pared to graphite was used to estimate the
proportion of n states in the material. This
lead to a value of 85 % sp 3 bonds - a figure
with which the neutron data of Gaskell et
al. (1991) agrees.
232 4 Models for the Structure of Amorphous Solids

E
Energy loss spectroscopy and 13 C magic
OPT
angle NMR have both been used to by
Jarman et al. (1986) to examine specimens
a-C: H prepared in a r.f. plasma discharge.
1.1
Specimens were characterised by the value
of the energy of the optical gap, Eg. NMR
data and EELS data are shown in Fig.
4-31. Peaks due to the various forms of
carbon are shown and the ratios measured
by each technique agree to about 10%.
Raman spectra for various forms of
amorphous carbon give relatively little in-
formation on the sp 3 /sp 2 ratio: most spec-
imens exhibit a broad region of scattering
which stretches from frequencies below
3.0 eV the fundamental mode of c-diamond
(1332 cm" 1 ) to about 1800 cm" 1 - that is,
"Nvv above the frequency corresponding to c-
graphite, 1550cm""1. The reason is likely
to lie in the larger Raman cross-section for
300 200 100 0 - 1 0 0
graphite: estimates suggest that the intensi-
Chemical shift/ppm vs T M S ty of the 1550 cm" 1 mode in graphite is 30
to 60 times larger than that for the
1332 cm" 1 mode of diamond. Since most
of the amorphous carbons contain at least
10% sp 2 carbon, the Raman spectrum
principally reflects the structure of this
component.
Raman spectroscopy does give impor-
tant indications of the extent of medium
range ordering, though. Specifically, the
extent to which sp 2 carbons cluster can be
examined by studying the ratio of the in-
tensities of the peaks at 1550 cm" 1 and at
1350 cm" 1 . These are related to a mode at

Figure 4-31. a) 13 C magic angle NMR spectra for

three amorphous carbon films measured with te-
tramethylsilane (TMS) as standard. The films are
characterised by their optical gaps, EOPT. b) EELS
spectra for the same amorphous carbon films with the
electron beam perpendicular to the substrate. The
305 295 285 energy gaps, £ g and the ratio of n/o states derived
Electron loss energy (eV) from these spectra are also shown (Jarman et al.,
1986).
 4.5 Elemental Tetrahedral Semiconductors
the centre of the Brillouin zone, and a zone
edge mode; the latter being inactive in a
perfect single crystal with activity induced
by the breakdown of ^-conservation due
to disorder. The ratio of these two modes
has been shown to relate to the size of
graphite microcrystallites (Tuistra and
Koenig, 1970):
k in the analysis of the experimental data.
(4-39)
^(1550) IT
where La is a characteristic mean intrapla-
nar length of graphite microcrystals and k
is a constant. Microcrystallisation of a-C
by annealing or irradiation is easily ob-
served by this means, therefore.
The extent of clustering of sp 2 carbon is
also observable through changes in the op-
tical band gap. Crystalline graphite - an
infinite cluster - is an anisotropic metal
and as the graphite crystallite size decreas-
es, the band gap increases (Robertson and
O'Reilly, 1987) - as discussed in Sec. 4.5.5.
4.5.3 Network Models - Static Properties
A number of CRN models for amor-
phous tetrahedral semiconductors were
built by hand using tetrahedral units and
plastic connectors. Polk (1971) produced a
519-atom model and calculated the rdf for
the unrelaxed coordinates. Energy-min-
imised versions using a Keating potential
were subsequently published by Steinhardt
et al. (1974) and by Duffy et al. (1974).
Beeman and Bobbs (1975) also produced a
number of random models and Connell
and Temkin (1974) generated a model with
even-membered rings only.
Models of other kinds were also pro-
duced. Grigorivici and Manaila revived a
pentagonal cluster model - known as an
"amorphon" - and Gaskell et al. (1977)
examined the properties of a multiply-
233
twinned structure with a 14-atom diamond
cubic motif.
Several of these models were tested
against experimental neutron scattering
data for a-Ge by Etherington et al. (1982).
They used the coordinates of each model
and calculated the pair function T(r) =
4nrb2Q(r) with the same procedure to
simulate termination smearing etc. as used
Their results are reproduced in Fig. 4-32.
Although most of the models produce an
approximate fit to the experimental data,
none is adequate in that agreement in de-
tail is not achieved.
The situation has been improved by sim-
ulations of the structure of a-Si by Wooten
and Weaire (1987) and co-workers. Their
approach is to start from a fully-bonded
diamond cubic lattice and to arrange for
certain types of bonds to be switched as
shown in Fig. 4-33. Specifically, bonds
that are parallel in the crystal, and almost
parallel in the disordered structure, are al-
lowed to switch. The method involves the
following steps. After an exchange of a
pair of atoms, the (Keating) energy is re-
duced after a few iterations of an energy
minimisation routine. The semi-relaxed
energy is calculated and the move accepted
or rejected according to the probability
given by a Boltzmann factor exp(—Ej
kB T\ with kB T typically 1 eV, correspond-
ing to the melting point. After a number of
steps at this temperature, sufficient to give
at least 0.3 bond switches per atom, the
crystal structure has lost the memory of its
ordered state and the temperature is then
reduced progressively to zero.
A large number of models have been
produced by this method using variations
in the heating/cooling cycles and results
are quite impressive. The fit between ex-
perimental data for a-Ge and calculated
values for T{r) are shown in Fig. 4-34.
234 4 Models for the Structure of Amorphous Solids

1 1 ! 1 1 1 1 1 1

6 Henderson 6 f Polk (500 atom) -

ill J,
U I*

0 Evans
2

r\

u^
1 "
» Polk (519 atom) ^

111
<
~ 2
r 2
ro Connell-Temkin / • i» Steinhardt
t_ i ;! (201 atom) r?

A- Figure 4-32. Distribution function,

t' (r), for a series of random net- "
2 2 work models (dashed lines) com-
pared with experimental data
0 Beeman
n
I
JIJ
1 1 1 1 I I 1 1
(solid lines) for a-Ge. Etherington
0 2 U -6 8 10 et al., 1982.
r(A)

6 8 10

Somewhat remarkably it is found that,

starting from the diamond cubic structure,
the final annealed structure either reverts
to the crystal (if the initial melting time has
been too short) or to a random structure
that is in very close agreement with the
experimental data. This argues for the
validity of the CRN model as a representa-
tion of the real structure of amorphous
tetrahedral semiconductors.
The method has several in-principle ad-
vantages. Not only is it simple and easy to
programme but the steps are relatively
transparent. Periodic boundaries can of
course be used. Moreover the number of
transitions over the energy barriers repre-
sented by bond switches is more than can Figure 4-33. Bond rearrangements between two al-
most parallel bonds a) before and b) after switching
be contemplated using MD simulations. atoms 1 and 6 and allowing relaxation of the atoms -
Note also that the number of constraints which are embedded in a 216-atom unit cell (Wooten
on the final model is relatively large: not and Weaire, 1987).
 4.5 Elemental Tetrahedral Semiconductors
— Calculated
— Experiment
Figure 4-34. Comparison of the distribution function,
t(r) = 4nr Q (r), for a-Si (scaled to Ge) with experi-
mental data for a-Ge (Wooten and Weaire, 1987).
only does the model preserve tetrahedral
bonding, but attempts are made to try to
find a global minimum of energy and the
comparison with the experimental T{r)
function - even if made only at the end of
the calculation - also acts as a valid con-
straint. In this, the method differs from
Monte Carlo simulations in which often
only one of these constraints is employed.
A number of MD simulations of a-Si
and a-Ge have been reported. Ding and
Andersen (1986) devised a Stillinger-We-
ber potential for a-Ge: as discussed in Sec.
4.4.3, this contains three-body terms, the
detailed parameters being obtained by fits
to properties such as the cohesive energy,
elastic constants etc. In this case, Ding and
Andersen were unable to find a set of
parameters that gave an acceptable fit to
liquid, crystalline and amorphous Ge.
Their parameters fitted the last two phases
mentioned only. Calculations were per-
formed on 216- and 512-atom clusters with
the box size fixed to agree with the experi-
mental density of a-Ge. A good fit to the
experimental rdf was observed (Fig. 4-35).
Ding and Andersen discussed the inabil-
ity of the potential to give an adequate
235
simulation of all three phases and conclud-
ed that the cause lay with inadequacies in
the potential, rather than any lack of real-
ism in the simulation of the quenching pro-
cess - due to incommensurate time-scales
etc. Biswas et al. (1987) re-examined this
question by investigating changes in the
strength of the three-body term which con-
strains the size of bond angle fluctuations.
Structural properties were compared with
experimental data, principally the vibra-
tional density of states function, with only
moderate agreement. Luedke and Land-
man (1989) also used MD simulations with
a S-W potential but with a slower quench
rate and found that it was possible to ob-
tain results representative of experiment ei-
ther by increasing the three-body term dur-
ing the initial stages of computer quench-
ing, or by using a slower quench rate. They
therefore suggest that the S-W potential
may be adequate but that care is needed to
reproduce the atomic transport and relax-
ation processes involved in (real) quench-
ing experiments. These authors give a
rather detailed comparison of the proper-
ties of their simulated model for a-Si with
experimental data but agreement is not
Figure 4-35. Comparison of the RDF for a-Ge by MD
simulation (solid line) with experimental data (dashed
line) with allowance for the modification function
used in transforming the experimental data (Ding and
Andersen, 1986).
236 4 Models for the Structure of Amorphous Solids
particularly impressive. For example, the
bond angle distribution is much broader
than that found experimentally. More-
over, the high proportion of 3- and 5-
bonded atoms is difficult to reconcile with
prejudice - if not with experiment.
A first-principles MD calculation (see
Sec. 4.4.4) of the structure of a-Si has been
performed by Car and Parinello (1988).
The pair correlation function calculated
for a-Si was compared with scaled experi-
mental data for a-Ge and found to be in
good agreement.
4.5.4 Models for Amorphous Carbon
With a shortage of hard experimental
facts, it is not surprising that the number
of structural models for a-C is rather
small. Beeman et al. (1984) produced a
number of hand-built models for a-C,
which were then energy-minimised. One
model consisted of four stacked 280-atom
warped sheets consisting of purely trigonal
carbon atoms. The sheets were rotated
with respect to each other. A second (356
atoms) contained approximately equal
proportions of tetrahedrally- and trigonal-
ly-bonded atoms and was designed to test
the model proposed by Kakinoki et al.
(1960). A third (340 atoms) contained
about 14% sp 3 atoms in the central core.
In the latter two models, 5- and 7-mem-
bered rings were included and sp 2 and sp 3
atoms were randomly mixed.
Computed rdfs and i(Q) data were
compared with the limited number of ex-
perimental results available at that time.
Agreement is poor in all cases - with signif-
icant errrors in the density. Robertson
(1991) has commented that from energetic
considerations, sp 2 atoms would tend to
cluster and odd-membered rings should be
disadvantaged; whereas Beeman et al.'s
model takes no account of this.
Tersoff (1988) has constructed several
216-atom, periodic boundary models
for a-C using Monte-Carlo techniques.
Models were produced either by quench-
ing from the vapour phase or from the
liquid using an empirical potential energy
function fitted to the cohesive energies
of carbon poly types. C-C bond lengths
(0.147 nm) close to graphite were found
and with a coordination number of only
3.1 - about 9 % of the atoms being 4-coor-
dinated and the bond angle distribution
peaked at 120°. To try to reproduce the
properties of hard carbon coatings, a simu-
lation was performed in which liquid car-
bon was quenched under lOOGPa pres-
sure. The resulting bond length was ob-
served to be </!> = 0.151 nm (diamond is
0.1554 nm) and the coordination number,
3.4, with almost half the atoms 4-coordi-
nated. A broad bond angle distribution
was found suggesting an overlap of peaks
corresponding to sp2 and sp3 carbon
atoms.
Galli et al. (1989) have conducted a first-
principle simulation of the structure of a-C
starting from a 54-atom periodic cell, with
a macroscopic density of 2000 kgm~ 3 . The
resulting model consists of 85% sp2 sites,
graphitic in nature with the remaining
15% sp 3 forming a distorted diamond-like
structure. At high temperatures, sp-bond-
ed carbons are also present but these dis-
appear on simulated cooling and the pro-
portion of sp 3 bonds increases. Interest-
ingly, this simulation shows that the sp 3
sites tend to cluster and interconnect the
essentially planar sp2 regions as shown in
Fig. 4-36. The electronic density of states is
also calculated and shows the appearance
of a sharp n and n * states and broader a
features (Fig. 4-37).
The notion that a-C consists of an essen-
tially granular two-phase structure with
graphitic islands separated by a sp 3 matrix
 4.5 Elemental Tetrahedral Semiconductors 237

O'Reilly (1987) calculated the energy of

the n states in "monomeric" ethylene,
through polyacetylene chains, aromatic
rings to condensed aromatic rings and then
a graphite layer. Calculations were also
performed of the electronic density of
states of the models of Beeman et al.
(1984). The energy gain produced by the
formation of compact fused rings is signif-
icant but it is the narrowing of the gap
between valence and conduction band
states (Fig. 4-38) that is particularly inter-
esting. Robertson and O'Reilly show,
Fig. 4-39, how the optical gap varies for
linear and compact condensed 6-fold rings
and the inset to this diagram indicates that
the clusters in a-C and a-C: H are likely to
contain 10 to 30 rings, corresponding to
islands of about 1.5 nm. The model pre-
sented is one in which sp 2 clusters are in-

Figure 4-36. Section through the a-C network gener-

ated by Car and Parinello, 1989. a) The entire set of
atoms in one MD cell Grey circle show atoms that
are four-fold coordinated; black - threefold, b) Ring
structures.

phase is a case most elequently made by

Robertson (1986, 1991), although the pro-
posal is an old one dating back to Kaki-
noki et al. (1960). Robertson's arguments
are based on the energetics of sp2 bonds
and the tendency to form planar ring and
-20 -10 0
sheet structures, with hard experimental Energy (eV)
evidence coming from calculations of the Figure 4-37. Electronic density of states for the model
electronic density of states and the optical of Car and Parinello, 1989. Positions of experimental
band gap. Specifically, Robertson and peaks are shown by arrows.
238 4 Models for the Structure of Amorphous Solids
2 1 0 - 1 - 2 - 3
Energy (/3)
Figure 4-38. Calculated electronic energy levels for
increasingly polymerised carbon atoms (Robertson,
1986; Robertson and O'Reilly, 1987).
terconnected by sp 3 bonds and it is argued
that the reason for the granular structure -
rather than the percolating patterns of sp2
and sp 3 bonds - is related to strain. Rather
than the strain being distributed randomly
and thus tending to homogeneity, strain is
relieved abruptly at the edges of the is-
lands. Planar sheets have parallel n or-
bitals and this is adduced at the main influ-
ence.
The electronic properties of a-C - on
this model - are not solely determined by
nearest neighbour interactions — the local
structure. Electronic and optical proper-
ties in the low energy range (< 6 eV) are
closely correlated with the extent of medi-
-0.1
0.01
1 10 100
Number of rings (M)
Figure 4-39. Minimum energy gap, Eg, for compact
(upper) and linear (lower) clusters of fused six-fold
rings of C atoms. Inset shows probable number of
rings per cluster in a-C and a-C:H (Robertson, 1986;
Robertson and O'Reilly, 1987).
um-range structural organisation. This is
in contrast to a-tetrahedral semiconduc-
tors where the dominant role is associated
with the local tetrahedral structure and
with defects - such as dangling bonds etc.
4.6 Amorphous Silica
4.6.1 Experimental Situation
Amorphous silicon dioxide is probably
the most extensively-studied glass. The
early work of Warren and co-workers
(1936) established the experimental sup-
port for Zachariasen's random network
model by a series of X-ray diffraction mea-
surements. Subsequently, Mozzi and War-
ren (1969) returned to the subject towards
the close of Warren's scientific career, to
complete a classic investigation by provid-
ing data corrected for Compton and multi-
ple scattering that is still almost un-
equalled. Static neutron structure factors

have been published from several investi-
gations by Wright and Sinclair (1985), and
Price and Carpenter (1987) have recently
reported experiments leading to the dy-
namical structure factor, S(Q,co). Al-
though static diffraction data exists to val-
ues of Qmax that are entirely adequate
(400 nm" 1 ), the information content is still
relatively small compared to, say, amor-
phous Ni-based binary alloys - due to the
absence of suitable isotopes of Si and O
and, therefore, accurate partial functions.
Complementary structural information
is also plentiful; good IR, Raman, and
neutron inelastic scattering data have been
available for some years for specimens pre-
pared by melting, by sol-gel routes and by
chemical vapour deposition. NMR, ESR
and vacuum ultraviolet spectroscopy are
useful ancillary techniques and, although
less obviously interpretable, high resolu-
tion transmission electron micrographs
have also been published.
4.6.2 Local Structure
4.6.2.1 Diffraction Data
Experimental data is adequate to form,
directly, a reasonably coherent description
of the structure out to second neighbours,
Wright (1988) quoted values obtained
from fits to the first two peaks of the neu-
tron correlation function and obtained
values quoted below:
<i^1>/nm cr1/nm TV
Si-O 0.1608 4.7 x l O " 13
3.85
±4xl0~4 ±0.16
O-O 0.2626 9.1 xlO" 3 5.94
4 oxygen bond angle (through the Si-O
±6xl0" ±0.25
The Si bond angle, assuming no correla-
tion between bond length and bond angle
variations is 109.7 ±0.6° with a standard
deviation of 4.5°. The value of a (9) ob-
4.6 Amorphous Silica 239
tained from the ESR data of Griscom et al.
(1977) is much lower than this, around
0.6°. The mean and standard deviation of
the oxygen bond angle is open to greater
uncertainty: here we quote Mozzi and
Warren's values, <e> = 144° and o-(e) = 15°.
These data have been questioned by Da
Silva et al. (1975) who suggest that Mozzi
and Warren's data can be interpreted with
a most probable oxygen bond angle of
152°. This result has, in turn, been ques-
tioned by Coombs et al. (1985) and by
Galeener (1985). The former point out that
a complete bond angle distribution calcu-
lated by Da Silva et al.'s method does, in
fact, peak at 144°.
4.6.2.2 Complementary Techniques
Vibrational spectroscopy clearly shows
that the symmetry of the local silicon-oxy-
gen unit is tetrahedral as in most of the
crystalline polymorphs of SiO2, rather
than octahedral as found in the high pres-
sure phase stishovite. Similar results can be
obtained from magic angle NMR - with
all four oxygens around Si being 'bridg-
ing', (i.e. species QA) the chemical shift is
observed as — 112ppm compared with
an almost identical value for crystalline
tridymite, and in contrast with values of
around —213 ppm found in high P-con-
tent phosphosilicate glasses (Dupree et al.,
1987) and c-SiP2O7 in which Si is octahe-
drally coordinated.
Magic angle NMR has also been used to
determine the distribution of oxygen bond
angles in a-SiO2. Several models exist
which relate the 29Si chemical shift to the
overlap integral, or alternatively the s-or-
bital participation in the hybridised O or-
bitals). Pettifer et al. (1988) have recently
reviewed the experimental data and the in-
terpretations based on each model. Results
240 4 Models for the Structure of Amorphous Solids

c-SiO2. The exceptions are, firstly, the in-

Figure 4-40. Various estimates of the oxygen bond
angle distribution, V(a), obtained from NMR a)-c),
and X-ray data (d) (Pettifer et al., 1988).
tense Raman continuum below about
500 cm" 1 which can be seen as a manifes-
tation of the breakdown of the crystal mo-
mentum selection rule imposed by disor-
der; secondly, a number of sharp lines are
seen in the Raman spectrum at about 495,
605 and 1200 cm" 1 , Fig. 4-41. Since these
features can, in some senses, be considered
to be "excess" modes and as their intensi-
ties change as a result of neutron bom-

TO LO TO LO TO L0
i i i i ( i 1 i i i |

are shown in Fig. 4-40. Significant varia- 10 -a) | vitreous -

Reduced / 1 SiO2
tions are found in estimates for the mean in 8 - raman / 1 -

\
unr
oxygen bond angle - from 151° to 142° and spectra ;/
1
even more in the breadth of the distribu- >> /
tion. All the NMR data suggests a signifi- HH/ I _
cantly narrower distribution than that ob-
1« /
1i\
< 2 / -
tained from Mozzi and Warren's X-ray
kv

J
data. 0

12
4.6.3 Medium-Range Structure "w
10 " Infrared ,

I
X-ray or neutron scattering data for 8 _ dielectric

I
N constant
a-SiO2 contains a prominent feature at J 6

I
about 15 nm" 1 . In the spirit of a crystallite

I
model, this feature could correspond to

I
2

I
a prominent interatomic correlation at i i i i
0
il
r = 2n/15 = 0A2 nm which could be due,
perhaps, to a preferred interlayer distance L
c)
or ring size. The interpretation of such Energy
3
"first sharp diffraction peaks" - common loss
function
features of S(Q) for chalcogenide glasses
such as a-GeSe2 (see Fig. 4-34) is a matter
for current debate simply because they are
not easily reproduced in models.
Vibrational spectra for a-SiO2 have add- 0 500 1000 1500
ed considerable fuel to the recent argu- UJ/cm"1
ments over the relative merits of crystallite Figure 4-41. Comparison of the reduced Raman spec-
and random network models and the rela- tra a) for a-SiO2 with b) the imaginary component of
tive populations of various ft-membered the dielectric constant, e2 = Im (e) and c) the energy
loss function, — Im(l/e) Peaks in e2 and in the loss
Si-O rings. The major peaks in the IR and function mark the frequencies of transverse and longi-
Raman spectra of a-SiO2 reproduce fea- tudinal optic modes, respectively (Galeener et al.,
tures seen in the corresponding spectra for 1983).

bardment, or the degree polymerisation
in glasses produced by condensation of
monomeric species in sol-gel preparations,
they are often considered to be ''defect"
modes rather than intrinsic vibrations of a
SiO2 "lattice". Galeener, in an extensive
series of publications (see Galeener et al.,
1983) has adduced arguments for treating
these modes as the signature of 3- and 4-
membered Si-0 rings. Phillips (1982) also
views these modes as defect modes - asso-
ciated with the non-bridging oxygens pos-
tulated in his micro paracrystallite model.
The arguments for both are presented in
Sec. 4.6.4.2.
Electron micrographs of SiO2 have been
published by a number of authors. Zar-
zycki and Mezard (1962), Zarzycki (1970)
published a series of medium resolution
micrographs of SiO2 and other glasses in
the form of thin filaments that had been
formed by in situ electron beam irradia-
tion. A domain-like structure was ob-
served on a scale of a few nanometres
which Phillips (1982) has interpreted in
terms of his granular model (see Sec.
4.6.4.1). Gaskell and Mistry (1978) showed
examples of bright-field images of particu-
late SiO2 specimens produced by precipita-
tion from a monomer solution and by the
high temperature hydrolysis of SiCl4.
There is some evidence for coherently dif-
fracting domains on a scale of about 1 nm
in the high temperature material but the
low temperature specimens shows more
extensive ordering.
4.6.4 Random Network Models
Bell and Dean's is the classic physical
model for a-SiO2. The model contained
614 atoms, was hand-built and the coordi-
nates established by optical metrology
(Bell and Dean, 1972). In addition to simu-
lating the X-ray and neutron scattering
4.6 Amorphous Silica 241
1 1—; [ r
a) Computed
b) Experimental
0.6 0.8
Figure 4-42. Computed and experimental radial dis-
tribution functions for a-SiO2 after Bell and Dean,
1972.
data, the authors have computed the vi-
brational spectra and configurational en-
tropy. Fig. 4-42 shows the calculated ra-
dial distribution functions.
The model has also been used as a basis
for computations of the energy-minimised
structure. Gaskell and Tarrant (1980) re-
ported a detailed calculation of the static
properties of several models relaxed under
a Keating potential with variations in oxy-
gen bond angle and with fixed and free
boundaries. Calculations included esti-
mates of thermal broadening, and termi-
nation ripple was modelled using the pre-
scriptions of Mozzi and Warren (1969).
More recently, Robertson and Moss (1988)
have made a similar set of calculations.
Evans et al. (1983) included Bell and
Dean's model in a comparative survey of
network models for a-SiO2. Specifically,
four existing models for amorphous tetra-
hedral semiconductors were modified by
adding oxygens midway between the sili-
con sites. A similar modification was made
242 4 Models for the Structure of Amorphous Solids
to Gaskell's (1975) polytetrahedral model.
All models were relaxed using the same
Keating potential and comparisons with
the experimental and neutron scattering
data of Wright and Sinclair (1985), Fig. 4-
43. The results of this work are that all the
models produce reasonable fits to the ex-
perimental data: none produces an ade-
8 close to those determined by Mozzi and
Figure 4-43. Computed total correlation functions,
T(r), for several models of a-SiO2 compared with
experimental data of Wright and Sinclair, 1985 (WS).
The models are based on CRN structures for amor-
phous tetrahedral semiconductors with added oxy-
gens. BD, Bell and Dean; P = Polk; CT=Connell
and Temkin (even membered rings); BB = Beeman
and Bobbs. PT is a polytetrahedral model for a-Si or
a-Ge (see Fig. 4-7) with added oxygen (Evans et al.,
1983).
quate fit. All models fail to reproduce the
experimental density - they are more than
4% too dense. Moreover, the calculated
enthalpy is too small by a factor ranging
from 2 to 7. In particular, the shape of the
Si-O(2) distribution near 0.4 nm is inade-
quate in all models. Evans et al. analyse the
reasons for this and suggest that it is the
narrow distribution of oxygen bond angles
- cr(s) - typically half that determined by
Mozzi and Warren - and that this, in turn,
reflects inadequacies in the topology of the
models. Paradoxically, even the random
models are too ordered - fluctuations in
local structure are too small. The relative
success of the polytetrahedral model in this
regard reflects the inherent strain accumu-
lated in the model which can increase until
the compressed regions in the interior of
the model collapse. Apart from the relative
merits of this particular granular model, it
can be argued that granularity - by intro-
ducing large interfacial strains or other-
wise - may be an important ingredient in
the model-building process.
Ching (1982) also produced models for
a-SiO2 and a range of suboxides, SiO^, by
adding oxygens mid-way between silicon
atoms in models for Si with periodic
boundaries. Three models, containing
about 170 atoms in the unit cell, were con-
structed and energy-minimised using a
modified Keating potential. Good agree-
ment with the measured density was ob-
served, and bond lengths and angles were
Warren (1969). Unfortunately, compari-
son with experimental X-ray data was only
qualitative, so that the accuracy of the
models cannot be adequately judged.
Recently, Gladden (1990) has taken up
the challenge of producing an acceptable
model for a-SiO2 that remedies the defects
of the models described above. She has
produced models containing 1-2000
 4.6 Amorphous Silica 243

Figure 4-45. Comparison of the detailed shape of T(r)

from 2 to 4 A with three models for a-SiO2. Experi-
mental results are shown by the crosses and com-
puted data for a model with a minimum ring size of
five units and oxygen bond angles of 140° (dashed
line); 143° (dotted line) and 150° (full line) (Gladden,
1990).

atoms by translating the operations in-

volved in handbuilding a "ball and stick"
model into a computer algorithm that al-
Q (A" 1 ) lows the automatic generation of CRN
models subject to constraints such as the
smallest ring size, mean O bond angle, con-
: c) nectivity, relative magnitude of terms in
the PE function etc. This has allowed a
thorough search of the parameter space
: /^ 0-0 and delineation of the parameters which
correspond to the best fit to experimental
data. Results are impressive - as shown in
',., Si-0 Figs. 4-44 and 4-45.
Si-Si Particular features of the experimental
IJ; 10
data to be given attention were the shape
of the Si-O (2) distribution near 0.4 nm and
r(A)
the intensity of the first sharp diffraction
Figure 4-44. Computed (full line) and experimental
(dashed line) data for a-SiO2. a) T(r); the computed
peak in Qi(Q) that had not been adequate-
curve being corrected for termination effects, thermal ly modelled hitherto. Gladden has shown
broadening and the finite size of the model, b) Q i (Q), that the best fit corresponds to a choice of
after correction for finite model size, c) The total func- a mean oxygen angle of 150° and a mini-
tion (full line) and the component pair distribution mum ring size of five SiO2 units. Arguably
functions calculated from the model. Finite model size
and thermal broadening corrections are included but
this work should now be taken as one of
convolution with the termination smearing function the most authoritative interpretations of
is omitted (Gladden, 1990). the scattering data for a-SiO2.
244 4 Models for the Structure of Amorphous Solids
4.6.5 Ordered Models
4.6.5.1 Quasi-Crystalline Models
Quasicrystalline models, described by
Wright and Leadbetter (1976), were men-
tioned earlier in Sec. 4.2.2.2. Two other
models, explicitly based on the network
topology of crystalline polymorphs of
SiO2 have been proposed by Konnert,
Karle and co-workers, and more recently,
by Phillips. Konnert, Karle and co-work-
ers base their models on X-ray data refined
as described in Sec. 4.4.6.1, so that details,
presented as r2 G(r), are obvious out to
distances of the order 2.0 nm. Computed
data were produced by broadening the
Bragg peaks in the powder patterns for the
crystalline polymorphs so that detail was
not apparent beyond 1.4 nm. Comparison
with experimental data suggested that the
topology of the tridymite lattice was more
closely associated with the structure of
amorphous silica than any other form. It is
not entirely clear what these crystal-based
models represent; Wright and Leadbetter
(1976) suggest that misunderstanding of
the nature of the model may have lead to
the controversy that subsequently sur-
rounded it. Konnert and Karle (1973) sug-
gest "a structure composed nearly entirely
of ordered regions similar to tridymite, . . .
having dimensions up to at least 20 A and
bonded efficiently together in configura-
tions analogous to twinned crystals. In
such a model the ordered regions have the
same bonding topology as the crystalline
polymorphs and are distorted slightly
owing to the junctions between the ordered
regions. However, microcrystalline bound-
aries are not implied. The junctions may
not vary significantly in energy and density
from the ordered regions". Konnert et al.
(1974) quote data for the RDF calculated
from broadened Bragg peaks correspond-
ing to tridymite crystals with a particle size
8 r(A) 12
Figure 4-46. Comparison of models for a-SiO2, based
on the crystal structures of tridymite, cristobalite and
quartz, with experimentally-derived data (Konnert
and Karle, 1973). Also shown (MODEL) data for a
1412-atom structure based on a model for a-Si by
adding oxygen, and experimental data (SILICA)
(Konnert et al., 1982).
between 1.1 and 2.0 nm. Konnert et al.
(1982) also present data (Fig. 4-46) for a
random network model of a-SiO2. Duffy
et al. (1974) model for a-Si formed the ba-
sis, with oxygen added. The authors also
list correlation coefficients, thus providing
a quantitative estimate of the goodness of
fit and quote values of 0.91 for the random
model compared to 0.83 for tridymite, and
0.68 for one based on cristobalite.
4.6.5.2 Microparacrystalline Models
Phillips (1982) produced a model for
a-SiO2 based on cristobalite. The details
again are subject to some re-interpretation
although, in this case, this arises from
modifications resulting from critical com-
ments rather than any lack of precision. As
mentioned earlier, Phillips argues that con-
straints imposed by bonding or connectivi-
ty can lead to broken "chemical order" if
the number of degrees of freedom proves
inadequate for that structure. In the case
of SiO 2 , departures from chemical order-
 4.6 Amorphous Silica 245

ing are considered to take the form of non-

bridging oxygens, Os*, that form surfaces
separating chemically-ordered regions.
Specifically, "large surface areas (corre-
sponding to low index crystal faces) are
covered by Os* atoms which are nearly
equivalent and are bonded to the cluster
interior as siliconyl units, namely, Os* =
Si-(O 1/2 ) 2 •" "In the present model the in-
ternal surfaces are intrinsic features of the
glass structure . . . " In its original form,
Phillips assumes a topology based on Figure 4-47. Phillips' (1982) sketch of the {100} inter-
paracrystallites of (3-cristobalite with di- face in cristobalite formed by removing a "molecular
plane" of thickness 0.37 nm and allowing the interface
ameters up to 6 nm and with 20 to 25 % of
to relax.
the Si atoms double-bonded (see Fig. 4-
47).
The arguments for this model are princi-
hedral microparacrystal comprising 3 or 4
pally based on vibrational spectra, rather
{111} planes, with an edge length of
than diffraction data and are considered in
1.25 nm. The glass is pictured as being
detail below. In response to criticism by
composed of microparacrystals with "par-
Galeener and Wright (1986), that quasi-
allel oriented twists of SiO 4/2 tetrahedra"
crystalline models based on (3-cristobalite
separated by grain boundaries where the
provide inadequate fits to X-ray or neu-
distortions are larger due to different ori-
tron data, even for correlation lengths as
entations of the rotation axes in adjoining
small as 2 nm, Phillips (1986) pointed out
domains. The fit to experimental data is
that such a literal view is inappropriate.
impressive, Fig. 4-48 c - the authors claim
Specifically, internal lattice defects - stack-
that their model fits experimental data to
ing faults or microtwins on a scale of 1 to
"within the thickness of the drawn line".
1.5 nm are postulated in an attempt to re-
The domain structure is compared with
move the difficulties. The suggestion of
several of the crystalline modifications of
> Si = O groups is also dropped in favour
SiO2 but is identical to none of them with
of = S i - O - O - S i = groups.
cristobalite being the closest approximant.
Hosemann et al. (1984, 1986) have pro-
duced a remarkable but little-understood
4.6.6 Simulation of Dynamical Properties
model for a-SiO2. A pair of SiO4 tetrahe-
dra, Fig. 4-48 a, form the basis for a f.c.c. As mentioned earlier, a number of fea-
lattice with a lattice constant of 0.715 nm, tures of the vibrational spectra of silica -
Fig. 4-48 b. In order to fit the density, te- particularly the polarised Raman Spec-
trahedra are given correlated twists of trum - have no obvious counterparts in
+ 22° parallel to the cell axes. The spacing spectra for crystalline forms of SiO 2 . Two
of the {111} planes of this lattice are al- of the Raman bands at 495 and 605 cm" 1
lowed to vary according to Eq. (4-2). A are sharp (see Fig. 4-41) and, since they are
good fit to experimental X-ray data is sensitive to preparation conditions and to
found with the interplanar variation con- radiation damage, they have been termed
stant, g = 0.12, corresponding to an octa- "defect" bands.
246 4 Models for the Structure of Amorphous Solids

Figure 4-48. a) The building

block, consisting of two sili-
con-oxygen tetrahedra, pro-
posed by Hosemann et al.
(1984, 1986) which is then
connected to form the struc-
ture shown in b). Circles are
oxygens and squares, sili-
cons. The fit to experimen-
tal data (Mozzi and Warren,
1969) is shown in c) with
component partials indi-
cated. The agreement with
experimental data is "within
the thickness of the drawn
line". The insert shows the
peak shape function with
a full width at half height
of 0.19 A compared to the
computed width of the first
peak of 0.21 A.
 4.6 Amorphous Silica 247

Interpretation of the defect bands by ment, the cluster-based calculations pre-

Galeener (see for example Galeener, 1983), dict a measure of IR and depolarised Ra-
Galeener et al. (1983) and by Phillips man activity at 600 cm" 1 .
(1982) starts from the assumption that cal- The matter is still controversial, there-
culated vibrational spectra, based on cou- fore.
pled SiO4 tetrahedra and for random net-
work models such as Bell and Dean's, do 4.6.7 Molecular Dynamics Models
not agree either with the number or the
Similation of the static structural prop-
frequency of those modes observed experi-
erties of a-SiO2 using molecular dynamics
mentally. Phillips (1982) then proposes
was pioneered by Woodcock et al. (1976).
that the two defect bands are assigned to
A modified Born-Mayer-Huggins poten-
localised vibrations of point defects or sur-
tial was used and the resulting distribution
face oxygens associated with the postulat-
functions are shown in Fig. 4-49.
ed 'broken chemical order' at the bonding
Soules (1979, 1982) and Mitra et al.
surface of (3-cristobalite microparacrystal-
(1982) have also produced fits to experi-
lites and involving a double Si = O bond.
mental X-ray data for SiO2 using larger
Galeener (1983) takes the view that the
models than that used by Woodcock et al.
additional features in the spectrum reflect
(54 molecular units in the periodic box).
the presence of three-membered rings
Mitra, for example, used 375 ions in a
(Si3O9) by analogy with vibrations near
600 cm" 1 in hexa methylcyclotrisiloxane,
and four-membered rings corresponding
to octamethyl cyclotetrasiloxane which
has a Raman active mode at about
480 cm" 1 .
These explanations fit uncomfortably
with the findings of Bell (1983) and Evans
et al. (1983). These authors calculated the
vibrational densities of states, g(co), for
several cluster models of a-SiO2, none of
which contain 3-membered rings but give
results that are in reasonable agreement
with the experimental data of Leadbetter
and Stringfellow (1974). Bell (1982) also
calculated the IR, polarised and unpolar-
ised Raman spectrum and observed Ra-
man and IR-active modes near 600 cm" 1 .
Evans et al. (1983) also found IR activity
in the energy-minimised Bell-Dean struc-
tures at 600 cm" 1 and peaks in g((o) for
all models considered in the region near Figure 4-49. Pair correlation functions, G(r), for a-
600 cm" 1 . The problem therefore, as Bell SiO2 obtained from the MD simulations of Wood-
cock et al., 1976 (full line). Experimental data of
says, is not what type of network defect Mozzi and Warren (1969) is also shown (dashed line).
could be responsible for the vibrations but N (r) is the running coordination number centred on
to understand why, in conflict with experi- Si.
248 4 Models for the Structure of Amorphous Solids

cubic box with dimensions adjusted to

provide agreement with the experimental
room temperature density. The results of
the MD simulation were compared with
experimental data without any attempt to
reproduce termination broadening or to
match thermal broadening. Good agree-
ment with experiment is reported, al-
though there are discrepancies in the de-
tail. For instance, the authors draw atten-
tion to the spread of ±7° in the Si bond
angle compared with a = 0.6° from ESR
data and (7 = 4.5° from neutron and X-ray
data. The oxygen bond angle distribution
agrees with that proposed by Da Silva with
a peak value of 151°. A few of the atoms
are abnormally coordinated as 3- or 5-co-
ordinated Si or singly- or triply-bonded
oxygens.
Kubicki and Lasaga (1988) have simu-
lated a-SiO2 using ionic and covalent po-
tentials parameterised by fitting ab initio
quantum mechanical potential energy sur-
faces for H 4 SiO 4 and H 6 Si 2 O 7 molecules.
Again the authors claim a good fit to ex-
perimental X-ray data but the second-
neighbour coordination numbers are in er-
ror by factors of 2 in some cases, and there
are also significant errors in nearest neigh-
bour bond lengths and in the breadth of
bond angle distributions (apart from ques-
tionable values of the mean oxygen angle).
A recent MD simulation of Feuston and
Garofalini (1988) has used Stillinger-We-
ber three body potentials adapted for a-
SiO 2 . The results, Fig. 4-50, are a great
improvement on earlier calculations based
on two- body terms - the bond angle distri-
butions and the numbers of over- and un-
der-coordinated atoms are more realistic.
MD simulations of a-SiO2 have thus far
failed to match the potential of the tech-
nique (or the claims of their adherents) - at
least in so far as realism is concerned.
None of the simulations matches experi-
Figure 4-50. Structure factor, S (Q\ for a-SiO2 calcu-
lated by Feuston and Garofalini (1988) using Stil-
linger-Weber potentials including three-body interac-
tions, compared with experimental data (Misawa
et al., 1980).
mental data to the accuracy of that data -
few authors have even tried to make mean-
ingful comparisons. Unphysical potential
energy functions are probably the cause of
the mismatch in early work, but the recent
efforts of Feuston and Garofalini using
Stillinger-Weber type three-body interac-
tions shows that the challenge of matching
experimental data to within statistical er-
ror still exists (see Fig. 4-50).
4.6.8 Monte Carlo Simulations
Guttman and Rahman (1988) have pro-
duced a number of models for a-SiO2 by
methods in which the central step involves
randomly-chosen exchanges of neighbours
followed by energy minimisation and ac-
ceptance or rejection of the move based on
an assessment of the changes in energy.
Variations in the number of n-membered
rings in the starting structures were tried,
as well as changes in the relative mag-
nitude of the terms in the modified Keat-
ing PE function. Once the energy had ef-

fectively converged, the reality of the mod-
els was tested by the fit to experimental
values of the density, elastic moduli and
Q(S(Q) — 1) data - particular attention
being paid to the position and intensity of
the first sharp diffraction peak at about
15 nm" 1 .
The most successful models (324 atoms)
were generated and energy-minimised in
the form of models for a-Si (with the den-
sity fixed at values appropriate to a-Si) and
oxygens only inserted at the final stage.
(Models based on SiO2 throughout were
less successful.) Agreement with g-space
data is (again) said to be "excellent", but
the best models fail to reproduce experi-
mental data to within experimental statis-
tics. Models with 3-membered Si-O rings
were observed to reproduce inadequately
the low Q features in the experimental re-
sults and with more than one 4-membered
ring per 10 Si atoms, errors are again no-
ticeable at low Q.
Keen and McGreevy (1990) have pre-
sented a simulation of the structure of a-
SiO2 using a "Reverse Monte-Carlo" al-
gorithm. The procedure, outlined in Sec.
4.4.5, takes an arbitrary starting structure
- in this case 2596 atoms in a periodic
cubic box of length 3.4 nm. Atoms are ran-
domly chosen and moved to minimise the
weighted difference between the structure
factors for the model and those obtained
from X-ray and neutron scattering mea-
surements for the same sample. At no
stage are energetic terms involved. Results
are shown in Fig. 4-51 and are clearly im-
pressive. The structural parameters de-
rived from the model are similar to those
derived "directly". However, the authors
draw attention to the low value of the Si-0
coordination number of 3.7. The average
oxygen bond angle is 141° in good agree-
ment with Mozzi and Warren's (1969) val-
ue, although the distribution is found to
4.6 Amorphous Silica 249
0.2-
,0.0:
-0.2:
0.2:
,0.0:
-0.2-
tt.O
Figure 4-51. Calculated neutron and X-ray structure
factors for a-SiO2 (solid line) using the Reverse Monte
Carlo method. The dashed line shows experimental
neutron and X-ray data (Keen and McGreevy, 1990),
be significantly broader, as is the Si bond
angle distribution. The Si-Si-Si angle dis-
tribution shows a significant peak at 60°
corresponding to three-membered rings,
which are also observed in projections of
the structure. Such rings are thus not in-
consistent with the diffraction data and it
remains to be seen just how the additional
constraints employed in many other con-
struction algorithms - particularly that of
Gladden (1990) - have lead to radically
different models.
This work certainly concentrates the
mind on the limited amount of informa-
tion available in diffraction data for amor-
phous solids and the extent to which other
prior knowledge - or prejudice - has been
incorporated in less objective constructs.
250 4 Models for the Structure of Amorphous Solids
4.7 Binary Alkali and Alkaline
Earth Silicates, Borates
and Phosphates
4.7.1 Apologia
These glasses may not be the most pop-
ular materials with academic scientists.
Their compositional complexity leads to
structural investigations that are necessari-
ly difficult and inconclusive. But it would
be artificial to exclude them from this
chapter. Silicates, borosilicates, alumi-
nosilicates and (less usually) phosphates,
form the basis of the modern glass indus-
try. Moreover, the class of ionic oxide
glasses represented here is of central im-
portance in the earth sciences. There is ev-
ery reason, therefore, to establish what we
now know about these materials - since it
is far from insubstantial - and how it may
be incorporated into our understanding of
structure of glasses in general.
Section 4.1.4 outlined the various ways
in which the structure of glasses can be
discussed - positional and compositional
ordering, local symmetry and coordina-
tion, network topology, speciation etc.
Each aspect merits attention in the case of
the binary oxide glasses. But in this section
we focus on two interwoven aspects - first-
ly, the local structure around an alkali (or
alkaline earth) element and especially on
the consequences this may have at the level
of medium-range structure. The reasons
for emphasising this topic were set out in
Sec. 4.2.3. If local order is observed in
close-packed regions, so that local struc-
tural units are highly interconnected and if
the bonds to nearest-neighbours are not
strongly directional, then the arguments of
Sec. 4.2.3 suggest that the perceived local
order is a consequence of medium-range
ordering. Local ordering around cationic
"network modifiers" like Li, Na, Mg, Ca,
and (possibly) the trivalent elements thus
gives very important clues to the degree of
ordering over distance scales much larger
than nearest-neighbour bond lengths.
Secondly, we consider several determi-
nations, chiefly by NMR, of the distribu-
tion of anionic species present in a glass -
speciation.
These questions focus attention on the
extent to which randomness inherent in the
Warren-Zachariasen model, actually rep-
resents the structure of real amorphous
materials. I am not aware of a modern
restatement of the Warren-Zachariasen
model for oxide glasses but the consensus
view seems to be the following. Elements
such as Si, B, P etc., bonded to oxygen,
constitute an extended network: such ele-
ments are thus the "network-formers". Al-
kali, alkaline earth and similar elements -
denoted here by M - "modify" the connec-
tivity and thus determine the dimensional-
ity of the network. The B-, P- and Si-0
bonds are regarded as the strongest and
most directional interactions - largely co-
valent, perhaps - whereas network modifi-
er, M-O links are considered to be weak -
mostly ionic and with isotropic, pairwise
forces. The Si environment should thus be
well-defined in contrast to M-0 correla-
tions, where variable coordination is possi-
ble (or probable). Moreover, the M-M dis-
tribution in the Warren-Zachariasen pic-
ture is viewed as being random - deter-
mined largely by composition; although it
is a common over-simplification to regard
the M ions as fitting into suitable cavities
in a silicate framework "formed" to satisfy
the coordination and bonding require-
ments of Si and O, as Zachariasen pointed
out in his original paper (1932).
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
4.7.2 Local Structure Around "Network
Modifiers" in Oxide Glasses
4.7.2.1 Diffraction and EXAFS Data
A major difficulty in establishing the
structure around atoms such as Li, Na,
Mg, Ca in oxide glasses stems from the fact
that M-O, M-Si and particularly M-M cor-
relations generally give only weak contri-
butions to the total scattered X-ray or neu-
tron intensity. This follows from the de-
pendence of the weighting factors in Eq.
(4-19) on the concentration and atomic
scattering factors, so that for light ele-
ments, M-M correlations can be virtually
invisible in X-ray scattering. Moreover,
M-0 first- and higher-neighbour peaks of-
ten lie at similar distances to the more in-
tense 0 - 0 correlations.
Some insight was gained in early work
by taking differences between scattering
data for specimens containing ions of two
chemically similar species which are as-
sumed to substitute isomorphously. Urnes
and coworkers (see for example, Hanssen
and Urnes, 1978) have used Si/Ge replace-
ment to identify features in K 2 O-SiO 2 and
Cs2O-SiO2 glasses and differences between
X-ray and neutron atomic scattering fac-
tors to identify features in silicates (Urnes
et al, 1978).
An exceptionally thorough survey of the
structure of silicate glasses and melts was
conducted by Waseda and Suito (1976,
1977) - work that probably did not receive
due attention until the results were later
republished (Waseda, 1980). X-ray and
neutron scattering data were collected to
Qmax = 170 nm" 1 from about eight compo-
sitions in each series of Li, Na, and K sili-
cate glasses both as the room temperature
glass and the melt. In addition, melts in the
CaO-, MgO- and FeO-SiO2 series were al-
so examined by X-ray scattering (Waseda,
1980). Structural parameters were estimat-
251
ed by fitting the reciprocal space data with
a modified Debye equation. Coordination
numbers were found to vary slightly with
concentration - at the metasilicate compo-
sition approximate values are Li-O 4, Na-
O 6, K-0 8, Mg-O 5 and Ca-O 7 (see also
Table 4-1).
Misawa et al. (1980) used pulsed neu-
tron scattering techniques to study SiO 2 ,
Li 2 O-2SiO 2 and Na 2 O-2SiO 2 and a
mixed Li/Na glass to Qmax = 4$Q nm" 1 . No
real attempts were made, however, to ana-
lyse the M-O contributions in detail apart
from indicating peak positions, 0.20 and
0.24 nm for Li-O and Na-O, respectively.
A further paper by Ueno and Suzuki
(1981) ona-Na 2 Si 2 O 5 to 0 max = 3OO nm" 1 ,
reported the position of the Na-O peak at
0.241 nm with a coordination number of 5,
in good agreement with values for c-
Na 2 Si 2 0 5 (0.241 nm and 5.0).
Also in 1981, Greaves et al. reported
studies on a-Na 2 Si 2 O 5 and other Na-con-
taining glasses using EXAFS. This repre-
sented the first use of a soft X-ray mono-
chromator on a synchrotron to obtain
"element-specific" local structural infor-
mation for a light-element in oxide glasses,
Fig. 4-52. The Na-O mean bond length
was established to be 0.23 nm with a =
0.004 nm and a coordination number of
5 + 0.5. This paper marked the beginning
of an impressive series of measurements
by Greaves and coworkers on the local
structure around modifying elements in
oxide glasses of scientific, commercial and
geological importance (see also Greaves
(1990)). Similar EXAFS investigations by
Brown and coworkers relate principally to
glasses relevant to the earth sciences. A
number of EXAFS results are collected in
Table 4-1.
There are some clear discrepancies be-
tween the results of Greaves and cowork-
ers and Brown et al. (1986), over the local
 N>
Table 4-1. Local structural parameters for silicate and phosphate glasses. Ol
I\D
Bond M-O/nm cr/nm CN Composition Reference Tech Comments

Li-O 0.207 ±0.001 0.010 3.9 ±0.3 Li2SiO5 Wasedaetal.(1977) X,N 6 other glasses and melts
Li-O 0.20 - - Li 2 Si 2 O 5 Misawa et al. (1980) N e max = 480nm- 1
Li-O
Na-O
0.212
0.240
0.009
0.012
4
5
Li2SiO3
a-Na 2 Si 2 O 5
Yasui et al. (1983)
-
X
X
Fitted data
Crystal data 1
CD_
Na-O 0.235 + 0.001 0.010 6.0 Na 2 Si 2 O 5 Waseda et al. (1977) X,N 6 other glasses and melts (/>

Na-O 0.24 - Na 2 Si 2 O 5 Misawa et al. (1980) N o*

Na-O 0.23(0) ±0.003 0.007 5 ±0.5 Na 2 Si 2 O 5 Greaves et al. (1981) E E-%r
CD
Na-O 0.24(3) ±0.003 0.012 2 ±0.5 Na 2 CaSi 5 O 12 Greaves et al. (1981) E CO
Na-O 0.241 0.02 5.0 Na 2 Si 2 O 5 Ueno etal.(1981) N a value estimated by Gaskell c
Q
Na-O 0.240 0.004 4.0 Na 2 SiO 3 Yasui et al. (1983) X Two estimates of a from fitting c"
Na-O CD
0.247 0.015 5 Yasui et al. (1983)
Na-O 0.261 0.010 6.4 Na 2 Si 2 O 5 McKeown et al. (1985) E o
Na-O 0.262 0.015 5.1 KNa3(AlSiO4)4 McKeown et al. (1985) E Nepheline glass
Na-O 0.257 0.019 5.5 KNa3(AlSiO4)4 McKeown et al. (1985) Nepheline crystal o
ZT
-t
Na-O 0.260 0.015 7.6 Na 2 Si 3 O 7 McKeown et al. (1985) Nepheline crystal •D
O
c
K-O 0.25(6) - 5 KCsSi2O5 Greaves (1989) E (/)
E Orthoclase glass CO
K-O 0.300 ±0.002 0.013 8.9 ±0.9 KAlSi3O8 Jackson et al.
K-O 0.303 ±0.002 0.015 9.6 + 1.0 Na 0 . 3 K 0 . 7 AlSi 3 O 8 Jackson et al. E oQ!_
c/)
K-O 0.306 ±0.002 0.015 10.4 ±1.0 Na 0 . 5 K 0 . 5 AlSi 3 O 8 Jackson et al. E
K-O 0.302 ±0.002 0.013 9.5 ±1.0 Na 0 . 3 K 0-7 AlSi 3 O 8 Jackson et al. E
K-O 0.278 0.0035 5 K 2 SiO 3 Yasui et al. (1983) X
K-O 0.288 0.023 6 K 2 SiO 3 Yasui et al. (1983)
Cs-O 0.308 0.015 5 Cs2SiO3 Yasui etal.(1983) X
Cs-O 0.318 0.028 6 Cs2SiO3 Yasui et al. (1983)
Cs-O 0.30(0) - 5 KCsSi2O5 Greaves (1989) E
Ca-O 0.243 ±0.001 0.016 6.8 ±0.3 (CaO)0.45(SiO2)0.55 Waseda (1980) X Data for melt also
Ca-O 0.241 ±0.001 0.013 6.9 ±0.3 (CaO)0-45(SiO2)0.55 Waseda (1980) N
Ca-O 0.241 0.01 6 CaSiO3 Yin et al. (1983, 1986) X Fitting with a crystal model
Ca-O 0.237 0.012 6.15 + 0.17 (CaO)0.48(SiO2)0.49 Eckersley et al. (1988) N Isotope substitution
(Al2O3)0.03
Ca-O 0.237 - 5.40 ±0.18 Ca(PO 3 ) 2 Matsubara et al. (1988) X Other compositions reported
Ca-O 0.264 0.022 7 CaAl2Si2O8 Binsted et al. (1985) E Asymmetric peak
Ca-O 0.263 0.023 8 CaMgSi 2 O 6 Binsted et al. (1985) E Asymmetric peak - mean value quoted
Mg-O 0.214 ±0.001 0.011 4.5 MgSiO3 Waseda (1980) X Data for melt also
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates 253

00 60 bo bfi
5 B 5
'8 '3 '8 T-J
(U « O (1) U 1?
TJ £ *O T3 T3 B
rt SH Cj d ^ VH
o o o o o o
M Q, u s-i M CL
a
^ ga ^5 X> X> g
o
d» co
o d« d d co
SIS 13

Q r •> r •» f •»

8-S 8 8 8 1 ^
b O b b b O S

X X X
al.(

oo OO OO OO
oo OO
oo oo
ON
a>
ara

ara
al.
al.

D 4J 4->
r-J
N 00 N N N
^ rt rf cj
to
c Figure 4-52. Atomic distribution centred on Na ob-
tained by fourier transforming normalised Na-edge
EXAFS spectra for a) vitreous sodium disilicate and
b) a soda-lime-silica glass (Greaves et al., 1981).

oo
2 22 o o
50
fin P« structure around Na and K particularly. In
i__, t, o3 .a
05 W cW a
*-i
part of this may be due to the different
2v5 ffl N N N
choice of specimen composition, but data
oo for Na 2 Si 2 0 5 do not allow this interpreta-
d tion. Differences are more likely to be the
m t-- !O ~H
</^ o t> o result of either adventitious composition
rH OO fO 't
changes or differences in experimental
techniques (transmission and total yield)
or even to systematic variations in data
p pop analysis procedures.
d c5 c5 c>
Many of the X-ray and neutron scatter-
ing studies of network modifiers in oxide
glasses have relied on some form of mod-
TH
io
n (N ^ ) M ^ h
O O\ t>- Qs O> O
elling to extract the weak M-O, M-Si cor-
CN CS T H CN ^ H <N
CD <D CD CD <^
^H
d> <D relations from total scattering data that is
dominated by Si-O and O-O correlations.
"8
Consequently many of the results are rela-
??ooooo tively imprecise: coordination number and
60 50 I ' i l l
S S £ PQ N N N o values, particularly, are subject to large
254 4 Models for the Structure of Amorphous Solids

uncertainties especially for the X-ray scat- more comprehensive and results (Fig. 4-
tering measurements involving M elements 53) show that the pair distribution func-
of low atomic number. The situation is tions for a-CaAl2Si2O8 and a-CaMgSi2O6
much more favourable, however, in phos- are very asymmetric and can be syn-
phates of the heavier divalent elements, thesized by 7 to 8 gaussian compo-
such as Zn, Cu, which provide a relatively nents stretching from 0.235 to 0.31 nm,
large contribution to X-ray scattering. with a standard deviation of 0.021 nm
Moreover, the M-O peak lies in the gap for CaAl 2 Si 2 O 8 and 0.019 nm for
between P-O correlations at 0.15 nm and CaMgSi 2 O 6 .
the first 0 - 0 peak at 0.25 nm. Neutron Eckersley et al. (1988) have used iso-
data, to Qmax = l%0 nm" 1 , has been re- topic substitution of Ca in neutron scatter-
ported by Matz et al. (1988), for Zn, Ca,'
Sr, Ba metaphosphates and X-ray data
(emax^lSOnm- 1 ) for Mg, Zn and Ca
20-
metaphosphates by Matsubara et al.
(1988). Musinu et al. (1989) have also stud-
ied Zn metaphosphate by X-ray scattering
(Q max =150 nm" 1 ) together with a mixed
CuZn metaphosphate. Results are given in
Table 4-1.
As with some of the EXAFS data, the
last three measurements are revealing in
that well-defined M-O first coordination
shells are observed. Typically, o values for
the Zn- or Mg-O distances are about
0.011 nm - a value that is larger than that
for the P-O peak by a factor of 2.5, but the
M-O distribution in the crystal is almost
equally broad (a = 0.012 in Zn(PO 3 ) 2 ).
There are, however, significant variations
in the coordination numbers outside the
estimated errors of the measurements.
Thus three values for the Zn-O coordina-
tion numbers are 3.75 (Matz et al., 1988),
3.90 (Matsubara et al., 1988), and 5.0
(Musinu et al., 1989). In c-Zn(PO3)2 the
Zn coordination number is 6. There are
Figure 4-53. Pair distribution functions for C a - O in
also unexpected differences in the Mg-O
amorphous silicates and aluminosilicates obtained
distance in a-Mg(PO3)2 between the two by curve-fitting the Ca K-shell EXAFS data. Each
datasets and, more understandably, in the C a - O distance has been broadened by a thermal
Ca-O distances: since this peak is not re- factor cr = O.OO85 nm. Spectra are shown for glasses of
solved in either the neutron or X-ray data. the composition of the minerals, anorthite CaAl2Si2O8
(upper diagram) and diopside, CaMgSi2O6 (lower).
EXAFS data for Ca in silicate glasses Dotted lines are the pair distribution functions for
has been reported by Geere et al. (1983), crystalline anorthite and diopside (Binsted et al.,
and Binsted et al. (1985). The latter is the 1985).
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
-0.2
r/nm
ing studies of a calcium metasilicate glass,
lightly doped with A12O3 to minimise the
risk of crystallisation on cooling from the
melt. Results shown in Fig. 4-54 indicate a
well-defined first neighbour shell of 6.15
oxygens around Ca, with a mean bond
length of 0.237 nm - almost identical to
the value found in c-CaSiO3. The distribu-
tion is also narrow: fitting the data with
gaussian peaks suggests a well-ordered en-
vironment around Ca for about 85% of
the oxygens which lie in a peak centred at
0.237 nm with a standard deviation of
0.012 nm. The remaining oxygens lie in
a broad tail stretching from 0.25 to
0.285 nm. There is a suggestion, therefore,
that the coordination polyhedron around
Ca in this glass is octahedral as in c-
CaSiO 3 .
Space does not permit a discussion of
the environment of transition metals and
other polyvalent elements that, within the
Warren-Zachariasen framework, could be
classed as network modifiers. Studies have
a long history - particularly by optical
spectroscopy. Generally, first peaks occur
at similar positions to those in the corre-
255
Figure 4-54. Pair distribu-
tion function, GCa (r), cen-
tred on the Ca atom (full
line). The dashed line repre-
sents data for c-CaSiO3
calculated with gaussian
broadening parameters
a = 0.01 nm for the first
(CaO) peak and a = 0.02 nm
for the remaining peaks.
The data for the crystal has
been convoluted with a
SINC function to repro-
duce the termination ripple
introduced into the experi-
mental data by a truncated
fourier transform (Eckersley
etal, 1988).
sponding crystals but EXAFS data indi-
cates some shortening. For an excellent re-
view see Calas and Petiau (1983). One re-
cent result, combining neutron scattering
with isotopic substitution and XAS gives
the flavour of the results in this area. Yark-
er et al. (1986) have measured the scattered
intensities (g max = 300 nm" 1 ) for a
K 2 O • TiO 2 • 2SiO 2 glass with substitu-
tion of 46 Ti and 48 Ti. The Ti-O peak is
split with two components at 0.165 and
0.196 nm (similar to distances observed in
crystalline Na2TiSiO5) with a a value (cor-
rected for termination broadening) of ef-
fectively zero (6 x 1 0 " 4 ± 2 x 10" 3 nm) for
the first peak and 0.01 ±0.001 nm for the
second. The environment of the Ti ion in
this glass is extremely well-defined.
Summarising the results on the local
structure around "modifer" ions in oxide
glasses: there is no doubt that experimental
data suggests that even weakly-bonded ele-
ments like Na have a reasonably well-de-
fined oxygen first shell. Representation of
the extent of disorder around a given atom
site is probably best achieved by compari-
son with the crystal. Thus if as is the static
256 4 Models for the Structure of Amorphous Solids
broadening parameter - after correction of
the experimentally measured a value for
termination and thermal broadening (see
Sec. 4.3.3) - and if ac is the standard devi-
ation of the corresponding distribution in
the crystal, then:
a A = <rc — an (4-40)
Here <rd is a measure of the increase in
disorder in the transition from crystal to
glass. Taking the example of CaSiO 3 . Ca
sites are distorted already in the crystal, so
that a c = 0.01nm. In Eckersley et al.'s
data, for the 85% of ordered Ca sites, od =
= (0.012 2 -0.01 2 ) 1/2 = 0.007nm. For the
Si-O correlations in amorphous and crys-
talline CaSiO 3 , <rd = 0.005 nm, so that the
additional disorder introduced into the Ca
sites by vitrification is only about 40%
more than that introduced into the Si-O
tetrahedra.
4.7.2.2 Complementary Techniques
The environment of alkali and alkaline
earth ions has been probed indirectly by
studies of defects associated with elements
like Tl + that are considered to be represen-
tative of the structure of alkali ions. Thus
Kawazoe (1985), Kawazoe and Takagi
(1983) report ESR measurements on Tl2 + ,
generated from Tl + by y-irradiation, in
K 2 O- and Na 2 O-SiO 2 glasses. Two sites
for the precursor Tl + atom were detected
one with a highly distorted ligand field, the
other being symmetrical. The former ap-
pears in glasses where both bridging and
non-bridging oxygens co-exist and the lat-
ter in glasses where all bridging or all non-
bridging oxygens are present - such as
mixed nitrate glasses. The concentration of
the two types of site are composition-de-
pendent.
The possibility of two types of sites in
alkali silicates is raised by Dupree et al.
(1986) in connection with the composition-
dependence of the 133 Cs MASNMR signal
in caesium silicate glasses. Their data is
interpreted in terms of a "wide range of
(Cs) sites which are based on two main
types and the range of these sites narrows
with increased Cs 2 O". Similar conclusions
emerge from optical spectroscopy - partic-
ularly of dopant ions. A recent discussion
by Belliveau and Simkin (1989) of the fluo-
rescence line-narrowed spectra of Eu 3 +
doped into silicate glasses, suggests that
the environment of the dopant may be rel-
atively constant, with perhaps a small
number of configurations, rather than a
continuous distribution as advocated by
others (e.g. Weber, 1981). This conclusion
is based both on the authors' own results
and similarities observed in the Eu 3 + spec-
tra in wide range of glass compositions,
and on the absence of any dependence on
the concentration of Eu 3 + spectra in these
glasses.
Vibrational spectroscopy provides am-
bivalent conclusions. Vibrations associat-
ed with ionically-bonded elements appear
in the low-frequency IR spectrum rather
than the Raman spectrum. The contribu-
tions of these modes to the total integrated
absorption - and therefore to the low fre-
quency dielectric constant is approximate-
ly half the contribution from all other
mechanisms combined - over the entire
spectrum from the high energy ultraviolet
to radio-frequencies as pointed out by
Birch et al. (1975) and Ellis et al. (1977).
The breadth of the "alkali" band - stretch-
ing from below 10cm" 1 to 103 cm" 1 ac-
cording to Ellis et al. suggests a multiplici-
ty of sites for Ca + + and Na + . The subject
has been treated more recently by Exarhos
(1983) and by Gervais et al. (1987). The
latter paper is particularly interesting as
the data is presented for the imaginary
part, e 2 , of the complex dielectric constant,
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
500 1000 1500
WAVENUMBER (cm-1)
Figure 4-55. Imaginary component of the dielectric
function for silica and silicate glasses containing Na
and K. Note the low frequency band assigned to the
stretching vibrations of alkali cations (Gervais et al.,
1987).
c, thus giving a direct, quantitative mea-
sure of the "oscillator strengths". (More-
over it gives an excellent overview of the
subject). Fig. 4-55 shows the low frequency
IR "continuum", compared to silica.
4.7.3 Medium Range Structure Centred
on "Network Modifiers" in Oxide Glasses
4.7.3.1 Diffraction Data
As mentioned in Sec. 4.3.5.5, the effec-
tive range of EXAFS data in amorphous
solids is limited by the breadth of second
and higher neighbour real-space correla-
tion functions. In practice it is difficult to
obtain quantitative information beyond
the first neighbours of atoms such as Na or
Ca which are of interest here. Diffraction
data thus proves to be most useful. We
focus on determinations of the M-M dis-
tance in oxide glasses in order to gain some
impression of the spatial distribution of
network modifier atoms.
One method for identifying peaks due to
network-modifying elements in total dif-
fraction data is to use a heavy element, so
that M-centred correlations are prominent
257
in X-ray scattering due to atomic number,
Z, contrast. In early work, a number of
authors used this technique in attempts to
prove that preferred M-M distances oc-
curred near 0.7 nm - a value predicted by
a structural theory of liquid-liquid immis-
cibility (Levin and Block, 1957). Results
overall were not conclusive. Although
peaks in real-space distributions near
0.4 nm in Ba- and Cs-silicates and borates
were "ascribed" to M-M distances by
Brosset (1963), the contribution from M-
M correlations calculated (by this author)
using Eq. (4-21) is small in all the composi-
tions and almost negligible in some of the
compositions where a peak is observed.
Similar comments apply to data for a bar-
ium borosilicate studied by Piermarini and
Block (1963). On the other hand, the Ba-O
peak is dominant and it is likely that the
feature ascribed to Ba-Ba, Cs-Cs is the sig-
nature of M-O(2) distances as Krogh-Moe
(1962) argues.
Some of the most impressive work is
that by Krogh-Moe and Jurine (1965) and
by Milberg and Peters (1969) on thallium
borates and silicates, respectively. Tl has a
high atomic number (Z= 81), so that Tl-0
and Tl-Tl pairs dominate the total distri-
bution functions. In fact, Tl-Tl contributes
51 % of the total scattering for the Tl-rich
silicate studied by Milberg and Peters.
Fig. 4-56 shows these data which were in-
terpreted as mainly Tl-O for the 0.5 nm
peak and Tl-Tl (Cs-Cs) for the peak at
0.7 nm by Krogh-Moe and Jurine, and
"probably" as Tl-Tl peaks at 0.4, 0.7 and
1.0 nm by Milberg and Peters. Note the
apparent composition-independence of
peak positions. Note also that all the au-
thors argued that their data indicates a
non-random distribution of network mod-
ifier atoms. More recently Hanson and
Egami (1986) investigated Cs-containing
silicate glasses (ZCs = 55). Their results are
258 4 Models for the Structure of Amorphous Solids
12
o (r)
Figure 4-56. a) "Electronic" radial distribution func-
tion, a(r) = rG (r), for Tl2O-SiO2 glasses containing
1) 34.5, 2) 22.8, 3) 16.1 mol% T12O (Milberg and Pe-
ters, 1969). b) Similar data for thallium and caesium
borate glasses measured by Krogh-Moe and Jurine
(1965). Upper curve (full line) shows data for a glass
containing 4.7 mol% T12O and the lower curve,
9.6 mol% T12O. Dotted curves show o (r) for borate
glasses with similar quantities of Cs2O.
in qualitative agreement with the X-ray
work of Yasui et al. (1983) and Guaker et
al. (1974). Hanson and Egami assigned the
main peak at 0.41 nm to Cs-Cs pairs and
further peaks at 0.69 and 0.8 nm to higher
Cs neighbours in random close-packing.
Yarker et al. (1986) have also obtained a
M-M distribution by taking second differ-
ences of their neutron scattering data for
three different isotopic ratios of Ti. There
is considerable scatter in their data -
shown in Fig. 4-57 as a composite curve -
however the first Ti-Ti peak at 0.34 nm is
2 4 6 r/A
Figure 4-57. Three estimates of the Ti-Ti distribu-
tion, T(r), for vitreous K 2 O TiO 2 -2SiO 2 (after
Yarker et al., 1986). A first peak is seen at about
0.34 nm suggesting Ti-Ti clustering at a smaller dis-
tance than the mean value 0.61 nm (arrow), calculated
for a spatially random distribution of Ti atoms
(Gaskell, 1985 b).
observable in all the component curves. As
pointed out by Gaskell (1985 b), the posi-
tion of this peak directly indicates a pre-
ferred Ti-Ti distance - corresponding to
clusters, perhaps - rather than a random
distribution of Ti throughout the glass.
The latter model would give a peak at
0.61 nm, close to the second peak in the
double difference data.
Double difference measurements for Ca
in a silicate glass have recently been report-
ed by Gaskell et al. (1991 a). Neutron scat-
tering from glasses consisting essentially of
calcium metasilicate with 3mol% A12O3
added to reduce the risk of devitrification,
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
0.010
- ' ' ' ' '
\
0.005 -
\ double difference data ob-
in
c
/ Y~— V*-
\ \V r V
*.
-0.005-
V traction of the C a - O dis-
;
-0.010 i i
-(A)
were measured with three isotopic concen-
trations of Ca and the resulting distribu-
tion is shown in Fig. 4-58. Assuming per-
fect composition matching and ideal data
reduction procedures, the resultant second
difference should represent Ca-Ca correla-
tions only. As shown in Fig. 4-57 there is
some "contamination" of Ca-O correla-
tions giving a peak at about 0.23 nm. The
prominent peak at 0.37 nm corresponds
closely to distances observed in c-CaSiO3
(0.36, 0.375 nm). For this composition, the
Ca-Ca distance in a "randomly-stuffed"
glass would correspond to 0.44 nm. The
experimental data has been fitted with a
series of gaussian peaks allowing the coor-
dination number to be estimated. The total
of 4.8 atoms are located in the two peaks
at 0.35 and 0.4 nm, with a further 0.95
atoms at 0.45 nm. In the crystal, 4.67 Ca-
Ca pairs are observed near 0.4 nm.
A further pronounced peak is observed
at 0.64 nm and a smaller one at 0.9 nm.
Interestingly, the first corresponds closely
to ^/3R1 where R1 is the first Ca-Ca dis-
tance of 0.37 nm. For a DRP cluster, sim-
ilar to that proposed by Hanson and
Egami (1986) for Cs-silicates? the second
peak would lie between 0.63 to 0.73 nm,
and the third peak near 0.94 nm.
259
- Figure 4-58, Distribution of
Ca-Ca neighbours for
A _ r > 0.25 nm inferred from
the fourier transform of the
J' tained in a calcium silicate
glass. There is some "con-
tamination" of the data by
a peak at 0.23 nm associ-
- ated with inadequate sub-
tances (Gaskell et al.,
, , , 1990 a).
10
4.7.3.2 Complementary Techniques
Relatively little conclusive information
on the M-M correlations has been ob-
tained from techniques other than diffrac-
tion. An exception is the work of Panek
and Bray (1977) who used 2O5T1 NMR to
show Tl-Tl pairing, even in Tl-dilute glass-
es.
4.7.4 Speciation
4.7.4.1 Borates
Borates differ from silicates in that while
Si is normally tetrahedrally bonded, boron
can exist in tetrahedral and trigonal coor-
dination. Experimental methods (chiefly
NMR and vibrational spectroscopy) allow
the B 4 ratio to be examined as a function
of composition, for instance. Crystalline
borates exhibit a wide range of anionic
groupings, combining B-O triangles and
tetrahedra linked through bridging oxy-
gens, Fig. 4-59. Vibrational spectroscopy
and X-ray diffraction have provided evi-
dence that such anionic groups persist in
glasses too, a review of this work being
given by Krogh-Moe (1965). NMR has al-
so figured prominently in attempts to un-
derstand the medium-range structure,
260 4 Models for the Structure of Amorphous Solids
J>
Figure 4-59. Anionic units in borates after Bray and
Liu (1983). a) Boroxol, b) pentaborate, c) triborate,
d) diborate, e) metaborate, f) pyroborate, g) orthobo-
rate, h) "loose" BO 4 unit.
chiefly through the research of Bray and
coworkers - for recent reviews see Bray
and Lui (1983), Bray (1987). 1XB NMR has
been used to determine the fraction of 4-
coordinated boron atoms in alkali silicate
glasses as a function of composition. Phys-
ical properties of alkali borates such as
density, coefficient of thermal expansion
and refractive index, show sharp changes
in the region 15-20 mol%. This had been
attributed to structural changes in which
BO 4 groups with bridging oxygens become
progressively replaced by trigonal groups
with at least one non-bridging oxygen.
Data shown in Fig. 4-60 indicates that the
fraction of tetrahedral B continues to in-
crease to about 40 mol%, however.
Computer fitting of similar wide-band
10
B NMR data, allows the medium-range
structure to be examined. Features in the
10
B NMR signal are sensitive to changes in
the local structure around the atom, and
these are reflected in variations in the
quadrupole coupling constant and the
asymmetry of the electric field gradient.
Fig. 4-61 shows computer fits to experi-
mental spectra using parameters derived
from the borate groups shown in Fig. 4-59.
Constraints include bond number and
charge conservation, together with de-
tailed rules relating the fraction of B 4 , B 3
and concentrations of the anionic groups
of which they form components. Addition-
al constraints preclude participation of a
given anionic group in composition re-
gions far from that appropriate to its com-
position. Effectively this follows the sug-
gestion of Krogh-Moe (1965) that glasses
contain structural groups appropriate to
compositionally-equivalent crystals.
4.7.4.2 Silicates
Relatively few conclusive results
emerged on the anionic species present in
silicates until the mid 1980's. Raman inves-
tigations - essentially qualitative - suggest
a broad species distribution. Since the ad-
vent of 29Si NMR applied to silicates, with
N4
0.5-
0.4-
0.3-
0.2-
0.1-
0.0
0.0 0.4 0.8 1.2 1.6 2.0
Figure 4-60. The fraction of 4-coordinated boron
atoms in lithium borate glasses determined by Bray
and Liu (1983) by X1B NMR spectroscopy. (R is the
ratio of molar concentrations of Li2O and B2O3.)
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates 261

100 KHz

Figure 4-61. Experimental 10B NMR data for lithium borate glasses as a function of composition expressed as
the ratio, R, of the molar concentrations of LiO 2 and B 2 O 3 . The smooth lines represent computed fits to the data
based on variations in the fraction of anionic units shown in Sec. 4.7.8 (Bray and Liu, 1983).

or without magic angle spinning, the situa-
tion has been transformed (Grimmer et al.,
1984; Dupree et a l , 1984, 1986 and
Schramm et al., 1986). The narrow peaks
obtained for the alkali silicates can be
analysed by fitting, using comparisons
with crystalline compounds, to give the
relative fractions of silicons of species
Qn(0<n<4).
For a glass of composition, say,
Na 2 Si 2 O 5 , a chemically-ordered model
would suggest that the glass contains Q3
species alone, whereas a random model fa-
vours a distribution with all species present
to some extent. For a composition corre-
sponding to the trisilicate, Na 2 Si 3 O 7 , a
mixture of Q3 and Q4 species is the mini-
mum binary combination according to an
ordered model but, again, all species are
possible in a random model.
Although the results differ in detail, all
the investigations conclude that alkali sili-
cates are more chemically-ordered than
random models predict. Analysis of the
data of Grimmer et al. (1986) and Dupree
et al. (1984) for lithium and sodium sili-
cates leads the authors to propose signifi-
cant ordering. Thus at "stoichiometric"
262 4 Models for the Structure of Amorphous Solids
compositions, corresponding to the disili-
cates and metasilicates, the magic angle
NMR data indicates a dominant contribu-
tion from g 3 and Q2 respectively. Interme-
diate compositions were analysed in terms
-60 -80 -100
ppm
Figure 4-62. 29Si NMR spectra of sodium silicate
glasses as a function of composition (the molar frac-
tion of Na 2 O is shown), a) Without sample spinning
- cross hatching shows the areas of the Q 4 peaks,
b) With magic angle spinning (Stebbins, 1987).
of binary weighted mixtures. Other work-
ers have fitted spectra with multiple peaks.
Thus Schramm et al. (1986), Selvaraj et al.
(1985), Murdoch et al. (1985), Hater et al.
(1989), interpret their data in terms of 3 to
5 species.
Stebbins (1987, 1988) has pointed out
that MASNMR alone, may not be the
most sensitive method for establishing the
proportions of silicate species and that a
combinatioin of spinning and static NMR
techniques improves the data. The reason
lies in the variation of the chemical shift
for 29Si with the symmetry of the site. Vari-
ations in local symmetry produce shifts of
the order of 150 ppm - depending on the
relative orientations of the anisotropy and
the external magnetic field. This is typical-
ly the breadth of the spectrum. This chem-
ical shift anisotropy is averaged out in
MASNMR leading to improvements in
resolution. Stebbins points out that for
highly disordered solids, resolution may be
better in static spectra, taking advantage
of differences in chemical shift anisotropy,
which will be small for a highly symmetri-
cal site such as a Q4 Si, and therefore the
contribution is less broadened. Thus Q4
sites can be detected much more easily in
the static spectra than in the spinning spec-
tra, Fig. 4-62 a. The MASNMR spectra
do, however, allow detection of the Q2 spe-
cies, Fig. 4-62 b.
The extent of any departure from a sin-
gle species, Qn, can be represented by an
equilibrium:
2Qn = Qm+1 + Qm~1 0<m<4
and an associated "equilibrium constant":
K = (4-41)
C2(n)
where C(n) is the concentration of species
Qn-
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
Thus, Kn = 0 implies a chemically-
ordered distribution with: C(n + 1) =
C(n — l) = 0;C(n) = l. For a non-stoichio-
metric composition lying between §iO
and Na 2 Si 2 O 5 , say, only a binary distribu-
tion of components Q3 and Q4 need be
considered. This was the result observed
by Grimmer et al. and Dupree et al. Kn > 0
implies the presence of at least three spe-
cies and therefore a contribution to the
configurational entropy.
Stebbins (1988) presents values for the
fraction of Q4 species in Li- and Na-disili-
cates (6.4 and 11.5%) leading to K3 values
of 0.005 and 0.022. For a random distribu-
tion, K3 would be much larger, 0.375,
(Lacy, 1965) corresponding to C(4) =
32%.
The extent of disorder is greater as the
field strength of the ion M increases - that
is for small polyvalent ions. Thus K3 for
Li + is greater than for Na + , and K 3 for
C a + + greater than for N a + . Even in the
latter case, however, the distribution is far
from the limit suggested by a random
model.
Gurman (1991) has produced a thermo-
dynamic model which describes the silicate
anion species present in alkali silicates as a
function of composition. Specifically, the
equilibrium constant given by Eq. (4-41),
is expressed in terms of a Boltzmann fac-
tor, exp( —2A£/£: B r), where AE = EBB +
+ ENN — 2 EBN. In this expression, EBB rep-
resents the energy of interaction between
two bridging atoms, B; ENN and £ B N , are
similar terms involving non-bridging and
bridging atoms. T is identified with Tg.
Gurman's expression is compared with ex-
perimental Raman and NMR data and
gives a pleasing explanation.
NMR, either static or spinning, is much
less useful for silicates with divalent
cations; spectra are broad and relatively
featureless (Kirkpatrick et al., 1986;
263
Schneider et al., 1987), and deconvolution
into the spectra of component species is
not possible. Schneider et al. suggest that
this is due to a combination of factors such
as the smaller differences between bridging
and non-bridging oxygens as the elec-
tronegativity of the modifier ion increases,
rather than the signature of a broad, con-
tinuous distribution of species. Structural
variables other than populations of Qn spe-
cies, variations in bond angles and lengths,
for example, are also important.
Stebbins and coworkers have also stud-
ied the temperature-dependence of silicate
speciation: directly, by measurements at
temperatures above Tg (Liu et al., 1987,
1988), and by variation of the fictive tem-
perature by quenching or annealing sched-
ules (Brandriss and Stebbins, 1988; Steb-
bins, 1988). Disproportionation was found
to increase for a sodium disilicate glass,
rapidly quenched so that its fictive temper-
ature was about 80 °C higher than that for
annealed glass. The Q4 population in-
creased from 0.06 to 0.08. This dispropor-
tionation is still smaller than that estimat-
ed either from Raman spectroscopy or
from the statistics of random models.
As the temperature is increased, not on-
ly does the average species population
change but also life-times decrease. NMR
studies show that silicon atoms exchange
rapidly among sites in the liquid at temper-
atures greater than 100 to 200 K above Tg.
At temperatures around 300 K above Tg9
the broad NMR signal shrinks to a narrow
line due to the rearrangements occurring
on a time-scale less than the experimental
time-scale (inverse of the static line width).
The atomistic picture is of a rapid reorien-
tation of the local symmetry axis for a Si
atom, involving interconversion of bridg-
ing and non-bridging oxygens on time
scales of a few microseconds for tempera-
tures above the liquidus, to nanoseconds at
264 4 Models for the Structure of Amorphous Solids
2000 K. Such structural rearrangements
are, of course, on time-scales much longer
than vibration frequencies of around
10~ 1 3 s.
4.7.5 Network Models
Compared with the effort devoted to
modelling all other families of glasses sur-
veyed in this chapter, simple metal oxide
glasses have been almost neglected. Apart
from a few simulations by MD techniques,
the essentially qualitative notions ad-
vanced as the random network model -
almost 60 years ago at the time of writing
- have hardly been given any thorough
quantitative examination. Difficulties in
producing physical models is a significant
factor of course, physical and computer-
generated models (apart from MD studies)
are virtually non-existent.
The classical picture of alkali silicate
glasses due to Warren and Zachariasen is
shown in Fig. 4-3 b. It can be considered as
being derived from the random network of
the glass-forming oxide - SiO 2 , say - by
addition of the network-modifying oxide
which breaks Si-O-Si bonds so that
for every oxygen atom of the modifier,
two bonds are broken to form nega-
tively charged non-bridging oxygens. The
charges are balanced by the M + cations in
the vicinity. The environment of the M +
cations is unspecified as the diagram indi-
cates.
One of the simplest physical properties
that appears to be quantitatively inconsis-
tent with this model for alkali silicate
glasses is the density. Clearly, this is not a
structural property but, as in many other
systems, density data is sensitive to the de-
tails of proposed structure - see Sec. 4.4.6.
Gaskell (1982) pointed out that differences
in density between alkali silicate crystals
and glasses is so small that an understand-
ing of the former leads to a model for the
latter. Specifically, lithium silicate glasses
are based on a close-packed oxygen sublat-
tice with Si and Li occupying the inter-
stices. The lattice is dilated mainly due to
the cations expanding the lattice in direc-
tions normal to the planes containing
sheets or chains. Also, the directional
S i - 0 bonding introduces an expansion
corresponding to the difference between
the tetrahedral oxygen bond angle (in
close-packing) and that observed (125 to
135°). This acts in the plane of the sheets
or chains. Simple geometrical arguments
based on these principles lead to good
agreement with experimental data for the
crystals. It then becomes difficult to see
why similar explanations should not aper-
tain in glasses too and leads to the conclu-
sion of dense packing around the alkali
cations, "probably within well-defined
channels" and that the silicate sheets, for
example, extend over distances of 2 to
3 nm in each direction. This follows from
the need for co-operative atomic motion to
achieve the necessary degree of close pack-
ing of oxygens around Li. Later simula-
tions described in Sec. 4.7.8 further illumi-
nate this point as (more) random models
disagree with density data.
In order to explain the well-defined co-
ordination around network modifier
atoms as observed by EXAFS, Greaves
(1985) proposed that such elements are in-
corporated into the structures in a manner
complementary to that of the network for-
mers like SiO2 so that "the overall struc-
ture will necessarily comprise two interlac-
ing sublattices: network regions construct-
ed from network formers and inter-net-
work regions made up of modifiers". Fig.
4-63 shows Greaves' pictorial represen-
tation of an archipelago structure " . . .
peninsulas and islands of network inter-
spersed by channels and lakes of modifier.
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates
Whether the modifier regions . . . extend to
precolation channels will depend on the
composition . . .". Greaves refers to this
model as a modified random network. The
chief difference between this model and
earlier CRN models for silicates is the
presence of modifier cations within an an-
ionic sublattice composed principally (or
entirely) of non-bridging oxygen ions. An
atom such as that marked in Fig. 4-3 b in
the Warren-Zachariasen picture would ap-
pear to be disallowed in Greaves' model.
Thus far, the modified CRN has been used
as a conceptual tool only, with no attempt
to build a model and test its structural
properties.
4.7.6 Molecular Dynamics
Much of the early work on alkali sili-
cates was carried out by Soules and co-
workers using a modified Born-Mayer-
Huggins potential. Soules (1989) has re-
cently reviewed MD simulations on oxide
glasses but more detailed treatments are
given in Soules (1979, 1985). Soules shows
that M + ions are associated with non-
bridging oxygens, but no discernable coor-
265
Figure 4-63. Schematic representa-
tion of the "modified random net-
work" structure proposed by
Greaves (1985). Strong covalent
bonds between the "network-
forming" atoms are shown by
double solid lines and ionic M - O
bonds by the dashed lines. The
shaded region delineates the net-
work regions and highlights the
percolation paths linking the M
cations.
dination shell is found. The number of
atoms increases continously with distance
- in contrast to the behaviour of B which
is a network former with a first coordina-
tion shell of 4.
Tesar and Varshneya (1987), have used
a similar potential to study alkali silicate
glasses over the composition range that is
subject to sub-liquidus immiscibility in the
real glasses, in an effort to identify compo-
sition fluctuations associated with phase-
separation. Although unsuccessful in this
aim - more definite evidence of a first co-
ordination shell of oxygens was observed.
Coordination numbers of 3 to 4 for Li, and
2 to 3 for Na and K are lower than exper-
imental values, however. M-M clustering
was not observed - the calculated M-M
pair correlation functions are essentially
featureless.
A far-reaching survey of the properties
of sodium silicate glasses (5 to 33 mol%)
has been reported by Mitra and Hockney
(1983 a, b). Total radial distribution func-
tions and interference functions were cal-
culated and compared with experimental
X-ray and neutron data and the fit is found
to be reasonably good. Unfortunately Mi-
266 4 Models for the Structure of Amorphous Solids
tra and Hockney did not compare their
computations with the high Qmax neutron
scattering data of Misawa et al. (1980)
(which in fact provides a good fit). The
partial distribution functions are particu-
larly revealing. A pronounced Na-O peak
is seen at 0.23 nm corresponding to about
4.8 to 5.0 oxygens is in good agreement
with experimental data of Greaves et al.
(1981). Moreover, a broad Na-Na peak is
seen (Fig. 4-64) around 0.32 nm for all
compositions - even those dilute in Na,
and there are indications from the models
of clustering on a scale of 1.0 nm diameter.
These are most obvious in the silica-rich
glasses. At 33mol% Na 2 O, the distribu-
Na-Na
Na2O/SiO2
33%
20%
10%
r(A)
Figure 4-64. Distribution of N a - N a pairs in several
sodium silicate glasses simulated by molecular dy-
namics. The first peak position is not dependent on
the Na concentration indicating N a - N a clustering
(Mitra and Hockney, 1983 a, b).
tion of Na + is more liquid-like. Mitra and
Hockney conclude that in the silica-rich
glasses (5 and 10 mol%), Na + ions occupy
holes in the silica network but as the Na
concentration rises, this influence on the
surrounding structure becomes more
prominent and a simple geometric model
of sodium occupancy of holes is inappro-
priate.
An interesting MD simulation of a sodi-
um trisilicate glass, Na 2 O • 3 SiO 2 , is that
by Newell et al. (1988), who introduced a
Stillinger-Weber three-body interaction in
addition to the Born-Mayer-Huggins pair
potential (see Sees. 4.4.4 and 4.7.6) in a
simulation. A sharp O bond angle distribu-
tion was obtained, a = 6° with very few
overcoordinated Si atoms. A broad oxy-
gen bond angle distribution (a = 12°) with
a mean of 149° was found. A broad Na-Na
peak at ^0.30 to 0.31 nm was observed
and a Na-O distance of 0.242 nm, with a
coordination number of 5.0 in good agree-
ment with the experimental value of
Greaves et al. (1981) and Misawa et al.
(1980). The proportions of Q4 and Q3 (and
other) silicate species were calculated - the
Q4 and Q3 concentrations being about 48
and 43% respectively with 8% Q2. Al-
though the authors did not attempt a de-
tailed comparison with experimental cor-
relation functions, the work indicates the
possibility of future progress.
4.7.7 Microcrystallite Models
The intensity and position of Raman
bands of alkali silicate glasses is interpret-
ed by Phillips in terms of vibrations inter-
nal to grains and to the "surface" modes of
disilicate and metasilicate clusters. The in-
terested reader is referred to Phillips (1982)
for details.
Several workers have used clusters com-
prising a number of unit cells of the corre-
 4.7 Binary Alkali and Alkaline Earth Silicates, Borates and Phosphates 267

2
600 _xlO

S 400 500

200

1 2 3 4 5 1 2 3 4 5
(a) (b)

Figure 4-65. Calculated

1000
RDFS (full lines) for
models of several alkali
4000 metasilicates containing,
a) Li; b) Na; c) K;
^ 500 d) Cs, compared with
experimental data
2000
(dashed lines) from
X-ray scattering mea-
surements (Yasui et al.,
0 1 2 3 4 5 0 1 2 3 4 5 6 7 1983).
Radius (A) Radius (A)
(c)

sponding crystalline phase as bases for 4.7.8 Stereo-Chemically Defined Models

models of the corresponding glasses. Thus
Yasui et al. (1983) and Imaoka et al. (1983)
have modelled alkali metasilicates and di-
silicates by distorting the geometry of the
silicate chain - specifically varying the cor-
rugation - with alkali positions altered to
maintain ionic radii. Variations in the net-
work topology were excluded so that no
attempt was made to introduce Q3 or Q1
species into models for metasilicates, say.
Agreement with experimental radial distri-
bution functions to 0.5 nm is quite impres-
sive (Fig. 4-65). Surprisingly, most of the
chains are almost straight in the models -
only for the sodium glass does the corruga-
tion (represented by 9) approach values for
the crystals. Results of a similar quality
were obtained for Na 2 Si 2 O 5 .
Barenwald et al. (1988) proposed a mod-
el for barium metaphosphate, Ba(PO3)2 in
which the chain structure of the crystal
forms the basis. This is then varied by a
Monte-Carlo process in which arbitrary
PO 4 tetrahedra comprising the chain are
rotated through a randomly-chosen angle.
Randomly chosen Ba atoms are given ran-
dom translations. Moves are accepted or
rejected according to the degree of im-
provement between experiment and model
data, although the authors do not make
clear what criteria are used. Results are
good to about 0.4 nm but somewhat
haphazard thereafter.
Gaskell (1985 b) constructed a model
for amorphous alkali chain metasilicates,
268 4 Models for the Structure of Amorphous Solids

starting from idealised structures of the neighbour shell of 4 oxygens, therefore.

crystalline phases. Crystalline Li 2 Si0 3 can Ordered insertion of Li and Si into a set of
be considered to be derived from a hexago- interstices running parallel to the hexad
nally close-packed (hep) oxygen sub-lattice axis provides a structure that is topologi-
with Li atoms occupying part of the tetra- cally identical to c-Li2SiO3, as shown in
hedral interstices and Si atoms occupying Fig. 4-66 a. If connections to nearest
the remainder. Each cation has a nearest neighbours are introduced, the structure

b)

20 . . . . 1 1 I . . I

15 : si-o -

10

T •
5

e? 0

-5

-10 i . . . . t , , , , i i . , , i , , , ,

1
r/A r/A
Figure 4-66. a) The hexagonally close-packed oxygen sub-lattice corresponding to an idealised (crystalline)
lithium metasilicate structure. Si atoms are shown by small circles and occupy tetrahedral interstices (at two
levels) forming chains running parallel to the hexad axis (out of the plane of the diagram). Each Si-O chain is
surrounded by six parallel Li-O chains (medium-sized circles), b) Computed partial pair distribution functions,
Gap(r), for random chain models of a-Li2SiO3 (Gaskell, 1985b).

can be seen to be a series of parallel chains
of interconnected silicon-oxygen tetrahe-
dra, each (SiO3)n chain being surrounded
by a sheath of six (LiO3)n chains. The actu-
al structure of the crystal involves geomet-
rical distortions to allow the atoms to fit
together but the only significant result of
this is that the pair correlation functions
become somewhat broader and the Li
atom aquires a fifth long Li-O bond.
Crystalline Na 2 Si0 3 is almost identical in
structure - the distortions are larger, re-
flecting the larger size of the Na ion and
the distances to all five near oxygens are
almost equal, so that Na can be regarded
as having a coordination number of five.
It is known that the density of lithium
silicate and other alkali silicate glasses is
only slightly less ( « 5 % ) than that of the
corresponding crystals suggesting that the
close-packed oxygen sublattice is common
to both phases. A model for the glass was
thus constructed by inserting Li (or Na)
into tetrahedral interstices but with a more
random choice. Specifically, the constraint
that Si-containing tetrahedra are sur-
rounded by Li-O chains was retained and
two-fold connectivity was preserved by re-
jecting Q4 or Q3 species - although chain
ends (Q1) were unavoidable. The sites were
chosen randomly subject to an overall
check on the Li/Si ratio. The result was a
set of random, self-avoiding Si-0 chains
surrounded by connected Li-O tetrahedra.
The model was then relaxed using a modi-
fied Keating potential with parameters
chosen so that a close-packed structure
which, as stated above, is topologically
identical to the crystal, relaxed to give the
geometrical structure of the crystal too.
Partial distribution functions were then
calculated (Fig. 4-65 b) and give a reason-
able representation of the major features
observed from inspection of the total rdf.
In particular, the environment of the Li
4.8 Concluding Remarks 269
atom which can be extracted from neutron
scattering measurements with isotopic
substitution, agrees quite well with the pre-
dictions of the model. There are similari-
ties too with the distribution functions
proposed by Mitra and Hockney (1983 a,
b).
Nonetheless, this simulation was judged
to be less than adequate. The values of the
density for the amorphous model proved
to be about 12% larger than values for the
crystal whereas the experimental value is
about 5% less. The discrepancy was
thought to be the result of incorrect topol-
ogy. Specifically, the disordered chain
model - despite the extensive constraints
on randomness - was thought to be still
too disordered. It was suggested that a
more successful model might be a domain
model in which small ( « 1 nm) bundles of
chains and therefore the local hexad axis of
the hep oxygen sublattice, ran parallel over
distances of 1 to 2 nm. Beyond, the struc-
ture is postulated to be statistically identi-
cal apart from a change of direction. The
underlying philosophy is thus identical to
Dubois et al.'s (1985) model for transition
metal-metalloid glasses (Sec. 4.2.4.4).
4.8 Concluding Remarks
It is perhaps only when one is confront-
ed with the mass of literature on the struc-
ture of glasses and amorphous solids, and
faces the task of distilling the essential fea-
tures into an article of this length, that the
magnitude of the human effort involved
becomes fully apparent. The reasons are
clear enough. As outlined at the start,
amorphous solids are socially and com-
mercially important. Moreover, they pre-
sent one of the more interesting challenges
in condensed matter science, and glasses
represent an entree into an even less
270 4 Models for the Structure of Amorphous Solids
tractable subject - the liquid state. In this
section, it might be worth summarising
just what has been achieved as a result of
all this effort, what is still needed and how
this might be done. What follows is neces-
sarily an even more personal judgement
than the foregoing.
4.8.1 Information Content
Firstly, a theme that runs throughout
this chapter, is the need to press for exper-
imental structural information of the
highest precision and information content,
and to interpret such data in terms of mod-
els that fully represent the detail disclosed
by experiment. The reasons will be clear
from reading any of the last three sections.
Certain types of experimental data are in-
formation-dilute - total scattering func-
tions for polyatomic solids, vibrational
density of states functions, high resolution
micrographs of thick specimens. Such data
can be shown to be almost equally consis-
tent with several models based on radically
different precepts. It is also clear that
where experimental information does have
high information content - a high resolu-
tion pair correlation function for an ele-
mental amorphous tetrahedral semicon-
ductor for example then, again, a variety
of models gives an approximate fit to ex-
periment. But until recently, it was not
clear that any model had achieved a fit
approaching the accuracy of experiment
(and this point may still be considered con-
tentious by some). It is only with the com-
bination of fast, cheap computing - and
patient research work - that enough op-
tions have been explored and tested to al-
low models to "home in" on the subtleties
of experimental results.
How should the situation be improved?
Experimental techniques are already
very sophisticated and it might be consid-
ered unrealistic to hope for major break-
throughs as a result of the application of
"new wonder" techniques. It is difficult to
see how elastic scattering measurements
for say, a-Ge could advance sufficiently to
allow any sort of quantum leap, although
the increasing use of high Qmax X-ray and
neutron scattering measurements will lead
to continued evolutionary developments.
For polyatomic solids, improvements are
clearly possible by making more use of
those techniques that allow investigations
of partials or weighted sums of subsets of
partials. Thus the application of neutron
scattering with isotopic substitution,
XAFS and the increasingly powerful X-
ray anomalous scattering techniques be-
come areas for further concentration of ef-
fort. Developments in XAFS have already
allowed great strides to be made and with
the increasing possibility of successful
analysis of the low energy region dominat-
ed by multiple scattering, it is possible to
hope that information can routinely be ex-
tended beyond nearest neighbours. Fur-
thermore the possibility of combining
techniques like X-ray anomalous scatter-
ing with XAFS, so that each complements
the other's weaknesses, continues to be an
exciting prospect. With recent develop-
ments in high voltage high resolution elec-
tron microscopes, there is now every pros-
pect that this technique - with immense
potential (in both senses) - can reach
something like that promise, with unam-
biguous information on just the scale, 0.5
to 1.5 nm that other techniques are cur-
rently finding difficult or impossible to
handle.
Structural techniques based on excita-
tions of the solid probably justify more
optimism for further growth in the near
future. In part this is because techniques
like neutron inelastic scattering have been
relatively used until recently. The extent of

new information in the dynamical struc-
ture factor remains to be seen: analysis of
the data that does exist in terms of struc-
tural models has hardly been tackled. The
possibilities raised by partial dynamical
structure factors are clearly immense but
the experimental difficulties and the cost in
terms of neutron beam time remain severe
drawbacks. Another reason for emphasis-
ing the progress possible in vibrational
studies comes from the fact that so much
remains to be done. I believe that it is still
correct to say that there is no convincing
comprehensive explanation of the vibra-
tional spectra of a single oxide glass. The
brief account of recent applications of
NMR to silicates should be sufficient to
convince the reader that the potential of
this technique too is immense. Improved
knowledge of anionic speciation as a func-
tion of preparation variables, composi-
tion, temperature, etc. should answer sev-
eral outstanding structural questions.
Computational power has now reached
the point where some of the limitations
imposed on structural simulations are no
longer insurmountable. The problem of
choosing the correct potential function re-
mains but constraints on computer time
should no longer force the unhappy com-
promise that was common previously. The
attractions of ab initio calculations for
even quite complex polyatomic amor-
phous systems is, clearly, a reason for great
optimism. Apart from the confidence con-
ferred on results calculated with realistic
potentials, increased computing power has
lead to advances in the use of more humble
simulation techniques. The drudgery in-
volved in constructing models can now be
removed, in principle at least, through the
use of molecular graphics programmes
similar to those used by molecular biolo-
gists. More thorough surveys of parameter
space are possible to establish the best set
4.8 Concluding Remarks 271
of atomic coordinates to represent the ex-
perimental data. An example is the recent
work (Sec. 4.6.4.1) on vitreous silica by
Gladden (1990), whose patience and com-
puter budget extended to a search of over
30 models. Automatic, blind, objective,
searches through parameter space using
maximum entropy or Monte Carlo fits to
experimental diffraction data are also ap-
pealing - and, again, there are recent ex-
amples to prove this, It certainly should be
possible now to leave the computer to pro-
duce a fit that agrees with experimental
data within statistical errors - and given
the precision of modern experimental neu-
tron scattering data this is a powerful con-
straint on any resulting model. But this
type of work has also raised the difficult
question of just how much structural infor-
mation is contained in such data and how
many additional constraints may be neces-
sary to specify the structure. There is
mounting evidence that even the most ac-
curate scattering data will be inadequate to
specify the structure of covalent amor-
phous solids to the degree necessary to
make progress in understanding the rela-
tionships between microscopic structure
and macroscopic properties. Indeed, the
spectre has been raised: all our accessible
information may be inadequate to "solve"
the structure in any real sense. Put another
way, the set of possible structures that ad-
equately fits all experimental data within
statistical errors may still be so broad that
subjective judgements alone distinguish
the final choice.
4.8.2 Microscopic and Macroscopic
Properties
A neglected area in this chapter has been
any attempt to relate any of the above to
macroscopic physical or chemical proper-
272 4 Models for the Structure of Amorphous Solids
ties of glasses. What use can any of this
esoteric investigation be to those who deal
with the production of these "socially and
commercially useful" materials or those
who have to live with their acknowledged
limitations? The answer must be that ap-
plications of microstructural knowledge
exist but that they are infrequent. Partly
this must be because microstructural
knowledge is so limited - certainly inade-
quate to sustain a large industry in the 20th
century - still less in the 21st. To conclude
this review, a brief account of some of the
areas where application has been made
and others where progress seems likely
soon.
Firstly, it can be argued that several of
the experimental techniques have been in-
volved in investigations of phenomena
that are central to the glassy state. Exam-
ples are electron microscopy, small angle
X-ray or neutron scattering that have been
central techniques in investigations of
crystal nucleation or catalysed crystallisa-
tion on which glass ceramics depend, or
with microstructural studies on a larger
scale involving phase separation, void for-
mation in amorphous semiconductors, sin-
tering of sol-gel glasses, studies of the fun-
damental transport processes involved in
the glass transition by quasielastic neutron
scattering etc. On a more rarified level,
techniques that probe the low frequency
vibrational characteristics illuminate de-
tails of the low temperature thermal prop-
erties - heat capacity, thermal conductivity
and thermal expansion.
Secondly, the potential exists now - even
if it has not often been expressed in the
past - to compute properties ranging from
the transport properties such as viscosity,
gas permeability, ionic mobility, to elec-
tronic densities of states and by extension,
optical and electronic properties. The ex-
tent to which first-principles calculations
will be involved remains to be seen but the
prospects appear promising.
Revision of models for the alkali sili-
cates have also allowed a qualitative ap-
preciation of the changes in certain physi-
cal properties with composition. For ex-
ample, Greaves has pointed out that the
percolation network of cations in the mod-
ified random network model will act as
conduction channels for ion transport and
that the regions where the modifying
cations lie represent regions of easy shear,
thus providing visualisation of the process-
es involved in viscous flow.
Perhaps the most potentially far-reach-
ing development has come from the explo-
ration of the constraint hypothesis, associ-
ated with the work of Phillips and Thorpe.
As mentioned in Sec. 4.2.1.2, Phillips
(1979) introduced the notion that the rela-
tion between the number of mechanical de-
grees of freedom and the number of con-
straints acting on an atom holds the key to
an understanding of the glass transition
and the composition-dependence of glass
formation. Specifically, Phillips related the
constraints to the forces acting on an atom
in a simple valence force field and arrived
at a specification of properties in terms of
the average atomic coordination number.
Compositions appropriate for easy glass
formation correspond to a mean coordina-
tion number of 2.4. Subsequently, Thorpe
(1983) examined the connection between
average coordination number and the
rigidity of a network, a subject that as
Phillips and Thorpe (1985) point out, dates
back to Maxwell. Thorpe showed that a
network would become floppy at a critical
value, 2.4, of the mean coordination num-
ber. This would then become apparent in
the elastic moduli and in the low frequency
vibrational spectrum. These propositions
have been confirmed (Thorpe and Cai,
1989) and the subject of rigidity percola-

tion and glass formation integrated
through the concepts of vector and scalar
percolation by Phillips and Thorpe (1985),
Robertson (1986, 1991) has used these no-
tions to describe the hardness of a-C films:
specifically to relate the mechanical prop-
erties to the ratio of sp 3 and sp 2 atoms and
the extent of medium range clustering - to
form graphitic islands, for instance.
4.8.3 Structural Models -
Present and Future
It is difficult to summarise the current
understanding of how the structure of
glasses may best be expressed. This de-
pends so much on the type of glass or
amorphous solid, the viewpoint - experi-
mentalist or theorist - personal taste even.
It is probably safe to say that the extreme
models - microcrystallite, random net-
work - are now recognised as being ex-
treme models, and that the truth probably
lies somewhere between them for most ma-
terials. Setting up the random network or
dense random packed hard sphere models
as the paradigm was certainly the most ra-
tional choice in early work - an expression
of Occam's razor. But more recent work
has shifted the balance of evidence towards
structures that are more complicated,
more diverse and more ordered - at least in
the sense that there may be an underlying
ordering or structure-forming principle.
Even the idea that a material is homoge-
neous on the scale of the medium range
structure - that a continuous random net-
work really is continuous - cannot now go
unquestioned and structures that are es-
sentially granular have gained in credibili-
ty. We can no longer assume, I believe, that
we can think in the seductive simplicity of
the language of randomness alone.
What should replace it is not clear. The
very diversity of the properties of the dif-
4.8 Concluding Remarks 273
ferent families of glasses suggests that we
should not allow our concepts to be shack-
led with the entrancing notions of some
kind of universal explanation - a grand
unified theory of everything amorphous.
Not yet, at least.
For amorphous monoatomic metallic
glasses, amorphous tetrahedral semicon-
ductors (probably), oxides like a-SiO2,
random models represent the safest as-
sumption. Despite recent evidence in fa-
vour of microcrystallite models for a-Si
and the charm of curved-space structures,
the experimental evidence is not, I believe,
enough to overturn the presumption in fa-
vour of a random model.
For many other glasses, especially those
that have close-packed regions - like the
amorphous transition metal-metalloid al-
loys, alkali and alkaline earth silicates,
phosphates and borates - randomness as a
central concept may have lost its useful-
ness. Experimental facts - local chemical
ordering, correlated domains in TM-m
glasses, M-M ordering in silicates, pre-
ferred ionic species in silicates - are incon-
sistent with the central tenet of random-
ness, that all possible structures are each
equally probable. Successful models for
these materials expressing the experimen-
tal facts above involve a considerable de-
gree of preference - bond lengths and an-
gles constrained to values close to those of
the crystal, compositional ordering, medi-
um-range "domains" as in models for a-C,
TM-m glasses and possibly in silicates,
preferred ionic species in borates.
Should we view such models as essen-
tially disordered but with impressed order-
ing reflecting a quenching rate in the real
system that is inadequate to prevent it? Or
are the models essentially ordered but with
a degree of disorder reflecting some kinetic
or topological constraint? The distinction,
is partly philosophical and semantic.
274 4 Models for the Structure of Amorphous Solids
Which is the more ideal glass - the most
rapidly quenched solid that can be envis-
aged or the slowly annealed material repre-
senting the region in configurational space
close to a local energy minimum? By anal-
ogy with the idealised single crystal, clearly
the latter. But should the distinction be
drawn on operational considerations -
which concept is the more useful, for a par-
ticular composition made under practical
preparation conditions? Again, there is
considerable appeal in the argument that
the structure of glasses is a reflection of a
structure-forming principle, of its inherent
stereochemistry - albeit inadequately ex-
pressed, due to compositional, kinetic, or
topological constraints.
What that structure-forming principle
may be varies from material to material. If
the only structure-forming principle in-
volves tetrahedral bonding and vertex con-
nection, as in SiO 2 , then the model is
clearly operationally disordered with con-
straints on randomness limited to the local
structure. In the alkali silicates, recogni-
tion that ionic cations have a local order is
expressed in the modified random network
model of Greaves (1985). But does this go
far enough to prescribe the extent of order-
ing? For certain glasses were the cations
show a tendency to cluster, especially at
concentrations where a percolation model
would suggest otherwise, or where the dis-
tance between atoms cannot easily be rec-
onciled with the limited constraints on ran-
domness implied by the modified random
network model - the answer is probably -
no. In these cases and that of the TM-m
alloys the question raised in the last para-
graph is less easily answered. The relative
success of the crystal-based models for sil-
icates, borates, phosphates and the TM-m
alloys suggests that defective order rather
than constrained disorder may represent
the better guide to the underlying struc-
ture-forming principle. Operationally,
therefore, it makes sound sense to consider
models based on a defective ordering prin-
ciple as well as those that are more truly
based on random applications of a struc-
ture-forming principle. Whether either of
these will prove to be generally applicable
must be left for the future.
4.9 Acknowledgements
In addition to the generous financial
support of Pilkington pic, I am indebted to
several individuals who have helped with
the preparation of this paper. Mrs. Pat
Perrett typed the script and Mr. Keith
Papworth photographed many of the fig-
ures. Discussions with Dr. Steve Gurman
and Mr. Mark Eckersley on the subject
matter of Sec. 4.7 have proved valuable
and various sections have benefitted from
discussions with Paul Fallon, Kai Gilkes,
Dr. Azmat Saeed and Jianguo Zhao.
Apart from plenteous moral support,
Catherine Gaskell has ironed out many of
my English infelicities.
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Soules, T. F. (1990), in: Glass Science and Technology,
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5 Oxide Glasses
Harold Rawson

Emeritus Professor of Glass Technology, University of Sheffield, Sheffield, U.K.

List of Symbols and Abbreviations 281

5.1 Glass Formation in Oxides Systems 282
5.1.1 The Zachariasen Random Network Hypothesis 283
5.1.2 Early Experimental Studies of Oxide Glass Structures 284
5.1.3 Some Factors Affecting Glass Formation 285
5.1.4 Bond Type and Glass Formation 285
5.1.5 Bond Strength and Glass Formation 286
5.1.6 Immiscibility in Oxide Systems 288
5.2 Commercial Oxide Glasses 289
5.3 Vitreous Silica 290
5.3.1 Manufacturing Processes and Impurity Contents 290
5.3.2 Devitrification Kinetics 291
5.3.3 Viscosity 292
5.3.4 Refractive Index 292
5.3.5 Structure 293
5.3.6 Defects in Silica 293
5.4 Alkali Silicate Glasses 294
5.4.1 Glass Formation and Devitrification Kinetics 294
5.4.2 Other Binary Silicate Systems 295
5.4.3 Physical Properties 296
5.4.4 Immiscibility and Properties 296
5.4.5 Chemistry of Alkali Silicate Glasses 296
5.4.6 Oxygen Ion Activity; Basicity 297
5.4.7 Structure 299
5.5 Boric Oxide Glass 301
5.6 Borate Glasses 302
5.6.1 Glass Formation in Binary Systems 302
5.6.2 Sub-Liquidus Immiscibility in Binary Borate Glasses 302
5.6.3 Structures of Binary Borate Glasses 303
5.6.4 Properties 304
5.6.5 Technological Applications of Borate Glasses 305
5.7 Borosilicate Glasses 305
5.7.1 Thermal Expansion Coefficient 306
5.7.2 Viscosity 306
5.7.3 Structure 306
Materials Science and Technology
Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
280 5 Oxide Glasses

5.7.4 Sub-Liquidus Immiscibility 307

5.8 Aluminosilicate Glasses 308
5.8.1 The Alumina-Silica System 308
5.8.2 Sodium Aluminosilicate Glasses 309
5.9 Phosphate Glasses 311
5.9.1 Phosphorus Pentoxide 311
5.9.2 Regions of Glass Formation in Binary Phosphate Systems 312
5.9.3 Properties of Binary Phosphate Glasses 312
5.9.4 Multi-Component Phosphate Glasses 313
5.9.5 Structure 314
5.10 Germanate Glasses 315
5.10.1 Germanium Dioxide Glass 315
5.10.2 Regions of Glass Formation in Germanate Systems 315
5.10.3 Structure 316
5.10.4 Properties 316
5.11 Aluminate Glasses 317
5.12 Tellurite Glasses 317
5.12.1 Glass Formation in Tellurite Systems 318
5.12.2 Structure 319
5.13 Vanadate Glasses 319
5.13.1 Glass Formation 320
5.13.2 Properties 320
5.13.3 Structure 321
5.14 Mixed Anion Glasses 321
5.14.1 Oxynitride Glasses 321
5.14.2 Oxyhalide Glasses 322
5.15 Ionic Salts and Solution Glasses 323
5.15.1 Nitrate Glasses 323
5.15.2 Acetate Glasses 324
5.15.3 Sulfate Glasses 324
5.15.4 Hydrates and Aqueous Solutions 324
5.16 References 324
 List of Symbols and Abbreviations 281

List of Symbols and Abbreviations

A symbol for chemical elements
B symbol for chemical elements
G reciprocal of the maximum growth rate in mm/min
K ratio of mol% SiO 2 and mol% B 2 O 3
M symbol for chemical elements
n count number
n* number average chain length
Q quality of extracted material
Qn SiO 4 tetrahedron containing n bridging oxygens
R ratio of mol% N a 2 O and m o l % B 2 O 3
r radius (of an ion)
R symbol for chemical elements
t time
Tg transformation temperature
Um maximum rate of crystal growth
x Pauling electronegativity value
x mole fraction of R 2 O in glass
x number of atoms in an entity
y number of atoms in an entity
z charge number of an ion
y cation factor, basicity moderating power
Y
\ (^m) temperature of maximum growth rate
A optical basicity
v_ Oi absorption frequency of probe ion
v_ fi absorption frequency of the free ion
v _ gi measured absorption frequency of the ion in glass
A.U. Angstrom unit
CVD chemical vapor deposition
DC direct current
ESCA electron spectroscopy for chemical analysis
ESR electron spin resonance
EXAFS extended X-ray absorption fine structure
MAS N M R magic angle spinning nuclear magnetic resonance
NBO non-bridging oxygen
PES photo-electron spectroscopy
r.m.s. root mean square
UV ultra violet
XAFS X-ray absorption fine structure
XANES X-ray absorption near edge structure
XRD X-ray diffraction
282 5 Oxide Glasses
5.1 Glass Formation
in Oxide Systems
Oxide glasses have been known and
used for more than 4000 years. During that
period an industry has grown up, devel-
oped initially by exploiting various ways of
using the glass-makers blowing iron, intro-
duced by the Romans. Techniques were
also developed for the cold working of
glass, e.g. by cutting and engraving. These
developments took place with no scientific
understanding of the nature of the material
or of the physical principles of the various
manufacturing processes. Yet generations
of craftsmen were able to produce articles
of the highest quality, some of a type which
is difficult to reproduce today.
Until the present century, the composi-
tion of the material has remained practi-
cally unchanged - most glasses have been
of the soda-lime-silica type, silica being the
major component (see Sec. 5.2). Small ad-
ditions of colouring materials were added
as required.
One new composition was introduced
by Ravenscroft in 1674 - a silicate glass
containing approximately 30 wt.% of PbO,
this component significantly increasing the
refractive index and giving a brilliant ap-
pearance to the glass when cut. The new
glass was an essential component in mak-
ing the first achromatic doublet lens in
about 1750 by Hall and Dolland. However
the development which can be regarded as
being the beginning of glass science was the
work of Schott, Abbe and Zeiss in the lat-
ter part of the nineteenth century. Schott
made a systematic study of the effects of the
composition of oxide glasses on their opti-
cal properties in order to develop glasses
that would make it possible to produce
lens designs of greatly reduced secondary
aberrations. Several oxides, e.g. BaO, were
incorporated which had not been used pre-
viously as glass constituents. The collabo-
ration led in 1886 to the foundation of Jena
Glass Works to manufacture and market
the new glasses.
There was no possibility at the time of
interpreting the property - composition re-
lationships in terms of glass structure and
very little progress was made in that direc-
tion until the early 1930's. Early papers on
the structure of oxide glasses were purely
speculative and much influenced by the
thinking of chemists, trained in the physi-
cal chemistry of solutions.
It was known by the early 1930's that a
few oxides would form glasses when melted
alone, namely SiO 2 , B 2 O 3 , GeO 2 , P 2 O 5
and As 2 O 3 and that extensive regions of
glass-formation existed in many binary
and more complex systems containing
these oxides together with a number of ba-
sic oxides, especially the alkali and alkaline
earth oxides. Some of the nineteenth cen-
tury work, which subsequently turned out
to be important, had been forgotten. Thus
Roscoe (1868) had shown that stable
glasses could be made in the BaO-V 2 O 5
system and Berzelius (1834) had studied
several tellurite glass systems.
It is now known that glass formation
occurs in many oxide systems which differ
considerably from one another chemically
and in other ways. In addition to the sys-
tems just listed, glass formation occurs
in several aluminate, gallate, tungstate,
molybdate, selenite, titanate, niobate and
tantalate systems. Although of little tech-
nological interest, there is also an interest-
ing group of glasses based on simple ionic
salts e.g. nitrates, sulfates, acetates, and
thiocyanates - some made from the fused
anhydrous salts, others from aqueous solu-
tions of these materials.
By very rapid cooling, more substances
can be added to the list of glass-formers or
the extent of the region of glass formation

in a particular system can be increased
(Scherer and Schultz, 1983). Most of the
compositions in the above list can be made
as glasses without using particularly high
cooling rates.
5.1.1 The Zachariasen Random Network
Hypothesis
In 1932 the first significant step was
made by W. H. Zachariasen towards an-
swering two fundamental questions which
are still not fully resolved today: what can
we say about the structure of oxide glasses
and why do some oxide compositions form
glasses whilst others do not?
Zachariasen's paper (1932) is remark-
able for the impact it had on thinking
about the structure and properties of oxide
glasses. The paper is also remarkable in
that it is entirely speculative and qualita-
tive - no new observations were reported.
The author was a crystallographer, very
familiar with the early X-ray diffraction
studies of the structure of crystalline sili-
cates. The central hypothesis of his paper is
that the vitreous form of an oxide should
5.1 Glass Formation in Oxide Systems 283
not have a significantly higher internal en-
ergy than the crystalline form. This re-
quires, he suggested, that both forms must
contain the same kind of oxygen polyhedra
and these must be joined together in a sim-
ilar way, except that in the glassy form
there is a range of bond angles and bond
lengths. Only substances in which the poly-
hedra are joined by their corners have
structures which are sufficiently flexible to
incorporate the disorder which is charac-
teristic of the glassy state without the lat-
tice energy of the structure being greatly
increased. (The emphasis on lattice energy
was subsequently criticized by Morey
(1934) who pointed out a number of exam-
ples of substances which appear to show
that such energy differences are not impor-
tant.)
Fig. 5-1 is a schematic diagram showing
the structure of a hypothetical oxide A 2 O 3
in both the crystalline and glassy forms. In
this material the basic 'polyhedron' is the
AO3 triangle. In both forms, the triangles
are joined only at their corners by 'bridg-
ing' oxygens. In silica glass, the basic poly-
hedron is the SiO4 tetrahedron. Again each
Figure 5-1. Schematic two-
dimensional representation
of the structure of (a) a hy-
pothetical crystalline com-
pond A 2 O 3 and (b) the
glassy form of the same
compound (from Zacha-
riasen, 1932; reprinted with
permission from Journal
of the American Chemical
Society, Copyright 1932
American Chemical Soci-
ety).
284 5 Oxide Glasses
tetrahedron is linked through each corner
to neighbouring tetrahedra. The appropri-
ates of the term 'random network' is obvi-
ous from Fig. 5-1.
Zachariasen argued that the require-
ment that disorder should not increase the
internal energy led to certain rules which
must be obeyed if an oxide is to form a
glass:
1. No oxygen atom may be linked to
more than two A atoms.
2. The number of oxygen atoms sur-
rounding atoms A must be small.
3. The oxygen polyhedra share corners
with each other but not edges or faces.
4. If it is required that the network be
threedimensional, at least three corners in
each polyhedron must be shared.
All the then known glass-forming oxides
obey the Zachariasen rules, as does the
glass-former BeF2, which has a silica-like
structure.
5.1.2 Early Experimental Studies
of Oxide Glass Structures
Shortly after the publication of Zacha-
riasen's paper (1932), Warren and his col-
leagues began a series of structural studies
of simple silicate glasses using X-ray dif-
fraction. The results were summarized by
Warren (1941). They were interpreted in
terms of the random network model and
important information was obtained con-
cerning the way in which the alkali and
alkaline earth ions are incorporated in the
structure. This is illustrated in Fig. 5-2. The
significant features are:
1. The cations are situated in the rela-
tively large voids in the structure.
2. For each additional oxygen anion in-
troduced, one A - O - A bridge is broken so
that two non-bridging oxygens are formed.
The positive charge on the cations intro-
• Si
O 0
Figure 5-2. Two-dimensional representation of the
structure of a sodium silicate glass (from Warren,
1941).
duced is locally neutralized by the negative
charge on the non-bridging oxygens.
Oxides which have a similar structural
effect to that shown are referred to as net-
work modifiers or simply modifiers.
Many structural studies have been car-
ried out on silicate glasses since then by
various techniques. Some workers have
contested particular aspects of Warren's in-
terpretation. Others have added a great
deal of detail, especially for those systems
in which a network-forming cation under-
goes a change in coordination number as
the glass composition is changed. Few
would question however that the Warren-
Zachariasen random network model has
provided a valuable basis for the discus-
sion of the structure and properties of ox-
ide glasses. It is worth noting that Cooper
(1982) in particular has considered it
worthwhile returning to Zachariasen's pa-
per, offering a re-interpretation in terms of
its topological implications.
However if one focuses on what Zacha-
riasen has to say about the conditions for
glass formation in particular, rather than

about the structure, the value of his contri-
bution is more open to question.
5.1.3 Some Factors Affecting
Glass Formation
The reason why a melt may form a glass
is that within a limited temperature range
below the liquidus temperature, the rate of
crystal growth and/or the rate of nucle-
ation is sufficiently low on a time scale de-
termined by the rate of cooling. It must be
possible to cool the melt to a temperature
below the transformation range without
crystallization occurring. That merely
moves the question of understanding glass
formation further back to a consideration
of the factors that determine the nucleation
and crystal growth rates for a particular
substance. Uhlmann and his colleagues in
particular have made many experimental
and theoretical studies of crystallization
and nucleation kinetics in supercooled ox-
ide melts (Uhlmann 1977, 1985; Uhlmann
and Yinnon, 1983). Their work has been of
great value in many areas of glass science.
However it has limited ability to provide
pointers to new glass-forming composi-
tions or to give a general understanding of
why some compositions form glasses more
readily than others. The equations of clas-
sical nucleation and crystal growth theory,
which describe the temperature depen-
dence of nucleation rate and crystal growth
rate, contain many thermodynamic and ki-
netic parameters, which are not easy to
measure or to relate in a simple way to
what may be known about the composi-
tion and structure of the material under
consideration.
Given this situation, it is not surprising
that many individuals have looked for sim-
ple criteria, preferably with some theoreti-
cal basis, which can direct attention to po-
tential glass-forming compositions.
5.1 Glass Formation in Oxide Systems 285
5.1.4 Bond Type and Glass Formation
Several authors have proposed criteria
for glass formation based on the nature of
the interatomic bonds rather than on the
structure of the material. The intention was
to find criteria that would cover a wide
range of materials including for example
the glass-forming elements such as sele-
nium as well as the oxides. Thus Winter
(1955) concluded that the ability of a mate-
rial to form a glass could be related to the
number of outer shell p electrons per atom.
The most favorable number was four but
glasses could be made from substances
containing between two and four p elec-
trons per atom. The reasoning behind this
correlation was not made clear and no ex-
planation was offered for the fact that there
is a considerable variation in glass-forming
ability amongst the substances which meet
the criterion.
Stanworth's electronegativity criterion
is more interesting in that it led him to the
rediscovery of tellurite glasses. In a series of
papers Stanworth (1946, 1948 a, b, 1952)
drew attention to the significance of the
degree of covalency of the interatomic
bonds, as measured by the electronegativ-
ity difference between the constituent
atoms. Using Pauling's electronegativity
values for silicon and oxygen (1.8 and 3.5
respectively) and Pauling's curve relating
the degree of covalency to the electronega-
tivity difference, one finds that the silicon-
oxygen bond is 50% covalent. For the
well-kown glass-forming oxides (or net-
work formers) the cation electronegativity
lies between 1.8 and 2.1. For the intermedi-
ate oxides which under suitable circum-
stances can behave as network-formers,
the range is 1.5 to 1.8 and for the modifiers,
i.e. the alkali and alkaline earth oxides, the
range is 0.7 to 1.2. Stanworth noted that
the electronegativity of Te is the same as
286 5 Oxide Glasses
that of P i.e. 2.1, suggesting that TeO2
might be a glass former, like P 2 O 5 - an
observation which led him to investigate
glass-formation in the tellurite systems
(Sec. 5.12).
In a later paper, reviewing more recent
information on glass-forming oxides, Stan-
worth (1979) recognizes that the bond type
alone is not a sufficient criterion. Thus he
states: 'the most general conclusion is that
the compounds Ax By can form glass from
their melts when they have sufficiently
open, sufficiently covalent network struc-
tures. Splat cooling is necessary unless the
structures are based on the very open ex-
tended three dimensional networks when
glass formation with slow cooling from the
melt is possible'. This seems to echo much
of the thinking behind the Zachariasen
rules.
A general comment one may fairly make
about these simple bond type criteria is
that they can hardly have any general fun-
damental significance, although they may
be of some value within a particular group
of compounds. Very many quite different
types of inorganic substances are known to
form glasses including simple fused salts in
which the relevant bonds are largely ionic
(e.g. fused nitrates, see Sec. 5.15) and a
large number of metallic systems.
5.1.5 Bond Strength and Glass Formation
Sun (1947) recognized that the processes
of melting and crystallization will often in-
volve the breaking of interatomic bonds.
The stronger the bonds, the more sluggish
will be the processes of structural rear-
rangement and hence the more likely will a
glass form on cooling. Using calculated
values of single-bond strengths, he noted
that these were particularly high in the
glass-forming oxides: SiO 2 , B 2 O 3 etc. He
was clearly aware of the limitations of such
a simple correlation, since he drew atten-
tion to the importance of structural factors.
In anisodesmic structures (Evans, 1946)
some bonds are very strong whilst others
are weak, and it is then not clear which
bond strength is relevant. An extreme ex-
ample of such a substance is CO 2 .
Rawson (1956) pointed out that if one is
to use a bond strength criterion, one
should also take into account the thermal
energy available at the melting point for
breaking the bonds. Thus glass formation
would be more likely the higher the ratio of
single bond strength to the melting point in
K. This may explain why a boric oxide
melt is almost impossible to crystallize.
The B - O bonds are very strong, yet the
melting point of the material is relatively
low (450 °C).
Rawson (1956,1967) extended this argu-
ment to binary and multicomponent sys-
tems, noting that one frequently finds re-
gions of glass formation or regions of
particularly low devitrification rates in re-
gions where the liquidus temperature is
low. Examples of the liquidus temperature
effect are shown in the next two figures.
Fig. 5-3 is based on the results of Dietzel
and Wickert (1956) for the Na 2 O-SiO 2
system. G is the reciprocal of the maximum
growth rate in mm/min. The highest value
of G, i.e. the lowest crystallization rate, is
for a composition very close to the eutectic
in the phase diagram between silica and
sodium disilicate. Fig. 5-4 shows the liq-
uidus temperature effect in the CaO-Al 2 O 3
system where neither oxide component is a
glass former (Rawson, 1967). In the related
CaO-Ga 2 O 3 system, Wichard and Day
(1984) have shown by critical cooling rate
determinations that the most stable glass is
the eutectic composition at 37.5 mol%
Ga 2 O 3 .
Commercial glass compositions are in
general quite complex - for a number of
 5.1 Glass Formation in Oxide Systems 287

2.8-
v One has to admit that the simple rela-
tionship between glass stability and a low
2.4-

2.0-
f /
A liquidus temperature appears to break
down in some oxide systems. That is not
surprising. Structural factors must also
play an important role. The kinetic and
1.6-
/ thermodynamic energy terms associated
1.2-
/ with these factors must change as one tra-
0.8-

u-
X>o—O^
/ \\ verses the system. One should also recog-
nize that some melts may contain appre-
ciable unknown percentages of compo-
0-
C 5 10 15 20 25 30 35 LQ Li nents such as CO 2 and combined water,
Mol % N Q 2 0 which affect the liquidus temperature and
Figure 5-3. Variation of log G with Na 2 O content in introduce a complicating factor which has
the system Na 2 O-SiO 2 (from Dietzel and Wickert, rarely been taken into account in studies of
1956). glass formation.
This emphasis on liquidus temperature
is clearly based on the qualitative ideas be-
\\
2500- \ hind the classical theory of nucleation and
\ crystal growth (a point clearly brought out
\
\ by Cohen and Turnbull (1961)). In spite of
\\
2300- \ the exceptions, the liquidus temperature
\
\
\
criterion has a wide range of applicability
\\ and appears to work equally well for a
2100- \
\
! !
number of quite different types of material
\ Glass- / e.g. for metallic glasses as well as for oxide
1900- \ 1 forming /
\ glasses. However the approach has limita-
\ ^ region j /
\
\ tions as a simple predictive tool since there
1700-
\ J
/I is no simple way of predicting melting
points of elements and compounds or the
\ /
V
1500- variation of liquidus temperature with
composition in binary and multicompo-
nent systems.
1300- i i i i 1
0 20 40 60 80 100
In an interesting recent contribution,
CaO Wt.°/o Al 2 0 3 Al 2 0 3 Chechetkina (1990) shows that there is a
Figure 5-4. The glass-forming region in relation to the relationship between bonding, melting
phase diagram for the CaO-Al 2 O 3 system (from point and glass formation. For most ele-
Rawson, 1967). ments and within particular classes of com-
pounds, a plot of melting point against the
averaged atomization energy shows points
reasons (see Sec. 5.2). One reason is that tightly clustered about a straight line. The
adding further oxide components often re- glass-forming compounds however fall
duces the liquidus temperature and so well below the line in each class. She postu-
makes the glass less prone to devitrifica- lates that the abnormally low melting
tion. point of the glass-forming substances is re-
288 5 Oxide Glasses

lated to a reversible and temperature-de-

1700-
pendent formation of 'three centre bonds'
which alternate with normal covalent
bonds at various points in the structure.
Although the relationship between melting
S 1600-
point and structure had been discussed
previously by Ubbelohde (1965), this work
appears to be the first to discuss the rela-
tionship in the context of glass formation.
1500-

5.1.6 Immiscibility in Oxide Systems

60 70 80 90
In many binary silicate and borate sys- Si0 2 (mol7o)
tems, the melt separates into two phases Figure 5-5. The extent of immiscibility in binary sili-
over a wide range of compositions. This is cate systems (from Levin and Block, 1957).
illustrated in Fig. 5-5 for a number of sili-
cate systems. Immiscibility is a feature of 1100
systems containing cations of relatively
high field strength. Note that although the
BaO- and Li 2 O-SiO 2 systems form single 1000
Xf / / Li20
\
\
phase melts, the liquidus curve in the silica- \
\
\
rich region of each system shows a marked \
900
deviation from ideality. Na2O
Although each component of a phase-
separated melt may form a glass on cool-
i// / \
\
ing, the resulting material will also be
phase-separated on a relatively coarse
scale and will be of no practical value.
However phase separated melts can usu-
ally be made single phase by adding a few
700

600
r /
/
/
/

/
/
/
i
K20

\ \
* \
\

1
I
percent of a third component, especially [
one of the alkali oxides (Shartsis et al.,
1958). 500
It is of much greater scientific and tech- 30 20 10
nological interest that in many binary and Mol.% R20
ternary systems, immiscibility occurs be- Figure 5-6. Regions of sub-liquidus immiscibility and
low the liquidus temperature. Regions of corresponding liquidus curves for the Li2O-, Na 2 O-
and K 2 O-SiO 2 systems (from Scholze, 1988).
sub-liquidus immiscibility in the R 2 O-SiO 2
systems are shown in Fig. 5-6. The separa-
tion in the glass is usually on a very fine enced above the transformation range. The
scale, detectable only by electron micros- physical and chemical properties of some
copy or by sensitive light scattering mea- glasses are markedly affected by sub-liq-
surements. The separation morphology de- uidus immiscibility, hence these properties
pends on the glass composition and on the may be affected in unexpected ways by
heat treatment which the glass has experi- heat treatment.
 5.2 Commercial Oxide Glasses 289

Early interpretations of immiscibility The first group of three glasses (1 to 3)

were in terms of competition for the avail-
able oxygen anions between cations of dif-
fering ionic potential (see for example
Levin and Block (1957)). The current ap-
proach introduced, in the discussion of
sub-liquidus immiscibility by Cahn and
Charles (1965), is based on the effects of
temperature on the free energy-composi-
tion curves of the various phases (as for
example in the interpretation of metallur-
gical phase diagrams - see Raynor (1970)).
5.2 Commercial Oxide Glasses
Table 5-1 gives the compositions of
a number of commercially important
glasses. The intention here is merely to in-
dicate the general features of each. For any
particular type, glass compositions vary
somewhat from one manufacturer to an-
other. Note that most glasses contain
many oxide components. This is largely
due to the fact that any commercial glass
has to meet a number of requirements,
some imposed by its applications and oth-
ers by the manufacturing process. (See also
Chapter 1 of this volume.)
are respectively float glass, container glass,
and the glass used to make incandescent
lamp bulbs. They are very similar in com-
position. They have suitable viscosity-tem-
perature characteristics for the fabrication
(shaping) processes which are used to make
the glassware required. They have ade-
quate chemical durability and the raw ma-
terial costs are relatively low. Apart from
meeting these main requirements, there are
no other important property requirements
to be met, except that for glass 3 the ther-
mal expansion coefficient has to be care-
fully controlled.
Glass 4 is a traditional lead crystal com-
position, in which the high PbO content
gives a high refractive index and a brilliant
appearance to the glass when it is cut. A
similar composition is used to make the
high electrical resistivity glass for the 'stem'
in incandescent lamps.
Glasses 5 to 7 represent the large and
important group of borosilicate glasses.
Composition 5 is widely used to make
chemical apparatus and domestic oven-
ware. It has good resistance to thermal
shock on account of its low thermal expan-

Table 5-1. Compositions of some commercial glasses (wt.%).

SiO2 A12O3 B 2 O 3 MgO CaO PbO Na 2 O K 2 O BaO Li2O La 2 O 3 Ta 2 O 5 ThO 2 ZnO

1 72.8 0.7 3.6 8.8 13.8

2 72.0 1.3 3.5 8.2 14.3
3 71.5 2.0 2.8 6.5 15.5 1.0
4 56.0 29.0 2.0 13.0
5 80.8 2.2 12.0 0.3 0.3 4.2 0.6
6 67.5 2.5 21.7 3.2 4.2
7 75.5 2.6 16.0 3.7 1.7
8 52.9 14.5 9.2 4.4 17.4 1.0 1.0
9 67.0 5.0 7.0 8.3 11.7 0.6
10 68.3 0.2 2.2 4.6 2.9 14.4 7.0
11 26.9 0.5 71.3 1.0
12 20.0 36.0 28.0 16.0
13 5.5 17.5 16.0 9.5 52.0
14 5.0 17.0 64.0 14.0
290 5 Oxide Glasses
sion coefficient and also has excellent resis-
tance to chemical attack, especially by
acids. Compositions 6 and 7 are sealing
glasses with expansion coefficients matched
to those of particular metals. Glass 6 seals
to the iron-nickel-cobalt alloys Kovar,
Nilo K or Fernico and is widely used both
in large seals of tubular design and also in
small terminal seals. Glass 7 has a some-
what lower expansion coefficient and seals
to tungsten.
Glass 8 is one of a group of high melting
point, low alkali, aluminosilicate glasses. It
is commonly known as E glass and is made
as continuous fibre for glass fibre rein-
forced composite materials and for weav-
ing into glass textiles used in electrical in-
sulation.
Glass 9 is a TV tube glass composition.
Glasses 10 and 11 are optical glasses, 10
having a refractive index of 1.518 and 11 of
1.805. The unusual composition 12 is also
an optical glass (refractive index 1.85), the
use of which makes it possible to design
more highly corrected lens systems than is
possible with the high lead glasses.
Glass 13 is resistant to attack by sodium
vapour at elevated temperatures and is
used as a coating on the inner wall of the
glass arc tube in low pressure sodium va-
pour street lamps.
Glass 14 is a 'solder' glass. It is quite
fluid at about 550 °C and is used to seal
together, without distortion, components
made from soda-lime glasses such as com-
position 3. It is necessary, of course, that
the expansion coefficient of the solder glass
should match that of the components to be
joined together.
A detailed account of the properties of
technical glasses has been given by Volf
(1961). Scholze (1988) and Rawson (1980)
summarize information on the property-
composition relationships in simpler sys-
tems.
Other glasses of technological impor-
tance will be referred to in later sections.
5.3 Vitreous Silica
5.3.1 Manufacturing Processes
and Impurity Contents
Vitreous silica or silica glass is the only
one-component oxide glass to have any
practical applications. These are of consid-
erable technological importance. Uses in-
clude envelopes for high-intensity arc
lamps and tungsten-halogen lamps, com-
ponents for chemical ware, in both labora-
tory and chemical plant applications, and,
more recently, optical communication fi-
bres (Beales and Day, 1980; Gambling,
1980, 1986).
There are several methods of manufac-
ture (Dumbaugh and Schultz, 1969; Da-
nielson, 1982) and the properties of the var-
ious grades of material available differ
according to their impurity contents, 'wa-
ter' content and their stoichiometry (Table
5-2). _
Initially the material was made exclu-
sively by the fusion of a pure sand or
crushed Brazilian quartz at a temperature
of about 2000 °C. In some early processes,
a boule of fused material was built up by
flame-spraying ground quartz onto a
target. Now the material is melted either in
vacuo or a reducing atmosphere in a re-
fractory metal or graphite crucible. The
glass contains impurities from the raw ma-
terial and crucible and is oxygen-deficient
as a result of the reducing conditions under
which it has been melted. According to Bell
et al. (1962), the composition of this type of
material should be written SiO 2 _ x where x
lies between 10" 4 and 10" 5 .
Much purer material, initially made to
meet the requirements of the semi-conduc-
tor industry, is produced by the hydrolysis
 5.3 Vitreous Silica 291

Table 5-2. Impurity contents of various grades of fused silica (Rawson, 1967).

Manufacturer Method Major metallic Water content Ref.

and type no. of manufacture impurities ppm.

Thermal Syndicate Flame fusion of rock crystal Al 10 0.04 wt.% a

grades OG & OH B<0.5 as OH
Ca 0.35
Fe 0.51
Na 0.06
Thermal Syndicate Electric fusion of rock crystal Al 50 0.003 wt.% a
grade IR Sb 0.23 as OH
B<0.5
Ca 0.4
Fe 0.74
Na 4
Thermal Syndicate Vapour phase hydrolysis Al<0.02 0.12 wt.% a
'Spectrosil' of SiCl4 in a flame Ca<0.1
Fe<0.1
Na<0.04
Thermal Syndicate Vapour phase oxidation As 'Spectrosil' AsIR. b
'Spectrosil WF' of SiCl4 plus 0.05 wt.% Cl
GE (USA) 201 Fusion of rock crystal Total impurity 'Water free' c
content = 240 ppm
Al 2 O 3 = 180ppm
GE (USA) 204 A Fusion of rock crystal Total impurity 'Water free' c
content =110 ppm
A12O3= 52 ppm
CaO= 23 ppm
Corning 7943 Flame hydrolysis of SiCl4 'Negligible' 0.001 wt.% c
Then fired on graphite Similar to as OH
mandrel in hydrogen 'Spectrosil'
Corning 7940 Flame hydrolysis of SiCl4 'Negligible' 0.1 wt.% c
as OH
Cab-O-SilO Vacuum fusion of powder made Al 2 O 3 = 100ppm 0.02 wt.% d
by hydrolysis of SiCl4 vapour Na 2 O<200ppm as OH

a. Hetherington and Jack (1962), b. Hetherington et al. (1964), c. Wagstaff et al. (1964), d. Brown and Kistler
(1959).

or oxidation of SiCl4 in a flame. The hy- 5.3.2 Devitrification Kinetics

drolyzed material has a high content of
'water', present as - O H groups. Various
modifications of the vapour phase process
are now used to make the very high purity
material required for optical communica-
tion fibres (Schultz and Smyth, 1972; Nas-
sau and Shiever, 1975; Gossink, 1977). (See
also Chapter 2 for sol-gel processing.)
The results of measurements on various
grades of material and in various atmo-
spheres have been summarized by Rawson
(1967).
At atmospheric pressure, the silica melt
crystallizes at temperatures below 1723 °C
to form the high temperature modification
292 5 Oxide Glasses

of cristobalite. Crystallization occurs from an equilibrium value, characteristic of the

the surface, eventually forming an opaque temperature of measurement. The rate of
coating which can only be removed by change is too low to be interpreted as a
etching with hydrofluoric acid. stabilization effect. It is more likely that it
Even trace quantities of impurities on signifies a chemical change either in - O H
the surface greatly increase the crystalliza- content or in stoichiometry.
tion rate. According to Dietzel and Wickert
(1956), as little as 0.32% Na 2 O added to 5.3.4 Refractive Index
silica glass increases the maximum devitri-
Silica glass doped with small percent-
fication rate by twenty to thirty times.
ages of oxides or fluorides is easily made by
Detailed studies of devitrification kinet-
the Chemical Vapor Deposition (CVD)
ics have been carried out by Ainslie et al.
process. These additions affect the physical
(1962), Brown and Kistler (1959) and
properties, including the refractive index as
Wagstaff et al. (1964). The surrounding at-
shown in Fig. 5-8. Such doping is a normal
mosphere was found to have a large effect,
feature of the manufacture of material to
the rates being much lower when the mate-
be made into optical communication fibre,
rial was heated under reducing conditions.
For the less pure grades, containing oxide
impurities, the crystal layer thickness in-
creased as t 1/2 whilst for the higher purity
grades the growth rate was constant. Not
all aspects of the results could be explained.
However they clearly demonstrate the im-
portance of impurities (including com-
bined -OH) and atmosphere on the crys-
tallization kinetics. The devitrification
kinetics of multi-component silicate glasses
are not so sensitive to atmosphere.
Fratello et al. (1980) have studied the
devitrification kinetics of the material un-
der pressure, when the crystalline phase is
quartz rather than cristobalite.

5.3.3 Viscosity
The viscosity data show considerable
scatter. At the highest temperatures
(> 1600°C) a large part of the variability is
probably due to experimental error, which
is difficult to eliminate in measurements at
such high temperatures. Data for the lower
temperature range is shown in Fig. 5-7. 1050 1150 1250 1350 U50
Here the viscosity is markedly affected by Temperature (°C)
the - O H content of the material. Figure 5-7. Viscosity-temperature results for fused sil-
Hetherington et al. (1964) noted that the ica obtained by various workers (from Bruckner,
viscosity changes slowly with the time to 1964).
 5.3 Vitreous Silica 293

1.50- to Wright, the mean Si-O distance is

1.608 + 0.004 A.U. the O-O peak distance
U9-
is 2.626 A.U. and the mean bond angle is
8 U8 109.7 + 0.6° with an r.m.s. bond angle vari-
ation of 4.5°.
o
Direct information about medium-range
order in silicate glasses has been obtained
I U6- by Magic Angle Spinning Nuclear Mag-
B203(fibre) netic Resonance (MAS NMR). Fig. 5-9 (El-
U5-
liott, 1989) shows results for the Si-O-Si
1.U
2 4 6 8 10 12 U 16 angle distribution obtained in this way.
Dopant concentration (mol°/o) The X-ray diffraction results of Mozzi and
Figure 5-8. The effect of dopants on the refractive Warren (1969) are included for compari-
index of vitreous silica (from Beales and Day, 1980). son.

5.3.6 Defects in Silica

the radial distribution of refractive index
being an important factor determining the The extensive literature on defects in sil-
propagation of light pulses along the fibre. ica has been reviewed by Griscom (1978 a,
1985). The subject is of practical impor-
5.3.5 Structure tance in a number of contexts, e. g. radia-
tion induced changes in the optical absorp-
Many studies of the structure of silica
tion of silica glass used in lamp envelopes
glass have been made during the past ten
and in communication fibres. The study of
years, which have refined but not greatly
defects has also made an important contri-
modified the picture based, on the early X-
ray diffraction work of Warren and the
repetition of that work by Mozzi and War-
ren (1969) (Wright and Leadbetter, 1976;
Wright, 1989; Elliott, 1989). The X-ray re-
sults provide information primarily about
the short range order. Some information
about medium-range order has been ob-
tained from attempts to fit together the
results of the experimental investigations
with those obtained from computer-based
models. Wright (1988, 1989) points out the
uncertainties in this approach, since it may
be possible for more than one computer
model to fit the experimental data equally
well. (See Chapter 4 of this volume.)
120 130 UO 150 160 170 180
Disregarding the effect of the low con- Intertetrahedral angle (degrees)
centration of structural defects, each sili-
Figure 5-9. Si-O-Si bond angle distribution for
con is surrounded tetrahedrally by four glassy SiO2 evaluated from 29Si NMR data compared
nearly equidistant oxygens and each of with distribution obtained by Mozzi and Warren
these is bonded to two silicons. According from X-ray diffraction (points) (from Elliott, 1989).
294 5 Oxide Glasses
bution to the general understanding of
electron energy levels in amorphous silica,
a subject of practical importance to the
semiconductor industry.
The number and nature of defects is
changed by irradiation of the material with
UV or more energetic radiation and, as
was discovered relatively recently, by
drawing the material into fibre. Tempera-
ture also has an important effect, especially
on the rate at which defects are annealed
out, either during or after irradiation. Most
studies have been based on Electron Spin
Resonance, ESR, and, to a lesser extent, on
optical absorption measurements. With
low energy radiation, the formation of a
detectable defect may involve no more
than the capture of an electron or hole by
a defect already present in the glass struc-
ture. With more energetic ionising radia-
tions, defects may be formed by the dis-
placement of an oxygen ion from its
normal position in the glass network. (See
Chapter 6.)
The formation of defects by irradiation
depends on the wavelength of the radia-
tion, the impurities present in the material,
including the - O H content, and the stoi-
chiometry. The variety of behaviour of the
material in this particular area is very large
and has been extensively studied.
5.4 Alkali Silicate Glasses
5.4.1 Glass Formation
and Devitrification Kinetics
Glasses can be made in all the alkali
silicate systems over ranges of composition
which are continuous from silica itself up
to a limit which may lie on the alkali-rich
side of the metasilicate composition. Thus
Imaoka (1962) made on a scale of 1-2 g,
melting in platinum, glasses containing up
to 33.5 mol% Li 2 O, 57.9 mol% Na 2 O and
54.5 mol% K 2 O. On a similar scale, Mari-
nov and Dimitriev (1964) made glasses
containing up to 59.4 mol% Rb 2 O and
61.0 mol% Cs 2 O. The glass-forming re-
gions are more limited at larger scales of
melting.
The glasses of low alkali content
( < 5 mol%) are difficult to prepare on ac-
count of the high viscosity of the melt and
the high rate of volatilization of the alkali
at the melting temperature. Those of high
alkali content are water-soluble. The solu-
tions are of considerable industrial impor-
tance and their properties have been exten-
sively studied (Her, 1979; Vail, 1952).
Phase diagrams of the systems have
been determined and are readily available
in the collections of Levin et al. (1956,1964,
1969) and Levin and McMurdie (1959,
1975). Fig. 5-6 shows the variation of liq-
uidus temperature with composition in the
R 2 O-SiO 2 systems. In all of them, there is
a large fall in liquidus temperature as the
first few percent of alkali is added. The
relationship between glass stability and
liquidus temperature in the Na 2 O-SiO 2
system has been discussed in Sec. 5.1.5.
Havermans et al. (1970) have determined
the critical cooling rates for glass forma-
tion of alkali silicate melts in the region
20-60 mol% R 2 O. They show that the
ease of glass formation greatly increases in
the order Li 2 O, Na 2 O, K 2 O, i.e. in the
order of decreasing liquidus temperature.
The ease of glass formation is increased
still further in the K 2 O-SiO 2 system by
replacing half the K 2 O by Na 2 O and, in
more complex systems still, the region of
glass-formation can be further extended to
compositions in which the average number
of bridging oxygens per SiO4 tetrahedron
is as low as one (Trap and Stevels, 1959,
1960 a, b). Such compositions clearly do
not obey Zachariasen's rule 4 (Sec. 5.1.1).

Detailed studies of nucleation and crys-
tallization in alkali silicate systems have
been carried out especially by Uhlmann
and his co-workers (Uhlmann, 1983).
Scherer and Uhlmann (1977) observed that
in potassium silicate glasses the size of the
crystals increases linearly with time, as is
observed in many other silicate melts. They
show that this behaviour, unexpected for a
diffusion-controlled growth process, is pre-
dictable, provided that the growing crys-
tals are dendritic, as in fact they are. Good
agreement was obtained between the mea-
sured growth rates and values calculated
using previously determined interdiffusion
coefficients.
Scherer and Uhlmann (1976) have in-
vestigated the effects of sub-liquidus im-
miscibility on crystal growth in three
Na 2 O-SiO 2 glasses, pointing out that
since immiscibility may greatly affect sev-
eral properties, especially viscosity, it
might be expected to affect crystal growth
rates also (Tomozawa (1972,1973) had pre-
viously observed effects of immiscibility on
crystal growth rates in lithia-silica glasses).
However for glasses containing 10 and
15 mole% Na 2 O, no effect of phase separa-
tion on crystallization kinetics was found.
They suggest that this may because the
scale of the phase separation texture is
much smaller than the size of the growing
crystals.
The interpretation of nucleation and
growth kinetics using the classical theory
depends on reliable kinetic and thermody-
namic data being available. James (1985)
has investigated nucleation and growth in
a number of congruently melting silicate
compositions. He notes that the nucleation
results for a number of such compositions,
especially Li 2 O • 2SiO 2 , do not appear to
fit the theory and require abnormally high
values of the pre-exponential factor. Hishi-
numa and Uhlmann (1987) suggest that the
5.4 Alkali Silicate Glasses 295
problem may arise from the unsuspected
crystallization of a metastable crystalline
phase and that the discrepancy will be re-
solved once the correct value for the bulk
free energy of crystallization of this phase
can be determined.
5.4.2 Other Binary Silicate Systems
The regions of glass formation in most
other binary silicate systems are limited by
immiscibility in the melt. In some, the liq-
uidus temperatures are also high.
Thus in the MgO-, CaO-, and SrO-SiO 2
systems, the silica-rich melts separate into
two phases and have liquidus temperatures
of the order of 1700°C (Fig. 5-5). However
Imaoka (1962) was able to make glasses in
the BaO-SiO 2 system containing up to
40 mol% BaO (1/80 mol scale, melted in
platinum, cooled in air).
Very high melting point glasses can also
be made in the A12O3 SiO2 system, but
only when the melt is rapidly quenched. By
flame spherulization, Takamori and Roy
(1973) were able to obtain glasses contain-
ing up to 80mol% A12O3.
Addition of only a few percent of an al-
kali oxide to immiscible binary melts
nearly always results in a single phase melt.
Many of these ternary compositions are
simplified versions of commercially impor-
tant glasses (Shartsis et al, 1958).
Binary silicate glasses can also be made
with other important glass-forming oxides,
especially B 2 O 3 and GeO 2 . According to
Imaoka (1962), glasses can be made
throughout the whole composition range in
the systems B 2 O 3 -SiO 2 and GeO 2 -SiO 2 .
At high SiO2 contents, volatilization of
B 2 O 3 makes composition control difficult.
(See also Sec. 2.7.6.)
The PbO-SiO 2 system is of particular
interest, partly for scientific and partly for
technological reasons. Stable glasses can
296 5 Oxide Glasses
be made on a scale of several grams con-
taining up to 70 mol% PbO. The melting
temperatures of the high PbO glasses are
relatively low. They form the basis of many
high refractive index optical glass composi-
tions.
5.4.3 Physical Properties
It is not possible to give here more than
a very brief and highly selective account of
the effects of composition and temperature
on properties. A very large amount of in-
formation is available, much of which is
summarized in the handbooks of Mazurin
etal. (1983, 1985, 1987). The books by
Rawson (1980) and Scholze (1988) are less
comprehensive but provide a certain
amount of interpretation of the informa-
tion.
The breakdown of the silica network
and the increasing number of non-bridging
oxygens which results from the introduc-
tion of alkali oxides has two important ef-
fects:
- an increase in thermal expansion coef-
ficient,
- a decrease in viscosity at any specified
temperature.
For example, in the Na 2 O-SiO 2 system,
the thermal expansion coefficient increases
almost linearly with mol% Na 2 O from
5 . 1 0 - 7 o C -i for s i l i c a
1
l O - ^ C T at 45mol% Na 2 O. For the
same composition range the transforma-
tion temperature Tg (temperature at which
the viscosity is 10 12 Pa s) decreases from
1200 to 350 °C. For comparison a typical
commercial container glass composition
has a thermal expansion coefficient of
90 - l O ^ C r 1 and a Tg of 520°C.
The DC conductivity and dielectric
properties are primarily determined by the
number and mobility of the alkali ions.
The electrical resistivity falls rapidly with
increasing temperature. Thus a flat glass
composition has a room temperature resis-
tivity of l O ^ f l m , falling to 0.03fim at
1400°C.
Those silicate glasses containing two al-
kali oxides e.g. Na 2 O and K 2 O, show a
pronounced maximum in resistivity as one
alkali is substituted for the other at con-
stant total alkali content (mixed alkali ef-
fect). Various interpretations have been
proposed (Isard, 1968/69; Hendrikson and
Bray, 1972 a, b; Moynihan and Lesikar,
1981) but none appears to be universally
accepted (Ingram, 1987).
5.4.4 Immiscibility and Properties
Several examples are given in this Chap-
ter of the effect of sub-liquidus immiscibil-
ity on properties. In any systematic study
of the properties or the structure of a series
of glasses, it is necessary to know whether
the glass is single phase or not. The subject
has been discussed by Uhlmann and
Kohlbeck (1976), Uhlmann (1982) and To-
mozawa (1989).
Tomozawa has discussed in detail the
dielectric relaxation properties in alkali sil-
icate glasses across the immiscibility re-
gion, showing that they can be interpreted
only by taking the immiscibility and non-
ideality of the system into account.
g l a s s t Q 2 0 0 .
5.4.5 Chemistry of Alkali Silicate Glasses
Flat glass and container glass composi-
tions having adequate resistance to chemi-
cal attack by moist atmospheres and neu-
tral aqueous solutions had been developed
empirically well before the beginning of the
present century. Any problems encoun-
tered could usually be attributed to inade-
quate control of the glass composition.
On the other hand, the chemical durabil-
ity of binary alkali silicate glasses is too

poor for them to be of any practical use.
Nevertheless the reactions between these
glasses and aqueous solutions have been
studied in considerable detail, the informa-
tion obtained being of value in understand-
ing the reactions involving the more com-
plex silicate glasses.
The main variables studied have been
glass composition, temperature and the
pH of the aqueous phase. Resistance to
attack at a given R 2 O content increases in
the order R = K, Na, Li. At low values of
pH (<9), the reaction is primarily one in
which alkali ions in the surface layers of the
glass are exchanged with H + or H 3 O +
ions from the solution. This involves diffu-
sion through the surface reaction layer and
the amount of alkali extracted increases as
(time)1/2. At higher values of pH, the silica
network itself is attacked and passes into
solution. In this regime, the weight of ma-
terial extracted is linearly proportional to
time. As material is extracted from the
glass, the composition of the aqueous
phase and its pH changes. This compli-
cates the interpretation of the results.
Reactions involving substantially pure
water of constant composition have been
studied using apparatus in which the water
condenses on glass granules suspended in-
side a distillation column. As the con-
densed water runs off, it is collected for
analysis. In this type of experiment, the
quantity of material extracted, Q, at first
increases as (time)1/2, but at long times, the
rate of reaction becomes constant. It is sug-
gested that at long times, the siliceous sur-
face film on the particles is dissolved at the
same rate as that at which it is formed i.e.
it attains a constant thickness, at which
point a constant rate of extraction is to be
expected.
The chemical durability is greatly in-
creased by the addition of oxides of diva-
lent and trivalent elements (e.g. CaO and
5.4 Alkali Silicate Glasses 297
A12O3) leading to the commercial soda-
lime-silica compositions (Sec. 5.2).
There is a considerable literature dealing
with the mechanisms of the reactions be-
tween simple and more complex glasses
with aqueous solutions and with the test-
ing of glasses of technological interest to
meet specific durability requirements. The
importance of this subject both to the tra-
ditional glass industry and for new applica-
tions of glass (e.g. for nuclear waste stor-
age, for controlled release of trace elements
and for prosthetic applications) cannot be
overestimated (Hench, 1977, 1985 a; Paul,
1982; Hench and Spilman, 1985; Knott,
1989).
Other ion-exchange reactions at the
glass surface are also of technological im-
portance. They are usually carried out at
elevated temperatures so that the entering
ions may penetrate one or two hundred
microns into the glass. Reactions of this
kind include:
- ion-exchange strengthening in which
sodium ions in the glass surface are re-
placed by larger ions e.g. K + , thus devel-
oping a comprehensive layer in the glass
surface (Garfinkel, 1969). (See Chapter 13.)
- manufacture of optical waveguides in
which the exchange reaction can be con-
trolled to produce a strip in the surface
having a higher refractive index than the
unmodified glass (Ramaswamy and Srivas-
tava, 1988). (See Chapter 15.)
5.4.6 Oxygen Ion Activity; Basicity
Oxidation-reduction reactions in glass
play an important role in the high temper-
ature chemistry of glass melting reactions.
Also changes in the state of oxidation of
transitional metal ions dissolved in glass
are of considerable scientific interest and of
technological importance because of their
effects on the spectral transmission. These
298 5 Oxide Glasses
reactions are markedly affected by the
glass composition.
Changes which affect the state of oxida-
tion of ions of elements such as Fe, Cr and
Mn are of particular interest. For example,
in a glass containing iron oxide which has
been brought into equilibrium with an at-
mosphere of controlled oxygen partial
pressure, the oxidation-reduction equilib-
rium of F e 2 + / F e 3 + can be written as fol-
lows:
4FeO + O ? + 2 O 2 4FeO 7 (5-1)
If the reaction proceeds to the right, fer-
rous iron is oxidized to ferric with a con-
sequent change in colour. The equation
written in this form is in accordance with
the dependence on oxygen partial pressure
of the experimentally determined (Fe 3 + /
Fe 2 + ) ratio in the glass, it being assumed
that each chemical symbol in the equation
represents the activity of that constituent
in the system.
There has been considerable discussion
arising from work of this kind as to
whether the term 'free oxygen ion activity'
or simply 'oxygen ion activity' (represented
by the term O2~ in Eq. (5-1)) has any real
meaning, whether it can be measured and
whether the discussion of the equilibria in
this way can be justified (Wagner, 1975;
Schreiber 1986). It does however seem to
represent a helpful way of discussing the
equilibria and has been widely used in
other contexts e.g. in work on metallurgi-
cal slags.
Increasing the alkali content of the glass
produces more singly bonded oxygens,
which has the effect of shifting the equi-
libria to the right giving a higher propor-
tion of the oxidized form. This, it is said, is
due to an increased oxygen ion activity in
the glass. In an equilibrium such as that
above, for a given R 2 O content in the
R 2 O-SiO 2 glasses, the proportion of the
higher valent form increases in the order
R = Li, Na, K. Thus the K 2 O glasses ap-
parently have the highest oxygen ion activ-
ity at a given R 2 O/SiO 2 ratio. Alterna-
tively they are said to have the highest
basicity - the concepts are closely related.
Oxygen ion electrodes using CaO-stabi-
lized zirconia electrolytes have been used
to measure the oxygen potential or oxygen
ion activity of glass melts as a function of
glass composition, temperature and the
composition of the gas in contact with the
melt (Tran and Brungs, 1980; Schaeffer
et al, 1982). Oxygen potentials were deter-
mined on a number of samples of sodium
disilicate glass containing iron oxide and
the F e 2 + / F e 3 + ratios in these glasses were
determined chemically. Results were com-
pared with earlier melt-equilibration stud-
ies on the same glass in which the F e 2 + /
Fe 3 + ratio was varied by equilibrating the
melts with CO/CO 2 gas mixtures. The re-
sults were self-consistent, supporting the
above equation for the interpretation of
the redox reaction and giving one of sev-
eral examples of the value of high tempera-
ture oxygen electrodes in the study of the
high temperature chemistry of glass melts.
High temperature equilibration mea-
surements are difficult and time-consum-
ing. It is therefore of considerable interest
that a much simpler method exists which is
capable of providing similar information.
In this method, developed by Duffy and
Ingram (1976) and by Duffy et al. (1978),
ions such as Pb 2 + , Tl + and Bi 3+ are dis-
solved in the glass. They cause an intense
UV absorption band, usually having a
sharp maximum due to a 6 s -• 6 p transi-
tion. The frequency of the band is greatly
reduced as the basicity of the glass is in-
creased due to orbital expansion effects
within the probe ion, bought about by elec-
tron donation from the oxygens.

An 'optical basicity' A of the glass is de-
fined by the equation:
= (%-v gi )/( v fi- v oi) (5-2)
where vn = the absorption frequency of the
free ion. This is determined by extrapola-
tion, the value being 60 700 cm"* for Pb 2 + .
voi = the absorption frequency of the probe
ion in an ionic oxide e.g. CaO. For Pb 2 +
this is 29 700 cm" 1 . vgi = the measured ab-
sorption frequency of the ion in the glass.
It has been shown that the optical basic-
ity of any oxide glass can be calculated
from its composition using a table of
cation factors, termed the basicity moder-
ating power, y. These factors are related in
a simple way to the corresponding Pauling
electronegativity value, x
' = 1.36(x-0.26) (5-3)
The papers by Duffy and Ingram (1976)
and Duffy et al. (1978) referred to above
give a number of examples illustrating the
value of this approach in interpreting re-
dox phenomena in oxide glasses and in
metallurgical slags.
5.4.7 Structure
Several new techniques have been ap-
plied to the study of oxide glass structure in
recent years. Some provide selective probes
for determining short-range order i.e. they
give information about the oxygen co-or-
dination number around some particular
ions or about some aspect of bonding be-
tween nearest neighbours. Other tech-
niques are beginning to provide long-
awaited information about medium-range
order. The combination of results from the
experimental techniques with those ob-
tained from the construction of computer-
based models is beginning to make it possi-
5,4 Alkali Silicate Glasses 299
ble to determine whether or not particular
conjectures concerning medium-range or-
der are likely to be correct.
As described in Sec. 5.1.2, each 'R 2 O
molecule' introduced produces two non-
bridging oxygens, the R cations being in-
corporated in the voids in the silica net-
work. The formation of non-bridging
oxygens can now be followed quantita-
tively by ESCA (Bruckner, 1978), a tech-
nique which is particularly informative
when applied to borosilicate and alumino-
silicate glasses. The cations are accommo-
dated close to the negatively charged non-
bridging oxygens so as to maintain local
electroneutrality in the structure. There
has been a conflict of evidence, reviewed by
Kreidl (1983), as to whether the non-bridg-
ing oxygens are produced entirely ran-
domly or whether there is a tendency to
form alkali-rich clusters.
Recent work using Magic Angle Spin-
ning NMR (MAS NMR) suggests that the
degree of clustering varies within a given
system as the alkali content is increased
and also varies from one system to an-
other. The technique can distinguish be-
tween Si-O tetrahedra containing between
one and four non-bridging oxygens. Du-
pree et al. (1984) report that Na 2 O-SiO 2
glasses containing 33.3 mol% of Na 2 O
contain only Q 3 groups i.e. groups con-
taining only one non-bridging oxygen per
SiO4 tetrahedron. With further addition of
Na 2 O, the Q 3 groups are progressively
converted to Q 2 (two non-bridging oxy-
gens per tetrahedron) and at 50 mol%
Na 2 O only Q 2 groups are present. Thus
there is no evidence of clustering in this
particular system.
Dupree et al. (1986) have extended their
use of the technique to other alkali-silicate
systems. No evidence of clustering was
found in the Cs 2 O- and Rb2O-containing
systems but in the lithia glasses, containing
300 5 Oxide Glasses
less than 30 mol% Li 2 O, clustering of the
lithium ions does occur.
Molecular dynamic modelling of the
structure of soda-silica glasses supports the
generally held ideas about the structure of
silicate glasses (Varshneya, 1987; Soules,
1989). The oxygen co-ordination number
around the sodium ions varies between 3
and 8, with a most probable value of 5. At
low soda contents, two Na ions are found
around each NBO and three at higher Na
contents.
Concerning the anionic structure, Yasui
etal. (1983 a, b) interpret their X-ray dif-
fraction results as indicating that infinite
chains of SiO4 tetrahedra exist in alkali
metasilicate glasses and that the disilicate
glass structures consist of infinite sheets. A
molecular dynamics study of the metasili-
cate glass structure by Inoue and Yasui
(1987) supports the conclusions of the X-
ray work.
Dorfield (1988) has used thermodynamic
data for the Na 2 O-SiO 2 system to calcu-
late the effect of composition on the rela-
tive proportions of various anionic species
assumed to be present. This is the most
recent of many studies of this kind. Al-
though the results are sensitive to small
errors in the thermodynamic data used and
depend on initial assumptions which have
to be made, it is interesting that he arrives
at similar conclusions about the constitu-
tion of metasilicate and disilicate glasses to
those inferred from the most recent X-ray
and MAS NMR investigations i.e. that the
disilicate glasses contain predominantly
Q 3 groups and the metasilicate melts pre-
dominantly Q 2 groups.
The variation in the physical and chemi-
cal properties of simple silicate glasses with
composition shows little evidence of
changes in trend at the disilicate and
metasilicate compositions. However the
recent results on the systematic changes in
the anionic structures remind one of the
work done many years ago by Huggins
and Sun (1943) and Huggins and Stevels
(1954) which involved very careful analysis
of the refractive index and density data.
This showed changes in slope at particular
alkali-silica ratios. The changes are small,
but the recent structural work suggests
that there are reasons for expecting them
to be real.
Results of recent structural studies of
PbO-SiO 2 glasses show features which
differ from those found in the alkali silicate
systems. This is not surprising in view of the
differences between the R - O and P b - O
bonds. The stability to devitrification of
glasses of particularly high PbO content
has often in the past been attributed to
directional characteristics of the P b - O
bond and to the supposed ability of that
oxide to act as a 'network former'. The
structural role of PbO in glasses has been
reviewed by Rabinovitch (1976).
An MAS NMR investigation has been
carried out by Dupree et al. (1987) on sev-
eral PbO-SiO 2 glasses containing up to
70 mol% PbO. The latter glass appears to
contain isolated SiO4 groups 'in a lead-
oxygen matrix'. The X-ray PES work of
Smets and Lommen (1982) also indicates
that some form of lead-oxygen network ex-
ists at the high PbO contents. Below
30 mol% PbO, the oxide acts as a conven-
tional modifier, but at intermediate com-
positions there is no indication of the pres-
ence of mixtures of Q n species as found
in the alkali silicate systems. As the PbO
content increased, the P b - O bonds were
found to become more covalent indicating
that the PbO was changing its role from
that of a modifier to that of an interme-
diate.
Another technique which can give infor-
mation about the anionic constitution of
silicate glasses is gas-liquid chromatogra-
 5.5 Boric Oxide Glass 301

phy pioneered by Masson (1977). Recent

results by this method on PbO-SiO 2
glasses have been reported by Smart and
Glasser (1978). The method can be applied
only to glasses containing more than
50 mol% PbO. In this region, most of the
51 was found to be present as SiO4 groups
- in agreement with the results of the NMR
work. However, significant proportions of
di-, tri- and tetramers were also detected.

5.5 Boric Oxide Glass

The properties of the oxide melt and the
glass are markedly affected by their - O H
contents. Bruckner (1964) found that as the
water content is decreased from 0.248 to
0.025%, the temperature at which the vis-
cosity is 103 Pa s rises from 537 to 550 °C.
An anhydrous melt is difficult to prepare
starting from orthoboric acid, but a sub- Figure 5-11. The structure of B 2 O 3 glass with
stantially water-free material was obtained (B3O6)3~ boroxol groups (from Krogh-Moe, 1969).
by Poch (1964) by melting the material for
several hours at a pressure of 1 mm Hg.
Fig. 5-10 shows that the viscosity of the
oxide at its melting point is much less than
that of silica yet crystallization is extremely et al, 1967). Recent structural studies
slow, except at high pressures (Uhlmann (e.g. Johnson et al., 1982) suggest that the
crystallization of the B 2 O 3 melt involves
greater structural changes than is the case
for SiO2. That, together with the much

A\
lower melting point of B 2 O 3 , makes the
T m =1115°C = 550°C difference between the crystallization rates
/
•«5- m
a-
T °c of the two materials understandable.
fS'°2 /
Fc;n / / V
The structure of the crystalline oxide
J
f consists of infinite chains of BO 3 triangles.
C/5
O r.
<J 3~ ^GeO2
</>
'•>
j3BeF2 Nearly all investigations of the glass struc-
3
ture, using various techniques, support the
model proposed by Krogh-Moe (1969)
i- if
i i (Mozzi and Warren, 1970; Griscom,
5 7 10 11 12 13 U 1978 b; Johnson et al., 1982). This is illus-
Figure 5-10. The relationship between log viscosity
trated in Fig. 5-11. The main feature is the
and 1/T K for some network liquids (from Mackenzie, preponderance of boroxol groups which
1960). constitute 60-80% of the structure.
302 5 Oxide Glasses

5.6 Borate Glasses Table 5-4. Crystallization rates of binary borate melts
(Bergeron, 1978).

5.6.1 Glass Formation in Binary Systems Compound M.Pt. n(um)

°C cm/sxlO" 4 Pas
Imaoka (1962) has determined the re-
gions of glass formation in many binary PbO-2B 2 O 3 775 2 6
systems with the results given in Table 5-3. SrO-2B 2 O 3 997 154 5
BaO-2B 2 O 3 910 35 32.2
The melts were prepared on a scale of 1 to
Li 2 O-2B 2 O 3 917 3000 0.3
3 g in a platinum crucible and were al- Na 2 O-2B 2 O 3 742 33 25
lowed to cool freely in the crucible. Cs2O 3B 2 O 3 837 140 23
As in the silicate systems, the regions of Na 2 O 4B 2 O 3 816 7 23
glass formation in the alkaline earth borate K 2 O-4B 2 O 3 857 12 15
BaO-4B 2 O 3 889 15 55
systems (and in some others) are limited by
immiscibility in the compositions of high
B 2 O 3 content.
It is interesting that two separate regions regarded as mixed anion glasses and not as
of glass formation exist in the Na 2 O-B 2 O 3 binary borates.
system. Sakka et al. (1978) and Martin and In the alkali borate systems, the liquidus
Angell (1984) have shown that the gap be- temperature increases rapidly with the first
tween the two can be closed by adding a addition of alkali. These glasses are much
small percentage of alumina. A more im- easier to crystallize than B 2 O 3 itself.
portant point brought out by Martin and Baeten et al. (1972) have shown that in the
Angell (1984) and by Lim et al. (1987) is N a 2 O - B 2 O 3 system, there is no simple re-
that considerable percentages of CO 2 are lationship between the stability of the glass
retained in the high alkali borate melts if a and its liquidus temperature, such as one
carbonate is used as the source of alkali. finds in the corresponding silicate and
This affects the stability of the glasses and other systems.
their properties. Such materials should be Table 5-4 (Bergeron, 1978) gives for a
number of congruently melting borate
compositions, the maximum rate of crystal
Table 5-3. Regions of glass-formation in binary borate growth t/m, the melting point and the vis-
systems (Imaoka, 1962). cosity of the melt at the temperature of
System
maximum growth rate (rj (Um)). The maxi-
mum growth rate is not inversely propor-
100.0-62.3 tional to q(Um) i.e. glass formation does
Na 2 O 100.0-62.0 not depend simply on the melt having a
33.5-28.5
high viscosity at or just below the melting
Li2O 100.0-57.3
BaO 83.0-60.2 point, nor is there a simple relationship
SrO 75.8-57.0 between glass stability and melting point.
MgO 57.0-55.8
81.0-71.8 5.6.2 Sub-Liquidus Immiscibility
100.0-55.5
in Binary Borate Glasses
ZnO 56.0-36.4
CdO 60.9-45.0 Information on immiscibility in borate
PbO 80.0-23.5
Bi2O3 78.0-34.7
systems has been reviewed by Macedo and
Simmons (1974). Shaw and Uhlmann
 5.6 Borate Glasses 303

(1968) have shown that sub-liquidus im- 900

miscibility occurs in all alkali borate sys-

Liquidus^.
tems, as is shown for the Na 2 O-B 2 O 3 sys- ~ 700-
tem in Fig. 5-12.
Uhlmann and Shaw (1969) and Shaw | 60 °" 8 ~ 8 ^ ^Region of sub-

and Uhlmann (1969) have discussed •500-

whether the presence of immiscibility in " U)0-
Approximate glass
these glasses may have led to misinterpre- transition temperature
300-
tation of property-composition relation-
ships in earlier work. For such properties
6 L 8 12 16 20 U 28 32 36
as density, refractive index and thermal ex- Mol.% Na20
pansivity, this is unlikely. However viscos- Figure 5-12. Region of sub-liquidus immiscibility and
ity may be markedly affected by phase sep- liquidus curve for the system Na 2 O-B 2 O 3 (from
aration and by the nature of the separation Shaw and Uhlmann, 1968).
microstructure.

5.6.3 Structures of Binary Borate Glasses

The structures of alkali borate glasses
have been investigated by a number of
techniques and the results summarized by
Griscom (1978 b). Nearly all the results are (a) (b)
in agreement with a model first proposed
by Krogh-Moe (1969). Fig. 5-13 shows the
four groups which have been shown to be
present in the borate network, depending
on the glass composition. They are also
found in anhydrous crystalline borates of
similar composition. Note that all contain
both three- and four-co-ordinated borons.
The lines in Fig. 5-14 are derived by ap-
plication of the lever rule, giving the rela- (0
tive proportions of each group as a func-
Figure 5-13. The borate groups postulated as existing
tion of glass composition. The NMR in alkali borate glasses containing less than 34 mol%
results in particular support this simple R 2 O. (a) The boroxol group, (b) the pentaborate
model very well. Recent molecular dynam- group, (c) the triborate group, (d) the diborate group
ics calculations (Inoue et al., 1987) also (from Krogh-Moe, 1969).
confirm the existence of boroxol groups in
vitreous B 2 O 3 and of diborate groups in
borate glasses. ing specific polyborate groups in a glass.
Although a large body of results has sup- They found that the technique failed to de-
ported the Krogh-Moe structural model tect structural differences between lithium
and the interpretation of data on which chloroborate and simple lithium borate
it is based, Button et al. (1982) doubt if glasses even though the physical properties
NMR, in particular, is capable of identify- of the glasses are significantly different.
304 5 Oxide Glasses
1.0-
0 0.1 0.2 0.3 0.4 0.5 0.6
Figure 5-14. The results of 10B NMR measurements
of the fraction of borons in five distinguishable sites
plotted as a function of R = x/(1 — x), where x is the
molar fraction of Na 2 O in the sodium borate glasses.
A Three-coordinated borons in boroxol groups and
'loose' BO3 triangles (B3), o three-coordinated borons
in tetraborate groups (T3), + four-coordinated bo-
rons in tetraborate groups (T4), • three and four-co-
ordinated borons in diborate groups (D 3 and D 4 ).
The straight lines and the symbols with suffixes corre-
spond to predictions from Krogh-Moe's theory (1969)
(from Jellison and Bray, 1978 a).
Fig. 5-15 shows some early NMR results
in which the fraction of four coordinated
boron atoms is plotted as a function of
alkali content. Recent X-ray diffraction
studies (Herms et al., 1986) appear to be in
agreement with this interpretation.
5.6.4 Properties
It is not surprising, considering the dif-
ferent structural effects of R2O additions in
silicate and borate melts that their proper-
Figure 5-15. The fraction N 4 of boron atoms in four-
coordination in alkali borate glasses, o K 2 O; • Na 2 O;
A Li 2 O; +Rb 2 O; x Cs2O (from Bray and O'Keefe,
1963).
ties should vary so differently with compo-
sition. Fig. 5-16 shows high temperature
viscosity data for several R 2 O-B 2 O 3 sys-
tems (Shartsis et al., 1953; Kaiura and
Toguri, 1976). In the corresponding silicate
glasses the viscosity decreases monotoni-
cally with increasing R2O content.
Clearly the effect of the alkali addition
depends markedly on temperature, sug-
gesting that temperature may also have a
marked effect on the melt structure. This
view is supported by the theoretical con-
siderations of Araujo (1979, 1983) and by
high temperature measurements of optical
basicity (Duffy and Grant, 1975). It seems
very likely that the value of N 4 , the frac-
tion of boron atoms in four-fold coordina-
tion decreases with increasing tempera-
ture.
Fig. 5-17 shows the effect of composition
on thermal expansion for the alkali borate
glasses. The shape and position of the min-
imum depends on the temperature range
over which the expansion coefficient is de-
termined (Ahmed et al., 1985; Mader and
Loretz, 1978). It is suggested that the initial
reduction in expansion coefficient in the
0-20 mol% alkali region is due to the re-
 5.7 Borosilicate Glasses 305

placement of BO3 triangles by BO4 tetra-

hedra, increasing the degree of three-di-
mensional bonding in the structure. The
increase in expansivity above 35 mol% al-
kali is due to the formation of non-bridg-
ing oxygens.

5.6.5 Technological Applications

of Borate Glasses
These are very limited. Borate optical
glasses containing high percentages of rare
earth oxides are used to manufacture lens
systems with high numerical aperture and
low spherical aberration (Meinecke, 1959).
Other applications are as solder glasses,
for making vacuum-tight seals between sili-
cate glass components without risking their
distortion during sealing. Solder glasses
based on the PbO-SiO 2 system are suit-
30 U)
Mol.7o R20 able for joining glass and/or metals having
an expansivity of about 90 10" 7 o C" 1 .
Figure 5-16. Isothermal viscosity curves for alkali bo-
rate glasses - all systems show similar trends (from
Materials with an expansivity of approxi-
Shartsis et al., 1953). mately 5 0 - 1 0 " 7 o C " 1 may be joined using
solder glasses based on the ZnO-B 2 O 3
system (Frieser, 1975).

5.7 Borosilicate Glasses

The ternary system Na 2 O-B 2 O 3 -SiO 2
forms the basis of a number of glasses of
considerable technological importance.
They include the glass commonly known
as Tyrex', used for chemical apparatus and
ovenware, a series of glasses used in the
electronics industry to make seals to
metals and other materials (Volf, 1961;
Kohl, 1967; Espe, 1968) and glasses used
for the vitrification of nuclear fission prod-
uct wastes (Hench, 1958 b). At a given al-
0 5 10 15 20 25 30 35 /.0
kali content, the addition of boric oxide to
Mol.%, R20 a silicate glass markedly reduces the ther-
Figure 5-17. Thermal expansion coefficients of alkali
mal expansion coefficient and enhances the
borate glasses as a function of composition (from chemical durability, especially to attack by
Uhlmann and Shaw, 1969). acids.
306 5 Oxide Glasses
5.7.1 Thermal Expansion Coefficient
Fig. 5-18 shows the effect of B 2 O 3 con-
tent at various levels of Na 2 O content on
the expansion coefficient (Streltsina, 1967;
Mazurin et al., 1969). These are mean val-
ues over the range 20-300°C It is clear
that variation in the alkali content has less
effect on the expansion coefficient the
higher the B 2 O 3 content. The borosilicate
glasses of technical importance have expan-
sion coefficients in the range 30-80 • 10" 7 .
50
Mol.% B203
Figure 5-18. Effect of B 2 O 3 content on the thermal
expansion coefficient of Na 2 O-B 2 O 3 -SiO2 glasses
at various Na 2 O contents (data from Streltsina, 1967,
and Mazurin et al., 1969).
5.7.2 Viscosity
Tait et al. (1984) have determined the
viscosity-temperature curves of 16 ternary
compositions in the system over the tem-
perature range 900 to 1500°C. The com-
positions were in the range 5-35 Na 2 O,
5-35 B 2 O 3 , 45-80 SiO2 mol%. Polyno-
mials were fitted to the viscosity-tempera-
ture data and these were used to plot vis-
cosity contours on the triangular compo-
sition diagram. Fig. 5-19 shows the viscos-
ity contours at two temperatures.
5.7.3 Structure
The results of several NMR investiga-
tions agree that when R ( = mol% Na 2 O/
mol% B 2 O 3 ) is less than 0.5, the additional
oxygen atoms introduced with the Na 2 O
are used entirely to convert BO3 units to
BO 4 units i.e. the glasses behave as if they
were sodium borate glasses with the silica
acting as an inert diluent.
Fig. 5-20 shows that above R = 0.5, the
value of N 4 , the fraction of boron atoms in
BO4 units, varies with R in a way which
depends on composition and in particular
on the value of the ratio K = mol% SiO 2 /
mol% B 2 O 3 . Yun and Bray (1978) postu-
late that for 0.5<i?<i? max , the added
Na 2 O is used solely to convert diborate
groups into (BSi 4 O 10 )" 1 units (a unit
found in the mineral Reedmergnerite,
Na 2 O • B 2 O 3 • 6SiO 2 ). This process con-
tinues until all the SiO2 has been taken
up in Reedmergnerite units. When further
Na 2 O is added beyond R = Rmax, the alkali
is divided between the borate and silicate
units in proportion to the amounts of
B 2 O 3 and SiO2 present in the glass. If these
relatively simple assumptions are accepted,
the results shown in Fig. 5-20 can be fully
accounted for.
 5.7 Borosilicate Glasses 307

1200°C
0.8

0.7 %

Figure 5-19. Viscosity con-

tours at 1050 °C and
1200°C for melts in the
system Na 2 O-B 2 O 3 -SiO 2
0.2 0.3 0.4 0.5 0.6 (from Tait et al., 1984).
B203

that running almost parallel to the silica-

boric oxide side of the diagram.
0.8-
Heat treatment below the miscibility
temperature results in a separation texture
which depends on the temperature and
time of heat treatment. The properties of
0.6-
the resulting material are greatly affected
by the separation, especially when the
high-silica phase is continuous (Mahoney
0.4-
et al., 1974). Fig. 5-22 shows the large in-
crease in viscosity with time which results
as phase separation takes place.
Heat treatment of glasses with composi-
0.2- tions in the immiscibility region produces a
texture consisting of two interconnecting
phases, one consisting largely of a sodium
borate glass (Na 2 O • 2.4B 2 O 3 • 0.16 SiO2)
and the other almost pure silica. The
0.5 1.0 1.5 2.0 2.5 3.0
R (mol%Na 2 0/mol% B203) sodium borate phase can be leached out
completely by immersing the material in
Figure 5-20. The fraction N 4 of boron atoms in BO4
units versus K=mol% Na 2 O/mol% B 2 O 3 for vari- acid. After drying and heat treatment at
ous values of K = mol% SiO 2 /mol% B 2 O 3 . A K = 0; 900-1200 °C, the silica skeleton densifies
A K = 0.5; o K = 1; • K = 2; n K = 3 (from Bray, 1978). to a transparent glass containing about
96 wt.% silica and with properties very
similar to those of silica glass itself. This
material, 'Vycor', a product of Corning
5.7.4 Sub-Liquidus Immiscibility
Glass Works, was patented by Hood and
Fig. 5-21 due to Haller et al. (1970) Nordberg (1938), many years before sub-
shows the regions of sub-liquidus immisci- liquidus immiscibility had been studied in
bility in the Na 2 O-B 2 O 3 -SiO 2 ternary detail and its nature appreciated. Detailed
system. The region of greater importance is accounts have been given by Kreidl (1983)
308 5 Oxide Glasses
10 60
Mol.% SiO2
and Volf (1961) of the various stages in the
manufacture of this material.
There are also interesting and important
applications for the porous silica skeleton
material produced by acid leaching the
phase-separated glass. These include uses
as carriers for enzymes and other catalysts,
desalination membranes etc. (Phillips
etal., 1974; Janowski and Heyer, 1982;
Schnabel and Langer, 1989).
10
Time (min)
Figure 5-22. Effect of time of heat treatment on the
viscosity at 560 °C and 600 °C for a glass of composi-
tion 70mol% SiO2, 23mol% B 2 O 3 , 7 mol% Na 2 O
(from Mahoney et al., 1974).
Figure 5-21. Region of sub-
\ liquidus immiscibility in
theNa 2 O-B 2 O 3 -SiO 2
system. In the shaded
region three amorphous
phases co-exist (from
Haller et al., 1970).
BO 100
5.8 Aluminosilicate Glasses
Table 5-5 gives the compositions of a
number of commercial aluminosilicate
glasses. They are used in situations where a
high softening point, a high electrical resis-
tivity and/or good resistance to chemical
attack by aqueous solutions are required.
Many fibreglass compositions belong to
this group of glasses.
Glasses in the systems Li 2 O-Al 2 O 3 -
SiO2 and MgO-Al 2 O 3 -SiO 2 are made
for subsequent conversion into important
classes of glass ceramics (Strnad, 1986).
Aluminosilicate melts are also of interest
to geochemists and metallurgists (volcanic
glasses and some metallurgical slags).
5.8.1 The Alumina-Silica System
Much information exists on the region
of stable and metastable immiscibility in
alkali- and alkaline earth silicate systems.
It has proved more difficult to investigate
metastable immiscibility in the alumina-
silica system. Liquidus temperatures across
10* the system are high and, in the region
above 30mol% alumina, glasses can be
made only by very rapid quenching. The
phase diagram is shown in Fig. 5-23 to-
gether with the region of metastable im-
miscibility as determined by McDowell
and Beall (1969).
Takamori and Roy (1973) have ex-
pressed doubts as to whether the immisci-
bility region has been determined with suf-
 5.8 Aluminosilicate Glasses 309
Table 5-5. Compositions of commercial aluminosili- ficient accuracy. On the other hand Risbud
cate glasses.
and Pask (1977) were able to show, by ther-
1 2 3 4 modynamic methods, that one should ex-
pect an immiscibility region in the position
SiO2 51.2 52.0-56.0 60.0-70.0 59.0-64.0 observed by McDowell and Beall and pos-
A12O3 22.6 12.0-16.0 0.0- 5.0 3.5- 5.5
B2O3 8.0-13.0 6.5- 7.0
sibly also a second region at higher alu-
1.5
P2O5 4.5 mina contents.
MgO 5.4 0.0- 6.0 2.5- 3.5 Jantzen et al. (1981) have used small an-
CaO 9.0 16.0-25.0 0.0-10.0 13.5-14.5 gle neutron scattering to study the kinetics
BaO 5.3 of phase separation in rapidly quenched
R2O 1.0 0.4- 0.7
glasses in the system. They confirmed the
ZrO 2 15.0-20.0
TiO 2 0.0- 5.0 existence of a metastable immiscibility re-
gion in the position reported by McDowell
1 High softening point glass for mercury arc dis- and Beall (1969) but with a much lower
charge lamps. critical temperature.
2 Glasses 2, 3 and 4 are fiberglass compositions. 2 is
E glass, resistant to neutral and acidic solutions
and used in making glass-reinforced plastics. 3 is a 5.8.2 Sodium Aluminosilicate Glasses
composition resistant to attack by highly alkaline
solutions. It is used in making glass fiber reinforced Glasses in this ternary system have at-
cement (Proctor, 1985). tracted considerable interest, not because
they have any great technological impor-
tance but on account of the marked
changes in the dependence of properties on
composition which are observed on pass-
ing across the line in the ternary composi-
tion diagram defining a Na 2 O/Al 2 O 3 ratio
2000* of 1. Two well known examples are shown
/corundum* in Figs. 5-24 and 5-25. Fig. 5-24 shows the
/ liquid
Si02+liquic lines of equal refractive index (isofracts) in
1800^
mullite* liquid the system and Fig. 5-25 shows the effect of
composition on the activation energy for
16002-
d.c. conduction. These and similar results
/ \ corundum* suggest that they might have a simple ex-
/ • • \ mullite SS
/ • • \
/ : '• \ planation in terms of glass structure.
• \
\
/ \ There is general agreement that when
uoo* \
\
/ j • \ the Al/Na ratio is significantly less than 1,
\ -mullite SS
\
each Al 3+ ion added substitutes for a Si 4+
1200^ \ ion in the network and two non-bridging
: \ \ ions are eliminated. The Al 3+ ion and a
: \
:
:
\
I
nearby Na + ion are together electrostati-
-l \

30
•

50
\

70 90
cally equivalent to one Si 4+ ion. Thus local
Mol.% Al 2 0 3 charge balance in the network is main-
Figure 5-23. The Al 2 O 3 -SiO 2 phase diagram show-
tained. It is possible to envisage this pro-
ing regions of metastable immiscibility (from Mc- cess continuing with increasing alumina
Dowell and Beall, 1969). content up to Al/Na = 1 at which point the
310
0 50 100
NQ 2 O NQ 2 0 Al 2 0 3
weight %> A 2 0 3
Figure 5-24. Lines of equal refractive index of glasses
in the system Na 2 O-Al 2 O 3 -SiO 2 (from Schairer and
Bowen (1956); reprinted by permission of Americal
Journal of Science).
glass would contain no non-bridging oxy-
gens.
Day and Rindone (1962) proposed that
beyond this point any further Al 3+ ions
introduced will be six-coordinated by oxy-
gen and behave as network modifiers. It
has been proposed that such a change
in behaviour, or something like it, could
0.5
Figure 5-25. Effect of composition on the activation
energy for DC conductivity in the system Na 2 O •
• x A12O3 • 2 (4-x) SiO2 (from Isard, 1959).
account for the property-composition re-
lationships described above. However
Lacy (1963) argued that the formation of
(A1O6)3" groups was unlikely on grounds
of their large packing requirements. He
proposed instead the formation of 'triclus-
ters' consisting of, for example, one A1O4
and two SiO4 tetrahedra sharing a com-
mon corner i.e. with one three-coordinated
oxygen ion. Such groups exist in some
crystalline silicates, but as yet no direct
structural investigation has shown conclu-
sively that they exist in glasses. Note that
such an arrangement breaks Zachariasen's
rule 3.
Recent results have tended to cast
doubts on the Day and Rindone model
(1962). Smets and Lommen (1981b) have
used X-ray photoelectron spectroscopy to
investigate glasses in the system 0.2 Na 2 O,
x A12O3, (0.8-x) SiO2. Their results show
that the signal due to non-bridging oxy-
gens disappears at x = 0.15 i.e. at Al/Na
= 0.75. They suggest that even below the
equivalence point of Al/Na = 1, some Al3 +
ions are probably incorporated into the
structure as (A1O6)3~ octahedra. They rec-
ognize that their results make it difficult to
account for the abrupt changes in physical
properties described above but make a
comment which reflects our limited under-
standing of the relationship between glass
properties and structure:
"It should be pointed out that there is
often no distinct relation between the phys-
ical properties of a glass and its short range
structure. A notorious example of this is
found with borate glasses."
McKeown (1987) studied by the energy
dispersive X-ray technique, Raman scatter-
ing, EXAFS and XANES a series of glasses
containing 75 mol% SiO2 with Al/Na
ranging from 0.02 to 1.61. He concludes
that all the Al3 + ions are tetrahedrally co-
ordinated throughout the series and sug-

gests therefore that since the local co-ordi-
nation environments do not change, longer
range structural changes must be responsi-
ble for the property changes. For example,
some tetrahedra may link across rings and
three-coordinated oxygens may form at
these links (as proposed by Lacy (1963)).
On the other hand Klonowski (1983), on
the basis of refractive index and ESR mea-
surements, appears to favour the original
Day and Rindone model (1962). Thus al-
though there are reasons to doubt the Day
and Rindone model, as yet there is no gen-
erally accepted alternative.
An example of a change in long range
order in the structure (though not neces-
sarily of the type envisaged by McKeown
(1987)) arises in the melting of the com-
pounds NaAlSi3O8 and KAlSi 3 O 8 . In the
crystalline materials, the SiO4 tetrahedra
are joined to form four-membered rings.
Taylor and Brown (1979) showed by X-ray
diffraction that six-membered rings are
present in the glass, indicating that a con-
siderable structural rearrangement must
take place on melting and on crystalliza-
tion. This fact together with the relatively
low melting points of the compounds and
their high viscosity at the melting point
may explain why they are so difficult to
crystallize (Schairer, 1951; Cranmer and
Uhlmann, 1981).
5.9 Phosphate Glasses
Small quantities of phosphate glasses
and P2O5-containing glasses are used in a
number of applications:
1. Aluminophosphate laser glasses con-
taining Nd 3 + in high power laser fusion
facilities (Jiang et al., 1986; Toratoni et al.,
1987).
2. Phosphate glasses containing transi-
tion metal oxides (controlled release
5.9 Phosphate Glasses 311
glasses). These are used for the treatment of
crops and animals suffering from trace ele-
ment deficiences (Knott, 1989).
3. Phosphate glasses doped with halides
have high ionic conductivities and are be-
ing studied for battery applications (Ra-
vaine, 1985).
4. A small percentage (6%) of P 2 O 5 is an
essential component of 'Bioglass™', a ma-
terial being used in prosthetic applications
(Hench and Spilman, 1985).
5. Some glass-ceramics use the oxide as
a nucleating agent (Strnad, 1986).
6. Some low melting phosphate compo-
sitions have been studied with the inten-
tion of producing articles from them using
standard polymer-processing equipment
(Ray, 1978).
Some of these applications are referred
to again later.
5.9.1 Phosphorus Pentoxide
All forms of the oxide, both crystalline
and vitreous, react readily with water.
Consequently the oxide glass is of no prac-
tical value.
There are three crystalline forms, all
having structures based on the PO 4 tetra-
hedron. In all of them one oxygen is non-
bridging. Crystals of the hexagonal form
melt at 422 + 6 °C, the liquid formed poly-
merizing rapidly. The tetragonal form
melts at 580 + 5 °C to form a very viscous
liquid which can readily be superheated to
temperatures well above the melting point.
The melts made from all three crystalline
forms can easily be supercooled to form a
glass, the properties of which depend on
the crystalline form from which it was
made. This suggests that the attainment of
equilibrium in the melt is sluggish. Cormia
et al. (1963) have studied the rates of melt-
ing and crystallization of the tetragonal
form.
312 5 Oxide Glasses

5.9.2 Regions of Glass Formation Table 5-6. Regions of glass formation in binary phos-
in Binary Phosphate Systems phate systems (Imaoka, 1962).

Information on regions of glass forma- Maximum percentage of second oxide

tion quoted in the literature should be 47.0
treated with reserve because of uncertainty Na 2 O 60.0
with regard to the amount of water re- Li2O 60.0
tained in the melt. The same applies to BeO 66.0
property values, which are also markedly MgO 60.0
CaO 56.0
affected by the amount of water retained.
SrO 56.0
However it is clear that the regions of glass BaO 58.0
formation in many binary phosphate sys- Ag2O 66.0
tems are very extensive and regions of im- T12O 50.0
miscibility, which are common in alkaline ZnO 64.0
earth borate and silicate systems, are rarely CdO 57.0
found in the corresponding phosphate sys- PbO 62.0
tems.
Table 5-6 gives Imaoka's results (1962)
for the maximum percentage of the second
oxide in glasses in a number of binary sys-
tems (melted on a 3 g scale in platinum).
Extensive regions of glass formation also
exist in the binary systems with the oxides
V2O5, TeO2, WO 3 and MoO 3 .

5.9.3 Properties of Binary Phosphate

Glasses
Fig. 5-26 shows the variation with com-
position of the thermal expansion coeffi-
cient of glasses in the systems R 2 O-P 2 O 5
(Takahashi, 1962) and RO-P 2 O 5 (Elyard
and Rawson, 1962). Fig. 5-27 shows Ray's
data (1974) for the Tg values of alkali- and
alkaline earth metaphosphate glasses.
Other properties are given in Mazurin
etal. (1985).
Physical property data for phosphate 6-
glasses is of little value without detailed
information about the melting schedule 0 20 &0 60
Mol.7o (R2O.RO)
and the raw materials used. It is now well
known that phosphate glasses retain ap- Figure 5-26. Effect of composition on thermal expan-
sion coefficient of some binary phosphate glasses.
preciable percentages of water, to an extent (Data for R 2 O-P 2 O 5 glasses from Takahashi (1962);
which depends on the composition and on data for RO-B 2 O 3 glasses; from Elyard and Rawson
the time and temperature of melting. (1962)).
 5.9 Phosphate Glasses 313

of water, 10% being not uncommon and

600- values as high as 30% having been re-
Mg ported. It is worth noting that very high
~- 500-
water contents can also be obtained in sili-
5 cate glasses, but only by melting under
"^ DQ
high pressures of water vapour. As in the
1" 600- phosphate systems, the presence of com-
bined water has a large effect on glass
11011

Li

1 300- properties.
cr
C3
K A number of investigations have shown
that the degree of cross-linking in water-
200- i
containing phosphate glasses and its effect
50 60 70 80
Oxygen density g-atom litre" 1 on glass properties can be calculated or
Figure 5-27. Effect of composition on the Tg values of interpreted using theories developed in the
alkali and alkaline earth metaphosphate glasses (from field of organic polymers (Eisenberg and
Ray, 1974). Sasada, 1965; Ray et al, 1973a, b, 1976;
Ray, 1978; Furdanowicz and Klein, 1983;
Gray and Klein, 1983).
By melting for long periods of time the
water content can be reduced with a
5.9.4 Multi-Component Phosphate Glasses
marked effect on glass properties. Thus
for a multicomponent glass containing Ray et al. (1973 a, b, 1976) have carried
70mol% P 2 O 5 , initially melted at 400 °C, out a wide-ranging program to develop
Ray and Lewis (1972) found the water con-
tent to be 4.5% and the transformation
temperature 119°C. Samples taken during
a subsequent 'refining' at 700 °C showed 240-
the water content decreasing to 0.3% and /
the Tg rising to 256 °C over a period of 96 h. 220-
Fig. 5-28 shows the transformation tem- /
perature plotted against the cross-link den- "^200-
/
sity, as calculated from the composition
(taking into account the water content). s 180-
The glass as initially melted at 400 °C dis-
solved in water to form a clear highly vis- ~ 160- So
cous solution. The material heated at
700 °C, however, was no longer soluble in
=>
*-*
a
r
r
cold water and dissolved only partly in I5 uo- /
boiling water. The changes in both the
" 120<
physical and chemical properties are
clearly related and reflect the effect of pro-
longed melting in increasing the cross-link- i I
0.2
i
0.3 U
I
0.5
I
3 0.1
ing by the elimination of water. Cross-link density
Some phosphate glasses have been Figure 5-28. Change in Tg with increasing cross-link-
shown to contain much higher percentages ing density (from Ray and Lewis, 1972).
314 5 Oxide Glasses
low-softening glasses of good chemical
durability which can be fabricated into
shapes by standard equipment used in the
plastics industry. The most promising
compositions had a Tg of about 170°C. The
incorporation of 5 mol% B 2 O 3 signifi-
cantly increased the durability without in-
creasing Tg.
Spierings et al. (1981) have shown that
one of Ray's compositions, made from ul-
tra-high purity materials, may be suitable
for use as an optical communication fibre
material.
Controlled-release glasses dissolve at a
controlled rate to release transition metal
additives and other active materials which
they contain. Knott (1989) has made wide
use of multi-component phosphate glasses
for this purpose.
An important application of alumino-
phosphate glasses is in making the large
laser amplifier discs which have been used
in several high power laser fusion facilities.
They are suitable for this application be-
cause of their large stimulated emission
•5 10-
T"
5 k
Number average chain length, n
cross section, low non-linear refractive in-
dex and satisfactory mechanical and chem-
ical properties.
Additions of B 2 O 3 and A12O3 increase
the degree of cross-linking in the glasses
and some borophosphate and alumino-
phosphate glasses have physical and chem-
ical properties similar to those of commer-
cial silicate glasses.
5.9.5 Structure
In the limited region of glass formation
on the modifier-rich side of the metaphos-
phate composition, interesting structural
information can be obtained by paper
chromatography. Summaries of this work
have been published by Van Wazer (1958)
and Westman (1960). Fig. 5-29 shows the
results for Na 2 O-P 2 O 5 glasses (Westman
and Crowther, 1954; Westman and Garta-
ganis, 1957). The curves give the percent-
age of the total phosphorus present in
chain molecules of various lengths i.e. with
n values ranging from 2 to 9. The curve HP
Figure 5-29. Constitution of
sodium phosphate glasses as de-
termined by paper chromatogra-
phy (from Westman, 1960).
3

gives the percentage present in linear
molecules for which n is greater than 9 and
that labelled C gives the percentage present
in cyclic molecules. The number average
chain length, n*9 is given approximately by:
: to offer in the way of properties that can-
= 2/(Na/P-l) (5-4)
Thus at the metaphosphate composition
(Na = P), ?2* is infinite and is 1 at the or-
thophosphate composition (Na = 4 P). As
the Na 2 O content is reduced towards the
metaphosphate composition, the propor-
tion of long chain phosphates gradually
increases at the expense of the short chain
anions.
Westman (1960) suggests that the pres-
ence of short chain molecules in composi-
tions just on the high-Na2O side of the
metaphosphate composition indicates that
a dynamic equilibrium exists in the melt
between the various anion species. Unless
the time of melting is very short, the equi-
librium should be independent of the na-
ture of the starting materials.
Results are also available for other bi-
nary and more complex alkali phosphate
systems. It is interesting that in the mixed
alkali systems, glasses can be made with
remarkably high alkali contents e.g.
72mol% R 2 O (ft* = 1.25). Such glasses
consist predominantly of small anionic
groups i.e. of mixtures of orthophosphate
and pyrophosphate anions.
A limited amount of work by paper
chromatography has also been carried out
on calcium and zinc phosphate glasses
(Meadowcroft and Richardson, 1965) with
similar results.
In borophosphate glasses, Scagliotti
et al. (1987) have shown by Raman spec-
troscopy how the BO4 groups act as links
between the phosphate chains with a con-
sequent increase in Tg. Villa et al. (1987)
have reported MAS NMR results on the
same series of glasses.
5.10 Germanate Glasses 315
5.10 Germanate Glasses
Glasses containing high percentages of
germania are rarely, if ever, used. The ox-
ide is expensive and the glasses have little
not be obtained in other ways. The oxide
has, however, been used instead of silica as
a minor constituent to improve the stabil-
ity against devitrification of calcium alumi-
nate infrared transmitting glasses (Sec.
5.11). The benefit is a slight shift of the long
wavelength transmission cut-off further
into the infrared. The oxide is also used as
a minor constituent to increase the refrac-
tive index in silica-based material for com-
munication fibres.
5.10.1 Germanium Dioxide Glass
The melt is very viscous (Fig. 5-10) and
readily forms a glass on a scale of many
grams. The melting and crystallization ki-
netics have been studied in detail by
Vergano and Uhlmann (1970 a, b) who ob-
served that the rate of crystallization was
affected by the stoichiometry of the mate-
rial. Oxygen deficient material crystallizes
more rapidly than the stoichiometric, the
opposite trend to that observed for silica.
This behaviour of GeO2 may be related to
the fact that the oxygen deficient melt has
a lower viscosity.
5.10.2 Regions of Glass Formation
in Germanate Systems
Imaoka (1962) has determined the re-
gions of glass formation in a number of
binary systems, melting on a scale of 1 - 3 g
and allowing the melt to cool in the
crucible (Table 5-7).
Nassau and Chadwick (1982) studied
glass formation in 21 binary melts of the
composition MOX • 9 GeO2 (melted in a
platinum crucible and water quenched).
316 5 Oxide Glasses
Table 5-7. Regions of glass-formation in binary ger-
manate systems (Imaoka, 1962).
Second oxide Region of glass formation (mol%)
Li2O 0-23.8
Na 2 O 0-38.0
K2O 0-59.5
CaO 15.5-35.5
SrO 14.0-39.0
BaO 0-10.0 and 17.5-29.6
T12O 0-47.5
ZnO 0-48.0
PbO 0-57.0
Bi2O3 0-34.0
Only a few systems gave clear glasses with
no sign of phase separation (M = Rb, Cs,
Tl, Pb, Bi, Sb, Ti). Some partly crystallized
(M = Sr, Ba, Zn, Ga, Mo, W) whilst others
showed excessive vaporization or could
not be melted. Three- and four-component
glasses were found to be much more stable.
Murthy and Scroggie (1965) have shown
that there are extensive regions of glass for-
mation in the alkali-aluminogermanate
glasses, especially those containing Na 2 O
and K 2 O and that the glass-forming region
is bounded on one side by the R2O/A12O3
tie line. This observation is at variance
with that of Trojer and Geyer (1972) who
were able to study the effects of composi-
tion on melt viscosities and glass refractive
indices for compositions on both sides of
the line.
5.10.3 Structure
Investigations have been carried out,
using various techniques, to study the co-
ordination number of germanium in ger-
manate glasses and melts. All the germa-
nium ions are four-coordinated in GeO 2
glass (Desa et al, 1988), but the addition of
alkali converts some to sixfold co-ordina-
tion. The higher co-ordination number is
also found in some crystalline alkali ger-
manates e.g. Na 4 Ge 9 O 2 0 and in the tetrag-
onal form of the crystalline oxide. The
change of Ge co-ordination with composi-
tion is shown by the XAFS and XRD work
of Sakka and Kamiya (1982) on alkali ger-
manate glasses, by XRD on Na 2 O-GeO 2
melts (Kamiya et al., 1986), and by X-ray
chemical shift measurements on N a 2 O -
GeO 2 glasses (Yin et al., 1984).
Smets and Lommen (1981 a) used photo-
electron spectroscopy, a technique sensi-
tive to the presence of non-bridging oxy-
gens, to study alkali germanate and alkali
silico-germanate glasses. They concluded
that up to 20 mol% alkali, the co-ordina-
tion number of some of the Ge ions is
changed from 4 to 6. Only beyond that
composition are non-bridging atoms
formed. Their conclusions are similar to
those obtained earlier by Raman spectros-
copy (Verweij and Buster, 1979) and may
be summarized as follows:
x = 0-0.18 GeO 6 groups are formed
with no non-bridging oxy-
gens,
x = 0.18-0.33 addition of alkali results
in the breakdown of some
GeO 6 , octahedra with one
NBO being formed per oc-
tahedron,
x = 0.33-0.5 germanate and silicate
glasses are isostructural in
this region.
(In the above, x represents the mole frac-
tion of R 2 O in the glass.)
In these simple glasses, the maximum
value of N 6 , the fraction of Ge atoms in
6-coordination, is about 0.25.
5.10.4 Properties
Structural changes of the kind described
in the previous section were earlier inferred
from studies of the effects of composition
on the properties of germanate melts and

glasses (Ivanov and Epstropiev, 1962;
Riebling, 1963 a, b). Thus in the R 2 O -
GeO 2 systems, there are maxima at be-
tween 10 and 20 mol% R 2 O in the curves
relating density or refractive index to com-
position (Murthy and Ip, 1964).
More recent property studies which in-
clude structural interpretation of the re-
sults are those of Riebling (1972) of (Ag,Tl)
aluminogermanates, Riebling and Kotian
(1973) of thallium germanosilicates, Rieb-
ling (1973) of (Na, K, Ag, Tl) germanates
and Osaka et al. (1986) of alkali ger-
manates.
Trojer and Geyer (1972) determined the
activation energy for viscous flow of melts
and the refractive indices of glasses in the
R 2 O aluminogermanate systems with a
constant GeO 2 content of 60 mol% and
with the R2O/A12O3 ratio increasing and
crossing the R2O/A12O3 = 1 line. The ef-
fects observed were very similar to those in
the corresponding aluminosilicate systems,
which have been interpreted in terms of a
change in the co-ordination number of the
Al (Sec. 5.8.2). There was no indication in
these compositions of any change in the
co-ordination number of germanium.
Other property-composition studies in-
clude Topping et al. (1974a) on PbO-GeO 2
glasses, Topping et al. (1974 b) on P b O -
GeO 2 SiO2 glasses and Nassau and Chad-
wick (1983) on (PbO, T12O, Bi 2 O 3 )-GeO 2
glasses.
5.11 Aluminate Glasses
Glasses in the CaO-Al 2 O 3 system were
discovered in the course of phase diagram
studies of that system and of the ternary
MgO-CaO-Al 2 O 3 system (Sheperd et al.,
1909). Glass formation is possible in small
melts (a few mg) when rapidly cooled. The
region of glass formation shown in Fig. 5-3
5.12 Tellurite Glasses 317
is for a 20 mg scale of melting, the melt
cooling freely in air.
The addition of ca. 5% of silica or ger-
mania greatly increases the stability so that
glass formation becomes possible on a
scale of many grams (Stanworth, 1948 a;
Sun, 1946, 1949). The aluminate glasses
transmit to somewhat longer wavelengths
in the infra-red than do the silicates and,
when vacuum melted to remove the IR ab-
sorbing - O H impurity, they have impor-
tant applications in various IR detection
systems, provided that the emitter is at a
relatively high temperature. The commer-
cial glasses can be made on a scale of kilo-
grams (Worrall, 1968). The development of
the manufacturing technology has been de-
scribed by Davy (1978).
The stability of the glasses is also im-
proved by making the composition more
complex and in this way Florence et al.
(1955) and Hafner et al. (1958) were able to
produce silica-free glasses on a commer-
cially useful scale. Elimination of the silica
results in a useful improvement in the long
wavelength IR transmission.
The glasses require high melting temper-
atures (ca. 1400°C) and have high Tg tem-
peratures (ca. 800 °C). Their thermal ex-
pansion coefficients are similar to those of
commercial soda-lime-silica glasses.
Glass formation also occurs in the re-
lated CaO-Ga 2 O 3 system (Baynton et al.,
1957 b; Wichard and Day, 1984). A number
of investigations have been made on this
system and especially on the gallosilicate
glasses with interesting results. However
there are no indications that these glasses
are of technological interest.
5.12 Tellurite Glasses
Tellurite glasses were first studied in de-
tail by Stanworth (1952, 1954). They are
318 5 Oxide Glasses
easily prepared by melting at low tempera-
ture - usually below 1100 °C. The melts are
very fluid and are easily homogenized. For
many compositions, specimens ranging up
to tens of grams can be made simply by
casting the melt into a metal mould. The
colour of the glass depends on the purity of
the raw materials used but it is usually pale
yellow. Their most notable properties are
the high refractive index (up to 2.3) and
high thermal expansion coefficient (up to
250 • 10~7 C" 1 ). Transformation tempera-
tures are low. Resistance to atmospheric
attack is generally good. Technological ap-
plications have been limited and only two
or three glasses of high TeO2 content are
commercially available as optical glasses.
Although Te forms two oxides, TeO2
and TeO3, and corresponding oxysalts, the
glasses are based on the lower oxide. The
structures of several crystalline tellurites
have been determined and the results used
to guide the interpretation of structural
studies of the glasses.
5.12.1 Glass Formation
in Tellurite Systems
It is uncertain whether or not pure TeO2
forms a glass. Stanworth (1954) originally
believed it did, but the glass in question
had been melted in an alumina crucible
and was found to contain several percent
of dissolved alumina which stabilizes the
glass. When the experiment was repeated
using a gold crucible, the melt devitrified.
However Bridge et al. (1986) report that a
TeO2 glass can be prepared, melted in alu-
mina but containing as little as 1.5% of the
oxide. They discount the significance of the
alumina contamination but stress the im-
portance of the temperature at which the
melt is cast. To obtain a "pure" TeO2 glass,
the melt should be cast at as low a temper-
ature as possible, when it is relatively vis-
cous.
The chemistry of TeO2 indicates that it is
an acidic oxide. It forms a number of crys-
talline compounds with basic RO and R 2 O
oxides but does not form compounds or
low melting point melts with SiO2. How-
ever it does form glasses with the other
glass-forming oxides B 2 O 3 , P2O5 and
GeO 2 . For these three systems, the ranges
of glass formation are (Vogel et al., 1974 d):
10-100 mol% GeO 2 ,
2-100mol% P 2 O 5 ,
12-100mol% B 2 O 3 .
The useful range of glass formation is
limited by immiscibility in the GeO 2 - and
B2O3-systems. In the former, immiscibility
is observed in glasses above 30 mol%
GeO2 and in the latter above 26.4 mol%
B 2 O 3 . Immiscibility in the TeO 2 -B 2 O 3
system has been studied in detail by Burger
et al. (1984).
Extensive studies to determine the re-
gions of glass formation have been carried
out by Imaoka (1962) and more recently by
Vogel et al. (1974, a, b, c, d) and Kozhu-
karov. et al. (1983). Glass formation has
been reported in a very large number of
binary and ternary oxide systems with
glasses being made on such a scale as to
make possible their practical application,
should the need arise. The systems studied
include binaries of TeO2 with:
1. Alkali and alkaline earth oxides
(Vogel etal., 1974 a).
2. The group: ZnO, A12O3, T12O, PbO,
Nb 2 O 3 , Ta 3 O 3 , WO 3 , La 2 O 3 , TiO 2 , ThO 2
(Vogel etal., 1974b).
3. Transition metal oxides (Kozhukarov
etal., 1978).
Amongst the more stable glasses are
those studied earlier by Stanworth i.e.
those in the systems: BaO-TeO 2 (8-35.7
mol% BaO), PbO-TeO 2 (12.8-22.6 mol%
PbO), WO 3 -TeO 2 (8.5-44.0 mol% WO3)
and V 2 O 5 -TeO 2 (7.5-58.0 mol% V2O5).
Regions of glass formation are limited in

systems containing the alkaline earth ox-
ides (other than BaO) and no glasses could
be made in the system containing CaO.
Glass formation was also absent from bi-
nary systems containing Cr 2 O 3 , Fe 3 O 4 ,
NiO andNi 2 O 3 .
It is remarkable that amongst the forty
or so binary systems investigated, only six
showed no sign of glass formation. The
glasses of Vogel, Kozhukarov et al. were
melted in gold or platinum crucibles on a
scale of 20-100 g and cooled relatively
slowly (8-10°C s"1) through the transfor-
mation range.
Glass formation has been reported in
many binary systems containing halides
and sulphates (Vogel et al., 1974 c). The use
of chlorides or bromides made glass-for-
mation easier than when the correspond-
ing oxides were used.
Vogel (1985) gives a useful summary of
the regions of glass formation in the binary
systems.
From this account of glass formation in
binary systems, it is not surprising that
there should be extensive regions of glass
formation in many ternary and quaternary
systems. Work on these more complex sys-
tems have been described by Marinov et al.
(1983).
5.12.2 Structure
Johnson et al. (1986) have summarized
the results of earlier structural studies of
tellurite glasses and related crystalline
compounds when reporting their own neu-
tron diffraction results for a V 2 O 5 -TeO 2
glass. This material contained 90 mol% of
TeO2 and would be expected to show the
structural features of a tellurite rather than
those of a vanadate glass. They conclude
that the glass structure contains units hav-
ing some similarity to those found in one
of the crystalline polymorphs of TeO2, /?-
5.13 Vanadate Glasses 319
o
o
6 6
Figure 5-30. (a) TeO4 and (b) Te2O6 structural units
(from Johnson et al., 1986).
TeO2. This unit, it is suggested, should be
considered to be a distorted trigonal bi-
pyramid. How the units are joined together
is not clear.
Their summary of structural studies of a
variety of binary tellurite glasses shows
that many kinds of structural unit have
been proposed, all with the tellurium atom
asymmetrically placed relative to the adja-
cent oxygens (Fig. 5-30).
In the V 2 O 5 -TeO 2 system, there is a
change in the co-ordination number of the
Te atoms from 4 to 3 at high V2O5 contents
(Dimitriev et al., 1977; Dimitriev and Di-
mitrov, 1978).
5.13 Vanadate Glasses
Most of the interest in vanadate glasses
has arisen from the fact that they are semi-
conductors with room temperature resis-
tivities which can be as low as l Q m , de-
pending on the V2O5 content and the
melting conditions. In general the melts are
very fluid. Also additions of V2O5 to borate
and phosphate melts, for example, greatly
reduce their viscosities. Use has been made
of this fact to develop low softening point
glasses.
320 5 Oxide Glasses

5.13.1 Glass Formation By very rapid cooling (i.e. roller quench-

ing), Dimitriev et al. (1981) were able to
Vanadium pentoxide melts at ca. 660 °C show that glasses could also be made in
and forms a glass only when very rapidly binary systems containing Li 2 O, Cu 2 O,
cooled (Wright, 1984; Rivoalen et al., CuO, Ag2O, MgO, CaO, SrO, CdO, B 2 O 3 ,
1976). In a number of binary systems, A12O3, Ga 2 O 3 , Nd 2 O 3 , CeO 2 , WO 3 ,
glasses are readily formed on a scale of Fe 2 O 3 , TiO 2 , Nb 2 O 3 , MnO, CoO, Cr 2 O 3 ,
several grams simply by casting the melt MoO 3 , NiO, SnO 2 , ZrO 2 , SiO2. The lower
into a cold steel mould. melting compositions were melted in
The regions of glass formation in several glazed porcelain crucibles. Those with
binary systems are given in Table 5-8. melting temperatures above 1100°C were
Although the glass-forming regions are melted in alumina. These simple binary
narrow in the barium and lead vanadate glasses are unlikely to be of any practical
systems, glasses in these systems can easily interest, though some could be if stabiliz-
be made on a scale of some tens of grams ing oxides were added.
by the addition of small percentages of
Another system in which glasses form
P 2 O 5 , TeO2 or GeO 2 . The addition of
only by rapid quenching is the Bi 2 O 3 -
B 2 O 3 has a similar effect on the zinc vana-
V2O5 system. Glass foils 0.5-1.0 mm thick
date glasses. Thus there is a wide range of
can be made by pressing the melt between
vanadate glass compositions available for
metal blocks. Ghosh et al. (1987) have
study and application.
studied the properties of these glasses in
Even without the addition of glass-form-
detail.
ing oxides, many stable glasses can be
Small percentage additions of V2O5 have
made containing between 30 and 70 mol%
been used in the development of low soft-
V2O5 simply by adding further compo-
ening point borate and phosphate glasses
nents i.e. making the composition more
(Denton and Rawson, 1956; Ray et al.,
complex. Thus stable glasses have been
1973 a, b; Wozniak and James, 1984).
made by Kawamoto et al. (1979) in the
system V 2 O 5 -BaO-K 2 O-ZnO. They also
studied the glass properties and some as- 5.13.2 Properties
pects of the phase diagram.
Most of the vanadate glasses, except
Table 5-8. Regions of glass formation in binary vana- those with a high P2O5 content, have a
date systems (Denton et al., 1954; Denton and Raw- good resistance to attack by normal ambi-
son, 1956). ent conditions. They can be enamelled
System Mol% Crucible used onto substrates of matched expansion co-
v2o5 efficient without difficulty. Thermal ex-
pansion coefficients are high (typically
P2O5-V2O5 <94 Platinum >100-10~ 7 o C" 1 ) and the expansion
GeO 2 -V 2 O 5 6-64 Platinum
TeO 2 -V 2 O 5 9-57 Silica and alumina curves are typified by an unusually large
As 2 O 3 -V 2 O 5 >52 Silica and aluminaa increase in slope above Tg.
BaO-V 2 O 5 58-69 Platinum The melts and glasses are far from stoi-
PbO-Y 2 O 5 51-67 Silica and alumina chiometric. For example, Szorenyi et al.
ZnO-V 2 O 5 46-72 Platinum (20 mg)
(1982) show that the V 4+ /V total ratio in-
a
Maximum content of As 2 O 3 limited by volatil- creases with the P 2 O 5 content in V 2 O 5 -
ization. P 2 O 5 glasses to more than 0.5 at 45 mol%

P 2 O 5 . The stoichiometry is also affected by
the melting atmosphere and the melting
temperature. The glasses are green or
brown when blown into thin films, but
thicker sections appear black. That they
are semiconductors was first shown by
Baynton et al. (1957 a), the first occasion on
which semiconductivity had been observed
in an oxide glass system. Studies on other
semi-conducting oxide glasses soon fol-
lowed, as part of a very large research effort
on the physics of conduction in amorphous
solids.
Electrical properties have been reviewed
by Owen (1970, 1977).
Structural studies have probably not
given sufficient attention to the effects of
melting conditions on the degree of stoi-
chiometry or have followed up indications
in the literature that some compositions
may be phase separated (Szorenyi et al.,
1980, 1982; Janakarama-Rao, 1966).
5.13.3 Structure
The available structural information on
vanadate glasses has been summarized by
Wright et al. (1985). On the basis of their
neutron diffraction study of P2O5-, BaO-
and PbO-V 2 O 5 glasses, they note that
there are no close similarities between the
structures of the glasses and those of re-
lated crystalline compounds. In all three
glass systems there is a vanadate network
'composed of interconnected, distorted tri-
gonal bipyramids'. The vanadium-oxygen
co-ordination polyhedra and the linkage
between them appears to be less regular
than in corresponding phosphate glasses
and crystals.
5,14 Mixed Anion Glasses
A very wide range of compositions can
be made and properties obtained within
5.14 Mixed Anion Glasses 321
the range of oxide glasses. This can be ex-
tended even further by the partial substitu-
tion of the oxygen anions by nitrogen or
halogen anions. This type of substitution
affects the cross-linking within the network
and greatly modifies the properties.
5.14.1 Oxynitride Glasses
The preparation and properties of these
materials has been summarized by Loeh-
mann (1985).
They first became of interest when it was
noted that the intergranular phase in sili-
con nitride and oxynitride ceramics is
partly vitreous. Subsequently many oxyni-
tride glasses were prepared and their prop-
erties studied.
The most effective method for making
nitrogen-containing silicate glasses is to
melt together mixtures of oxide and nitride
powders in a protective atmosphere of ni-
trogen or argon. In this way nitrogen con-
tents of ca. 10at.% can be attained. An-
other method is to heat a silicate gel com-
position containing a high concentration
of - O H groups in an atmosphere of am-
monia (Brinker, 1982).
If the composition contains alumina, the
nitrogen solubility is increased and the
melt more readily forms a glass. It has been
suggested that the beneficial effect of alu-
mina is related to the fact that the A1O4
and Si (O, N) 4 tetrahedra are of similar size
(Jack, 1977). Also the aluminium and oxy-
gen ions readily substitute into the lattice
of crystalline Si 3 N 4 to form phases such as
jg-SiAlON.
Substitution of divalent oxygen by triva-
lent nitrogen increases the degree of cross-
linking in the network. Presumably each
nitrogen anion is shared between three te-
trahedra - another violation of the Zacha-
riasen rules. The properties change with
increasing nitrogen content in a way to be
322 5 Oxide Glasses

1000-
{= 7-

it= 6"~

900-

Figure 5-31. Effect of nitro-

/ gen content on Tg and ex-
pansion coefficients of
glasses in the system
800- Y - S i - A l - O - N (from
Loehmann, 1985).
i i i I i i
2 L 6 2 L 6
Atomic percent nitrogen Atomic percent nitrogen

expected from increased cross-linking. 5.14.2 Oxyhalide Glasses

Thus Fig. 5-31 shows the effect of increas-
Substitution of oxygen anions by halo-
ing nitrogen content on properties of
gen anions has the opposite effect to that
glasses in the system Y - S i - A l - O - N .
produced by the nitrogen substitution. The
Their compositions are given in Table 5-9.
degree of cross-linking within the network
The marked decrease in expansion coeffi-
is reduced.
cient and increase in glass transformation
Large percentages of halides can be in-
temperature both indicate an increase in
troduced into most low-melting point ox-
the degree of cross-linking. Oxynitride
ide glass, especially into phosphate and bo-
glasses based on phosphate glasses have
rate compositions. In silicate melts, similar
been studied by Marchand (1983) and on
to commercial soda-lime-silica composi-
borate glasses by Wilder (1980), and Wil-
tions, the addition of more than 2 - 3 % of
der et al. (1983).
a halide results in the crystallization of a
halide phase on cooling. This is the basis
for the manufacture of the well-known flu-
Table 5-9. Compositions of Y - S i - A l - O - N glasses oride opal glass (Rothwell, 1956).
(Loehmann, 1985). Extensive development work has been
carried out on fluorophosphate glasses,
Sample Glass composition (at.%)
number initially for use as optical glasses but more
Y Si Al O N recently for use in high power lasers. It is
interesting that stable glasses can be made
SG6 10.3 17.6 11.7 54.0 6.5 with P2O5 contents as low as 2%. Thus
SG7 6.4 19.0 9.9 57.6 7.0
SG8 5.6 20.3 8.1 60.3 5.7
Heidenreich (1983) made a wide-ranging
SG10 8.9 20.9 2.8 65.8 1.6 study of glasses containing 3.4 mol%
SG11 16.6 15.0 3.2 63.6 1.5 Ba(PO 3 ) 2 , the rest of the composition be-
SG12 12.7 18.6 6.7 57.6 4.4 ing made up of mixtures of the fluorides of
SG13 15.2 14.3 7.9 57.5 5.1 Mg, Ca, Sr, Ba and Al.
SG14 9.6 18.8 7.5 57.8 6.3
SG15 16.6 15.0 3.2 65.1 0.
Some compositions of high halide con-
tent have very high ionic conductivities

and are being studied for possible use as
battery electrolytes (Ravaine, 1985; Mi-
nami, 1985). Examples of some of these
unusual compositions are the following:
0.7 LiPO 3 • 0.3 (LiCl, LiBr, Lil); 0.85 Agl
• 0.15 Ag 4 P 2 O 7 ; 0.60 Agl • 0.30 Ag2O •
10B 2 O 3 .
5.15 Ionic Salts
and Solution Glasses
This section deals with groups of oxide
glasses which are quite different from those
described earlier. They consist of simple
salts such as nitrates, sulphates or acetates,
the structures of which contain discrete an-
ions. Often glass formation is confined to
certain ranges of composition in binary or
more complex mixtures of these salts or in
aqueous solutions containing them. How-
ever there is no anionic network as in the
glasses considered earlier and hence the
concepts of network former and network
modifier are not relevant, nor are the
Zachariasen rules.
There may therefore be some difficulty
in understanding why such materials form
glasses. In a valuable summary of this
group of materials, Angell (1983) implies
that an important factor is the 'geometrical
asymmetry of the anion and the packing
problems that follow, particularly in un-
balanced cation force fields'. This view is
also expressed by Thilo et al. (1964) and
van Uitert et al. (1971) who have made
extensive studies of glass-formation in ni-
trate and acetate systems respectively.
They note that glass formation is most
probable in those systems in which the
electrical field strength, z/r2, of the two
cations differ by 0.7 or more. It is suggested
that the higher field strength cations tend
to form clusters with the anions and that
5.15 Ionic Salts and Solution Glasses 323
these inhibit the nucleation of crystalline
phases with different structures.
No doubt structural factors have impor-
tant effects on the kinetics of nucleation
and crystal growth but one should also
note that in these systems, the regions of
glass formation usually coincide with re-
gions of low liquidus temperature. It may
be sensible to enquire to what extent the
shape of the liquidus curve is determined
by the cation field strength difference.
Structure, melting and glass formation are
clearly interrelated. One needs to examine
all the interrelationships before one can
form a view as to which is the most impor-
tant. The opportunities for doing so are
probably greater in the ionic salt systems
than in the technologically more impor-
tant but structurally more complex glass-
forming systems.
Some of the pure salts themselves have
low melting points. Thus the alkali metal
nitrates melt at much lower temperatures
than the corresponding chlorides. This is
discussed further by Rawson (1967).
5.15.1 Nitrate Glasses
Dietzel and Poegel (1954) made the first
detailed study of a binary nitrate glass-
forming system -KNO 3 -Ca(NO 3 ) 2 . The
region of glass formation was found to be
54-67 mol% KNO 3 , the most stable glass
having the composition 60mol% KNO 3 ,
40 mol% Ca(NO 3 ) 2 with a Tg as low as
60 °C. This glass is very stable indeed with
a maximum crystallization rate as low as
the most stable of the sodium silicate
glasses. The eutectic temperature is 146 °C,
much lower than the melting points of
the constituent nitrates (KNO 3 337 °C,
Ca(NO 3 ) 2 561 °C).
Thilo et al. (1964) and van Uitert et al.
(1971) have investigated many other ni-
trate systems containing both univalent
324 5 Oxide Glasses
and divalent cations. Although the liq-
uidus effect is evident, it is interesting that
the glass-forming region does not always
contain the eutectic composition. Angell
(1983) draws attention to the difficulty of
dehydrating some compositions. It is pos-
sible therefore that some of the glass-form-
ing regions reported are for poorly defined
compositions.
Angell and Helphrey (1971) have shown
that stable glasses can be made in nitrate
systems containing only monovalent ions
(e.g. LiNO 3 -AgNO 3 -NH 4 NO 3 ).
5.15.2 Acetate Glasses
Although carbonate glasses can be
made, usually by melting under pressure,
considerably more work has been carried
out on the acetates. From the viewpoint of
anion shape, the acetate ion can be thought
of as a carbonate ion with one of its oxy-
gens substituted by a methyl group, thus
reducing its symmetry and favouring glass
formation.
The acetate glasses have been studied by
Bartholomew and Holland (1969), Duffy
and Ingram (1969) and van Uitert et al.
(1971). Glass transition temperatures are
approximately 30 °C higher than for the
corresponding nitrate glasses and they are
more resistant to atmospheric weathering.
5.15.3 Sulfate Glasses
The first mixed cation sulfate glass to be
studied was KHSO 4 (Forland and Weyl,
1950). An equimolar KHSO 4 -NaHSO 4
glass was subsequently found to be ex-
tremely resistant to crystallization. Several
studies have been made of glasses and glass
formation in the ZnSO 4 -K 2 SO 4 system
(Ishii and Akawa, 1965; Angell, 1965;
Kolesova, 1975; Narasimhan and Rao,
1978), in the Tl 2 SO 4 -ZnSO 4 system (Ishii
and Akawa, 1965) and in the NH 4 SO 4 -
ZnSO 4 system (Wong, 1970).
5.15.4 Hydrates and Aqueous Solutions
Many crystalline hydrates melt at tem-
peratures lower than the corresponding
anhydrous salts. In some e.g. Ca(NO 3 ) 2
• 4 H 2 O the water molecules co-ordinate
the cation. In others, e.g. K 2 S 2 O 3 • 5H 2 O,
they co-ordinate the anion. Glass forma-
tion and glass properties have been investi-
gated in many binary mixtures of hydrates
of both types (Angell and Helphrey, 1971;
Moynihan, 1966; Moynihan et al., 1969;
Jain, 1978).
Vuillard (1954, 1955, 1957) has shown
that many concentrated aqueous solutions
of inorganic acids, bases and salts readily
form glasses. Shepley and Bestul (1963) and
Angell and Sare (1970) have investigated
some systems in detail and have deter-
mined the phase diagrams.
Although none of the glasses listed in
this section is likely to be of any technolog-
ical importance, they are all of consider-
able scientific interest and importance. Ex-
perimentation with such low melting point
materials is in general easier than with the
higher melting oxide systems and their
study gives a broader perspective to the
study of oxide glasses in general. It may
indeed throw light on many unsolved ques-
tions relating to the more conventional
glasses.
5.16 References
Ahmed, A. A., Abbas, A.R, Solman, S. M. (1985),
Phys. Chem. Glasses 26, 17-23.
Ainslie, N. G., Morelock, C. R., Turnbull, D. (1962),
in: Symposium on Nucleation and Crystallization
and Melts: Reser, M.K., Smith, G., Insley, H.
(Eds.). Columbus, OH: American Ceramic Soci-
ety, pp. 97-107.
Angell, C.A. (1965), J. Am. Ceram. Soc. 48, 540.

Angell, C.A., Sare, E. (1970), J. Chem. Phys 52,
1058-1068.
Angell, C. A., Helphrey, D. B. (1971), J. Phys. Chem.
75, 2306-2312.
Angell, C.A. (1983), in: Glass Science and Technol-
ogy, Vol.1: Glass-Forming Systems: Uhlmann,
D.R., Kreidl, N . I (Eds.). London: Academic
Press, pp. 209-223.
Araujo, R. J. (1979), Phys. Chem. Glasses 20, 115,
Araujo, R. J. (1983), /. Non-Cryst. Solids 58, 201-208.
Baeten, M.H.C., Stein, H.N., Stevels, XM. (1972),
Silicates Ind. 37, 33-36.
Bartholomew, R., Holland, H. (1969), /. Am. Ceram.
Soc. 52, 402-403.
Baynton, P. L., Rawson, H., Stanworth, J. E. (1957 a),
J. Electrochem. Soc. 104, 237-240.
Baynton, P. L., Rawson, H., Stanworth, J. E. (1957b),
Nature 179, 434-435.
Beales, K.J., Day, C.R. (1980), Phys. Chem. Glasses
21, 5-21.
Bell, T., Hetherington, G., Jack, K.H. (1962), Phys.
Chem. Glasses 3, 141-146.
Bergeron, C, G. (1978), in: Borate Glasses: Pye,
L.D., Frechette, V.D., Kreidl, N . I (Eds.). New
York: Plenum Press, pp. 445-461.
Berzelius, XI (1834), Ann. Phys. Chem. 32, 511.
Bray, P.X (1978), in: Borate Glasses: Pye, L.D.,
Frechette, V.D., Kreidl, N.X (Eds.). New York:
Plenum Press, pp. 321-351.
Bray, P. X, O'Keefe, X G. (1963), Phys. Chem. Glasses
4, 37-46.
Bridge, B., Bavins, T. E., Woods, D., Woolven, T.
(1986), J. Non-Cryst. Solids 88, 262-270.
Brinker, C.X (1982), /. Am. Ceram. Soc. 65, C 4 - 5 .
Brown, S. D., Kistler, S. S. (1959), J. Am. Ceram. Soc.
42, 263-270.
Bruckner, R. (1964), Glastech. Ber. 37, 413-425.
Bruckner, R. (1978), Glastech. Ber. 51, 1-7.
Burger, H., Vogel, W, Kozhukharov, V., Marinov,
M. (1984), J. Mater. Sci. 19, 403-412.
Button, D.P., Tandon, R., King, C , Velez, M.H.,
Tuller, H. L., Uhlmann, D. R. (1982), /. Non-Cryst.
Solids 49, 129-142.
Cahn, X W, Charles, R. X (1965), Phys. Chem. Glasses
6, 181-191.
Chechetkina, E. A. (1990), to be published in /. Non-
Cryst. Solids.
Cohen, H. M., Turnbull, D. (1961), Nature 189, 131-
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5.16 References 329
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330 5 Oxide Glasses
General Reading
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Wong, X, Angell, C. A. (1976), Glass Structure by
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Zallen, R. (1983), The Physics of Amorphous Solids.
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Masson
Zarzycki, J. (1991), Glasses and the Vitreous State.
Cambridge: Cambridge Univ. Press.
6 Optical and Magnetic Properties of Ion Implanted Glasses
Robert A. Weeks

Department of Materials Science and Engineering, Vanderbilt University,

Nashville, TN, U.S.A.

List of Symbols and Abbreviations 332

6.1 Introduction 334
6.2 Distribution of Implanted Ions in Wide Band-Gap Materials 336
6.2.1 Atomic Collisions and Ionization Processes 336
6.2.2 Distributions of Implanted Ions 338
6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses 340
6.3.1 Optical Absorption Spectra, and the Imaginary Part of the Refractive Index 341
6.3.1.1 Optical Absorption Spectra of Glasses Implanted
with H, He, Ne, Ar, Kr, Xe . 341
6.3.1.2 Ions from the First Transition Series of Elements 343
6.3.1.3 Refractive Index, Real Part 349
6.3.1.4 Infrared Spectra 351
6.3.2 Alkali Silicate Glasses 351
6.3.2.1 Noble Gas Ions 351
6.3.3 Multi-Component Glasses 352
6.3.3.1 Noble Metals 352
6.3.3.2 Halide Glasses 353
6.4 Non-Linear Optical Properties 353
6.5 Magnetic States 355
6.5.1 Paramagnetic Defect States of Silica Substrates 355
6.5.2 Magnetic Properties of Implanted Ions 359
6.5.2.1 Magnetic States of Implanted Oxygen in Silica 359
6.5.2.2 Elements of the First Transition Series 360
6.6 Glasses Produced by Implantation of Crystalline Substrates 368
6.7 Conclusions and Prognosis 370
6.8 References 371

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
332 6 Optical and Magnetic Properties of Ion Implanted Glasses

List of Symbols and Abbreviations

A absorptivity coefficient
B2 energy band
c speed of light
C contamination factor
E, E' energy center
Et electric field of the photons
F local field correction
/ volume fraction of particles
g g-tensor
h Planck's constant
H magnetic field
I intensity
k absorptivity
K extinction coefficient
Kahs extinction coefficient for absorption
kB Boltzmann constant
Kscat extinction coefficient for scattering
m integer smaller than 5
M magnetization
n complex refractive index
n neutron
n0 real part of the refractive index
n2 non-linear index
Nt number density of f th constituent ion
R particle radius
S spin
T absolute temperature
V volume per particle
a absorption coefficient
e electronic interaction processes
80 dielectric constant of the vacuum
X photon wavelength
\x nuclear interaction processes
v spectrometer frequency
X susceptibility
X(l) i'th term of the expansion of the susceptibility
Xt polarizability of fth constituent ion
CD photon frequency
CEMS conversion electron Mossbauer spectroscopy
EMR electron magnetic resonance
EPR electron paramagnetic resonance
 List of Symbols and Abbreviations 333

FMR ferromagnetic resonance

FWHM full width at half maximum amplitude
NBOH non-bridging oxygen
POR peroxy radical
TEM transition electron microscopy
334 6 Optical and Magnetic Properties of Ion Implanted Glasses
6.1 Introduction
Optical properties of oxide glasses have
been of interest since the first papers on
glass were published. These first "papers"
were clay tablets and the language was
cuneiform and they were published about
4000 years ago (Oppenheim et al., 1970).
The efforts of these glass scientists were to
prepare glasses with particular colors. Fol-
lowing their instructions Robert H. Brill
(1986) reports that the glasses produced in
his laboratory do have the colors described
in the original reports.
The properties of oxide glasses contin-
ued to be a primary interest of glass makers
and scientists until approximately 1900
A.D. Since then oxide glasses have become
a subset of the universe of solid materials
which can be formed into a non-crystalline
form. Some of the materials which are now
part of this universe are metals, semi-con-
ductors, other chalcogenides, halides, and
organic compounds. With the develop-
ment of communication technologies in
which oxide glasses form a critical part re-
search into the interaction between pho-
tons with energies in the range of ~0.1 to
~ 10 eV and wide band-gap glasses has be-
come important to the development of
these technologies.
The properties of wide band-gap glasses
which are of primary importance for opti-
cal technologies are electric and magnetic
susceptibilities. In many materials mag-
netic susceptibilities are small relative to
electric susceptibilities. Resolution of these
properties by measurement techniques are
possible. Most wide band-gap glasses have
electric susceptibilities in which first order
terms are many orders of magnitude
greater than higher order terms. In the past
photon sources did not have sufficient in-
tensity for the measurement of higher or-
der terms. With the development of lasers
and the increase in intensities of these
sources higher order terms in electric sus-
ceptibilities could be measured. Develop-
ment of glasses with greatly increased val-
ues of second and third order terms
became of interest.
The development of glasses with higher
values of the first order term or their mag-
netic susceptibilities and small values of
the first order term in their electric suscep-
tibilities is also of importance to the appli-
cations of glasses in optical technologies.
Some techniques by which these suscep-
tibilities are measured are optical (Raman,
infrared, visible, and vacuum UV) and
magnetic (electron paramagnetic reso-
nance, and nuclear magnetic resonance)
spectroscopies. These techniques may be
used to also measure the time-dependence
of the electronic excitations induced by
irradiation with the probing photons.
Pulsed lasers with pulse duration times of
the order of femto-seconds (fs) provide the
means for investigating processes which
may occur in times of the order of a few
atomic vibrations. The processes, by which
energy deposited into a glass by incident
photons is redistributed from the locale in
which the deposition occurs, affects the de-
position process. For example the de-
posited energy may be redistributed by
emission of another photon, by increasing
the vibration energy of the atoms in the
material, or by both processes. Other pro-
cesses may be involved such as disruption
of local atomic structure.
The electro-magnetic susceptibilities are
a function of the electronic states of a glass.
These states are determined by the atoms
and their structure comprising the glass.
First order terms of the susceptibilities
contain information about these states. A
major fraction of the literature on the elec-
tronic states of wide band-gap glasses is
derived from measurements of these terms.

One of the most important reviews of these
states in many glasses is found in the book
Glass: Structure by Spectroscopy (Wong
and Angell, 1976). Since that time there
have been a number of reviews of some of
the topics included in the Wong and Angell
book. An excellent review of electron para-
magnetic resonance spectroscopy of oxide
glasses has been published recently (Gris-
com, 1990).
In the past several years optical proper-
ties of glasses have been modified by diffu-
sion of ions into surface regions (Vogel
et al., 1989) and by exchanging ions
through diffusion (Brow et al., 1990). An-
other technique for modification is ion im-
plantation. There are many reasons for im-
planting glasses. They range from the wish
to study the fundamental physics and
chemistry of the effects, via the develop-
ment of practical devices such as optical
waveguides and lasers, to increasing the
fracture resistance and decreasing rates of
corrosion. Implantation into glasses can-
not disrupt crystalline order, hence order-
ing effects of the substrate on the im-
planted ions are minimal. The ion implan-
tation induced transition from the crys-
talline state to the amorphous state does
not occur in the case of glasses. Interac-
tions between implanted ions and sub-
strate ions are not those which occur for
interactions in thermal or chemical equi-
librium. Thus, the atomic and chemical
structure of implanted materials produced
under conditions far from equilibrium are
of fundamental interest.
The implantation process provides con-
trol over concentrations of ions, the depths
to which ions are implanted inside the sub-
strate, their distribution through implanta-
tion at various energies, mixtures of ions
by subsequent implantations, geometries
of implantation, chemical interactions be-
tween substrate ions and implanted ions
6.1 Introduction 335
and between implanted ions through con-
trol of substrate temperatures, and an in-
fluence over most of these parameters by
the imposition of external electric and
magnetic fields and thermal gradients.
Substrate composition is another vari-
able which has profound influence on the
consequences of implantation. Because the
compositions of glasses are extremely var-
ied, implantations have frequently been
made into relatively simple glasses in an
effort to reduce the varieties of implanted
ion-substrate ion interactions. The enor-
mous variety of glass forming materials
and compositions and the possibility of im-
planting almost the entire periodic table
provide a range of experiments that cannot
be encompassed within any theoretical
framework at the moment. Thus much of
the research is dictated by potential appli-
cations and guided by empirical experi-
ments.
Ion implantation into wide band-gap
crystalline materials will, in some materi-
als, produce an amorphous layer in the im-
planted region. For example, an amor-
phous layer can be produced on single
crystal A12O3 (sapphire) (McHargue et al.,
1989). These amorphous layers are also of
interest since they may have optical or
magnetic properties that have applications
in electronic and optical devices. In some
materials the mechanical and chemical
properties of surfaces can be changed to
improve their usefulness. Sapphire is also
a material for which such improvements
have been demonstrated (White et al.,
1989). We expect that there are a number of
materials used in optical devices for which
improved optical properties (e.g., decreases
in reflectivity of lenses), increase in resis-
tance to corrosive gases (e.g., windows in
excimer lasers), increases in mechanical
hardness (e.g., windows of chalcogenide
glasses for use in infrared devices), may be
336 6 Optical and Magnetic Properties of Ion Implanted Glasses
achieved through ion implantation of sur-
face regions of many materials. We expect
that there are many materials which can be
implanted to form optical waveguides in
integrated circuits (Townsend, 1987 a), to
form second harmonic generators (Oster-
berg, 1989), lasers (Townsend, 1987 b; Fri-
borg and Smith, 1987), optical switches
with switching times determined by the
mobilities of electrons in noble and other
metals (Hache et al., 1986) or graded-index
optical devices. This is only a partial list
of the potential applications for ion-im-
planted glasses and for amorphous layers
formed on crystalline substrates.
Materials that can be prepared in the
glassy state with current techniques are
metal alloys (see Vol. 15, Chapter 6), semi-
conductors, and an enormous range of in-
organic and organic compounds. The vari-
ety of glasses on which implantation exper-
iments have been performed is quite lim-
ited. Those glassy materials which have
wide band-gaps, > 2 eV, which are inor-
ganic and on which ion implantation ex-
periments have been performed are a sub-
set and consequently, much smaller in
number. It is this subset which will be dis-
cussed in this review.
The purview of this review will be:
i. Optical properties of ion-implanted
glasses, including first, second and third
order terms in the susceptibility of the glass
to electromagnetic radiation within the
band-gap of the material and ranging from
band-gap energies to the infrared vibra-
tional bands.
ii. Magnetic properties of implanted ions
and of the substrate modified by implanta-
tion.
iii. Optical and magnetic properties of
amorphous materials produced by im-
planting insulating crystalline substrates.
iv. Structures in the implanted materials.
v. Most of the glasses with which this
review will be concerned will be wide band-
gap materials.
The review will not be comprehensive,
that is, it will not note, neither in the cita-
tions nor in the text, all papers published
on these topics. The selection of papers is
idiosyncratic and, of course, biased to the
author's interests. The selection has also
been guided by our perception of good ex-
periments and those which may have tech-
nical applications at some time in the fu-
ture. A review of the literature clearly
shows that this topic of research is being
diligently pursued in only a few laborato-
ries. These laboratories are best identified
by reference to the names of a few individ-
uals in these laboratories whose names ap-
pear, almost consistently, with many co-
authors. The research of these individuals,
M. Antonini, G. W. Arnold, P. Mazzoldi,
A. Perez, P. D. Townsend and their collab-
orators, will be frequently cited in this re-
view.
6.2 Distributions of Implanted Ions
in Wide Band-Gap Materials
6.2.1 Atomic Collisions
and Ionization Processes
Implanting ions (+1 or + 2 charges)
into metals (see Vol.15, Chapter 6) or
semiconductors does not have the problem
of substrate charging which occurs in in-
sulating materials, i.e., wide band-gap ma-
terials. In the case of metals and semicon-
ductors attaching ground to a substrate
provides a route through which a charge to
compensate the charge introduced by im-
plantation can move into the implanted
material. In the case of wide band-gap
materials which may have resistivities
>10 1 8 Qcm at room temperature, the
 6.2 Distributions of Implanted Ions in Wide Band-Gap Materials
source of compensating charge and the
process of compensation is not evident. Be-
fore briefly reviewing the process of im-
plantation we will discuss briefly some as-
pects of the charging phenomenon when
implanting wide band-gap materials.
Charging of insulating materials when
irradiated with charged particles fre-
quently results in electrostatic discharges
within the material. Another consequence
is the growth of an electric field which re-
pels subsequent charges. Irradiation of
some insulating materials with a y-ray
beam also will produce catastrophic dis-
charges if there are trapping sites for the
Compton electrons, predominantly scat-
tered in the direction of the y-ray photons,
which are stable at the ambient tempera-
ture of the material (Gross, 1964; Hilczer
and Malecki, 1986; Weeks et al., 1977).
These effects may be ameliorated if there
are ions in the material with sufficient mo-
bility to redistribute in the electric field
produced by the added charge. This redis-
tribution reduces the field generated by the
additional charge. The field due to the irra-
diating particles may be compensated by
injection of charge of the opposite sign.
In the case of irradiating with positively
charged particles the injected charge would
be electrons. If the material is in contact
with an electron source, if the potential
barrier to injection is small and if the mo-
bility of the injected charge is not too small
then the charge added by irradiation may
be compensated. Both of these processes
appear to be active, depending upon the
material, when insulating materials are im-
planted with positively charged ions.
It is possible to implant insulating
glasses with a range of compositions with-
out catastrophic electrostatic discharges.
Some of the compositions which have been
implanted are silica, alkali silicates (Arnold
and Mazzoldi, 1987) and fluoro-zirconates
337
(ZBLAN) (cf. Chapter 8; Mazzoldi, 1990).
All of these glasses have resistivities at
room temperature, the usual temperature
of implantation, >10 1 2 ficm. Samples
used for these investigations have usually
been either discs with a thickness of
~ 1 mm or parallelpipeds with one dimen-
sion of the order of 1 mm. During implan-
tation, samples have been mounted on
grounded metal supports. Thus the sup-
port has provided a source of electrons to
compensate the positive implanted charge.
Zuhr and Weeks (1988) observed that a
discharge could be induced in silica disc
samples of 0.2 cm thickness mounted on a
grounded metal sample support when the
current was >20jiAcm~ 2 . The discharge
was between the planar faces of the sample.
The current in this case was more than an
order of magnitude greater than that used
to implant SiO2 in the experiments of
Whichard (1989). Beam currents used in
experiments are often not reported in pub-
lished papers. In view of the potential for
charging effects during implantation of in-
sulting materials, it is essential that experi-
mentalists report the conditions, average
(ions c m ~ 2 s - 1 ) and instantaneous cur-
rents, sample mounting geometries, and
grounding circuits for their experiments.
For ions with energies greater than a few
keV, the initial loss of energy after imping-
ing on a target is primarily through excita-
tion of substrate electrons (Biersack, 1987).
An implanted particle slows with this loss
of energy, elastic collisions with substrate
ions absorb the remainder of energy of the
implanted particle (Biersack, 1987). These
elastic collisions displace substrate ions
creating disorder in the substrate, or in the
case of glass substrates changing the al-
ready disordered structure to a different
type of disorder (Wittels and Sherill, 1954).
In the last part of the loss of energy by an
implanted ion, in the case of wide band-
338 6 Optical and Magnetic Properties of Ion Implanted Glasses
gap materials, the implanted ion changes
its charge state and reacts with substrate
ions to form an implanted phase (Perez
etal., 1987).
6.2.2 Distributions of Implanted Ions
The experimental and theoretical bases
for calculating the distribution of ions im-
planted in a solid material through the use
of a probe ion elastically scattered from the
substrate and implanted ion is thoroughly
described in many papers and books (see
also Vol. 15, Chapter 6). Only one reference
will be given here. It cites many of the most
pertinent references and it also provides a
table of ion ranges in many materials. It is
the first chapter in "Ion Beam Modifica-
tion of Insulators", written by Biersack
(1987). Calculations based on the TRIM
model (Biersack and Eckstein, 1984) give a
distribution of the implanted ion that is
approximately Gaussian about the mean
range projected on the velocity vector of
the ion beam. Implanting a planar surface
then results in a distribution of ions which
is shown in Figure 6-1 (Whichard, 1989). In
the case of a material in the glass phase
there is no channeling effect (Kelly, 1987).
Implanting ions with large mass, greater
than the mass of substrate ions, and with
energies of the order of a few keV, sputters
ions and atoms from the substrate (Kelly,
1987; Wang et al., 1987). Hence, there is a
loss of substrate material and implanted
ions. In some cases the loss of material by
sputtering has a significant effect on the
distribution as a function of distance from
the surface into which ions are implanted.
The range of an implanted ion is a func-
tion of ion energy and density of the sub-
strate. For low-density substrates the
range is larger than for high-density sub-
strates for identical ion energies. Implant-
ing an ion with an atomic mass greater
than that of substrate ions produces a back
scattering spectrum shown in Figure 6-1
(Whichard, 1989). The distribution of ions
as a function of distance from a surface on
which the implanted ions were incident can
be calculated. An example of such is the
TRIM 17 calculation. The distribution
shown in Figure 6-2 (Whichard, 1989) is
typical of the profile observed for many
ions with atomic masses >Si when im-
planted in a silicate glass at a single energy.
The partition of energy of implanted
H , He + , O + , Ar + , Kr + , and Xe + between
+
electronic and nuclear interactions is given
in Table 6-1 (Arnold, 1973). This table
shows that, for an energy of 250 keV, the
fraction of energy dissipated in nuclear in-
teractions increases with increasing atom
mass. Although the relative fractions of en-
ergy will change with changing implant en-
ergies, these partitions will be representa-
tive for most of the ion energies used in
experiments which will be reviewed here.
There are two reports, to our knowl-
edge, that describe implantations at a sin-
gle energy for which distributions do not
have Gaussian shapes. Arnold and Borders
(1977) observed a bimodal distribution of
Ag ions implanted in alkali silicate glasses.
In the other case (Whichard, 1989), a bimo-
dal distribution is observed for Cu-im-
planted samples of SiO2 glass in as-im-
planted samples when the implanted dose
Table 6-1. Partition of 250 keV accelerating energy
into electronic (s) and nuclear (u) interaction pro-
cesses for various ions.
Ions ji(keV) e (keV)
H+ 0.6 249.4
He + 6.5 243.5
O+ 67.6 182.4
A+ 158.4 91.6
Kr + 208.3 41.7
Xe + 221.7 28.3
 6.2 Distributions of Implanted Ions in Wide Band-Gap Materials 339

Mn implantation profile in SiO2

a Weeks C 0.014
A Weeks C 0.015
° Weeks C 0.016

Figure 6-1. Energy spectrum of

He + ions back-scattered from
6***www«rt^Don^ SiO2 glass implanted with Mn + .
0.4 0.6 0.8 1.0 1.2 1.4 1.6
Energy in MeV

Fe implantation profiles in SiO2

+ -0.95 E16 Fe-cm" 2 Weeks I 0.035

A -2.77 E16 Fe-cm" 2 Weeks I 0.036
x -5.43 E16 Fe-cm" 2 Weeks I 0,040

Figure 6-2. Depth profiles of Fe

implanted in SiO2 glass samples.
Energy of the ions was 160 keV,
at a current of 4 uA cm" 2 . Ion
backscattering data were used to
calculate the implanted ion distri-
butions.
0.00 0.05 0.10 0.15 0.20 0.25
Depth in pm

Cu implanted in SiO2

#68 5.4 E16/cm2

#67 2.8 E16/cm2
- #66 1.0 E16/cm2

)
o o
°0 Figure 6-3. Depth profiles of Cu
o o ions implanted in SiO2 glass
o samples. The energy of the ions
°o < > was 160 keV at a current of
OgA A
A
* ooo 4 uA cm" 2 . The TRIM calculation
w. °°O0
<fc>o< >v >§
«*$ ftA4 222f
was used to calculate the distribu-
tion.
0.00 0.10 0.20
Depth in |j
340 6 Optical and Magnetic Properties of Ion Implanted Glasses
was 10 16 ions/cm 2 and the ion energy was
160 keV. The distribution for three doses is
shown in Figure 6-3 (Magruder et al.,
1989). The bimodal distribution was ob-
served for substrate temperatures during
implantation which ranged from 100 to
673 K (Magruder et al., 1989).
Implantation of an ion at a single en-
ergy, with the exceptions noted above, pro-
duces a Gaussian distribution, the peak of
the distribution being determined by the
projected range of the ion in the material
implanted. By implanting ions at two or
more energies, distributions approaching a
step function can be produced. By choos-
ing energies with a sufficient difference, two
well resolved Gaussian distributions can
be produced. Accelerators which can pro-
duce ions with energies > 1 MeV can im-
plant, in many materials, ions to depths of
several microns. After one ion has been
implanted, another ion or ions can be im-
planted with the same energy to produce a
layer in which the ions may interact with
each other and the substrate ions. Thus the
number of possible combinations of sub-
strate/ions/energies is quite large.
6.3 First-Order Optical Properties
of Implanted Wide Band-Gap
Glasses
Optical properties of wide band-gap
glasses have usually been described in
terms of the first order approximation of
the electric susceptibility of glass materials.
With the development of coherent and in-
tense light sources it is now necessary to
consider higher order terms in the suscepti-
bility of a material to interaction with pho-
tons (see Chapter 12). In wide band-gap
materials it is usually assumed that inter-
action with photons whose energies fall
within the band-gap can be described in
terms of a linear function of refractive in-
dex and absorptivity. It has been demon-
strated that for very high fluxes of photons
this linear relation is insufficient to de-
scribe the interaction (Taylor et al., 1988).
The higher order terms are usually small
when compared with the first order terms.
Consequently, before laser sources were
available, the higher order terms were of
little consequence.
The polarization due to photon-material
interaction can be expressed in terms of the
susceptibility of the material, a property of
the elements comprising the material and
their structure. The susceptibility can be
written as an expansion (Bloembergen,
1965):
+ X(3)E1-E2-E3...) (6-1)
in which e0 is the dielectric constant of vac-
uum, x(l) is the fth term in the expansion,
and Et is the electric field of the photons.
Each of the x are complex and experiments
have been developed to measure the first 3
terms (Milonni and Elerly, 1988).
The first order term can be written, using
the Lorentz-Lorenz model:
X
w
=FZNiXi(co) (6-2)
i
in which F is the local field correction, Nt
is the number density of the fth constituent
ion, and Xi *s the polarizability of this ion.
(The hypothesis that the ion polarizabili-
ties are independent of each other and their
surroundings and that the total polariz-
ability of a material is a linear sum of these
ion polarizabilities has been questioned
(Lines, 1990). Then (Joos, 1934):
n2-l = 4nZNixi(co) (6-3)
i
where n is the complex refractive index,
and
n= (6-4)
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses 341

2U

I20
o 16 5x1015 400 keV XeVcm 2 Figure 6-4. Optical density (arbi-
trary units) vs. wavelength in
Xenon implant plus nm for Corning silica 7940 which
has first been implanted with
1x 10 u 400 keV HVcm 2 5 • 1015 400 keV Xe+ ions cm" 2
and then with 6 • 1014 400 keV
1x10 u 400 keV HVcm 2 H + ions cm""2. Bottom curve is
for a similar sample with 1 • 1014
400 keV H + ions cm" 2 only.
150 200 350

where n0 is the refractive index and k is the
absorptivity.
The absorption coefficient, A, of a mate-
rial is (Frohlich, 1958):
A = 2kco/c
where co is the photon frequency and c is
the speed of light.
In Section 6.3.1 we will review the effects
of ion implantation on n and k for some
glasses. In the following section (Sec. 6.4)
the effects on # (2) and %(3) will be reviewed.
the E' center (Weeks and Nelson, 1960).
Also evident in the spectrum of the He-
implanted sample is a band emerging at
250 nm. With increasing mass of the im-
planted ion this band becomes well re-
(6-5)
solved. It has been labeled the B 2 band
(Arnold, 1973) and attributed to the E"
center (Arnold, 1973; Weeks and Nelson,
1960).
Xe\

\ i1
B2
trar>' units

6.3.1 Optical Absorption Spectra

and the Imaginary Part
of the Refractive Index JQ
A\\ \ -A
6.3.1.1 Optical Absorption Spectra
O
C
\X
\ \ \\
of Glasses Implanted He \ \ \
Absorpition

\ \
with H, He, Ne, Ar, Kr, Xe
^ \
H—'""Y
The absorption of silica implanted with
H, with Xe, and with H and Xe sequen-
tially, as a function of photon wavelengths,
i i
in the range 350 to 190 nm, is shown in 200 250 300 350
Figure 6-4 (Arnold, 1973). The absorption A in nm
in silica samples each implanted with one Figure 6-5. Optical density (arbitrary units) vs. wave-
of the following ions: H, He, A, Kr, and Xe, length in nm for Corning silica 7940 implanted with
at various energies and integrated fluxes, is H, He, Ar, Kr, and Xe ions at various energies and
fluences. Individual curves have been displaced verti-
shown in Figure 6-5 (Arnold, 1973). The cally for clarity. Relative values of absorption can be
most intense band produced by implanting obtained by normalizing all curves to zero optical
H or He is at 210 nm. This band is due to density at 350 nm.
342 6 Optical and Magnetic Properties of Ion Implanted Glasses

The assignment of this band to the E" 18

center is based on deductions based on the 16 Corning 79£0
relative intensities of the band in the spec-
1 x 1016 250 keV OVcm 2
tra of samples irradiated with energetic
ions of differing elements. This model for "12
this band is placed into question by the
•e 10
absorption spectrum of samples implanted a
with O + . The optical absorption spectrum
of a sample, so implanted, is shown in Fig-
o. 6
ure 6-6 (Arnold, 1973). In this spectrum the o
in
intensity of the 250 nm band is much •9 4
greater relative to the intensities of the
210 nm bands shown in Figure 6-5. It has
been suggested that the peroxy molecule 200 250 300 350
ion has an absorption band at ~ 250 nm A in nm
(Friebele et al., 1987; Hosono and Weeks, Figure 6-6. Optical density (arbitrary units) vs. wave-
1990 a). In a sample implanted with O + it length in nm for Corning silica 7940 implanted with
would be expected that the oxygen mole- 1 -1016250keVOionscnr2.
cule ion would be produced. The EPR
spectra of Derryberry et al. (1990) clearly gas ions and the substrate ions. Even
show that there is a relatively high concen- though these data may be interpreted as
tration of such molecule ions and very showing noble gas ion-substrate interac-
small concentrations of E' centers com- tions, such interactions are very small
pared with concentrations in silica samples when compared with implanted cation-
implanted with other ions. We suggest that substrate ion interactions. This disparity of
in the spectra of oxygen-implanted sam- effect is demonstrated in Figure 6-8 (Ar-
ples the absorption at ~ 245 nm is due to
oxygen molecule ions. The paper by Derry-
berry et al. is discussed below in Section
E-Band
6.5.1. A
Antonini et al. (1982) have also im-
planted silica with these ions and others.
Figure 6-7 (Antonini et al., 1982) shows the
5 -
ooo Experimental points

Computer fitted components

in vacuum UV
A
spectra of one of their samples. The range
of wavelength over which these measure-
ments were made extends into the vacuum
3 -

2 -
\i\ 1!
10.5 eV ft
/
ultra-violet, to 120 nm. These data show
B2 E- Al
that well-resolved bands are produced v
near the band edge at ~120 nm. It is evi-
dent from these data that the variety of 6
Energy in eV
7
J i
bands and their production rate is depen-
dent upon the element implanted. That Figure 6-7. Absorption spectrum of v-SiO2 after R.T.
irradiation with 46.5 MeV Ni + 6 ions (~ 1014 parti-
there should be such a dependence on a
cles cm" 2 ). Solid line, bestfit spectrum; dotted lines,
particular noble gas ion may be indicative computer resolved structures in the vacuum u. v. (low
of chemical reactions between the noble energy details omitted).
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses 343

0.500
1017 B, Si and N/Ar implants in Si 0 2
current of ~ 1 JIA cm 2. Conversion elec-
tron Mossbauer, optical absorption and
0.400 - electron magnetic resonance spectros-
copies, among other techniques, were used
.2 0.300 -
to determine some of the properties of the
! 0.200 - implanted glass (Perez et al., 1983 a, b,
1985, 1987; Griscom et al., 1988).
0.100 -
On the basis of their Mossbauer and
0.000 TEM (transmission electron microscopy)
200 220 240 260 280 300
Wavelength in nm data, they identify several chemical states
Figure 6-8. Optical absorbance vs. wavelength (nm) for Fe after implantation, and a major frac-
for samples implanted with 50 keV B, 95 keV Si and tion of the implanted ions are found in
50 keV N. The 50 keV N implant yield somewhat less separate phases. The relative fractions of
absorbance than a 250 keV Ar implant, but on this Fe in differing charge states and sites are
scale the differences are not visible. All implants were
given in Table 6-2 in as-implanted samples
at the 1 10 17 fluence level. The B 2 absorbance is at
245 nm. as a function of dose and in Table 6-3 as a
function of annealing temperature for one

nold etal, 1990). The absorption bands Table 6-2. An abstract of Table 1 in the paper of Perez
due to E', B 2 and a background absorp- et al. (1987). The numbers are relative areas of
tion which increases with decreasing wave- Mossbauer components in the conversion electron
Mossbauer spectra of implanted silica samples.
length are more than an order of magni-
tude greater for implants of B and Si than Components Doses (ions cm 2)
for N or Ar. We suggest, as did Arnold
(1978) in a comparison of the optical ab- 4-10 1 6 6-10 1 6 14 10 16
sorption spectra of Al (200 keV, 1016 ions Fe° 13 20 2
cm" 2 ) and Ne (180 keV, 1.1-10" 16 ions Fe 3 O 4 single line 29 40 12
cm" 2 ), that this difference is, in large part, Fe + 2 35 21 8
due to chemical reactions between B, Al, Si Fe + 2 23 19 13
Fe° (sextet) 65
and other cations with substrate Si and O.
The noble metal cations and Cu are an
exception which will be discussed below.
Table 6-3. An abstract from Table 2 in the paper of
Perez et al. (1987) implanted with a dose of 1.4 * 10 17
6.3.1.2 Ions from the First Transition Series 250 keV Fe ions cm ~ 2 and subsequently annealed in
of Elements air at 600 and 800 °C. The values are percentages of
each species of Fe ion.
The group in the Departement de Phy-
sique des Materiaux, Universite Claude Components Annealing temperature (°C)
Bernard has been investigating the proper-
600 800
ties of ion-implanted glasses for several
years. This group has implanted the iron Single line Fe 3 O 4 10 13
ion in a variety of materials (Perez, 1984). Doublet Fe + 2 10
High purity silica was their choice of a Doublet Fe 2 O 3 37 21
Sextet Fe° 33
glass for implantations of iron. Their beam Sextet Fe 2 O 3 10 66
energies were 100 and 200 keV at a beam
344 6 Optical and Magnetic Properties of Ion Implanted Glasses
dose. The various types of Fe in the as
implanted samples are Fe° in colloid parti-
cles, and Fe + 2 in two distinct environ-
ments one of which is Fe 3 O 4 particles. The
fraction of ions in these various states was
a function of the dose in the range 4 • 1016
to 14 • 1016 ions cm" 2 for 25°C substrate
temperature during implantations. The
precipitates were crystalline and ranged
from 2 to 50 nm in size.
a) Cr, Mn, and Fe
The optical absorption of the implanted
samples, shown in Figure 6-9 (Perez, 1987)
as a function of dose, was reasonably ex-
plained by the Mie theory (Mie, 1908) for
absorption and scattering by small parti-
cles (dimensions ^ the wavelength of the
incident light) suspended in a material
whose refractive index differs from that of
the particles. The optical absorption was
due primarily to absorption by the precip-
itated particles of iron and iron oxides. The
absorption spectrum of samples implanted
to a dose of 12 • 10 16 cm ~ 2 and annealed at
800 °C in air contained three peaks at 220,
400 and 550 nm (curve e in Figure 6-9, indi-
cated by arrows), which were attributed to
Fe + 3 charge transfer bands.
Stark et al. (1987) have described the op-
tical absorption spectra of high-purity sil-
ica implanted with Cr, Mn and Fe to doses
ranging from 10 16 to 6 10 16 cm~ 2 at a
substrate temperature of ~ 25 °C during
implantation. Beam currents were ~ 4 JIA
cm" 2 and beam energy was 160 keV. The
spectra observed, shown in Figure 6-10
(Stark et al., 1987) for the three ions after
implanting a dose of 1016 cm" 2 consisted
of two bands with peaks at ~ 5 and 5.8 eV
and the tail of a band with a peak at higher
energy. Their measurements were limited
to energies less than or equal to 6 eV. They
attributed these bands to defects of the sil-
300 400 500 600 700
Wavelength in nm
Figure 6-9. Optical absorption of Fe-implanted SiO2
glass samples, a) 1016 ions cm" 2 , b) 3 • 1016 ions
cm 2, c) 6 20- 1016 ions cm" 2 ,
16 ions cm" 2 heated for 20 h at
d) sample with 20 • 10 ^
800 K in air.
ica substrate produced by the implanted
ions. The defects were the B 2 band (An-
tonini et al., 1982) and the E' center (Weeks
and Sonder, 1963).
In this regime of doses, and for the same
dose, the absorptivity was a function of the
ion implanted, as shown in Figure 6-10 b.
Iron was the most absorbing and Mn the
least. This ion-dependent absorptivity is
attributed to the differing absorptivities,
i.e., differing complex refractive indices, of
particles of Cr, Mn and Fe oxides.
The absorption spectra in samples im-
planted with 0.5 • 1016, 2 • 1016, and 6 • 1016
160 keV Fe ions cm" 2 have been measured
in the range from 5.5 to ~ 8 eV (Hosono
et al., 1990). The spectra of the three sam-
ples have a single very intense peak at
~ 7.6 eV whose peak absorption increases
with increasing dose. The peak is attrib-
uted to a transition from the ground state
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses 345

of a neutrally charged Si-Si bond, labeled

1 x 1016 ions/cm 2
3x 1016 ions/cm 2 homo-bond (Imai et al., 1988). The model
15 - 6x 1016 ions/cm 2 proposed for the homo-bond is indistin-
guishable from that of the E" center. For
10 - Cr doses < 3 • 1016 ions c m ' 2 the amplitude
of the absorption peak is the same for ei-
5 - ther Cr, Mn, or Fe. It is much larger for Ti.
For larger doses the amplitude for Cr and
(/) 0 Mn are almost the same and larger than
for the Fe-implanted sample. The ampli-
tude in the case of the Ti implanted sample
is almost twice larger. Assuming an im-
plantation layer thickness =140 nm and
an absorption cross-section for the transi-
tion of 8 • 10~~17 cm" 2 , the calculated con-
centration of the homo-bond as a function
of dose is approximately equal to the dose
in the case of the Cr-, Mn-, and Fe-im-
planted samples. The concentration of ho-
mo-bonds in the sample with the largest
dose of Ti ions is approximately 1.5 times
larger than the dose.
At higher doses, spectra for Cr, Mn, Fe
implanted samples in the range 2 eV
(700 nm) to 6 eV (190 nm) were similar in
3.0 4.0 5.0 6.0 that the absorptivity increased approxi-
(a) Energy in eV mately linearly with increasing photon en-
ergy from ~ 2 to 6 eV. This linear increase
with increasing energy is similar to that
15 reported by Perez et al. (1987) and attrib-
Cr* 3x1016 ions/cm2/side uted to absorption by particles with diame-
Mn+ 3 x 1016 ions/cmVside
Fe+ 3 x 1016 ions/cmVside ters much less than the wavelength of the
£ 10 light, i.e., Mie absorption. For particles
with radii smaller than the incident photon
o 5
wavelength the extinction coefficient, for
both absorption and scattering, is given
approximately by (Arnold and Borders,
2.5 3.0 3.5 4.0 Lb 5.0 5.5 6.0 6.5 1977):
Energy in eV
(b) (6-6)
Figure 6-10. Optical absorption of SiO2 glass samples
implanted with ions from the first transition series of
where Kahs is the absorption by small par-
elements, Cr, Mn, Fe ions each implanted to three ticles and Kscat is the scattering by small
doses, (b) comparison of optical absorption of sam- particles. These two terms are given by:
ples implanted with Cr, Mn, Fe with the same dose of
3-10 1 6 ions c m ' 2 (160 keV, 4uAcm~ 2 , substrate
Kabs = - (6 TI/A) / Im ((n2 - n20)/(n2 + 2 n2)
temperature ~30°C). (6-7)
346 6 Optical and Magnetic Properties of Ion Implanted Glasses
and (6-8)
Kscai = (24 7i VN/X*) ((n - n 0)/(n + 2 n2))
3 2 2 2
where n is the complex refractive index of
the particles, n0 is the real part of the re-
fractive index of the material in which the
particles are imbedded, V is the volume per
particle, / is the volume fraction of the
particles, X is the wavelength of the inci-
dent photons, and N is the particle concen-
tration.
The spectrum will be approximately a
linear function of photon energy for parti-
cles with R < X and with small conductivi-
ties. For metallic particles of Ag, Cu, and
Au and for J^ < 20 nm, an absorption max-
imum will be observed at photon energies
< 5 eV (Arnold and Borders, 1977). In the
case of Cr, Mn, and Fe ions implanted at
energies of the order of 200 keV, the distri-
bution, as typically in Figure 6-2, has a
width at half maximum amplitude of
~ 140 nm. Hence most (~ 80%) of the par-
ticles which form will have radii < 70 nm.
For wavelengths > 200 nm both the ab-
sorption and scattering equations will
be applicable. Absorption-plus-scattering
spectra would be expexted to have a de-
pendence on photon energy which falls
somewhere between being proportional to
photon energy and photon energy to the
fourth power.
Since the absorption spectra of Cr- and
Mn-implanted samples are similar to those
of the Fe-implanted samples and this Fe
spectrum is similar to that reported by
Perez et al. (1987), it is reasonable to attrib-
ute a major fraction of the absorption spec-
tra of the Cr- and Mn-implanted samples
to Mie absorption of precipitates contain-
ing Cr and Mn and with sizes that are
small compared to the wavelength of the
incident photons.
It is interesting to note that the absorp-
tion spectra shown in Figure 6-5, although
containing well resolved components due
to the E' center and the B 2 band, have a
background component which is approxi-
mately linear with photon energy. The
rather featureless spectra, without well re-
solved bands, are surprising since Perez
et al. (1987) have identified several charge
states for implanted Fe, given in Table 6-2,
from conversion electron Mossbauer spec-
tra. Although for a dose of 6 • 1016 ions
cm" 2 the fraction of ions in the + 3 state is
~ 27% no bands attributable to charge
transfer bands are resolved. Given the sim-
ilar oxygen activities of Fe, Cr, and Mn
(Table 6-4) we expect that the fraction of
ions in the 0, + 2 and + 3 charge states of
implanted Cr and Mn to be similar to
those of Fe. After an anneal at 800 °C,
bands are resolved in Fe-implanted sam-
ples which are attributed to charge-trans-
fer bonds of Fe 3 + (see Figure 6-9).
The absorption spectra of Cu implanted
SiO2 glass differ from the spectra observed
for ions of the other transition series of
elements. Only at doses <10 1 6 cm~ 2 do
the spectra of Cu implanted samples re-
semble the spectra of samples implanted
with other ions. For these doses optical
bands in the 4 to 6 eV range due to silica
defect states are more intense than those
due to implanted ions. Thus, for these
doses the spectra of Cr-, Mn-, Fe- and Cu-
implanted samples are similar.
b) Copper
The spectra of Cu-implanted silica sam-
ples for several doses is shown in Figure
6-11 (Magruder et al., 1989). These spectra
show that several bands are resolved and
that one of these, with a peak at 2.2 eV,
increases with increasing dose. The refrac-
tive index, measured at 633 nm, also in-
creases with the increasing intensity of this
band, as shown in Figure 6-12 (Weeks
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses
et al., 1989). For doses > 1016 ions cm~ 2
and for several substrate temperatures the
refractive index as a function of the optical
absorption at 2.2 eV is well fitted by a lin-
ear function. Weeks et al. (1989) attribute
2000
1.00 3.00 5.00 zoo
Energy in eV
Figure 6-11. Optical absorption of SiO2 glass sam-
ples implanted with Cu ions, (a) 6-10 16 ionscm~ 2 ,
(b) 3 • 1016 ions cm" 2 , (c) 1016 ions cm" 2 , (d) 0,5 • 1016
ions cm' 2 , (e) 0.3 • 1016 ions cm" 2 (160 keV, 4 A
cm" 2 , ~30°C).
1.5 1.6
Refractive index
Figure 6-12. The optical density measured at 2.2 eV
(the peak of the first resolved band in the spectra
shown in Figure 6.6) is plotted as a function of the
refractive index, measured at 1.9 eV (633 nm) by an
ellipsometric technique. The numbers and symbols
have the following meanings: A, dose = 1016 ions
cm" 2 ; n, dose = 3 • 1016 ions cm" 2 ; o, dose = 6 • 1016
ions cm" 2 : 1, substrate temperature ~ 100 K; 2, sub-
strate temperature — 300 K; 3, substrate temperature
~ 700 K.
347
this linear relation to the case in which the
imaginary part of the refractive index is
much larger than the real part.
Magruder et al. (1989,1991) have attrib-
uted the absorption band in the region of
4.2 and 2.2 eV to spherical particles of Cu°
and oblate or prolate colloidal spheroids of
Cu with an axial ratio of ~ 2, respectively.
The 4.2 eV band is attributed to spheroidal
colloids of Cu with diameters ranging from
a few nm to ~ 10 nm. Calculations have
shown (Arnold and Borders, 1977) that for
Ag particles with radii > 10 nm the peak
absorption shifts to lower energies. In the
spectra of samples implanted with doses
> 3 • 1016 Cu ions cm" 2 there is a shift to
lower energies of the shoulder at ~ 4.2 eV
observed in the spectra of samples im-
planted with smaller doses (1016 Cu ions
cm ). Spectra calculated for Ag particles
shows that for particle radii > 25 nm the
absorption splits into two maxima, one at
the wavelength of the absorption for parti-
cles with radii < 14 nm and one with a
wavelength that shifts to longer wave-
lengths with increasing particle radii and
whose width at half maximum amplitude
also increases. With the bimodal distribu-
tion of Cu shown in Figure 6-3 for doses
> 1 • 10 16 ions cm" 2 the fraction of Cu
particles with radii > 200 nm must be very
small. Most of the spheroidal Cu particles
have radii < 50 nm, assessed on the basis
of the shift of the 4.2 eV shoulder.
Another property of colloidal particles
which produces a splitting of the absorp-
tion is deviation of particle shape from
spherical (Trotter et al., 1982). Thus, an ab-
sorption band at 2.2 eV, observed by Ma-
gruder et al. (1989) was attributed to oblate
or prolate spheroids with a major-to-mi-
nor axis ratio of ~ 2 .
Optical absorption of Cu + 1 in silicate
glasses has been observed at ~ 5.2 eV
(Parke and Webb, 1972). The absorption
348 6 Optical and Magnetic Properties of Ion Implanted Glasses
spectra of implanted silica samples have a
shoulder at ~ 5.2 eV which may be due to
Cu + 1. Weeks et al. (1989) report that no
spectral component attributable to Cu + 2
was detected in the EPR spectra of im-
planted samples. Thus it appears that in
the case of Cu implanted into silica a major
fraction, perhaps as high as 99%, is in the
Cu° and C u + 1 states.
Weeks et al. (1989) did not detect any
EPR spectral component attributable to
Cu + 2 in Cu implanted borosilicate and
aluminosilicate commercial glasses. They
also note that neither is an optical absorp-
tion band detected at 2.2 eV nor at ~ 4 eV.
They tentatively conclude that most of
the Cu in these glasses is in the + 1 state.
They comment that optical absorption
measurements could not be made at ener-
gies > 4 eV because of very intense absorp-
tion at these energies in their samples.
We noted above that the chemical reac-
tivity between implant ions and substrate
ions will, in part, determine the optical ab-
sorption spectra directly attributable to
implanted ions and also, as we will discuss
below, the paramagnetic states of defect
states in the substrate structure. Magruder
etal. (1989) have discussed these reactivi-
ties in terms of the relative oxygen activi-
ties of some implant cations and the sub-
strate cation, Si. These relative activities
are given in Table 6-4. From this table we
note that Ti has a higher free energy of
Table 6-4. Gibbs free energy, G*, of formation at
298 K (Kcal/mol) (per mol oxygen).
Reduced oxide G* Oxidized oxide G*
a-SiO2 -189.9
TiO -233.8 TiO 2 -212.4
MnO -173.5 Fe 2 O 3 -118.3
Cr 2 O 3 -168.8 MnO 2 -111.3
FeO -117.3 CrO 3 - 80.6
Cu 2 O - 35.5 CuO - 61.7
formation with oxygen than does Si. Hence
we expect that displaced oxygen ions will
react with implanted Ti ions to form oxides
and that these reactions will result in
higher concentrations of E' centers, E"
centers, and smaller concentrations of oxy-
gen related paramagnetic centers such as
peroxy molecule ions. The lowest free en-
ergy of formation is between Cu and O. In
this case the reactions between Si and O
will dominate. The result will be smaller
numbers of E' and E" centers, higher num-
bers of oxygen related centers as compared
with those for Ti implanted samples. We
expect that the numbers of these centers in
Cr, Mn, and Fe implanted samples will be
intermediate between those for Ti and Cu.
The optical absorption spectra of lithia-
alumina-silica glasses implanted with Ag
and Au will be described below in Section
6.3.3.1. Colloidal particles also form in
these glasses during implantation and in
some glasses after thermal treatments.
c) Titanium
There is little to report on the absorp-
tion of Ti-implanted silica. For doses
< 5 - 1 0 1 5 Cu ions the optical spectra
shown in Figure 6-13 is due primarily to
the bands of B 2 and E' centers. With in-
crease in dose the absorption at energies
> 5.5 eV increases three-fold while there is
little change at energies < 5 eV. Becker
et al. (1990) note that the absorption of Ti
implanted samples increase by a factor of
two with an increase in dose from 1 • 10 16
to 6 • 1016 ions cm" 2 . Their measurements
of the absorptivities of samples implanted
with Ti have values of a ~ 5 • 103 cm" 1 for
a dose of 1016 ions cm" 2 , assuming that
the thickness of the absorbing layer is
equal to the width at half maximum ampli-
tude of the distribution as a function of
depth, i.e., 2-130 nm = 260 nm, since both
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses 349

ellipsometric technique. The variation in

the index near the implant surface of the
as-received sample may be due to surface
contaminants and polishing defects. The
heat treatment appears to have removed
these. In the treated sample there does ap-
pear to be a small maximum in the index at
a depth of ~200nm and at a depth of
~ 600 nm the effects of implantation dis-
appear. The increase in index over the en-
tire range in the heat treated sample is
0
An/n -0.005.
4.00 5.00 6.00 7.00 The refractive index changes produced
Energy in eV by various ions are shown in Figure 6-15
Figure 6-13. Optical absorption as a function of pho- (Webb and Townsend, 1976). The data in
ton energy of Ti implanted samples with (a) 1 • 1015 this figure illustrates, in our opinion, the
ions cm" 2 and (b) 3 • 1015 ions cm" 2 .
effects of chemical reactions between sub-
strate ions and implanted ions. For ex-
ample a dose of 1015 20keVH + or B +
sides of their samples were implanted with
ions cm" 2 increases the index of the im-
the same dose.
plant surface as much as 10 16 20 keV He +
The non-linear properties of the absorp-
ions cm" 2 . The much greater range of the
tion spectra of Cu and Ti implanted sam-
H + ions produces an increase in the index
ples will be discussed below.

63.1.3 Refractive Index, Real Part

Neutron irradiation of silica increases After"! 90minat425°C
the density by 2.5% (Wittels and Sherill, 0.010
1954). Implantation of noble gas ions, for
An
which chemical reactions with substrate n
ions would be expected to be negligible,
produce increases in refractive index An/n 0.005
~ 1.5% (Bayly and Townsend, 1973). The
refractive index as a function of distance
from the implant surface is shown in Fig- =n
ure 6-14 (Boyly and Townsend, 1973) after
implanting 1016 Ar ions cm" 2 at 300 keV. LJ

Although no information about substrate 0.010

nK •—I
temperature is given, the lack of informa- j—'
tion is probably indicative of nominal 0.005
—>

J
i
i
b n_
r
1

room temperature. Shown in the figure are 0

r__.j
1
H
L..J 1 2 3 4 5
profiles for two samples, one as received Range in nm
and one thermally treated for 90 min at Figure 6-14. Refractive index profiles of samples im-
425 °C. Samples were sectioned by three planted with 300 kV Ar, 1016 ions cm" 2 , with and
techniques and the index measured by an without prior annealing for 90 min at 425 °C in air.
350 6 Optical and Magnetic Properties of Ion Implanted Glasses
800
Figure 6-15. Refractive index profiles for implanta-
tions of silica with (a) 20 keV B + to a dose of 1 • 1015
ions cm" 2 , (b) 20keV He + to 1 • 1016 ions cm" 2 ,
(c) 20 keV H + for 1 • 1015 ions cm" 2 , and (d) 2000 keV
Bi + for 1 -10 ionscm~ 2 .
that extends to a depth > 400 nm. The
maximum change in the index in the three
cases is An/n ~ 0.017.
A high energy (2000 keV) implant of Bi
increased the index to a depth of ~ 800 nm,
with the maximum at a depth of ~ 600 nm.
The increase was slightly larger than in the
case of the H ions. Reactions between Bi
and substrate ions may be a factor in this
increase, also. Some data on the effects of
Cr, Mn, and Fe implanted in silica on re-
fractive index have been reported (Whi-
chard et al, 1988). These data show that
the index, measured by an ellipsometric
technique at ~ 633 nm, increases with in-
0.3
Depth in jjm
creasing dose when the dose is 1016 ions
cm" 2 or greater and the increases are sim-
ilar for the three ions. The values for the
refractive indices were calculated for a
"single layer" model. In this model it was
assumed that the change in index was uni-
form throughout the implanted layer. For
the highest dose, 6 • 1016 ions cm" 2 , the
indices increased ~ 5%, with the largest
increase in the Fe implanted sample
(Whichard and Weeks, 1989).
One of the interesting features of the
changes in refractive index produced by
heavy ions is that the variation in the index
with depth from the implanted surface is
not large until the end of the range of the
implanted ions. A comparison of the index
change, together with vacancy and im-
planted ion distributions calculated with
the TRIM program, are shown in Figure
6-16 (Faik et al., 1986). Before annealing
the index is almost constant to a depth at
which the distribution of the implanted ion
is a maximum. After annealing it varies in
the same way as the calculated vacancy
concentration and not as the implant ion
distribution.
The temperature of the anneal (450 °C)
was sufficient to remove most of the elec-
tronic states which were paramagnetic
Figure 6-16. A comparison
of the experimentally deter-
mined refractive index pro-
files (a) before and (b) after
annealing at 450 °C with
TRIM calculations of (c)
vacancy and (d) impurity
distributions. The N + ion
- U6 energy was 0.18 MeV for a
 6.3 First-Order Optical Properties of Implanted Wide Band-Gap Glasses
states of intrinsic defects (Perez et al.,
1983 b). It was not sufficient to remove the
chemical disorder introduced by the im-
plantation. At the dose used for these mea-
surements and calculations, 1016 180keV
N + ions cm = 2, all of the substrate ions will
have been displaced a least once. Weeks
and Sonder (1963) and Stevens et al. (1958)
showed that for a neutron dose sufficient
to displace all silica ions at least once the
concentration of intrinsic paramagnetic
states begins to decrease. At neutron doses
much higher (1021 n cm" 2 ) than this dose
(3 • 1019 n cm" 2 ) the decrease is almost a
factor of two. For implant doses >10 1 4
ions cm" 2 most substrate ions have been
displaced at least once. Thus for all of the
implant doses, discussed thus far, we ex-
pect that the vacancy concentration as
measured by intrinsic paramagnetic states
is less than the maximum concentration
observed in the case of neutron irradiation.
It is difficult to interpret the TRIM calcula-
tion of vacancies per ion when the vacan-
cies per ion exceeds the concentration of
ions. It may be that the agreement between
the index after thermal treatment and the
number of vacancies per ion is fortuitous.
In Section 6.5.1 we review the data of
Hosono and Weeks (1990 b) in which it is
shown that E' centers, i.e., singly charged
vacancies, have a higher concentration
near the implant surface and peroxy radi-
cal centers, i.e., interstitial oxygen, has a
higher concentration at the peak of the im-
planted ion distribution. Thus the distribu-
tion of defects is a function of the type of
defect and is not uniform.
6.3.1.4 Infrared Spectra
One of the problems in measuring the
effects of ion implantation on the vibra-
tional bands of silica is the measurement of
a very thin layer on a thick substrate, both
351
of which are principally SiO 2 . The usual
technique is to measure the reflectivity of
implanted samples. This technique, for
wavelengths > 5 jim, samples a layer that
is less than ten times thicker than the im-
planted layer (Magruder et al., 1990 a) if
that layer is < 300 nm thick. Quantitative
measurement of relative amplitudes of
bands is difficult whereas relative measure-
ment of peak positions of bands is more
accurate by this method.
In our review of the literature reports of
bands due to implanted ion-substrate ion
vibration bands have not been detected.
The effects reported are due to changes in
the bands observed in silica before implan-
tation (Arnold and Borders, 1977; Arnold,
1978,1980,1981). These changes are attrib-
uted to changes in the SiO2 structure.
6.3.2 Alkali Silicate Glasses
Glasses with alkali silicate compositions
are an extensive group with many uses. For
most applications, additional elements are
added to design a glass with particular
properties. In most of the research on ef-
fects of ion implantation on properties,
three-component (alkali, silicon, oxygen)
glass compositions have been chosen for
investigation. The vast literature on prop-
erties of these glasses provides an excellent
basis for interpreting effects produced by
ion implantation.
6.3.2.1 Noble Gas Ions
During implantation of Xe a depletion
of Li and Na in Li 2 O:SiO 2 (Arnold and
Peercy, 1980) and Na 2 O:nSiO 2 (Bach,
1975) glasses, respectively, in the implanted
layers has been observed. In the case of the
Li 2 O:SiO 2 glass samples, Arnold and
Peercy (1980) observed that H, already
present in their samples, diffused into the
Li-depleted region. In the case of the
352 6 Optical and Magnetic Properties of Ion Implanted Glasses
Na 2 O: n SiO2 glass samples, this effect was
not reported (Arnold, 1978). In either case
the optical absorption spectra produced by
the implantation of Xe ions would be af-
fected. In the paper of Bach (1975) the ab-
sorption spectra of the Xe implanted
Li 2 O:SiO 2 glass samples are only given
after the samples have been annealed at
500 °C. In these spectra an intense band
with a peak at 470 nm is present. The spec-
tra of samples of silica implanted with Li
have a band with a peak at ~ 500 nm
(Arnold and Peercy, 1980). The peak posi-
tion shifts to smaller wavelengths after an-
nealing. In both cases the band in annealed
samples is attributed to colloidal Li.
We note that bands in the region of
500 nm in silica and in alkali silicate
glasses have been attributed to non-bridg-
ing oxygen hole centers (Friebele and Gris-
com, 1986). The band, produced by radia-
tion with energetic photons, electrons,
protons, or noble gas particles in either
glass system, disappears after an anneal at
temperatures above 300 °C. The absence of
a decrease and the presence of an increase
with annealing at temperatures above
500 °C is strong evidence that the
~ 500 nm band in both systems implanted
with Xe or Li is not due to non-bridging
oxygen hole centers. The stability and in-
crease in intensities is certainly consistent
with the formation and growth of colloidal
Li particles.
The specular reflectances of samples of
a soda-lime glass implanted with Ar ions
has been reported (Geotti-Bianchini et al.,
1984). The samples had a composition
73.4 wt.% SiO2,13.6 wt.% Na 2 O, 6.8 wt.%
CaO, 3.8 wt.% MgO and 2.4wt.% of
other oxides. Measurements were made
over a range of wavelengths from 300 to
~ 2000 nm. The reflectance decreased with
increasing doses of Ar (2 JIA cm~ 2 , 50 keV)
with a minima in the range of 700 nm and
with no measurable change at ~ 380 nm
for doses less than or equal to 5 • 1016 ions
cm" 2 . At higher ion energies the wave-
length dependence of the reflectivity was
more complex. The maxima and minima
shifted to longer wavelengths with increas-
ing ion energy.
6.3.3 Multi-Component Glasses
Four-component glasses such as alkali-
alkaline earth-silica compositions have
many applications and, consequently,
there is considerable research on the mod-
ification of the properties of these glasses
by ion implantation. The alkali alumino-
silicate compositions are used in many ap-
plications and glasses with these elements
have been frequently chosen for ion im-
plantation experiments.
6.3.3.1 Noble Metals
In Section 6.2 we noted that Ag im-
planted in samples with those composi-
tions have a distribution similar to that of
Cu in silica. This ion also forms colloids as
implanted and after implantation and sub-
sequent thermal treatments. Figure 6-17
(Arnold and Border, 1977) shows the ab-
sorption spectra of samples implanted with
1016 Ag ions cm" 2 at an energy of 275 keV.
Arnold (1975) and Arnold and Borders
(1977) attribute this spectrum to colloidal
Ag particles with radii of the order of 2 nm.
The spectrum has only one well resolved
peak at a wavelength of ~410nm. The
spectrum for Cu in silica is much more
complex (see Section 6.3.1.2, above). The
peak, in the spectrum of samples given
isochromal (30min) anneals, shifts to
longer wavelengths until a 400 °C anneal.
After an anneal at 500 °C the peak shifts to
a shorter wavelength. These shifts are due
to an increase in particle radii from 15 to

1016 275 keV Ag+ ions/cm 2
(no annealing)
this experiment
MIE theory. R =
fl = 1.75nm ) Kreibic and
/9 = 2.75nml v - Fragstein
data
340 380 420 460 500 540 580 620
A in nm
Figure 6-17. Measured optical extinction K (arbitrary
units) as a function of wavelength A (nm) for 1 • 1016
275 keV Ag ions cm ~ 2 as implanted into a lithia-alu-
mina-silica glass compared with Equation (6-1) evalu-
ated for R ~ 20 A, contamination factor C ~ 1, and
d = 2.2.
~ 40 nm and then a decrease to 10 nm af-
ter the 500 °C anneal.
The formation of colloidal particles in as
implanted samples is attributed to beam
heating by Arnold and Borders (1977). In
the Cu implanted silica colloids formed at
substrate temperatures ~100K. We sug-
gest that colloid formation may be due to
other processes.
In the case of Au implantation into the
lithia-alumina-silica glass samples, colloids
did not form until samples were annealed
(Arnold and Borders, 1976). Implanting
Ag into crystalline LiNbO 3 , A12O3, and
a-quartz caused colloids to form upon
implantation (Rahmani and Townsend,
1989). At implant doses > 5 • 1016 ions
cm" 2 , the implanted layers were amor-
phous in the three crystals.
6.4 Non-Linear Optical Properties 353
6.3.3.2 Halide Glasses
Halide glasses composed of Zr, Ba, Al,
and other cations have been considered as
potential fiber optic glasses for applica-
tions in the 2 to 10 jim wavelength range
(cf. Chapters 8 and 15). They have the po-
tential for attenuations that are one to two
orders of magnitude lower than silica
fibers. The effects of implanting samples of
various compositions have not been exten-
sively reported. Most of the research has
been in the laboratories of P. Mazzoldi
(1990).
One of the effects of implanting Ar is an
increase in the relative amounts of Zr and
Ba in the implanted layer. The reflectance
of the surface increased in the range 350 to
2500 nm. The absorptivity of the samples
also increased in the range from 250 to
2000 nm. The wavelength dependence of
the absorptivity was observed to be a func-
tion of the implanted ion species, e.g., N
produced the largest increases compared
with H and Ar. The data reported were for
differing doses of these ions and hence a
comparison for the same dose is not pos-
sible.
6.4 Non-Linear Optical Properties
It was noted above that the polarization
of a wide band-gap material can be ex-
pressed as a power series of electric fields
interacting with the material. The third or-
der term, expressed as the refractive index,
is
n = no + n2E3 (6-9)
in which n0 is the first order term of the
refractive index, n2 is the non-linear index,
and E is the electric field. In the case of
photons, E is the field of the photons. Thus
to measure the value of n7 the E-field of
354 6 Optical and Magnetic Properties of Ion Implanted Glasses

incident photons must be varied. One tech-

nique for this measurement is called the
z-scan method (Sheik-Behae et al., 1989).
Becker et al. (1990) have made such mea-
surements on Ti and Cu implanted silica.
They used a frequency-doubled Nd-YAG
laser (532 nm, 100 ps FWHM pulse width,
76 MHz pulse repetition rate, and 1.8 W
average power). Both samples absorbed
strongly at this wavelength. Absorption at 500 1000
Laser power in mW
532 nm in samples implanted with Ti to
doses of 1015, 3 • 1015, 10 • 1015, 60 • 1015 Figure 6-18. Absorption of Ti implanted samples as a
function of incident photon power, X = 532 nm. Doses
and 60 • 10 15 ions cm~ 2 is shown in Figure (1015 ions cm" 2 ): o = 60, A = 60, + =10, x = 3, * =1.
6-18 (Beeker et al., 1990) as a function of
photon power in mW. Interesting features
of this absorption are: the similar ab-
sorptivity of samples with 1 to 10 • 1015
ions cm" 2 and the two samples with a dose
of 60 • 1015 ions cm" 2 , absorptivity in the
low dose samples saturates and absorption
decreases from 17% to 12% with increase
of power from 100 to 1300 mW, absorptiv-
ity in the high dose samples was indepen-
dent of power in the same range, and the
550 600 650 700 750 800
increase in absorptivity with increase of Wavelength in nm
dose from 10 to 60 • 10 16 ions cm" 2 is from
Figure 6-19. Laser induced fluorescence of Ti im-
17% to 30%. A 17% decrease in transmis- planted fused silica. The structure in the region of
sion represents a very large change in ab- 5500 nm is stray light from the laser.
sorption coefficient since the thickness of
the absorbing layer is only 120 nm. The
en
absorption coefficient is of the order of
1 uni

Cu h
H^cm" 1 .
(JDJ

Luminescence stimulated by the 532 nm \

i arbit

photons is shown for one Ti-implanted pure FS

l_Lirm •tLIULJiTl-lWW.-MiP'*
sample in Figure 6-19 (Beeker et al., 1990).
(NJ * ->>
Luminescence in Cu-implanted sample Q
detector

was similar, with the peak occurring at a

wavelength ~ 30 nm greater than that for
the Ti samples. c
o
The z-scan data are shown in Figure >^ pure FS
6-20 (Beeker et al., 1990) for Ti- and Cu- U)

implanted samples. The z-scan spectrum <u

"r
for an unimplanted silica sample is also Distance from focus in arbitrary units
shown in both parts of the figure. The Figure 6-20. Results of z-scan for pure silica Ti- and
shape and amplitude of the two spectra are Cu-implanted fused silica.

similar. However, structure is resolved in
the Cu spectrum on both sides of the focus.
Becker et al. (1990) do not have an expla-
nation for the structure. These data clearly
show that the ion implanted samples have
n2 that are very large (~ 10" 8 M2/W) com-
pared with unimplanted silica.
These data are tantalizing. The values of
n2 are large. For such values there is the
possibility of optical switching with switch-
ing times that are a function of the transit
times of conduction electrons in colloidal
particles, if the colloidal particles are the
source of the non-linear index.
These non-linear effects may be due to
properties other than those of the im-
planted ions. Tsai et al. (1989) have shown
a correlation between second harmonic
generation and defects in an optical fiber.
The defects are those usually observed in
silica, i.e., E' centers. The differences be-
tween the z-scan data for Ti- and Cu-im-
planted samples does indicate that some
part of the effect is related to implanted
ions.
Although not produced by ion implan-
tation, non-linear optical properties of
glasses have been noted by a number of
investigations. These may be of interest to
readers who wish to consider glass systems
in which non-linear optical properties are
observed (Friberg and Smith, 1987; Ross,
1989; Taylor et al., 1988; Vogel et al., 1989;
cf. Chapter 12).
6.5 Magnetic States
Magnetic states of implanted materials
have two sources (see also Volume 3 of this
series). One is unpaired electronic states of
substrate ions. These states are usually due
to defects of crystal structure or, in the case
of wide band-gap glasses, chemical disor-
der. The lowest energy states of these de-
6.5 Magnetic States 355
fects usually have energies between the va-
lence and conduction bands. In the case of
silica, the E' and peroxy radical centers,
discussed above, are examples. - The sec-
ond source is the implanted ion. Ions are
usually implanted either in the + 1 or + 2
states. For some ions these states will have
unpaired electrons and hence lead to mag-
netic states. An example is the Fe ion,
which will be discussed below. Some frac-
tion of ions implanted in the + 1 or + 2
states will have a final state that ranges
from 0 to + 4 (the + 4 state has been de-
tected in A12O3 implanted with Fe and will
be discussed in Section 6.6).
The intrinsic defect states of implanted
samples will be reviewed first, followed by
a review of magnetic states of implanted
ions.
6.5.1 Paramagnetic Defect States
of Silica Substrates
Energetic ions implanted in a material
displace ions of the substrate creating in-
terstitial ions and vacancies. In a simple
compound such as SiO2 or elemental ma-
terial such as Si in the glass state intersti-
tials and vacancies are usually labeled
"chemical disorder" or "defects". Another
consequence of the deposition of energy by
the implanted ions is excitation of elec-
trons. The excited electrons may be
trapped in states that are between the va-
lence and conduction bands. In some case
these states are paramagnetic. Thus im-
planted glasses can have paramagnetic
states associated with implanted ions and
defects in the glass produced by displace-
ment and ionization processes. The para-
magnetic states of defects in the substrate
will be discussed followed by a discussion
of magnetic states of implanted ions.
Magnetic states of implanted ions can be
detected by various techniques, one of
356 6 Optical and Magnetic Properties of Ion Implanted Glasses
which, conversion electron Mossbauer
spectroscopy, was discussed above (Perez
et al., 1987); another is a vibrating magne-
tometer (Perez, 1984). Electron paramag-
netic (or ferromagnetic) resonance spec-
troscopy is a technique particularly useful
for detecting small (of the order of 1012
spins with S = 1/2 and a line width
~ 0.1 mT) numbers of paramagnetic states
or ferrimagnetic particles. The reader is re-
ferred to standard texts for detailed de-
scriptions of these techniques (Orton,
1970; McMillan, 1968).
Models for paramagnetic defect states
are usually deduced from a fit of observed
spectra to a "spin Hamiltonian" (Orton,
1970). In the case of wide band-gap glasses,
the spin states of most defects are either 1/2
or 1. The effects of the Coulomb field of
nearest neighbor ions on the spin state of
defects is a second order effect. Conse-
quently, the magnitude of the external
spin-aligning magnetic field for a reso-
nance transition between spin states differs
only slightly from that field required for
transitions between the spin states of a free
electron. In a solid these Coulombic field
effects are incorporated into the Hamilto-
nian in the "g-tensor". The eigenvalues of
this ^-tensor are observed in the spectrum
of a defect in a glass as singularities of the
"powder pattern" (McMillan, 1968). These
singularities provide one means for identi-
fying defects in a glass. Thus defects pro-
duced in glasses by ion implantation can
be identified in most case by these singular-
ities. It will be noted in the following dis-
cussion that one type of defect has several
variants in ion-implanted silica. Many of
the electronic states due to chemical disor-
der (defects) in SiO2 have been described
(Weeks, 1956, 1967; Griscom, 1980; Gris-
com etal., 1988). The three defects for
which detailed atomic structures have been
developed are the singly charged oxygen
vacancy (E' center) (Weeks and Nelson,
1990; Griscom, 1980; Weeks, 1967; Ar-
nold, 1978; Arnold etal., 1990; Antonini
et al., 1982), neutral non-bridging oxygen
(NBOH center) (Griscom, 1980), and sing-
ly charged oxygen molecule ion (POR)
bonded to a Si (Friebele et al., 1979; Pur-
cell and Weeks, 1969). These paramagnetic
states are not detected in well annealed
samples of the purest silica.
Implanting ions in silica produces these
defects since in most cases ion energies are
sufficient to produce many displacements.
In Section 6.3 we described the optical
bands produced by implanting a variety of
ions into silica. Although EPR spectra
were not reported in the papers referenced
in Section 6.3, the three paramagnetic de-
fect states discussed above were produced.
Whichard (1989) measured the concentra-
tion of E' centers as a function of type
of implanted ion and dose. Figure 6-21
(Whichard, 1989) shows E' center con-
centration in the implanted layer as a
function of dose and of ion type for doses
>10 1 6 cm" 2 . The highest concentrations
are found for a dose of 1016 cm~ 2 Cr or Fe
ions. The concentrations decrease with in-
E1 type signal
a. 60 - • Mn A Fe
O Cr o Ti
.£ 40 -
I o
•£ 20 - O
D A
A
• 8
I I l 1 ! i
1 2 3 4 5 6
Q.
Implantation dose in 1016 ions/cm 2
Figure 6-21. The concentrations of E' centers in the
implanted layer as a function of dose. The thickness of
the implanted layer was assumed to be 200 nm (see
Figure 6-1).

creasing dose. In the case of Ti and Mn the
concentration is, within the errors of mea-
surement, invariant with dose and less than
for Cr and Fe.
Whichard notes that for a dose of 1015
cm" 2 every substrate ion in the implanted
layer is displaced at least once. He then
notes that in the case of the production of
defects by neutron irradiation, concentra-
tions of E' centers in silica or in a-quartz
decrease with increasing dose when the
dose is sufficient to displace every ion at
least once (Stevens, 1955; Stevens et al,
1958; Weeks, 1965). The decrease in the
case of ion implantation is due to the same
factors that cause a decrease in the case of
neutron irradiation (Weeks, 1965). The dif-
ferences between types of implanted ions is
attributed to differing reactions between
substrate defects and ion types. Magruder
et al. (1990 b) have attributed the differing
reactions between implanted ion types and
substrate ions to differences in the reactiv-
ity of the implanted ions with oxygen (see
Table 6-4).
Hosono et al. (1990) have investigated
paramagnetic defects in silica samples im-
planted with ions of the first transition se-
ries of elements. The EPR spectra of sam-
ples implanted with Ti, Fe and Cu, to a
nominal dose of 6 • 1016 cm" 2 , have rela-
tively intense components due to the POR
and E' centers. In the spectrum of a sample
implanted with Cr to a nominal dose of
6-10 1 6 cm~ 2 only E' centers were ob-
served. Measurements at room tempera-
ture as a function of power show that there
are two distinct E' components. Neither is
the one observed in y-ray irradiated silica.
One of these centers saturates at the
highest power (~ 200 mW) while the other
is not saturated. On the basis of the tem-
perature dependence, shapes of the first de-
rivative of the absorption, and gf-values,
one of these components is attributed to
6.5 Magnetic States 357
sites in which the Si, on which the para-
magnetic state is localized, is bonded to
two oxygen ions and one Si ion. They (Ho-
sono et al., 1990) show that an optical ab-
sorption band with a peak at ~ 7.5 eV due
to a transition of the E" center, i.e., the
neutral oxygen vacancy, has an intensity
that increases approximately linearly with
dose in the Cr, Mn, and Fe implanted sam-
ples.
Hosono and Weeks (1990 b) have mea-
sured the dose dependence and depth de-
pendence of the E' centers and POR con-
centrations in Cr-implanted samples.
Figure 6-22 (Hosono and Weeks, 1990 b)
shows the spectra as a function of dose for
three doses. The spectrum of the sample
with the lowest dose (0.5 • 1016 cm" 2 ) has
components due to POR's, E' centers, and
to Cr + 3 . With increasing dose all the re-
solved components decrease. The POR
and Cr + 3 components are not detected at
a dose of 6 • 1016 cm" 2 . Two types of E'
centers, shown on the right side of the fig-
ure, are detected.
By etching the implanted surfaces with
dilute HF solutions, material was removed
to increasing depths. The depths of ma-
terial removed were determined by mea-
suring, by means of the backscattering
technique, the distribution of Cr ions re-
maining after each etching treatment. The
concentrations of POR and E' centers
were measured as a function of distance
from the implanted surface of the sample.
Figure 6-23 (Hosono and Weeks, 1990 a)
shows the changes in intensities of these
two defects with distance from the im-
planted surfaces. The E' center concentra-
tions are highest at the surface and de-
crease with distance from the surface. The
POR concentration increases with dis-
tance from the surface and is a maximum
at the depth at which the implanted ion
concentration is a maximum. On the basis
358 6 Optical and Magnetic Properties of Ion Implanted Glasses

2.0072

2.069

336 346 2U2

Magnetic field in mT

Figure 6-22. The EPR spectra of SiO2 samples implant-ed with Cr. On the left of the figure the spectra at three
doses, (a) 0.5 • 1016 ions cm" 2 , (b) 3 • 1016 ions cm" 2 , (c) 6 • 1016 ions cm~2, measured at a temperature of 110 K
and attenuation of the microwave power of 0 db. On the right the spectra in the region of the E' center measured
at 300 K and the two power levels indicated on the figure. The thin arrows on the left side indicate the g-values
of the peroxy radical center and the fat arrow indicates the X component. The X component is the one shown
in the lower part of the right side of the figure.

(b)

E' type E"' type

|
Figure 6-23. Concentrations of E'
and peroxy radical (POR) centers
as a function of distance from the
1 i
implanted surface. AN, number of
0.1 0.2 0.3 0.1 0.2 0.3 centers removed by an etch; Ad,
Depth in pm Depth in pm
the thickness of material removed
in an etch, (a) Sample implanted
POR with 0.5 • 1016 ions cm" 2 , (b) sam-
ple implanted with 6 • 1016 ions
cm" 2 . The measurements for the
POR spectra were made at 0 dB
attenuation and 110 K and the E'
center measurements were made
at 40 dB and 300 K.
0.1 0.2 0.3
Depth in pm
 6.5 Magnetic States 359

of their data they concluded that oxygen with increasing dose. The dose dependence
ions were predominantly displaced in the of these two centers are shown in Figure
direction of the implanted ion velocity vec- 6-24. The number of E' centers is three
tors. This preferential displacement of oxy- order of magnitude less than the number of
gen ions provides a reservoir of oxygen at POR's as shown in Fig. 6-24 a.
the peak of the implanted ion concentra- The intensities of the E' center compo-
tion with which the implanted ions can re- nent increase with decreasing temperature,
act. in good agreement with a Boltzmann func-
tion, i.e. for hv <^feB7^I ~hv/kBT, where /
6.5.2 Magnetic Properties is the intensity of the component, h is
of Implanted Ions Planck's constant, v is spectrometer fre-
quency, /cB is Boltzmann's constant and T
In many implanting experiments the ion
is absolute temperature. The intensity of
is implanted in the + 1 charge state. In this
state some ions are paramagnetic and if
they retained this charge state after coming Dose dependence EPR signals
to rest their magnetic properties may be
detected. As noted above in Section 6.1, the
final charge states are a consequence of
reactions between the implanted and sub-
strate ions. The ion may have several possi-
ble charge states, ranging from 0 to ± m,
where m is some integer, usually < 5 (Perez
et al, 1987). In the case of noble gas and
metal ions the final state may well be 0.
These charge states and reaction with
4.0 8.0 12.0
substrate ions determine the magnetic
(a) Dose in 1016 ions/cm 2
properties of the implanted ions. The prop-
erties are also a function of dose, dose rate
POR temperature dependence
and substrate temperature during implan- 15
tation.
O 8 -10 15
6.5.2.1 Magnetic States o 1.6-1016
of Implanted Oxygen in Silica 8 10 16
A u • 10
16
a 8- 10
There are few reports (Arnold, 1973) on
the states of oxygen implanted in glasses. a
The only paper, to our knowledge, on mag- I 5
netic states of implanted oxygen is one by
Derryberry et al. (1990). They report that
the most intense paramagnetic state is the 0
0.002 0.004 0.006 0.008
POR. Beginning with a dose of 0.8 • 10 16
(b) 1/7 in K"1
cm" 2 the number of POR's decreases with
Figure 6-24. (a) Dose dependence of the EPR compo-
the next increase in dose and then increases nents (POR and E') in the spectra of oxygen-im-
with further increases in dose. The E' cen- planted SiO2 glass samples, (b) temperature depen-
ter numbers decrease to a constant number dence of the POR component.
360 6 Optical and Magnetic Properties of Ion Implanted Glasses
the POR component deviates markedly
from a Boltzmann function. With decreas-
ing temperature, the increase of intensity of
the POR component is much greater than
expected for a Boltzmann dependence, for
the highest dose, 6 • 10 16 cm" 2 , as shown
in Figure 6-24 b (Derryberry et al., 1990).
This temperature dependence may have
two possible sources. One of these may be
a wide distribution of relaxation times for
the POR spin-lattice relaxation. With de-
crease in temperature the line width for
these spins decreases and contributes to
the observed component. The second may
be exchange interactions between POR's
in clusters with the result that the clusters
are super-paramagnetic. With decrease in
temperature the relaxation times for the
magnetization of the clusters increase.
With decrease in temperature increasing
number of clusters contribute to the com-
ponent. In this case the shape of the com-
ponent should change with decreasing
temperature. The singularities would dis-
appear into an almost symmetrical line
shape. Derryberry et al. (1990) do not re-
port such a change in line shape.
6.5.2.2 Elements of the First Transition
Series
The paramagnetic resonance spectra of
elements of the first transition series intro-
duced into many glassy solids by thermal
processes have been described in several
thousand papers since Sands' publication
(1955) describing the spectra of F e + 3 in an
oxide glass. An excellent review of the
paramagnetic resonance spectra of the 3 d,
4d and 5d elements in a few oxide glasses
has recently been published (Griscom,
1990).
When concentrations of these ions ex-
ceed approximately 1 mol%, magnetic in-
teractions change the EMR spectral prop-
erties. The magnetic properties of such
glasses have been labeled "spin glasses". A
major fraction of the published research on
these materials concerns metallic glasses
(Moorjani and Coey, 1984). One chapter in
Moorjani and Coey's book, chapter V, dis-
cusses the properties of insulating spin
glasses. Spin glasses are materials in which
the concentrations of magnetic ions or
states are sufficient for spin-spin interac-
tions, such as St'Sj, to be the largest en-
ergy term in the spin Hamiltonian and in
which the spin states do not have transla-
tional symmetry. This lack of symmetry
and a coupling of spins in which the sum-
mation pathway determines the net mag-
netic moment produces spero- and speri-
magnetic materials (Moorjani and Coey,
1984). Implanting magnetic ions in a sub-
strate insures the absence of translational
symmetry. Although the ions may form
separate phases, ion doses for which the
concentrations of implanted ions in the im-
planted layer are greater than a few percent
of the substrate ions in the layer occur for
doses ^ 1016 ions cm" 2 when implanted at
one ion energy. Even with the formation of
separate phases particle-particle magnetic
interactions may be expected to lead to the
properties of spin glasses.
We note that implanting ions at one en-
ergy into a substrate material such as SiO2
will result in a concentration of ions at the
maximum of the distribution of the order
of 1 mol% for a dose of 1015 cm" 2 . In the
case of transition elements, magnetic inter-
actions between ions with a random distri-
bution in a substrate is a significant deter-
minant of the electron magnetic resonance
(EMR) spectra of the implanted ions. An-
other factor affecting the EMR spectra of
ions, implanted at one energy in most
oxide glasses is the distribution of ions.
This distribution has a width at half max-
imum amplitude ~120nm for 160 keV

ions. When implanted into a flat surface
these ions form a thin film in which two
dimensions of the film are several orders of
magnitude greater than the thickness of the
film.
Weeks et al. (1985, 1986), Whichard and
Weeks (1989) and Whichard (1989) have
measured the EMR spectra of silica im-
planted with Ti, Cr, Mn, Fe, and Cu. In
addition to spectral components due to
paramagnetic defect states of silica pro-
duced by the implantations, they attribute
other components to magnetic states of the
implanted ions in the case of Ti, Mn, and
Fe. In the case of Cr a spectral component
attributed to Cr was observed at doses
^ 3 • 1016 cm" 2 (Hosono et al., 1990). At a
dose of 6 • 1016 ions cm~ 2 it was not re-
solved. In the case of Cu ions no compo-
nent due to Cu + 2 was detected (Magruder
etal, 1991).
The magnetic properties of each of these
ions implanted in various glasses will be
considered in turn. The order in which they
will be discussed will be the order of the
intensities of the magnetic resonance spec-
tral component attributable to the im-
planted ion. We will begin with the most
intense component.
a) Fe Ions
The spectrum of a silica sample im-
planted with 6 • 1016 ions cm" 2 is shown in
Figure 6-25 (Whichard, 1989; Weeks et al.,
1985) for two orientations of the implanted
surface of the sample with respect to the
laboratory magnetic field (Arnold, 1975).
The shift of the peak of the component to
a higher field when the field is perpendicu-
lar to the implanted surface is due to an
internal field within the implanted layer.
This field, produced by exchange inter-
actions between the Fe ions, is oriented in
the implanted plane. This internal field
6.5 Magnetic States 361
3000 £000
Magnetic field in G
Figure 6-25. The EPR spectra of a SiO2 glass sample
implanted with 6 • 1016 Fe ions cm" 2 with a current
of 4 JJA cm" 2 and substrate temperature of 300 K.
(1) implanted surface parallel to the laboratory mag-
netic field; (2) implanted surface perpendicular to lab-
oratory field.
decreases with decreasing dose and is not
resolved for doses < 3 • 1016 ions cm" 2
(Whichard, 1989). In the case of a dose
6 • 1016 cm" 2 , this internal field increases,
the line width of the component increases,
and the intensity increases to ~ 200 K and
then decreases, below 200 K, with decreas-
ing temperature. Whichard (1989) con-
cludes that these magnetic properties are
due to a spin glass being formed in the
implanted layer. These properties are illus-
trated in Figure 6-26 (Whichard, 1989).
Whichard (1989) showed the transition
to a magnetically ordered state occurred
over a range of doses. This transition is
illustrated in Table 6-5. The intensity of the
component increased from 1 to 33 (relative
units) when the dose increased from 2 to 3
in units of 1016 ions cm" 2 . Since this in-
crease in intensity is much greater than the
increase in dose, Whichard attributed the
excess to an ordering of the Fe ions into a
ferrimagnetic state. Even the state for doses
362 6 Optical and Magnetic Properties of Ion Implanted Glasses

Temperature dependence of Fe EPR signal observed at ~ 300 K instead of the 7%

Resonance field line width and intensity
fraction observed and given in Table 6-5.
o
£000 Fe 6x10 16 ions/cm 2 /side At a dose of 6 • 1016 ions cm~ 2 the order-
-E 3800 ing effect increases, since the table shows
v
T3 • v that the intensity increases by a factor of
" 3600 -
• 5 with an increase of dose of only a factor
• V
§3400 oo o o o o o V of 2.
c
o o I 8
2 3200 - o S o 8 ° B o • o •
Weeks et al. (1986) heat-treated a sample
. . • o
a: ooooo implanted with 3 • 1016 Fe ions cm" 2 for
i 1 j
3000 | | 20 h in air at 800 °C. The intense com-
1200 A ponent due to the iron ions remained
Orientation
1000 but its temperature dependent properties
A 180° O1350
o • • • 160° • 110°
changed. The magnitude of the internal
•£ 800 A
o 90° field decreased from ~ 50 mT to ~ 10 mT
£1
T3
•° O
A
A at 300 K and then increased only to
I 600 • A
A
# A
~ 30 mT at ~ 5 K. The intensity decreased
C ° i A
3 £00 - • O fl
A
#A A
A
- 1 5 % from 200 to 5 K as compared to the
• fio
• °4 A 75% decrease in an as implanted sample.
200
, % These data are consistent with the relative
500
fractions of Fe charge states given in Table
6-3.
^A00
ID
8
Griscom et al. (1988) also observed an
c
| 300 I** 8 intense electron magnetic resonance spec-
CD
—21

A
•
tral component in samples implanted with
.g 200 r A O
A |
(0.8, 1.3 and 2.8) • 1017 Fe ions cm" 2 . The
A ° spectra shown in Figure 6-27 show that
tr 100
- A •
with an increase in dose above that used by
0 i | i |

0 100 200 300 400 500 Whichard the internal magnetic field in-
Temperature in K creases, and for a dose of 2.8 • 10 17 ions
Figure 6-26. The temperature dependence of the reso- cm" 2 it has a value of ~ 0.7 T.
nance field, line width, and intensity of the Fe EPR
component in the spectrum of a SiO2 glass sample
Using KitteFs conditions for resonance
implanted with 6 • 1016 ions cm" 2 . The implanted for ferromagnetic material with a planar
surface of the sample is parallel to the laboratory field geometry and assuming that the implanted
for the angle 180°, and perpendicular for the angle samples are ideal continuous films (Kittel,
90°. The error in the each data is represented by the 1948), Griscom calculates the magnetiza-
size of the symbol for the data.
tion, M, of the implanted layer based on
the fields for resonance with the applied
laboratory field in the plane and out of the
< 1 • 10 16 ions cm 2 was not a paramag- plane of his samples. He finds that there is
netic state. The reason for this assertion is reasonable agreement between the param-
that if it is assumed that the component is eters of the spectra, #-value and magnetiza-
a paramagnetic component then it would tion, M, at room temperature measured at
be expected that because of the Boltzmann - 9 and - 35 GHz.
dependence of paramagnetic states only The temperature dependence of the in-
0.1% of the total number of ions would be tensity of a sample implanted with 8 • 1016
 6.5 Magnetic States 363

Table 6-5. The g-value, line width, and relative intensity of the Fe EPR signal for three implantation doses.

Nominal dose 9 Relative intensity AH Fractiona

(1016 ions/cm2) (arbitrary units) (G)

Fe 6 1 1.897 + 0.003 171 497 ± 8 340 + 5

6 II 2.130 + 0.004 168 358 + 6 350 + 5
31 2.014 ±0.002 31 321 ± 9 120 ± 5
3 11 2.082 + 0.003 33 295 ± 5 125 ± 5
21 2.070 + 0.003 1 315 + 11 7+5
2|| 2.079 + 0.003 1 264 ± 30 7±5
a
1 = perpendicular, || = parallel, = fraction of implanted ions assuming a paramagnetic system.

ions cm 2 is shown in Figure 6-28 over the 4 7i M and finds, as expected, that it has the
temperature range of ~100 to ~58OK. same temperature dependence as the inten-
The temperature dependence has the ap- sity.
pearance of a Curie transition with T/C Whichard (1989) showed that the onset
- 5 0 0 K . Griscom (1988) also plots the of the ordered magnetic phase occurs for
value of A = Hres(out of plane)— Ho = doses < 1016 cm" 2 . Based on his data and
using the equation given above we find
that the magnetization, M, of Whichards
(a) A g=2.0
samples implanted with 6 • 1016 ions cm" 2
is M = 0.0002 T. The Griscom et al.'s sam-
ple (1988) with 8 • 1016 ions cm" 2 has M
~ 0.02 T. An increase in dose by a factor of
1.4 increases the magnetization by a factor
/— /-/out of plane of ~ 100. The dose dependence of the mag-
netization is given in Table 6-6.
The Griscom et al. samples were im-
(b) r-H in plane planted with ions whose energy was

AL
H out of plane
OC ~ 100 keV and for the Whichard samples it

Ir
was 160 keV. The concentration of im-
105K"
planted ions at sample surfaces in Griscom
et al.'s samples was much higher than in
/-105K
the Whichard et al.'s samples. The mag-
290 K-U
netic layers in Whichard samples were
0.0 0.1 0.2 0.3 (U 0.5 0.6 0.7 0.8 0.9 1.0
Magnetic field in T

Figure 6-27. X-band (9.2 GHz) FMR spectra of two

Table 6-6. Dose dependence of magnetization of Fe
planar Fe-implanted silica samples for various angles
implanted silica.
between the applied magnetic field and the sample
plane: (a) sample implanted with 8 • 1016 ions cm" 2 : Dose in (1017 ions cm 2) M in (T)
(b) sample implanted with 1.3 • 1016 ions cm" 2 . Spec-
tra of (a) were obtained at 290 K; those of (b) were 0.58 0.0002
recorded at the indicated temperatures. (The dimen- 0.8 0.02
sions of the implanted dose are given on the original 1.3 0.04
figure as ions/cm3. We believe these dimensions to be 2.8 0.10
in error and should be ions/cm2).
364 6 Optical and Magnetic Properties of Ion Implanted Glasses

Figure 6-28. Integrated FMR in-

tensity (•) and parameter A (O) VS.
temperature (of Fe implanted
sample, dose 8 • 1016 ions cm" 2 ).
100 200 300 400 500 600
Temperature in K

completely buried. It would be interesting

to determine whether the exposure of the
samples examined by Griscom et al. to

V
normal atmosphere after implantation
Fe /
changed the relative fractions of the chem-
ical states of Fe. The diffusivity of oxygen
at room temperature in silica implanted
with Fe is unknown. In silica it is very
small (Schaefer, 1974). It is known (Webb
et al., 1976) that ion implanted silica has a
Mn / much higher etching rate in dilute HF than
x20 ./ does silica. This higher etching rate may be
Ml .II. ' - * — < * < ^

indicative of a porosity of the surface of

dH implanted samples that enhances the etch-
ing rate. If such is the case, then it might be
expected that the diffusivity of oxygen
would be enhanced and the oxidation of
Ti
implanted ions near the implanted surface
*50 would occur.

b) Mn Ions
Figure 6-29 (Whichard, 1989) shows the
Cr.Cu relative amplitudes of the first derivative of
*50 the absorption of the ion related compo-
nent in the EMR spectra of Fe, Mn, Ti, Cr
and Cu ions implanted to the same dose
6 • 1016 ions cm" 2 . The very narrow com-
i i i
2000 3000 4000 G 5000 ponent in the spectra of the Ti, Cr and Cu
Figure 6-29. EPR spectra of silica samples implanted
implanted samples is due to the E' center.
with 6-10 1 6 ions cm" 2 at 300 K, 4|aAcm~ 2 , and The receiver gain for the spectrum of the
160 keV. Fe implanted sample was too small to de-
 6.5 Magnetic States 365

tect the E' center. At higher gain it is de- state. No hyperfine components (Mn)
tected as shown in Figure 6-21. (Whichard, 1989) were resolved in the spec-
The temperature dependence of the line tra of the Mn implanted samples. Thus
width, relative intensity and resonance
field of the component due to the Mn ions
Temperature dependence of Fe EPR signal
are shown in Figure 6-30 (Whichard, 1989). resonance field, line width and intensity
No long-range ordering of Mn spins was 3550
detected. The resonance field decreased
and the line width increased to the lowest
temperature at which measurements were
made, ~ 5 K. The relative intensity in-
creased to ~ 80 K and then decreased with
decreasing temperature. This temperature
dependence of these magnetic parameters
are similar to those of the Fe component in
the Fe implanted samples. Thus it is rea-
sonable to assume that the magnetic prop-
erties of that fraction of Mn ions contribut-
ing to the resonance component are in a
spin glass state.
It is evident from Figure 6-29 that the
fraction of Mn ions contributing to the res-
onance component is approximately a fac-
tor of 50 less than the fraction of Fe ions
contributing to the Fe component. Given
the chemical similarities of Mn and Fe im-
planted into the same substrate composi-
tion, it is reasonable to assume that the
chemical states of Mn ions after implanta-
tion are similar to those of Fe. On the basis 100 200 300 £00 500
Temperature in K
of estimates by Perez et al. (1987) of the
fraction of Fe ions in the 0, + 2, and 4- 3 Figure 6-30. The temperature dependence of the reso-
nance field, line width, and signal intensity of the Mn
states, there should be approximately the spectral component in the spectrum of a sample im-
same fraction of Mn ions in these states for planted to a dose of 6 • 1016 ions cm~2 (at 4 uA cm" 2 ,
the same dose as there are Fe ions in this 160 keV, and substrate temperature 300 K).

Table 6-7. The g-value, line width, and relative intensity of the Mn EPR signal for three implantation doses.

Nominal dose 9 Relative intensity AH Fractiona

(1016 ions/cm 2) (arbitrary units) (G)

Mn 6 1.995 ±0.004 3.3 196 ±12 6.0 ± 0.5

3 1.996 ±0.002 2.4 208 ±11 7.5 ± 0.5
1 1.998 + 0.003 1.0 235 ±23 9.2 ± 0.5

Fraction of implanted ions assuming a paramagnetic system.

366 6 Optical and Magnetic Properties of Ion Implanted Glasses
the magnetic interactions between the Mn
ions apparently suppressed the hyperfine
structure of any Mn + 2 ions. We note that
Whichard did not report detection of a
g = 4.3 component in Mn implanted sam-
ples. It appears that Mn ions, randomly
distributed in the silica structure, at least in
sites which have crystal fields which pro-
duce the g = 4.3 component, have not been
detected.
Table 6-7, taken from Whichard's disser-
tation (1989), shows that the relative inten-
sity and fraction of ions detected based on
the "paramagnetic assumption" as a func-
tion of dose differ markedly from the de-
pendence shown in Table 6-7. Whichard
attributes this dose dependence to an anti-
ferromagnetic or speromagnetic ordering
of the Mn spins. He notes that MnO has a
Neel transition at 118 K and MnO 2 one at
90 K and ascribes the maximum in relative
intensity which occurs at ~100 K, shown
in Figure 6-30, to the onset of such transi-
tions.
c) Cr Ions
Hosono et al. (1990) have detected a
component in the spectra of samples im-
planted with doses between 0.5 and
3 • 1016 ions cm" 2 . The #-value (1.97) and
line shape are those expected for Cr + 3 in
oxide glasses (Landry et al., 1967). The
absence of a component due to Cr ions
when the dose of implanted ions > 3 • 1016
ions cm ~2 is evident in Figure 6-22. The
intensity of this component (# = 1.97) de-
creases with increasing dose and is not de-
tected in the spectrum of the sample im-
planted with 6 • 10 16 ions cm" 2 .
The argument which we proposed above
that the fractional distribution of chemical
states in the Mn case is similar to that of
the Fe case can also be made for the Cr
case. The paramagnetic resonance spectra
of Cr + 3 has most often been observed in
silicate glasses (Arnold, 1978). If, as in the
case of Fe, Cr forms oxide precipitates the
various chromium oxide phases, CrO,
Cr 2 O 3 and CrO 2 , would determine the
magnetic properties and the EMR spectra.
The Neel transition of Cr 2 O 3 is - 307 K
(Gray, 1957). Thus we suggest that in the
case of Cr the tendency to anti-ferromag-
netic or speri-magnetic ordering is well es-
tablished at 300 K and no EMR compo-
nent due to Cr precipitates would be ex-
pected. The Neel transition of Cr colloids
would be - 4 7 5 K (Arnold, 1980). As dis-
cussed in Section 6.3 the optical absorption
properties of the Cr, Mn and Fe implanted
samples are consistent with absorption ex-
pected for particles whose sizes are small
compared to the wavelength of the ab-
sorbed light.
d) Ti Ions
A component due to Ti 3 + is well re-
solved in the spectrum shown for a Ti im-
planted sample in Figure 6-31 (Whichard
and Weeks, 1990). The temperature depen-
3000 3500 4000
Magnetic field in G
Figure 6-31. The EPR spectrum of a sample im-
planted with titanium to a dose of 6 • 1016 ions cm" 2
(at 4 uA cm ~ 2, 160 keV and substrate temperature
300 K).

dence of the intensity of the component is
well fitted by a Boltzmann function down
to ~ 5 K. Within experimental error the
line width and field for resonance are in-
variant with temperature from 300 to 10 K
for doses from 1 to 6 • 1016 ions cm" 2 .
Hence the Ti + 3 ions which contribute are
paramagnetic from 300 to 5 K. Table 6-8
shows that the number of Ti + 3 ions de-
tected is not a linear function of the dose
and that the fraction of ions contributing
to the component decreases between < 1
and > 3 • 1016 ions cm" 2 . A major fraction,
- 9 0 % for a dose of 6 • 1016 ions cm" 2 ,
is not detected in the EPR spectrum.
Whichard et al. (1990) have found that the
magnitude of the exchange integral for the
paramagnetic fraction of the Ti 3 + ions
ranges from 10 to 1.6 • 10 ~6 eV. They as-
sume that the paramagnetic fraction is that
fraction in the tails of the ion distribution
measured by ion back scattering, as shown
in Figure 6-32 (Whichard et al., 1990) by
the triangles. The temperature dependence
from 5 to 300 K of line width, resonance
field and intensity for all doses was that
expected for a paramagnetic state.
The chemical states of the large fraction
of Ti ions not detected in the EPR spectra
were not identified. It is plausible to as-
sume that some fraction of those unde-
tected Ti ions are in + 2 and + 3 states. On
the basis of this assumption we then sug-
gest that these Ti ions have large exchange
Table 6-8. The g-value, line width, and relative inten-
sity of the Ti EPR signal for three implantation doses.
Nominal dose g AH Relative
(1016 ions/cm2 ) (G) intensitiy
(arbitrary
units)
Ti 6 1.936 + 0.007 145 + 15 6 Cu + 1 . They note that in the case of silica
3 1.931 ±0.007 180 ± 15 3 implanted with Cu, the optical absorption
1 1.941 ± 0.005 205 + 15 4
6.5 Magnetic States 367
RBS of Ti ion implanted silica
Ti dose in ions/cm2
A 1 x10,16 0.15 E
° 3
0.10 -2
0.05 £
1- a
°o
A.2 °A ^ '
0.00
0.0 0.1 0.2 0.3
Depth in |jm
Figure 6-32. The backscattering depth profiles for ti-
tanium implanted samples. The outlined regions in
the tails at depths > 150 nm account for half of the
implanted ions detected by EPR in that sample. The
other half of the detected ions are assumed to be
located in the tail near the sample surface.
interactions which are either anti-ferri-
magnetic or speri-magnetic. Whichard
(1989) reports some experiments in which
he detected transient signals that were at
least two orders of magnitude more intense
than the paramagnetic component. He
does not describe an experimental proce-
dure which ensured reproducible data. He
did note that the transient signal was de-
tected again when a sample was removed
from the EPR spectrometer and magnetic
field for more than three days.
e) Cu Ions
The only EMR or EPR components de-
tected in Cu implanted samples were those
due to silica defects. Weeks et al. (1989) im-
planted silica and two other types of glass
samples. The other two samples were a
standard Corning borosilicate and alumi-
no-silicate glasses. In none of these glasses
did they detect any compoent attributable
to Cu + 2. They suggest that implanted Cu
is either in a colloidal state, i.e. Cu°, or
spectra of samples, with a range of doses
368 6 Optical and Magnetic Properties of Ion Implanted Glasses
>10 1 6 ions cm 2, contained no resolved
band at 5.2 eV, the energy of a band attrib-
uted to Cu + 1 in silicate glasses. They note
that in the case of the samples of the other
glasses the optical absorption at energies
> 4 e V were too intense to observe this
band. By comparison with the absorption
spectra of Cu in silica samples in which the
absorption bands in the 2 to 4 eV range are
attributed to Cu colloids, the absence of
these bands in implanted samples of the
other glasses leads to the conclusion that in
these glasses a major fraction of the Cu is
in the + 1 state.
6.6 Glasses Produced
by Implantation
of Crystalline Substrates
Irradiation of one of the crystalline
forms of silica, a-quartz, with neutrons
transforms the crystal to a glass with a
density that is ~ 2 . 5 % greater than the
density of a silica glass formed by thermal
processing (Lines and Arndt, 1960; Primak
et al, 1955). The increase in the refractive
index of silica implanted with noble gas
ions is ~ 2%. This is the increase expected
from the increase in density which results
from the modification of the structure of
thermally processed silica by atomic dis-
placements. In addition to the changes in
structure which produce the increase in
density, optical absorption bands and
paramagnetic states due to defects are in-
troduced by the irradiation.
Among other wide band-gap crystals
which have been observed to trans-
form to the amorphous state under
some conditions of ion implantation are
A12O3 (McHargue et al., 1990a, b), SiC
(McHargue et al., 1990 c), Si^N* (Arnold
and Borders, 1976), CaTiO 3 (White et al.,
1989), KTaO 3 (Arnold and Borders, 1976),
and many naturally occurring silicates
(Wangetal., 1990).
Townsend et al. (1990) have fabricated
optical waveguides in A12O3 by implanting
group IV elements. The amorphous state is
produced by elements of the group IV col-
umn at doses and substrate temperatures
during implantation, less than for the ele-
ments in other columns of the periodic
table. The dose is < 10% of the dose and
the substrate temperature during implan-
tation may be 300 K compared with a tem-
perature of ~ 80 K required for other ele-
ments (McHargue et al., 1985). Figure 6-33
(Townsend et al., 1990) shows the refractive
index of A12O3 implanted with 5 • 1016 car-
bon ions cm" 2 . The data show that larger
decreases in the refractive index are pro-
duced when the implanted face of an A12O3
crystal is the Z face. The damage profile
and the carbon ion profile have substantial
differences as shown in Figure 6-34 (An-
tonini et al., 1982; Arnold, 1980).
The chemical state of the C ion has not
yet been investigated. Townsend et al.
(1990) suggest that the column IV ions act
as catalysts in the process of forming a
glass network: "The distortions associated
I./D
Y Z
n
h
/77 = 2
1.76 Z
m=1
- m-\
1.77
\
1.78 i i
1
Depth in nm
Figure 6-33. Waveguide refractive index profiles (for
an implanted dose of 5 • 1016 carbon ions cm" 2 ):
6MeV.
 6.6 Glasses Produced by Implantation of Crystalline Substrates
Figure 6-34. Comparison of ion range and damage
distributions (for 6 MeV carbon implants in A12O3).
with the tetravalent bonding are not local-
ized at a single site but influence some tens
of neighboring lattice atoms." This quota-
tion clearly indicates that Townsend et al.
have assumed that the C ions are multiva-
lent. The chemical reactions between im-
planted ions and substrate ions affect the
structure of substrate ions far beyond the
nearest neighbor range. The mechanism
for such a long range interaction is not
obvious, as is indicated by the use of the
term "catalyst". In this case C ions cannot
react directly with each of the "tens of
neighboring ions" as is the case for those
chemical reactions usually labeled "cata-
lytic".
Conversion electron Mossbauer spec-
troscopy (CEMS) has been used to deter-
mine the chemical states of Fe and Sn im-
planted in A12O3 (McHargue et al., 1987,
1990 b). The chemical states of Fe, as a
function of dose implanted at ~ 300 K, are
shown in Figure 6-35 (Perez, 1984). The
implanted layers for these doses implanted
at ~ 300 K are still crystalline. A substrate
temperature ~ 80 K is necessary for the
formation of an amorphous layer. The
chemical states of Fe in this case are shown
in Figure 6-35 (Perez, 1984). The data show
that there are differences in the chemical
states which form at the two temperatures.
369
The major differences are the production
of Fe + 4 which increases with increasing
dose in two different sites and the absence
of Fe + 3 in samples implanted at 77 K. A
decrease in Fe + 2 in two differing sites with
increasing dose occurs in both cases. The
fraction of Fe in the Fe° state is invariant
with dose for implantation at 77 K but
increases with dose for implantation at
300 K.
The optical absorption of the implanted
layer, implanted at ~ 300 K, has a depen-
dence on photon energy that is similar to
that of Fe implanted silica (Stark et al.,
1987). Optical absorption of A12O3 im-
planted at 77 K has not yet been reported.
Based on this similarity, the explantation
proposed by Perez et al. (1987) for the pho-
ton energy dependence of the absorption in
Fe: SiO2 is also applicable to the Fe: A12O3
case.
In the case of implanted C ions in A12O3,
Townsend et al. (1990) suggested that col-
umn IV elements were much more effective
in producing an amorphous state in A12O3
than were other elements. McHargue et al.
(1990) have determined the chemical states
and their fractions of implanted Sn ions in
the amorphous layer of A12O3 produced
by implantation at - 3 0 0 K of 4 • 1016
ions cm" 2 . The final charge states of the Sn
ions were + 2 and + 4. The possibility that
some small (< 2%) fraction of the Sn was
in the 0 state could not be resolved. Neither
refractive index nor optical absorption of
Sn implanted samples have been reported,
to our knowledge. If the Sn ions interact
with the substrate ions to form the amor-
phous state does this interaction also affect
the defect states of the substrate?
McHargue et al. (1990 b) have used
CEMS to determine the chemical states of
Fe implanted in single crystal SiC. Their
samples were implanted with doses ranging
from 1 to 6 • 1016 ions c m ' 2 at - 3 0 0 K .
370 6 Optical and Magnetic Properties of Ion Implanted Glasses

(a) (b)
Ion fluence in 10 16
ions cm Ion fluence in 1016 ions cm" 2
) 2 4 6 8 10 0 2 4 6 8 10
i

20 -
A*
n
40

20
60
Fe
40 : \
.£ °
in 40
20
2+
§20 Fe
n i 1 1
a
CD
Figure 6-35. (a) Fluence (in-
1
' I 1 1
iS ° 40 tegrated flux) dependence of
•i 40 the different components
20 ^ - • — • •
present in the Mossbauer
or
Fe'2 + - F e 3 <
\ ^ spectra (A12O3 single crys-
20 0 1 1 tals implanted with 160 keV
57
0 1 I 1
Fe at 77 K). (b) Fluence
40 - (integrated flux) dependence
40
of the components present
20 20 in the Mossbauer spectra of
Feu '. Fe° iron-implanted crystalline
0 n- a-—°~~ r A12O3 (300 K).
10 20 30 10 20 30
Concentration Fe/AI in % Concentration Fe/AI in %

The implanted layers were amorphous for phenomena which will appear upon ion
all doses. The CEMS spectra were attrib- implanting samples chosen from the enor-
uted to a single charge state in sites with mously wide range of glass systems. The
small differences in local symmetries. Re- final charge state of ions from the first tran-
fractive indices, optical absorptions and sition series of elements implanted into sil-
magnetic properties have not been re- ica, range from 0 to + 3 . Implanted Cu has,
ported. apparently, only one charge state, i.e. 0.
Implanted into a boro- or alumino-silicate
glass the charge state is only + 1 . Thus it
6.7 Conclusions and Prognosis was possible, in this case, to control the
charge state of the implanted ion by chang-
This review has been primarily about ing the composition of the substrate. It
ion implanted silica. The reason for the may be possible to control the charge
absence of other glass systems is that little states of the transition elements and other
research has been reported on substrates elements by substrate composition.
other than silica. In our opinion, there are Successive implantation of two or more
many fascinating, scientifically interesting, ions from the first transition series in silica
and useful possibilities in the unknown is still to be done. To our knowledge, co-

implantation into substrates of other com-
positions has not been performed either.
The revolution in communication tech-
nology which has taken place over the past
two decades with the introduction of glass
fibers may continue with the development
of optical circuit elements by implantation
technologies.
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7 Chalcogenide Glasses

Stephen R. Elliott

Department of Chemistry, University of Cambridge, Cambridge, U.K.

List of Symbols and Abbreviations 377

7.1 Introduction 380
7.1.1 Classification of Amorphous Chalcogenide Materials 380
7.2 Preparation of Amorphous Chalcogenide Materials 381
7.2.1 Melt Quenching 381
7.2.2 Vapour Deposition 389
7.2.3 Other Preparation Methods 391
7.3 Structure 391
7.3.1 Definitions 391
7.3.1.1 Short-Range Order 391
7.3.1.2 Medium-Range Order 393
7.3.1.3 Long-Range Structure 395
7.3.2 General Aspects of the Structure of Amorphous Chalcogenide Materials . . 395
7.3.2.1 SRO in Chalcogenides 395
7.3.2.2 MRO in Chalcogenides 396
7.3.3 Structure of Specific Amorphous Chalcogenide Materials 401
7.3.3.1 Structure of Pure Chalcogens 401
7.3.3.2 Structure of V-VI Materials 403
7.3.3.3 Structure of IV-VI Materials 409
7.3.3.4 Structure of III-VI Materials 414
7.3.3.5 Metal Chalcogenide Materials 414
7.3.3.6 Structure of Halogen Chalcogenides 416
7.4 Defects 416
7.4.1 Introduction 416
7.4.2 Wrong Bonds 417
7.4.3 Coordination Defects 420
7.4.4 Experimental Probes for Defects 423
7.4.4.1 Electron Spin Resonance 423
7.4.4.2 Photoluminescence 425
7.5 Opto-Electronic Properties 427
7.5.1 Electronic Structure 427
7.5.2 Optical Properties 428
7.5.3 Electrical Properties 432
7.5.4 Photo-Induced Changes 438

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
376 7 Chalcogenide Glasses

7.6 Applications 441

7.6.1 Infrared-Transmitting Optical Components 441
7.6.2 Xerography 442
7.6.3 Lithography 444
7.6.4 Solid Electrolytes 445
7.6.5 Threshold and Memory Switching 446
7.7 References 448
 List of Symbols and Abbreviations 377

List of Symbols and Abbreviations

D characteristic coherence length

DJQ) molecular-packing structure factor
d spatial repeat distance
EA valence band edge
EF Fermi energy (level)
Eg bandgap
E« viscosity activation energy
Es thermopower activation energy
Ea conductivity activation energy
E" configuration of edge-sharing tetrahedra (ft = 0-2)
e electronic charge
/»(Q) molecular form factor
G{E) vibrational density of states (eV"1)
g Lande ^-factor
g(E) electronic density of states (eV" 1 cm" 3 )
i current
k Boltzmann constant
m average coordination number
N number of valence electrons per atom
number of mechanical constraints
Nd number of degrees of freedom
n refractive index
coordination number
pNL non-linear electronic polarizability
Q scattering vector
Qn configuration of coordination polyhedron in terms of number n of bridging
ligands
load resistor
r bond length
s thermopower
S(Q) structure factor
S(Q,co) dynamic structure factor
T temperature
T% glass-transition temperature
quench temperature
U effective correlation energy
strain potential energy
vB voltage applied by a bias battery
holding voltage
vth threshold voltage
w electronic hopping energy
X mole fraction
378 7 Chalcogenide Glasses

a optical absorption coefficient

a~* electron localization length
as bond-stretching force constant
P bond-bending force constant
y temperature coefficient of b a n d g a p
F Urbaeh-edge parameter
s dielectric constant
r\ viscosity
rja asymmetry parameter of electric-field gradient tensor
9 b o n d angle
ju electronic drift mobility
n Peltier coefficient
Q electrical resistivity
a- bonding orbital
•a-* antibonding orbital
<r dc d.c. electrical conductivity
o0 pre-factor for d.c. conductivity
G(CO) a.c. conductivity
(j> dihedral angle
X electronegativity
co radial frequency

a- amorphous
C chalcogen
CBH correlated barrier hopping
COCRN chemically ordered continuous random network
CON chemically ordered network
CRN continuous random network
CVD chemical vapour deposition
CW continuous wave
DOS density of states
EPR electron paramagnetic resonance
ESR electron spin resonance
EXAFS extended X-ray absorption fine structure
FSDP first sharp diffraction peak
g- glassy
IR infra-red
IRMRO intermediate-range medium-range order
IVAP intimate valence-alternation pair
LP lone pair (non-bonding) orbital
LRMRO long-range medium-range order
LRS long-range structure
MAS magic-angle spinning
MD molecular dynamics
MHC minimum holding current
 List of Symbols and Abbreviations 379

MRO medium-range order

NB non-bridging
NBO non-bridging oxygen
NMR nuclear magnetic resonance
NQR nuclear quadrupole resonance
ODMR optically-detected magnetic resonance
P pnictogen
PECVD plasma-enhanced chemical vapour deposition
PL photoluminescence
PLE photoluminescence excitation
RCN random covalent network
RDF radial distribution function
RI refractive index
SRMRO short-range medium-range order
SRO short-range order
STAG Si~Te-As-Ge alloy
STE self-trapped exciton
T tetragen
TPC transient photoconductivity
UV ultra-violet
UPS ultra-violet photoemission spectroscopy
VAP valence-alternation pair
VB valence band
VDOS vibrational density of states
XPS X-ray photoemission spectroscopy
1D one-dimensional
2D two-dimensional
3D three-dimensional
380 7 Chalcogenide Glasses
7.1 Introduction
Chalcogenide materials are compounds
containing elements from Group VI (B) of
the Periodic Table, viz. S, Se, Te. Strictly
speaking, oxides should also be included in
this category, but they are often considered
separately. There are two reasons for this
division, one historic and one scientific.
Oxide materials, particularly those based
on silica, are the oldest-known glass-form-
ing systems, and it has become traditional
to treat them separately from the more re-
cently discovered chalcogenide materials.
Furthermore, although oxygen is also a
Group VI element, the physical behaviour
of oxides is often rather different from that
of chalcogenides, principally because the
former have a much more significant ionic
contribution to the chemical bonding than
the latter, which are essentially completely
covalent materials (in the absence of net-
work-modifying cations). For example, ox-
ides are generally insulators, with large val-
ues of the bandgap (~ 10 eV in the case of
SiO2), whereas for chalcogenides the gap is
generally considerably smaller (1-3 eV),
and hence these materials are semiconduc-
tors.
Chalcogenide materials are of interest
for a variety of reasons: they can be pre-
pared in amorphous form in a variety of
ways, either as vapour-deposited thin films
or as melt-quenched glasses; they mostly
form glasses continuously over wide com-
position ranges, the physical properties of
which also vary in a continuous fashion;
they exhibit behaviour which is often
unique; finally, there are a number of ac-
tual and potential technological applica-
tions of such materials.
In spite of the undoubted importance
of chalcogenides as a major category
amongst amorphous materials, there have
been few previous reviews devoted entirely
to general properties of these materials,
with the exception of the book by Borisova
(1981); glass-formation aspects have been
emphasized in the book by Rawson (1967)
and the review by Kreidl (1983), and the
physics of chalcogenide materials (as well
as that of other amorphous solids) has
been discussed by Elliott (1984, 1990) and
Zallen (1983).
In this review, we will follow the nomen-
clature proposed by Elliott (1984, 1990),
namely that the term amorphous (or equiv-
alently, non-crystalline) applies generally
to those materials lacking the long-range
translational periodicity characteristic of
crystals, whereas the term glassy (or equiv-
alently, vitreous) is reserved only for those
amorphous materials (not necessarily pro-
duced by melt-quenching) which exhibit a
glass transition, i.e. a discontinuity in heat
capacity, or a change in slope of the den-
sity, at the glass-transition temperature, Tg.
7.1.1 Classification of Amorphous
Chalcogenide Materials
A number of families of chalcogen-con-
taining amorphous systems can be distin-
guished (see Table 7-1). Simplest amongst
these are materials consisting either of
a single chalcogen (C) element (e.g. S, Se,
Table 7-1. Categories of amorphous chalcogenide
systems.
Class Examples
1. Pure chalcogen S, Se, Te, SxSe1_x
2. Pnictogen-chalcogen As 2 S 3 , P2Se
(V-VI)
3. Tetragen-chalcogen SiSe2, GeS2
(IV -VI)
4. Ill-VI B2S3, I n ^ e ! _ x
5. Metal chalcogenide MoS 3 , WS 3 ,
Ag 2 S-GeS 2
6. Halogen-chalcogenide As-Se-I, Ge-S-Br,
Te-Cl
 7.2 Preparation of Amorphous Chalcogenide Materials
Te) or alloys or compounds of two such
chalcogens. (The conditional glass-former,
TeO2 - viz. a material which by itself does
not form a glass, but which does when al-
loyed with another material - could also be
considered to be a member of this family.)
Two common chalcogenide systems con-
sist of V-VI materials, i.e. compounds
with pnictogen (P) atoms from Gp VB (e.g.
P, As, Sb), where the glass-forming regions
are mostly centred around the stoichio-
metric composition P 2 C 3 , and compounds
with Gp IVB elements, i.e. Si, Ge (denoted
tetragens, T, in view of the prevalent tetra-
hedral coordination associated with such
elements), where binary glass-forming I V -
VI compositions are centred around the
composition TC 2 , i.e. analogues of silica,
SiO 2 . In addition, amorphous binary III—
VI compounds can be formed with ele-
ments from Gp III B . Of course ternary
(or higher) compounds within each of the
above categories can also be made amor-
phous (e.g. As-S-Se), as well as ternary (or
higher) compounds between categories (e.g.
Ge-As-Se).
Binary metal chalcogenide systems are
rather rare, exceptions being the com-
pounds with the Gp VIA metals molybde-
num and tungsten, viz. MoS 3 , WS 3 or the
selenium analogues, which are unusual in
that they can only be prepared in amor-
phous form (see Sec. 7.2.3). More fre-
quently, monovalent metals such as the al-
kalis (Gp IA) or the Gp IB elements, Cu and
Ag, can be incorporated as a ternary com-
ponent to form amorphous chalcogenide
compounds.
Finally, halogens (e.g. Cl, Br or I) from
Gp VIIB can also be incorporated in
chalcogenide materials, e.g. in the binary
system Te-Cl, or its ternary derivatives
(Zhang et al, 1988) or as ternary compo-
nents in Ge- or As-chalcogenide systems
(Sanghera et al, 1988).
381
It can be seen from the discussion above
that the range of possible chalcogenide ma-
terials forming amorphous solids is essen-
tially infinite in extent, taking into account
the fact that, in general, the composition of
materials within a particular class of chal-
cogenide can be varied over a wide range
whilst still retaining an amorphous struc-
ture, and also the possibility of forming
multicomponent systems, i.e. involving
combinations of the classes shown in Table
7-1, allows very many other permutations
of composition to be achieved.
7.2 Preparation of Amorphous
Chalcogenide Materials
Very many methods can be used to pro-
duce chalcogenide materials in an amor-
phous form, some of which lead to bulk
materials, whilst others yield thin films de-
posited upon a substrate. The composi-
tional range for which chalcogenide mate-
rials can be rendered amorphous depends
on the preparation method used, the more
rapid vapour-quenching (thin film) tech-
niques in general permitting a wider com-
position range to be produced in non-crys-
talline form than is the case for those
methods producing bulk material, notably
melt-quenching.
7.2.1 Melt Quenching
The technique of preparing bulk glasses
by means of rapid quenching of a melt is
historically the most established and is still
the most widely used in the preparation
of amorphous chalcogenide materials.
Very many chalcogenide materials are, in
fact, good glass formers and the melts of
such materials, held in sealed evacuated
(silica) ampoules, will often vitrify when
cooled relatively slowly ( ^ l - l O O K s ^ 1 )
by quenching in either air or water. More
382 7 Chalcogenide Glasses

rapid quenching techniques have also been

used, e.g. roller-quenching for Sb 2 S 3 (Cer-
vinka and Hruby, 1982) and melt-spinning
for Te-Se, Ge-Se, and Te-Ge alloys
(Dembovsky et al., 1987) (see also Chap. 2).
Glass formation, however, is a poorly-
understood phenomenon, and many fac-
tors appear to be important in determining
whether or not a particular material read-
ily vitrifies. The overwhelming consider-
ation, of course, is the avoidance of crystal-
lization in the quenching process; thermo-
dynamic, kinetic and structural factors can
influence this process.
Thermodynamic aspects relating to the
melt can sometimes be important; for in-
stance, Rawson (1967) has emphasized the
fact that the sharp decrease in the liquidus
temperature associated with eutectic for-
mation in alloys facilitates glass formation
for compositions straddling the eutectic
composition due to the relatively low
amount of thermal energy present in such
melts which is available for atomic migra-
tion and which could lead to the formation 100 -
of crystalline nuclei. However, in chalco-
genide materials, such behaviour does not
seem to be prevalent; instead, compound
formation and the resulting atomic struc-
ture seem to be the dominant controlling
at% As
influences. For example, Fig. 7-1 shows the
Figure 7-1. Phase diagram for the As-Se system
phase diagram for the As^Se^,, system, (Kadoun et al., 1983). The dashed zone is the range of
whence it can be seen that the liquidus tem- measurements. The compositional dependence of the
perature exhibits a pronounced maximum glass-transition temperature is given by the open and
at the stoichiometric composition x = 0.4, filled circles.
corresponding to the compound As2Se3, in
which the structure can be completely
chemically ordered, viz. each type of atom Another important quantity which af-
exerts its normal valence (As = 3, Se = 2) fects glass-forming ability is the viscosity of
with unlike atoms as nearest neighbours the melt. Generally speaking, the more vis-
(see Sec. 7.3). This composition also corre- cous the melt at a given temperature above
sponds to that at which the glass-forming the melting point, the greater is the pro-
ability is optimum, as evidenced by the pensity for glass formation. On cooling
maximum in the glass-transition tempera- (and ultimately supercooling) the melt, the
ture, Tg, at the same composition (Fig. 7-1). viscosity rj invariably increases even fur-
 7.2 Preparation of Amorphous Chalcogenide Materials 383

ther since it is usually thermally activated,

viz.
i, = i/oexp(£lf/fcr) (7-1)
Consequently crystal formation is kineti-
cally constrained, since the necessary
atomic mobility in the liquid to form crys-
tallites becomes increasingly difficult.
In this regard, the compositional depen-
dence of the isothermal viscosity of the sys- 0.001
tem As x S 1 _ x is of interest (Fig. 7-2a), for
which three regions can be distinguished: Figure 7-2 a). Compositional dependence of the iso-
a pronounced maximum of r\ occurs at thermal viscosity of As^S^^ liquids at 900 K, calcu-
x = 0.4 (II), with Y\ rapidly decreasing to lated (dashed line) and experimental values (vertical
a very low value at an As content of bars) (Chaussemy et al., 1983).
JC^O.5 (region I), whilst on the S-rich side
of the stoichiometric composition, the vis-
cosity decreases more slowly (region III) , , _ r
En(eV)
(Chaussemy et al., 1983). This behaviour
1 1.0
for rj is due to a similar compositional de-
pendence of the viscosity activation energy
[ * AsxS1_x |
(Fig. 7-2 b). Similar, but smaller, anomalies
in the viscosity at the stoichiometric com-
position are also observed in the chemi-
0.5 - v=v o exp(E n /kT)

-4 ,
cally similar system As^Se^^ (Kadoun
et al., 1983).
0 i i .. ..

The compositional dependence of the 0.5 0.6 0.7 0.8

isothermal viscosity can be understood in 1-x

terms of the dominant structural moieties
present in the liquids of these binary
arsenic chalcogenides at a given composi-
tion (Fig. 7-3). The addition of As atoms
to the pure chalcogen (sulfur or selenium)
structure causes the chains therein to be-
come increasingly cross-linked by the three-
fold coordinated As atoms (Fig. 7-3 a); as
a result, the viscosity steadily increases
with increasing As content (region III of
Fig. 7-2 a). This process continues until the
stoichiometric composition (x = 0.4) is at-
tained, for which (ideally) the structure is
completely chemically ordered (Fig. 7-3 b)
and the viscosity is a maximum (region II
of Fig. 7-2 a). At still higher As contents,
discrete molecular species, e.g. As 4 S 4 for
Figure 7-2 b). Compositional dependence of the vis-
cosity activation energy, E^, for liquid As x S!_ x
(Chaussemy et al., 1983).
the As^Sj _x system (Fig. 7-3 c) increasingly
are formed which, being almost spherical
and therefore contributing little to the vis-
cosity, cause the precipitate drop in rj at
x^0.45 (region I of Fig. 7-2 a). (Since the
As 4 S 4 molecule is thermodynamically
more stable than the As4Se4 entity, this
accounts for the fact that in the As^Se^^
system a pronounced drop in rj for x > 0.45
is not observed, but only a small dip at
x^0.5 - the structure of the melt in this
case is still extensively cross-linked with
384 7 Chalcogenide Glasses
©As OX
a high proportion of wrong As-As bonds
(Kadoun et al., 1983).)
This behaviour of the viscosity of the
melt, and its microscopic cause in terms of
the structure of the liquid, is consequent-
ly responsible for the glass-forming region
in the As^S^^ (0<x<0.43) system being
appreciably smaller than that for the
AsxSe1 _x system (0<x <0.57). The spheri-
cal nature of the As 4 S 4 molecules means
that there are insufficient steric constraints
present to prevent As-rich As-S melts so-
lidifying into a crystalline (realgar) struc-
tural arrangement on cooling.
Similar considerations apply also to the
^xSex _x system, in which the quasi-spheri-
cal P 4 Se 3 molecule is also very stable ther-
modynamically. As a result, melts with this
composition (x = 0.57) cannot be vitrified,
and this composition in fact divides two
glass-forming regions, viz. 0 < x < 0 . 5 and
0.63 < x < 0.85, the latter being centred
around the composition P2Se (Borisova,
1981).
Another factor that can influence the
glass-forming ability of chalcogenide mate-
rials concerns the kinetics of the quenching
process: in general, the faster the rate of
quenching of a melt, the greater is the
likelihood of forming a glassy and not a
crystalline product. Thus, some materials
can only be produced as bulk glasses with
Figure 7-3. Structural con-
figurations in the As x X 1 _ x
(X = S, Se) system (Kadoun
etal, 1983). a) As cross-
links in chalcogen-rich ma-
terial; b) stoichiometric,
chemically ordered struc-
ture (x = 0.4); c) As4X4
quasi-spherical molecule.
extreme difficulty, and then only using very
high quenching rates; an example is As2Te3
which, unlike its chemical analogues As 2 S 3
and As2Se3, is very difficult to vitrify.
A further factor controlling glass-form-
ing ability can be regarded in terms of a
process of frustration; that is crystallisa-
tion in a multicomponent melt is prevented
from occurring readily, either by a compe-
tition between the formation of several dif-
ferent types of crystal (with different com-
positions) or simply due to the (entropic)
difficulty of rearranging many different
types of atoms to form a multicomponent
crystal. Thus, whilst in some cases glass
formation is difficult, in the case of say bi-
nary compositions (e.g. As2Te3), the addi-
tion of a third (or additional) element usu-
ally leads to an appreciable improvement
in glass-forming ability (e.g. Si-As-Te al-
loys readily form glasses over rather a wide
range of compositions).
In the case of ternary compositions, the
glass-forming region (for a given quench-
ing rate) can be represented in a triangular,
two-dimensional plot. Fig. 7-4 shows the
glass-forming regions of the Ge-As-
chalcogenide (S, Se, Te) system; it can be
seen clearly that, whilst the sulphide and
selenide materials are both good glass-
forming materials (i.e. the areas enclosed
by the glass-formation boundaries are ex-
 7.2 Preparation of Amorphous Chalcogenide Materials 385

complicated. For instance, for the case

As
S(SeJe) 20 40 60 80
Figure 7-4 Glass-formation regions in the systems
1) Ge-As-S; 2) Ge-As-Se; 3) Ge-As-Te (Borisova,
1981).
tensive and comparable), the glass-forming
ability of the ternary telluride system is
somewhat worse than that of the S- or Se-
analogues (and limited to two glass-form-
ing regions), but nevertheless glass forma-
tion is easier than for the binary As-Te
system. Fig. 7-5 shows further examples of
glass-forming regions in ternary I V - V - VI
systems.
In the case of materials with more than
three components, representation of the
glass-forming regions becomes much more
of a quaternary compound, a three-dimen-
sional figure (tetrahedron) is required; an
example is shown in Fig. 7-6 for the case
of the Hg-Ge-Se-Te system (Feltz and
Burkhardt, 1980).
Chemical factors can also determine the
ease of glass formation for chalcogenide
materials. Thus, it is generally found that
glass formation becomes progressively
more difficult as an element in a given
group of the periodic table is substituted
by heavier elements in the same group.
This trend has already been seen in the case
of chalcogen substitution (S-»Se->Te), but
it is also true, for example, for the case of
pnictogens. In general, only a few atomic
percent of Bi can be incorporated in a mul-
ticomponent chalcogenide material before
devitrification occurs, whereas a few tens of
percent of Sb can be so introduced (see Fig.
7-7); in contrast, As-containing glasses are
generally relatively much better glass form-
ers (see Fig. 7-4).
One possible reason for this decrease in
glass-forming tendency with increasing
metallicity (or equivalently atomic number
in a given group of the periodic table)
stems from the fact that, in general, heavy

Si,Ge

80,

P Te As,P
20 40 60 80 20 40 60 80
Figure 7-5. Glass-formation regions in the systems 1) Ge-P-S; 2) Ge-P-Se; 3) Ge-P-Te; 4) Si-As-Te;
5) Si-P-Te; 6) Ge-As-Te (Borisova, 1981).
386 7 Chalcogenide Glasses
HgSi
Figure 7-6. Glass-formation region in the quaternary
system Hg-Ge-Se-Te between the Hg-Ge-Se front
plane and the Ge-Se-Te basal plane of the tetrahe-
dron (Feltz and Burckhardt, 1980). E^^ and E 2 are
eutectics. Glass-formation regions in the sub-system
(A) HgSe-GeSe-GeSe 2 , (B) HgTe-GeSe-GeSe 2 ,
and (C) HgTe-GeTe-GeSe 2 are also indicated.
Figure 7-7. Glass formation region in the systems (1)
Bi-Ge-S and (2) Sb-Ge-S (Borisova, 1981).
elements such as Sn or Pb, Bi and Te tend
to adopt structures (in the crystalline
state) with high coordination numbers, e.g.
(quasi-) octahedral rather than trigonal or
tetrahedral, as a result of the delocalization
of the bonding charge associated with the
increased metallicity. The empirical rules
for glass formation proposed by Zacha-
riasen (1932) asserted that glass formation
was favourable only for those materials
whose structure consists of cation-centred
polyhedra having a small number (three or
four) of anionic ligands (in this case chalco-
gen atoms) surrounding a cation such as
Ge or As etc. Cooper (1978) has shown that
these rules in fact arise from topological
considerations; topological disorder can
readily be introduced into structures con-
sisting of corner-sharing triangular or te-
trahedral polyhedra, and even also into
one consisting of such polyhedra con-
nected together in an edge-sharing fashion
(thereby forming chains), but not if connec-
tion between such small polyhedra is by
means of sharing of faces, or if large (e.g.
octahedral) polyhedra constitute the struc-
tural units (even with corner-sharing con-
nections). In the latter cases, insufficient
degrees of geometrical freedom remain
after the connections between units (poly-
hedra) are all satisfied for disorder to be
introduced and consequently only crys-
talline structures are possible. (Structural
aspects of chalcogenide materials are dealt
with in more detail in Sec. 7-3.)
Finally, the glass-forming ability of chal-
cogenide materials can be discussed in
terms of constraint theory (Phillips, 1979).
Most inorganic, covalently-bonded glass-
forming systems have relatively low values
of (average) coordination number-chal-
cogenides are a canonical example. The
propensity for glass formation can then
be understood in terms of the mechanical
constraints, i.e. the degrees of freedom as-
sociated with bond-stretching and bond-
bending interactions, in a perfectly con-
nected structure.
An atom having all covalent bonds satis-
fied obeys the so-called 8 —JV rule (Mott,
1967), where N is the number of valence
 7.2 Preparation of Amorphous Chalcogenide Materials
electrons and the coordination number nc
is given by the relation
nc = 8 - N (7-2)
Strictly speaking, this relation is only valid
for elements from Groups IV-VII of the
periodic table, although Liu and Taylor
(1989) have generalised this expression tak-
ing account of (formal) charge-transfer ef-
fects. Thus, a chalcogen (from Group VI)
will have a coordination number nc = 2.
For a binary alloy AXB1_X, the average
coordination number, m, is given by
(l-x)nc(B) (7-3)
In general, of course, m is non-integral; for
example, for GeSe2 m = 2.67 and for As 2 S 3
m = 2.4. Thus, m can be regarded as being
the coordination number of a hypothetical
pseudoatom forming a structure whose to-
pology is identical to that of the real mate-
rial.
Phillips (1979) proposed that glass-form-
ing tendency is maximised when
Nc = Nd (7-4)
where Nc is the number of (mechanical)
constraints, Nc, experienced by each atom
(due to the interatomic forces acting on it),
and Nd is the number of available degrees
of freedom. The number of constraints per
atom depends on the coordination num-
ber, and the number of degrees of freedom
is related to the spatial dimensionality of
the system. A material is said to be overcon-
strained if Nc> Nd, and cannot then easily
form a glass (by quenching from a melt),
although an amorphous structure may still
be obtained by employing very rapid (va-
pour) quenching techniques.
The mechanical constraints experienced
by an atom can be considered in terms of
the interatomic forces acting on an atom in
the valence-force-field model, in which the
(strain) potential energy Us is expressed as
387
a sum of contributions from bond-stretch-
ing and bond-bending forces:
C/s = ia 8 Ar 2 + ±j8rgA02 (7-5)
where as and f} are the bond-stretching and
bond-bending force constants, respective-
ly, and Ar and A6 represent small devia-
tions in bond length and bond angle from
the equilibrium values for the bond length,
r 0 , and bond angle, 0O.
For a binary alloy, AXB±-X9 there is only
one bond-stretching interaction (as), but
there are two bond-bending force con-
stants, ft (BAB) and p (ABA), for bending
motions centred on atoms A and B, respec-
tively. For simplicity it is assumed at the
outset that p(BAB) = p(ABA)9 and that
all three force constants act as rigid me-
chanical constraints. Then, the number of
constraints per pseudoatom is given by
(Phillips, 1979):
ATC = m/2 + m(m-l)/2 = m2/2 m^Nd-l
where the first term is associated with as
interactions (the factor of \ arises because
a bond-stretching mode involves two
atoms) and the second term arises from
P interactions. Eq. (7-6) is only valid for
m ^ JV d -l (Dohler et al., 1980). Otherwise,
the fact that Nd + 1 bond angles (in JVd-di-
mensional space) are not linearly indepen-
dent must be taken into account (Dohler
et al., 1980). For a two-fold coordinated
atom (such as a chalcogen), there is one
angular constraint associated with the sec-
ond term in Eq. (7-5), whereas adding each
additional bond gives two more con-
straints because the angles with two exist-
ing bonds must be specified (Thorpe, 1983).
This yields
Nc = m/2 + (Nd-l)(2rn-Nd)/2 m^Nd-l
For ideal glass formation, iVc = Nd (Eq.
(7-4)), and so from Eq. (7-7) the optimum
388 7 Chalcogenide Glasses

average coordination number is given by Table 7-2. Glass-transition and melting temperatures
for some chalcogenide materials.
-1
(7-8) Material Tg(K) Reference rm(K) Reference

For a system in 3D space, Nd = 3, and so S 246 1 392 1

from Eq. (7-8) mc = 2.4. Thus, the stoichio-
metric composition for V-VI materials,
e.g. As 2 S 3 , corresponds, in this picture, to
the optimum glass-forming condition it-
self; experimentally, this appears to be the
case (Fig. 7-1). For IV-VI materials, such
as Ge^Se! _ x , use of Eq. (7-3) together with
Eq. (7-8) yields for the optimum glass-
forming composition xc = 0.2, i.e. GeSe 4 .
The tendency for glass formation in this
system has been investigated experimen-
tally by finding for each composition the
minimum quenching rate needed to avoid
crystallization, and this is shown in Fig. 7-8
for three quenching methods, viz. water-
quenching, air-quenching and slow-cool-
ing. It does appear that the optimal glass-
forming composition corresponds to a
state of mechanical stability rather than
chemical stability (i.e. at the compound
composition GeSe2).
Chemical Mechanical Glass-forming
stability stability difficulty
I Water
quenching
Air
quenching
Slow
cooling
30 20 10 0 model to take account of the presence of
GeSe2 A t %
Ge Se
Figure 7-8. Glass-forming ability (tendency) in the
Ge^Se^^ system (Elliott, 1990). Experimental data
are indicated by solid horizontal bars for various
rates of cooling (water, air and slow quenching). The
solid line is drawn through the data to guide the eye;
the prediction of Phillips' mechanical constraint the-
ory is shown by the dotted line.
Se 318 2 490 1
As 2 S 3 478 2 573 5
As2Se3 468 2 633 5
As2Te3 379 3 633 6
GeSe2 695 2 980 5
GeS2 765 4 1073 6
References: 1) Van Uitert, L. G. (1979), I Appl. Phys.
50, 8052; 2) de Neufville, I P . and Rockstad, H.K.
(1974), in: Proc. 5 th Int. Conf. on Amorphous and
Liquid Semiconductors: Stuke, J. and Brenig, W.
(Eds.). Taylor and Francis, p. 419; 3) Seeger, C.H.
and Quinn, R.K. (1975), J. Non-Cryst. Sol. 17, 386;
4) Wright, A.C., Etherington, G., Erwin Desa, J.R.,
Sinclair, R.N., Connell, G.A.N., and Mikkelson,
J.C. (1982), /. Non-Cryst. Sol. 49, 63; 5) Weast, R.C.
and Astle, M. J. (Eds.) (1980), Handbook of Chemistry
and Physics (61st edn). CRC; 6) Trotman-Dickensen,
A.F. (Ed.) (1973), Comprehensive Inorganic Chemis-
try, Vol. 2. Pergamon.
However, this simple model has to be
treated with some caution, for it predicts
that glass formation in the Si^C^ _x system
should also be favoured at x = 0.2, instead
of the stoichiometric composition x = 0.33
(viz. SiO2) as is found experimentally. This
contradiction can be circumvented by not-
ing that the distribution of Si-O-Si bond
angles is rather wide, and so the con-
straints associated with these bond angles
should be relatively weak; if these are ne-
glected, Eq. (7-8), suitably modified, then
yields xc = 0.33 (Thorpe, 1983). Tanaka
(1989 b) has also modified the constraint
2D-like MRO, and obtains the value
mc = 2.61.
Finally, in this section dealing with glass
formation of chalcogenide materials, val-
ues for the glass-transition temperature Tg
for various representative materials are
given in Table 7-2.
 7.2 Preparation of Amorphous Chalcogenide Materials
7.2.2 Vapour Deposition
Although the technique of melt quench-
ing is much used to prepare chalcogenide
materials in bulk glassy form, there are
also several techniques based on vapour-
deposition methods which can yield amor-
phous thin films deposited onto substrates
(see Chap. 2). These techniques can be re-
garded as having extremely fast quenching
rates and therefore can be used to produce
chalcogenide materials in amorphous form
which are difficult to vitrify (e.g. As2Te3) or
to extend the compositional range for
which a given system can be made amor-
phous compared with that attainable using
conventional melt-quenching techniques.
Such vapour-deposition techniques can
be divided into two categories, depending
on whether the process involved is physical
in nature, i.e. atomic or molecular species
are converted into the vapour phase from
either solid or liquid sources with no chem-
ical modification, or alternatively reactive,
in which either the vapour species are
chemically modified with respect to the
source material or a solid-vapour reaction
occurs in the condensation process of the
vapour on the substrate. Thus, three differ-
ent vapour-deposition techniques can be
identified which can fall into either or both
of the above categories: these are evapora-
tion, sputtering and chemical vapour de-
position.
Thermal evaporation is perhaps the sim-
plest vapour-deposition technique, and in-
volves resistive or electron-beam heating in
vacuo of a boat containing the material to
be evaporated; the melt so produced then
evaporates and the vapour is condensed
onto a substrate, forming a thin amor-
phous film if the adatom mobility is suffi-
ciently restricted to preclude atomic recon-
struction leading to crystallization. Chal-
cogenides are particularly suitable mate-
389
rials for use in evaporation deposition be-
cause of their relatively low melting points
(see Table 7-2); the technique is widely
used, as for example in the deposition of
the selenium-rich alloys onto cylindrical
drums used until recently as the photo-
sensitive component in the xerographic
process.
However, a number of complications
can arise in the use of this technique. One
such concerns differential evaporation, in
which the various elements in a (non-com-
pound) multicomponent melt can evapo-
rate at substantially different rates due
to the differing melting temperatures and
hence vapour pressures of the constituents.
As a result, the chemical composition of
the deposited thin film can differ apprecia-
bly from that of the melt and also vary
significantly through the thickness of the
film. This problem is obviously exacerbat-
ed for the case of those materials contain-
ing both high and low melting point ele-
ments, e.g. the so-called STAG (Si-Te-As-
Ge) alloys showing electrical switching be-
haviour. In order to obviate this problem,
the variant, termed flash evaporation, may
be used, in which powder of the material to
be evaporated is dropped from a hopper
onto a very hot filament, and the mate-
rial is thereby volatilized almost instanta-
neously; since a melt-vapour equilibrium is
not established in this process, differential
evaporation effects can be minimised.
A further complication can arise in the
case of thin evaporated films deposited at
oblique angles of incidence which, in cer-
tain cases (particularly where adatom mo-
bility on the surface of the substrate is min-
imised), can be structurally inhomoge-
neous. A shadowing effect of material on
the substrate for incoming evaporant
atoms incident at an oblique angle of inci-
dence leads to the formation of a colum-
nar-growth morphology (see Fig. 7-9). In
390 7 Chalcogenide Glasses
Evaporation source
\ I
Film
Figure 7-9. Schematic illustration of the formation of
a columnar growth morphology for thin films evapo-
rated at oblique angles of incidence. Note that the
columns do not lie parallel to the evaporation beam
direction.
general, the direction of the columns in the
films (at an angle /? to the film normal) and
the evaporant beam direction (at an angle
a) do not lie parallel to each other; instead
they are found to obey the empirical rela-
tion (Leamy et al., 1980)
tana = 2 tan/? (7-9)
This effect is observed for many different
types of evaporated materials (see Leamy
et al., 1980 for a review). In chalcogenide
materials, it is particularly prevalent for
the Ge chalcogenides (Rajagopalan et al.,
1982; Spence and Elliott, 1989), but curi-
ously seems to be much less pronounced
for the case of, say, the As chalcogenides.
Consequently, the film porosity increases
and the density decreases as the angle of
incidence of the evaporant beam (a) in-
creases (Rajagopalan et al., 1982; Spence
and Elliott, 1989). Such obliquely-evapo-
rated chalcogenide films possessing a co-
lumnar microstructure exhibit enhanced
photostructural effects (see Sec. 7.5.4).
A final complication which can arise in
thermal (but not flash) evaporation con-
cerns the possible formation of stable
molecular vapour species, and the possible
effect this has on the final composition and
structure of the evaporated film. As an
example, the equilibrium vapour above a
melt of As 2 S 3 consists primarily of As 4 S 4
(and S2) molecules; the relative stability of
the quasi-spherical As 4 S 4 molecules has
been commented upon already in Sec.
7.2.1. Thus, the structure of as-evaporated
films of amorphous "As 2 S 3 " in fact consists
of an aggregate of such As 4 S 4 molecules
(Apling etal, 1977; Daniel et al., 1979,
1980), and the composition of the films can
differ from that of the starting material (e.g.
As2S3) if the lighter molecular species (e.g.
S2) are pumped away before they can con-
dense onto the substrate. Such as-evapo-
rated chalcogenide films are also unstable
with respect to thermal annealing or opti-
cal illumination (see Sec. 7.5.4), such treat-
ment causing the rupture of bonds within
the cage-like As 4 S 4 molecules and subse-
quent reformation to form a more near-
ly cross-linked structure (Nemanich et al.,
1979).
The technique of sputtering is also wide-
ly used to prepare amorphous thin films of
chalcogenides. In this, an r.f. electric field
(in the case of non-metallic materials such
as chalcogenides) is applied between the
target material and the substrate in a vac-
uum chamber in which a low pressure of an
inert gas (e.g. Ar) is present at a pressure of
~10mTorr. After a plasma is struck, ions
are accelerated by the field onto the target,
material from which is then (physically)
sputtered away and condenses onto the
substrate. The advantage of this technique
is that differential deposition rates for
multicomponent systems are much lower
than for the case of evaporation because
sputtering rates are comparable for most
elements; thus, r.f. sputtering has been used
to deposit STAG and similar component
chalcogenide films. Furthermore, this tech-
nique is advantageous in that reactive
sputtering can take place when a reactive
gas, e.g. hydrogen, is introduced into the
sputtering chamber, and which then can
react chemically with the material sput-

tered from the target, and be incorporated
into the growing film.
Finally, another technique which can be
used to deposit thin films from the vapour
phase is chemical vapour deposition (CVD).
In its simplest form, precursor materials in
the vapour phase either decompose or re-
act together in a heated reactor tube or on
a heated substrate; the reactions involved
can be homogeneous (nucleated in the gas
phase) or heterogeneous (occurring at the
surface of the substrate). A variant uses
plasma enhancement (PECVD), or equiv-
alently glow discharge decomposition, in
which plasma excitation rather than ther-
mal energy provides the driving force for
the reaction. There have been a few reports
of chalcogenide materials prepared using
PECVD, namely films of As 2 S 3 : H and
As 2 Se 3 : H prepared by the glow-discharge
decomposition of mixtures of AsH 3 with
H 2 S or H2Se, respectively (Smid and Fritz-
sche, 1980), and Ge-Se films prepared
from GeCl 4 and Se2Cl2 (Blanc and Wilson,
1985).
7.2.3 Other Preparation Methods
A number of other techniques can be
used to prepare chalcogenide materials in
amorphous form, many of which are only
of academic interest. The simple act of
grinding a powder can introduce such a
degree of shear-induced strain that crystals
are transformed into an amorphous phase;
this effect occurs for the case of GeSe 2 , for
example. The solid precipitated products
of reactions occurring in solution can also
be amorphous. Thus, a-As2S3 is formed
by passing H 2 S gas through a solution of
As 2 O 3 in dilute hydrochloric acid. Simi-
larly, powdered a-WS3 and a-MoS 3 can
be produced by the thermal decomposition
of ammonium tetrathiotungstate (Deroide
et al, 1986) or tetrathiomolybdate (Bhat-
7,3 Structure 391
tacharya et al., 1987) or the acid-catalysed
decomposition of solutions of these com-
pounds. Finally, thin films of chalcogenides
have been prepared by spin-coating, i.e. by
placing on a substrate a solution of a chal-
cogenide material dissolved in a suitable
solvent, rapidly spinning the substrate to
produce a thin uniform film of the liquid
and then finally evaporating the solvent to
leave a solid chalcogenide layer. This tech-
nique has been used by Hajto et al. (1987)
to prepare thin films of a-As2S3 using an-
hydrous n-propylamine as a solvent.
7.3 Structure
7.3.1 Definitions
In order properly to discuss the struc-
ture of amorphous chalcogenide materials,
it is necessary at the outset to outline a
framework within which the structural fea-
tures can be described. With this in mind,
it is convenient to consider the structure on
three different ascending length scales ac-
cording to the scheme proposed by Elliott
(1990) (see also Chap. 4 and Vol. 1 of this
series).
7.3.1.1 Short-Range Order
In covalently-bonded amorphous mate-
rials with strongly directed bonding, such
as chalcogenides, short-range order (SRO)
can be defined in terms of rather well-
defined coordination polyhedra (see Fig.
7-10). Thus the parameters which are suffi-
cient to describe topological SRO are the
type and number Nj of nearest neighbours
j around an origin atom of type i, the near-
est-neighbour bond length rtj, the bond
angle subtended at atom i, 6t, and the cor-
responding quantities when atom j is re-
garded as the origin, viz. Nt and 9j. Thus,
this description involves both two and
392 7 Chalcogenide Glasses
j J
Figure 7-10. Short-range order of covalent materials
in terms of coordination polyhedra.
three-body correlation functions associat-
ed with rtj and 6j9 respectively. Note that
in this description of SRO, nothing is
said about the connectivity of the coordina-
tion polyhedra (e.g. corner-, edge- or face-
sharing); the form of connection of the
polyhedra essentially determines the type
and extent of the medium-range order (see
Sec. 7.3.1.2).
An additional parameter is required if
the degree of chemical SRO also needs to
be described, e.g. when different types of
atoms constitute the coordination polyhe-
dron centred on a given origin atom. Thus,
for non-stoichiometric compositions, for
example, excess atoms must be accommo-
dated by the introduction of wrong, i.e.
homopolar, bonds (in the absence of co-
ordination or valence changes), breaking
thereby the chemical order (i.e. heteropolar
bonding) which might otherwise occur at
the stoichiometric composition; the pa-
rameter of relevance here would then be
the proportion of wrong bonds.
A related type of chemical SRO is when
the different types of atomic species in the
coordination shell around a given origin
atom are in fact the same element, but
such atoms may have a different charge
state, bonding connectivity, etc. An exam-
ple of this are the non-bridging ligands in-
troduced into an otherwise fully-bonded
structure by the introduction of charged
modifier atoms, e.g. alkali ions or Ag + .
Chalcogen (or oxygen) atoms can act as
such non-bridging sites, in which case they
are singly coordinated and (formally) carry
one unit of negative charge (see Fig. 7-11);
such sites can be regarded as defects in an
otherwise perfectly connected amorphous
structure (see Sec. 7.4). Such species can be
described by the symbol Qn (first intro-
duced for the case of non-bridging oxygen
sites in modified silicate glasses), where n is
the number of bridging ligands around a
central cation, e.g. 0 < n < 4 for I V - VI ma-
terials, and 0 < n < 3 for V-VI materials.
NQ2S
NQ+S-
S
-NQ+
-G/'
-A Ge
e
\
Figure 7-11. Schematic illustration of the formation
of non-bridging chalcogen sites in the Na 2 S-GeS 2
system.
The question of chemical ordering in co-
valent systems is most simply discussed for
the case of binary alloy systems such as
A_xB1_:c where, if the elements A and B
are in columns a and b of the periodic
table, they will have coordination numbers
na = & — a and nb = & — b by the 8 —AT rule
(neglecting the effect of any coordination
defects such as dangling bonds). In general,
A-A, A-B, and B-B bonds can coexist
in an alloy with an arbitrary composition,
and two extreme models can describe the
distribution of such bond types (Lucovsky
etal, 1977).
One model is the random covalent net-
work (RCN) model which treats the distri-
bution of bond types in purely statistical
terms, determined only by the local coordi-
nations na and nb and the concentration
variable x, and which neglects any prefer-
ential ordering effects (e.g. arising from
 7.3 Structure 393

differences in bond energies). The RCN A,_,BA 3:2

o
model, therefore, admits A-A, A-B, and Random covalent network
*5s
B-B bonds at all compositions except at c Chemically ordered covalent network
o
x = 0 and 1. Thus, for a 4 : 2 alloy (e.g.
A = Ge, £ = Se), the RCN model predicts
1.4
the following relations for the numbers of
1.2
the different types of bond (Lucovsky et al,
1977): 1.0
0.8
= 4(l-x)2/(2-x) (7-10 a) 0.6
(7-10 b) 0.4
NBB=x2/(2-x) (7-10 c) 0.2
°°1 0.8 0.6 0.4 0.2 0.0
These bond-counting statistics are shown
(a) <— JT. Atomic fraction B
in Fig. 7-12, together with those for a 3 : 2
system (e.g. AsJCSe1_x). A.-.B, 4:2
The other model is the chemically-or- Random covalent network
dered network (CON) model, in which het- 2.0 : Chemically ordered covalent network

eropolar A-B bonds are favoured; a com- 1.8

pletely chemically-ordered phase thus oc- 1.6 AB

curs at the stoichiometric composition 1.4

1.2
; = nj(na • (7-11) 1.0
0.8
(e.g. as in As 2 Se 3 , GeS2). In contrast to the
0.6
RCN model, only A-A and A-B bonds
0.4
are allowed for ,4-rich compositions
(1 > x > x c ) and only B-B and A-B bonds 0.2
for 0<x<xc. Thus, the bond statistics for O.CJ
0.8 0.6 0.4 0.2
the CON model for a 4 : 2 alloy are, for the (b) * - x. Atomic fraction B
,4-rich region Figure 7-12. Bond-counting statistics (Elliott, 1990)
for (a) 3:2 networks (e.g. As 2 Se 3 ) and (b) 4 : 2 net-
= 2-3x (7-12 a) works (e.g. SiO 2 ).
N.AB = 2x (7-12b)
NBB=0 (7-12 c)
7.3.1.2 Medium-Range Order
and for the B-rich region The question of medium-range order
(MRO), or equivalently intermediate-range
(7-13 a) order, in amorphous materials is currently
(7-13 b) extremely contentious; even a definition of
= 3x-2 (7-13 c) MRO is subject to much debate (Elliott,
1987; Galeener, 1988; Cervinka, 1987, Lu-
These bond-counting statistics are also covsky, 1987) and it is very difficult experi-
shown in Fig. 7-12, together with those mentally to investigate MRO. In this ar-
for a 3 : 2 network. ticle we will use the definition of MRO
394 7 Chalcogenide Glasses

proposed previously (Elliott, 1987, 1990),

which is simply that it is the next highest
level of structural organization beyond
SRO (see Sec. 7.3.1.1), extending over a
length scale of say 5-20 A. In practice, and
particularly for covalently-bonded materi- (a)
als, it is convenient to divide MRO into
three categories, corresponding to progres-
sively increasing length scales.
At the shortest length scale (say 3 - 5 A),
short-range MRO (SRMRO) is concerned
with the type of connection between, and
relative orientation of, pairs of the coordi-
nation polyhedra which form the basic
structural units in the SRO description
given above; SRMRO will be pronounced
if the degrees of freedom associated with
the relative orientation of pairs of neigh-
bouring polyhedra are restricted in some
way, e.g. by the occurrence of edge- (or
face-)sharing connections. However, even
where polyhedral units are interconnected
by corner-sharing, for which free rotation
about the common bonds could occur in
principle, nevertheless certain orientations
may be more favourable than others (e.g. (b)
due to steric effects). A structural parame- Figure 7-13. Dihedral angles in covalent networks,
ter which is a measure of such orienta- (a) Definition of dihedral angle 0 characterising the
tional correlations for covalent systems relative angle of rotation between two neighbouring
polyhedra. (b) Correlations between neighbouring
with well-defined bonds is the dihedral (or dihedral angles.
torsion) angle, </>, defined as in Fig. 7-13 a.
This is the angle of rotation about a com-
mon bond required to bring into coinci-
dence the projections, onto the plane per- tionships) between pairs of dihedral angles
pendicular to this bond, of the two bonds for neighbouring bonds, i.e. it accounts
either side of the common bond forming for triplet correlations between connected
parts of the two connected polyhedral polyhedra, or equivalently five-atom corre-
units; obviously this is a four-body correla- lations (see Fig. 7-13 b). A simple measure
tion function (see Fig. 7-13). of such correlations between dihedral an-
gles involves the two order parameters
At the next largest length scale, say 5 -
given by the average sum (Ps) and difference
10 A, in an hierarchical sense intermediate-
(Pd) of the two dihedral angles for adjacent
range order is determined by the type and
bonds (Luedtke and Landman, 1989), viz.
extent of SRMRO present. Such intermedi-
ate-range MRO (IRMRO) is therefore as- (7-14a)
sociated with correlations (i.e. phase rela-

and
(744 b)
Thus, a pronounced degree of IRMRO is
associated with triplets of coordination
polyhedra lying in well-defined relative
orientations; this circumstance naturally
leads to the presence of super structural
units (Elliott, 1987 b) consisting of several
basic polyhedra connected together, e.g.
forming rings or clusters of atoms, and
which exist in a significantly higher pro-
portion than would be expected on a pure-
ly statistical (random) basis.
Finally, on a yet larger length scale,
say greater than 10 A, long-range MRO
(LRMRO) can be associated with the lo-
cal dimensionality of a covalently-bonded
amorphous network; this can be ascer-
tained by finding the dimension traced out
locally (over distances ~10 A) by bond
percolation among the covalent bonds of
the structure, neglecting the much weaker
Van der Waals bonds (Zallen, 1983). A lo-
cal dimensionality different from 3 (corre-
sponding to isotropy) can arise from two
causes: either the type of connection be-
tween coordination polyhedra may impose
such a reduced dimensionality (e.g. in the
ID chain-like structures resulting from
edge-sharing of tetrahedra), or it may re-
sult from network depolymerization due
to the introduction of network-modifying
atoms into the structure.
As will be seen later, all three variants
of MRO are observable in amorphous
chalcogenide materials; MRO is prevalent
in such systems primarily because of the
structural flexibility associated with the
low coordination of the chalcogen atoms.
7.3.13 Long-Range Structure
Although there is no long-range (trans-
lational) order in amorphous materials, by
7.3 Structure 395
definition, nevertheless not all such mate-
rials are isotropic on a macroscopic scale,
at length scales of say 50-1000 A. An ex-
ample of such inhomogeneous long-range
structure (LRS) is the columnar micro-
structure associated with obliquely-evapo-
rated films (see Sec. 7.2.2).
7.3.2 General Aspects of the Structure
of Amorphous Chalcogenide Materials
Before discussing the structure of indi-
vidual chalcogenide materials in detail, it is
perhaps useful to mention some general
features of the structure of such materials
and it is convenient to divide such a discus-
sion into three parts as above, dealing with
SRO, MRO, and LRS, respectively.
7.3.2.1 SRO in Chalcogenides
In the case of pure amorphous chalco-
gen (C) elements or alloys (class 1 in Table
7-1), the fundamental structural unit is
based on a single atom and as such the
SRO is rather straightforward. In the case
of binary (or more complex) compositions,
the situation is more complicated, and co-
ordination polyhedra centred on the non-
chalcogen component can be identified.
Thus, in the case of the III-VI glass, B 2 S 3 ,
the structural unit is a planar BS 3/2 trian-
gular unit, as confirmed from B 1 1 NMR
studies (Rubinstein, 1976; Hiirter et al.,
1985). The structural unit in the case of
V-VI glasses, e.g. As 2 S 3 , is also trigonal
(e.g. AsS3/2), but pyramidal, with the pnic-
togen atom raised above the plane defined
by the three chalcogens. This geometry is
confirmed by X-ray diffraction results (e.g.
Cervinka and Hruby, 1982). For the case of
materials in the I V - VI system, e.g. GeSe2,
the polyhedral unit is a tetrahedron cen-
tred on the tetragen, e.g. GeSe 4/2 . This ge-
ometry is consistent with the vibrational
characteristics found from inelastic neu-
396 7 Chalcogenide Glasses
tron scattering measurements (Walter et al.,
1988), which can be understood in terms of
essentially vibrationally decoupled (molec-
ular-like) excitations of GeSe 4/2 tetrahe-
dra, with a vibrational frequency compara-
ble to that of GeBr4 molecules.
It has been assumed in the above that
the materials are completely chemically or-
dered, and hence each apex of the polyhe-
dral units is occupied by a chalcogen atom,
which acts as a bridging link between two
units. In the case of more complicated
(e.g. ternary) systems, or those containing
wrong bonds, often the type of the poly-
hedral unit remains unchanged but the
chalcogen atoms at the apices are substi-
tuted by other elements, thereby changing
the local connectivity of the units. In some
cases, however, the addition of network-
modifying cations causes a change in the
geometry of the structural unit. An exam-
ple is glassy B 2 S 3 ; the addition of either
Li + or Tl + ions causes the coordination of
the B to change from planar trigonal to
tetrahedral (Eckert, 1989), exactly as in the
corresponding borate systems.
7.3.2.2 MRO in Chalcogenides
As mentioned in Sec. 7.3.1.2, MRO is
generally prevalent in amorphous chalco-
genide materials due to the low (two-fold)
coordination associated with the chalco-
gen atoms; as a result, the degree of cross-
linking is sufficiently low so that a three-
dimensionally isotropic structure does
not necessarily result, and superstructural
units may form. However, it is difficult to
probe quantitatively the type and extent of
MRO in glasses: in general, those tech-
niques, such as diffraction and EXAFS,
which are sensitive to pair correlations of
atoms are rather insensitive to MRO, and
instead it is techniques such as vibrational
spectroscopy (e.g. Raman scattering), which
probe the collective behaviour of several
atoms, which are more useful in this regard.
Nevertheless, one aspect of the diffrac-
tion results on chalcogenide materials has
been ascribed to the influence of MRO,
and this is the so-called first sharp diffrac-
tion peak (FSDP) or pre-peak in the struc-
ture factor, S ( 0 . This peak almost invari-
ably occurs at a value of scattering vector
Q ~ 1 A" 1 in amorphous compound chal-
cogenides. This feature is referred to as a
pre-peak because Fourier transformation
of S ( 0 , both including and omitting this
peak, produces essentially indistinguish-
able real-space correlation functions, indi-
cating that the peak does not contain
structural information about SRO, being
associated instead with subtle MRO struc-
tural arrangements.
The FSDP is anomalous in a number of
ways. It is observed in a wide variety of
mixed chalcogenide amorphous materials,
e.g. As 2 S 3 , As 2 Se 3 , GeS 2 , GeSe2, as well
as the corresponding oxide materials (e.g.
SiO 2 , B 2 O 3 ) and also a-P and a-As, but
it is not present for the case of the pure
chalcogen a-Se, or Ge or Si. Although the
position of the FSDP is at Q±«1 A" 1 for
the case of the chalcogenides (and As and
P), it is somewhat larger (Qx«1.5 A"1) for
oxide materials. Nevertheless, if the struc-
ture factor is plotted against the reduced
variable Qr l9 where rx is the nearest-neigh-
bour bond length, the FSDP's of chalco-
genides and oxides alike fall at approxi-
mately the same value, viz. Q1r1^ 2.5
(Wright et al., 1985) (see Fig. 7-14), perhaps
indicative of a common origin.
The FSDP alone of all the peaks in S (Q)
shows anomalous behaviour as a function
of temperature and pressure. The intensity
of the FSDP increases with increasing tem-
perature in for example a-As2S3 (Busse,
1984), As2Se3 (Busse and Nagel, 1981) and
GeS 2 (Lin et al., 1984), as well as in SiO 2
 7.3 Structure 397

(Soklakov and Nechaeva, 1967). (All other

Figure 7-14. Experimental structure factors, S (Q), for
oxide and chalcogenide glasses plotted versus the re-
duced variable where rA_x is the nearest
neighbour bond length between A and X atoms
(Wright et al, 1985).
peaks in S(Q) decrease in intensity with
increasing temperature, in accordance with
the normal behaviour of the Debye-Waller
factor.) Indeed, the FSDP is still pro-
nounced even in the liquid state of chalco-
genide materials, e.g. GeSe2 (see Fig. 7-15)
(Uemura et al., 1978; Susman et al., 1988).
The application of pressure also produces
an anomalous behaviour of the FSDP in
amorphous chalcogenide materials (Tana-
ka, 1987, 1989 a); its intensity decreases
and the position of the peak shifts to higher
values of Q with increasing pressure (see
Fig. 746).
The intensity of the FSDP increases as
the atomic number of the chalcogen C
decreases for a particular type of chalco-
genide glass, e.g. GeC 2 , As 2 C 3 (Susman
etal., 1988). Furthermore, it appears that
cation-cation correlations are primarily
responsible for the FSDP; anomalous
X-ray scattering results for a-GeSe2 indi-
cate that Ge-centred correlations (Ge-Ge,
Ge-Se) contribute predominantly to the
FSDP intensity (Fuoss et al., 1981).
There has been, and remains, much con-
troversy over the structural origin of the
FSDP in covalent glasses, and a number of

2.5 r-
g-GeSe2

2.0- 10 K Glass

1.5
a
i/)
1.0

Figure 7-15. Structure fac-

0.5
tor, S(Q), for GeSe 2 in
both glassy and liquid
0.0 states (Susman et al., 1988).
0.0 8.0 12.0 16.0 20.0
398 7 Chalcogenide Glasses

Figure 7-16. Pressure-de-

pendent X-ray diffraction
patterns for amorphous
As2S3 in (a) bulk glass and
(a') thin-film forms, and
amorphous GeSe2 in (b)
bulk glass and (V) thin-film
forms (Tanaka, 1989 a).

explanations have been proposed. These Using this relation, correlation lengths in
can be effectively divided into two cate- the range D& 20-30 A are inferred from
gories, depending on how the peak in S (Q) the width of the FSDP. In addition, the
is assumed to originate. position of the FSDP in this picture is de-
One model assumes that the FSDP is termined by the periodicity in real space via
separate from the rest of S(Q), i.e. it is
regarded as a single Fourier component :2n/Q± (7-15 b)
in reciprocal space arising, therefore, from
where d is the spatial repeat distance. For
a (quasi-)periodic correlation function in
Q± ~ 1 A" 1 , this implies a repeat distance
real space characteristic of the MRO. The
of d - 5 - 6 A.
width of the pre-peak in S (Q) then arises
This model, essentially based on a mi-
from the damping in the amplitude of
cro- or quasi-crystalline approach in which
the real-space oscillations, and the Debye-
regions of the structure have a more- or
Scherer equation relating diffraction line
less-ordered structural arrangement, has
broadening to crystallite size can be used
some appeal since many crystalline chalco-
to provide a relationship between the
genides are layer materials, and the repeat-
FSDP peak width AQ and D, a characteris-
ing element is then taken to be the inter-
tic coherence length over which the period-
layer separation which is assumed to per-
icity in real space is maintained:
sist into the amorphous phase (e.g. Vai-
(7-15 a) polin and Porai-Koshits, 1963; Leadbetter

and Apling, 1974; Busse, 1984). Various
variants of this picture involving interlayer
correlations have also been proposed, e.g.
that involving crumpled layers (Tanaka,
1988), and that of Cervinka (1988) in which
a parallel ordering in a particular orienta-
tion of pairs of configurations of between
two and five connected coordination poly-
hedra (effectively forming layers) is as-
sumed to occur.
The second interpretation of the FSDP
is in terms of a cluster picture which is, in
Fourier terms, the converse of the above
model. In the simplest case, there is a single
(broad) peak in real space at rm characteris-
ing the MRO, which produces a strongly
damped sinusoidal function in reciprocal
space of which the observed FSDP is sim-
ply the first, most intense peak. Thus in this
picture, the FSDP in itself has no struc-
tural significance (c.f. Eq. (7-15)). This ap-
proach is therefore similar to that used in
the interpretation of the scattering from
molecular liquids such as CC14. In this
case, the total measured structure factor
can be written as the sum of two terms
S(Q) = fm(Q) + Dm(Q) (7-16)
where Dm(Q) is the molecular-packing
structure factor describing the inter-molec-
ular interference arising from the scatter-
ing of neutrons or X-rays from structural
(molecular) entities separated by an aver-
age distance rm, and fm(Q) is the molecular
form factor describing the mtra-molecular
scattering. Dm(Q) is dominant at low Q val-
ues and is highly damped because of the
large fluctuations in rm, whereas fm(Q) is
much less damped (because fluctuations in
intra-molecular covalent bond lengths are
considerably smaller than those for rm),
and it therefore dominates at high values
ofQ.
The cluster picture has been proposed
for the case of amorphous chalcogenides in
7.3 Structure 399
general by Moss and Price (1985) and
Fowler and Elliott (1987), perhaps associ-
ated with the packing of coordination
polyhedra (although the precise clusters
were not identified). Veprek and Beyeler
(1981) have further proposed that, whilst
the FSDP may result from many Fourier
components of the real-space correlation
function, nevertheless it may be associated
with regions of low atomic occupancy
characterised by the minimum in the radial
distribution function (RDF) beyond the
SRO correlations (related to the packing of
coordination polyhedra and the interstitial
voids between them). However, one incon-
trovertible example of a cluster origin for
the FSDP is provided by thin evaporated
films of As-S materials. These contain
quasi-spherical As 4 S 4 molecules (see Sec.
7.2.2) and the very intense FSDP in the
diffraction pattern of such films has been
convincingly explained in terms of scatter-
ing from such clusters (Wright et al., 1985).
Whilst the explanation of the FSDP in
terms of scattering from a quasi-ordered
stacking of layers is appealing, it is unlikely
to be a general solution for several rea-
sons: an FSDP is observed at approxi-
mately the same value of reduced coordi-
nate (Qr±) even for those cases (e.g. SiO2)
where there is no evidence whatsoever for
layering in either crystalline or amorphous
phases; furthermore, a quasi-regular stack
of layers extending over a correlation
length D « 20 A would not be expected to
survive in the liquid state; and finally, if
such a quasi-microcrystalline stacking of
layers were to occur in the glassy phase,
many more peaks would be expected to be
observed in the structure factor, S(Q)
(Wright et al., 1987). Conversely, in the ab-
sence of well-defined molecular species
such as As 4 S 4 in the structure, it is difficult
to associate particular structural features
with clusters. For instance, such clusters
400 7 Chalcogenide Glasses
cannot be related to just the coordination
polyhedra themselves, but instead may be
defined by the excluded volume, i.e. the
interstitial space, surrounding a particular
coordination polyhedron and which re-
sults from steric effects (see e.g. Galeener,
1985).
Finally in this section on general aspects
of MRO in amorphous chalcogenides,
mention should be made of experimental
data relating to the local dimensionality of
the structure. In the case of IV-VI mate-
rials, where the coordination polyhedron
is a tetrahedron centred on the tetragen,
both corner- and edge-sharing of these
units is possible whilst maintaining the
normal two-fold coordination of the chal-
cogen (Fig. 7-17), and both types of con-
nection are found in varying proportions
in the crystalline compounds of this sys-
tem. Thus, for silica (SiO2) and germania
(GeO2), only corner-sharing of tetrahedra
occurs; as a result, a three-dimensional
covalently-bonded structure results. In the
case of crystalline GeSe2 and GeS 2 , how-
ever, a proportion of edge-sharing connec-
tions also occur; as a consequence, a two-
dimensional (2D), layer-like structure re-
sults (see Fig. 7-17 a). Finally, for the case
of crystalline SiSe2 and SiS2, only edge-
sharing connections occur, with the result
b)
that the structure becomes chain-like
or one-dimensional (ID) (see Fig. 7-17b).
The structures of the corresponding glassy
phases of these materials are believed also
to contain similar structural elements.
Consequently, the bonding in amorphous
Si and Ge chalcogenides with ID or 2D
structures has a weak Van der Waals com-
ponent between the chains or layers, re-
spectively, in the structure as do the As
chalcogenides which, because of the trigo-
nal pyramidal coordination, also can be
regarded as being layer-like (see Fig. 7-3 b).
This is in contrast to the case of three-
dimensionally bonded materials (e.g. Ge or
SiO2) in which covalent bonding is domi-
nant.
Such weak Van der Waals interactions,
characteristic of low-dimensional solids,
can be investigated using pressure as a
probe. Extensive measurements of the
pressure dependence of the optical absorp-
tion edge have been performed for chal-
cogenide materials (see e.g. Besson et al,
1981), and some results due to Tanaka
(1989 a) are shown in Fig. 7-18. It can be
seen that indeed chalcogens, As and Ge
chalcogenides, in both amorphous and
crystalline forms, exhibit marked red shifts
in the optical gap with increasing pressure,
due to the preferential compression of the
Figure 7-17. (a) Crystal
structure of GeSe2, show-
ing a layer-structure
formed from edge- and cor-
ner-sharing tetrahedra,
termed a raft, (b) Crystal
structure of SiSe2, showing
one-dimensional chains
formed from edge-sharing
tetrahedra.
 7.3 Structure 401
i i i i
k
figurations which can be formed are lim-
-GeS..(2D
ited essentially to rings or chains, these
—^c-Gei7(3l7 configurations being held together in the
3
*•> "c-ZnSe structure by Van der Waals interactions.
The determination of the proportion of
hAs2S3(g) \ G e S 2 (g)
m
i_ rings to chains in the structure of amor-
Q) ^>As2S3(f) Si:H(50%)
(2
0)
phous chalcogens has long been a con-
2 = = tentious issue.
U.
Si: H (10%) ^ ^
o ^ . For the case of sulfur, several crystalline
Oi
Ban<

-n
GeSe 2
^ t r a n s ^
1 ^—iGe
ir
[ H> - — c-Se
i i i i
50 100
Pressure (kbar)
Figure 7-18. Pressure dependence of the optical
bandgap for glasses (g) and amorphous thin films (f)
and crystalline (c) semiconductors (Tanaka, 1989 a).
GeS2 crystals have both two-dimensional (2D) and
three-dimensional (3D) forms. (Polyacetylene is ab-
breviated as PA).
space between chains or layers; the de-
crease in the gap arises because of an in-
crease in the broadening of the top of the
valence and the bottom of the conduction
band due to an increase in repulsive inter-
actions (overlap) between filled lone-pair
p-orbitals associated with the chalcogen
atoms. In contrast, crystalline Ge or a-Si: H
exhibit essentially zero pressure coefficients
of the optical gap, reflecting the lower com-
pressibility of these 3D materials.
7.3.3 Structure of Specific Amorphous
Chalcogenide Materials
In this section, we will discuss the struc-
tures of specific chalcogenide materials,
classified according to the categories given
in Sec. 7.1.1 (see Table 7-1).
7.3.3.1 Structure of Pure Chalcogens
Since chalcogen elements are normally
two-fold coordinated, the structural con-
allotropic forms are known, each based
on a packing of S 8 (cyclooctasulfur) rings
(Rawson, 1967). The high-temperature
form melts at 388 K to a low viscosity
liquid, consisting of monomeric S8 rings;
at the so-called ^-transition point (433 K),
the rings start to break and a high viscos-
ity liquid forms, consisting of long (10 5 -
106 atoms) polymeric chains (Myers and
Felty, 1967). Glassy sulfur can be quenched
from melts above the X point; however, the
low value of Tg (=246 K) has precluded
extensive work on this material. Three
structural modelling studies have been per-
formed for glassy sulfur: an early simula-
tion by Malaurent and Dixmier (1977) was
based on a freely rotating chain model (in
which the dihedral angle is not con-
strained). More recently, Popescu (1987)
has modelled the structure of liquid and
glassy S in terms of two models, one a re-
laxed packing of chains and the other with
a stacking of S 8 rings, assuming a nearest-
neighbour bond length of r1 = 2.07 A and
a bond angle of 0 = 108°; the structure of
the glassy phase was inferred to comprise a
mixture of these two structural configura-
tions, although the experimental data com-
pared with were very old (Tompson and
Gingrich, 1959). Furthermore, Stillinger
etal. (1986) have performed a molecular
dynamics simulation of cyclooctasulfur in
the liquid state and produced a quenched
amorphous solid structure from the liquid
starting state. More recently, Winter et al.
(1990) have performed a high-resolution
402 7 Chalcogenide Glasses
neutron-scattering study of glassy sulfur,
prepared by quenching the melt in liquid
nitrogen. They find that the structure of the
melt and of the quenched glass are rather
similar with a bond length of 2.06 A, al-
though the experimental RDF of the glass
differs in significant details from that of the
molecular dynamics S 8 model of Stillinger
et al. (1986), indicating that, as expected,
the structure of the glass comprises an ap-
preciable fraction of chains.
The structure of amorphous (and liquid)
Se has been much more extensively studied
than is the case for S, and reviews have
been given by Andonov (1982) and Corb
et al. (1982). Four crystalline forms exist:
the most stable trigonal (or hexagonal)
form consists of helical chains packed in a
parallel fashion, whereas the a- and /?-mon-
oclinic forms are composed of S8 rings but
packed differently; in all cases the bond
length is ^2.32 A and the bond angle is
0^105°. What distinguishes the various
polymorphs is the dihedral angle, or more
specifically the correlation between neigh-
bouring dihedral angles. Fig. 7-19 shows
how <fi is defined in terms of a four-atom
correlation; this angle is fixed at a value
<t>«102° for the crystalline forms. Fig. 7-19
also shows the two distinct five-atom con-
TRANS
CIS
Figure 7-19. Definition of dihedral angle <j> for the ture. This picture has been supported by
case of a Se chain, and the atomic configurations of neutron diffraction measurements (Edeling
the cis and trans conformers.
figurations possible, depending on the
phase relationship between two neigh-
bouring dihedral angles: if the sense of se-
quential 0's is fixed (+ + +, or ), the
trans configuration results, which has a
c/iam-like symmetry with either right- or
left-handed helicity; on the other hand, if
the phase of cj) alternates (H h — etc.),
the cis configuration results, which has a
ring-like symmetry. Misawa and Suzuki
(1978) have estimated that the cis config-
uration is energetically more stable than
the trans configuration by only « 0.03 eV/
atom, implying that in the glassy phase
both configurations may coexist. This pre-
diction is supported by the assignment of a
weak feature in the Raman spectrum in
terms of monomeric Se8 rings in a propor-
tion of 5-10% (Lucovsky et al., 1967; Gor-
man and Solin, 1976), as well as from disso-
lution studies in CS 2 (Briegleb, 1929).
A modelling study of a-Se by Corb et al.
(1982), based on X-ray diffraction results
by Wei et al. (1982), has indicated that
whilst a model with (f) = lO2° and mostly
trans configurations gives a reasonable fit
to the data, a better fit was achieved by
allowing both the distribution of <j> to
broaden about an average value of 4> ~ 105°
and to allow some randomness in the
phase relationship between neighbouring
dihedral angles. The fit of this model to the
X-ray data is shown in Fig. 7-20, for which
60% of configurations were trans-like and
40% cis-like. A model of freely-rotating
chains does not seem to give as good a fit.
With increasing temperature, above the
melting point (493 K) in the liquid domain,
it is expected that the ring-chain equilib-
rium should shift in favour of chain-like
molecules, the average chain length de-
creasing rapidly with increasing tempera-
and Freyland, 1981; Bellisent and Tourand,

1 1 1 1 1 1 1 1
1
2 _-
i1
5
1 1
6
°
1
Experimental
Model n
1 1
r(A)
Figure 7-20. Comparison of the RDFs predicted by
the quasi-random coil model and measured experi-
mentally for a-Se (Corb et al, 1982).
1980) as well as by NMR studies (Warren
and Dupree, 1980). Glassy Se is more easy
to prepare by melt quenching than is the
case for S (Rawson, 1967), probably be-
cause Se8 rings are more unstable; how-
ever, the glass-transition temperature for
Se is also low (Tg = 303 K).
Te, unlike S and Se, has only one crys-
talline form; this trigonal modification
comprises infinite spiral chains packed in a
parallel arrangement (as in trigonal Se)
with a bond length of 2.86 A and a bond
angle of 9 = 102°. Above the melting point,
at 726 K, the chain structure starts to
break up, with the shortened chains be-
coming entangled and cross-linked by
three-fold coordinated Te sites with the
melt ultimately becoming metallic; recent
neutron scattering measurements by Me-
nelle et al. (1987, 1989) indicate that the
nearest-neighbour coordination number
increases from a value of N± «2.5 just
above the melting point to Nt^3 at
T = 1100K. A very recent molecular dy-
namics simulation of the structure of liquid
Te has confirmed this picture (Hafner,
1990). It is not possible to quench the high-
temperature low-viscosity (metallic) melt
into a glassy form (Moffat et al., 1964); a
possible reason for this is that at high tem-
7.3 Structure 403
peratures the average nearest-neighbour
coordination number (Nx«3) is much
larger than the optimum coordination
number mc = 2.4 for glass formation (Eq.
7-8) resulting from the application of con-
straint theory (see Sec. 7.2.1). Perhaps Te
could be prepared as a glass by very rapid
quenching from the high-viscosity liquid
state just above the melting point, where
JVi « 2.5. However, amorphous thin films
of Te can be prepared by vapour deposi-
tion, in which a chain-like structure also
seems to exist (Ichikawa, 1972).
Some structural investigations have been
carried out on alloys of chalcogen elements,
e.g. on Se^Te^^ using neutron diffraction
(Bellisent and Tourand, 1980). It was found
that the structure of amorphous alloys
(l>x>0.6) and liquid alloys (l>x>0.3)
could be well fitted by a chain-like model,
in which Te substitutes for Se atoms whilst
maintaining two-fold coordination. In the
more Te-rich liquid alloys, however, the in-
fluence of three-fold coordinated Te atoms
could not be neglected. Finally, an interest-
ing feature of Se-Te alloys is that if the
metallic crystalline phase (of Se67Te33),
produced by the application of high pres-
sure to the amorphous form, is quenched
to atmospheric pressure and 223 K, the
semiconducting trigonal form results but,
when heated up to 300 K, the material be-
comes amorphous again (Mushiage et al.,
1983).
7.3,3.2 Structure of V-VI Materials
The most commonly studied materials
in this system are the As chalcogenides,
based on the stoichiometric compositions
As 2 S 3 , As2Se3 and As2Te3.
The structure of amorphous As 2 S 3 , in
both bulk glassy and amorphous thin-film
forms has been studied by Daniel et al.
(1979), and the experimental data are
 404 7 Chalcogenide Glasses

6000

£000
ft /^
2000

-1200 0
V
0 24 10
r(A)
2.4
0.8 •

2.0
o <
0.4 i 1.6

a
z
0.0

-0.-4 f
i
\j
A \\
r
A
\JVw\
in
c
o
_Q
1.2

0.8

0.4
f\ k
i
\7
^

a
-0.8 0.0 Vn
0 16 20 24 4 6 8 10
Qi r(A)
Figure 7-21. X-ray (X) and neutron (n) diffraction data for samples of amorphous As 2 S 3 : - bulk glass, thin
film, annealed film (Daniel et al, 1979).

shown in Fig. 7-21. Although superficially
similar, in fact there are a number of signif-
icant differences in the structure between
film and glass. The structure of the glass is
both chemically and topologically more
ordered than that of the evaporated film:
the asymmetry on the high-r side of the
first peak in the real-space correlation
function for the films (due mainly to As-S
bonds, with a length of 2.26 A) can be ac-
counted for by the presence of a significant
proportion of As-As wrong bonds with a
bond length of ~2.5 A. The structure of
the stoichiometric glass is thus consistent
with that expected from the 8-N rule (see
Fig. 7-3 b) where chemical order is domi-
nant, with an As-S bond length of 2.28 A
and bond angles at the As and S atoms
inferred to be 102° and 99.5°, respectively
(Cervinka and Hruby, 1982), whereas the
structure of the film is well described by a
packing of quasi-spherical As 4 S 4 mole-
cules which contain As-As homopolar
bonds (Wright et al., 1985) (see Fig. 7-3 c).
Yang et al. (1987) have also studied the
occurrence of like-atom bonds in glassy
As^Si-* using EXAFS.
The question of broken chemical order in
stoichiometric glassy As 2 S 3 , i.e. the exis-
tence of homopolar As-As and S-S bonds,
has been much discussed. There now ap-
pears to be incontrovertible evidence for
the existence of a small concentration
(~1%) of such homopolar bonds in stoi-
chiometric material; evidence comes from
Raman scattering measurements (Ewen
and Owen, 1980; Tanaka et al., 1985) where
the stretching frequency for As-As bonds
(at ^220 cm" 1 ) is readily distinguishable
from that corresponding to As-S bonds in
 7.3 Structure 405

AsS 3/2 units (344 cm 1), as well as from
Mossbauer spectroscopy (Boolchand et al.,
1986), and it appears that the concentra-
tion of wrong bonds increases markedly
with increasing temperature from which
the melt is quenched (Tanaka et al., 1985).
As K-edge EXAFS measurements have
also revealed an increase in the static disor-
der of the nearest-neighbour (As-S) bond
length with increasing quench temperature
(Yangetal., 1987).
A number of models have been con-
structed to simulate the structure of glassy
As x S 1 _ x alloys. The stoichiometric mate-
rial has been simulated using computer-re-
laxed ball-and-stick models with perfect
chemical order and connectivity (Pfeiffer
et al., 1989), a model generated by a three-
step process involving packing atoms ran-
domly in a box with subsequent structural
relaxation and reformation of bonds to
give a low-energy structure (Fujiwara et al.,
1981), and various models generated by
Finally, Pfeiffer et al. (1989) have
analysed the MRO in their models in terms
of the correlation between dihedral angles
subtended by the S atoms. In the orpiment
structure there are two distinguishable S
sites: one occurs in a helical (H) arrange-
ment of alternating As and S atoms and is
associated with two different dihedral an-
gles (68°, 146°); the other is in a bridging (B)
site between two different helices, for which
the two dihedral angles are identical (163°,
163°). Pfeiffer et al. (1989) found in their
models a slight preponderance for B and H
sites (see Fig. 7-22), indicating that perhaps
the structure of glassy As 2 S 3 retains ves-
tiges of the helical arrangement found in
the crystal, which would be one manifesta-
tion of the MRO. However, there are two
distinct (distorted) As sites in the orpiment
structure as well, and these can be identi-
'B .'

bond-breaking and reformation or atomic 160 • Type of atom

B-Bridging
Fraction of total
0.124
V.
decoration of existing continuous random H-Helical 0.245
Ill-defined 0.632
network models (Fowler and Elliott, 1987). U0
Models for the non-stoichiometric alloys • ..• i. •
have been constructed by the three-step •• * :

,120
procedure (Itoh et al., 1982) and by a
Monte Carlo repositioning of atoms in or-
der to give the best fit to the experimental 100 * • • • *

scattering data (Rechtin et al., 1974; Ren-

ninger et al., 1974). Although none of these
80-•
models give perfect agreement with experi-
mental data, nevertheless, they do indicate
that a restricted local layer-like structure 60
60 80 100 120 160
persists, reminiscent of the layer structure 0.1 (deg)
of the crystal orpiment; however, a micro-
Figure 7-22. Correlation diagram for the two dihedral
crystallite-like stacking involving orpiment- angles subtended at the sulphur atoms in a CRN
like layers is not necessary to give rise to model for a-As2S3 (Pfeiffer et al., 1989). The dihedral
the FSDP at Qx~1.2 A" 1 (N.b. the orpi- angle is here defined as the angle between the As-cen-
ment 020 reflection lies close to this value), tred vector along the symmetry axis of an AsS3/2 unit
and the S-centred vector along the bisector and in the
since many of these models, which do not
plane of an SAs2/3 unit. The values denoted by B and
have such a quasi-periodic structural re- H refer to bridging and helical S sites, respectively, in
peat, also reproduce the FSDP. the orpiment structure.
406 7 Chalcogenide Glasses
fied using 75As nuclear quadrupole reso-
nance (NQR) spectroscopy in terms of two
distinct asymmetry parameters rja of the
electric field gradient tensor (Rubinstein
and Taylor, 1974). However, in glassy
As 2 S 3 (and As2Se3), similar measurements
have revealed that in fact 70% of the sites
are symmetric, with only 30% which could
have an environment similar to that in
crystalline orpiment (Szeftel and Alloul,
1979). The interpretation here is that a sig-
nificant part of the structure can be de-
scribed in terms of a CRN, with only a
relatively minor proportion having a MRO
in the form of cross-linked helical chains.
Phillips et al. (1980) (see also Phillips, 1981)
have also proposed that MRO in the form
of orpiment-like structural elements exists
in the glass. They proposed that the struc-
ture consists of the twelve-membered rings,
found in orpiment, linked together in a
chain-like fashion by bridging chalcogen
atoms, with two extra chalcogens (outrig-
gers) bordering each raft on the other sides
of the ring from the chain connections.
The structure of glassy As2Se3 appears
to be more-or-less isomorphous with that
of g-As2S3, as found from NQR studies
(Szeftel and Alloul, 1979) and X-ray diffrac-
tion data (Cervinka and Hruby, 1982), ex-
cept that the As-Se bond length (2.43 A) is
correspondingly larger than for As-S, and
the bond angles subtended at As and Se
atoms are inferred to be smaller, viz. 100°
and 95°, respectively (Cervinka and Hruby,
1982). Chen et al. (1984) have reported a
large-scale domain structure in evaporated
thin films of a-As2Se3, in the form of polyg-
onal domains with diameters up to 1000 A.
75
As NQR measurements have also been
carried out on the mixed chalcogenide glass
system, As 2 S x Se 3 _ x (Treacy et al., 1983).
These studies found that S substituted for
Se, so that the basic structural units com-
prised AsS x/2 S (3 _ x)/2 pyramids, with no
evidence being apparent for anionic subsite
segregation.
In contrast to the case of the S- and
Se-based As chalcogenides, where the SRO
of glass and crystal appear to be very sim-
ilar, the structure of the glassy and crys-
talline forms of As2Te3 appear to be very
different: crystalline As2Te3 contains As
sites which are octahedrally coordinated
by Te, whereas the glass contains mainly
AsTe3/2 pyramidal units with an As-Te
bond length of 2.65 A, an As bond angle of
98° and Te bond angles in the range 9 5 -
98°, as found from X-ray diffraction stud-
ies (Cornet and Rossier, 1973; Cervinka
and Hruby, 1982), from 75As NQR (Szeftel
and Alloul, 1979), and from 125Te absorp-
tion (Faigel et al., 1983) and 129 I emission
Mossbauer experiments (Boolchand et al.,
1982 a, b). However, there is also evidence
that some of the Te atoms in glassy As2Te3
are three-fold coordinated (Cornet and
Rossier, 1973; Boolchand et al., 1982a, b).
125
Te and 129 I Mossbauer measurements
have also been performed on the binary
(As2Se3)JC(As2Te3)1_JC glass system (Wells
and Boolchand, 1987) in which evidence is
adduced for broken chemical order, i.e. the
presence of chalcogen-chalcogen wrong
bonds. Vazquez et al. (1986) have under-
taken an X-ray diffraction study on the
binary system As0 2Se0.5Te0 3 , and have
simulated the structure using a Monte
Carlo approach in which As atoms were
assumed to be either three-fold or four-fold
coordinated.
The structure of the Sb chalcogenides
has been relatively little studied. Cervinka
and Hruby (1982) performed an X-ray dif-
fraction study of two forms of bulk amor-
phous Sb 2 S 3 , one formed by very rapid
(roller) quenching, and the other formed by
a chemical reaction technique (precipita-
tion of Sb 2 S 3 by passing H 2 S through a
solution of SbCl3). In both cases, trigonal

pyramidal coordination of Sb atoms by S
was found (with an Sb-S bond length of
2.50 A), S atoms being coordinated by two
Sb atoms, with an Sb bond angle of 90°
and an S bond angle of 100.7°. The struc-
tures of the two amorphous forms were
rather similar, and could be understood in
terms of a CRN arrangement of SbS 3/2 py-
ramidal units. More recently Dalba et al.
(1989) have also studied amorphous Sb 2 S 3
(in both bulk glassy and thin-film forms),
by X-ray diffraction and EXAFS. Their
findings for the glass agree with those of
Cervinka and Hruby (1982), and more
particularly they find, unlike in some ear-
lier studies (Zacharova and Gerasimenko,
1972; Tatarinova, 1972), that the structure
of the glassy and thin-film forms are very
similar. Watanabe et al. (1983) have stud-
ied amorphous thin films of Sb x S 1 0 0 _ x
by Raman scattering. The stoichiometric
film (x = 0.4) exhibits a narrow band at
170 cm" l and a broad band at 290 cm" 1 ,
the latter band increasing in intensity and
the former band decreasing in intensity
with increasing S content (decreasing x).
The band at 290 cm" 1 was ascribed to
Sb-S vibrations (in say SbS 3/2 units), and
the band at 170cm" 1 was ascribed to
Sb-Sb vibrations; thus, even at the stoi-
chiometric composition, the chemical or-
der in the films appears to be broken.
Finally, we discuss the structure of
amorphous phosphorus chalcogenide ma-
terials. In a sense, these exhibit perhaps the
most interesting structural features of all
the members of the V-VI family because
of the propensity to form P4Xn (n = 3-10;
X = S, Se) cage-like molecules (see Fig. 7-
23). As mentioned in Sec. 7.2.1, the PxSe1 _x
system exhibits two glass-forming regions,
I (0<x<0.52) and II (0.63<x<0.85), sep-
arated by the stoichiometric composition
P4Se3 (x = 0.57). Neutron diffraction, EX-
AFS and Raman measurements have been
7.3 Structure 407
performed by Price et al. (1984) on glasses
in region I, including Se isotopic substitu-
tion diffraction measurements for x = 0.4
and 0.5 (Arai et al., 1986), and neutron dif-
fraction and EXAFS measurements have
also been performed by Verrall and Elliott
(1988,1989,1990) and Verrall et al. (1988 a)
for glasses in both composition region I
(where the results agreed with those of
Price et al., 1984) and in II, the latter cen-
tred around the composition P2Se. Price
et al. (1984) inferred from their neutron dif-
fraction results on the Se-rich glasses that
there was some evidence for the existence
of P4Se5 and P4Se3 molecules in the struc-
ture, depending on the composition, these
presumably being embedded in a Se-rich
matrix. The Raman spectrum for glassy
P 50 Se 50 has many features in common
with that of the molecular species P 4 Se 3 ,
supporting the supposition that a reason-
able proportion of such molecules exists in
the structure of this glass. Furthermore,
magic-angle spinning (MAS) NMR experi-
Figure 7-23. Schematic illustration of the structural
arrangement of the cage-like molecular species P4Xn
(X = S, Se;tt= 0-10). Chalcogens tend to be inserted
preferentially at edge (E) positions, rather than the
double-bonded apical (A) positions.
408 7 Chalcogenide Glasses

0 50 100 150 200 250 300 350 400 (cm'1)

15 i 1 r 1 1 > 1 1 1 '

V V V V V V
5 6 7 8 9 10
10 -

>

LJLJ
o

v 10 v 9
tltt Uti tl
ti t u , I , , , , I
10 20 30 50 60
a) E(meV)

ments on P-Se glasses also provide evi-

dence for the existence of P4Sen clusters in
the structure (Lathrop and Eckert, 1988;
Eckert, 1989). In particular, the proportion
of tetrahedral P sites (with a doubly-bond-
ed Se terminator atom, viz. Se = PSe3/2)
progressively increases with decreasing P
content (see Fig. 7-25); this is evidence for
the existence of say P 4 Se 10 clusters (see
Fig. 7-23) at low P contents.
In the case of glassy P2Se, evidence that
the structure consists almost entirely of
P4Se3 molecules (with a small excess of P)
is overwhelming. The static structure fac-
tor S(Q) for g-P2Se can be fitted almost
exactly for Q 2> 6 A" 1 by the form factor
calculated for the P4Se3 molecule (Verrall
and Elliott, 1989). Inelastic neutron scat-
tering studies of the vibrational excitations
of g-P2Se reveal a highly structured density
300 400 500 of states (see Fig. 7-24 a), the peaks in
b) Raman shift/cm"1 which can be assigned to the vibrational
Figure 7-24. (a) Vibrational density of states (VDOS) excitations of a P4Se3 molecule (Verrall
for glassy P2Se measured by inelastic neutron scatter- and Elliott, 1988 a, 1989); Raman measure-
ing (Verrall and Elliott, 1988). (b) Raman spectra of ments by Phillips et al. (1989) support this
a-PxSe1_x alloys (0.67 < x < 1.0) (Phillips et al., 1989). finding, and the higher resolution of this
In both cases, the cage-like vibrational modes of the
P4Se3 molecule are indicated, together with an assign-
technique allows more of the vibrational
ment of features in the VDOS and Raman spectrum modes to be distinguished (Fig. 7-24 b). Fi-
in terms of these modes. nally, quasi-elastic neutron scattering mea-
 7.3 Structure 409

surements have been performed on g-P2Se, PSe3/2 Se=PSe3/2

and a quasi-elastic broadening of the elas-
tic line was observed at elevated tempera-
tures (300-450 K), indicative of the pres-
ence of atomic motion (Verrall and Elliott,
1989). These findings have been interpreted 5.0
in terms of a rotational diffusion of P4Se3
molecules in the glassy structure, similar
to that which occurs in the plastic phase
(T > 355 K) of crystalline P 4 Se 3 .

7.3.3.3 Structure of I V - V I Materials

The Ge and Si chalcogenides also ex-
hibit a rich variety of structural features,
particularly related to MRO, as a result of
the propensity for the formation of edge-
sharing tetrahedra compared with their
oxide counterparts. A survey of the struc-
tural features of amorphous IV-VI mate-
rials determined by diffraction methods
has been given by Wright et al. (1982). It
is significant that in the AX2 materials
(A = Si, Ge; X = O, S, Se), oxides have an
A-X-A bond angle greater than the tetra-
hedral angle of 109.47°, where the corre-
sponding chalcogenide materials have an
angle 6 (A-X-A) which is smaller than
this.
The structure of amorphous GeS 2 has 400 300 200 100 0 -100 -200 -300
been relatively little studied, perhaps be- ppm
cause of the difficulty of preparing exactly Figure 7-25. 31 P magic-angle spinning NMR spectra
stoichiometric material in a glassy form of various P^Se^^ glasses (Eckert, 1989). Assign-
(Voigt etal, 1978). Feltz et al. (1985) and ments of the two principal features in the spectra in
terms of trigonal PSe3/2 and tetrahedrally-coordi-
Cervinka etal. (1987) have performed nated Se = PSe 3/2 units are indicated.
X-ray diffraction studies on glassy GeS 2 ,
finding the Ge-S bond length to be 2.23 A
or 2.26 A, respectively and the Ge-S-Ge high-temperature form of) crystalline GeS 2
bond-angle distribution to be centred at (and GeSe2) consists of two types of struc-
115°. From a ball-and-stick structural tural configuration, one which contains
modelling study, Feltz etal. (1985) infer corner-sharing tetrahedra in a chain-like
that the structure consists mainly of cor- configuration, and the other containing
ner-sharing GeS 4/2 tetrahedra, but that edge-sharing units bridging two chains (see
about 25% of the tetrahedra form edge- Fig. 7-26). Cervinka (1988) has discussed
sharing connections. The structure of (the the MRO in glassy GeS 2 , particularly as-
410 7 Chalcogenide Glasses
C-Configuration
E-Configuration
Figure 7-26. Chain (C) and edge (E) sharing configu-
rations in GeX2 (X = S, Se) (Cervinka, 1988).
sociated with the FSDP at Qx«1 A \ in
terms of correlations between such struc-
tural configurations; a reasonable fit to the
first two peaks in the X-ray scattering pat-
tern was achieved in terms of a parallel
packing of chain-like clusters separated by
about 7-8 A.
The structure of glassy Ge 2 S 3 has been
studied by X-ray diffraction by Pohle et al.
(1985); the structure could be well de-
scribed in terms of the structural unit being
the ethane-like grouping [Ge2S6], with all
chalcogens being two-fold coordinated in
corner-sharing links.
4: 2 coordination of Ge and S, respec-
tively, was found for the case of a-GeS
by Drahokoupil et al. (1986) using X-ray
emission and EXAFS, despite the fact that
in the structure of crystalline GeS the Ge
(and S) atoms have a 3 : 3 coordination.
Drchal and Malek (1988) have constructed
two structural models for a-GeS, one a 3D
structure containing Ge(Ge 4 _ n SJ tetrahe-
dra of all types, and the other a layered
model in which Ge(Ge 2 S 2 ) units were pre-
dominant, the former giving the best fit
with experimental scattering data.
There have been many more structural
investigations of glassy GeSe 2 . An X-ray
diffraction study has been performed by
Feltz et al. (1985), an anomalous X-ray
scattering study by Fuoss et al. (1981) and
neutron scattering measurements made by
Uemura et al. (1978), Nemanich et al.
(1983), Wright et al. (1987), and Susman
et al. (1988); a Ge-Se bond length of 2.37 A
is found. As for the case of g-GeS2, the pres-
ence of a significant proportion (—15%, c.f.
25% for the crystal) of edge-sharing con-
nections between GeSe 4/2 tetrahedra in the
structure of g-GeSe2 has been suggested on
the basis of diffraction data (Nemanich
etal., 1983), Raman scattering (Briden-
baugh et al, 1979; Sugai, 1987) and a mo-
lecular dynamics (MD) structure simula-
tion involving two-body interaction poten-
tials only (Vashishta et al, 1989).
MRO in glassy GeSe2 has been the sub-
ject of much controversy, and two experi-
mental features have been the centre of dis-
cussion, namely the FSDP at Q ^ l A " 1
and the so-called companion line to the
main Ge-Se stretch mode in the Raman
spectrum. From neutron scattering mea-
surements the FSDP found in the glassy
phase remains with the same intensity
(Susman etal, 1988), or even enhanced
(Uemura et al, 1978) in the liquid state -
see Fig. 7-15. (This behaviour is also repro-
duced by the MD simulation of Vashishta
et al, 1989). This observation makes it un-
likely that any microcrystalline-like struc-
tural ordering is responsible for the FSDP.
The anomalous X-ray scattering results of
Fuoss et al. (1981) indicate that Ge-centred
(Ge-Ge, Ge-Se) correlations contribute
primarily to the FSDP; this conclusion is
supported by X-ray diffraction measure-
ments on GeSe 2 -GeTe 2 glassy alloys, in
which the FSDP grows in intensity as Te is
replaced by Se, thereby enhancing the Ge
contribution (Moss, 1974). The MD simu-
 7.3 Structure 411

lation study by Vashishta et al. (1989) also

found that Ge-based correlations were
mainly responsible (although for the simu-
lated structure the FSDP appears at a
larger value, Q 1 ^1.35A"" 1 , than observed
experimentally), and they ascribed this
to Ge-Ge correlations at separations of
9-10 A (since the FSDP disappeared if
only atomic correlations less than 8.8 A
were included in the calculation of S (Q)).
The companion line at ^220 cm" 1
(26.5 meV) to the main At symmetric-
stretch breathing mode of GeSe 4/2 tetrahe-
dra at ^200 cm" 1 (25 meV) observed in
the Raman spectrum of g-GeSe2 has also
been taken to be a signature of MRO in
this material. The band is unusally narrow
and strongly polarized; moreover it ex-
hibits an unusually strong compositional 300 200 100 0
dependence (Nemanich et al., 1977), vary- Raman shift Icrrf1)
ing as ~x5 in the alloys Ge^Se^,,, where- Figure 7-27. Raman (solid line) and depolarization
as the intensity of the Ax mode varies lin- (dashed line) spectra of a-GexSe1 _x. Note the anoma-
lous composition dependence of the companion line at
early with x as expected from a progressive
^220 c m ' 1 compared with the symmetric-stretch At
break-up of GeSe 4/2 tetrahedra with in- breathing modes of GeSe4/2 tetrahedra at %;200 cncT1
creasingly off-stoichiometric composition (Nemanich et al., 1977).
(see Fig. 7-27). Nemanich et al. (1983) and
Sugai (1987) have ascribed the anomalous
companion line to the vibration of the (Elliott, 1990), and thus it is not clear
four-membered (Ge2Se2) rings associated whether the anomalous compositional
with edge-sharing tetrahedra (Fig. 7-26), changes in the Raman intensity of the
whereas Bridenbaugh et al. (1979) have as- 220 cm" 1 band are due entirely to a sys-
cribed it to the vibrations of Se-Se bonds tematic change in the structure (e.g. in the
(dimers) bordering what they have termed a proportion of edge-sharing tetrahedra), or
raft, namely a 2D section of the crystalline from a change in the Raman matrix ele-
structure containing edge-sharing units ment.
cross-linking parallel chains of corner- An experiment probing the vibrational
sharing tetrahedra (see Fig. 7-17 a). (Wright density of states which is less sensitive to
et al. (1987), however, have indicated that matrix-element effects is inelastic neutron
the structural correlations associated with scattering, and two such experiments have
such rafts are incompatible with the mea- been reported for g-GeSe2 (Gladden et al.,
sured RDF; in particular, the third peak at 1988; Walter et al., 1988). The dynamic
~4.7A is much too pronounced in raft- structure factor S (Q, co) is shown in Fig.
like structures). However, matrix-element 7-28 a and the vibrational density of states
enhancement of Raman bands can occur in (VDOS) G(E) in Fig. 7-28 b (Walter et al.,
the case of symmetric vibrational modes 1988). The four modes labelled v1-vA, in
412 7 Chalcogenide Glasses

a) 6O O.O

GeSe 2 DOS13K

Figure 7-28. (a) Dynamical

neutron structure factor,
S(Q, w), of glassy GeSe2
with the elastic contribu-
tion removed (Walter et al.,
1988). (b) Vibrational den-
sity of states of glassy
GeSe2 obtained from in-
elastic neutron scattering
(Walter et al., 1988).
10 20 25
b) E(meV)

Fig. 7-28 b correspond to the vibrational
modes of GeSe 4/2 tetrahedra which, in
the central-force-field model of Sen and
Thorpe (1977) where bond-bending forces
are neglected, are vibrationally decoupled
as long as the chalcogen bond angle is near
90°. The origin of the other features in the
VDOS is less clear, although Bridenbaugh
et al. (1979) and Kumagai et al. (1977) have
assigned a (Raman) peak at 265 cm 1 (and
175 cm""1) to vibrations of Ge-Ge bonds
in ethane-like (Ge2Se6/2) structural group-
ings. Unfortunately, even the highest-reso-
lution inelastic neutron scattering spec-
trometers available have a considerably
worse energy resolution than is routinely
attained in Raman scattering experiments;
as a result, the companion line has not yet

been unambiguously resolved from the A±
mode in inelastic neutron scattering mea-
surements (Gladden et al., 1988).
There has been some controversy con-
cerning the atomic coordination in the ma-
terial a-GeSe (see Fowler and Elliott, 1982,
for a review), although the anomalous
X-ray scattering data of Fuoss et al. (1981)
seem to favour 3 : 3 coordination, with a
Ge-Se bond length of 2.4 A and an aver-
age bond angle of ^106° (Uemura et al.,
1974). A modelling study by Fowler and
Elliott (1982), in which 3 : 3 coordination
was assumed, gave good agreement with
the neutron scattering results of Uemura
et al. (1974) and also the anomalous X-ray
scattering results of Fuoss et al. (1981).
Pohle et al. (1985) have investigated the
structure of amorphous Ge 2 Se 3 using X-ray
diffraction, and found that the structure
can be understood in terms of corner-
sharing (Ge2Se6/2) structural units, i.e. con-
taining a Ge-Ge homopolar bond.
The macrostructure of obliquely-evapo-
rated a-GeSe2 (and GeS 2 and GeSe3) films
exhibiting a columnar microstructure has
been investigated by Rayment and Elliott
(1983), Spence and Elliott (1987) and Ver-
rall etal. (1988 b) using small-angle neu-
tron and X-ray scattering.
The Si chalcogenide glasses SiS2 and
SiSe2 also exhibit extremely interesting
structural features. The crystalline modifi-
cations of these materials are chain-like
structures consisting entirely of edge-
shared SiX4/2 tetrahedra (X = S, Se), and
there is much experimental evidence that
this form of MRO persists in the glassy
phase as well. Neutron diffraction mea-
surements have been carried out on the
glassy Si x Se!_ x system (Johnson etal.,
1986; Johnson, 1986), and many Raman
scattering studies have been performed on
both SiS2 and SiSe2 glasses (Tenhover
etal., 1983a, 1983b; Griffiths etal., 1984;
7.3 Structure 413
Malyj etal. 1985; Tenhover etal., 1984,
1985; Susman et al, 1986; Sugai, 1987). In
addition, 29Si MASNMR experiments have
been performed on these materials (Ten-
hover et al, 1988; Eckert, 1989) as well as
inelastic neutron scattering measurements
(Arai et al, 1988). Although there is no
consensus concerning the detailed assign-
ment in terms of vibrational modes of the
various bands observed in the Raman
spectra of these glasses (Arai etal, 1988),
nevertheless it is generally agreed that the
structure of the glasses cannot be under-
stood in terms of either being completely
chain-like (i.e. 100% edge-shared units) or
completely corner-sharing (as in SiO2), but
that both types of connection are present
with edge-sharing being dominant. 29Si
MASNMR results (Tenhover etal, 1988;
Eckert, 1989) provide evidence for three
distinct types of Si environment in the glass
compared with the single site in the crystal
(Fig. 7-29); these have been ascribed to
SiX4/2 units (X = S, Se) having zero, one
and two edge-sharing connections (labelled
E°, E 1 , E 2 , respectively). Tenhover et al.
(1988) find that in glassy SiS2 and SiSe2 the
proportions of these sites are approxi-
mately 25% E°, 50% E \ and 25% E2.
An extensive structural modelling study
of glassy SiSe2 (SiS2) has been undertaken
by Gladden and Elliott (1987, 1989) in
which the neutron diffraction data of John-
son et al. (1986) is best fitted by a mixture
of structural groupings, including about
15% of the cross-linked chain cluster (essen-
tially a 12-membered ring consisting of
four E 1 and two E° units) proposed by
Griffiths etal. (1984) (see also Griffiths,
1986) with the rest of the structure in the
form of random chains containing an aver-
age of seven E 2 units, of which approxi-
mately 15% show some degree of local
parallelism between two chains extending
for two or three E 2 units. Fig. 7-30 shows
414 7 Chalcogenide Glasses
+50
-150
29
Si (ppm)
Figure 7-29. 29Si magic-angle spinning NMR of
glassy and crystalline SiS2 (Tenhover et al., 1988). The
assignment of the peaks in the spectrum of the glass
in terms of En (n = 0-2) configurations, where n is the
number of edge-sharing connections per SiS4/2 tetra-
hedron, is shown.
the fit of the model to the experimental
structure factor and RDF with, in the latter
case, an indication of which MRO features
contribute to particular regions of the RDF.
7.3.3.4 Structure of III-VI Materials
Relatively little structural work has been
undertaken on the boron chalcogenide
glasses, mainly because of their great sen-
sitivity to hydrolysis; moreover, neutron
scattering measurements are not possible
with the naturally occurring isotopic mix-
ture of boron due to the very high absorp-
tion cross-section of the 10B nucleus.
Nevertheless, there have been a number of
X1
B c.w. (broad-line) NMR studies of the
structure of boron chalcogenides (Hen-
drickson and Bishop, 1975; Rubinstein,
1976; Hintenlang and Bray, 1985; Hiirter
et al., 1985). For the case of the stoichio-
metric B 2 X 3 materials (X = S, Se), the
NMR spectra exhibit clear evidence for
second-order quadrupolar splitting due to
the presence of an appreciable quadrupole
coupling constant associated with trigonal
planar BX 3/2 units. These triangular units
are presumably connected by corner-shar-
ing at the apical chalcogen atoms, as in the
corresponding oxide glass, B 2 O 3 . The ad-
dition of the modifiers Li2S (Hintenlang
and Bray, 1985) and T12S (Eckert et al.,
1984) to B 2 S 3 converts the coordination of
the B from trigonal to tetrahedral; the pro-
portion of tetrahedrally-coordinated B is
a maximum at about 40mol.% modifier,
as for the analogous behaviour found in
the alkali borates, and at higher modifier
contents trigonal B units are created with
non-bridging (singly-coordinated) sulfur
atoms.
7.3.3.5 Metal Chalcogenide Materials
In many cases, metals are present in
amorphous chalcogenide materials as ter-
nary (or higher) constituents, acting as net-
work modifiers. In such cases, a major
structural influence of the modifier is to
alter in some way the structure of the net-
work-forming matrix, either by a change
in coordination of the network-forming
cation (e.g. from 3 to 4 for B as evidenced
by NMR studies (Eckert et al., 1984) - see
Sec. 7.3.3.4) or of the network-forming
anion, usually a reduction in coordination,
resulting in a network depolymerisation

b)
Figure 7-30. (a) Experimental neutron scattering in-
tensity function, i(Q) (dashed line) for glassy SiSe2
(Johnson et al., 1986) compared with that calculated
for the model of Gladden and Elliott (1987, 1989)
(solid line), (b) Experimental RDF for glassy SiSe2
(points) (Johnson et al., 1986) compared with that cal-
culated for the model of Gladden and Elliott (1987,
1989) (solid line). The contributions of various struc-
tural groupings to the RDF are also indicated.
7.3 Structure 415
and the creation of non-bridging chalco-
gen atoms (e.g. in Tl 2 S-As 2 S 3 studied by
XPS by Heo et al. (1988)). However, the
structural environment of the metal (modi-
fier) atom is often difficult to investigate in
such multicomponent materials and atom-
specific structural probes must be used.
Thus, as examples, the technique of EX-
AFS has been applied to the Ag-As-S sys-
tem (Steel etal, 1989), anomalous X-ray
scattering to the Ag-Ge-Se system (West-
wood and Georgopoulos, 1989) and iso-
topic substitution neutron scattering to the
Ag-As-S system (Penfold and Salmon,
1989). From such studies, it is found that
the Ag atoms are generally coordinated by
~ 3 chalcogen atoms.
Less common are (binary) metal chalco-
genide systems in which the metal atoms
play a significant structural role. The struc-
ture of a-MoS 3 has been extensively stud-
ied by X-ray diffraction and EXAFS mea-
surements (Liang etal., 1980a, 1980b;
Chien etal., 1984) and Raman scattering
(Bhattacharya et al., 1987). Octahedral co-
ordination of Mo atoms by S atoms was
found with a bond length of 2.47 A, and
evidence was also found for Mo-Mo
dimers with a bond length of ~ 2.9 A, con-
siderably shorter than the normal Mo-Mo
416 7 Chalcogenide Glasses
bond length of 3.4 A (Chien et al., 1984).
The structure proposed by Chien et al.
(1984), based on modelling studies, is of a
chain-like structure built from Mo atoms
with an alternating sequence of long and
short bonds and with disulphide (S-S)
bonds between two S atoms in alternate
octahedra. It is interesting that the X-ray
scattering intensity shows a sharp intense
FSDP at Q i - l A " 1 (Chien et al., 1984)
which, because of the relative weightings of
the scattering factors involved, must be due
almost entirely to Mo-Mo correlations.
Chien et al. (1984) account for this feature
in terms of a local parallel coupling of
chains, much as in the case of g-SiSe2 or
SiS2 (Gladden and Elliott, 1989).
7.3.3.6 Structure of Halogen Chalcogenides
The structural and other properties of a
wide range of halogen-containing chalco-
genide glasses have recently been exten-
sively reviewed by Sanghera et al. (1988).
In general, the structural effect of the in-
clusion of halogens is for the atoms to act as
network terminators, i.e. singly-coordinated
halogen atoms substitute for two-fold co-
ordinated chalcogens, and as a result the
structure is depolymerised and the viscos-
ity is concomitantly dramatically lowered
(Rawson, 1967). Although direct structural
techniques (e.g. diffraction) appear to have
been seldom used for these materials, with
the exception of the (GeS2)JCBr1__x and
(GeS^Ji _x systems (Wagner et al., 1988),
Raman spectroscopy has been widely ap-
plied, e.g. for the As-S-I system (Koudel-
ka and Pisarcik, 1982, 1984), As-S-Br
(Koudelka et al., 1979; Koudelka and
Pisarcik, 1983), Ge-S-Br (Koudelka et al.,
1984), and G e - S - I (Sanghera et al., 1988).
In all cases it appears that the halogens (H)
replace the chalcogens (C) in the structure,
i.e. As-H or, Ge-H bonds form preferen-
tially with respect to C-H bonds. As a
result, in some cases there appears to be
evidence, from the Raman spectra, for a
type of microphase separation in which
discrete molecular species, e.g. AsBr3
(Koudelka et al., 1979) and S8 rings (pre-
sumably formed from the chalcogens dis-
placed by the halogens) are dissolved in the
remaining glassy matrix.
In the case of the binary halogen-
chalcogen Te-X (X = Cl, Br) materials dis-
covered recently (Zhang et al., 1988; Lucas
and Zhang, 1990), bonds between halogens
and chalcogens must occur. Zhang et al.
(1988) suggest that the structure of glassy
Te3Cl2 or Te3Br2 is similar to that of the
corresponding crystal (Kniep et al., 1973),
which is based on helical Te chains, in
which every third Te atom is bonded ax-
ially to two additional halogen atoms,
making such Te atoms tetrahedrally coor-
dinated (see Fig. 7-31 a), and the structure
of glassy Te2Cl and Te2Br is also proposed
to be similar to that of the crystalline mod-
ification (see Fig. 7-31 b), which consists of
a ladder-like structure of two intercon-
nected Te chains, with bridging halogen
atoms. However, there does not yet appear
to be any direct structural evidence for
these proposed structures.
7.4 Defects
7.4.1 Introduction
Defects can only be discussed sensibly in
the context of some reference structure
which is non-defective. In the case of crys-
talline materials, this requirement is read-
ily satisfied, in terms of a perfect single
crystal, but in the case of amorphous mate-
rials the situation is not as clear-cut: what
is to be taken as the reference, non-defec-
tive (i.e. ideal), non-crystalline structure?

b)
In the case of covalently-bonded systems,
at stoichiometric compositions, the ideal
reference structure may be taken to be
a chemically-ordered continuous random
network (COCRN) (Elliott, 1984, 1990).
Thus, defects in such a structure can be
wrong (homopolar) bonds and coordina-
tion defects, e.g. over-coordinated atoms
or under-coordinated atoms (dangling
bonds). However, in certain cases for
amorphous materials it is difficult to de-
cide whether or not a particular structural
feature is a defect under the above defini-
tion. For instance, should the negatively-
charged non-bridging (NB) chalcogen
sites, denoted by the symbol C^~ (where C
stands for chalcogen, and the superscript
and subscript are the charge state and
atomic coordination, respectively), result-
ing from the introduction into chalco-
genide glasses of network-modifier cations
(e.g. alkalis, Ag + , Tl + ) and which compen-
sate the positively charged cations (see e.g.
7.4 Defects 417
Figure 7-31. Structure of
crystalline Te3Cl2 (a) and
Te2Cl (b) (Kniep et al,
1973),
Heo etal., 1988), be regarded as defects?
We will take the viewpoint that if the struc-
ture intentionally and necessarily contains
say modifier cations, the concomitant
changes in the structure (e.g. over-coordi-
nated boron atoms - Sec. 7.3.3.4) or NB
chalcogens (see Sec. 7.3.3.6) should not be
regarded as constituting defects, but in-
stead they are a natural feature of the
(modified) structure. However, any such
structural entities which are present with a
concentration in excess of that otherwise
normally expected should be regarded as
defects.
7.4.2 Wrong Bonds
If the COCRN is taken as the ideal
structure for a compound chalcogenide
material with stoichiometric composition,
wrong or homopolar bonds occurring in a
real material are obviously defects in the
structure since they represent broken
418 7 Chalcogenide Glasses

chemical order. However, for the case of

off-stoichiometric compositions, wrong
bonds can naturally occur as the response
of the structure in accommodating the ele-
ment in excess. In this case, such wrong
bonds should not be regarded as defects.
(Wrong bonds also obviously have no
meaning in the case of elemental chalcogen
materials.)
It is often difficult to detect the presence
of wrong bonds, and there are several rea-
sons for this. Often, they are present in very
low concentrations (<1%), and conven-
tional direct structural probes, such as dif-
200 400
fraction, are often not sufficiently sensitive;
a) Raman shift (cm"1)
furthermore, in the electronic ground state,
such defects are diamagnetic and therefore
electron spin resonance cannot be used. TqCC)
However, both Raman and Mossbauer 500
spectroscopies have been used successfully
to detect wrong bonds in chalcogenide
glasses.
Wrong bonds in glassy As 2 S 3 have al-
ready been discussed in Sec. 7.3.3.2. In the
Raman spectrum, in addition to the domi-
nant band at 344 c m - 1 due to As-S vibra-
tions in AsS 3/2 pyramidal units, small peaks
at 220-230 cm" 1 and 450-500 cm" 1 are
also observed (see Fig. 7-32 a), ascribed to
vibrations of homopolar As-As and S-S
bonds, respectively (Ewen and Owen, 1980;
Tanaka et al., 1985; Kawazoe et al., 1988).
The ratio of Raman intensities I (As-As)/ b)
I (As-S) markedly increases with increas- Figure 7-32. (a) Raman spectrum of as-quenched and
ing quenching temperature (see Fig. 7-32 b) annealed glassy As2S3 (Tanaka et al., 1985). The dom-
(Tanaka et al., 1985), indicating that homo- inant peak at 344 cm" 1 is ascribed to the symmetric
polar bonds are more prevalent in glasses stretching mode of AsS3/2 units, and the small feature
at 220 cm" 1 is ascribed to homopolar As-As bonds,
quenched from high melt temperatures, as (b) Ratio of the Raman intensities of the 220 cm" 1
expected. Mossbauer spectroscopy results (As-As) and the 344 cm" 1 (As-S) modes as a func-
also support the idea of broken chemical tion of glass quench temperature.
order at the 1% level in glassy As 2 S 3
(Boolchand et al., 1986).
Similar experiments have been performed
for glassy Ge x Se 1 _ x where again wrong
bonds are found in a proportion of ~ 1 %
 7.4 Defects 419

600
91 0.28 032 036

a) 0 b)
VELOC!TY(mm/s)
119
Figure 7-33. (a) Sn Mossbauer spectra of glassy (Ge0 99Sn0 01)xSe1_JC alloys near the stoichiometric composi-
tion (x = 0.333) showing evidence for two chemically inequivalent sites (Boolchand, 1986). Site A is a singlet
centred near v = 0 mm s ~1 and site B is a doublet displaced to about 2 mm s ~1. (b) The intensity ratio IB/(IA + IB)
as a function of composition for the B site in Sn-doped GexSe! _x alloys. The compositional dependence of the
glass-transition temperature, Tg, is also shown (Boolchand, 1986).

for the stoichiometric composition (see
Boolchand, 1986, for a review). Raman
spectra have revealed the presence of a
small peak at 180 cm" 1 which appears as a
shoulder to the main peak at —200 cm" 1
which is the Ax breathing mode of GeSe 4/2
tetrahedra (Murase et al., 1983 a, 1983 b);
the feature at 180cm" 1 is ascribed to the
vibrations of Ge-Ge homopolar bonds
in ethane-like Ge 2 Se 6/2 units. Boolchand
and coworkers have used Mossbauer spec-
troscopy to probe chemical ordering at
both the cation and anion sites in glassy
Ge^Se!^ (see Boolchand, 1986, for a re-
view). The cation (Ge) sites have been
probed using 119 Sn absorption Mossbauer
experiments in Sn-doped material (Bool-
chand et al., 1982) and even at the stoichi-
ometric composition (x = 0.333) evidence
was found for two chemically inequivalent
sites (see Fig. 7-33), the dominant one (A)
ascribed to Sn substituting for Ge in a
chemically-ordered environment (viz. a
GeSe 4/2 tetrahedron) and the other minor
site (B) ascribed to Sn substitution in
Ge 2 Se 6/2 units, i.e. in homopolar bonds.
The anion (Se) sites have been probed us-
ing both 125 Te absorption (Boolchand
etal, 1982b) and 129 I emission (Bresser
et al., 1981) Mossbauer experiments in Te-
420 7 Chalcogenide Glasses

doped Ge^Se^^ glasses. In the emission

experiments, unstable 129 Te m atoms are
used as the dopant and the local structure As 2 Se 3
is studied by monitoring the nuclear hyper-
fine structure of the daughter 129 I atoms
formed by p-decay from the 129 Te m parent
atoms. As for the cation sites, two chemi-
cally-inequivalent sites are discernible, C 2 (C.P)
which are ascribed to Te substitution in
chemically ordered Se(Ge2) and disor-
dered, i.e. homopolar Se (SeGe), sites.
It has been suggested by Halpern (1976)
P 3 (P.2C)
that wrong bonds are the dominant type of
defect in chalcogenide glasses because of
their low formation energy. In the case of
As 2 S 3 , the difference AE in bond energies
D can be estimated from the As-S electro- Figure 7-34. Electronic density of states for arsenic
negativity difference A/ (Halpern, 1976; chalcogenides with heteropolar (a) and homopolar
Vanderbilt and Joannopoulos, 1981; Ta- bonds (b, chalcogen-chalcogen; c, pnictogen-pnicto-
naka et al., 1985): gen) (Vanderbilt and Joannopoulos, 1981).

AE - D(As-S) - i[D(As-As) + D(S-S)] «

^(Ax) 2 = 0.3eV (7-17)
Thus, the fraction of wrong bonds frozen-
in on quenching from temperatures in the
range 625 < Tq < 1370 K, given by the
Boltzmann expression exp(— AE/kTq), is
expected to be 0.4-8%. It is significant
that the activation energy for homopolar
bond formation derived from the quench-
temperature dependence of the Raman
intensity ratio for homopolar and hetero-
polar bonds (see Fig. 7-32) is 0.32 eV for
Tq > 1070 K (Tanaka et al, 1985).
Vanderbilt and Joannopoulos (1981)
have calculated the electronic properties of
wrong bonds in the case of glassy As 2 Se 3 ,
and find that such defects give rise to elec-
tron states lying in the bandgap between
valence and conduction bands (see Fig.
7-34). The Se—Se wrong bond, denoted by
C 2 (CXP) where the symbols in parentheses
refer to the type of nearest neighbours
(C = chalcogen, P = pnictogen), gives rise
to a deep-lying gap state due to an anti-
bonding a| e state associated with the a-
bonded pair of p Se orbitals of the Se-Se
bond; the defect is neutral when the afe
state is unoccupied. Similarly the As-As
bond also gives rise to a deep gap state,
now due to the TI* combination resulting
from a ^-interaction between the aAs bond
orbital of the homopolar bond and two
neighbouring pSe orbitals; the defect is neu-
tral when this gap state is fully occupied.
7.4.3 Coordination Defects
Much discussion has also been devoted
to coordination defects in chalcogenide
glasses, i.e. those defects arising from bro-
ken bonds where, if atomic reconstruction
does not subsequently take place, the de-
fects will be under-coordinated, and if local
reconstructions can occur, the defects may
be over-coordinated with respect to the
normal bonding configurations in a chemi-
cally-ordered network. Such reconstruc-
tions are favourable in chalcogenide mate-

rials owing to the presence of the non-
bonding p-like lone-pair orbitals of the
chaleogens, forming the top of the valence
band in the electronic density of states
(Kastner, 1972; see Sec. 7.5.1), and which
can take part in dative-bonding reactions.
In Fig. 7-35 is shown the hypothetical
transformation of two neutrally-charged
chain-end dangling bonds (C?) to a neg-
atively-charged under-coordinated defect
(Cf) and a positively-charged overcoordi-
nated (Cj) site, viz.
2c?^c 3 + + e r (7-i8)
The transfer of an electron from one Cj
centre to another in Fig. 7-35 involves a
change in energy U, the effective correla-
tion (or Hubbard) energy, with
C/R (7-19)
where Uc is the positive coulombic energy
cost involved in placing a second electron
at a site (i.e. in forming a Cj~), and UR are
the energy changes involved in any subse-
quent reconstructions at the defects, e.g. in
the formation of the dative bond between
the empty p-orbital of a Ct+ centre (after
the removal of an electron from Cf) and
the occupied lone-pair p-orbital of a neigh-
bouring normally-bonded chalcogen, viz.
7.4 Defects 421
Anderson (1975), in a general discussion
of defects in chalcogenide materials, ar-
gued that the effective correlation energy
U should be negative, i.e. reaction (7-18)
should be exothermic, essentially because
the structure of an amorphous material
will minimise its energy by ensuring that
electron pairing always occurs, either in
covalent bonds or lone-pair (non-bonding)
orbitals. Subsequently, Mott et al. (1975)
and Kastner et al. (1976) applied the
general spin-pairing picture of Anderson
(1975) to the specific case of point (dan-
gling-bond) defects in chalcogenide glasses,
as in Fig. 7-35, where it was assumed from
simple chemical-bonding arguments that
U was negative, so that the spin-paired,
oppositely charged valence-alternation pairs
(VAPs; Kastner et al., 1976) would be en-
ergetically favourable.
Realistic total-energy calculations for a-
Se by Vanderbilt and Joannopoulos (1980)
have indicated that the neutral undercoor-
dinated C° centre is lower in energy, i.e.
more stable, than the overcoordinated C°
centre and that the C° defect produces a
deep-lying gap state due to a 71-bonding
interaction between the unpaired spin and
a lone-pair orbital on the neighbouring
chalcogen atom. However, subsequent cal-
culations by Vanderbilt and Joannopoulos
Figure 7-35. Schematic il-
lustration of the formation
of valence alternation pair
coordination defects (D + ,
D~) from neutral dangling
bonds in a-Se (Elliott,
1990).
422 7 Chalcogenide Glasses
(1983 a, 1983 b) have shown that for the
case of a-Se, in fact the effective correlation
energy is positive, U«0.4 eV, since al-
though the relaxation UR in Eq. (7-19) as-
sociated with the process C^ -»C J is nega-
tive (^ — 0.5 eV), the intra-site couloumb
repulsion energy for the process C?->C^ is
much larger in magnitude {Uc~ +0.9eV).
Hence, diamagnetic spin pairing in a-Se is
predicted to be energetically unfavourable.
The situation is considerably more com-
plicated for compound chalcogenide mate-
rials, e.g. V-VI materials, where both pnic-
togen- and chalcogen-based defects could
occur in principle (e.g. C j , C^, P 2 , P4,
PJ, and the neutral centres C°, P 2 and
possibly P^); furthermore the type of atoms
(P or C) which are nearest neighbours of
the coordination defect should also be
specified since they affect the energy levels
of the associated gap states. In summary,
the theoretical calculations of Vanderbilt
and Joannopoulos (1981) indicate that for
V-VI materials, deep gap states associated
with neutral paramagnetic defect centres
only occur when homopolar bonds are im-
mediately adjacent to the defect (e.g. C° (C),
P°(2P),P°(P,C)).
Dangling-bond defects at which the lo-
cal bonding is chemically ordered (viz.
CX(P) and P2(2C)) give rise to electron
states which prefer to be charged and dia-
magnetic, i.e. Cj~, P j ; the empty non-
bonding orbital (NBO) associated with the
P^ centre can, in principle, take part in
further dative-bonding reactions with a
nearby Se p-like NBO, thereby forming a
C3 centre, or even with the s-like NBO of
a nearby As atom, thereby resulting in an
overcoordinated P4 centre at which sp 3
hybridization has occurred.
Although realistic total-energy calcu-
lations have not been performed for
amorphous compound chalcogenides, e.g.
As2Se3, nevertheless it is likely that the
effective correlation energy U for such sys-
tems would be negative (Vanderbilt and
Joannopoulos, 1981).
The concentration of such coordination
defects will be determined by the VAP cre-
ation energy EVAP associated with the de-
fect creation reaction
(7-20)
2C°2
£y AP might be expected to be relatively low
(^0.5 eV) since reaction (7-20) involves es-
sentially just a bond flip. The concentra-
tion of randomly-distributed VAP centres
frozen-in on quenching through Tg will
then be given by (Vanderbilt and Joanno-
poulos, 1981):
nR « n0 exp(-£ VAP /2/e T) (7-21)
where n0 is the total atomic density.
Experimental evidence for the existence
of such thermally-generated defects in
As2Se3 has come from transient photocon-
ductivity (TPC) measurements in the
glassy state below Tg and in the liquid state
above Tg (Thio et al., 1984). If neutral de-
fects (C?) are the dominant recombination
centres, measurement of the recombina-
tion time from TPC measurements yields
an estimate for the concentration n of such
defects. Thio et al. (1984) found that n was
thermally activated, with an activation en-
ergy 0.35 eV and a pre-exponential factor
of ^ 4 x 1017 cm" 3 for T < Tg, whereas for
T > Tg, the activation energy was 0.8 eV
and the pre-factor ^ 6 x 1022 cm" 3 . Above
Tg, defects are created thermally from nor-
mally-bonded atoms (C2) with a number
density of —1022 cm" 3 ; the activation en-
ergy involved in the creation of (C°) recom-
bination centres from C^ or C^~ centres
will be therefore (\U\ + EyAP)/2, which is
identified with the value of 0.8 eV found
experimentally. However, for temperatures
below Tg, the total defect concentration is
frozen-in, but the conversion of C? centres

from C^ or Cx centres (the reverse of reac-
tion (7-18)) continues to be thermally acti-
vated with an activation energy \U\/2; ex-
perimentally this value is 0.35 eV. Thus,
these results indicate that for a-As2Se3,
£ VAP ^0.9eV and E/«-0.7eV.
7.4.4 Experimental Probes for Defects
In this section we will review some ex-
perimental techniques which are sensitive
to the presence of small concentrations of
defects, particularly coordination defects,
utilising their opto-electronic properties.
Those techniques which are sensitive to
homopolar bond defects, i.e. Raman and
Mossbauer spectroscopies, have been dis-
cussed in Sec. 7.4.2 (see also Chap. 6).
7.4.4.1 Electron Spin Resonance
Electron spin resonance (ESR), or equiv-
alently paramagnetic resonance (EPR), is
a probe for unpaired electron spins asso-
ciated, say, with neutral (paramagnetic)
dangling-bond defects, e.g. C° or P°; the
method has the advantage of having a high
sensitivity (^10 1 5 spins cm" 3 ).
ESR signals in pure chalcogenide glasses
are generally observed only after optical
excitation (see Bishop et al.91977), the ma-
terials being diamagnetic in cold, dark con-
ditions (Agarwal, 1973). (It was this obser-
vation that prompted Anderson (1975) to
propose the negative effective correlation
model.) An exception to this rule concerns
glassy G e ^ S i ^ materials which, excep-
tionally, do exhibit an ESR signal in the
absence of optical excitation (Cerny and
Frumar, 1979; Kordas et al., 1985; T. Shi-
mizu, 1985; Watanabe et al., 1988). The na-
ture of the spin centres in a-Ge^S^^ has
been the subject of some disagreement:
Cerny and Frumar (1979), Gaczi (1982),
and T. Shimizu (1985) have ascribed them
to Ge or S dangling bonds depending on
7.4 Defects 423
the stoichiometry (x>0.33 and x<0.33,
respectively), whilst Kordas et al. (1985)
have suggested that the ESR line consists
of two components, one being associated
with paramagnetic electron hopping be-
tween sites and the other to conduction
electrons in Ge-rich regions. It is likely,
however, that dangling bonds with a distri-
bution of correlation energies, U, are re-
sponsible: indeed T. Shimizu (1985) finds
that the ESR intensity decreases with tem-
perature up to T « 200 K (due to a sub-set
of defects with a negative U) and increases
at higher temperatures (due to a sub-set of
defects with a positive U).
In general, however, chalcogenide glasses
are normally diamagnetic and exhibit an
ESR signal only after illumination with
bandgap light. Two types of behaviour can
be distinguished, depending on the inten-
sity of the light used to induce the signal.
Low intensity (~lmWcm~ 2 ) irradiation
of chalcogenides, with photons of energy
comparable to the bandgap, at low tem-
peratures (~ 10 K) produces an ESR inten-
sity which saturates with illumination time
(Bishop et al., 1977), indicating that pre-
existing diamagnetic defects are being
transformed by optical excitation into
paramagnetic centres. Freitas et al. (1985)
have also shown that irradiation with low-
intensity sub-bandgap light produces simi-
lar effects. In the case of the As chalco-
genides, both chalcogen-based and pnicto-
gen-based paramagnetic centres have been
identified (Bishop et al., 1977; Hautala
et al., 1988), viz. C? or P° centres, respec-
tively, presumably resulting from the trap-
ping of photo-created holes and electrons
by the diamagnetic defects C^ or P^. The
photo-induced ESR signals for a series of
a-AsJCS1_x alloys are shown in Fig. 7-36
(Hautala et al., 1988): the S-related signal,
seen in the S-rich samples, is rather nar-
row, and has an anisotropic g-tensor with
424 7 Chalcogenide Glasses

tics of the s-p hybridized centre P° do not

agree with experiment (Gaczi, 1982).
With high-intensity (^100mWcm~ 2 )
illumination at low temperatures, on the
other hand, the photo-induced ESR signal
does not saturate (Benoit a la Guillaume
etal, 1977; Biegelsen and Street, 1980;
Hautala et al., 1988); furthermore, if such
an irradiated glass is thermally annealed
(at ~ 300 K) and then reilluminated at low
temperature, a very rapid re-inducing of
the ESR signal up to the previous level
occurs, followed by a further much slower
non-saturating growth (Fig. 7-37). The slow
non-saturating growth of the ESR signal is
ascribed to the creation of new defects (by
bond-breaking), and it is assumed that on
annealing these photo-generated paramag-
netic defects convert to a diamagnetic form
but do not disappear; subsequent illumi-
nation causes a rapid transformation of
these defects back to a paramagnetic state
by charge trapping, followed by further
(slower) bond-breaking defect creation. In
fact, Hautala et al. (1988) have shown that
four different metastable light-induced
ESR centres can be induced in a-As^Si-^
3.5 by prolonged illumination. Type-I defects,
consisting of an As and a S centre, anneal
Magnetic Field (kG) out at a low temperature (180 K) and their
Figure 7-36. Photo-induced electron-spin resonance
spectra measured at 20 K for As x S 1 _ x glasses (Hau-
tala et al, 1988).

gi = 2.00, g2 = 2.02, and g3 = 2.07 (Bishop

et al., 1977), whilst the As-related signal,
which is dominant in As-rich samples, ex-
hibits a characteristic hyperfine splitting
resulting from the interaction of the un-
paired electron spin with the 75As nucleus.
From an analysis of the hyperfine splitting,
50 100 150 200 250 300
it is concluded that the wavefunction of Exposure time (s)
the As-related unpaired electron is almost Figure 7-37. Kinetics of photo-induced ESR spin den-
completely p-like in character (Bishop sity and that reinduced after annealing for glassy
et al., 1977); the predicted ESR characteris- As2S3 measured at 20 K (Hautala et al., 1988).

concentration is independent of x; type-II
defects, also consisting of an As and a S
centre, anneal out at a higher temperature
(300 K), and Asn defects dominate in As-
rich material and S n in S-rich glasses, with
the Asn centres being more purely p-like
than the Asj centres. Elliott and Shima-
kawa (1990) have discussed in detail the
bond-breaking mechanisms leading to
such defects, and ascribe the type-I centres
to As^(2S) and S?(As) defects, and the
type-II centres are ascribed to As^As, S)
and S? (S) defects; such an interpretation is
in accord with the theoretical description
of the electronic states of such defects by
Vanderbilt and Joannopoulos (1981).
7.4.4.2 Photoluminescence
The technique of photoluminescence
(PL) probes the radiative recombination of
optically-created electron-hole pairs in a
material. Coordination defects can act ei-
ther as radiative or non-radiative recombi-
nation centres. Steady-state (c.w.) optical
excitation of chalcogenide materials (both
amorphous and crystalline) produces a sin-
gle, rather broad luminescence band,
which is significantly Stokes-shifted from
the peak in the photoluminescence excita-
tion (PLE) spectrum (see Fig. 7-38); note
that a-SiO2 behaves in a qualitatively sim-
ilar fashion. Reviews of the subject have
been given by Street (1976) and Kastner
(1985). The model first proposed for (c.w.)
PL in chalcogenide glasses involved the
trapping of one member of the photo-gen-
erated electron-hole pair by an isolated
charged defect, say Cj~ +h->C?; the re-
maining carrier was then supposed to re-
combine radiatively with the trapped car-
rier, viz. C? -+- e -»C[" -h h vPL. The lumines-
cence and excitation photon energies differ
(by a Stokes shift) if a structural relaxation
occurs upon charge trapping.
7.4 Defects 425
a-As2Se3
10
/a-As 2 S 3
PL
- /A\ , a
PLET
-// \
10 -
- /-- \~
\ i / i
10
5 10
Photon energy (eV)
Figure 7-38. Comparison of spectra for steady-state
(c.w.) photoluminescence (PL), photoluminescence
excitation (PLE), optical absorption (a) and photo-in-
duced absorption (dashed line) for two chalcogenide
and an oxide glass (Elliott, 1990).
However, this simple model for the PL
process has had to be revised in the light of
time-resolved (transient) PL studies (e.g.
Murayama, 1983; Higashi and Kastner,
1983; Robins and Kastner, 1984). For both
amorphous and crystalline chalcogenides,
the PL decay exhibits a knee in a double-
logarithmic plot (see Fig. 7-39). Thus the
PL decay behaviour can be divided into
two regimes, one being dominated by
processes characterised by short times
(t^ 10" 6 s) and the other by longer times
(t^lO~ 4 s); the long-time processes ac-
count for most of the PL quantum effi-
ciency and therefore they dominate the
steady-state (c.w.) behaviour. The origin of
these two decay processes is still not en-
tirely clear but probably is as follows.
426 7 Chalcogenide Glasses

if)
J
Ditrar>f uni

105 To 10"6 = 2.56eV

c
2.15 eV
104
bio- 7
a
103
1.78 eV
intensit

2
^ icr
10

i £ 10"
10 c

1 _L _L I 10"
6
10" 10' 10"* 10-2 10-6 10"* 10-2
Time delay (s) Time (s)
ta) (b)
Figure 7-39. Photoluminescence time decays in chalcogenide materials: (a) amorphous As2Se3 (Higashi and
Kastner, 1983), (b) crystalline As2Se3 (Robins and Kastner, 1984).

The short-time behaviour seems to be where a describes the spatial extent of the
consistent with a mechanism of donor- wavefunction, varying the distances R be-
acceptor pair recombination (Higashi and tween the donor and acceptor sites pro-
Kastner, 1981; Depinna et al., 1983), in duces a correlation between the PL energy
which radiative recombination occurs and the time at which the PL is measured.
when an electron of a neutralized donor is From Eqs. (7-23) and (7-24), the mean PL
transferred to a neutralized acceptor; the energy is predicted to shift to lower photon
centres are equally and oppositely charged energies with increasing delay time accord-
in the ground state (e.g. CJ, C^ pairs) and ing to (Higashi and Kastner, 1981)
neutral in the excited state. There is an
extra coulombic contribution Ec to the PL 2cce2
<£„(*)> = £» + (7-25)
recombination energy, resulting from the 47tee0 ln(vot)
interaction between ionized donor and ac-
and the width A(t) of the PL peak is also
ceptor, given by
predicted to narrow with increasing time
= e2/4nss0R" (7-22) delay.
with the PL energy therefore being I" 2 a e2 1
2
(7-26)
Ep = E» + Ec (7-23) L47i££ o ln (i? o 0j

where E™ is the energy corresponding to where a is the width of an assumed Gauss-

infinite separation. Since the rate of radia-
tive recombination is governed by the rate
at which the electron tunnels between sites,
given by
v = v0 exp(—2aJR)
ian homogeneous line shape. The time de-
pendence embodied in Eqs. (7-25) and
(7-26) appears to have been observed ex-
perimentally (Higashi and Kastner, 1981).
For the case of PL decays at long times,
(7-24) Higashi and Kastner (1983) have suggested

that such slow rates (long times) are deter-
mined by a forbidden quantum-mechani-
cal selection rule involving spin, in particu-
lar resulting from the (formally forbidden)
transition between a spin triplet excited-
state configuration and a singlet (i.e. spin-
paired) ground state. Further evidence in
support of the triplet excited state has
come from optically-detected magnetic
resonance (ODMR) measurements (see e.g.
Cavenett, 1981). Two possible candidates
for PL centres involving triplet excited
states are a self-trapped exciton (STE),
where the initially free photo-created exci-
ton can subsequently lower its energy by
forming self-trapped (localised) states in
which the lattice is locally distorted (see
Fig. 7-40) (Emin, 1980; Murayama et al.,
1980); Street (1977) has suggested that a
metastable version of such an STE state
could arise from a photo-induced bond
switch, resulting in an intimate valence al-
Energy
Configuration coordinate
Figure 7-40. Schematic illustration of the model for
self-trapping of excitons in chalcogenide glasses. Op-
tical excitation (I) to an exciton state can be followed
by two non-radiative decay channels (Street, 1977),
either directly back to the ground state (III) or to the
metastable self-trapped exciton (STE) state (IV),
which can be regarded as a D + - D ~ pair (IVAP).
Alternatively, STE states can form where the lattice
distortion is less severe, and may then act as the (trip-
let) radiative recombination PL centre (II) (Elliott,
1990).
7.5 Opto-Electronic Properties 427
ternation pair (IVAP) (see Fig. 7-40). Alter-
natively, previously existing IVAP defects
could act as sites for triplet excitation (Hi-
gashi and Kastner, 1981).
7.5 Opto-Electronic Properties
7.5.1 Electronic Structure
The electronic density of states (DOS) in
chalcogenide materials comprises a va-
lence band, composed principally of p-like
bonding (a) orbitals, and a conduction
band formed from antibonding (a*) or-
bitals, with the top of the valence band
being composed of chalcogen-derived p-
like non-bonding orbitals and the non-
bonding s-states lying at the bottom of the
band (see Fig. 7-41 for a schematic repre-
sentation for the case of As2Se3 and Fig.
7-34 a for a calculated DOS (Vanderbilt
and Joannopoulos, 1981)). Numerous cal-
culations of the DOS for various chalco-
genides have confirmed this general pic-
ture, although it appears that the lone-pair
band is less distinct, i.e. there is more
mixing of p - a and p-7i states, in the As
chalcogenides (Bullett, 1976; Althaus et al.,
1978) than for either the pure chalcogens
(Joannopoulos et al., 1975) or the Ge
chalcogenides (Louie, 1982). The electronic
DOS can be probed experimentally using
photoemission techniques and this has
been done, for example, for the case of Se
(Takahashi, 1982), As 2 X 3 (X = S, Se, Te)
(Bishop and Shevchik, 1975) and GeX2
(X = S, Se) (Takahashi and Harada, 1980;
Hindo et al., 1980); the lone-pair band at
the top of the valence band can be seen
clearly (see Fig. 7-42). The changes in XPS
and UPS spectra have also been used to
demonstrate that a-GeSe films deposited
onto cooled substrates have 3 : 3 coordina-
tion, but this changes to 4 : 2 after thermal
annealing (Takahashi and Sagawa, 1982).
428 7 Chalcogenide Glasses

BULK BASIS DEFECTS

r—"i
cr# BAND \ AS
\ / a
V
/
\
• /
/
i
v v / ' c*
Se b

> 2.
a.1
|
V

\
\
N

.
,
p
/
/

/
/
/ p
*s
t
a.
V Y 5
O
cc 0
ui
.1... ft.
Se /
/
/\ \
y
Pc
Se
^
/
/ \
.N
\
i. Figure 7-41. Schematic
origin of the electronic den-
sity of states in As2Se3 in
z / , ' ' \

UJ
\
\
\
\
terms of atomic and molec-
i V <r >'' \
Q
2 ular orbital states (Vander-

BAI
/ N
-2
a
b
/
/
/ v Se
b
bilt and Joannopoulos,
1981). The positions of var-
ious defect states are also
marked.

Amorphous chalcogenide materials are where AmC1_m is the stoichiometric com-

invariably semiconductors, with the size of position.
the bandgap varying in the range ~ 1 -
3 eV. Several factors influence the magni- 7.5.2 Optical Properties
tude of the gap: the gap generally increases
as chalcogen atoms are substituted at fixed In this section, we will consider only
composition by other chalcogens in the se- those optical properties of amorphous
ries Te-*Se->S; furthermore, the gap for chalcogenide materials resulting from opti-
chalcogenide alloys varies with composi- cal transitions across the bandgap, be-
tion and often exhibits extrema at stoichio- tween electron states at the top of the va-
metric compositions, for example, minima lence band (i.e. the p-n lone-pair band)
in the case of A s ^ S ^ (Fisher et al., 1976) and the bottom of the conduction band,
and As^Se^^ (Kosek et al., 1976), and a neglecting, therefore, the transitions occur-
maximum in the case of GexSe1_JC (Tronc ring at higher energies (in the UV and X-
etal, 1973). Shimakawa (1981) has ac- ray regions) from states deeper in the va-
counted for such compositional variations lence band or from the core states.
in terms of a simple alloying model in In the case of the semiconducting amor-
which the energy gap, Eg of a chalcogenide phous chalcogenides, the optical absorp-
alloy AXC±_X (e.g. ,4 = Ge, As; C - S , Se) tion coefficient, a, changes rapidly for pho-
can be represented as the sum of two con- ton energies comparable to that of the
tributions, one associated with the gap of bandgap, Eg9 giving rise to an absorption
aji ordered (stoichiometric) composition, edge. Three regions can be distinguished:
and the other associated with the element I - at the largest photon energies where
in excess, both weighted by the appropriate a is concomitantly also the highest
atomic fractions, e.g. (^10 4 cm" 1 ), and tends to a saturated
value, interband transitions occur between
Eg = yEg(A) + (l-y)Eg(AmC^m) (7-27) valence and conduction bands; II - in the
 7.5 Opto-Electronic Properties 429

region I exhibits a power-law dependence

on photon energy hco if the densities of
states in the valence and conduction bands
also have a power-law energy dependence
in the vicinity of the gap, viz.
(7-28 a)
0 c (E-E o )ocE« (7-28 b)
whence
(DOL{(D) GC (hco — Eo) (7-29)
and where Eo is some measure of the band-
gap. In the special case, where both valence
and conduction band edges have a para-
5 10 15 20
Binding energy (eV) bolic shape (p = q = \\ Eq. (7-29) becomes
a)
cooc(co) oc (hco — E 0 ) 2 (7-30)

V) s.
Monochromatized XPS
(hv = U86.6eV)
Thus, Tauc plots of (ahco)112 versus hco
should be linear and extrapolate to values
uni

\
n\
of the (optical) gap, Eo. Fig. 7-43 shows
larb.

\ As2S3 glass (bulk)

\r\ ^ ^
\
\ /
f **—""* * \
III >v
this quadratic dependence for chalco-
;ity

genide glasses (and a-Si). However, not all

V)
C
CD
J >v \ J As2S3 crystal ^V
chalcogenide materials exhibit this be-

J\
a
\ (orpirnent) ^
XPS ii

haviour for coa(co): a-Se exhibits a linear

I !
5 10
Binding energy (eV)
b)
Figure 7-42. (a) X-ray photoemission spectra (XPS) of
amorphous, trigonal (t) and monoclinic (m) Se taken
using Mg Ka radiation (Takahashi, 1982). The upper
and lower 4 p bonding bands are indicated by bars in
the spectra of t- and m-Se, and the approximate 4 s
bandwidths are indicated by dashed lines, (b) XPS of
glassy and crystalline As2S3 (Bishop and Shevchick,
1975).
region of the edge itself (10 < a < 104 cm 1);
and III - at the lowest photon energies and
at low values of a ^ 10 cm" 1 where transi-
tions between (defect) states in the gap and
the bands take place. Under certain condi-
tions (in the random-phase model, where
the k-selection rule breaks down - see El-
liott, 1990), the absorption coefficient in
energy dependence, and multicomponent
i
15 chalcogenide alloys (e.g. Ge-As-Te-Si)
show a cubic energy dependence. It should
be noted that Eo, obtained in this way, is
not necessarily exactly equal to the true
gap £ g between mobility edges in the va-
lence and conduction bands. Part of the
uncertainty arises from a breakdown of the
random-phase approximation for photon
energies hco& Eg (Dersch et al., 1987; Abe
and Toyozawa, 1981); as a result, the opti-
cal absorption is not just determined by
the joint density of states, as in Eq. (7-29),
but also depends on energy-dependent ma-
trix-element terms.
The optical absorption edge in amor-
phous semiconductors is not as sharp as
predicted from Eqs. (7-29) or (7-30), but ex-
hibits a long tail into the gap region, and
which almost invariably depends exponen-
430 7 Chalcogenide Glasses

Figure 7-43. Tauc plots of

optical absorption coeffi-
cient ([ahco]112 vs. hco) for
various chalcogenide
glasses (Mott and Davis,
1979).
1.0 U 1.8 2.2 2.6 3.0
Photon energy (eV)

tially on the photon energy: ergy dependence of a arises from an expo-

a((o) = oc0 exp[— r(Ef0 — hco)]
where E'o is an energy comparable to the
threshold energy Eo involved in inter-
band transitions (see Eq. (7-30)), and F is a
temperature-dependent constant, typically
having values in the range 10-25 eV" 1 .
This Urbach-edge behaviour is also exhib-
ited by chalcogenide materials (Fig. 7-44).
The origin of the Urbach edge is still
unclear, but two general mechanisms may
be responsible: either the exponential en-
nential energy dependence of the valence
(7-31)
and conduction band densities of states at
the band edges (neglecting matrix-element
effects), or a particular universal absorp-
tion mechanism exists which gives rise to
the exponential behaviour of a, e.g. the
field-broadened exciton model of Dow and
Redfield (1970). In the former case, Abe
and Toyozawa (1981) and Soukoulis et al.
(1984) have shown theoretically that expo-
nential band tails can result from potential
fluctuations associated with structural dis-

10-

0) GeTe
S 103

_Q Figure 7-44. Urbach edges for

< CdGeAsJ chalcogenide glasses (Mott and
Davis, 1979).
0.8 1.2 1.6 2.0 2.L 2.8
Photon energy (eV)

order, where the inverse of the slope pa-
rameter in Eq. (7-31), T" 1 , is related di-
rectly to the extent of disorder.
Experimental evidence for the existence
of exponential band tails (at least for the
valence band) in a-As2Se3 has come from
the transient hole photoconductivity mea-
surements of Orenstein and Kastner (1981)
and Monroe (1985) - see Kastner (1985) for
a review. The observed power-law time de-
pendence of the photocurrent decay re-
quires an accurately exponential density of
states in the multi-trapping model (Oren-
stein and Kastner, 1981).
Although there is experimental evidence
in the case of a-Si: H that the magnitude of
F " 1 is determined by the degree of disor-
der (Cody, 1984), the position for chalco-
genides is not as clear-cut. For example,
Tanaka et al. (1985) have reported that the
slope of the Urbach absorption edge (viz.
F) for glassy As 2 S 3 does not change as
a function of the quench temperature Tq,
even though the EXAFS measurements of
Yang etal. (1987) have indicated that the
structural disorder (in the As-S bond
length) does increase with increasing Tq.
However, the optical gap (in particular, the
photon energy at which a = 2x 10 3 cm~ 1 )
does decrease slightly with increasing Tq,
perhaps due to the influence of the in-
troduction of homopolar bonds (Tanaka
et al., 1985). These rather contradictory re-
sults could be explicable, however, in terms
of the lone-pair (LP) nature of the top of
the valence band (VB) in chalcogenides.
If the tailing of the VB is mainly responsi-
ble for the Urbach edge, intra-molecular
(bond-length and bond-angle) fluctuations
should have relatively little effect on the
width of the LP band and hence on F.
However, the application of pressure
would be expected to change the width of
the LP band due to an increase in L P - L P
repulsive interactions with increasing pres-
7.5 Opto-Electronic Properties 431
sure in those materials with a local dimen-
sionality less than 3 (see Sec. 7.3.2.2). This
effect would lead to a pressure-induced de-
crease in the gap (see Fig. 7-17), as well as
to an increase in the degree of tailing at the
band edge; a decrease in F (increase in F ~x)
with pressure is indeed observed in amor-
phous chalcogenide materials (see Fig.
7-45) (Tanaka, 1989 a).
Finally, we discuss the low-energy re-
gion of the optical absorption profile in
amorphous chalcogenides. The exponen-
tial decrease in a with decreasing photon
energy characteristic of the Urbach edge
implies great transparency in the IR region
for such pure (i.e. impurity- and defect-free)
materials. This characteristic, of course,
makes chalcogenides attractive materials
for low-loss optical transmission (Savage,
1985) in the window region, corresponding
to the minimum in a, between the optical
absorption edge and the multiphonon edge,
i.e. the high-energy side of the vibrational
density of states (see Fig. 7-46 (Strom et al.,
1974)). However, in this low-a, low-fre-
quency region, oxide and other prevalent
impurities can give rise to unwanted ex-
trinsic absorption bands (see Fig. 7-47). In
addition, intrinsic defects, such as coordi-
nation defects, in chalcogenide glasses can
100
50
Pressure (kbar)
Figure 7-45. Pressure dependence of the slope param-
eter, F, of the Urbach edges of amorphous chalco-
genide materials (g = glass, f=film) (Tanaka, 1989 a).
432 7 Chalcogenide Glasses

80 I I I 11 i tinl i—r—r
also give rise to optical absorption in mid- ~i—r
gap. This is particularly so when samples
are illuminated at low temperatures under
r (a) -

conditions where a metastable ESR signal 40-

is induced (see Sec. 7.4.4.1); a mid-gap ab-

sorption in excess of the Urbach edge is
_LLL I 1 I I I I 11 I \ 1
induced thereby (see Fig. 7-48), the precise
shape of the absorption band depending (b) -
on the intensity and wavelength of the in-
ducing light (Biegelsen and Street, 1980).
These mid-gap absorption bands have
been ascribed to electron or hole transi-
tions to the conduction band or valence £ 0 I M i l l I i ,' \ I A I 1
band, respectively, from optically-induced
neutral paramagnetic defect centres, e.g.
C? (Bishop etal., 1977; Biegelsen and 40
Street, 1980).
A collection of optical properties for var-
ious amorphous chalcogenide materials is
given in Table 7-3.
id) .

40

01 I I 11 I I I 1 I I I1 I
0.5 1.0 5 10 50
Wavelength (pm)

Figure 7-47. Transmittance spectra of chalcogenide

glasses, with (dashed curve) and without (solid curve)
extrinsic impurities: a) Ge 30 As 20 S 50 ; b) Ge 34 As 8 Se 58 ;
c) Ge 30 As 13 Se 27 Te 30 ; d) Ge 10 As 50 Te 40 (Savage, 1985).

7.5.3 Electrical Properties

As mentioned in the previous section,
amorphous chalcogenides typically have
bandgaps in the range l-2.5eV and are
therefore semiconductors. As a consequence,
the temperature dependence of the dx.
10-3
conductivity <rdc is very often observed to
10* 103 102 10 10"
1
be simply thermally activated,
Wavelength (cm" )
Figure 7-46. Vee-shaped optical profile for glassy <T6c = a0exp(-EJkT) (7-32)
As2S3 showing the window region of optical trans-
parency between the optical absorption and multi- where the pre-exponential factor takes val-
phonon edges (Strom et al., 1974). ues typically in the range K ^ - K ^ f l T 1
 7.5 Opto-Electronic Properties 433

TO4 Table 7-3. Optical properties of chalcogenide glasses.

As 2 S 3 Material Eo (eV) Reference
30K

Se 2.05 1
3
As 2 S 3 2.32 2
10 -
As2Se3 1.76 2
As2Te3 0.83 3
o
SiSe2 3.35 4
= 2.41 eV SiTe3 1.33 5
/ INITIAL GeS2 3.07 6
102 GeSe2 2.18 7
8 Sb2Se3 0.70 7
o
References: 1) Davis, E. A. (1970), J. Non-Cryst. Sol.
4, 107; 2) Mott, N.F. and Davis, E.A. (1979), Elec-
tronic Processes in Non-Crystalline Materials. OUP;
101
3) Weiser, K. and Brodsky, M.H. (1970), Phys. Rev.
El, 791; 4) Harris, XH. and Tenhover, M. A. (1986),
EY = 2.41 eV /. Non-Cryst. Sol. 83, 272; 5) Madhusoodanan, K.N.,
Philip, X, Asokan, S., Parathasarathy, G., and Gopal,
E.S.R. (1989), /. Non-Cryst. Sol. 109, 255; 6) Ticha,
1.4 1.6 1.8 2.0 2.2 2.4 2.6 H., Tichy, L., and Cernoskova, E. (1983), Phys. Stat.
PHOTON ENERGY (eV)
Sol. B119, K135; 7) Shimakawa, K, (1981), /. Non-
Cryst. Sol. 43, 229.
Figure 7-48. Mid-gap optical absorption in glassy
As2S3 at 30 K induced by 2.4 eV light with intensities
of 10 (dashed line) and 100 mWcm~ 2 (solid line). The Table 7-4. Electrical properties of chalcogenide
optical absorption spectrum before illumination is glasses.
shown by the dotted line (Biegelsen and Street, 1980).
Material r (eV) a (300 K) Reference

cm * and the activation energy Ea is usu-

ally approximately half the optical gap, £ g ,
indicating that the Fermi level lies near
mid-gap (Elliott, 1984,1990). For the most
part, the d.c. electrical behaviour in such
systems can be understood in terms of a
picture involving transport in extended
states in the valence or conduction band,
beyond a mobility edge separating ex-
tended and localized gap states (Mott and
Davis, 1979; Elliott, 1984). Some data re-
lating to the d.c. conductivity of amor-
phous chalcogenides is given in Table 7-4,
and an extensive collection is given in
Borisova (1981).
It is noteworthy that in chalcogenides
£ o w £ g / 2 and that plots of lna dc vs. 1/T
are generally linear except at the lowest
temperatures; both these features are indic-
ative of the Fermi level at E F being pinned
Se 1.10
As 2 S 3 1.14
As2Se3 0.91
As2Te3 0.42
GeS2 0.72
GeSe2 0.95
References: 1) Hartke, XL. (1962), Phys. Rev. 125,
1111; 2) Seager, C.H. and Quinn, R.K. (1975), 1
Non-Cryst. Sol. 17, 386; 3) Ticha, H., Tichy, L.,
Rysava, N. and Triska, A. (1985), /. Non-Cryst. Sol.
74, 37; 4) Narasimhan, P.S.L., Giridhar, A., and
Mahadevan, S. (1981), /. Non-Cryst. Sol. 43, 365.
near mid-gap. It appears that E¥ does not
itself lie in a band of states (e.g. in the ab-
sence of illumination there are no mid-gap
states apparent from optical absorption
measurements), but rather is pinned be-
tween two bands of states lying near the
valence and conduction bands, correspond-
434 7 Chalcogenide Glasses

ing to negative-U VAP defects (e.g. CJ, Cx

- see Sec. 7.4.3) (Adler and Yoffa, 1976). As
a result of this pinning of the Fermi level by
native defects, it is extremely difficult to
dope chalcogenides so as controllably to
vary their electrical characteristics.
Nevertheless, it appears that under cer- •
tain circumstances, amorphous chalcoge-
nides can be electrically doped. For exam-
ple, the addition of more than ~10at.% £
o
Bi to chalcogenide glasses causes them to
become n-type (Schottmiller et al., 1968;
Tohge et al., 1979) - for a review see Elliott
and Steel (1987). (Such a phenomenon is >
perhaps better described as one of chemi- 10 8
•
cal modification rather than conventional
doping, since the concentration of impurity
required to effect the change is so large.)
The d.c. conductivity increases by about 106
seven orders of magnitude with the incor- 6 8 10 12
poration of about 10 at.% Bi in the case a) x(at.% Bi)
of Ge-S (Tichy et al., 1985) and Ge-Se 3.0
glasses (Tohge et al., 1980) (see Fig. 7-49 a),
and the sharp change in adc at the p - n
doping transition is accompanied by an
equally precipitate drop in the conductiv-
ity activation energy, E a , at the same Bi
content. On the other hand, the optical
gap, E g , decreases continuously with in-
creasing Bi content until a plateau is
reached (see Fig. 7-49 b). The change in Eg Sb-Ge-Se
with Bi content is much more marked than
\~ I Bi-Ge-Se
is the case for incorporation of Sb, which Sb-Ge-Se
obeys approximately the alloying model of
Shimakawa (1981) (see Eq. (7-27)). 1.5
~--j- -i—jBi-Ge-S
Two different explanations have been
advanced to account for the effect of Bi:
one ascribes the change in electrical prop- Bi-Ge-Se
erties to an inhomogeneous (percolation) 1.0
b) 10 15
transport mechanism in which microphase x (at. %)
separation into (microcrystalline) clusters Figure 7-49. Chemical modification of electrical and
of n-type Bi 2 X 3 (X = S, Se) occurs (Tichy optical properties of chalcogenide glasses by the in-
corporation of Bi (Elliott and Steel, 1987); a) electrical
et al., 1985); the other supposes that the Bi
resistivity, Q (circles Bi-Ge-Se, crosses Bi-Ge-S),
impurities are distributed homogeneously b) optical gap, Eg (solid curves, calculated from Eq.
in the glass structure in a charged state, (7-27)), dashed curves, guides for the eye).

causing the relative proportion of charged
coordination defects to change and there-
by unpinning the Fermi level (Nagels et al.,
1983; Saiter et al, 1985; Elliott and Steel,
1987). The Bi Lm-edge EXAFS results of
Elliott and Steel (1986,1987) for Bi-Ge-S
glasses indicate that Bi is always 3-fold co-
ordinated by chalcogen atoms, but that a
marked change in Debye-Waller factor oc-
curs at —5 at.% Bi; this change has been
ascribed to an increase in the static disor-
der at the Bi sites associated with the for-
mation of positively-charged Bi^. In the
case of sputtered thin films of amorphous
Bi-Ge-Se, however, Sotiropoulos and
Fuhs (1989) found no abrupt change in £ a ,
and therefore ascribed the change in oAc to
an alloying-induced decrease in the band-
gap.
Modification of the electrical properties
of amorphous chalcogenides has also been
found for other impurities, e.g. Pb in P b -
Ge-Se glasses (Tohge et al, 1987), Ni in
co-sputtered As2Se3 films (Barclay et al,
1985) and K and Rb in a-Se thin films
(Abkowitz et al, 1985).
Holes are the dominant current charge
carriers in amorphous chalcogenide mate-
rials, i.e. they are p-type semiconductors in
general. The sign of the charge carriers
cannot be determined from measurements
of the Hall effect, which is invariably
anomalous (see e.g. Elliott, 1990), but can
be obtained from the thermoelectric power
(thermopower), S, where
= n/T (7-33)
and where 17 is the Peltier coefficient. In
the model of conduction in extended states
beyond the mobility edge, the thermo-
power can be written as (Mott and Davis,
1979)
7.5 Opto-Electronic Properties 435
where Es = £ c , y is the (linear) coefficient of
the temperature dependence of the band
edge (where conduction takes place) with
respect to EF and A k T is the average en-
ergy of the transported electrons with re-
spect to the mobility edge. Thus, in this
model both <rdc and S should have the same
activation energy, viz. EG. In fact, chalco-
genide glasses very often exhibit a thermo-
power activation energy £ s which is about
0.1-0.15 eV smaller than that of the d.c.
conductivity (see e.g. Nagels, 1979; Mott
and Davis, 1979). This discrepancy has
been explained in two ways. In the two-
channel model proposed by Nagels (1979),
it was assumed that the conduction could
take place simultaneously in two paths,
one in extended states beyond the mobility
edge, and the other in the localized band-
tail states below the mobility edge; in the
latter case, the activation energy for adc is
given by Ea = (EF - EA + W\ where EA is
the beginning of the (valence) band tail and
W is a hopping energy, and it is assumed
that none of the energies are temperature
dependent, whereas in the case of the ther-
mopower, the activation energy is given
simply by £ s = EF — £ A , differing from Ea
by W (Nagels, 1979; Mott and Davis, 1979;
Elliott, 1984).
A very different picture has been pro-
posed by Emin (1973, 1976) in which the
charge carriers (e.g. holes in chalcogenide
materials) form small polarons as a result of
a strong electron-phonon coupling. In this
model, a difference in activation energies
between adc and S is also predicted, since
the polaron hopping energy only appears
in the expression for Ea. Conclusive exper-
imental proof in favour of either model has
been lacking, although the small-polaron
theory does predict, under certain circum-
stances, that the Hall mobility, /% should
also be thermally activated, with an activa-
tion energy equal to one third of that of the
436 7 Chalcogenide Glasses

d.c. conductivity mobility; such a weakly

temperature-dependent //H has been found
for chalcogenide glasses (see Fig. 7-50 (Na-
gels, 1979)). Furthermore, for certain ge-
ometries of hopping sites for small-polaron
motion, an anomalous sign of the Hall co-
efficient is also predicted (see Elliott, 1984,
1990).
More recent theoretical work on con-
duction processes in amorphous semicon-
ductors has tended to lead to a sort of
harmonization of these opposing points of
view. Since the work by Abrahams et al.
(1979) on a scaling theory of localization
concluded that a sharp mobility edge most
likely does not exist in three-dimensional ( K"1 )

materials, the two-channel model has be-

come less tenable. A theoretical consider-
ation of electron-phonon interactions has
led Miiller and Thomas (1984), Fenz et al.
(1985) and Dersch and Thomas (1987) to
propose that a phonon-induced delocaliza-
tion occurs, whereby at finite temperature,
electron states in the band tails become
delocalized, essentially by allowing electri-
cal transport to occur by phonon-assisted
hopping processes.
At very low temperatures, and particu-
larly in highly-disordered chalcogenide
materials prepared by vapour deposition,
variable-range hopping conduction has
been found, as characterised by the Mott
law for the d.c. conductivity (see Mott and
Davis, 1979):
adc = G'oexp(-A/TV4) (7-35)
in, for example, a-As2Te3 films deposited
using r.f. sputtering onto substrates held at
77 K (Hauser and Hutton, 1976). In such

Figure 7-50. Electrical transport data for five

AsTe! 5Six glasses (the values of x are indicated in the
figures) and an As0 3 Te 0>48 Si 0 . 12 Ge 0A glass for a) d.c.
electrical conductivity; b) thermopower; c) Hall mo-
bility (Nagels, 1979).

cases, conduction takes place by variable-
range hopping between (paramagnetic) de-
fect states lying at EF in mid-gap. In chal-
cogenide bulk glasses, or well-annealed
thin films, variable-range hopping conduc-
tion is not normally observed because the
negative effective correlation energy asso-
ciated with the coordination defects in
chalcogenides results in the formation of
spin-paired, charged defects lying away
from EF (see Sec. 7.4.3), and for which the
electron-phonon coupling is so large that
the hopping rates become unobservably
slow (Phillips, 1976).
In common with other amorphous
semiconductors, chalcogenides also exhibit
a frequency-dependent (a.c.) conductivity
which, in the frequency range 10<o><
1 0 9 s ~ \ exhibits a power-law frequency
dependence, viz.
a(co) = Acos (7-36)
where s < l and both A and s can be
(weakly) temperature dependent. At high
temperatures and/or low frequencies, the
d.c. conductivity becomes dominant since
it has a much larger temperature depen-
dence than that of o{co\ so that the total
measured conductivity can be written for-
mally as:
^totM = crdc + ^ M (7-37)
(Eq. (7-37), as written, implies that the d.c.
and a.c. conductivities arise from different
mechanisms; if they arise from the same
mechanism, adc is just the co-+0 limit of
a{co).) Elliott (1987 a) has given an exten-
sive review of the a.c. conductivity behav-
iour of amorphous chalcogenide materials.
The mechanism which seems best able to
account for the experimentally observed
a.c. behaviour is the correlated barrier hop-
ping (CBH) model proposed by Elliott
(1977, 1987 a). In this, two electrons (a
bipolaron) are assumed to hop under the
7.5 Opto-Electronic Properties 437
Se- -Se Se Se
Se- -Se :Se- -Se
i
D+) Se Se Se
Se Se Se Se
a)
Conduction band
Figure 7-51. The correlated barrier hopping (CBH)
model for a.c. conductivity in chalcogenide glasses
(Elliott, 1987). a) Schematic illustration of two-elec-
tron transport in a-Se causing the interconversion of
D + , D~ (C3, Cf) defect centres, b) Schematic illus-
tration of the lowering of the activation energy barrier
from WM to W for two-electron hopping for two op-
positely charged defect centres separated by a dis-
tance R due to a coulomb interaction. A site disorder
energy A is also shown.
influence of the applied a.c. field between
oppositely-charged coordination defect
sites (e.g. C^, C^ - see Fig. 7-51 a), or pos-
sibly single polarons are assumed to hop
between C^, C? or Cf, C° pairs of sites.
The hopping rate involved in such pro-
cesses involves an activation energy W
which is correlated with the intersite sepa-
ration R through a coulombic interaction
between charge carrier and defect (see
Fig. 7-51 b); for the case of a bipolaron
W=WM-2e2/n880R (7-38)
where WM is the maximum barrier height
(for R = 00) and which has a value com-
parable to the (optical) bandgap (Elliott,
438 7 Chalcogenide Glasses

1987 a). The a.c. conductivity can then be

calculated to be (Elliott, 1977, 1987 a)

a(co)=7^N28sowRi (7-39)

where N is the concentration of defects and

the hopping distance R^ at a frequency co
is given by
100 200 300 400 500 600
(a)

where T0 is a characteristic relaxation time. 'E

The frequency exponent s of the a.c. con- h in
10
^A 100 kHz
ductivity can then be evaluated to be

nduc t i v i t y
10

6kT
(7-41) v. 10 kHz
[W M -fcrin(l/eoT o )] o id" *•—* •
o
The success of this model in accounting for
the experimental a.c. data for, say, amor- A.c.
N ^ 1 kHz
phous As2Se3 (Hirata et al., 1983; Giuntini 10 12

etal., 1981) is demonstrated in Fig. 7-52. 6 8 10

(by 1000/T (K"1)
However, in certain cases, the temperature
dependence of a(co) at elevated tempera- Figure 7-52. Application of the CBH model to exper-
imental data for glassy As2Se3 (Elliott, 1987). a) Tem-
tures (^300K) in chalcogenides, particu-
perature dependence of the frequency exponent s.
larly those with smaller bandgaps, is con- b) Temperature dependence of the a.c. conductivity
siderably stronger than is predicted for at three frequencies.
bipolaron CBH (Eqs. (7-39), (7-40)). Shi-
makawa (1982) has explained this be-
haviour in terms of the thermal creation of
comparable to the optical bandgap (or by
neutral, paramagnetic centres (C?) from
irradiation by electrons or ions). Such
pre-existing charged spin-paired centres
changes may conveniently be divided into
(the reverse reaction of (7-18)), which is an
two categories, namely transient and meta-
activated process; single polaron transport
stable changes. Transient changes occur
involving such defects is then assumed to
only whilst the sample is illuminated: ex-
be dominant. It can be seen from Fig. 7-53
amples include photoluminescence (see Sec.
that, with this modification, the CBH
7.4.4.2) and photoconductivity (see Sec.
model can account for the a.c. conductivity
7.4.3), and these will not be considered fur-
of amorphous chalcogenides over a wide
ther here. By contrast, metastable changes
range of temperatures and frequencies.
remain after being induced, and these can
be sub-divided into two further categories,
7.5.4 Photo-Induced Changes
namely irreversible and reversible, i.e. the
A wide variety of changes can be in- latter of which can be annealed out by
duced in amorphous chalcogenide materi- heating the samples to the glass-transition
als by the absorption of photons of energy temperature, T . Some reversible changes

Figure 7-53. Prediction of the CBH model for glassy
Se with both single (S) and bipolaron (B) hopping
contributions (Shimakawa, 1982).
are associated with the photo-excitation of
pre-existing (coordination) defects, e.g.
light-induced ESR (see Sec. 7.4.4.1) and op-
tically-induced mid-gap absorption (see
Sec. 7.5.2), and these also will not be dis-
cussed further. Reviews of photo-induced
phenomena have been given by Ka.
Tanaka (1982), Owen et al. (1985), Elliott
(1986), and Ke. Tanaka (1990).
Amongst the class of irreversible photo-
induced changes are a variety of chemical
changes, including the phenomena of
metal photo-dissolution, photo-crystal-
lization and giant photo-densification of
films. In the photo-dissolution process, a
layer of metal (e.g. Ag, Cu or Zn) in contact
7.5 Opto-Electronic Properties 439
with an amorphous chalcogenide film dis-
solves into the chalcogenide upon irradia-
tion with light having an energy compara-
ble to the bandgap of the chalcogenide
(Kostyshin et al., 1966; Ka, Tanaka, 1982;
Doane and Heller, 1982; Owen et al., 1985;
Lyubin, 1987). The actinic radiation ap-
pears to be absorbed at the interface be-
tween the metal-doped and undoped chal-
cogenide (Owen et al., 1985; Rennie and
Elliott, 1985, 1987), and the speed of the
reaction, as well as the formation of a sharp
boundary between doped and undoped
layers, appears to be a consequence of the
fact that the doped chalcogenide material
acts as a superionic conducting matrix for
the dissolving metal ions. Another irre-
versible photo-induced chemical change
observed in chalcogenides is photo-vapor-
ization (Janai, 1981), in which an amor-
phous thin film (e.g. As2S3) is first photo-
oxidised (Kolobov et al., 1989), and the
resulting volatile surface oxide subsequent-
ly evaporates. Many amorphous chalco-
genide materials, particularly those with
low values of Tg, crystallize upon optical
irradiation (e.g. Se (Dresner and Stringfel-
low, 1968) and As-Te-Ge (Weiser et al.,
1973)). Finally, obliquely evaporated thin
films of amorphous Ge chalcogenides, ex-
hibiting a columnar morphology, undergo
giant (~20%) changes in thickness (den-
sity) after optical excitation (Singh et al.,
1980); this effect has been found to be due
to a photo-induced collapse of the void
structure comprising the columnar micro-
structure (Spence and Elliott, 1989). An-
other type of irreversible photo-structural
change involves the photo-polymerization
of As 4 S 4 molecules in as-deposited amor-
phous As-S films (Nemanich et al., 1978;
Treacy et al., 1980; Lowe et al., 1986) to
form a more nearly continuously bonded
random network; the same process occurs
in the photo-decomposition of realgar (c-
440 7 Chalcogenide Glasses

As4S4) to give orpiment (c-As2S3) (Porter
and Sheldrick, 1972).
Reversible photo-induced charges in
chalcogenides are less well understood
than their irreversible counterparts; re-
views of the subject have been given by
Elliott (1986) and Ke. Tanaka (1990). Per-
haps the most studied reversible change
is photo-darkening, whereby an increase
in the optical absorption at a particular
wavelength, resulting from a parallel shift
of the Urbach edge to lower energies, oc-
curs on illumination (see Fig. 7-54 a). The
magnitude of the shift A£ in the optical
edge is largest for illumination at low tem-
peratures (see Fig. 7-54 b), and A£ de-
creases to zero at Tg, where the change is
annealed as fast as it is induced. It is inter-
esting to note that A£ in chalcogenide al-
loys appears to exhibit a maximum at an
average atomic coordination m^2.67 (see
Fig. 7-54 c), the optimum value for satisfac-
tion of mechanical constraints if a 2D-like
MRO exists in the glass (Tanaka, 1989 b)
(see Sec. 7.2.1). A very interesting variant of
this is the photo-induced anisotropy (e.g.

104 I I i < 1 1 i i

oo
0.15 - • Ge-As-S
o
o A Ge-S Q

c a Ge-Se
0) w w
o * As-S o
o As-Se •
0.10 -

o •
•
"Q.
o
LU A
C—
<
o
•
annealed 0.05-- g

* * * •
10' o
2.2 2.U 2.6 i i i 1 1 1 i
HhD —i L-«-

fioofeV) 2.5
a) c) Z

0.2
o As 2 S 3 ,
S Figure 7-54. Photodarkening in chalcogenide glasses
GeS2 (Tanaka, 1990). a) Reversible change in optical ab-
As 2 Se 3
sorption coefficient for glassy As 2 S 3 showing the en-
3. 0.1 * \ A Se
ergy shift AE. b) Photodarkening shift AE for various
LU D\ • GeSe2 chalcogenide glasses as a function of temperature,
As2Te3 normalized to the glass-transition temperature, Tg.
c) Photodarkening shift AE for various chalcogenide
glasses as a function of effective coordination num-
i i i i i i i —J—rt_oJ ber Z.
0.5
b)

dichroism and birefringence) induced in
the optical properties of amorphous chal-
cogenides by illumination with linearly-
polarized light (Grigorovici et al., 1983;
Janossy et al., 1984; Kimura et al., 1985;
Lee and Paesler, 1987). A number of theo-
retical models for the reversible photo-
darkening effect have been proposed in-
volving local heating effects (Malinovsky
and Zhdanov, 1982), subtle photo-induced
structural configurational changes (Kolo-
bov et al., 1981), involving bond-twisting
(Tanaka, 1986, 1990), and intra- and inter-
molecular bond-breaking (Elliott, 1986),
but unambiguous experimental structural
evidence for these mechanisms is still lack-
ing.
7.6 Applications
A number of actual and potential techno-
logical applications for amorphous chalco-
genide materials exist, exploiting their ease
of fabrication in either bulk-glass or thin-
film forms and the ability selectively to
vary their physical properties by alloying
over rather wide composition ranges.
Some of these applications are outlined in
the following.
7.6.1 Infrared-Transmitting Optical
Components
Chalcogenide glasses are of considerable
interest for use as optical elements in IR-
transmitting applications because of their
transparency over a wide wavelength range
in the IR region (see Fig. 7-47), and a vari-
ety of possible applications can be envis-
aged depending on the wavelength of the
light involved (see also Chap. 12 and 15).
Long-distance telecommunication trans-
mission along optic fibres involves laser-
generated radiation in the 1-4 jim range,
7.6 Applications 441
and although a theoretical loss of
^10~ 2 dB/km at 4.5 jim has been pre-
dicted for glassy GeSe3 by Shibata et al.
(1981), actual losses for chalcogenide fibres
are considerably higher (10-10 3 dB/km at
« 3 jim) than the predicted intrinsic losses
(Andriesh, 1985; Kanamori et al., 1985;
Savage, 1987). Three factors can limit the
transmission in the IR window, namely im-
purity absorption, Rayleigh scattering and
defect absorption. Oxygen, hydrogen and
carbon are prevalent impurities and it is
necessary to reduce the concentration of
these below the ppm level (see Fig. 7-47).
Rayleigh scattering from microscopic den-
sity and compositional fluctuations in the
glass has a characteristic XA wavelength de-
pendence (Shibata et al., 1981):
l
-\)2xkTJX4 (7-42)
where n is the refractive index, x is the
isothermal compressibility and it is as-
sumed that fluctuations are quenched-in
on cooling through Tg. Eq. (7-42) would
therefore indicate that chalcogenide glasses,
with rather low values of Tg ( ^ 1 5 0 -
250 °C), would have correspondingly low
levels of Rayleigh scattering. Instead, it ap-
pears that defect-related mid-gap absorp-
tion limits the transmission loss in chalco-
genide glasses (Nishii et al., 1987), and the
relatively low values of Tg for these mate-
rials is a distinct disadvantage, since this
leads to high defect concentrations (c.f.
Eq. (7-21)). Thus, it appears that chalco-
genides will not be suitable for long-dis-
tance trunk communication applications.
However, for smaller scale applications,
the relatively high losses are less impor-
tant. One such requirement is for high-
power transmission of the 10.6 jim radia-
tion from a CO 2 laser for surgery, cutting
or welding applications. Bornstein and
Croitoru (1985) and Bornstein et al. (1985)
have reported on the use of As-Se glass
442 7 Chalcogenide Glasses
fibres up to 500 jim in diameter, both
solid (multimode) and hollow, for this ap-
plication, where attenuations of less than
0.5 dB/cm have been achieved.
Savage (1985, 1987) has reported on the
use of chalcogenide glasses as IR-trans-
mitting optical elements for the 3-5 jim
and 8-14 jim windows in the atmospheric
transmission spectrum in thermal surveil-
lance devices detecting hot and room-tem-
perature objects, respectively.
Cimpl and Kosek (1987) have described
the use of amorphous chalcogenide thin
films as antireflection coatings for IR op-
tics (e.g. filters), taking advantage of the
fact that the refractive index (RI) may be
varied over quite a wide range (2-3.5 for
A-s-S and Te-based systems, respectively)
by varying the composition so that good
matching of the RI of the film (n^ to that
of the optical element itself (n) may be
achieved - for zero reflectivity
(7-43)
Thus, for optical elements made from crys-
talline Ge (n = 4), relatively good RI match-
ing can be achieved using S-rich As-S
films (Cimpl and Kosek, 1987).
Finally, Andriesh (1985) has reviewed
the possible application of amorphous
chalcogenide films as both passive and ac-
tive elements (wave-guides) for integrated
optics. The acousto-optical coefficient of
chalcogenide glasses is rather large (about
two orders of magnitude larger than that of
vitreous SiO2), making it possible to use
acoustical modulation of transmitted laser
radiation in active elements; such wave-
guides have been estimated to have losses
of 3-5 dB/cm at 0.63 jim and less than
1 dB/cm at 1.15 \xm (Andriesh, 1985).
Non-linear optical properties of materi-
als are becoming increasingly important in
high-power laser applications (see Chap.
12). One such non-linear quantity is the
refractive index
(7-44)
where n0 is the intensity-independent term
and <£2> is the mean-square electric field
associated with the light incident on the
material. The non-linear term, n 2 , can be
due to electrostrictive, thermal, electronic
polarizability or resonant-absorption ef-
fects. Of these, only the latter two mecha-
nisms lead to fast (picosecond) non-linear
responses.
Large non-linear effects have been found
in semiconductor-doped glasses (e.g. CdS-
doped silicate glasses), although in these
cases the non-linearity is due to the reso-
nant absorption effect, corresponding to
the imaginary part of the third-order non-
linearity term in the expression for the
non-linear electronic polarizability
(7-45)
where x(2) and #(3) are the second- and
third-order electronic susceptibilities, re-
spectively. However, materials having high
refractive indices such as chalcogenide
glasses are also candidates for exhibiting
large third-order non-linearities (Nasu and
Mackenzie, 1987). Recently, Nasu et al.
(1989) have found that chalcogenide
glasses such as As 2 S 3 and GeS 3 have val-
ues of x(3) = 10~ 12 e.s.u., which are about
an order of magnitude larger than that of
semiconductor-doped glasses (in the opti-
cally transparent region) and two orders
of magnitude larger than that of vitreous
silica. Thus, such chalcogenide materials
hold considerable promise in applications
involving high-speed non-linear elements
for use with highly transmitted light.
7.6.2 Xerography
Until very recently the most widespread
use of amorphous chalcogenides was in
 7.6 Applications 443

Corona wire xerography or electrophotography (see

< R Mort, 1973; Pfister, 1979; and Madan and
• • + • + • • + Shaw, 1988, for reviews of the subject). The
Se film
active photo-receptor used was evaporated
a-Se in thin-film form, with perhaps a small
amount of As or other elements added to
(a)
inhibit crystallization.
The essential feature of electrophotogra-
phy is the conversion of an optical image
into an electrostatic one; this process is il-
lustrated in Fig. 7-55. The surface of the
photo-conducting Se film is first charged
positively to a surface potential of « 700 V
(b) by moving the film under a corona charg-
ing device. The charged photo-receptor is
now exposed to light reflected from the
page to be copied; light is reflected prefer-
entially from the white areas of the page
and these photons, on striking the film, are
strongly absorbed near the surface and
create electron-hole pairs. The photo-elec-
(c)
trons neutralize the positive charges locally
at the surface, while the holes drift across
Toner the thickness of the film under the action of
©00© 0 00
• +•• the field resulting from the surface poten-
• • 4- tial and neutralize the negative charge
induced on the Al substrate. A negative
image is therefore formed in the surface
charge distribution. The latent image is de-
veloped by means of negatively, triboelec-
Paper
trically charged toner particles (each being
Heater
a carbon black particle ^10 jim in diame-
ter surrounded by a low-melting plastic
carrier bead ^100 jim in diameter); these
are attracted to the remaining positively
charged areas on the photo-receptor film.
(e)

Figure 7-55. Schematic illustration of the Xerox pro-

cess utilising a-Se as the photoreceptor (Elliott, 1984,
1990). a) Positive charging of the surface by a corona
discharge, b) Exposure of the photo-receptor by
photons reflected from the document to be copied,
c) Discharge of the surface potential locally by the
photo-generated electrons, the holes drifting across
the thickness of the film, d) Development of the latent
image by means of negatively charged toner particles
which are attracted to the remaining areas of positive
surface charge, e) Transfer of the image to paper by
means of a second corona discharge and subsequent
fixing by heating the paper to melt the toner particles
into place.
444 7 Chalcogenide Glasses
Finally, the developed image is transferred
by attracting the toner particles to a sheet
of paper, corona-charged to the opposite
polarity of that of the toner, whereupon the
paper is heated, thereby melting the toner
particles and fixing them in position.
Certain conditions are required for a
material to be a suitable photo-receptor.
It must be highly resistive in the dark
(Q ^ 1012 Q cm) so that the surface potential
Vo does not decrease appreciably after light
exposure and so that image contrast is not
lost by lateral charge flow on the surface of
the film. (See Madan and Shaw (1988), for
a fuller discussion of the conditions neces-
sary.) The material must be highly photo-
conductive, with a quantum efficiency for
carrier generation near unity at the output
wavelengths of suitable lamps. Further-
more, defect-free large-area films must be
produceable, and the material must be
both mechanically robust and chemically
inert under conditions of exposure to in-
tense light and high electric fields. Al-
though a-Se satisfies these requirements, its
relative softness, toxicity and propensity to
crystallization have led to it being super-
ceded by a-Si:H as the photo-receptor
(Kawamura and Yamamoto, 1982; I. Shi-
mizu, 1985).
7.6.3 Lithography
Chalcogenide materials have been used
as resists in a variety of lithographic (print-
ing) applications, all of which utilize pho-
to-structural changes (see Sec. 7.5.4) as the
basis of the imaging process. For instance,
illumination of chalcogenide glasses or
thin films, sufficient to cause photo-dark-
ening, leads to concomitant changes in the
chemical properties, notably the etching
characteristics in alkaline solutions. For
instance, Petkov et al. (1988) have found
that irradiation of evaporated As-S films
chalcogenide- Ag deposition
oxide- '
substrate-
photo-doped—I
exposure
Ag etch
vq chalcogenide
etch
oxide etch
photo-doped
chalcogenide etch
Figure 7-56. Lithographic process based on the pho-
todissolution of Ag into chalcogenide glasses (Elliott,
1985).
can lead to a ten-fold increase in dissolu-
tion rate; this behaviour can be used as the
basis of a positive lithographic process (see
Fig. 7-56 a), resulting in line-widths below
1 jim. Although the precise mechanism re-
sponsible for this behaviour is not known,
most likely it involves photo-induced bond
breaking.
Another lithographic process, based on
photo-induced effects in chalcogenides,
utilises the phenomenon of metal photo-
dissolution (see Sec. 7.5.4). In this, irradia-
tion with light with energy comparable to
that of the bandgap of the chalcogenide (or
with electrons or ions) causes metal ions
(usually Ag + ) to diffuse into an amorphous
chalcogenide material from a metal-rich
reservoir in contact with it; the reservoir
can be in the form either of an evaporated
metal film or as a dipped layer consisting of
Ag2X (X = S, Se) formed by immersing the
chalcogenide material in a solution of
AgNO 3 . The Ag + ions diffuse through the
thickness of the chalcogenide film (up to

distances of - 2 0 jim (Kokado et al, 1976))
with negligible lateral diffusion under the
action of the incident radiation until either
the chalcogenide film becomes saturated
throughout its thickness with metal or the
reservoir becomes exhausted (Doane and
Heller, 1982). This behaviour results in a
negative lithographic process, since the ex-
posed (photo-dissolved) regions become
alkali-resistant in development by wet
etching; alternatively the unexposed re-
gions of the resist can also be etched prefer-
entially in a dry process, using plasma-
etching with CF 4 or SF 6 . A schematic
illustration of this lithographic process is
shown in Fig. 7-56 b.
The dissolution of metal and subsequent
transport of the ions is greatly facilitated
by the fact that the metal-doped chalco-
genide acts as a highly-conducting (super-
ionic) medium for the metal ions, as found
from diffusion studies (Kawamoto and
Nishida, 1977). Sub-micron (0.3-0.5 \xm)
resolution using Ag-Ge chalcogenide re-
sists is possible, in particular using dipped
films and UV irradiation (Huggett and
Lehmann, 1985). This exceptional perfor-
mance results partly from an edge-sharpen-
ing effect for dipped films (Tai et al, 1982),
wherein fast lateral Ag + diffusion occurs in
the superionic Ag2Se reservoir layer from
unexposed Ag-rich areas into exposed Ag-
depleted regions; this lateral diffusion oc-
curs predominantly at the edges of patterns
where the concentration gradient is the
greatest, and the effect therefore counter-
acts the usual diffraction-related exposure
profile. Extremely high resolution patterns
can also be achieved using focussed elec-
tron-beam irradiation of Ag-Ge chalco-
genide resists (Yoshikawa et al., 1977);
sub-micron (0.3 ^im) resolution is readily
achievable and the ultimate resolving
width may in fact only be several hundred
angstroms.
7.6 Applications 445
7.6.4 Solid Electrolytes
In general, oxide glasses are only rather
poor ionic conductors (aion ~ 10~6 Q" 1
cm" 1 ). However, replacement of the oxy-
gen anions by sulfur leads to a marked
enhancement of the ionic conductivity; for
example, Li 2 S-GeS 2 ~LiI (Carette et al.,
1983), Li 2 S-B 2 S 3 -LiI (Burckhardt et al,
1984), Li 2 S-SiS 2 -LiI (Kennedy and Yang,
1987), and Li 2 S-P 2 S 5 -LiI (Mercier et al,
1981) are superionic materials with cxion
3 ]
10 £ T cm at room temperature
(Souquet, 1981; Pradel and Ribes, 1989)
(see Chap. 14). The conductivity in these
materials is almost entirely due to ionic
transport, with an ionic transport number
of unity; for instance, the electronic com-
ponent to the conductivity for an Ag 2 S-
GeS 2 -AgI glass is about eight orders of
magnitude smaller than the ionic part
(Robinel et al, 1983). The increase in ionic
conductivity caused by the substitution of
S can be understood as a result of the con-
comitant increase in dielectric constant of
the conducting glassy matrix, either in
terms of the Anderson-Stuart (1954) model
affecting the energetics of the microscopic
ion jumps or in terms of the weak-elec-
trolyte model (Ravaine and Souquet, 1977)
where the conducting ions M + are pre-
sumed to arise from the equilibrium
M 2 O ^ M + + O M " . Primary cells (bat-
teries) utilizing ionically-conducting sul-
phide bulk glasses as the electrolytes are
now being manufactured (Akridge and
Voulis, 1986) (e.g. the Li/Li 2 S-P 2 S 5 -LiI/
TiS2 cell of Eveready), and have the advan-
tage that the leakage problems associated
with liquid electrolytes are avoided. Fur-
thermore, these materials can be made in
thin-film form and so the prospect arises of
being able to manufacture thin-film batter-
ies integrated into microelectronic circuits
(Creus et al, 1989).
446 7 Chalcogenide Glasses
Finally, Owen (1980) and Tohge and
Tanaka (1986) have demonstrated that
chalcogenide glasses (e.g. As2Se3) doped
with the appropriate metal can be used as
the basis of ion-selective electrodes (elec-
trochemical sensors) for Cu2 + , Pb 2 + ,
Hg 2 + , and Cd 2 + ions in solution.
7.6.5 Threshold and Memory Switching
The discovery of electrical switching
phenomena in (multicomponent) amor-
phous chalcogenide materials by Ovshin-
sky (1968) marked the start of a 10-year
period of intense investigation of such ma-
terials with the prospect that they would
find use in high-speed switching applica-
tions. Although it has turned out that
the new technology involving so-called
"Ovonic" switches has not supplanted that
based on crystalline semiconductors (e.g.
Si), nevertheless these switching phenom-
ena were found to involve some interesting
physics. Electrical switching behaviour is
not confined to chalcogenide glasses, how-
ever, but has been observed in a variety of
materials, both crystalline and amorphous
(see e.g. Madan and Shaw (1988) for a re-
view). Amongst these non-chalcogenide
amorphous materials which have been
shown to exhibit switching are the alloy
Cd 23 Ge 12 As 65 (Homma etal., 1980) and
a-Si:H (Le Comber etal., 1985), but the
latter only shows switching behaviour after
the application of an initial, irreversible
"forming" voltage pulse.
Chalcogenide STAG, Te-based alloys
within the quaternary Si Te-As-Ge glass-
forming region are normally used as (re-
versible) threshold switching materials: the
composition Se 18 Te 40 As 35 Ge 7 is typical
(Homma etal., 1980). Normally, a sand-
wich sample geometry is employed, with a
sputtered or evaporated film of the chalco-
genide a few microns thick between elec-
trodes of graphite or metals such as Mo.
Reviews of switching behaviour in amor-
phous chalcogenide materials have been
given by Adler et al. (1978, 1980), Henisch
et al. (1985), and Madan and Shaw (1988).
A schematic illustration of the type of
threshold switching (current-voltage) char-
acteristics observed in amorphous chal-
cogenide materials is shown in Fig. 7-57.
In the OFF-state, the chalcogenide mate-
rial has a high resistivity (typically Q =
107 Q cm at room temperature) with linear
I—V characteristics at low electric fields
(<10 3 Vcm" 1 ). At higher fields in the
OFF-state, a pronounced non-linearity is
evident. In the field range 10 3 -10 5 Vein" 1 ,
this non-linear response arises from a con-
tact-limiting of the current by the Schottky
barriers at the contacts; at still higher
fields, the conduction becomes bulk-lim-
ited and exponentially dependent on the
Figure 7-57. Schematic illustration of the threshold
switching characteristics exhibited by amorphous
chalcogenide materials under continuous a.c. excita-
tion; a load resistor in series with the device deter-
mines the load line. Switching from a high-resistance
(OFF) state to a low-resistance (ON) state occurs
when the applied voltage exceeds the threshold
voltage VTH. A minimum holding current (MHC), or
equivalently a minimum holding voltage, FTH, needs
to be maintained for the material to remain in the ON
state.

applied field (Adler et al., 1980). The cur-
rent in the OFF-state is proportional to
the electrode area (in sandwich geometry).
At a critical ("threshold") voltage, FTH
(typically 10 V for a 10 \xm thick film), the
material switches extremely quickly (in a
time <10~ 10 s)(Ovshinsky, 1968) to a low-
resistance (ON) state along the "load line"
- see Fig. 7-57. The form of the load line is
determined by a load resistor RL in series
with the switching device through the rela-
tion
= IRL+V (7-46)
where VB is the applied voltage provided by
a bias battery, / is the current flowing
through the switch and V is the voltage
dropped across it; the slope of the load line
is then given by — 1/RL. Once in the ON-
state, the dynamic resistivity is as low as
0.08 Q cm (Adler et al., 1978), and this state
is maintained as long as a minimum hold-
ing current JH flows through the switch or,
equivalently, as long as a minimum hold-
ing voltage, FH, is applied. FH is compara-
ble to the (optical) band gap of the material
(Adler et al., 1978); for STAG materials this
is of the order of 1 V. The ON-voltages are
only very weakly dependent on the chalco-
genide thickness, implying that in the ON-
state most of the potential difference across
the switch is dropped near one or both of
the electrodes (Henisch et al., 1985). Fur-
thermore, the ON-currents are independent
of electrode area, except for samples with
diameters of the order of 10 jam, indicating
that conducting channels (filaments) of this
size carry the current in the ON-state (Pe-
tersen and Adler, 1976). In addition, there
is convincing experimental evidence that,
in the ON-state, the conducting-channel
area increases in proportion to the current,
indicating that the ON-state current den-
sity is more-or-less constant over a wide
range of operating conditions.
7.6 Applications 447
Two types of switching behaviour may
be distinguished. Threshold switching is as
described above when the OFF-state may
be recovered from the ON-state by reduc-
ing the applied voltage below VH. Memory
switching occurs when the ON-state, and
hence the conducting filament, is meta-
stable; this can arise when the conducting
channel is caused to crystallize through
prolonged application of voltages higher
than Vn and is prevalent in less stable
chalcogenide glass compositions (i.e. those
more prone to crystallization, such as Te-
rich alloys). The OFF-state in such devices
can only be recovered following the appli-
cation of a large voltage pulse, sufficient to
cause local melting and subsequent revitri-
fication of the conducting channel.
There was considerable controversy at
first as to whether the switching mecha-
nism was of a thermal or electronic nature
(Adler et al., 1978; Madan and Shaw, 1988).
The thermal model (Madan and Shaw,
1988) assumes that the high current density
in a conducting channel is sufficient to
cause appreciably local heating (say sev-
eral hundred degrees centigrade) so that
eventually a region having a negative
differential conductivity appears (as in a
thermistor). However, it is now accepted
that thermal effects do not play a dominant
role in threshold switching in chalcogenide
alloys (Adler et al., 1978, 1980): direct and
indirect estimates for the temperature of
the conducting channel indicate that it is
only 1-10 K above ambient; furthermore,
the ON-state switches to the OFF-state
when the applied voltage is reduced below
VH in a sharp, discontinuous fashion,
rather than with a gradual decay expected
if thermal effects were dominant. Addi-
tional evidence for the switching mecha-
nism being primarily electronic in nature
comes from experiments in which the
switching behaviour is monitored as a
448 7 Chalcogenide Glasses
function of light intensity, the chalcogenide
film being illuminated through a semi-
transparent electrode (Kroll, 1974); no
change in FTH is observed, despite the fact
that the threshold current in such circum-
stances increases by at least a factor of 10
as a result of the photoconductivity, indi-
cating that the threshold switching is asso-
ciated with a critical electrical field, inde-
pendent of the carrier density.
A picture for the electronic behaviour
associated with threshold switching is as
follows. As the electric field in a chalco-
genide sample is increased, the current in-
creases non-linearly, perhaps as the result
of impact-ionization processes (Adler et al.,
1980; Henisch et al., 1985). This field-in-
duced carrier generation causes the filling
by electrons and holes, respectively, of
C^ and C^ gap-state defect centres (see
Sec. 7.4.3), and a critical field is reached
when all traps are filled. At this point,
switching occurs to a high-conductivity
(ON) state where the conductivity is no
longer trap-limited, as it is in the OFF-
state (where the dominant hole drift mobil-
ity is jih ^ 10 ~5 cm2 V " l s " *), and instead
the carrier mobility becomes equal to that
characteristic of the bands, viz. \i = 10 cm2
V ^ s " 1 (Adler et al., 1978, 1980). In the
ON-state, the current is maintained by
double injection into the chalcogenide at
the electrodes, electrons tunnelling through
an energy barrier at one electrode and
holes through a barrier at the other (Mott,
1969; Henisch, 1969).
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bridge, Mass., 27-31 Aug. 1979". /. Non Cryst.
Sol 35136, 1-1328.
Somogyi, I. Kosa (Ed.) (1987), "Proc. 8th Intl. Conf.
on Non-Crystalline Semiconductors", /. Non
Cryst. Sol. 90, 688.
Tanaka, K., Shimizu, M. A. (Eds.) (1983), Proc. 10th
Intl. Conf. on Amorphous and Liquid Semicon-
ductors, Tokyo, Japan, 22-26 Aug. 1983", J. Non
Cryst. Sol 59/60, 1-1326.
Zallen, R. (1983). The Physics of Amorphous Solid.
New York: Wiley.
8 Halide Glasses
Jacques Lucas

Universite de Rennes-Beaulieu, Laboratoire de Chimie Minerale, Rennes, France

List of Symbols and Abbreviations 457

8.1 Introduction 458
8.2 Glass Formation in Halide Systems 459
8.2.1 The Fluoride Glasses 459
8.2.1.1 The MF2-Based Glasses 459
8.2.1.2 The MF3-Based Glasses 460
8.2.1.3 The ZrF4-Based Glasses 460
8.2.1.4 Multicomponent Zr-Free Heavy Metals 461
8.2.2 Glasses Based on Heavy Metals 462
8.2.2.1 Glasses Based on Divalent Metal Halides 462
8.2.2.2 Glasses Based on Trivalent and Quatrivalent Metal Halides 463
8.2.2.3 Miscellaneous Non-Conventional Vitreous Halides 463
8.2.2.4 The Tellurium Halide Glasses 464
8.3 Halide Glasses as Optical Materials 465
8.3.1 Optical Properties of Bulk Glasses 465
8.3.1.1 The Bandgap Absorption 465
8.3.1.2 The Multiphonon Absorption Edges 466
8.3.1.3 Refractive Index of Halide Glasses 470
8.3.1.4 Origin of Scattering Losses in Fluoride Glasses 471
8.3.2 Fluoride Glass Fibers 472
8.3.2.1 Introduction 472
8.3.2.2 The Optical Losses in Fluoride Glass Fibers 472
8.3.2.3 Fluoride Glass Fiber Presentation 474
8.4 Fluoride Glasses: A new Host for Rare-Earth and Transition Metals 475
8.4.1 Active Optical Properties 475
8.4.2 Absorption Spectra of Rare-Earth and Transition Metal Ions 476
8.4.2.1 Rare-Earth Ions 476
8.4.2.2 Transition Metal Ions 476
8.4.3 Fluorescence Spectra of Rare-Earth and Transition Metal Ions 477
8.4.3.1 Radiative Emission of Rare-Earth Ions 477
8.4.3.2 Non-Radiative Processes in Rare-Earth Doped Glasses 479
8.4.3.3 Multidoped Fluoride Glasses 480
8.4.3.4 Up-Conversion or Photon Addition in Fluoride Glasses 481
8.4.4 Interest of Rare-Earth Spectroscopy in Fluoride Glasses 481
8.4.4.1 Analysis of Impurities by Photoluminescence 481

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
456 8 Halide Glasses

8.4.4.2 Crystallization and Structure Investigations 482

8.4.4.3 Temperature Measurements by Optical Means 482
8.4.4.4 Lasers and Fiber Lasers 482
8.5 Tellurium Halide Glasses (TeX Glasses): New Materials
for Low Loss Infrared Fibers 483
8.5.1 Optical Characterization 483
8.5.2 Optical Fibers Operating Between 3 and 14 jim 483
8.6 Stability of Halide Glasses against Chemical Attack and Devitrification . . . 484
8.6.1 Chemical Durability 484
8.6.2 Devitrification of Fluoride Glasses 485
8.7 Preparation of Fluoride Glasses and some Physical Properties 486
8.7.1 Preparation of Fluoride Glasses 486
8.7.2 Magnetic Properties of Fluoride Glasses 487
8.7.3 Electrical Properties of Fluoride Glasses 488
8.8 References 488
 List of Symbols and Abbreviations 457

List of Symbols and Abbreviations

A, a material parameters
aext extrinsic scattering
at total intrinsic attenuation coefficient
B Rayleigh factor
B Racah parameter
C constant dependent on source of scattering
D A independent scattering
Dq crystal field parameter
E band gap
AE energy gap
/ force constant
m mass
n refractive index
n2 non-linear refractive index
n
o nd> nF indices at X\ d = 0.589 mm, F = 0.486 mm, c = 0.656 mm
T glass softening point
Tf freezing temperature
T glass transition temperature
energy transfer rate
multiphonon emission rate
wR radiative rate
attenuation coefficient
n quantum efficiency
9 Curie-Weiss temperature
X wavelength
V- reduced mass
v0 vibrational frequency
Q2 indicator of the covalent character bonding
Qt phenomenological parameters with t — 2, 4, 6
CN coordination number
F.L.N. fluorescence line narrowing
RAP reactive atmosphere processing
R.E.-R.E. rare earth-rare earth
T.M.-R.E. transition metal-rare earth
Composition of glasses
BATY 20BaF 2 , 29A1F3, 22ThF 4 , 29YF 3
BiGaZYT Ba 3 0 In 1 8 Ga 1 2 Zn 2 0 Y 1 0 Th 1 0
BIZYT Ba 3 0 In 3 0 Zn 2 0 Y 1 0 Th 1 0
BTYbZ 16 BaF 2 , 28 ThF 4 , 28 YbF 3 , 28 ZnF 2
ZBL 60ZrF 4 , 33BaF 2 , 7LaF 3
ZBLA 55ZrF 4 , 35BaF 2 , 6LaF 3 , 4A1F3
ZBLAN Zr 5 3 Ba 2 0 La 4 Al 3 Na 2 0
458 8 Halide Glasses
8.1 Introduction
Halide materials are usually reputed to
exist in the crystalline state when cooling
down from a molten halide salt; they also
form easily volatile molecular species when
the halogen is associated with small, highly
charged cations. Only a limited number of
halide systems lead to glass formation and
usually the glass to crystal or glass to mol-
ecule competition is very severe.
Considerable progress has been made
during the last two decades both in the
discovery of new halide glass-forming com-
positions based on the anions F, Cl, Br, I,
the elements of group VII of the periodic
chart, and in knowledge of the optical
properties of these exotic glasses. The main
justification for research in this field is the
possibility of extending the infrared trans-
parency domain towards long wavelengths
and of consequently achieving mid-infra-
red ultratransparency.
There are at least three intrinsic factors
which limit the technological and scientific
development of such vitreous materials
and in which they are inferior to oxide
based glasses, especially silicates.
The first factor, typical of almost all
halide compounds, vitreous or otherwise,
is their susceptibility to corrosion by water
or moisture, which can strongly affect their
optical properties. This poor chemical
durability can be explained by the fact that
the M - O H 2 , M - O H , or M O bonds are
usually stronger than the M - X bond (M =
metal; X = F, Cl, Br, I).
The second factor is also associated with
the weakness of the M - X bond compared
with the M - O bond: halide-based materi-
als have low characteristic temperatures.
For example, glass transition tempera-
tures, Tg, are low and range from room
temperature to a maximum of 400 °C. As a
direct consequence, the thermal expansion
coefficients of halide glasses are usually
high, and these materials are sensitive to
thermal shock. Their mechanical strength
is also poor compared with traditional ox-
ide glasses.
The last factor impeding the develop-
ment of these glasses is that they are
formed from the most electronegative ele-
ments of the periodic chart, especially in
the case of fluorine F, which has a strong
tendency to form ionic crystalline materi-
als. A direct consequence is that the glass-
crystal competition in halide systems when
crossing the strategic liquidus-solidus line
often favors microcrystallite formations.
Hence, the optical properties, especially
the scattering losses, suffer from the ten-
dency to devitrify.
Thus it is not surprising that only a lim-
ited number of halide glasses among the
numerous compositions which have been
described in the literature may be suitable
for practical applications. The study of op-
tical properties requires the samples to be
of reasonable size and optical quality and
to have a strong resistance to corrosion
from atmospheric moisture. This explains
why only a few halide glasses have been
thoroughly investigated. This chapter will
briefly review the halide compositions
which have been proven to be glass form-
ers, even if the glasses have little chance of
becoming optical materials because of their
poor stability. Particular attention will be
paid to the limited number of stable glasses
and to their specific optical properties.
Among them, the fluoride glasses occupy a
dominant position, especially those based
on ZrF4 or other multicomponent com-
positions. These are usually termed heavy
metal fluoride glasses.
Most of the investigations on fluoride
glasses have been motivated by the poten-
tial to develop ultralow-loss optical fibers
operating in the mid I.R. Several general
 8.2 Glass Formation in Halide Systems
articles reviewing the optical properties of
these materials have been published (Bald-
win etal., 1981; Tran et al., 1984; Drex-
hage, 1985; France etal., 1987; Lucas,
1986) as well as four international confer-
ence proceedings (Almeida, 1987; Lucas
and Moynihan, 1985; Drexhage etal.,
1987). This fast growing field of glass sci-
ence has a short history, only about twelve
years, since the only halide materials previ-
ously known to give glasses were beryllium
fluoride, BeF2, and zinc chloride, ZnCl 2 .
Because of the toxicity of the former and
the hygroscopicity of both, investigations
of their optical properties have been very
limited, despite the interest expected in
them (Weber, 1986; Van Uitert and Wem-
ple, 1978).
The goal of this review is to try to set up
for these special glasses relations between
the chemical composition, which deter-
mines the structure and nature of the
bonds, and their optical properties. In ad-
dition to the development of very large op-
tics often difficult to realize with crystalline
materials, an important property of vit-
reous materials is the potential to develop
very transparent optical waveguides or op-
tical fibers. The formation of fibers from
crystalline materials is a very difficult oper-
ation, while the glassy state, with its unique
viscosity-temperature dependence, repre-
sents the ideal situation for transforming a
bulk material into a very long waveguide.
Among the different objectives for develop-
ing these optical waveguides are the possi-
bility of repeaterless long distance telecom-
munication links and analytical applica-
tions such as remote I. R. spectrometry, py-
rometry and thermal imaging, and energy
transfer of the output of powerful lasers for
welding, cutting, and surgical operations
(see Chap. 15).
459
8.2 Glass Formation
in Halide Systems
As indicated already, the term halide
glass refers to any vitreous material in
which the anions come from the group
VIIA elements of the periodic table,
namely F, Cl, Br, and I. Because of its size
and electronegativity, fluorine is often con-
sidered a special halogen which has to be
treated separately. In this article, we shall
also discuss the fluoride glasses as a special
family owing to the very large research ef-
fort devoted to this group during the last
ten years, and we shall examine the so-
called "heavy halide glasses", namely chlo-
rides, bromides, and iodides, together as a
separate family.
8.2.1 The Fluoride Glasses
Fluoride glasses can be classified accord-
ing to structural considerations, and, al-
though glass formation has been observed
in many fluoride systems, the vitreous ma-
terials obtained cannot be considered of
equal interest because of the high tendency
for most of them to devitrify.
8.2.1.1 The MF 2 -Based Glasses
The MF2-based glasses are represented
only by the BeF2 glass family which shows
a strong resistance to devitrification. Ac-
cording to Baldwin et al. (1981) it is gener-
ally agreed that these vitreous materials
are isotypic with SiO2-based glasses. X-ray
and molecular dynamics studies clearly in-
dicate that the aperiodic framework is
based on the BeF4 tetrahedron. BeF2 is the
only fluoride giving a viscous melt which
easily vitrifies on cooling. BeF2-based
glasses are of special interest for some opti-
cal applications for high power lasers ow-
ing to their low linear and non-linear re-
fractive indices (see Chap. 12). However,
460 8 Halide Glasses
because of their toxicity, they have received
only limited attention.
8.2.1.2 The MF3-Based Glasses
These glasses are represented by the
A1F3 or transition metal fluoride groups
and result from the formation of an aperi-
odic 3-D framework based on MF6 octahe-
dra. The MF 3 materials, which have been
proven to give glasses when combined ap-
propriately with other fluorides, are A1F3,
FeF 3 , CrF 3 , and GaF 3 (Sun, 1947; Jaco-
boni et al., 1983). The other fluoride com-
ponents are usually ZnF2 or MnF2 and
PbF2 which seems to play the important
role of modifier. In the typical glass form-
ing ternary system, FeF 3 -MnF 2 -PbF 2 , the
glass composition PbFeMnF 7 , which falls
in the vitreous domain, corresponds to a
glassy material extremely rich in magnetic
cations which exhibits interesting spin-
glass properties at low temperatures (Re-
nard et al., 1981). The glass-crystal compe-
tition is also very severe in this family, and
the aperiodicity introduced in the ReO 3
structure by rotating or tilting the octahe-
dra can be easily destroyed, with the for-
mation of ordered crystalline materials. A
significant improvement in the stability of
A1F3-based glasses has been obtained by
incorporating ZrF4 to this glass.
8.2.1.3 The ZrF4-Based Glasses
These glasses were the first of the so-
called "heavy metal fluoride glasses". Their
discovery in the author's laboratory in
1974 (Poulain et al., 1975) attracted con-
siderable interest because the glasses had
very promising properties for mid I.R. ap-
plications. Although ZrF 4 by itself cannot
be vitrified, if it is combined with an appro-
priate modifier such as BaF2 it leads, by
fast quenching, to simple binary glasses
which are useful for structural investiga-
tions. As indicated in Fig. 8-1 the stability
of the glasses towards devitrification is
strongly improved by using a third fluoride
such as ThF4 or LaF3. The glass called
ZBL, corresponding to the composition
60 ZrF 4 , 33 BaF2, 7 LaF3 and located in the
middle of the vitreous area of Fig. 8-1, is a
rather stable glass. The rate of crystalliza-
tion can also be significantly decreased by
using a small amount of A1F3. For in-
stance, an optimized composition giving
a good technical glass called ZBLA is
55ZrF 4 , 35BaF2, 6LaF 3 , 4A1F3.
Many others compositions have been
developed in order to decrease the nucle-
ation rate and avoid scattering losses in
optical fibers. It appears that the so-called
confusion principle can be also applied in
this domain of glass science and, for in-
stance, one of the best candidates for fiber
drawing is the multicomponent fluoride
ZBLAN, with the molar cation composi-
tion Zr 53 Ba 20 La 4 Al 3 Na 20 . In this glass,
60ZrF4
33BaF 2
7LaF 3
LaF3 BaF2
ZBLA Glass :
ZBLAN Glass
Figure 8-1. Glass forming domain in the ternary dia-
gram ZrF 4 -BaF 2 -LaF 3 . Some compositions are
given in molar percentage, for example, for the binary
unstable glass ZB, the ternary ZBL and the four and
five-component glasses ZBLA and ZBLAN, which
are the most resistant to devitrification.
 8.2 Glass Formation in Halide Systems
Zr OF Ba
Figure 8-2. A structural model for the binary glass
2 ZrF 4 -l BaF2. Elementary polyhedra ZrF7 and ZrF8
sharing corners and edges form a 3-D aperiodic
framework. The large Ba 2+ cations play the role of
lattice modifiers.
where the modifier Ba2 + has been partially
replaced by Na + , an interdiffusion barrier
to crystallization has been introduced be-
cause of the competition between Na and
Ba in crystalline fluorozirconate forma-
tion.
The usual way to prepare these fluo-
rozirconate glasses is by melting the differ-
ent starting fluorides in vitreous carbon or
platinum crucibles in a dry atmosphere. In
order to convert some materials starting as
oxides to fluorides or to prevent any pyro-
hydrolysis during heating, it is convenient
to add NH 4 HF 2 to the mixture to avoid
the presence of O 2 ~ in the melt.
461
These new stable fluoride glasses have
been widely investigated, and abundant lit-
erature on them exists, as discussed by
Drexhage (1985). In the field of structural
modelling, relationships have been estab-
lished between the structure of BaZr 2 F 10 in
its crystalline and vitreous states (Phifer
etal., 1987). Figure 8-2 presents the 3-D
aperiodic framework built up by the con-
nection of Zr 2 F 13 bipolyhedra originating
from ZrF7 and ZrF8 edge-sharing polyhe-
dra. The Ba 2+ cations playing the role of
modifier elements are inserted in the frame-
work and interact mainly with the non-
bridging ions. This model has been ob-
tained from X-ray and neutron diffraction
studies, molecular dynamics simulations,
and local probe spectroscopies.
8.2.1.4 Multicomponent
Zr-Free Heavy Metal Fluoride Glasses
Research into new Zr-free fluoride
glasses has been motivated by the need to
synthesize glasses having the widest optical
windows. The transmission range for the
fluorozirconate family is limited in the
multiphonon region to about 7 jim be-
cause of Zr-F, especially by Al-F vibra-
tional modes. It has been demonstrated
that heavy metal fluoride glasses not con-
taining Zr 4 + exist but they are more diffi-
cult to prepare (Lucas, 1987), and at least
three fluorides need to be incorporated to
realize the conditions of glass formation.
Three-Component Fluoride Glasses
Depending on the quenching rate, small
glassy chips can be obtained from ternary
liquids. For instance, glasses have been
prepared by fast quenching from the fol-
lowing ternary melts: BaF 2 -ZnF 2 -LnF 3 ,
BaF 2 -ZnF 2 -ThF 4 , BaF 2 -ZnF 2 -CdF 2 or
YF 3 -ZnF 2 -ThF 4 .
462 8 Halide Glasses
Four-Component Glasses
Systematic investigations of the quater-
nary diagram YbF 3 -ThF 4 -ZnF 2 -BaF 2
show that, when BaF2 is added to the
glass forming composition YnThZnF9, the
tendency to devitrify decreases signifi-
cantly. For instance, the fluoride glass
Ba 16 Th 28 Yb 28 Zn 28 , called BTYbZ, can be
obtained in about a 10 mm thickness. The
same kind of observation has been made
in the system BaF 2 -InF 3 -ZnF 2 -ThF 4 ,
where the stable composition is
Ba 3 0 In 3 0 Zn 3 0 Th 1 0 .
Five-Component Glasses
To demonstrate that the multiplication
of cations having a flexible coordination
was a suitable factor for retarding the
crystallization, a systematic investigation
has been done of the fluoride system
Ba 30 In 20 Zn 30 _ x Y c Th 10 . For x = 10, the
melt has a maximum viscosity, and sam-
ples of 20 mm thickness can be obtained.
This so-called BIZYT glass, with the
composition Ba 30 In 30 Zn 20 Y 10 Th 10 , is the
most stable Zr-free fluoride glass and has
been proven suitable for fiber drawing
(Bouaggad et al., 1987). The partial sub-
stitution of In by Ga, for example, in
the glass BiGaZYT with the composition
Ba 30 In 18 Ga 12 Zn 20 Y 10 Th 10 allows us to
decrease the critical cooling rate Rc from
about 120°C/min to 10°C/min.
The structure of these multicomponent
glasses is obviously a subject of speculation
because of the great number of pair inter-
actions. Nevertheless, an analogy exists be-
tween these glasses and the fluorozirconate
glasses in the sense that the variety of ZrFn
polyhedra in these glasses are replaced by
a variety of other equivalent MFn building
elements.
8.2.2 Glasses Based on Heavy Halides
This terminology refers to glasses in
which the electronegative part is a heavy
halogen such as Cl, Br, I. Most of these
materials suffer, in terms of their techno-
logical development, from their hygro-
scopicity, low softening temperature, and
the tendency to devitrify.
Research activity in this field (Macken-
zie, 1987) has been largely motivated by the
fact that, from a simple consideration of
masses of anions associated with cations,
chloride, bromide, and iodide glasses
would be expected to be more transparent
in the I.R. than the fluoride glasses.
8.2.2.1 Glasses Based
on Divalent Metal Halides MX2
Vitreous materials have been prepared
with M = Zn 2 + , Cd 2 + and X = C1", Br~,
I~. ZnCl 2 is the best and most widely
known glass former. With an I.R. edge in
the 12-13 jim region, it is of interest for
optics operating in the 8-12 jim atmo-
spheric window and has a potential for ul-
tratransparency (Van Uitert and Wemple,
1978). Many attempts have been made to
increase its resistance to water corrosion
and to devitrification by the addition of
other halides such as KBr or PbBr 2
(Yamane et al., 1985). Nevertheless, hygro-
scopicity remains very high and severely
affects the optical properties in the I.R. re-
gion. The glass transition temperature of
such mixed halide glasses is also low, about
50 °C. The glass forming ability is ex-
plained by the formation of a 3-D aperi-
odic framework based on ZnCl 2 tetrahe-
dra.
The isotypic ZnBr2 is also known to be
a glass former with an expected I.R. cut-off
in the 20|im region (Hu et al., 1983), but
vitreous ZnBr2 exhibits very poor chemi-
cal durability and a weak resistance to de-
 8.2 Glass Formation in Halide Systems
vitrification. Addition of a glass modifier
such as KBr (Kadono etal.? 1987) im-
proves these two properties.
Cadmium chloride CdCl 2 has also been
proven to lead to vitreous materials, when
associated with other halides such as Pbl 2
or PbCl 2 (Angell et al., 1987). In this case,
the I.R. transmission extends to 20jLim.
When CdCl2 glasses are stabilized by a
mixture of chloride and fluoride such as
CdF 2 -BaF 2 -NaCl (Matecki et al., 1987),
the multiphonon edge is determined by the
metal-fluoride bond and shifts back to the
8-12 jim region. Although they appear less
sensitive to humidity than the zinc chlo-
ride-based glasses, these CdCl2 glasses
cannot be kept in an ambient atmosphere
without surface corrosion occurring.
A large glass forming domain has been
discovered by Cooper and Angell (1983) in
the CdI2-based system when Cdl 2 is asso-
ciated with KI and Csl as modifiers. With
an I.R. edge shifted towards the 30 |im re-
gion, those glasses have the largest optical
window of any known vitreous material.
Unfortunately, but as expected, the me-
chanical properties are very poor and the
hygroscopicity is high, essentially owing to
a Tg ranging from 10 to 35 °C. One can
speculate that these glasses contain a Cdl 4
tetrahedron as a structural module.
8.2.2.2 Glasses Based on Trivalent
and Quadrivalent Metal Halides
Angell and Ziegler (1981) reported sev-
eral glasses based on BiCl3 with I.R. edges
located in the 14 jam region. These glasses
also suffer from low glass temperatures,
around 30 to 50 °C, and the rapid attack of
atmospheric moisture.
Hu and Mackenzie (1982) succeeded in
preparing vitreous chlorides based on
ThCl 4 associated with NaCl and KC1. The
I.R. edge is located near 14 |im, but strong
463
corrosion due to a high sensitivity to mois-
ture affects the optical transmission severe-
ly. In this kind of glass, the structure can be
reasonably described as a 3-D framework
of connected MC1 6 , MC1 7 , and MC18
polyhedra.
8.2.2.3 Miscellaneous Non-Conventional
Vitreous Halides
The concept of the aperiodic framework
can be applied to the previous glasses, but
fails to explain the existence of some multi-
component monovalent cation halide
glasses. It has been demonstrated (Angell
et al., 1985, for instance), that large vit-
reous areas exist in the middle of the
AgCl-Agl-CsCl and CuCl-PbCl 2 -RbCl
systems. Even in binary systems such as
AgX-CsX (X=Br, I) glasses can be ob-
tained by rapidly quenching the melt. The
addition of 2% of PbX 2 improves glass
formation and allows for the preparation
of samples 10 mm thick (Nishii et al., 1985).
I.R. transmission occurs out to 15 |im,
but the glass temperature is rather low
(T g =21°C) for the stabilized glass
59AgX-39CsX-2PbX 2 . Some attack by
atmospheric moisture is observed after sev-
eral hours.
One explanation for glass formation in
multicomponent systems involving halides
such as AgCl, CuCl, Agl, and CsCl can be
based on the observation that the eutectic
points in these systems are at relatively low
temperatures, giving melts where the ionic
diffusional processes are slow. Also, the nu-
cleation and crystal growth mechanisms
are highly impeded by the fact that the four
halides AgCl, CuCl, Agl, and CsCl belong-
ing to four different non-miscible struc-
tural types have to compete in forming in-
dividual crystallites.
464 8 Halide Glasses

8.2.2.4 The Tellurium Halide Glasses cussed in Sec. 8.3.1.2 which is devoted to
the multiphonon edge, the TeX glasses can
The author's group recently discovered be divided into two groups: a) the light
a new family (Lucas and Zhang, 1986; Lu- TeX glasses containing light elements such
cas et al., 1987) of halide glasses based on as S or Cl and having an I.R. cut-off at
the combination of tellurium Te with chlo- 13 |im, and b) the heavy TeX glasses with a
rine, bromine or iodine. These tellurium multiphonon edge near 20 jim.
halide glasses, called "TeX glasses", have
The very large glass-forming domain in
been obtained in the following binary or
the Se-containing ternary system is due to
ternary systems: Te-Cl, Te-Br, Te-Cl-S,
the fact that the binary glass, Te3Cl2 for
Te-Br-S, Te-Br-Se, T e - I - S , Te-I-Se.
instance, has the same structure as the Se
Addition of S or Se to the binary TeX
glasses. The chain-like structure of crys-
glasses decreases the devitrification rate,
talline Te3Cl2 is represented in Fig. 8-4 and
and some of these ternary compositions
is obviously isotypic with the spiral-type
are very resistant to crystallization. In Fig.
structure of crystalline Se giving a broad
8-3 the large vitreous domains in the six
domain of solid or liquid solution between
different systems are shown. The glass
the two components. Densities and molar
Te3Cl2 with Tg=82°C crystallizes at
volume measurements indicate that all the
189 °C on heating, but the glass Te3Cl2S
Te-Br-Se glasses are very homogeneous
with T g =81°C shows no devitrification.
consisting of infinite mixed Te and Se
Most of these TeX glasses are not corroded
chains and no phase separation has been
by atmospheric water, except for those
observed.
having a high halogen content. As dis-

Q\ 20 40 60 80 20 40 60 80 j 20 40 60 80

Q 20 40 60 80 B r 20 40 60 80 Se j 20 40 60 80

Figure 8-3. Glass formation in tellurium halides systems. The TeX glasses are stabilized against devitrification by
S or Se addition. A large domain of glass formation is shown between the TeX glasses and the selenium due to
the similarity in their chain-like structure.
 8.3 Halide Glasses as Optical Materials: Passive Properties
OTe
• Cl
Figure 8-4. The chain-like structure of the crystalline
form of Te3Cl2. After melting and a moderate
quenching rate, Te3Cl2 easily vitrifies. The spiral
structure is induced by the steric effect of the lone pair
of electrons represented on one Te atom.
8.3 Halide Glasses as Optical
Materials: Passive Properties
8.3.1 Optical Properties of Bulk Glasses
For definitions, see Chap. 12.
8.3.1.1 The Bandgap Absorption
The U.V. edge in halide glasses MxXy is
associated with the excitation of electrons
from lower to higher energy states on the
molecular orbital diagram of the M - X
bond. It is obvious, because of the great
polarizing ability of cations such as Be2 + ,
Al 3+ , and Zr 4 + and the high value of the
corresponding ionization energy, that the
M - F bond in fluoride glasses has a
strongly covalent character. Consequently,
the energy gap between the bonding level
and the first unoccupied antibonding level
465
is estimated to be rather high unless impu-
rities such as cations with partly filled d or
f levels or heavy halogens such Cl~, Br~,
or I~ introduce parasitic levels which can
strongly modify the absorption mecha-
nisms in the U.V.
A study by Brown (1982) shows that for
most of the ZrF4- and HfF4-based glasses
the U.V. edge is in the region E = 5 eV, cor-
responding to X = 0.25 jim, according to
the relation /I (jam). £(eV) = 1.24. Com-
pared to very pure vitreous SiO2 where
£ = 8.0eV (vl = 0.16 jim), the fluorozir-
conate glasses are less interesting in terms
of U.V. transmission.
The U.V cut-off, of course, depends on
other M - F bonds if additional metallic
fluorides are added to the melt. The cut-off
is also governed by the M-Cl molecular
orbital diagram if Cl~ anions (Adam and
Poulain, 1983) are present in the glass due
to Reactive Atmosphere Processing using
CC14, for example. It is often observed that
CC14 treatment leads to a yellowish col-
oration of the glass due to a shift of the
U.V edge into the visible region.
Although no thorough investigation has
been done in this area, it is expected that
for most heavy halide glasses the U.V. edge
will shift towards the visible region pro-
gressively, from Cl to I, due to the increas-
ing size and decreasing electronegativity of
the corresponding halogen.
Visual observation of TeX glasses shows
clearly that these "black glasses" have their
band gaps in the near I.R. lying typically
between 1.40 eV (0.9 \im) in TeSe6Br3 and
0.7 eV (1.8 jim) in the binary glass Te 3 Cl 2 .
These glasses have a chain-like structure in
which the lone pair of 5 s2 electrons associ-
ated with the Te have an important stereo-
chemical effect. The low band gap in these
glasses is due essentially to the excitation
of these electrons located in non-bonding
orbitals.
466 8 Halide Glasses
8.3.1.2 The Multiphonon Absorption Edges
The possibility of shifting the I.R. edge in
halide glasses to longer wavelengths has
served as a catalyst for much of the re-
search activity on these materials. The syn-
thesis of a glass having multispectral capa-
bilities is of interest to many infrared
technologies, especially if a potential for
ultratransparency exists. It is well known
that the multiphonon absorption mecha-
nisms are among the most important for
explaining the optical losses in a material
(see Chap. 12).
The I.R. or multiphonon edge in a trans-
parent solid results from combinations and
overtones of the far-infrared fundamental
vibrational frequencies of the bonds be-
tween anions and cations. The position of
the fundamental frequencies is governed by
the Szigeti equation (Szigeti, 1950), which
shows the dependence of the vibrational
frequency v0 on the reduced mass \i of the
atoms A and B and the force constant /
for the bond between them: VO = (1/2TT)
(//AO 1 / 2 - The reduced mass is given by
fi = mAmB/(mA + mB). It is obvious that
heavier atoms and weaker bonding are
preferable for extended I.R. transmission.
As discussed by Lines (1986) and Ben-
dow et al. (1981 b), at the far infrared end of
the optical spectrum, the attenuation is
dominated by absorption from polar
modes of lattice vibrations. This absorp-
tion extends as an exponential tail to
shorter wavelengths from the intense single
phonon band. This tail is the result of ab-
sorptions involving the simultaneous exci-
tation of more than one phonon. The de-
pendence of this so-called "multiphonon
loss" on wavelength is expressed by the
general equation a = A exp (— a/A), in
which A and a are material parameters and
a is the attenuation coefficient.
Infrared Edge in Fluoride Glasses
The fundamental vibrational modes of
the fluoride glass matrix occur in the far
infrared at wavelengths between 15 and
50|im. Bendow et al. (1983a, 1983b) and
Drexhage (1985) have measured and dis-
cussed the reflectivity spectra of several flu-
oride glasses, which show the composi-
tional variation of the I.R. edge absorption.
Figure 8-5 shows the percentage of reflec-
tivity directly related to the absorption co-
efficient versus the wavelength for different
kind of glasses:
a) a ZBL glass in the system ZrF 7 4 -
BaF 2 -LaF 3 ;
b) a multicomponent Zr-free heavy
metal fluoride glass BTYbZ having the
composition 16BaF2, 28ThF 4 , 28YbF3,
28ZnF 2 ;
c) the same BTYbZ glass doped with
about ten percent A1F3, which often plays
the role of stabilizing the glass; and
d) a "BATY" glass, in which A1F3 plays
the important role of glass former, with the
composition 20BaF 2 , 29A1F3, 22ThF 4 ,
29YF3.
The interpretation of these spectra is as
follows: The absorption in the region
250 cm" 1 is attributed to the B a - F bond,
the bands in the range 400-450 cm" 1 are
due to T h - F or Y b - F bonds, and the
large absorption near 550 cm" x in the fluo-
rozirconate is attributed to the Z r - F vi-
bration. The Al-F vibrational mode,
which corresponds to a strong M - F bond
involving a small and highly charged
cation Al3 + is located in the 600-650 cm" 1
region and shows the detrimental effect of
A1F3 in fluoride glasses in shifting the
multiphonon absorption towards shorter
wavelengths. These results, obtained in the
far I.R. part of the spectra, are also verified
when examining the evolution of the I.R.
edge in different kinds of fluoride glasses.
 8.3 Halide Glasses as Optical Materials: Passive Properties 467

WAVELENGTH (pm)
50 25 20 15

Figure 8-5. Reflectivity spectra in

the single phonon band for several
fluoride glasses: a) a ZrF4-based
glass; b) a heavy metal Zr-free
fluoride glass; c) the same glass as
b) but doped with A1F3, and d) an
AlF3-based glass.
100 300 500 700 900
FREQUENCY (cm"1)

Figure 8-6 shows the position of the I.R.
cut-off for different fluoride glasses having
a thickness of about 3 mm. Spectrum 1 cor-
responds to a BeF2-based fluoride glass in
which the strong Be-F bond between two
light elements places the I.R. cut-off almost
in the same region as the Si-O vibration of
the silica glass (Baldwin, 1979). Spectrum 2
corresponds to fluorozirconate of Zr-free
fluoride glasses doped with a few percent of
A1F3, for example ZBLA glass (4% A1F3).
Spectrum 3 is that of a pure fluorozir-
conate glass such as ZBL in which the I.R.
cut-off is governed by the vibrational
modes of Z r - F bonds. Finally, spectrum 4
corresponds to the so-called Zr-free multi-
component heavy metal fluoride glasses
such as BTYbZ or BIZYT (see the previous
section for an explanation of the acronym).
In these glasses, the multiphonon edge is
governed by the T h - F or I n - F bonds, and
the corresponding atomic weights and
force constants are such that the I.R. cut-
off is in the 8 jim region, leading to glasses
having the widest optical window for sta-
ble fluoride glasses. Chung et al. (1987)
have recently measured the multiphonon
edges of single crystal specimens obtained
from the different fluoride used for glass
preparation. They also concluded that
AIF3 or LiF addition to the glass shifts the
I.R. edge to a higher frequency.
Figure 8-7, which uses data taken from
Chung et al. (1987) and from France et al.
(1987) and Takahashi (1987), provides an
indication of the wavelength dependence of

100
Figure 8-6. Infrared absorption
.BIZYT Glass edges of several fluoride glasses
compared to SiO2 glass. Spec-
z " \ trum 1 corresponds to BeF2-based
o ZBL Glass^
||SiO2 Glass\ 1 glasses, spectrum 2 to the ZrF4-
50 . \ \ \ \ based glass ZBLA stabilized by
I 3
CO
\ 1
I 2
\ V AIF3, spectrum 3 is a pure ZrF4-
z BeF2 Glass 1 ZBLA Glas based glass ZBL, and spectrum 4
corresponds to a heavy metal
Zr-free fluoride glass such as the
\ , :
1 2 3 4 5 6 7 8 9
WAVELENGTH (jim)
468 8 Halide Glasses

the absorption coefficient or loss in dB/km
for a fluorozirconate glass from the far I.R.
region (50 to 15 |im), corresponding to the
high absorption region of the stretching
vibration, to the potential ultralow loss re-
gion in the mid I.R. region (2-4 |im). The
data were obtained in the far I.R. region by
reflectivity measurements, in the 5 to
10 jim region by absorption measurements
on bulk samples, and in the 2 to 5 jim from
optical losses in fibers ranging from a few
meters to one hundred meters in length.
Figure 8-7 also shows the intrinsic mini-
mum loss expected in the 2 - 4 |im region,
which is estimated to be in the range of
10" 2 dB/km.
The Infrared Edge in Heavy Halide Glasses
As discussed before, the metal heavy
halide glasses have the general formula
MxXyKz, where M = Zn 2 + , Cd 2 + , Bi3 + ,
Th 4 + , X = Cl, Br, I, and A is a large cation
WAVELENGTH (Mm)
2 3 5 10
i i
From reflectivity spectra
108
From bulk sample ./
Y
i/Km)
playing the role of modifier (Cs + , K + ,
Rb 2 + , Pb 2 + ,...). The position of the I.R.
cut-off in such materials is associated with
the atomic weight of the two glass former
partners M and X and with the force con-
stant of the M - X bond. The character of
the bond in all these halides is typically
ionocovalent, and the bonding forces are
inversely proportional to the interatomic
distances and directly proportional to the
charge of M. Also, the bond distances
M - X are related to the sizes of M and X,
which are in turn proportional to their
atomic weight. Consequently, the two fac-
tors, weight and force constant, are evolved
in the same way, and it is not surprising to
see that the I.R. cut-off of halide glasses is
very sensitive to the nature of the halogen.
In Fig. 8-8 the multiphonon absorption
regions are shown for several metal heavy
halide glasses. ZnCl 2 glass transmits up to
13 jim (Robinson et al, 1982) but has a
multiphonon absorption region which can
be strongly affected by the presence of wa-
ter in this highly hygroscopic glass; simi-
larly, the ThCl4-based glasses (Hu and
Mackenzie, 1982), have their I.R. cut-off in
/ \
the same region. The absorption starts at
13-14 jim and is also affected by moisture
corrosion. The identical positions of the
Zn 2 + -Cl and Th 4 + -Cl vibrations can be

104
explained by the fact that the difference in
m
TJ From fiber , atomic weight between Zn and Th is com-
</) 102 pensated by a higher force constant in
CO
O
_i
Th 4 + -Cl due to the higher charge of Th 4 +
10° compared to Zn 2 + . The same remarks can
Intrinsic loss /
be made for the BiCl3 glass I.R. cut-off
10" 2
r _.j_y (Angell and Ziegler, 1981). For a thickness
i i i of about 1 mm, similar to that of the other
5000 3000 1000 chloride glasses, the I.R. absorption begins
1
WAVENUMBER(cm ) at 14jim. Examination of ZnBr2-based
Figure 8-7. Evolution of the optical loss in fluoride glass shows that the I.R. cut-off is around
glasses from the far I.R. corresponding to the one 20 jim when the material is not too cor-
phonon absorption regime to the low loss region. The
theoretical intrinsic low loss around 2.6 jam is ex- roded by moisture (Hu et al., 1983; No-
pected to be close to 10" 2 dB/km. gami et al., 1985).
 8.3 Halide Glasses as Optical Materials: Passive Properties
As expected, the iodide glasses have their
multiphonon edges in the far I.R. part of
the spectrum around 25-30 (am (Cooper
and Angell, 1983; Nasu et al., 1985). It is
interesting in Fig. 8-8 to compare the posi-
tions of the I.R. edge for the four families of
halide glasses. For samples of about 1 -
2 mm thickness, the four zones of I.R. ab-
sorption are the following: zone I, 6-8 |im
fluoride glasses; zone II, 12-14 |im for the
chloride glasses; zone III, 19-21 |um for the
bromides, and zone IV at about 30 jim for
the iodide glasses.
It must be remarked that as the vibra-
tional frequencies decrease from fluoride
glasses to iodide glasses, the thermal and
mechanical properties correspondingly de-
crease, giving soft, low Tg glasses difficult to
use in practical applications.
Analysis of the I.R. edges for the multi-
component halide glasses, whose glass
forming concept is not well understood,
shows that glassy materials such as AgCl-
Agl-CsCl and CuCl-PbCl 2 -RbCl (An-
gell et al., 1985) or AgBr-CsI-PbBr 2 (Ni-
shii et al., 1985) have their I.R. edges
slightly shifted towards longer wavelengths
compared to the other halide glasses. This
could be explained by the low charges of
Wavelength (jim)
o
25 - halide glasses in-
2500 1OOO 750
Wavenumber (cm" )
469
the different cations composing the glass. It
must be noted that, at the same time, these
glasses also have a low Tg, sometimes close
to room temperature.
The tellurium halide glasses, i.e., the TeX
glasses previously discussed, form a special
group of glasses due to the semi-metallic
nature of tellurium and also because of
their chain-like structure which is very sim-
ilar to the model proposed for glassy Se
(see Sec. 7.3.3.1). Figure 8-4 represents the
structure of the parent crystalline material
Te3Cl2 (Kniep et al., 1973), which can be
taken as a model for explaining the good
glass-forming ability of the TeX glasses. As
discussed before, the general formula of
these glasses is Te-X (S, Se). Addition of S
or Se strongly decreases the devitrification
rate. The vibrational modes limiting the
I.R. transparency are here associated with
the Te-X and Te-S or Te-Se bonds.
Examination of the I.R. cut-off for several
glass compositions shows clearly two fami-
lies of materials: the light TeX glasses con-
taining S or Cl, which limit the transmis-
sion to 13 jim and the heavy TeX glasses
free of light elements and based on Te, Se,
Br or I, with a cut-off in the 20 jim region.
Figure 8-9 represents the I.R. cut-off for
30 40
Figure 8-8. Multi-
phonon absorption
edges for several
cluding fluoride,
chloride, bromide,
and iodide glasses.
" ' 500 250
1
470 8 Halide Glasses
Wavelength(jam)
7 8 10 12
80 1-Te3l3Se4(3.1mm)
£ 2-Te3Br2Se(3.5mm)
c 60
CO
r 40
3-Te3Br2(4.2mm)
c 20
2000 1600 1200
Wavenumber(cm-I)
several members of the heavy TeX glass
group, namely Te 3 Br 2 , Te3Br2Se, and
Te 3 I 3 Se 4 .
8.3.1.3 Refractive Index of Halide Glasses
Except for fluoride glasses, which have
received particular attention during the
last ten years, the halide glasses in general
suffer from a lack of precise information on
their optical properties, especially refrac-
tive index measurements which require
samples of reasonable thickness, good op-
tical quality, and resistance to moisture
corrosion.
Special attention has been paid to the
fluoride glasses, which were considered to
be the best candidates for high-power glass
lasers (see Chap. 12). To minimize self-
focusing effects in short pulse high-power
lasers, glasses with a low non-linear refrac-
tive index n2 are necessary. As discussed by
Weber et al. (1978), the materials with high
Abbe numbers (see below) and low refrac-
tive indices n are the materials having the
lowest n2 values. Among all the glasses
examined, the BeF2-based glasses are of
special interest with a refractive index
near ft = 1.27, an Abbe number v = 100,
and a non-linear index n? = O.25xlO~ 13 .
30
Figure 8-9. Position of LR.
cut-off for three different
TeX glasses containing only
heavy atoms such as Te,
Se, and Br, or I.
800 400
For comparison, the ZrF4-based glasses
have the following values: n = 1.50, v = 70,
and n2 = 0.7xl0~ 1 3 .
Fluoride glasses have been proposed as
potential candidate materials for very low-
loss optical fibers, and two key parameters
associated with this technology are the re-
fractive index dispersion versus the wave-
length (Jeunehomme et al., 1981; Poignant,
1981) and the possibility of controlling re-
fractive index variation in order to realize
core-clad waveguides (see Chap. 15).
Several reports have been devoted to the
n versus X dependence, which has been
measured on different types of glasses such
as ZBGA (G means Gd instead of La) by
Mitachi and Miyashita (1983), ZBL by
Bendow et al. (1981 d), ZBLA, ZBL AN,
BZYT by Brown and Hutta (1985) and
Brown and Suscavage (1987) and BIZYT
by Fonteneau et al. (1987).
Figure 8-10, based on data from Mitachi
and Miyashita (1983), shows the index
of refraction versus A for two classical
glasses, ZBLA and ZBLAN. The Abbe
number is a partial dispersion defined by
v = (nd— l)/(ft F — nc) where nd, nF, and nc
denote respectively the indices at the fol-
lowing A: d = 0.589 mm, F = 0.486 mm,
and c = 0.656 mm. As an indication, the
 8.3 Halide Glasses as Optical Materials: Passive Properties
1 5 1
X
u loss due to composition and density fluctu-
Q ^ ^ " \ ^ ^ ZBLA
Z
~ 1.49
h-
o
< 1.47
DC
UJ
DC
1.45
^******^*^ ZBLAN
1.43
1 2 3 4 5
WAVELENGTH (pm)
Figure 8-10. Refractive index versus wavelength for
two fluoride glasses ZBLA and ZBLAN; in the latter,
half of the Ba 2+ content has been substituted by Na + .
values of v for ZBLA and ZBLAN reported
by Brown and Hutta (1985) are 62 and 64,
respectively.
As with the oxide glasses, the refractive
index of fluoride glasses is dependent on
the composition. As expected, the intro-
duction of heavy polarizable cations, espe-
cially those having non-symmetrical lone
pairs such as P b 2 + or Bi3 + , increases n
significantly, while light elements do the
opposite.
8.3.1.4 Origin of Scattering Losses
in Fluoride Glasses
The total intrinsic attenuation coeffi-
cient at as a function of wavelength X in an
ideal vitreous material is given by the
equation:
(5-1)
ax = A exp ( - a / 2 ) + B /T 4 + C exp {c/X)
The first term is associated with multi-
phonon absorption mechanisms, as al-
ready discussed, and is dependent on the
position of the I.R. edge. The third term,
also called the Urbach tail, is related to
absorptions due to electronic transitions
which are only important in the U.V. and
can be neglected in the mid I.R. region far
471
from the U.V. cut-off. The second term,
B / T 4 represents the Rayleigh scattering
ations on a microscopic scale. The effect of
this parameter on the potential ultratrans-
parency of fluoride glasses has recently
been examined by several authors (Tran
etal., 1982; Tsoukala etal., 1987; Saka-
gouchi and Takahashi, 1987) and the theo-
retical value of the Rayleigh factor B was
first calculated by Poignant to be around
0.4, about half of the measured value for
fused silica. Tran et al. (1982) were the first
to demonstrate that the measured light
scattering in fluoride bulk glasses was in-
deed Rayleigh in character. For all these
investigations, very low losses, typically
0.01 dB/km, in the mid I.R. region are pre-
dicted. These are much lower than those
observed in fused silica.
When a glass follows "Rayleigh behav-
ior", it is also observed that the B factor
changes according to composition and, as
demonstrated by Hattori etal. (1987), is
also very sensitive to the presence of small
submicron particles of ZrO 2? which cause a
Rayleigh scattering about two orders of
magnitude larger than that caused by ZrF 4
particles. This confirms the previous obser-
vations of Mitachi et al. (1985), who found
that the optical fibers having the highest
loss were made of glass with a higher con-
tent of oxygen. The oxygen impurities mea-
sured by activation analysis which are ob-
viously at the origin of the nucleation and
growth of ZrO 2 crystallites, which are
known to have a high lattice energy, nucle-
ate very easily from the glass matrix.
It is also observed that the general rela-
tion between scattering loss a and wave-
length X follows the relation a = BA~"4 + C,
where C is a constant indicating a source of
scattering independent of X. This type of
scatter is, for the moment, the major limita-
tion to low losses in fluoride glasses and
472 8 Halide Glasses
optical fibers. It is due to imperfections
larger than the wavelength of light, which
have been identified to be isolated crystals
such as LaF 3 , A1F3 or metallic particles (Lu
etal., 1987) or bubbles (McNamara and
McFarlane, 1987).
These sources of extrinsic scatter depend
on the glass processing and especially on
the quality of the raw materials. The major
origin of these scattering centers is poor
dissolution in the melt of a few fluoride
crystals or the contamination of the melt
by insoluble species originating from the
crucible during the heat-treatment.
8.3.2 Fluoride Glass Fibers
8.3.2.1 Introduction
The propagation of light through glass
fibers is becoming the preferred mode of
transmitting audio and visual information.
Research into optical communication sys-
tems began back in 1966 and the present
generation of optical fibers is based on
fused silica. In twenty years, the field has
developed extensively, and monomode
fibers operating at 1.3 and 1.55 |im with
losses close to 0.2 dB • km, form a substan-
tial basis for many telecommunications
systems around the world. (See Chap. 15.)
The efficiency of an optical communica-
tion system is measured as the product of
the carrying capacity, namely the number
of bits of information transmitted per sec-
ond, the length of fiber over which the
pulses injected into the fiber remain recov-
erable in terms of pulse spreading due to
dispersion, and the energy loss due to at-
tenuation.
The development of CVD techniques
around 1970 for preparing high quality
SiO2 fibers led very rapidly to optical fibers
with the minimum intrinsic loss, estimated
to be 0.16dB/km at 1.55 jam. This means
that if lower optical attenuations are
needed, it is necessary to develop new fiber
materials operating in the mid I.R. region,
as proposed independently by Pinnow
et al. (1978), Van Uitert and Wemple (1978)
and Goodman (1978) at the end of the sev-
enties.
Fluoride glasses have been widely recog-
nized as an exellent medium for ultralow
loss transmission in very long repeaterless
communication links. With a minimum in-
trinsic loss close to 0.01 dB/km which
means a factor of at least ten better than
silica, this provided sufficient motivation
for working on these systems.
8.3.2.2 The Optical Losses
in Fluoride Glass Fibers
Intrinsic Factors
For a glass of ideal optical quality and
free of all kinds of absorbing impurities, the
total intrinsic optical attenuation at for flu-
oride glasses can be expressed, as discussed
before, by the equation at = A exp (— a/A) +
BA~4, where the first term is the multi-
phonon absorption and the second the
Rayleigh scattering contribution. The Ur-
bach tail contribution in these fluorides
which have a U.V. cut-off around 0.25 jum
is negligible in the mid I.R.
The combination of those two mecha-
nisms gives the well-known V-shaped
curves shown in Fig. 8-11 for SiO2 glass
and two fluoride glasses, the fluorozir-
conate glass ZBLA and BIZYT glass.
These curves show unambiguously that the
predicted loss for fluoride glasses is in the
range of 10" 2 -10~ 3 dB/km in the optical
window between 2 and 4 |im. As discussed
before, the measured multiphonon absorp-
tion of bulk glasses and fibers is in good
agreement with the predicted values, and
one can estimate that the absorption in
the low loss region corresponding to the
six and seven phonon regime will be
 8.3 Halide Glasses as Optical Materials: Passive Properties
10
10
ffi
•o
o kaguchi and Takahashi, 1987).
LU
id 2
Rayleigh Scattering
-3
10
104
0.3 0.5 1 2 3 4 5 678
WAVELENGTH (um )
Figure 8-11. Low loss region for SiO2 glasses and two
typical fluoride glasses, a ZrF4-based ZBLA and a
InF3-based BIZYT. Intrinsic absorption mechanisms
are considered, namely band gap, multiphonon ab-
sorption, and Rayleigh scattering.
around 0.005 dB/km. Estimates for the
Rayleigh scattering coefficient B are in the
range 0.14 to 0.70 dB/km, as discussed by
different authors (Drexhage et al., 1987)
and by Day et al. (1987). Adding the scat-
tering and absorption contributions in the
above equation leads to an estimate of
0.02dB/km for the intrisic total attenua-
tion of ZBLAN fibers at the wavelength
close to 2.5 |im.
Extrinsic Factors
a) Scattering Loss
As mentioned before, is has been found
in many fluoride glasses that the extrinsic
scattering is represented by the expression
a
ext = C A2 + D. The first term corresponds
to the MIE scattering and results from im-
perfections comparable in size to the wave-
length and originating from a partial devit-
473
rification of the glasses. The second term,
which is wavelength-independent, is due to
larger defects. Kanamori (1987) suggested
that micron-sized particles, some of them
several microns in diameter, were mono-
clinic ZrO 2 ; these particles have been iden-
tified by Raman microprobe analysis (Sa-
According to Day et al. (1987), the value
of C can be decreased by improving mate-
rials and processing. Analysis of the atten-
uation in ZBLAN fibers made at BTRL
have yielded values of D in the range of 3
to 10 dB/km. These values are of course a
function of fibre length because the larger
particles which give rise to wavelength-
independent scattering are randomly dis-
tributed along the fiber.
b) Absorption Loss
The absorption losses in fluoride glasses
are due to the intrinsic factors discussed
before and due to all the parasitic ab-
sorbing impurities present in the glass.
Absorption due to the hydroxyl group
OH ~ is potentially the most significant be-
cause its absorption coefficients are large.
According to Mitachi et al. (1987), the
presence of 1 ppm of O H " introduces a
loss of 3000 to 5000 dB/km at 2.9 jam. The
observed loss values at 2.9 |im in the best
fluoride glass optical fibers lie from 20 to
100 dB/km, indicating that the OH con-
centration in these fibers is in the range of
2 to 10 ppb.
The transition metals Fe 2 + , Co 2 + , Ni 2 + ,
Cu 2 + are among the most deleterious im-
purities, because their absorption regions
extend into the 2 to 3 jim region. The rare-
earth Pr 3 + , Nd 3 + , Sm 3+ , Eu 3 + , Tb 3 + and
Dy 3 + are also among the most absorbing
species in the mid I.R. region. Detailed ab-
sorption spectra have been published by
France et al. (1968) and Ohishi et al. (1981).
474 8 Halide Glasses

By melting under oxidizing conditions a The preform approach leads necessarily to

gas such as O 2 or NF 3 , the divalent Fe 2 +
is converted into Fe 3 + which has no ab-
sorption in the near I.R. region. However,
this operation stabilizes Cu 2 + , which re-
mains the most absorbing cation in the
2.5 jim region.
Among the rare-earths, Nd 3 + can be
particularly troublesome because it has an
absorption peak at 2.55 jim, exactly in the
ultratransparency window. It is found as
the major contaminant of La 3 + in LaF3
which is one of the constituents of the glass.
It has been calculated that loss introduced
by Nd 3 + at 2.55 ^im is a = 0.22(dB/km)pb.
8.3.2.3 Fluoride Glass Fiber Preparation
Fluoride glasses are known to be prone
to devitrification, and fiber techniques pro-
duction have to take this into account in
order to avoid the formation of microcrys-
tallites which have a drastic effect on scat-
tering loss. In order to keep the light inside
the optical waveguide, when carrying the
optical signals over very long distances, the
core must have a refractive index n slightly
superior to the clad. This is achieved by
modifying the chemical composition of
both glasses; typically a small amount of
limited fiber lengths, which will require the
development of low-loss splicing tech-
niques. In order to prepare ultralong fibers,
a continuous fabrication process appears
to be very attractive. The so-called double
crucible technique, which is based on the
direct preparation of core/clad fibers from
two concentric melts, is in principle the
most promising. Since fluoride melts are
known to have very steep viscosity-tem-
perature curves, diameter control during
fiber drawing requires precise control of
the melt temperatures.
The major efforts conducted by Nippon
Telegraph Telephon (Japan), Naval Re-
search Laboratories (U.S.A.), and in
British Telecommunication Research Lab-
oratories (U.K.) have led to continual im-
provement in the absorption losses, and
values as low as 0.7 dB/km at 2.55 jim have
been obtained using traditional purifica-
tion techniques. Figure 8-12 represents
typical transmission spectra for the best
fluorozirconate glass fibers prepared in
England, Japan, and the U.S.A. The BTRL
140
1
\NTT 3

:i
PbF2 increases n, while LiF does the in- t
» N
\
_ 2+ _ 2+ _ '
•t
I
E 100
verse. As Co Cr Ni Cu Fe If
Present fluoride glass fiber technology "*• \ -/' | p r 3 ; Tb 3+ 3+ 3+

relies strongly on the preform casting ap- CO NRL>c\

Nd Sm
T I/
' w / !
proach. In this approach, core melts are 3 V '
V /
directly cast into cladding tubes to form 20 > I:
V
waveguide preforms. Fluoride glass clad- Nil •if

ding tubes with uniform wall thickness can
be obtained by rotating this mold while
casting the cladding melt. The preforms are
then drawn into fiber near the glass soften-
ing point, T=350°C, in order to avoid
crystallization. After drawing a preform of
10 mm diameter and 20 cm length, the
usual fiber diameters are about 150 jam.
0.5 1.5 2.5 3.5
WAVELENGTH (urn)
Figure 8-12. Typical transmission spectra for fluoride
glass optical fibers. The data are from three different
research groups: NTT Japan, NRL USA, BTRL UK.
Transition metals, rare-earth, and OH ~ are the most
critical absorbing impurities. Also a continuous ab-
sorbing background is due to A independent scatter-
ing.
 8.4 Fluoride Glasses: A new Host for Rare-Earth and Transition Metals
transmission curve is flat over a large
wavelength range and shows a minimum of
about 3dB/km for a 200 m fiber length.
The NRL curve is for an unspecified length
and shows a minimum of 0.9 dB/km. NTT
data correspond to the lowest value,
0.7 dB/km on a 30 m long fiber.
According to France et al. (1987) a real-
istic total loss of 0.035 dB/km could be ex-
pected if the impurity levels were main-
tained in the range 0.1 to 5 parts per
billion. Also, the extrinsic scattering loss,
which seems to be due essentially to ZrO 2
microcrystallites (Takahashi, 1987), could
be significantly decreased by lowering the
O 2 ~ impurity content. A 0.035 dB/km loss
value corresponds to a capability of re-
peaterless information transmission over a
distance of 1500 km.
Recent improvements of the surface of
the glass by etching the preform rod have
been found to increase the strength of
fibers, as described recently by Schneider
et al. (1987). (See Chapter 13.)
A key quantity in optical fiber communi-
cation is the pulse broadening associated
with the material dispersion, which is pro-
portional to d2n/dX2. The zero material
dispersion wavelength, for most of the fluo-
ride glasses, is located around 1.7 (im,
which is relatively far from the 2.6 jim ul-
tratransparency region. Fortunately, the
slope of the dispersion curve, changes
slowly compared to SiO 2 , as described by
Bendow et al. (1981a). It has been demon-
strated by France et al. (1987) and Taka-
hashi (1987) that, in using a simple step
index design, the dispersion characteristics
of the fibers can be tuned to give zero dis-
persion at a 2.55 jim operating wavelength.
Among the potential uses for fluoride
glass optical fibers, the realization of very
long repeaterless telecommunications links
(for undersea systems, for example) is the
most challenging and will need additional
475
research efforts, especially in chemical pu-
rification. At the moment, the actual level
of transparency of fluoride glass optical
fibers is such that these new waveguides
can be used in many short length devices.
For example, for remote sensing and ther-
mal imaging out to about 5 jum. Other pos-
sible commercial devices include the cou-
pling between an Er 3 + YAG laser emitting
at 2.9 jum and a fluoride glass fiber for
power delivery in surgical applications,
since water in tissues is very absorbent at
this wavelength. Gas lasers, such as HF
emitting at 2.6jiim and DF emitting at
3.8 jam, can also be used as power sources.
Low loss bulk optical components made of
fluoride glass may also be very useful for
prisms and lenses, operating in the mid
I.R., as well as for optical windows with
high damage thresholds for high energy
lasers such as HF.
8,4 Fluoride Glasses:
A new Host for Rare-Earth
and Transition Metals
8.4.1 Active Optical Properties
Active optical properties of fluoride
glasses have generated a great deal of inter-
est as well (see Chapter 12). Among the
various families described earlier in this re-
view, the ZrF4-based and other multicom-
ponent heavy-metal fluoride glasses are
certainly the most attractive materials.
Their relatively long wavelength I.R. edge,
their good stability, and their ability to eas-
ily accommodate active rare-earth ions
make these glasses preferred candidates for
laser application. Except for a few studies
dealing with the optical properties of diva-
lent europium (Shafer et al., 1979), tetra-
valent uranium (Aliaga et al., 1978), and
uranyl ions (Reisfeld et al., 1986 c), exten-
476 8 Halide Glasses
sive investigations have been carried out
on fundamental or applied spectroscopy of
trivalent rare-earth and transition metal
ions. Either bulk glasses or fibers are suit-
able for practical applications. Fibers are
of special interest because of their flexibil-
ity and compactness which allows for light
systems with good concentration of the
light and easy cooling of the medium for
laser operation. This is especially impor-
tant for glasses whose thermal conductiv-
ity is lower than that for crystals. Besides
these applications, luminescence is a reli-
able technique for analysis of optically
active impurities in fluoride glasses. Also,
fluorescence line narrowing is a useful
tool for structural investigations on heavy
metal fluoride glasses and beryllium-based
fluoride glasses.
8.4.2 Absorption Spectra of Rare-Earth
and Transition Metal Ions
8.4.2.1 Rare-Earth Ions
Absorption spectra of trivalent rare-
earth ions (R.E.) in heavy-metal fluoride
glasses are well-known (Adam and Sibley,
1985; Lucas et al., 1978; Ohishi and Taka-
hashi, 1985; Adam et al., 1987a; Alonso
et al, 1988; Perry et al, 1981; Adam et al,
1988; Ohera et al, 1988; Tanimura et al,
1984; Shinn et al, 1983; Jorgensen et al,
1982; Guery et al, 1988; Sanz et al, 1987;
Yeh et al, 1986) except for radioactive
Pm 3 + and of course Lu 3 + which is opti-
cally inactive with its completely filled 4f-
shell. A survey of all results will not be
presented here. We have arbitrarily chosen
to emphasize only the optical properties of
Nd 3 + , Ho 3 + , and Er 3 + which can be con-
sidered as being among the most interest-
ing ions with regard to their applications in
photoluminescence.
Glasses are well-known for having a
larger distribution of different sites in com-
parison with crystals (see Chaps. 4 and 6).
This results in inhomogeneous broadening
of absorption bands, each site having its
own spectrum. This can be observed in the
absorption spectrum of Nd 3 + ions (Lucas
et al, 1978) where the bands have widths at
half-maximum equal to a few hundreds of
wavenumber. Among the various lines, at-
tention is directed to the 4 F 3/2 absorption
at 867 nm. This level gives rise to strong
emissions at 1.05 and 1.35 jim, as it will be
discussed later on in this chapter. From the
spectrum, it is obvious that the 4 F 3/2 level
should be excited via more efficient pump-
ing levels such as ( 4 F 5/2 , 2 H 9/2 ) at 796 nm,
( 4 F 7/2 , 4 S 3/2 ) at 741 nm, or ( 4 G 5/2 , 2 G 7 / 2 ) at
576 nm.
The ability for an absorption band to
efficiently excite the corresponding level is
quantitatively accounted for by its oscilla-
tor strength. For Ho 3 + and Er 3 + the posi-
tions of the excited states indicate that
emission, especially I.R. emission, should
occur at quite a few levels. The 5 G 6 level
of Ho 3 + and the 4 G 1 1 / 2 level of Er 3 + ex-
hibit a high oscillator strength at 450 nm
and 378 nm, respectively. This permits effi-
cient pumping for applications in the Vis-
LR. range. In addition to the experimental
studies, oscillator strengths may be investi-
gated as a function of three phenomeno-
logical parameters Qt, with t = 2, 4, 6, us-
ing the Judd-Ofelt theory (Judd, 1962;
Ofelt, 1962). These parameters are charac-
teristic of an ion-host combination. For a
given ion, they vary slightly between fluo-
ride glasses. Reisfeld and Jorgensen (1987)
pointed out that Q2 was an indicator of the
covalent character of bonding, higher Q2
corresponding to higher covalency.
8.4.2.2 Transition Metal Ions
Like rare-earth ions, the absorption
spectra of 3d transition metals (T.M.) have
 8.4 Fluoride Glasses: A new Host for Rare-Earth and Transition Metals
been widely studied (Esnault et al., 1986;
Fonteneau et al, 1978; Ohishi et al, 1983;
Reisfeld et al, 1986a; Feuerheim et al,
1984; Suzuki et al, 1987; Poulain et al,
1987), mainly in fluorozirconate glasses. 3d
ions are very sensitive to the crystal field
strength and therefore to the local environ-
ment. This of course influences the spectro-
scopic behavior of these ions as reported in
the famous diagrams established by Ta-
nabe and Sugano (1954 a, b) for octahedral
crystal fields. Previous studies have shown
that transition metal ions could reasonably
be expected to occupy an octahedral-type
environment in fluorozirconate glasses,
with crystal fields ranging from low to
medium, even though some discrepancies
may occur. For example, Ti 3 + ions which,
under a reductive atmosphere, may be sta-
bilized in ZBLA glass by substitution for
Al 3+ ions: the absorption spectrum analy-
sis shows that Ti 3 + ions are not simply em-
bedded in pure octahedral symmetries, but
also in perturbed geometries such as mono-
capped (coordination number CN = 7) and
bicapped (CN = 8) octahedra (Esnault
etal, 1986).
The Cr 3 + ion is probably among the
most important active ions in spectros-
copy, as a local probe for microcrystalliza-
tion studies (Miniscalco et al, 1985) and as
an efficient pumping system for energy
transfer application, to Nd 3 + for instance.
The analysis of the absorption spectrum of
Cr 3 + ions in ZrF4-based glasses strongly
suggests that Cr 3 + ions are in an Oh-type
environment. The best fit to the energies
gives the crystal field and Racah parame-
ters (see Chap. 12) which are Dq =
1531cm"1 and B = 721 cm" 1 in the pres-
ent case. These values correspond to low
fields compared to crystals and can be in-
terpreted as being due to a more open lat-
tice for the glass, leading to longer T M - F
average bonds.
477
Because of its transition energies, Mn 2 +
is, like Cr 3 + , often used as a sensitizer of
rare-earth luminescence. Actually, Mn 2 +
absorption is very weak as reported by
Suzuki etal. (1987) for ZBLA glass. The
highest experimental oscillator strength for
this ion is weak compared to transitions of
Ni 2 + and Co 2 + ions, respectively. This can
be overcome by using fluoride glass hosts
with ZnF2 as a major constituent, such as
PZG glass (22mol% ZnF2) where Zn 2 +
ions are easily substituted by Mn 2 + , It has
been even experimentally shown that
BIZYT glass was more stable in the pres-
ence of MnF2 and valuable compositions
with up to 20mol% MnF2 could be ob-
tained (Le Gall, 1988).
A number of papers deals with the opti-
cal absorption of other 3d ions in heavy
metal fluoride glasses. They are V3 +
(France et al, 1986; Fonteneau et al, 1978;
Ohishi etal, 1983), Fe 2 + (France etal,
1986), Fe 3 + (Ohishi etal, 1983), Co 2 +
(France etal, 1986; Ohishi etal, 1983;
Suzuki etal, 1989; Poulain etal, 1977),
Ni 2 + (France etal, 1986; Ohishi etal,
1983; Reisfeld etal, 1986a; Suzuki etal,
1987) and Cu 2 + (France etal, 1986). In
summary, except for Cu 2 + , all ions were
found to be in octahedral-type sites with
lower crystal fields compared to crystalline
materials.
8.4.3 Fluorescence Spectra of Rare-Earth
and Transition Metal Ions
8.4.3.1 Radiative Emission
of Rare-Earth Ions
The wide range of transparency of fluo-
ride glasses makes them attractive materi-
als for infrared luminescence (see Chap.
12). Emission spectra have been reported
in various glasses for almost every rare-
earth. Many ions such as Pr 3 + (Adam and
Sibley, 1985; Eyal et al, 1985), Nd 3 + (Lu-
478 8 Halide Glasses
cas et al., 1978), Eu 3 + (Adam et al, 1987 a;
Blanzat et al., 1980; Reisfeld et al., 1983),
Gd 3 + (Alonso et al., 1988), Tb 3 + (Perry
etal., 1981), Dy 3 + (Adam et al., 1988b;
Orera et al., 1988), Ho 3 + (Tanimura et al.,
1984; Reisfeld etal., 1985), Er 3 + (Shinn
etal., 1983) and Tm 3+ (Sanz etal., 1987)
have been studied in fluorozirconate-type
glasses while only Ho 3 + (Eyal et al., 1987;
Adam etal, 1987b), Er 3 + (Eyal etal.,
1987a), Tm 3+ (Guery etal, 1988) and
Yb 3 + (Yeh et al, 1986) have been studied in
(Ba, Zn, Th, Y)-based fluoride glasses. Also
Reisfeld and coworkers (Jorgensen et al,
1982) have reported luminescence of Er 3 +
ions in (Pb, Zn, Ga)-fluoride glasses.
The first two infrared emissions of Nd 3 +
ions in fluorozirconate glass are shown in
Fig. 8-13. The 4 F 3 / 2 -» 4 I 1 1 / 2 transition is
found to peak at 1040 nm with an experi-
mental lifetime of nearly 450 JIS. In that
same figure, the optical spectrum for Nd 3 +
ions in NdZr 7 crystals is superimposed. It
is important to note that the emission
peaks for the glass are just as broad as
they are for the crystal. This suggests that
the Stark splitting of the levels involved is
io 3 cm~ 1
ANM
11. 3/2
1100
'11/2
1000
900
9/2
800
NdFG-V
Figure 8-13. Emission spectra of Nd 3 + in two parent
fluoride matrices. NdFG is a 0.5 Nd 3 + doped fluoride
glass of the ZBLA family. NdZrF7 is a crystalline
material containing Nd 3 + in a NdF8 polyhedron. The
emission bandwidth is the same in the glassy and
crystalline materials.
about the same in both materials. The
number of non-equivalent sites is certainly
small in heavy metal fluoride glasses, com-
pared to oxide glasses in general. This
arises from the specific structure of fluoride
glasses where rare-earth ions are part of
the framework and, as glass formers, are
in well-defined sites. Conversely, in oxide
glasses rare-earth ions are in modifier sites,
that is in ill-defined sites. This is confirmed
by the decay time measurements of the
emitting levels. Usually in glasses, because
of the great number of non-equivalent
sites, the decay curves are non-exponential,
each type of site having its own time con-
stant. In heavy metal fluoride glasses, the
decays can generally be fitted to nearly sin-
gle exponentials with a ratio between the
first and third e-folding times equal to 0.8-
0.9 (Lucas etal., 1978; Adam etal., 1988;
Tanimura et al., 1984; Shinn et al., 1983).
The relatively large number of isolated
levels of Ho 3 + and Er 3 + ions yields rich
emission spectra ranging from near U.V. to
mid I.R. In the visible range, the well-
known intense green emission of these two
ions ( 5 S 2 , 5 F 4 ) -> 5 I 8 for Ho 3 + and 4 S 3 / 2 ->
4
I 1 5 / 2 for Er 3 + are reported to peak at
537 and 542 nm, respectively, in fluorozir-
conate glasses. In the infrared region,
Ho 3 + ions exhibit four emissions at 1.2 jam
(5I6-5I8), 1.38 Mm ( 5 S 2 + 5 F 4 ^ % ) ,
2.04 m ( I 7 ^ I 8 ) , and 3 ^m ( 5 I 6 ^ 5 I 7 ) .
5 5
The 2.04 jim emission is of particular inter-
est as it is located in a transparent window
of the atmosphere. Even though that tran-
sition terminates on the 5 I 8 ground level,
laser action has been demonstrated in
Ho 3+ -doped fluorozirconate fibers at
room temperature (Brierley et al., 1986).
However, low-temperature absorption
measurements have shown that 5 I 8 was
made of two components in these glasses,
separated by 230 cm" 1 . Er 3 + ions exhibit
three I.R. emissions at 0.975 jam ( 4 In / 2 ->
 8.4 Fluoride Glasses: A new Host for Rare-Earth and Transition Metals
4
1.52 {im L
13/2" • I15/2), and
4
2.78 pm ( I 1 1 / 2 - e have previ-
ously reported that the minimum loss of
fluoride glass fibers could be reasonably
expected at 2.55 jim. At the moment, the
4
111/2 ->4113/2 emission of Er 3 + is the only
one available in that region, for use with
solid state lasers. That wavelength would
of course be better matched by using U 3 +
ions whose 4 I 11/2" I 9/2 transition peaks
at nearly 2.5 jim.
8.4.3.2 Non-Radiative Processes
in Rare-Earth Doped Glasses
Another important parameter for evalu-
ating the lasing potentiality of a given tran-
sition is the quantum efficiency rj:
n = WK/{W^Wu^W^) (8-2)
where WR is the radiative rate and WMJ> and
WET are the multiphonon emission and en-
ergy transfer rates, respectively. The last
two quantities correspond to non-radiative
processes and have to be as small as possi-
ble in order to have a quantum coefficient
equal to or near unity.
The multiphonon emission rate varies
exponentially according to the following
empirical law:
WMP = Ce-«*E (8-3)
where C and a are constants for a given
host and AE is the energy gap between the
emitting level and the next lower-lying
level. The evolution of WMP as a function of
AE is portrayed in Fig. 8-14 for ZrF4-based
glass (Adam and Sibley, 1985; Tanimura
et al., 1984; Shinn et al, 1983), BeF2-based
glasses (Layne and Weber, 1977), and vari-
ous oxide glasses (Yeh et al., 1987; Layne
et al., 1977; Reisfeld and Eyal, 1985). As far
as the quantum efficiency is concerned, the
superiority of fluorozirconate glass is obvi-
ous with multiphonon emission rates lower
479
by one to four orders of magnitude when
compared with other glasses. In conse-
quence, fluorescence is more intense and
occurs from a greater number of levels in
heavy-metal fluoride glasses.
This special feature is directly related to
the fundamental vibration mode of the
host. In fluorozirconate glasses, phonon
energies are as low as 500 cm" 1 , compared
to 1000 cm" 1 in silicates. For a given en-
ergy gap, a greater number of phonons is
then required, leading to lower non-radia-
tive probabilities. The WMP=f(AE) curve
for YAG crystals (Krupke, 1974) is also
shown in Fig. 8-14. It should be noted that
WMP is even lower for the ZrF4-based glass
in the 2500-5000 cm" 1 region.
Energy transfer between ions of the same
nature causes a well-known phenomenon:
1OC
H\\\
LU
<
M
*\ \ *\ \ \\\ \
en
o •ZBLA
o F-BERYLLATE
CL
H 1O
2 TELLURITE
GERMANATE
SILICATE
PHOSPHATE
YAG
\ \
10 I L
2 3 4
ENERGY GAP (1O 3 cnT 1 )
Figure 8-14. Multiphonon emission rate, namely heat
dissipation by phonon relaxation for different glass
matrices doped with rare-earth materials. The YAG
crystal is also mentioned for comparison.
480 8 Halide Glasses

fluorescence quenching. This occurs when 8.4.3.3 Multidoped Fluoride Glasses

ion-ion interactions become non-negligi-
ble, that is, when rare-earth concentration While energy transfer between ions of
is around 1 mol%, in general. However, a the same nature is usually troublesome, en-
peculiar behavior has been observed for ergy transfer between different species can
the Ho 3 + - 5 I 7 - » 5 I 8 emission at nearly be very useful in improving the pumping
2jim (Adam et al., 1987); this lifetime is efficiency of a given optical system. Sensi-
reported in Fig. 8-15 as a function of con- tized luminescence of rare-earth ions has
centration in various heavy-metal fluoride been investigated in R.E.-R.E. and T.M.-
glasses. Examination of Fig. 8-15 shows R.E systems. The transfer efficiency de-
that there is less energy transfer in BIZYT pends directly on the emission and absorp-
glass than in ZBLA and less in ZBLA than tion abilities of sensitizer and activator
in BATY glass. This is explained as being ions, respectively. The knowledge of emis-
due to a perturbation effect of Al3 + ions on sion properties of 3d ions is necessary in
Ho 3 + sites. From that same figure, it is to this case and has generated a number of
be noted that no concentration quenching studies, especially dealing with Mn 2 +
is observed until 5 mol% for Ho 3 + -doped (Feuerhelm et al., 1984; Suzuki et al., 1979;
BIZYT glass. This makes this glass a LeGall, 1988; Jorgensen et al., 1986) and
promising material for luminescence appli- Cr 3 + (LeGall, 1988) ions. The 4 T l g ^ 6 A l g
cations in the infrared (Adam et al., 1988 a). emission of Mn 2 + is observable at room
temperature in fluoride glasses, rendering
sensitization possible at that temperature.
16 The peak wavelength is very sensitive to
I 7 Level BATY Mn 2 + concentration (LeGall, 1988; Jor-
12 T=295K
gensen et al., 1986). High concentration
8 causes a red shift of the band due to a
4 change of the average local symmetry. Jor-
gensen et al. (1986) pointed out that Mn 2 +
E O
w
16 ions are mainly distributed in approxi-
ZBLA
mately octahedral sites, a non-negligible
|±j 12
part is likely embedded in 7 or even 6 (non-
H B
octahedral)-coordinated geometries. For
KH 4 =14.9ms instance, the 4 T l g -> 6 A l g emission peaks, at
-J o 568 nm in BIZYT: Mn 2 + (2 mol%) and at
602 nm in the 5%-doped glass. According
16
to these values, Mn 2 + ion is suitable for
12 BIZYT - sensitizing the 4 F 3/2 emissions of Nd 3 + .
8 M n 2 + - > N d 3 + transfer has been investi-
'=15.8ms
gated in PZG (Reisfeld et al., 1986d),
BIZYT (LeGall, 1988) and ZBLA glasses
O 2 4 6 8 10
(Jorgensen et al., 1986). The transfer effi-
CONCENTRATION (1O 2 O cm~ 3 )
ciency was found to be as high as 0.94
Figure 8-15. Lifetime of the Ho 3 + emission 5 I 7 -> 5 I 8
for PZG glass containing 24 and 2 mol%
versus concentration in three different fluoride glass
matrices: BATY is an AlF3-based glass, ZBLA is of MnF2 and NdF 3 , respectively. Energy
based on ZrF4, and BIZYT contains mainly InF 3 . transfer from Mn 2 + to Tm3 + ions has been
 8.4 Fluoride Glasses: A new Host for Rare-Earth and Transition Metals
observed in that same glass (Eyal et al,
1987 b) with a 0.95 efficiency.
In contrast to Mn 2 + , Cr 3 + ions do not
emit at room temperature because when
the 4 T 4 is excited the related vibronic levels
are thermally populated at room tempera-
ture.
R.E.-R.E. systems are of special interest
because they allow direct sensitization of
I.R. emitting levels, compared to Cr 3 + and
Mn 2 + in which the first excited states are
located in the visible range. Depending on
the purpose, combinations of Ho 3 + , Er 3 + ,
Tm3 + , and Yb 3 + ions have been studied
(Eyal et al., 1987 a; Yeh et al, 1989; Adam
et al, 1987; Rubin et al, 1987; Moine et al,
1988) as well as N d 3 + - > Y b 3 + energy
transfer (Eyal et al, 1986). As pointed out
before, the 5 I 7 -» 5 I 8 emission of H o 3 + at
2 jim is quite interesting. Efficient sensitiza-
tion of Ho 3 + could be achieved in heavy
metal fluoride glasses by the use of the ap-
propriate concentration of Er 3 + or Yb 3 +
ions. Yeh et al. recently reported energy
transfer between Er 3 + and Tm 3+ in
BIZYT-type fluoride glasses. Tm 3+ ions
act as quenching centers for the green lu-
minescence of the Er 3 + 4 S 3 / 2 -• 4Ii5/2 tran-
sition. Unfortunately, transfer from 3 H 4
(Tm 3+ ) to 4 I 9 / 2 (Er 3+ ) that could enhance
the Er 3 + - 4 I 1 1 / 2 -• 4 I 1 3 / 2 emission at nearly
2.8 jLim is not observed.
8.4.3.4 Up-Conversion or Photon Addition
in Fluoride Glasses
The conversion of infrared light to visi-
ble light has received special attention in
view of applications for I.R.-detectors and
improved visible sources. Two-photon up-
conversion processes have been demon-
strated in heavy metal fluoride glasses at
room temperature for the (Yb3 + - E r 3 + )
(Yeh etal, 1987; Quimby et al, 1987;
Quimby, 1988; Okada et al, 1988), (Yb3 + -
481
Tm 3+ ) (Yeh et al, 1988; Yeh etal, 1989)
and (Er3 + -Tm 3 + ) (Yeh et al.) systems and
also for Er 3 + ions alone (Yeh et al.; Okada
et al, 1988; Quimby, 1989). Quimby et al.
(1987) have determined the up-conversion
efficiency of infrared light ( = 1.0 |im) into
green light ( = 0.55 |im) for the (Yb3 + -
Er 3 + ) combination in (Th, Zn, Lu)-based
fluoride glasses. A very important result
is that the efficiency (lxlO~ 3 ) is found
to be of the same order of magnitude as
that for crystalline materials such as CaF2
(2.1 x 10 ~3) and four orders of magnitude
higher than that for silicate (2x 10"7) or
phosphate (6 x 10 ~8) glasses. Heavy metal
fluoride glasses appear to be a very good
compromise that holds the good optical
efficiency of crystals and easy preparation
of glasses permitting the elaboration of the
bulk of the fiber optical system.
8.4.4 Interest of Rare-Earth
Spectroscopy in Fluoride Glasses
8.4.4.1 Analysis of Impurities
by Photoluminescence
While optical properties of rare-earth
and transition metal ions are of great inter-
est with regard to laser applications, the
optical properties of these elements are un-
desirable for ultralow loss fiber communi-
cations. 3d ion and rare-earth ion analysis
can be successfully carried out by photo-
luminescence measurements (Miniscalco
and Thompson, 1986; Freitas, 1987). In
particular for rare-earth ions, the oscillator
strengths of the transitions are lower and
the absorption spectra are more compli-
cated making photoluminescence a power-
ful tool. Ohishi et al. (1986) for instance
have determined a Pr 3 + impurity content
of 25 ppb in a fluorozirconate optical fiber
by using this method, and Freitas et al.
(1988) a Nd 3 + content of 40 ppb in similar
conditions.
482 8 Halide Glasses
8.4.4.2 Crystallization
and Structure Investigations
The luminescence of local probes such as
Cr 3 + , Pr 3 + , Nd 3 + , or Eu 3 + ions is an ef-
ficient technique for crystallization and
structure investigations. Miniscalco et al.
(1985) have studied the evolution of the
Cr 3 + emission in fluorozirconate glasses as
a function of heat treatment. They found
two crystalline phases in devitrified sam-
ples: j8-BaZrF6 for samples at 375 °C and
a-BaZrF6 for higher-temperature treat-
ment (426 °C).
By use of the 1 D 2 -> 3 H 4 emission of
Pr 3 + , Ferrari et al. (1988) have shown the
presence of two micro-crystalline species
in a fluorozirconate glass sample heated
above Tg. This suggests that Pr 3 + ions are
distributed in two main families of sites in
the glass. This finding confirms the results
obtained for Eu 3 + -doped fluorozirconate
glass by fluorescence line narrowing
(F.L.N.) (Adam et al., 1987 a). The study by
F.L.N. of transitions from the 5 D 0 singlet
state clearly shows emissions from two
different types of sites. Comparison with
spectroscopic data obtained for crystals,
EuF3 (coordination number CN = 9) and
EuZrF7 (CN = 8), indicates that the two
types of sites in the glass are likely to derive
from the 8-coordinated geometry of rare-
earth sites in EuZrF 7 . Even though the
5
D 0 -> 7 F 0 transition is forbidden (J = 0 -»
-> J' = 0), one can observe it around 17 300
cm" 1 in some glasses. Its one-component
structure (initial and final states are singlet)
makes that transition very useful for struc-
tural investigations. F.L.N. experiments
again have shown that the 5 D 0 -» 7 F 0 ho-
mogeneous line width is smaller in ZBLA
glasses compared with silicate glasses
(Durville et al., 1985). This is directly re-
lated to the respective structures and is ex-
plained as being due to weaker chemical
bonds and larger interatomic distances
which induce smaller electron-lattice in-
teractions in the fluoride host.
A number of studies have been devoted
to the structure of fluoroberyllate glasses
(Brecher et al., 1978; Brecher and Risberg,
1980; Weber and Brawer, 1982). Like fluo-
rozirconates, they exhibit narrower ab-
sorption or emission lines compared to ox-
ide glasses, which means also fewer types of
non-equivalent sites. Conversely, the local
environment of rare-earth ions is found to
be a 9-fold coordinated site in fluoroberyl-
lates.
8.4.4.3 Temperature Measurements
by Optical Means
Thermalization effects in emission or ab-
sorption spectra of rare-earth ions are well-
known phenomena and have been widely
described in heavy metal fluoride glasses
(Adam and Sibley, 1985; Shinn et al., 1983;
Guery, 1988). The process for the (7F0, 7 FJ
-> 7 F 6 absorption of Eu 3 + is given by
Ohishi and Takahashi, 1986. At 4K, only
the 7 F 0 -> 7 F 6 transition occurs. When tem-
perature increases, the 1F1 level is ther-
mally populated according to Boltzmann's
distribution law and the 7 F 1 -• 7 F 6 transi-
tion shows up accordingly. Thus, the inten-
sity ratio between the two transitions is
directly related to the temperature. The
measurements accuracy can be modulated
by varying either the rare-earth concentra-
tion or the optical path length. With the
above system, accuracy of 0.5 K in the 7 7 -
150 K temperature range could be achieved.
8.4.4.4 Lasers and Fiber Lasers
The goal of most of the studies reported
above is to evaluate the potentially for
 8.5 Tellurium Halide Glasses (TeX Glasses): New Materials for Low Loss Infrared Fibers
lasers of rare-earth-doped heavy-metal flu-
oride glasses (Reisfeld et al., 1986 b). Laser
action in multimode fluorozirconate fibers
has been effectively obtained for several in-
frared transitions such as the 1.05 and
1.3 mm emissions of Nd 3 + (Brierley and
France, 1987; Brierley and Millar, 1988),
the 1.38 and 2.08 mm emissions of Ho 3 +
(Brierley et al., 1988) and the 2.71 and
1.00 mm emission of Er 3 + (Allain et al.,
1988). These results show the feasibility of
fluorozirconate fiber lasers. As already sug-
gested by the much lower threshold ob-
tained for Nd 3 + ions by Brierley and
France (1987) and Brierley et al. (1988)
compared to that of Allain et al. (1988),
further technical improvements will un-
doubtedly be achieved in that field. These
are, for instance, the optimization of rare-
earth concentrations and the reduction of
fiber core diameter taking advantage of the
optical properties of single-mode fibers.
Lasing operation for the Er 3 + -2.78mm
emission has also been reported in bulk
heavy metal fluoride glasses (Pollack et al.,
1988). From that study, it appears that
very good optical quality is a more critical
issue in bulk lasers than in fiber lasers.
Wavelength (jim)
10 5 4 3
e
o Figure 8-16. Low loss region for
2000 4000 6000
Wavenumber (cm"1)
483
8.5 Tellurium Halide Glasses
(TeX Glasses): new Materials
for Low Loss Infrared Fibers
8.5.1 Optical Characterization
As described before, the TeX glasses
have their multiphonon edge located in the
20 |im region while the band gap absorp-
tion mechanisms start around 1 jim. In
taking into account these two basic intrin-
sic factors of optical loss it can be seen from
Fig. 8-16 that the low-loss region is situ-
ated in the 8-12 jim band. The V-shaped
curve represented in Fig. 8-16 has been de-
termined for the glass Te4Se3Br3, which is
a very stable glass, versus devitrification
and moisture or water corrosion. For this
glass the lowest attenuation is around
11 jim and estimated to be close to 10 dB/
km. This family of vitreous materials is the
only class of stable glasses showing so high
a transparency in this strategic atmo-
spheric window from 8-12 \xm and at the
CO 2 laser wavelength peaking at 10.6 jim.
8.5.2 Optical Fibers Operating
Between 3 and 14 fim
Monoindex optical fibers can be pre-
pared easily from TeX glasses using either
the TeX glass Te4Se3Br3. Lowest
attenuations are expected in
8-12 Jim region.
8000
484 8 Halide Glasses
the rod or crucible method (Lucas et al.,
1989). The drawing temperature is around
130°C depending on the composition of
the glass and the diameter of the fiber usu-
ally ranges from 100 to 300 jim.
Figure 8-17 shows the optical loss curve
of a fiber having the composition Te 3 Se 4 I 3 .
11 -
Attenuation (dB/m)
n Te3Se4l3 fiber
9-
7"
5"
3-
e> 7 8 9 1 0 1 1 1 2
W a v e l e n g t h (jLim)
Figure 8-17. Transmission spectra of a TeX glass opti-
cal fiber.
The attenuation spectrum shows that the
low loss region is, as expected, in the 8 -
12|im region and that the loss is domi-
nated by X independent scattering due to
the imperfections of the fibers. Bubbles and
fluctuations in diameter are the main rea-
sons of loss and explain the difference be-
tween expected and experimental values.
Due to the extreme hygroscopicity of the
other chloride, bromide and iodide glasses,
it has never been possible to draw fibers
from those materials and TeX glasses are
the only vitreous heavy halide materials
drawn into optical fibers. These new wave-
guides are very promising materials for
carrying the CO 2 laser light to targets for
laser surgery and industrial operations
such as cutting, welding, surface treatment,
etc.
8.6 Stability of Halide Glasses
against Chemical Attack
and Devitrification
Owing to their technological interest,
only the heavy metal fluoride glasses have
been deeply investigated in respect to their
tendency to be corroded by moisture or
other chemical reagents. Also, special ef-
forts have been made in order to under-
stand the devitrification mechanisms in
these exotic glasses.
8.6.1 Chemical Durability
First it must be noted that all the chlo-
ride, bromide, and iodide glasses, except
the TeX glasses are strongly corroded by
13 moisture and that this hygroscopicity has
limited the interest in them as optical mate-
rials.
Fluoride glasses are strongly resistant to
corroding agents such as F 2 , HF, and UF6
gases. In considering their optical trans-
parency and good resistance to corrosion,
they are ideal materials for photochemical
reactors which contain these aggressive
reagents.
These materials are not hygroscopic and
can stay in the normal laboratory atmo-
sphere without any attack on the surface.
Nevertheless, the water molecule, H 2 O, re-
acts with fluoride glass and the corrosion
mechanisms depend on the temperature
and if the water is a liquid or a vapour.
When a piece of glass is immersed in
water, the corrosion kinetics depend on the
pH; under acidic conditions, the proton
H + reacts rapidly with the F~ ions of the
glass to form HF, the corresponding OH ~
takes the place of the F~ in the structure;
at the same time, the modifier cations such
as Ba 2+ or Na + diffuse into the solution.
According to Simmons and Simmons
(1986), the total mechanism leads to a dis-
 8.6 Stability of Halide Glasses against Chemical Attack and Devitrification 485

solution of the matrix with a very fast mi- 8.6.2 Devitrification of Fluoride Glasses
gration of certain species such as Li + , Na + ,
As discussed by Moynihan and co-
Al 3+ into the solution. The direct conse-
workers (Moynihan, 1987; Chrichton et al.,
quence is that the ZrF4-based glasses have
1987), one of the major problems encoun-
chemical durability in non-basic solutions
tered in the development of heavy metal
comparable to the poorest silicates. The
fluoride glass has been the tendency for the
direct result of these chemical modifica-
glasses to devitrify above the glass transi-
tions is the devitrification of the corroded
tion temperature. Also, during the cooling
surface which crystallizes and forms an
process of the melt, a critical cooling rate is
opaque film on the surface. In basic solu-
necessary to avoid nucleation (Esnault-
tions, the stability of the glass is much
Grosdemouge et al., 1985) and then growth
higher and some compositions could stay
of the crystallites (Bonsai et al., 1985).
in these conditions for a few weeks without
apparent corrosion. The main feature illustrating the special
thermal behaviour of fluoride glasses is the
The corrosion by H 2 O vapour is quite
temperature dependence of the viscosity
different (Loehr et al., 1987); depending on
which is represented in Fig. 8-18. It is clear
the composition, it usually starts just be-
that there is a large gap between the high-
low the glass temperature around 300 °C.
temperature viscosity data collected in the
The mechanism of corrosion is illustrated
melt (Hu and Mackenzie, 1983) and the
by the following reaction:
highly viscous zone just above Tg. This sit-
ME, (glass) 4- y H 2 O (vapour) -> /g_^ uation is due in part to the tendency of
-> MF,_ y OH^ (glass) + y HF (vapour) these melts to crystallize mainly because
the viscosity is only a few dPa s at tem-
This attack becomes significant when the peratures significantly below the liquidus
temperature increases and is visually easy allowing relatively high mobility of the
to detect when a fluoride glass melt is
treated in a normal atmosphere due to the
formation of white fumes. The result of this
corrosion is the presence of a strong OH T(° C)
absorption peak at 2.9 jim in the glass and 900 700 500 400 300
the potential formation of oxides playing
the role of nucleation agents according to
the reaction:
2OH O2 +H.O/' (8-5)
The practical effect of this corrosion
phenomenon leading to hydroxyl and then
oxide formation, is the risk of nucleation
and crystallization originating from the 0.001 0.0014 0.0018
surface; consequently the only way to pre-
pare good optical glasses is to operate in a Figure 8-18. Viscosity versus temperature for two dif-
dry glove box. ferent fluoride glasses ZBLA and ZBLAN. Experi-
mental points are missing in the middle of the dia-
gram due to crystallization on cooling TXC or
heating TXH.
486 8 Halide Glasses
ions for nucleation and crystallization pro-
cesses.
Figure 8-18 is a comparison of two good
technical glasses:
1) ZBLA with the composition
Zr 55 Ba 35 La 6 Al 4 and
2) ZBLAN with the composition
Zr 55 Ba 17 La 6 Al 4 Na 18 .
The second has been proven to be more
resistant to devitrification and is one of the
best candidates for fibre drawing. This in-
teresting behaviour is explained by an in-
terdiffusion barrier to crystallization due
to the competition between two crystalline
forms. Indeed, it has been noticed that a
partial substitution of the modifier cation
Ba2 + by Na + cations introduces a compe-
tition between sodium fluorozirconate and
barium fluorozirconate formation during
the crystallization process and conse-
quently delays the devitrification phenom-
ena.
This observation appears to be a kind of
illustration of the so-called "confusion
principle" and could show that one route
to finding fluoride glasses compositions
more stable against crystallization may be
to incorporate into the melt additional
components which will inhibit the first
crystalline species formation.
8.7 Preparation of Fluoride Glasses
and some Physical Properties
The interest in fluoride glasses is mainly
related to their passive or active optical
properties and in both cases the search for
materials having excellent optical quality is
essential. The preparation route then be-
comes a key factor especially when ultra
pure glass is the ultimate goal. This con-
straint is less critical for some physical in-
vestigations, such as electrical and mag-
netic properties.
8.7.1 Preparation of Fluoride Glasses
The conventional route for preparing
fluoride glasses is the melting of the start-
ing fluorides into an inert atmosphere us-
ing vitreous carbon, gold, or platinum
crucibles. The liquidus temperature for
heavy metal fluoride glasses is around 550
to 650 °C, and then heating until 800 to
950 °C is needed to obtain an homoge-
neous melt.
Another convenient way to prepare the
melt is the ammonium fluoride route using
NH 4 FHF which easily converts oxides in
fluorides. The conversion reaction takes
place at temperatures around 300 to 400 °C
and an excess of ammonium fluoride is
needed to completely transform the oxides
in a mixture of metallic ammonium fluo-
rides which are then decomposed by heat-
ing at 800 °C. This treatment eliminates the
excess of NH 4 FHF and produces a melt
which is poured in preheated brass moulds.
The glasses are then annealed at a temper-
ature close to Tg.
As mentioned before, the development
of high optical quality optics or optical fi-
bres is governed by the production of high-
purity materials where one must avoid the
presence of transition metal, rare-earth,
complex anions such as OH, SO 4 ~, P O | ~ ,
... which absorb in the optical window of
fluoride glasses.
Sublimation of volatile fluoride, such as
ZrF 4 , as well as solvent extractions are the
most common techniques used for purify-
ing the starting fluorides from the most
poisonous absorbing cations such as Fe 2 + ,
Cu 2 + , Co 2 + , Ni 2 + , Nd 3 + , Ce 3 + , Pr 3 + . It
must be noted that 1 ppm of these impuri-
ties leads to parasitic absorption in the
range of 10 to 100 dB/km and that the tol-
erated level of contamination for reaching
the ultimate transparency values will have
to be at the part per billions level.
 8.7 Preparation of Fluoride Glasses and some Physical Properties
Purification based on chemical vapour
deposition also seems to be a solution for
separating transition metals. The vapour
pressure of ZrCl 4 and ZrBr 4 is, for in-
stance, a few orders of magnitude higher
than the transition metal equivalents.
Their conversion in ZrF 4 through the va-
pour state via a fluorinating agent is an
elegant way of producing very pure start-
ing materials (Folweiller and Guenther,
1985).
The natural impurity of the fluoride ma-
terial is OH~ due to hydrolysis with HF
formation. In order to decrease the level of
OH" which introduces a large absorption
band in the middle of the optical window,
a "reactive atmosphere processing" (RAP)
technique has been developed, initially by
Robinson (1985). A gaseous atmosphere,
such as CC14, SF6, NF 3 , CS 2 used above
the melt helps the substitution of OH ~ and
O 2 ~ impurities by Cl~, S 2 ~, etc. An NF 3
atmosphere also maintains an oxidizing
situation above the melt which allows iron
impurities to be retained in the trivalent
non-infrared absorbing Fe 3 + state.
It must be noted that an O2~ impurity
in fluoride glasses has two effects: it modi-
fies the multiphonon absorption mecha-
nisms by the formation of M - O vibra-
tional modes which introduce shoulders in
the multiphonon region; depending on the
degree of contamination, O 2 ~ could con-
tribute to the formation of ZrO 2 crystallite
particles having a high lattice energy and
producing a very poor effect on the Ray-
leigh scattering factor even if the particles
are of the 0.2 jam range size (Takahashi,
1987). Using the RAP technique for de-
creasing the oxygen content in glasses is
consequently justified especially for lower-
ing the scattering loss mechanism in long-
distance repeaterless optical fiber for tele-
communication.
487
8.7.2 Magnetic Properties
of Fluoride Glasses
Fluoride glasses offer unique opportuni-
ties to study the magnetic properties of
amorphous disordered systems because
they exhibit a large range of glass composi-
tions, high atomic concentrations, and var-
ious associations of magnetic ions belong-
ing either to the 3d or 4f series. These
properties have been essentially investi-
gated by Dupas and co-workers (Dupas
et al., 1981) on many FG compositions
containing either high concentrations of
magnetic lanthanides or 3d metals such
as iron or a combination of both species.
As an example, we shall select the glass
PbMnFeF 7 belonging to the 3d metal sys-
tem PbF 2 /MnF 2 /FeF 3 and a rare-earth
rich material with the composition 20 BaF2,
30 H0F3, 45 ZnF 2 . Most of these magnetic
glasses are usually not resistant to devitrifi-
cation and need to be obtained by quench-
ing.
The magnetic susceptibility of doped flu-
oride glasses follows a Curie-Weiss law over
a wide range of temperature. These systems
exhibit very low values of the Curie-Weiss
temperature (0 ~ 100 K) and thus evidence
of antiferromagnetic interactions.
At low temperatures, a cusp occurs in
the thermal variation of the a.c. suscepti-
bility, indicating the onset of spin-glass
ordering. The spin-freezing temperature,
Tf = 10 K is remarkably high for the
glass PbFeMnF 7 which contains large
amounts of 3d 5 cations Fe 3 + and Mn 2 + ,
compared to the Ho 3+ -containing glass
where Tf ^ 1 K.
Many investigations have been con-
ducted on this type of magnetic material in
order to see the effect of metallic substitu-
tions on the properties and to clarify the
nature of the spin-glass interactions in
these insulating materials (see also Chap. 6).
488 8 Halide Glasses
8.7.3 Electrical Properties
of Fluoride Glasses
Electrical investigations on fluoride
glasses have been initiated by Ravaine
(1985). They concluded that the main fea-
tures of the electrical behaviour of this new
vitreous materials were that:
(a) as expected, they are very poor elec-
tronic conductors taking into account the
very electronegative character of the fluo-
rine atoms;
(b) the conductivity measured on many
samples and compositions is in the range
of 1 0 " 6 Q - 1 c m " 1 at200°C;
(c) the conductivity mechanism is only
due to F~ ion mobility which gives to these
glasses solid electrolyte properties and
makes them candidates for a solid-state
battery involving F2 or derivatives at one
electrode;
T(°C)
250 150 100 50
-8
1.5
Figure 8-19. Anionic F conduction in fluoride
glasses based on ZrF4 or Zr-free BTYZ glass for ex-
ample, versus temperature. For comparison the best
F conductors, such as PbSnF4 are given.
(d) the activation energy is very depen-
dent on the composition and is in the range
E = 0.66 to 0.89 eV.
Kawamoto and Nohara (1985) con-
firmed these results and Inoue and Yasui
(1987) have proposed a conductivity mech-
anism from molecular dynamics simula-
tions which shows that the dominant fac-
tor of the conduction is due to the migra-
tion of the non-bridging fluorine ions. The
fluorine mobility can be explained by the
plurality of the ZrFn polyhedra (n = 6, 7, 8)
in the glass, as discussed in the section on
structure. This situation can be compared
to the mixed valence effect in electronic
semiconductors (see Chap. 7).
Figure 8-19 shows the conductivity-tem-
perature diagram for different crystalline
and vitreous fluoride conductors. It ap-
pears that the conductivities of all fluoride
glass compositions are located in the same
order of magnitude, approximately be-
tween the very good fluorine conductors
such as PbSnF4 and the poor fluorine con-
ductors such as CaF 2 .
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9 Metallic Glasses
Robert W. Cahn

Department of Materials Science and Metallurgy, University of Cambridge,

Cambridge, U.K.

List of Symbols and Abbreviations 495

9.1 Introduction 496
9.1.1 Quenching from the Vapor 496
9.1.2 The Origins of Quenching from the Liquid State 497
9.1.3 Treatment of Metallic Glasses in the Series 498
9.2 Methods of Making Metallic Glasses and Amorphous Alloys 499
9.2.1 Melt-Quenching 499
9.2.2 Vapor-Quenching 500
9.2.3 Electrolytic Deposition 501
9.2.4 Ion Implantation and Ion Mixing 502
9.2.5 Amorphization by Irradiation 502
9.2.6 Amorphization by Interdiffusion and Reaction 503
9.2.7 Mechanically Aided or Induced Amorphization 506
9.2.8 Amorphization at High Pressure 507
9.2.9 Composition Ranges of Glass Formation and Glass Structures
for Different Preparation Techniques 507
9.3 Amorphizable Alloy Systems 508
9.3.1 Favorable Combinations of Metals 508
9.3.2 Composition Ranges for Glass Formation 510
9.3.3 Criteria for Glass Formation 510
9.3.4 The Special Case of Silicon 517
9.4 Diffusion, Relaxation and Crystallization 518
9.4.1 Diffusion 518
9.4.2 Relaxation 521
9.4.3 Thermal Embrittlement 526
9.4.4 Relaxation of Magnetic and Elastic Properties 528
9.4.5 Crystallization 530
9.5 Chemical Properties 535
9.5.1 Corrosion Resistance 535
9.5.2 Heterogeneous Catalysis and Electrocatalysis 536
9.6 Applications 536
9.6.1 Magnetic Applications 537
9.6.2 Brazing Foils 538
9.6.3 Mechanical Properties 539
9.6.4 Chemical Properties 540

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
494 9 Metallic Glasses

9.6.5 Diffusion Barriers 542

9.6.6 Metallic Precursors for Devitrification 542
9.7 Acknowledgement 543
9.8 References 543
 List of Symbols and Abbreviations 495

List of Symbols and Abbreviations

B magnetic flux density
b characteristic distance
c#m minimum solute concentration of element B
D diffusion constant
E Young's modulus
G(r) total reduced atomic pair radial distribution
H magnetic field strength
HLY large-atom hole-formation enthalpy
Hsy small-atom hole-formation enthalpy
KP first peak of the X-ray scattering curve
k Boltzmann constant
kF fc-vector of the Fermi energy
Rc critical quenching rate
r interatomic distance
T temperature
To temperature at which two phases of identical composition have equal free
energies
TBD ductile-to-brittle transition temperature
Tf thermodynamic freezing temperature
Tg glass transition temperature
7^° ideal freezing temperature
Ts limiting glass transition temperature from entropy crisis models
Tx, Tcryst crystallization temperature
7^ limiting glass transition temperature from free volume models
t time
vA, vB atomic volumes
g strain rate
rj viscosity
a stress
CALPHAD calculation of phase diagrams
CSRO chemical short-range order
DSC differential scanning calorimeter or calorimetry
GFA glass forming ability
SRO short-range order
SSAR solid-state amorphization reaction
TEM transmission electron microscopy
TSRO topological short-range order
496 9 Metallic Glasses
9.1 Introduction
A solid alloy with a liquid-like atomic
arrangement is called a metallic glass, or
alternatively an amorphous (metallic) al-
loy. A glass is, strictly speaking, a liquid
which has been cooled into a state of rigid-
ity without crystallizing, while a material
with a similar structure made by some pro-
cess other than cooling is properly called
"amorphous" rather than "glassy". This
fine distinction, which is not always ob-
served, will be retained here. Very few pure
metals can be made amorphous, so the use
of the word "alloy" is mostly appropriate
in this context. Unlike the production of,
say, an oxide glass, which can be accom-
plished by very slow cooling of a siliceous
melt, the making of a metallic glass by sim-
ple cooling requires very rapid quenching
of an alloy melt: with two known excep-
tions, a minimum cooling rate of about
103 K~ x is required, and minimum rates of
104 to 106 K " 1 are common (see Chap. 2).
9.1.1 Quenching from the Vapor
The earliest observations of amorphous
alloys did not involve starting with a liquid
alloy, but were made by physicists who
used thermal evaporation to prepare metal
films intended for the study of supercon-
ducting properties. The condensation of a
metallic vapor on a cold substrate is func-
tionally equivalent to an ultrarapid quench
from the melt. In the 1930s, a German
physicist, Kramer (1934, 1937) claimed to
have generated amorphous Sb by this ap-
proach; he was one of the early users of
electron diffraction in support of this re-
search. Much later, Buckel and Hilsch in
Gottingen evaporated metals such as Bi,
Ga and Sn and Sn-Cu alloys on to sub-
strates held at 4 K (because they were pre-
paring their films for superconductivity
measurements). Their papers (Buckel,
1954; Buckel and Hilsch, 1952,1954,1956)
have become classics. They believed, from
electron diffraction findings, that their
films were ultrafine-grained, and they also
found that the normal, very slight solubil-
ity of Cu in Sn could be extended beyond
20 at.%, and that of Bi in Sn to 45 at.%. A
little later, it had become clear that several
of the films originally believed to be ultra-
fine-grained were in fact amorphous: this
was true of Bi, Ga and Sn-Cu.
Buckel and Hilsch had thus discovered,
before the first researches on rapid quench-
ing from the melt were performed, two of
the key features of rapid quenching: the
extension of solid solubility and vitrifica-
tion. Curiously, there is still today dis-
agreement whether the Bi films made by
Buckel and Hilsch's method were truly
amorphous or only microcrystalline. Thus
Comberg et al. (1975) claimed, on the basis
of Hall effect measurements in particular,
that vapor-quenched bismuth is in fact mi-
crocrystalline, and the issue was further
discussed in a review, by Bergmann (1976),
of amorphous superconductivity. Berg-
mann also describes experiments which
showed that other metals besides Sn, in-
cluding Pb, In and Tl, could be forced into
the amorphous state by co-depositing
them with 10-20 at.% of a second compo-
nent. Ge (Haug et al., 1975) and Sb (Muller
et al., 1975) were made amorphous only by
coevaporating them with a high concentra-
tion of solute (e.g., 50 at.% Au); this sug-
gests that Kramer's prewar claim to have
amorphized pure Sb should be regarded as
suspect. - The special case of amorphous Si
will be discussed later in this chapter.
The continuing debate between those
who believe that Bi films made by the
Buckel method are amorphous and those
who regard them as microcrystalline is an
echo of a long-standing disagreement of

this kind, most vigorous in the 1970s, con-
cerning a number of supposed metallic
glasses. A good discussion of this type is to
be found in a paper by Dixmier and
Guinier (1970): these authors examined
two alloys, P t - C and N i - P , the former
made by evaporation, the latter by electrol-
ysis. Examination of the X-ray scattering
pattern proved to be an uncertain basis for
deciding between the amorphous and mi-
crocrystalline options, but Dixmier and
Guinier discovered that the two alloys be-
haved quite differently on annealing. In
Pt-C, the scale of the structure gradually
coarsened, with a progressive sharpening
of the diffraction lines, whereas in N i - P ,
diffraction lines due to Ni and Ni 3 P ap-
peared and gradually strengthened while
the pattern due to the N i - P itself remained
unaltered. - This, they held, implied that
the P t - C was microcrystalline and under-
went progressive grain growth, a quasi-ho-
mogeneous process (see Vol. 15, Chap. 9)
whereas the N i - P t was truly amorphous
and crystalline phases were nucleated from
it and grew heterogeneously. - A technique
has however now been perfected which
should obviate arguments as to the amor-
phousness/microcrystallinity of any spe-
cific phase. Chen and Spaepen (1988,1991)
have used a scanning differential calorime-
ter (see Vol. 2, Chap. 4) in isothermal mode,
to establish the form of the heat release of
the contentious alloy: the "fingerprint" of
the heat release of an alloy undergoing
normal (i.e., uniform) grain growth is quite
different from that of an alloy undergoing
nucleation and growth of one or more
crystalline phases from a true glass.
9.1.2 The Origins of Quenching
from the Liquid State
Pol Duwez, a highly original metallur-
gist at the California Institute of Technol-
9.1 Introduction 497
ogy, is universally regarded as the father of
rapid quenching from the liquid state. He
was not the first to use such methods, but
earlier innovators were interested only in
using rapid quenching as a production
method for cheaply making the relevant
shapes, whereas Duwez explicitly investi-
gated the metallurgical consequences of
rapid quenching from the melt, that is, he
was using the technique from a researcher's
viewpoint while his predecessors were see-
ing it from a production engineer's view-
point. - The various experimental tech-
niques of rapid quenching from the melt,
alias rapid solidification processing, are
fully explained in Vol. 15, Chap. 2, and will
not be further described here. - In his own
account of his early researches in the field,
Duwez (1967 a, b) describes his concern to
resolve the paradox of the failure of the
Ag-Cu system to generate a continuous
series of solid solutions while the Ag-Au
and Cu-Au systems did have such a series.
He wrote later that "the possibility of re-
moving this rather exceptional case from
the list of binary alloys which did not fol-
low the Hume-Rothery criteria was the
main incentive for finding an experimental
technique capable of achieving extreme
rates of cooling from the liquid state". He
concluded that quenching from the melt
might force concentrated Ag-Cu alloys
into a state of solid solution which was
only just unfavorable from a free-energy
viewpoint, if it were done fast enough, and
he understood the quenching process well
enough from his earlier attempts to accel-
erate cooling in the solid state (Duwez,
1951) to recognize the need to bring a thin
layer of liquid rapidly into contact with a
cold solid chill-block: thus the Duwez gun,
a device for atomizing a metallic melt and
impelling the small droplets against a cop-
per sheet, was born; at about the same time
Duwez also developed the piston-and-
498 9 Metallic Glasses
anvil apparatus. Duwez and his colleagues
used this new equipment to show that
melt-quenched Cu-Ag alloys did indeed
form a seamless series of solid solutions
(Duwez et al., 1960). It would be difficult to
find a clearer example of the truth that the
exercise of curiosity concerning fundamen-
tal scientific issues can launch an experi-
mental programme leading to momentous
technological consequences.
Very soon after the first publication just
cited, the same group of investigators de-
cided to look for the formation of a metal-
lic glass in a melt-quenched alloy and
promptly found it in the Au-Si system
(Klement et al., 1960). Thereupon Cohen
and Turnbull, who happened to be sharing
the same room at the Cavendish Labora-
tory at the time, wrote a key paper (Turn-
bull and Cohen, 1961) in which they sug-
gested that the ready formation of a metal-
lic glass in the Au-Si system near 25 at.%
Si was connected with the existence of a
deep eutectic in equilibrium near this com-
position: this gave the melt the opportu-
nity to cool stably to a temperature at
which its viscosity had become quite high
and therefore diffusion in the melt had be-
come sluggish. This immediately provided
a logical basis for finding other glass-form-
ing systems, and led, inter alia, to the dis-
covery of the important glass in the Pd-Si
system (Duwez et al., 1965) on which much
of the early systematic work on metallic
glass properties was done. Duwez began
this process by examining the Pd-Si glass
by transmission electron microscopy and
studying its crystallization in situ. - Turn-
bull has analyzed the many stages in the
recognition and characterization of the
metallic glass state (Turnbull, 1985).
9.1.3 Treatment of Metallic Glasses
in the Series
Different aspects of metallic glasses are
treated in several Volumes of the Series.
The structure of both molten and amor-
phous binary alloys is treated in Vol. 1,
Chap. 4, together with a discussion of the
requisite instrumental methods, including
not only wide-angle X-ray diffraction but
also small-angle X-ray scattering and X-
ray absorption methods. A more extensive
treatment of models of glass structure and
the problems encountered in deriving such
models from diffraction and spectroscopic
data is to be found in Vol. 9, Chap. 4; this
treatment covers all kinds of glasses, in-
cluding metallic ones. Physical properties
of metallic glasses (as well as metallic
melts), including particularly magnetic and
electrical properties, are treated in Vol. 3,
Chap. 9. A chapter on the deformation and
fracture of glassy materials in Vol. 6,
Chap. 11 includes some discussion of de-
formation and fracture mechanisms in
metallic glasses. The formation of amor-
phous alloys by ion implantation and ion-
mixing is treated in Vol. 15, Chap. 6.
Because of this varied coverage, and to
avoid needless duplication, the remainder
of this chapter will be restricted essentially
to the following topics: (1) Methods of
making metallic glasses and amorphous al-
loys; (2) the systematics of the alloy sys-
tems and composition ranges in which it
has been possible to make such materials,
and, more generally, criteria for glass for-
mation in alloy systems; (3) diffusion and
crystallization in metallic glasses; (4) struc-
tural relaxation of metallic glasses and its
consequences for properties, including em-
brittlement; (5) corrosion resistance and
catalytic activity of metallic glasses; and (6)
applications.
 9.2 Methods of Making Metallic Glasses and Amorphous Alloys
9.2 Methods of Making Metallic
Glasses and Amorphous Alloys
9.2.1 Melt-Quenching
The various methods currently used for
rapidly abstracting heat from thin sections
of molten alloys are fully described in
Vol.15, Chap. 2. (See also this Volume,
Chap. 2.) They include melt-spinning (in
which a jet of melt is projected against a
spinning polished copper wheel), to make
narrow ribbons; planar flow-casting, in
which a slit through which the melt flows
is held within a fraction of a millimeter of
the surface of the copper wheel, to make
wide sheet up to about 25 cm in width;
melt extraction, itself available in several
variants, in which a sharp-edged wheel
barely touches a molten surface and ex-
tracts a ribbon of D-shaped cross-section
from it; the piston-and-anvil method, in
which a free-falling melt droplet is caught
between rapidly colliding metal plates to
make a disc; free jet melt-extrusion, in
which a jet is spun under conditions which
discourage break-up into discrete droplets,
so that the wire cools freely in contact with
the surrounding cold gas; the twin-roller
technique, in which a flat melt-jet is
pinched between counter-rotating rollers;
the in-rotating-water spinnning process, in
which a fine jet of melt is injected into a
rotating annulus of water, to make an
amorphous wire; laser treatment, in which
a laser beam focused to a small area is
traversed across a solid surface so as to
melt it in a transient fashion, the underly-
ing solid acting as a chill-block, or else
nanosecond or picosecond pulses are ap-
plied to a spot on a stationary substrate
(see also Vol. 15, Chap. 3); atomization, in
which an alloy melt jet is broken up by a
cold, transverse liquid or gaseous jet into
alloy droplets which solidify by depositing
499
their heat in the atomizing fluid, to make a
melt-quenched powder; the Taylor wire
method, which creates a fine alloy wire en-
capsulated in an oxide glass sleeve through
which heat is abstracted; and several other
methods such as spark erosion which are
curiosities rather than mainline tech-
niques. Four of the mainline methods are
shown schematically in Fig. 9-1.
In all these methods, the melt is given a
geometrical shape in which one or more
dimensions are small, so that heat can be
removed fast. In melt-spinning or planar
flow-casting, ribbon or sheet thickness is
typically in the range 20-50 jam, wires
made by the in-rotating-water method are
typically 50-100 jim in diameter, powders
have a size distribution typically 20-100 jam
diameter. The cooling rate in these various
methods varies with the dimensions of the
melt and the experimental variables such
as wheel speed or piston-and-anvil speed,
and it also varies as the sample cools, being
fastest when the sample is hottest. The
common practice of citing a single figure
for the cooling rate during a melt-quench-
ing operation thus has little physical mean-
ing without further information. - Fig.
9-2a shows a series of measurements on
free-falling drops of pure molten iron,
quenched in an electromagnetically oper-
ated piston-and-anvil apparatus; the tem-
perature versus time plots were obtained
by means of microthermocouples built into
the anvil (Duflos and Cantor, 1982). It is
clear that cooling rates decline greatly dur-
ing the solid-state phase of cooling. - Can-
tor subsequently used ingenious pyromet-
ric methods to map the cooling-rate
history of glass ribbons during melt-spin-
ning (Fig. 9.2 b) (Hayzelden et al., 1983;
Gillen and Cantor, 1985); it is to be noted
that none of the methods for estimating
cooling rates which depend upon measure-
ment of microstructural features such as
500 9 Metallic Glasses

LEVITATION COIL
MELT
PRESSURE
/INDUCTION
/ COIL
OPTICAL MELT
SENSOR DROPLET

SUBSTRATE PISTONS
(a) (b)

PRESSURE MELT
FEED

INGOT ROD
INDUCTION
COIL
MELT DROPLET

\ RIBBON
SUBSTRATE WHEEL

(c) (d)
Figure 9-1. Principal methods of quenching alloys from the melt: (a) Drop-smasher or piston-and-anvil method,
(b) Melt-spinning, (c) Pendant-drop melt extraction, (d) Twin-roller quenching device.

dendrite arm spacing (Vol. 15, Chap. 2) can 9.2.2 Vapor-Quenching

be used with metallic glasses. With regard
to atomization as used to make powders,
only computational methods are available
for assessing cooling rates.
Systematic studies (Clemens et al., 1987)
have shown that metallic multilayer films
(here Ni and Zr) can be converted to glass
by microsecond current pulses which take
the film above the glass transition tempera-
ture but not above the melting-point of the
constituent metals; the effective quenching
rate is I O ^ I O ^ S " 1 .
The early work of Buckel and Hilsch on
vapor-quenching of a number of metals
and alloys has, rather surprisingly, not
had a great deal of follow-up. Dahlgren
(1983) has reported on the method of high-
rate vapor-quenching, based on sputtering
rather than thermal evaporation (Vol. 15,
Chaps. 7, 8), to make glassy objects of
substantial thickness. Others (Bickerdike
etal., 1986; Gardiner and McConnell,
1987) developed high-rate thermal evapo-
 9.2 Methods of Making Metallic Glasses and Amorphous Alloys 501

107
ration methods on to cold substrates to
make objects up to ingot size, but these
techniques appear to have been used only
to manufacture crystalline, not amorphous
7in 106 alloys. Dahlgren's approach appears to be
c too expensive to have found large scale ap-
plication, but vapor-quenching has been
used in connection with electronic and
E io 5 magnetic amorphous films, as will be seen
c below.
"o
o 900 V A A
o 750 V • D
500 V • o 9.2.3 Electrolytic Deposition
0.5g 1g
Many years ago (Brenner et al., 1950) it
was discovered that N i - P alloys, contain-
500 1000 1500
ing more than about 10at.%P, can be
(a) Temperature, T in K
electrodeposited in amorphous form to
give an ultrahard surface coating. Much
further research has been done on this fam-
ily of electrodeposits (see Brenner, 1963),
more recently in relation to electroplating
1600 variables such as steady or pulsed current
(Lashmore and Weinroth, 1982). Indeed, it
seems that N i - P amorphous layers elec-
trodeposited by steady and pulsed currents
are structurally distinct (Lashmore et al.,
1982). Electrodeposition allows good con-
trol of glass production.
Some account of this method will be
found in Vol. 15, Chap. 11, including the
generation of amorphous alloy multilayers
by electrodeposition. Not much search for
other amorphous alloys that can be made
by electrodeposition has been reported,
though apparently C o - W - B is one other
candidate. Also, it has been established
that bright amorphous chromium of very
1200 high hardness can be electrodeposited

(b) t in ms

Figure 9-2. (a) Data from many cooling curves ob-
tained from a microthermocouple built into the anvil
of a piston-and-anvil quenching apparatus, during
drop-smashing of pure iron. The voltages are acceler-
ating voltages: higher values imply faster quenching.
Larger specimens had greater superheat. (After Du-
flos and Cantor, 1982.) - (b) Cooling Curves for Ni-
5 wt.% Al ribbons melt-spun on a copper wheel, us-
ing temperature-calibrated color photography, at a
superheat of 200 K, ejection pressure of 42 kPa, and
circumferential wheel speeds of 12 (A), 24(B) and
36 (•) m s" 1 . (After Gillen and Cantor, 1985.)
502 9 Metallic Glasses
from a chromic acid solution with addi-
tives (e.g., formic acid or iron) (Hoshino
et al., 1986; Tsai and Wu, 1990).
It is also possible to deposit a few glasses
by electroless deposition, and this method
has been particularly used to produce
glasses for magnetic investigations, N i - P
in particular (Dietz, 1977). Recently, it has
been shown that certain organic materials,
for instance polyacetylene, can be used as
catalysts to aid the deposition of glasses
such as N i - C o - B and N i - C o - P (Kam-
rava and Soderholm, 1990).
9.2.4 Ion Implantation and Ion Mixing
A number of amorphous phases have
been prepared by implanting high-energy
solute ions into metallic surfaces, or by
mixing successively vapor-deposited layers
of different elements by means of the ther-
mal energy of injected rare-gas ions. The
most thoroughly researched such phase is
the wear-resistant amorphous layer ob-
tained by injecting Ti and C into a Fe sur-
face. This, and other instances, are dis-
cussed in detail in Vol. 15, Chap. 6, Sec. 3.4.
9.2.5 Amorphization by Irradiation
A number of intermetallic compounds
have been amorphized by irradiation with
high-energy electrons, heavy ions such as
Ni + or fission fragments. This was first dis-
covered when the compound U 6 Fe was
bombarded with fission fragments (Bloch,
1962); much research was then done with
more familiar compounds, notably NiTi,
Zr3Al and the nickel aluminides. The last
of these remained crystalline, whichever ir-
radiation projectiles were used, while the
first two are instances of compounds which
became amorphous, the former with elec-
trons, the latter only with heavy ions. Pri-
mary solid solutions can never be amor-
phized by this approach.
There has been much dispute over the
criteria which determine the ability to
amorphize such compounds. The principal
earlier overview was by Russell (1985):
low temperature, high doses and high
dose rates were generally found necessary.
There is still some disagreement about the
principal criterion, viz., that compounds
with a narrow or vanishing homogeneity
range amorphize most readily; the diffi-
culty is that for many intermetallic com-
pounds, the homogeneity range is not
known with precision. This criterion may
well prove to be generally valid: since irra-
diation knocks a proportion of atoms off
their proper crystal sites, wrong atom pairs
are generated, and compounds with a nar-
row homogeneity range necessarily have
free energies which rise very steeply with
departure from stoichiometry such com-
pounds therefore rapidly gain free energy
as they are irradiated, which would favor
amorphization. Such compounds also nec-
essarily have high ordering energies, which
by implication therefore is one of the cri-
teria for amorphizability by irradiation.
Luzzi and Meshii (1986) propose as one
criterion that an amorphizable compound
is ordered up to its melting-point; again,
this is another way of saying that its order-
ing energy is high. They also suggest that
compounds with constituents separated by
more than two groups in the periodic table
and those with a relatively complex struc-
ture are favored for amorphization. None
of these criteria, in the light of later evi-
dence, appears to be watertight ... except
possibly the one calling for a high ordering
energy.
More recently, Luzzi and Meshii (1988),
concentrating on 2 MeV electron irradia-
tion, have accumulated evidence that de-
struction, not necessarily complete, of long-
range crystallographic order (i.e., of the
superlattice) is a precondition of amor-
 9.2 Methods of Making Metallic Glasses and Amorphous Alloys
phization by irradiation. Others interpret
such disordering as implying a mechanical
destabilization of the lattice, such as has
been proposed by some as a precondition
of melting also. The evidence for this is well
assembled by Okamoto et al. (1988), who
examined Zr3Al. It is not quite clear at
present whether the crucial feature is disor-
dering per se, or the lattice expansion
which accompanies it, but the most recent
analysis prefers the second alternative. - A
recent, illuminating comparison of melting
with amorphization in the solid state,
which includes irradiation as one variant
(Wolf etal, 1990), makes the point that
there are two forms of melting, and two of
amorphization: one involves heteroge-
neous nucleation at interfaces or defects,
one is homogeneous. Wolf et al. conclude
that the destruction of a superlattice
"merely drives the crystal to a critical com-
bination of volume and temperature at
which the amorphous phase can form het-
erogeneously or homogeneously". These
fundamental issues have also been ana-
lyzed by Fecht and Johnson (1990). - In
this connection, it has been suggested
(Vepfek etal., 1982) that a microcrystal-
line-to-amorphous transition in silicon is
driven by lattice expansion.
9.2.6 Amorphization by Interdiffusion
and Reaction
An extraordinary phenomenon was dis-
covered by Schwarz and Johnson in 1983 -
the formation of an amorphous alloy by
the interdiffusion of two pure polycrys-
talline metals. They deposited successive
thin films of Au and La, 10-50 nm in
thickness, in a multilayer configuration,
and annealed the multilayers at a low tem-
perature (50-100°C). The final composi-
tion of the mixed phase was controlled by
adjusting the relative thickness of the two
503
films. This study followed an earlier, acci-
dental discovery of a related phenomenon:
the compound Zr 3 Rh, in a metastable
crystalline form, could be amorphized by
reacting it with hydrogen to form a
metastable amorphous hydride (Yeh et al.,
1983). The very fast diffusion of hydrogen
was thought to be a crucial aspect of this
process, named a solid-state amorphization
reaction (SSAR). For the second study, the
somewhat exotic combination of La and
Au was chosen because Au was known to
be a "fast diffuser" in crystalline La (in the
technical sense that Au diffusion in La is
many orders of magnitude faster than self-
diffusion in La), and it was assumed that a
similar disparity in diffusion rates would
extend into the amorphous phase, if one
was formed. (A discussion of fast diffusion
can be found in Warburton and Turnbull,
1975).
The 1983 discovery that a compound
(Zr3Rh) could be amorphized by hydro-
gen absorption has now been generalized
(Aoki et al., 1991). 'Hydrogen-induced
amorphization' has been found to be possi-
ble in many binary metal compounds of
which one constituent is a hydride former.
Examples include R2A1, R3In, R 3 Ga, RFe 2
(where R is a rare-earth metal), Zr3Al, and
others.
The apparent thermodynamic paradox
that two stable phases can generate a
metastable phase was dealt with by means
of two hypotheses: (a) The amorphous
phase has a lower free energy than the ini-
tial mixture of elements; this arises from
entropy terms, due to the fact that the
amorphous phase has a large negative heat
of mixing, whereas the crystalline elements
have a large positive heat of mixing, (b)
There are indeed intermetallic crystalline
compounds with a still lower free energy
than the amorphous phase, but they can-
not form because one constituent diffuses
504 9 Metallic Glasses
(relatively) very sluggishly, and apparently
both constituents must diffuse reasonably
fast if crystalline nuclei of an intermetallic
phase are to form. The intermetallic phase
cannot be prevented from nucleating if the
annealing temperature is chosen too high.
The essentials of the situation are shown in
Fig. 9-3.
In the seven years since this discovery, a
very great deal of research has been done
on the SSAR and hundreds of papers pub-
lished. Reviews (Johnson et al., 1985; John-
son, 1986) and a conference devoted to
SSAR (including amorphization by irradi-
ation, which is now generally included in
the SSAR designation) (Schwarz and John-
son, 1988) have marked this burgeoning of
E
o
-90
L r=373K
"a - u ' •#
i
\ the experimental obstacles by using a
S -ioo
Au + \ Am+
c Am La
<D
-110 -
V /
-120 --
0 0.2
\/ i i
0.6
1
0.8
Au
Figure 9-3. Gibbs free energy vs composition for a
mixture of crystalline Au and La (dotted line) and for
amorphous A% _xLax alloy. The approximate free en-
ergy curve for the amorphous phase was estimated
from Miedema's predictions for liquid Au-La alloys.
The tangents predicting two-phase regions were
drawn on the assumption of zero intersolubility of Au
and La. A wholly amorphous reaction product was
found only in the central concentration range, as pre-
dicted. (After Schwarz and Johnson, 1983.)
research. A recent review which places the
SSAR (including also the mechanical
methods to be discussed in the next Sec-
tion) in relation to more conventional
quenching methods, has been published by
Schwarz (1988), while another (Greer,
1990) discusses in depth the quite complex
thermodynamics of amorphization by in-
terdiffusion. A number of interesting issues
have been raised in very recent work, but
there is space here only for a few of them to
be briefly treated.
Only recently has the postulated large
disparity in diffusivities between the two
constituent metals in a system capable of
SSAR been experimentally confirmed. The
determination of the slower of the two dif-
fusivities is an exceedingly difficult experi-
mental problem, discussed further in Sec.
9.4.1, below. Greer et al. (1990) performed
the measurement for the Ni-Zr system, on
which much of the recent research on
SSAR has been performed. They overcame
method in which the interdiffusion of Zr
and Hf (an element closely similar to Zr) in
a multilayer consisting of a-Ni 65 Zr 35 and
/) a-Ni65Hf35 was measured by X-ray diffrac-
// tion from the multilayer at various stages
of anneal. The outcome was that, at 573 K,
the diffusivity of Zr in the amorphous solid
solution was ^ 1 0 6 times smaller than the
1.0
diffusivity of Ni - a very large factor of
disparity indeed. The disparity is attrib-
uted to the large size difference of the Zr
La and Ni atoms; this aspect is further dis-
cussed in Sec. 9.4.1. - One consequence of
very fast diffusion of one constituent in an
amorphous layer which has sometimes
been observed is the formation of voids in
the layer, e.g., in the Al-Pt system where
Al is the fast diffuser (Legresy et al., 1988).
Another issue is the nucleation of the
amorphous phase at the start of the SSAR.
Schroder et al. (1985) established that grain
 9.2 Methods of Making Metallic Glasses and Amorphous Alloys 505

boundaries in the polycrystalline Zr films 20

played a part in nucleating the amorphous in (c) (d)
(e) (f)
layer. The fact that such layers do indeed I 15 - \ i

have to be heterogeneously nucleated was

i

4- —H
c (g)
0 -r-
made very clear by a subsequent experi- O

ment by Vredenburg et al. (1986). They at- a 10 -

tempted to grow amorphous films in a bi- J ~ Ni
Ni

Dstra
0)

225 A
211 A
\
layer consisting of polycrystalline Ni
deposited on a Zr single crystal, and found (b) D
CO Zr
this to be impossible. Only if the interface (a) Zr

was first disturbed by mixing it with a 1 1 1 i

0 200 400 600

bombardment of high-energy Xe + ions
could the SSAR get started. - The more
general issue of the "nucleation of disor-
der" in SSAR, melting and destruction of
atomic long-range order, as posed by ob-
servations such as that just described, has
been discussed by Cahn and Johnson
(1986), and brought up to date in a stimu-
lating thermodynamic approach by Wolf
etal. (1990).
The kinetics of growth of amorphous
layers during diffusive SSAR has been de-
duced from continuous measurements of
electrical resistivity of the multilayers dur-
ing the reaction. Schroder and Samwer
(1988) have done this with Co-Zr multi-
layers under isothermal conditions, while
Rubin and Schwarz (1989) have made mea-
surements for Ni-Zr under continuous
heating (Fig. 9-4). By means of a simple
model that relates resistivity change to
amorphous layer thickness, Rubin and
Schwarz were able to estimate the effective
diffusivity of Ni in a-Ni5OZr5O. (Their find-
ings are further discussed in Sec. 9.4.1).
Schroder and Samwer found that at long
times, the isothermal growth in thickness
of the amorphous layer tends towards a
yft law, expected for an interface-limited
reaction. This law has also been estab-
lished by direct microscopic examination
(Johnson et al., 1985).
It has been repeatedly observed that if
the individual layers in a reacting multi-
Temperature, T in °C
Figure 9-4. Electrical resistance of multilayer system
of Ni and Zr thin films during continuous heating and
cooling at lOKmin" 1 . The thermal cycle was re-
peated; during the second cycle, the resistance follows
the line f-g traced during the cooling part of the first
cycle, a line characteristic of a wholly amorphous
material. (After Rubin and Schwarz, 1989.)
layer are too thick, then during reaction a
stage is reached when the growth of the
amorphous layers is interrupted by the nu-
cleation of intermetallic compounds just
ahead of the layers. Thus in Ni-Zr, at
300°C the critical thickness ^lOOnrn
(Newcomb and Tu, 1986); the compound
NiZr is nucleated at the interface of the
amorphous layer and Zr. Meng et al. (1988)
found that in this system, at a somewhat
higher temperature, the freshly nucleated
NiZr can grow backwards and consume
the previously formed amorphous layer.
Highmore (1990) has interpreted the criti-
cal thickness quantitatively in terms of
transient nucleation theory (see Sec. 9.4.5):
as the interface slows down progressively, a
stage is reached when nucleation of NiZr
becomes effective before the advancing
amorphous layer can overwhelm the em-
bryo.
506 9 Metallic Glasses
9.2.7 Mechanically Aided
or Induced Amorphization
When diffusion-induced amorphization
was first discovered, it was soon recognized
that deposition of multilayers from the va-
por phase was not the only possible ap-
proach: it was also possible to roll or wire-
draw composites of foils or wires of the
constituent metals, to reduce the scale of
the microstructure and weld the consti-
tuents, and then anneal the product - an
approach which had already proved its
worth in superconductivity research. Such
mechanically aided amorphization has been
achieved successfully by several investiga-
tors (e.g., for Cu-Er by Atzmon et al.,
1985). The amorphization reaction can
also take place during the rolling itself if
the end thickness of the layers is small
enough, as for instance in the amorphiza-
tion of rolled Al-Pt multilayers (Bordeaux
and Yavari, 1990) where the layers finished
up only « 60 nm thick.
From this it was only a short extrapola-
tion in technique to experiment with ball-
milling, a process which combines defor-
mation, comminution and mixing. A small
amount of powder is ground in a rotating,
"planetary" or vibrating container with a
number of hardened steel balls. This tech-
nique has been intensively developed by
metallurgists in recent years because it per-
mits mechanical alloying, that is to say,
atomic-scale mutual solution or chemical
combination of two metals achieved by in-
tensive ball-milling. The process and its
various uses, including mechanically in-
duced amorphization, are treated in detail
in Vol. 15, Chap. 5. These are instances of
mechanically induced amorphization.
The first to achieve mechanically in-
duced amorphization by co-deformation
of a layered composite appears to have
been Schultz (Ni-Zr), who has traced
the history of this process and also sur-
veyed the underlying principles (Schultz,
1989).
The formation of amorphous phases by
mechanical alloying of elemental metal
powders was first reported in Russia (Yer-
makov et al., 1981, 1982). Subsequently,
Schwarz and Koch (1983) prepared Ni-Ti
and Ni-Nb amorphous powders by ball-
milling the elemental powders. The process
is closely akin to that outlined the preced-
ing paragraph, and indeed intimate layer-
ing of the constituents has been observed
at an intermediate stage of the process. Lee
et al. (1988), among others, showed that
many amorphous phases can be produced
indifferently by ball-milling or by ball-
grinding a readymade intermetallic com-
pound or indeed a mixture of two com-
pounds in the same system. (This is not
always true: thus Mg 70 Zn 30 can only be
amorphized by grinding the intermetallic
compound, not from the elements (Calka
and Radlinski, 1989).) Careful comparative
studies, using differential scanning micro-
calorimetry (Schwarz and Petrich, 1988)
have made it clear that in the case of me-
chanical alloying of Ni and Ti, the amor-
phization reaction takes place directly be-
tween Ni and Ti zones brought into
intimate contact by milling.
In the case of grinding of an intermetal-
lic compound, disordering is mechanically
induced. As in the case of irradiation-in-
duced amorphization, the lattice expan-
sion caused by disordering can be regarded
as the proximate cause of amorphization. -
The range of compositions in a given sys-
tem which can be amorphized by one of
these techniques can be extended either by
grinding mixtures of intermetallics, as
mentioned, or else by grinding an already
amorphous powder with excess of one of
the constituent metals in powder form
(Weeber and Bakker, 1988).
 9.2 Methods of Making Metallic Glasses and Amorphous Alloys
Various recent researches (e.g., Weeber
et al., 1988) have shown that for a given
system and composition, different results
can be obtained according to the nature
and severity of the ball-milling operation
(in particular, planetary or vibrational
ball-mills). Martin and Gaffet (1990) point
out that in ball-milling, particles undergo
repetitive and competitive shearing and
annealing (healing) processes, and the end-
result depends on the balance between
these. A recent Soviet paper (Gerasimov
et al., 1991) shows that in the Ti-Cu and
Zr-Co systems, increasing ball energy led
to a tendency towards a crystalline as op-
posed to an amorphous product.
The criteria for amorphizability in the
case of mechanical alloying or grinding
(see, for instance, Schultz and Hellstern,
1987) are generally presumed to be the
same as in the case of irradiation, but no
critical comparison of the two techniques
seems to have been made. An important
new approach however is that due to Beke
et al. (1990). They estimated the additional
elastic (mismatch) energy which is stored in
an ordered solid solution when its long-
range order is destroyed, whether mechan-
ically or by irradiation; this depends, of
course, inter alia on the atomic sizes. This
new quantity was then compared to the
ordering energy, and it was concluded that
amorphization is possible if (a) the (virtual)
critical disordering temperature is above
the melting temperature, and (b) the ratio
of the elastic mismatch energy to the order-
ing energy is high enough. A comprehen-
sive test against known experimental facts
gives widespread though by no means uni-
versal agreement.
9.2.8 Amorphization at High Pressure
Much research on amorphization under
high confining pressure has been done
with non-metals, but a few experiments on
507
metallic systems have been reported (Bat-
tezzati, 1990). For instance, alloys in the
Cd-Sb, Zn-Sb and Al-Ge systems have
been pressurized to produce unstable crys-
talline phases which decay after a while to
leave metastable amorphous solids. An-
other approach was to heat Cu-Sn alloys
under confining pressure by direct electric
heating and to quench them by suddenly
switching off the current. In this way,
amorphous Cu-12-17at.% Sn amor-
phous phases could be made, which is not
possible under atmospheric pressure. For
further details of these observations, and of
the relevant thermodynamics, Battezzati's
paper should be consulted. - Very recently,
Ponyatovsky and Barkalow (1991) have
further developed the process which they
call 'thermobaric quenching', and have
made glasses in the Cd-Sb, Zn-Sb and
Al-Ge systems by this means.
Another novel and interesting approach
has just been reported and probably be-
longs under this heading. Suslik et al.
(1991) have been able to make nearly pure
amorphous iron by sonochemical synthesis,
i.e., ultrasonic irradiation, of a liquid, iron
pentacarbonyl. The formation, growth and
collapse of liquid bubbles is associated
with extremely rapid heating and cooling.
9.2.9 Composition Ranges of Glass
Formation and Glass Structures
for Different Preparation Techniques
A number of investigators have com-
pared the range of compositions over
which amorphous alloys can be prepared
when various forms of rapid melt-quench-
ing, vapor-quenching and SSAR are used.
A good example is seen in Fig. 9-5 (Gartner
and Bormann, 1990), which refers to the
Co-Zr system. As a crude generalization,
in agreement with theoretical expectation
(Schwarz, 1988), melt-spinning favors amor-
phous phases near deep eutectics, mechan-
508 9 Metallic Glasses
Co-Concentration
Figure 9-5. The observed concentration ranges (from
the literature) in the Co-Zr system for melt-spinning
(m.s.), ion-mixing (i.m.), co-condensation (c.c), me-
chanical alloying (m. a.). (After Gartner and Bormann,
1990.)
ical alloying (and indeed the other meth-
ods) favor amorphous phase formation
around the compositions at which com-
pounds form. The role of deep eutectics is
further discussed in the next Section.
Most observers have found that the
properties, as tested most often by mea-
surements of crystallization temperatures,
(mechanically alloyed, Schwarz et al. 1985)
N
UoTi6o
(rapidly quenched.Wagner &Lee 1980)
10
r (A)
Figure 9-6. Total reduced atomic pair radial distribu-
tion G (r) of amorphous Ni 40 Ti 60 prepared by me-
chanical alloying (solid curve) and rapid solidification
(dashed curve). (After Schwarz and Nash, 1989.)
are almost identical for amorphous solids
of a given composition, irrespective of their
mode of production (Schultz and Hell-
stern, 1987). Hydrogen storage capacity,
which is particularly sensitive to the topo-
logical fine structure of a glass (Harris
et al., 1988), is also similar. Judged more
directly from radial pair distribution func-
tions derived from X-ray scattering (see
Vol. 1, Chap. 4 and Vol. 9, Chap. 4), glass
structures are again seen to be very similar
for melt-quenched and mechanically al-
loyed glasses (Fig. 9-6). A particular sen-
sitive test is to examine viscous flow at a
range of temperatures. This has been done
for glasses of composition close to Pd 80 Si 20
made by melt-quenching and by sputter-
ing, and the flow properties far below Tg
were found to be closely similar (Volkert
and Spaepen, 1990).
9.3 Amorphizable Alloy Systems
9.3.1 Favorable Combinations of Metals
Metallic glass systems are generally di-
vided into 5 categories, shown in Table 9-1.
The two major classes are 1 and 2; origi-
nally, research attention was mostly con-
centrated on the metal-metalloid glasses,
category 1, which were the first metallic
glasses to be made by rapid solidification
and are also the most useful kind, but more
recently, attention has shifted towards the
metal-metal glasses (more, it seems, be-
cause this kind of glass is amenable to
theoretical interpretation, than because
of their applicability). Metal-metalloid
glasses, as a class, are the easiest to make
by rapid solidification, and two of them
(Pd 40 Ni 40 P 20 and Pd 7 7 5 Cu 6 Si 1 6 5 ) can be
made at cooling rates as slow as 1 K s ~1 if
heterogeneous surface nucleation is hin-
dered by appropriate measures (see Sec.
9.4.5).
 9.3 Amorphizable Alloy Systems 509

Table 9-1. Classification of glass-forming alloy systems.

Category Representative systems Typical composition range, at.%

1. T2 or noble metal Au-Si, Pd-Si, Co-P, Fe-B, 15-25 m

+ metalloid (m) Fe-P-C, Fe-Ni-P-B,
Mo-Ru-Si, Ni-B-Si
2. T1 metal +T 2 (or Cu) Zr-Cu, Zr-Ni, Y-Cu, Ti-Ni, 30-65 Cu or T2,
Nb-Ni, Ta-Ni, Ta-Ir or smaller range
3. A metal + B metal Mg-Zn, Ca-Mg, Mg-Ga Variable
4. T1 metal-f A metal (Ti,Zr)-Be, Al-Y-Ni 20-60 Be, 10Y-5Ni
5. Actinide-f-T1 U-V, U-Cr 20-40 T1

A metal: Li, Mg groups; B metal: Cu, Zn, Al groups. T 1 : early transition metal (Sc, Ti, V groups): T 2 : late
transition metal (Mn, Fe, Co, Ni groups).
This table is a modified form of one published by Polk and Giessen (1978).

Categories 3 and 5 may be classed as and thereby to stabilize the structure

curiosities, very much a minority interest.
This was also true until recently of cate-
gory 4 (the Be-bearing glasses excited
much interest at one time as potential low-
density, high-strength reinforcement rib-
bons, but were dropped because of the
health hazard associated with beryllium):
however, the position of category 4 glasses
has been transformed by the recent discov-
ery of Al-rich glasses, of which there is now
a great variety (Inoue and Masumoto,
1990; He et al., 1988). Glasses which have
been studied in categories 1 and 4 are most
often ternaries, those in category 2, most
often binaries. - Almost all research on
methods of glass formation other than
rapid solidification has been done with
glasses of category 3.
The metal-metalloid glasses always con-
sist of small solute atoms dissolved in
larger metal atoms; for greatest ease of
glass formation, the total concentration of
metalloids, which may be of more than one
species, is generally around 20 at.%. At an
early stage, Polk (1972) proposed that the
relatively easy formability of this kind of
glass was to be attributed to the ability of
the metalloid atoms to "stuff" the voids in
the Bernal dense random packing struc-
ture (an early model for metallic glasses),
against ready crystallization. This much-
quoted idea has been critized by Gaskell
on the grounds that an exact examination
of the Bernal structure indicates that there
are by no means enough large voids to
accommodate most metalloid atoms, but
this objection in turn has been thrown
back into the melting-pot by TurnbulFs
observation that the effective size of a
metalloid atom depends on the nature of
the metals in which it is dissolved. The
matter is further discussed by Gaskell
(Vol. 9, Chap. 4).
A word is in order here about the new
category of Al-rich glasses. The curious
history of these materials, independently
discovered in France, U.S.A. and Japan,
and driven by both fundamental and prac-
tical considerations, has been outlined by
Cahn (1989). The most interesting proper-
ties (very high strength combined with
toughness and lightness) attach to glasses
consisting, typically, of « 80 at.% Al and
^ 1 0 at.% each of a transition metal such
as Ni, Co or Fe and a rare earth metal such
as Y, Ce or La, though in the search for
applicable alloys, complex compositions
such as Al 69 Cu 17 Fe 10 Mo 1 Si 3 have been
recorded. The Japanese and American re-
searchers established that, while binary
510 9 Metallic Glasses
aluminum-rare earth combinations could
be induced to form glasses, the composi-
tion ranges were narrow and could be
much widened by adding a ternary constit-
uent, a transition metal.
9.3.2 Composition Ranges
for Glass Formation
In a given alloy system, the range of
compositions over which glasses can be
made depends (in the case of rapid solidifi-
cation) on the cooling rate achieved. As we
saw in Fig. 9-5, the concentration ranges
for different techniques can also be sub-
stantially different. Most such measure-
ments have been for binary alloys, but
some have been for ternaries also. Fig. 9-7
shows such information relating to F e -
Si-B glasses, which are of ferromagnetic
importance, and for A l - Y - M glasses. (In
these instances, the cooling rates were not
specified by the investigators .) - It is gen-
erally true that wider composition ranges
can be vitrified by the vapor quenching
route, since the effective quenching rate is
much higher than in quenching from the
liquid state.
9.3.3 Criteria for Glass Formation
The possible criteria determining the
feasibility of making amorphous alloys,
from intermetallic compounds by irradia-
tion or mechanical grinding, by mechani-
cal alloying of pairs of elements, or by in-
terdiffusion, have already been briefly dis-
cussed in Sections 9.2.7, 9.2.6 and 9.2.5, re-
spectively; here we concentrate mainly on
glasses made by rapid solidification. - The
generic term most commonly applied to
represent what we are trying to explain
here is glass forming ability, or GFA. It is
usually taken to mean the critical cooling
rate, Rc, which is necessary to turn a melt
into a glass: when this is in the experimen-
tally accessible range for mainline rapid
solidification processes such as melt-spin-
ning, approximately up to 107 K s" 1 , then
the alloy can be vitrified by such a process;
if theory tells us that Rc is higher than this,
then, at best, tiny amounts of glass can be
made by a much faster quenching process
such as picosecond quenching with a
pulsed laser, which can provide cooling
rates as high as l O ^ K s " 1 (Lin and
Spaepen, 1984). (As we saw earlier (Fig.
9-2), cooling rates are not constant during
a quench from the melt; so presumably the
Rc values discussed in theories mean the
maximum experimental values, which refer
to temperatures at and slightly below the
equilibrium freezing temperature.)
Motorin (1983) calculated from first
principles the expected homogeneous nu-
cleation rates of crystals in supercooled
pure metal melts, using known physical
parameters as input. For Ag, Cu, Ni and
Pb, minimum cooling rates of 10 1 2 -10 1 3
K s " 1 were derived, which shows clearly
enough why no pure metals have been vit-
rified by melt-quenching. Not even pico-
second laser quenching has been successful
in this respect. Thus the GFA criteria refer
in practice only to alloys.
The range of ideas and approaches
which have been proposed to get an under-
standing of why some alloy systems can be
vitrified and others not, and of what deter-
mines the composition ranges over which
glasses can be made, is almost disconcert-
ingly wide. There are almost as many crite-
ria for glass formation as there are for the
good life, and almost as little agreement
among protagonists as to which are to be
preferred.
A valiant early attempt to come to grips
with this difficult issue was by Polk and
Giessen (1978). The best comprehensive
overview of the development of these crite-
ria is by Ramachandrarao (1984). Cahn
 9.3 Amorphizable Alloy Systems 511

20

Al-Y-M ,'Ni
•

20 -
\

/<0* \ /
Figure 9-7. Glass-forming ranges for rapidly solidified
5 "' Cu
— 10 ternary alloy systems, (a) Fe-Si-B alloys, showing
\ \ five independent experimental estimates for the glass-
Co
- I forming range. (After Luborsky et al., 1979.) (b) Al-
-e / Y - M alloys, where M = Cu, Co, Fe or Ni. (After
—.^~ i Inoue and Masumoto, 1990.)
10 20 30
(b) M in at. %

(1986 a), Hafner (1986) and Massalski early experiments on vapor-quenching, in

(1986) have published more specialised
treatments. Here we can attempt only a
bird's eye view.
In spite of a tendency by some theorists
to regard this claim as culpably naive,
there can be no doubt that atomic size is
the single factor that plays the major role
in determining GFA. The recognition that
the constituent atoms in a melt must have
sufficiently different Goldschmidt radii to
permit glass formation goes back to very
a classic study by Mader et al. (1967). A
critical radius mismatch of ^ 1 5 % fitted
the results, and this value has been ac-
cepted ever since. This criterion might be
termed an anti-Hume Rothery criterion,
since Hume Rothery's celebrated law laid
it down that a radius mismatch not ex-
ceeding 15% was necessary for extensive
solid solution formation in terminal alloy
phases. - Mader himself had simulated
glass formation by jiggling populations of
512 9 Metallic Glasses
wooden balls of different sizes on a tray,
and found that the radii had to differ suf-
ficiently for "crystallization" to be pre-
vented; subsequently, Simpson and Hod-
kinson (1972) performed the first of several
simulations of this kind with rafts of soap
bubbles of ^ 1 mm diameter which better
simulate real interatomic forces, and again
found a critical radius mismatch of « 1 5 % .
The next stage was a series of attempts
to create GFA maps, in which radius mis-
match was plotted against one axis of a
graph and some measure of bond strength
such as the negative heat of mixing or heat
of evaporation - the idea presumably being
that strong interatomic bonds render crys-
tallization more difficult. One of several
such attempts was by Giessen (1981). Such
graphs suggest that the bond strength does
indeed play a part, but it is a "weak" vari-
able compared to the size mismatch.
A very important development of the ra-
dius mismatch approach is due to Egami
and Waseda (1984), followed by a further
development of the same ideas by Egami
and Aur (1987). These authors were inter-
ested in calculating the microscopic stress
levels at the scale of individual atoms in a
glass or a crystalline solid solution. Briefly,
they concluded that in a glass, neither the
local stress fluctuations nor the total strain
energy vary much with solute concentra-
tion when these quantities are normalized
with respect to the elastic moduli, whereas
in a crystalline phase the strain energy rises
steadily with solute content. Thus, beyond
a critical solute content, glass becomes fa-
vored over crystal formation, and in this
way, not only GFA but also the glass-form-
ing composition range can be calculated.
The conclusion is that c#in (vh-vA)&0.1,
where c™n is the minimum solute concen-
tration of B in A required for a glass to
form and the v9s are atomic volumes. The
agreement with observation is good for
many systems, though melt-quenching by
normal melt-spinning is not necessarily
fast enough to give agreement with Egami
and Waseda's criterion. Fig. 9-8, for the
Ni-Nb system, shows at the bottom the
results of applying Egami and Waseda's
criterion, and also three different experi-
mentally determined glass-forming ranges.
The "faster" methods agree very well with
the theoretical criterion. This was the first
theory to allow the glass-forming composi-
tion range to be interpreted, as distinct
from theories which only interpret the
identity of glass-forming alloy systems.
Several other theories, of a thermody-
namic nature, based on atomic volumes
have appeared. One version is due to Ra-
machandrarao (1980): he estimated the de-
parture from ideality of melts, in terms of a
kind of deviation from a liquid Vegard's
Law, and concluded, both theoretically
Ni
Atom fraction
sputtering
L frx*:::*:^^
ns laser quenching
melt-spinning
msmm
prediction
Figure 9-8. The Ni-Nb phase diagram, experimen-
tally determined glass-forming ranges for three meth-
ods of decreasing effective quenching speed, and the
range predicted by Egami and Waseda's theory. (After
Greer, 1989.)

and by comparison with experiment, that
melts with a large deviation, in the sense of
having an anomalously small atomic vol-
ume, were most likely to form glasses. This
finding was interpreted in terms of the en-
hanced viscosity associated with a small
atomic volume (which implies little free
volume available to support atomic mo-
tion in the melt). - Yavari et al. (1983) inde-
pendently developed a closely related idea,
by establishing empirically that a zero (or
negative) change of specific volume on
melting of a crystalline species favors glass
formation on subsequent rapid solidifica-
tion. In effect, their idea is that if a crystal
is denser than the melt from which it
grows, then in growing it rejects free vol-
ume into the melt and thereby reduces its
viscosity; thus crystal growth becomes self-
catalytic. Contrariwise, a less dense crystal
raises viscosity and favors glass formation.
Theoretical physicists have developed a
number of models to rationalize GFA. The
best known is that due to Nagel and Tauc
(1977). They proposed that a glass was
most likely to form if its electronic energy
lies in a local metastable minimum with
respect to composition change. They
showed that if the structure factor corre-
sponding to the first, strong peak of the
diffuse X-ray scattering curve, Kv, satisfies
the relationship Kp = 2fcF,where kF is the
wave vector at the Fermi energy, then the
electronic energy does indeed occupy a lo-
cal minimum. A number of familiar glasses,
in the Au-Si, Au-Ge and C o - P systems
for example, accurately obey this criterion,
but there are also exceptions, e.g., some
obscure glasses in the C s - O and R b - O
systems. This kind of approach, using
modern approaches such as pseudopoten-
tial theory, has been taken much further in
recent years, but a discussion would take
us too far here. For further details, the
reader is referred to reviews by Hafner
9.3 Amorphizable Alloy Systems 513
(1981, 1986). However, as we shall see be-
low, the ability, demonstrated by Hafner,
to make theoretical estimates of the glass
transition temperature of unknown glasses
offers a novel way to estimate GFA.
Theories based more explicitly on the
need to prevent nucleation of a crystalline
phase take two main forms. First, there are
models based on an explicit calculation of
homogeneous nucleation rates (this begs
the question whether heterogeneous nucle-
ation plays a role). The standard approach
here is due to Davies (1976). He adapts a
theory of isothermal crystallization kinet-
ics due to Uhlmann and calculates the crit-
ical cooling rate necessary to bypass the
"nose" of the time-temperature-transfor-
mation plot thus calculated. (The nose is
the minimum time required to initiate ho-
mogeneous nucleation, at some tempera-
ture well below the thermodynamic freez-
ing temperature). The principal difficulty
here is to estimate the viscosity of a super-
cooled melt, but there are a number of em-
pirical relationships which allow a rough
estimate to be made. (There is now avail-
able a critical survey of known viscosities
of molten metals and alloys, by Battezzati
and Greer, 1989.) Fig. 9-9 shows some cal-
culated critical quenching rates obtained in
this way, and Fig. 9-10 shows how the cal-
culated value of Rc varies with composi-
tion across a phase diagram. It will be seen
from this second figure that, as a number of
people have pointed out and as follows
from Davies' theory, the ratio TJTf (Tg is
the glass transition temperature, 7^ is the
thermodynamic freezing temperature) is a
crucial figure of merit in determining GFA,
for purely kinetic reasons associated with
the need to avoid crystallization. The lower
this ratio, the more viscous the melt be-
comes before it is ever undercooled and the
more difficult crystallization becomes, thus
enhancing GFA and reducing Rc.
514 9 Metallic Glasses

A somewhat related, more thermody-

namically biased approach derives from a
paper by IW. Cahn (1980) on the thermo-
dynamics of metastable equilibria. From
this, the role of the relative values of Tg and
To becomes clear; here, To is the tempera-
ture at which liquid and solid of the same
composition have the same free energy. A
glass forms readily if Tg > To; what this
means is that the melt rigidifies before
reaching the temperature at which freezing
without composition change (and thus
0.8 without long-range diffusion), also known
as solute-trapping, becomes possible. The
implications of this are clearly set out in
Figure 9-9. Calculated critical quenching rates, Rc,
for glass formation, and examples of limiting rib- the review by Massalski (1986) and applied
bon thickness. Key: (1) F e 8 9 B n ; (2) Au 78 Ge 14 Si 8 ; to a detailed analysis of GFA across the
(3) Fe 8 3 B 1 7 ; (4) Fe 41 . 5 Ni 41 . 5 B 17 ; (5) Co 75 Si 15 B 10 ; Cu-Ti system in a paper published about
(6) Fe 7 9 Si 1 0 B l i ; (7) Fe 80 P 13 C 7 ; (8) Pd 82 Si 18 ; (9) the same time (Massalski and Woychik,
Ni 6 3 Nb 3 7 ; (10) Pd 77 . 5 Cu 6 Si 16 . 5 ; (11) Pd 40 Ni 40 P 20 .
1985). The problem is that, before a glass
(After Davies, 1978.)
has actually been made, its Tg is not
known. Here, Hafner's (1983, 1986) ability
(a) 1600 to calculate glass transition temperatures
comes into its own. In Fig. 9-11, for the
* U00 Ca-Mg system, the calculated To values
c are shown, and also two estimates for Tg,
an upper limit based on the "entropy-cri-
^ 1200
sis" or Kauzmann model, and a lower limit
based on a free-volume model. (For a fuller
(b) explanation, see Hafner (1983).) Theoreti-
700 cal composition ranges for glass formation
600 are shown for two cooling rates; here the
500 criterion Tg > To is the central consider-
Experimental ation; agreement with experiment is quite
(c) glass range good. - Another detailed thermodynamic
8
7 analysis of metallic glass formation near
6 eutectic troughs was published by High-
c
*°
more and Greer (1989).
1*
Another set of theories is based on the
log!

2 postulate that metallic melts are not homo-

10 15 20 25 geneous in composition but contain com-
Atomic % Si
positional clusters. Such clusters are held
Figure 9-10. Equilibrium freezing temperature, Tf,
glass transition temperature, Tg, figure of merit TJT{ to aid crystal nucleation, and their absence
and calculated critical quenching rate, Rc, for a range or weak development to aid glass forma-
of Pd-Si alloys. tion. Contrariwise, short range order (the
 9.3 Amorphizable Alloy Systems 515

converse of clustering), which is believed

(though there is a singular absence of ex-
perimental evidence on this point) to in-
crease with falling temperature of a glass,
just as it does in a crystalline solid solution,
should enhance GFA. (See, for instance,
Wagner's survey of SRO in metallic
glasses, 1986; at least, it has been estab-
lished for Cu-Ti that a glass has higher
SRO than the melt from which it is
quenched (Sakata et al., 1981).) Indeed,
there is some evidence that some Cu-Ti
alloys show clustering in the melt whereas
the glass has SRO. This field of research,
which has a large literature, is at present
somewhat beset by controversy: for further
details, the reader is referred to Ramachan-
drarao (1980, 1984).
A further development is the application
of CALPHAD (CALculation of PHAse
Diagrams) methods to calculate from first
principles the part of a phase diagram in
which the free energy of a supercooled melt
(i.e., a glass) is particularly low relative to
that of the competing terminal phases, and
only slightly higher than that of a compet-
ing intermetallic phase. A successful begin- Figure 9-11. Calculated phase diagram, To values and
upper and lower limits (Ts, 7^) for Tg for the Ca-Mg
ning with this approach has been pub- system, with theoretical and observed glass-forming
lished by Saunders and Miodownik (1986). ranges. (After Hafner, 1983, 1986.)
The method has been applied in detail to
one particular system, Ni-Ti, by Nash and
Schwarz (1988). NiTi has also been studied
by Zollzer and Bormann (1988) who have related GFA to quantities (such as TJT{)
made E.M.F. measurements on a-NiTi at which involve Tg, when normally this is
613 K to complement purely theoretical unknown unil a glass has been made and
estimates of free energy. - The free energies examined. They proposed that a good test
of a-Cu/Zr phases have also been calcu- of GFA is the extent to which the equilib-
lated by a least-squares fitting program rium freezing temperature of an alloy melt
from available thermodynamic data (Bor- is depressed below the ideal value, which
mann et al., 1988). they calculated simply by linear interpola-
Finally, we return to a less sophisticated tion between the freezing points of the con-
"figure-of-merit" approach which has been stituent metals. This simple method was
quite successful in rationalizing GFA. then developed by Whang (1983), who
Donald and Davies (1978) long ago recog- took into account the modification re-
nized the awkwardness of theories which quired to allow for possibly extensive solid
516 9 Metallic Glasses

\J.\J
solution of one metal in the other, in the
solid state. This is necessary because solid o Ga
solubility reduces the slope of the To versus Al
Bi o
composition curves (like those shown in 0.1 c oB o
Fig. 9-11). Whang generated figure-of- NON-GFA
merit maps in which one axis gave TLR,
defined as TLR = AT/T£, where AT is the oRe
0.2
difference between the ideal freezing tem- GFA
perature for an alloy (Tj°), defined as \
oAg
above, while along the other axis is C er , a Cr Mn \

simple measure of the amount of the solu-

bility of the minor constituent in the major
at the eutectic temperature. - A large value
of TTR implies a severely depressed liq-
uidus, while a small Cer implies a steeply
sloping To versus composition curve ...
both factors favouring easy glass forma-
tion. In fact, the maps so generated show a
clear boundary between glass-forming and
non-glass-forming alloys. - Dubey and
Ramachandrarao (1990) have developed
Whang's model to show that most eutectic
phase diagrams can be expected to show
an asymmetry of GFA, in the sense that
glass formation is easier just to one side of
the eutectic composition than on the other;
the melt-spinning range indicated in Fig.
9-8 shows an example of this.
Whang's theory was then adapted by
Tendler (1986) to show, for a series of Zr-
based alloys, that alloys which according
to Whang's criterion should be good glass-
formers are also those in which there is fast
diffusion, in the special sense used before
(Warburton and Turnbull, 1975). Fig. 9-12
shows one of Tendler's figures for a series of
Z r - M alloys. All the alloys showing fast
diffusion (Zr-Cr, Mn, Fe, Co, Ni, Cu and
Be) are also glass-formers. For fast diffu-
sion, the solute atom must be much smaller
than the solvent (for details see Tendler's
paper) and this clearly also favors GFA. In
fact, some years ago Turnbull (Turnbull,
1974) had predicted an association be-
tween good GFA and fast diffusion.
*• v \
0.3 - #
Pt. \Ru
Os • \
iBe Rh #
kI . Co
Ni • •
Cu»
• Fe
i i i i ' \
1.0 0.8 0.6 0.4 0.2
Figure 9-12. A number of Z r - M alloys plotted on a
Whang graph, separating glass-formers (GFA) from
non-glass-formers. (After Tendler, 1986).
This by no means exhaustive overview
of the models and theories that have been
advanced to make sense of glass-forming
systems and ranges might well seem dis-
couraging, because at first sight they are
mutually exclusive. In fact, hidden cross-
connections undoubtedly exist: the linkage
between Whang's thermodynamic ap-
proach (related to terminal solid solubili-
ties) and Tendler's association between fast
diffusion and GFA clearly comes from a
correlation of both solid solubilities and
fast diffusion with atomic size ratios. Per-
haps in due course even the electronic
criteria studied by Nagel and Tauc and by
Hafner may prove to be linked with some
of the other ideas, e.g., the free volume ap-
proach due to Ramachandrarao and
Yavari. My own view is that simple geome-
try ... atomic sizes ... will prove to be the
main criterion that in various subtle ways
incorporates the others.

9.3.4 The Special Case of Silicon
Metallic glasses resemble oxide glasses
in that the transition from the liquid to the
glassy state is a continuous, seamless one.
The atomic configuration changes with
temperature during cooling, fast or slow
according to the type of material, until a
temperature range is reached in which dif-
fusion cannot keep up and a non-equilib-
rium configuration is "frozen in"; this is of
course the glass transition range. "Frozen
in" has been put in quotes because the glass
transition is not at all like real freezing,
which is a first-order phase transition with
a well defined equilibrium temperature, at
which the Gibbs free energies of the liquid
and crystalline phases are equal. In con-
trast, the glass transition temperature
(temperature range is a more suitable
phrase) is a function of cooling rate and is
kinetically, not thermodynamically, deter-
mined (see Chap. 3). Correspondingly, of
course, on heating a glass, the glass transi-
tion (softening) temperature is again vari-
able, whereas the melting of a crystal hap-
pens at a well defined equilibrium tempera-
ture.
We briefly discuss silicon here because it
breaks this simple, clear distinction be-
tween freezing and vitrification, between
melting and softening. It is true that crys-
talline silicon is not metallic and so does
not strictly belong to this chapter, but
molten silicon does have a metallic charac-
ter. Amorphous silicon is quite distinct from
the liquid form, and resembles the crys-
talline form in having covalently bonded
character. Amorphous silicon can be made,
with difficulty, by quenching liquid silicon
with ultrafast, picosecond laser pulses (Liu
et al, 1979). The more common way, how-
ever, of making a-silicon is by ion implan-
tation, especially by self-ion bombard-
ment. (This process has some peculiar
9.3 Amorphizable Alloy Systems 517
features, such as a dependence on the ori-
entation of the initial crystalline silicon:
Yater and Thompson, 1989.) On the basis
of microcalorimetric measurements of such
a-silicon layers, Spaepen and Turnbull
(1979), and Bagley and Chen (1979), inde-
pendently proposed that a-Si (and also
a-Ge) undergo first-order melting to the
metallic liquid on heating. This bold hy-
pothesis, implying a latent heat of melting
for an amorphous solid, could only be
tested some years later, when it became
feasible (e.g., Thompson etal., 1984) to
measure transient electrical conductance
and reflectance of silicon films: since a-Si
and 1-Si have drastically different bond
character, their electrical and optical prop-
erties are also quite different. In this way,
the prediction made in 1978, that a-Si
melts at a well defined temperature more
than 200 K below the melting temperature
of c-Si, was confirmed: the a-Si melting
temperature was experimentally found to
be 225 + 50 K. These experiments and the-
oretical calculations are excellently re-
viewed by Poate et al. (1987).
It would, however, be a mistake to as-
sume that the melting temperature of a-Si
is well defined thermodynamically, because
the structure of a-Si is itself not well de-
fined and can be altered by a relaxation
anneal. Fig. 9-13 (Sinke etal., 1988 a)
shows a series of estimated free energy
curves, which show clearly that the inter-
sections between the a-Si and 1-Si curves
come at quite different temperatures for
different degrees of relaxation; according-
ly, the melting temperature should vary in
the same way. Indeed, if a-Si could relax to
the theoretical limit at each temperature
(curve 5 in the figure) it should intersect the
c-Si curve before it intersects the 1-Si curve,
and thus in that hypothetical case, a-Si
should not melt at all, but crystallize di-
rectly. Thus, a-Si resembles a conventional
 9 Metallic Glasses
Figure 9-13. Calculation of the isobaric Gibbs free
energy of a-Si (curves 1 to 5) and of /-Si relative to that
of c-Si, using strain energies deduced from Raman
spectra. Curves 1 to 4 represent increasing degrees of
thermal relaxation of the a-Si. Curve 5 is an estimated
curve for a-Si prepared in a wholly unrelaxed form,
but allowing it to relax to an equilibrium degree at
each temperature. (After Sinke et al, 1988 a.)
glass in having a variable melting (transi-
tion) temperature. - More will be said
about relaxation of a-Si in Section 9.4.2.
9.4 Diffusion, Relaxation
and Crystallization
When a metallic glass of amorphous
solid is heated to a sufficiently high temper-
ature, the constituent atoms begin to dif-
fuse. This permits the amorphous structure
to relax towards the state corresponding to
the ideal congealed liquid. If diffusion is
fast enough, the amorphous structure be-
gins to crystallize. These three linked phe-
nomena are treated in this Section.
9.4.1 Diffusion
The first experimental study of atomic
diffusion in a metallic glass was made as
recently as 1978 (Chen et al., 1978). The
reason for this tardy start was the experi-
mental difficulty of such measurements.
The duration of a diffusion anneal of a
metallic glass is limited by the need to en-
sure that no crystallization takes place, and
this in practice means that penetration of
the diffusing species is limited to a few
tenths of a micrometer. Normal methods
depending on mechanical sectioning and
chemical analysis are therefore not appli-
cable, and investigators have mostly used
Rutherford back-scattering (used in Chen
et al.'s initial study), ion erosion combined
with radioactivity measurements, sec-
ondary ion mass spectrometry, nuclear re-
action analysis and X-ray diffraction from
multilayer films. These methods can mea-
sure diffusion coefficients as small as 10~ 20
-10~ 2 6 m 2 s" 1 . In the last few years, over
a hundred publications have appeared on
this theme and there is room here only for
a brief account of the principal generaliza-
tions that can be made with confidence.
More detailed information can be found in
reviews by Cantor (1986), Cahn (1986),
Mehrer and Dorner (1989) and Cahn
(1990).
Fig. 9-14 shows a characteristic set of
measured diffusion coefficients for B diffus-
ing in a Ni-Nb glass (Kijek et al., 1986).
The xl B(p,a) 8 Be nuclear reaction was ex-
ploited; this has a strong resonance for a
particular proton energy and by varying
the energy of the probing beam, B concen-
trations at different small depths below the
surface could be determined. It is clear that
(as first discovered by Chen et al. 1978) a
relaxation anneal reduces the diffusivity.
Other studies have determined the kinetics
of this reduction and shown that it satu-
rates, and have also shown that the diffu-
sivity falls as the atomic volume reduces
during an anneal ... i.e., as the amount of
free volume diminishes (Chason and Mi-
 9.4 Diffusion, Relaxation and Crystallization 519

• Fe
82 B 18
A Zr 61 Ni 39
10"19 =-\
\r
: Uu
in

CO
io- 2 T
\ \
v
• Sb
: \
"5 : s,.\
Q \
10-,21 \«Au\
S b
\ \
10
0.12 0.U 0.16 0.18
(a) Atomic radius in nm

1.2 U 1.6 1.8

1 0 0 0 / T i n K"1
Figure 9-14. Diffusion coefficients of X1B in Ni 6 0 Nb 4 0 Ni Co Fe Cu Au Ti Zr
glass. O unrelaxed; x relaxed 420 s at 878 K. (After
Kijek et al., 1986.)
10"19

zoguchi, 1987; see also discussion by Cahn,

1990). Fig. 9-14 also shows that, after re-
laxation, the diffusivity obeys an Arrhe-
nius-type temperature variation, a fact
which has occasioned much surprise, be-
cause a well defined activation energy
would seem to imply that all atomic jumps
go over similar energy barriers, which
clearly is not true in a glass. The rather
unsatisfactory present situation with re-
gard to the theory of diffusion in metallic
glasses is reviewed by Frank et al. (1988)
and by Mehrer and Dorner (1989).
The best established generalization con- 10-27
cerning diffusion in metallic glasses is its 10 12 U 16 18 20
great sensitivity to the relative sizes of the (b) Atomic vol. in 10"30m3
diffusing and host atoms. Sharma has done Figure 9-15. (a) The dependence of diffusivity of dif-
much to establish this (see Sharma et al., ferent metals in two metallic glasses on atomic radius
of the diffusing species. (After Sharma et al., 1989.)
1989) and the previously cited study by
(b) Diffusivities of various metals in amorphous N i -
Greer et al. (1990) on the asymmetry of Zr, with a Ni content in the range 50-65 at.%, as a
diffusivity of Zr and Ni in a-Ni-Zr has function of the atomic volume of the diffusion species.
neatly confirmed it. Fig. 9-15 shows graphs (After Greer et al., 1990.)
520 9 Metallic Glasses
from these two studies. This is reminiscent
of the behavior of diffusing species in crys-
talline metals, but is particularly pro-
nounced here. This size sensitivity of diffu-
sivity in metallic glasses still does not tell
us for sure whether the diffusing process
should be regarded as being mediated by
vacancy-like holes or whether it is to be
regarded as primarily interstitial. A recent
study, via indirect diffusion measurements
under hydrostatic pressure, of the activa-
tion volume for diffusion in a metallic glass
(Limoge, 1990) suggests a vacancy-like
mechanism. Further, the reduction of diffu-
sivity as a result of relaxation has been
closely correlated with the loss of free vol-
ume, and this indicates that "holes" play an
essential part in diffusion. It is clear that
the ultrafast diffusion of H in metallic
glasses is of an interstitial nature, but it is
also to be noted that the small number of
interstitial spaces of large sizes act as traps
for hydrogen, so that (e.g., Kirchheim
etal., 1982; Kirchheim 1988, Kirchheim
et al., 1991) the diffusivity of H in metallic
glasses becomes extremely sensitive to con-
centration (which has not been established
for any other diffusant). Whether such
large units of free volume are to be re-
garded as holes or interstitial spaces is re-
ally a matter of lexicography; it may turn
out that the vigorous debate as to whether,
in general, diffusion in metallic glasses is to
be perceived as an interstitial or as a va-
cancy-type mechanism is a matter of shad-
ow-boxing. The one thing which is unam-
biguously clear is that free volume plays a
vital role in determining diffusivity.
A very recent study (Faupel et al., 1990)
has shown, for a Co-rich glass, that there is
no pressure dependence at all of cobalt dif-
fusivity and a very small isotope effect. The
conclusion is that diffusion is not mediated
through quasivacancies in thermal equilib-
rium, but rather takes place by a 'direct'
mechanism involving about 10 atoms co-
operatively.
One well-known theoretical approach
to diffusion in metallic glasses is firmly
predicated on the notion of diffusion via
atom-sized holes. Buschow (1984) was able
to estimate the heats of formation of holes
in various metallic glasses, using a method
introduced by Miedema, and was able to
show that the crystallization temperature
scales as does this heat of formation. (He
assumed that the diffusion of holes of the
same size as the smaller constituent atoms
was the important variable.) A larger heat
of formation, as with crystal vacancies, im-
plies a smaller concentration of holes, thus
a smaller diffusivity at a given temperature
and, in consequence, more sluggish crystal-
lization. Barbour et al. (1987) have devel-
oped this approach by computing also the
heats of formation for holes of the same
size as the larger constituent atoms of each
glass, and concluded that the readiness of a
particular amorphous alloy to be formed
by the interdiffusion SSAR mechanism de-
pends on a large difference between the
heats of formation for the larger and
smaller holes, and this of course relates to
the size difference of the constituent atoms.
A large size difference implies a large diffu-
sivity difference, as we have seen. Fig. 9-16
shows the results of the calculations by
Barbour et al.
As we saw above, diffusion is an essential
process in some of the solid-state amor-
phization mechanisms. It is not known
what the state of relaxation of an amor-
phous alloy made by interdiffusion of
layers is, but it is no doubt significant that
the diffusivity calculated from measured
growth kinetics (Rubin and Schwarz, 1989)
of such an alloy layer in Ni/Zr and the
directly measured diffusivity of Ni in a
Ni/Zr glass made by melt-quenching, have
quite different activation energies (1.01 eV/
 9.4 Diffusion, Relaxation and Crystallization
1500
.9
11000
CD
C
o transition metal amor-
N
5 500
o larger constituent atoms
50 100 150
HSw (A) or HLy ( • ) in kJ mole
atom in the first case, 1.45 eV/atom in the
second). It will be interesting to see more
critical comparisons of diffusivities in melt-
quenched and SSAR amorphous alloys.
Relaxation does not always depress the
diffusivity in an amorphous solid. a-Si is a
notable exception. A recent study (Polman
et al, 1990) has established that the diffu-
sivity of Cu in a-Si made by ion implanta-
tion increases by a factor of 2 to 5 when the
silicon is relaxation-annealed. The expla-
nation is that as-implanted a-Si contains a
large concentration of defects (point de-
fects and agglomerates) which act to trap
Cu atoms; relaxation destroys many of
these defects and thus enhances mobility of
the Cu. Free volume seems to be of sec-
ondary importance here.
9.4.2 Relaxation
As we have already seen in connection
with diffusion, annealing a metallic glass
below its crystallization temperature re-
duces the free volume and thereby de-
creases the self-diffusivity. (a-Si behaves
differently.) The reduction in free volume
521
Figure 9-16. Crystallization
temperatures for various
phous alloys plotted
against the calculated heats
of formation of holes
equivalent in size to the
(HLV) or the smaller con-
stituent atoms (HSY). (After
Barbour et al., 1984.)
200 250
also affects many other physical and me-
chanical properties: changes of physical
properties are briefly discussed in this sec-
tion, relaxation-induced embrittlement in
the next. Oxide glasses behave similarly:
for instance, when an optical glass is an-
nealed close to its glass transition, the re-
fractive index changes steadily. Relaxation
in oxide glasses is treated in Chap. 3 of this
Volume.
Table 9-2, modified by Cahn (1983) from
a compilation by Egami, lists the proper-
ties the changes of which on thermal relax-
ation have been most frequently studied. A
distinction is made between those phenom-
ena which change in a primarily irre-
versible way and others which change in a
primarily reversible way as the annealing
temperature is cycled; recent research has
however made it clear that no property
changes in a wholly irreversible or a wholly
reversible way. Thus, length changes,
which are most directly tied to free volume
changes, while almost wholly irreversible
have nevertheless recently been shown to
have a small reversible component (Huizer
and van den Beukel, 1987). The principal
522 9 Metallic Glasses

Table 9-2. Changes in physical and mechanical prop- perature in metallic glasses only, although
erties during structural relaxation. (After Egami et al. no direct diffraction evidence of this has
(1982), slightly modified.)
ever been reported (it would be more diffi-
Properties Direction of Reversible (R) cult to obtain in glasses than in crystals).
change during or irreversible Because of this postulated reversible varia-
relaxationa (I) below Tg tion of chemical SRO with temperature,
Volume D I
changes in properties that are particularly
Specific heat I I sensitive to it, such as elastic properties or
I/D R Curie temperature, have a large reversible
Young's modulus I I component to their changes on relaxation.
I/D R Very recently Haruyama and Asahi (1991)
Internal friction b ' c D I
Electrical resistivity I/D I
claim to have found calorimetric and resis-
I/D R tometric evidence of reversible SRO in
Diffusivityb D I N i - C r - B glasses.
Viscosity15 I I One test of Egami's rationalization of
Embrittlementb I I
the two types of relaxation effect would be
Thermal resistivity D I
Curie temperature I/D I/R to test whether the incidence of reversible
Coercive field I/D I/R changes of property are correlated with the
Magnetic anisotropy, magnitude of chemical SRO present in dif-
field-induced I/D R ferent glasses: thus, Cu-Ti glasses are
Superconductive tran- known to order strongly, Fe-Ti glasses
sition temperature D I
have recently been found to have no chem-
a
I denotes increase, D decrease. ical SRO, and comparative measurements,
b
These properties are conventionally (for crystalline for instance of Young's modulus, between
solids) considered to be structure-sensitive, and in- them might serve as a test of what is still,
deed do show large changes in amorphous solids
upon annealing.
after 9 years, no more than a very reason-
c
This property is itself a reversible relaxation phe- able hypothesis: the association between
nomenon. reversibility of property changes and
chemical SRO. - An excellent overview of
difference between these two fundamen- known facts concerning relaxation of
tally distinct types of relaxation-induced metallic glasses in the light of Egami's hy-
change was first recognized by Egami pothesis was published more recently
(1981). He proposed a distinction between (Egami, 1986).
topological short-range order, or TSRO Fig. 9-17 shows some characteristic ex-
(which in effect describes the density of amples of relaxation-induced property
packing of atoms) and chemical short-range changes. The kinetics of such processes, es-
order, or CSRO, which defines the extent pecially reversible ones, became an inter-
to which atoms have unlike nearest neigh- esting problem when the so-called crossover
bours. effect was discovered in metallic glasses,
On relaxation annealing, TSRO changes with respect to properties such as the Curie
through the progressive, irreversible re- temperature and elastic moduli (Greer and
moval of free volume, and this causes irre- Spaepen, 1981; Scott and Kursumovic,
versible property changes. Chemical SRO, 1982). This effect is most easily understood
by analogy with crystalline alloys (see by reference to Fig. 9-18, which actually
Cahn, 1982) is assumed to vary with tem- refers to earlier work done with respect to
 9.4 Diffusion, Relaxation and Crystallization 523

jL0*?0'{5) p

Relaxed at 623 K
{Pre-relaxed 30 m'm
at 5/3 K)
Fe
40 Nl40 B
20
- ; •

179-

-3-

623
1000
time (s)
-4

60

Figure 9-17. Manifestations of relaxation of metal-

lic glasses: (a) irreversible length change of a
Fe 40 Ni 40 B 20 glass; (b) short-term reversible changes
of Young's modulus of Co 58 Fe 5 Ni 10 B 16 Si 11 glass cy-
cled between 623 K and 723 K; (c) longterm change of
Young's modulus in the same glass at various temper-
atures, from the as-quenched state; (d) changes of
Curie temperature of Fe 80 B 20 glass as a function of
holding time at various temperatures above the Curie
temperature, substantially reversible; dashed lines in-
dicate incipient crystallization; (e) reversible changes
of coercive field of the above-mentioned Co-rich
10 12 U
glass, a composition of low magnetorestriction, dur-
tjh] ing cyclic annealing. (After Cahn, 1983.)
524 9 Metallic Glasses
1.5U60
Equilibrium line
1.51430
200 300 400
Time in minutes
Figure 9-18. Refractive index vs. time in a crossover ex-
periment on a borosilicate glass. The glass was held at
temperature Tx until the index reached the value char-
acteristic of equilibrium at a second, higher tempera-
ture T2. The temperature was then changed abruptly
to T2: instead of remaining steady, the index followed
the curve shown, returning eventually to the T2 equi-
librium value. (After Macedo and Napolitano, 1967.)
the refractive index of a borosilicate glass
(Macedo and Napolitano, 1967). The cap-
tion indicates the treatment used. - Such
behavior can only mean that two or more
distinct atomistic processes, with different
activation energies and different kinetics,
operate simultaneously: it also implies that
there is not a one-to-one relationship be-
tween measurable properties and the inter-
nal state of the glass, in the sense that the
same value of a property can be associated
with distinct states generated by different
heat-treatment programs. A thorough
analysis showed that, in fact, not two but a
spectrum of activation energies has to be
operative (Gibbs et al., 1983; Leake et al.,
1988), and this idea has had a major effect
on subsequent theories of relaxation phe-
nomena. The idea has been used to partic-
ularly good effect in a long series of papers
by van den Beukel and colleagues, in which
the relaxation of a number of properties,
including viscosity, length changes, resis-
tivity, Young's modulus and Curie temper-
ature, mostly in Fe 4 0 Ni 4 0 B 2 0 glass, was
analyzed experimentally and theoretically
in great detail. Their entire programme of
research has been summarized (van den
Beukel, 1986). This work is too complex
and extensive to treat here.
Most commonly, relaxation kinetics of
various properties follow a In t law, which
has been shown to be consistent with the
existence of a spectrum of activation ener-
gies.
Not only melt-quenched glasses relax.
Thus Riveiro and Hernando (1985) mea-
sured the relaxation of coercive field in an
electrodeposited Co 91 P 9 glass, and found a
drop by two orders of magnitude. They
were able to analyze this change in terms of
the spectrum of activation energies and de-
cided that at least 4 distinct processes were
in play; they also concluded that the diffu-
sion of P atoms from "unstable" to "stable"
holes was the main relaxation process.
When a metallic glass is stressed at a
high temperature, it undergoes homoge-
nous flow by a purely viscous process. (At
room temperature, flow proceeds inhomo-
geneously, along shear bands - see Vol. 6,
Chap. 11). As creep proceeds, free volume
is progressively annealed out and since the
viscosity is directly linked to free volume
(see Chap. 3, this Volume), the creep rate
under constant stress progressively dimin-
ishes. The relation between viscosity, rj,
stress, <T, and strain rate, £, is: rj = (1/3) a/s.
Instead of a constant-stress creep test, one
can also measure stress relaxation at con-
stant strain or perform a bend stress relax-
ation experiment (a ribbon is elastically
bent and held at a fixed radius while it is
annealed, and then released to see how far
it springs back). A brilliant series of exper-
iments to study these processes, mostly
with Pd 82 Si 18 glass, was performed by
Spaepen and Taub and reviewed by them
(Spaepen and Taub, 1983).
According to the Stokes-Einstein rela-
tion, t] = k T/D b, where D is a self-diffusiv-
ity and b is a characteristic distance of the
same order as the interatomic distance

1O 1;
1011
>10 1 0
-a
/ <100
Tensile creep
] 104
9 I 117
10 Tensile stress f 100-400
relaxation (100-400
Bend stress { 30-330
relaxation
108
1.4 1.6 1.8 2.0 2.2
10 3 / T in K"1
(Nachtrieb, 1976). The rise in viscosity on
relaxation due to reduced free volume is
thus associated, as we have already seen,
with a fall in diffusivity.
The free volume model of flow and vis-
cosity, originated by Cohen and Turnbull,
can be outlined as follows: Each atom is
confined in a cage defined by its nearest
neighbors; that cage can vary in volume,
and the free volume is that part of a cage in
which the atom can move without an en-
ergy change. Normally the atom can only
oscillate, but if there is a density fluctua-
tion, there is a computable probability (de-
pendent of course on temperature) that the
atom will jump to a neighboring cage if
the fluctuation generates an instantaneous
local free volume exceeding a critical
amount. Such jumps define both viscosity
and creep rate under stress. Relaxation di-
minishes the average free volume and thus
increases the viscosity, linearly with time as
it turns out. Fig. 9-19 shows how the (lin-
ear) rate of increase of viscosity varies with
temperature for a metal-metalloid glass. -
9.4 Diffusion, Relaxation and Crystallization 525
10 A
Figure 9-19. Rate of
a change of viscosity of
O Fe 40 Ni 40 P 14 B 6 glass with
V
time as a function of tem-
A
perature, as measured by
• three different experimental
• techniques. (After Spaepen
and Taub, 1983.)
2.4 2.6 2.8
Attempts to interpret such relaxation-in-
duced changes quantitatively are still beset
by some difficulties, notably the need to
assume that the concentration of flow de-
fects (unlike free volume collectively) to
some extent changes reversibly with tem-
perature. A "flow defect" here is a particu-
lar configuration of free volume of a kind
which favors atomic jumps, as sketched
out above. For details of the theoretical
considerations involved, the reader is re-
ferred to Spaepen and Taub's review, and
to other detailed reviews by Chaudhari
et al. (1983) and Spaepen et al. (1986). It is
undoubtedly very difficult to define in an
acceptable operational manner what is
meant by a defect in an amorphous struc-
ture; one very recent attempt to do so
(Calvo, 1991) leans on a method originally
introduced for quasicrystals.
Although the theory of the glass transi-
tion is not discussed in this Chapter, it is
worth pointing out that an effective theory
linking the glass transition and relaxation
in terms of free volume has recently been
526 9 Metallic Glasses

(1985), by measurement of the change of

X-ray absorption by a foil of metallic glass.
The change of density of Pd-Si based
glasses in these two studies ranged from
0.14 to 0.25% (Fig. 9-20). - The most direct
way of measuring changes in TSRO would
be to monitor changes in the diffraction
pattern. This is exceedingly difficult be-
cause the changes are so small. The first
serious attempt to detect such changes was
120 240 360 by Egami (1978): he used the highly sensi-
Time in min tive energy-dispersive X-ray diffraction
Figure 9-20. Relative change in the density of method. Later, Chason et al. (1985), in the
Pd 82 Si 18 glass as a function of annealing time at study just cited, determined the change in
260 °C, determined from changes in x-ray absorption. the profile of the first diffuse X-ray diffrac-
(After Chason et al., 1985.)
tion peak from Pd 82 Si 18 and related this to
the measured change in resistivity, which is
published by van den Beukel and Sietsma closely linked with the structure factor in
(1990). the neighborhood of the first peak. The
To conclude this Section, we consider observed and calculated change of resistiv-
the possibility of direct experimental anal- ity matched well.
ysis of changes in TSRO during relaxation. The structural relaxation of a-Si (see
On a coarse scale, one can estimate the Sec. 9.3.4) has been determined by X-ray
reduction in free volume by measuring the diffraction (Roorda, 1990) and here the
change in length (e.g., Huizer and van den changes are much more substantial than in
Beukel, 1987) or even more directly, the a metallic glass (Fig. 9-21). The changes
change in density resulting from relax- correspond to enhanced ordering over a
ation. This last has been measured in an range of several atomic distances, but with-
experimental tour de force by Chason et al. out any change in nearest neighbor separa-
tions. The nature and kinetics of the relax-
ation process in this material has also been
20
V)
studied by Raman spectroscopy, which is
Annealed at 500°C sensitive to the distortion of covalent bond
Annealed at 230°C
S 15 as implanted angles - a method not applicable to metal-
lic glasses (Sinke et al., 1988 b).
^ 10
c
9.4.3 Thermal Embrittlement
c
0)
Many metallic glasses are capable of a
moderate degree of plastic deformation at
room temperature: the process is heteroge-
0 2 4 6 8
k in A"1
neous and involves the formation of shear
Figure 9-21. X-ray diffraction pattern of a-Si made by bands approximately along a plane of
ion implantation, before and after relaxation anneals. maximum resolved shear stress. A ductile
(After Roorda, 1990.) metal ribbon can generally be plastically
 9.4 Diffusion, Relaxation and Crystallization 527

bent sharply back on itself. Some such

glasses, mostly those based on iron (one 350°C-2hr
might call these "glassy steels"), show (1) a r BD =97°C
—•—1
ductile-brittle transition temperature and
c 10°
(2) the phenomenon of thermal embrittle-
ry
• •••
o -
t_
ment, which is marked by an increase in the In

ing
ductile-brittle transition temperature on
T3 1
annealing below the crystallization tem- c
0)
perature. Fig. 9-22 exemplifies these phe- .a 1n -1
»
Q> 1U
nomena. The mechanism of the embrittle- •3
•
•
••
(_)
0
I •
ment process has given rise to a great deal «_
• • •
li_ L • •• -n
of debate and investigation. •
••
Spaepen (1977) first put forward the idea 10"2
• • •
••
that shear band formation (morphologi-
cally similar to slip bands in crystalline
metals) is to be attributed to a multiplica- 1 1 1 1 1 1
30 50 70 90 110 130 150 170
tion of free volume at an incipient band,
(a) Testing temperature in °C
which reduces the flow stress locally so
that the shear band develops preferentially.
Cahn et al. (1984) showed that the overall
density reduction in a Pd-Cu-Si glass due
to a 40% rolling reduction was 0.14%, 300
which implied a much larger density reduc- 260 - Isochronal annealing, fA = 2hr
tion within the narrow shear bands them- \
1
220 - 1
selves. This notion was further analyzed by i
1

Argon et al. (1985), and they concluded, 180

Crystallization 1 ' *
from measured overall density changes in 140
heavily deformed glasses (rolling or wire- O 100 -
drawing) and the observed shear band ge- o

ometry, that within a shear band itself the .£ 60 -

.§
local dilatation due to free volume can be K

J
20
as large as 50%. - Cahn et al. (1984) further -20
showed that the excess free volume in the
shear bands was dissipated during a relax-
ation anneal, while Krishnanand and
-60

-100 \
A
Cahn (1975) had earlier shown that after -140
such a relaxation anneal and renewed plas-
-180
tic deformation, the new population of 240 280 320 360 400
shear bands was not in the same sites as the (b) in °C
old ... i.e., the old shear bands had been Figure 9-22. (a) Strain at fracture in a bending test as
totally "healed" by the relaxation anneal. a function of temperature for a Fe 79 3 Be 16 4 Si 4 0 C 0 3
It can thus be taken as well established glass, annealed for 2 h at 350°C after melt-spinning.
TBD is the ductile-brittle transition temperature,
that free volume plays a central role in (b) Change of TBD with isochromal anneals at progres-
both homogeneous (creep) and heteroge- sively increasing temperature: same glass. (After
neous plastic flow in metallic glasses. Spaepen et al., 1986.)
528 9 Metallic Glasses
The theories to explain thermal embrit-
tlement fall into two categories: (1) the hy-
pothesis that annealing removes excess free
volume and (2) the hypothesis that the ho-
mogeneous glass structure separates into
two distinct amorphous phases. The basis
of the first hypothesis is clear from the fore-
going: further, Wu and Spaepen (1986)
have assembled detailed evidence on ther-
mal embrittlement consistent with this
model. The second hypothesis leans on ob-
servations such as that due to Walter et al.
(1976), who by Auger electron spectros-
copy established an enrichment of P at
fracture surfaces of a Fe 40 Ni 40 P 14 B 6 glass,
and Piller and Haasen (1982) who used
field ion microscopy to demonstrate the
formation, during relaxation annealing of
Fe 4 0 Ni 4 0 B 2 0 , of minute zones enriched in
boron to 25 at.%. However, tests by X-
ray small-angle scattering of some other
glasses have failed to demonstrate phase
separation of this kind, whereas other ex-
periments have given contrary results. The
literature is quite extensive.
A possible marriage between the two
types of hypothesis has been proposed in
an interesting paper by Yavari (1986). By
analyzing the volume per metal atom in
Fe-B glasses of different compositions, he
shows that a local enrichment of B will
need to "suck" free volume from the adja-
cent matrix, reducing the free volume con-
centration there. He suggests, therefore,
that the phase separation hypothesis re-
solves itself, indirectly, into the free volume
hypothesis. According to Yavari, the fact
that some additives (e.g., Ce) delay embrit-
tlement to higher temperatures, whereas
others such as Sb promote it, can also be
interpreted on the basis of his model. -
Another observation (Yamasaki et al.,
1985) to the effect that Fe-based glasses
whose compositions fall close to an equi-
librium eutectic composition embrittle
much more sluggishly, if at all, is attributed
to a reduced tendency to phase separation
for such compositions.
The clearest demonstration to date of
the central role of free volume in determin-
ing the incidence of thermal embrittlement
comes from an important series of publica-
tions by Gerling et al. (1985, 1988, 1989,
1990) relating to Fe 4 0 Ni 4 0 B 2 0 glass.
Briefly, they have established in circum-
stantial detail how this glass is embrittled
by the loss of free volume on annealing; for
instance, the embrittlement behavior
varies with ribbon thickness, because the
quenched-in free volume varies also. They
have further shown that a glass which has
been thermally embrittled can be reduc-
tilized by neutron irradiation, which cre-
ates fresh free volume. The new ductility
can in turn be removed by a second relax-
ation anneal.
9.4.4 Relaxation of Magnetic
and Elastic Properties
Changes in the Curie temperature,
which is particularly affected by CSRO,
and of the coercive field, have already been
discussed. A number of other magnetic
properties have also been studied in rela-
tion to relaxation.
The magnetic and mechanical properties
of soft ferromagnetic metallic glass sheets,
which are now widely used for transformer
laminations (see Sec. 9.6.1) are consider-
ably affected by relaxation anneals. Be-
cause of the role of magnetostriction in
enhancing core losses, it is important to
remove residual stresses without changing
glass structure appreciably. Taub (1984)
has shown that a short pulsed anneal at
high temperature is much more effective in
achieving this than a long anneal at a lower
temperature. A comprehensive study of the
effect of annealing on a range of properties,
 9.4 Diffusion, Relaxation and Crystallization
with special emphasis on magnetic ones
(Liebermann et al, 1989) of Fe 78 B 13 Si 9
glass has reached the conclusion that em-
brittlement is associated with clusters as
small as 0.3 nm in size. The authors also
established that stress relief was complete
at annealing temperatures lower than
those at which embrittlement began; it is
thus possible to achieve the desirable ob-
jective of stress relief without embrittling
the laminations.
Another form of magnetic relaxation
which is of practical importance is the gen-
eration of magnetically induced uniaxial
(ferromagnetic) anisotropy. This is a form
of "magnetic annealing" well known in fer-
romagnetic crystalline solid solutions
(Graham, 1959) but less familiar in glasses.
The relevant theory is well established. The
phenomenon is of practical concern be-
cause an induced uniaxial anisotropy af-
fects the response of magnetic components
to applied fields. - An alloy is annealed in
a magnetic field at a temperature high
enough to permit exchange of places be-
tween neighboring atoms, and pairs of un-
like atoms tend to line up preferentially
parallel to the field, inducing a magnetic
anisotropy. The statistical tendency for
this to happen is very weak, but magnetic
measurements are ultrasensitive even to
minute amounts of directional short-range
order which would be too weak to measure
by X-ray diffraction. The phenomenon is
best defined where two distinct kinds of
metal atom are present (usually, Fe and Ni)
and is most pronounced for concentrated
solid solutions, since it depends on the
presence of numerous pairs of unlike
nearest neighbor atoms. The kinetics of re-
orientation of the preferred magnetic direc-
tion when the field direction is changed
depends on self-diffusivities in the alloy
concerned, although no attempts have
been made to measure diffusivities in this
529
way. The establishment of directional SRO
(which can exist at the same time as normal
isotropic SRO) is reversible, in the sense
that a change in direction of the applied
field, or its removal, will redirect or destroy
the directional SRO. The phenomenon,
which deserves more exploitation than it
has had as a useful way of measuring struc-
ture change kinetics in metallic glasses, is
described in detail by Luborsky (1980).
Evetts and Hodson (1985) have in fact ana-
lyzed the kinetics of the process (which
they term 'polarization') in terms of the
concept of a spectrum of activation ener-
gies, mentioned in Sec. 9.4.2.
A closely related process is stress-in-
duced ordering; here the external influence
is a stress instead of a magnetic field, and
the measured property is anelastic strain
instead of a magnetic anisotropy. In an
experimental tour de force, Suzuki et al.
(1987) were able to show directly, by ener-
gy-dispersive X-ray diffraction from a
stress-annealed Fe 40 Ni 40 Mo 3 Si 12 B 5 glass
done successively with two orthogonal dif-
fraction vectors, that directional order
(they called it 'bond-orientational an-
isotropy') was induced by stress-annealing
and decayed on subsequent stress-free an-
nealing. The ordering kinetics followed In t
kinetics, characteristic of a material with a
spectrum of relaxational activation ener-
gies. According to their model, bond-orien-
tational anisotropy involves a directional
variation in the number of all kinds of
bonds, whereas the accepted theory as ap-
plied to crystalline alloys involves, as we
have seen, anisotropies in different kinds of
bonds. In fact, a more recent study from
the same laboratory (Tomida and Egami,
1991) recognizes that chemical as well as
topological anisotropy is involved in bond-
orientational anisotropy.
A recent study of stress-induced order-
ing in Fe 4 0 Ni 4 0 B 2 0 glass, by Leusink and
530 9 Metallic Glasses
van den Beukel (1988), has proved that the
ordering kinetics is determined by the
amount of free volume present. As these
authors point out, this is a good way of
estimating the kinetics of establishment of
CSRO in a metallic glass; the fact that the
state of order here is anisotropic rather
than isotropic is of no consequence.
Other special forms of relaxation, partic-
ularly magnetoelastic and thermoelastic
relaxation in metallic glasses, and internal
friction, are reviewed by Kiinzi (1983). In-
ternal friction can be used to monitor
structural changes; this was done, for in-
stance, in a study by Sinning et al. (1991) on
crystallization of a C o - Z r - H glass, to be
cited in the next Section.
9.4.5 Crystallization
When a metallic glass is heated, it will
crystallize to form some combination of
intermetallic compounds and metallic
solid solutions, just as an oxide glass crys-
tallizes to form a glass-ceramic. The
nomenclature of the product poses a prob-
lem: "Glass-alloy" has not found favor,
"Pyromet" by analogy with "pyroceram" is
excluded because the word is a registered
trademark; there is a family of engineering
alloys made by crystallizing, or "devitrify-
ing" metallic glasses with the trade name
"Devitrium"; probably "devitrified alloy"
is the best available generic term.
Crystallization mechanisms of metallic
glasses are generally divided into three cat-
egories - polymorphous, eutectic and pri-
mary crystallization (Koster and Herold,
1981) - to which a fourth, crystallization
with phase separation, can usefully be
added:
- In polymorphous crystallization (e.g.,
of Fe 7 5 B 2 5 glass), a single intermetallic
compound crystallizes without change of
composition.
- In eutectic crystallization (e.g., of
Fe 8 0 B 2 0 glass), the glass transforms to two
phases growing in a closely coupled form.
In the example cited, the constituent
phases are a-iron and Fe 3 B. There is no
change in overall composition between the
glass and the eutectic colony.
- In primary crystallization (e.g., of
Fe 8 6 B 1 4 glass), a primary phase, here a-
iron, crystallizes out first, which involves a
change in composition of the residual
glass; later, a compound, here Fe 3 B, crys-
tallizes separately (i.e., not in closely cou-
pled form).
- In crystallization with phase separa-
tion, the glass itself phase-separates into
two distinct amorphous phases with differ-
ent compositions and glass transition tem-
peratures, and these then crystallize at dif-
ferent temperatures during further heating.
A good example of a glass behaving like
this is Zr 3 6 Ti 2 4 B 4 0 (Tanner and Ray,
1980).
Early studies of crystallization of metal-
lic glasses largely depended on the use of a
differential scanning calorimeter (DSC),
which generates curves such as that shown
in Fig. 9-23. In this particular instance, it is
not certain whether the double peak is due
to amorphous phase separation (there is a
faint indication of a second glass transi-
tion) or to primary crystallization followed
by crystallization of a small amount of re-
sidual glass at a higher temperature. This
uncertainty indicates that micrographic
examination is really necessary as well to
determine crystallization mechanisms for
certain, and this has been widely done for
a variety of glasses (see reviews by Koster
and Herold, 1981; Scott, 1983; Koster and
Schunemann, 1992). A very large literature
exists on the results of such investigations,
which it would not be profitable to review.
Many studies have examined the effect on
crystallization mechanisms and kinetics of
 9.4 Diffusion, Relaxation and Crystallization
I I I I I
230 270 310 350 390 430 470 510
Temperature in °C
Figure 9-23. Differential scanning calorimeter record
during heating, at 20Kmin~ 1 , of Pd 77 5 Cu 6 Si 16 5
glass. The ordinate represents power released (exo-
therm upwards) or absorbed (endotherm down-
wards). Tg is clearly differentiated from the first crys-
tallization peak, Txl.
changing the proportion of the constituent
elements. A good, very recent specimen of
this literature is a paper by Sprengel et al.
(1990) on the crystallization of a range
of Co-Zr glasses. Other investigations,
which are increasing in frequency, have ex-
amined the effect of systematically varying
ternary additions to a fixed binary compo-
sition (e.g., Bhatnagar et al., 1990, with re-
spect to NiZr 2 plus Al or Ga; Ghosh et al.,
1991, with respect to "micro-additions" to
Ni 24 Zr 76 ). - For detailed information the
reader is referred to the cited overview arti-
cles.
The crystallization temperature not only
depends on the alloy system but also varies
somewhat with the composition of the
glass within a given system. This is exem-
plified by Fig. 9-24, for the Fe-B system:
this shows that the same system can show
single or double crystallization peaks, ac-
cording as the type of crystallization
531
changes between the various categories
listed above.
The activation energy for the crystalliza-
tion process as a whole, which is usually
well defined, is obtained by varying the
heating rate in the DSC and applying a
theory developed by Kissinger (1957) to
the measured peak values of crystallization
temperature. However, as often in physical
metallurgy, little useful has been done with
the activation energies once they have been
determined! They could be compared with
activation energies for the self-diffusion of
the constituent species, where known, to
help define rate-determining process in
crystal growth, but this does not appear to
have been widely done. (However, Koster
and Herold (1981) have used crystalliza-
tion kinetics as an indirect way to estimate
diffusion rates, without being able to deter-
mine which diffusing species is rate-deter-
mining.)
DSC studies can only encompass a lim-
ited range of heating rates, approximately
5-100 K/min, and until recently no meth-
ods were available to study crystallization
kinetics and mechanisms at very high heat-
ing rates or isothermally at high tempera-
tures. This has been altered by the intro-
350,
Figure 9-24. Crystallization temperatures Tcryst (peak
in DSC continuous-heating records for different heat-
ing rates) of Fe-B metallic glasses. The various sym-
bols refer to different investigators. (After Koster and
Herold, 1981.)
532 9 Metallic Glasses
duction of time-resolved X-ray diffraction,
in which extremely intense monochro-
mated X-ray beams from a synchrotron
source are combined with very rapid
(«10 4 K s ~x) electrical self-heating of glass
ribbons to constant high temperature (Sut-
ton et al, 1989). With the aid of position-
sensitive X-ray detectors, an entire diffrac-
tion pattern can be determined in as little
as 3 ms. In this first study by the new
technique, polymorphous crystallization
of NiZr 2 was studied up to 680 K (at
which temperature, 50% crystallization is
achieved in 4 s) and it was established that
at these high temperatures, a transient pre-
cursor phase is formed initially.
From a practical viewpoint, plots like
that shown in Fig. 9-25 are useful. These
are obtained by isothermal anneals (less
often used than continuous heating ones)
at a range of temperatures.
Metal-metal glasses are of particular
interest because some of them have very
high crystallization temperatures. Notable
among these are W 65 Ru 35 , W 50 Re 50 (both
with T x ^800°C, and Ta 55 lr 45 , with T x ^
^900°C (Denier van der Gon et al., 1987).
Such glasses have found an unexpected ap-
Temperature. T in °C
450 400 350
Fe*oN'*opuB6
1.4 1.5 1.6 17
1000/7" in K"1
plication because of their resistance to
crystallization (Sec. 9.6.5). These high crys-
tallization temperatures have been success-
fully rationalized on the basis of Buschow's
hole model of diffusivities (Sec. 9.4.1).
Attention has recently moved from the
simple determination of crystallization
temperatures to the investigation of nucle-
ation mechanisms, in particular, whether
nucleation in particular case is homoge-
neous or heterogeneous, and to a study of
the role of heterogeneous nucleation at the
free surface of a glass.
The leading investigator in recent years
into nucleation mechanisms and kinetics
has been Greer. His series of papers began
with an important study of the crystalliza-
tion of Fe 8 0 B 2 0 glass (Greer, 1982). His
approach combines DSC and micro-
graphic observation with modelling. Iso-
thermal DSC runs (with elaborate correc-
tions for various sources of error) were
used to fit the parameters of the standard
Johnson-Mehl-Avrami equation, x (t) =
l - e x p ( - K t " ) , where x{t) is the frac-
tion crystallized in time t and K = Ko
• Qxp( — E/kT). Special steps are taken to
make allowance for the mutual impinge-
300
Figure 9-25. Time for the start of
crystallization of a range of metal-
lic glasses as a function of temper-
ature. (After Luborsky, 1980.)
1.8
 9.4 Diffusion, Relaxation and Crystallization 533

ment of growing grains. TEM established

the growth rate of crystals at specific tem- as-quenched
peratures. These correspond to an expo-
nent, n = 3 in the above kinetic equation.
Putting all this information together al-
lowed a computer model to be set up for 3 0.4

the crystallization kinetics during continu-

ous heating in a DSC, which permits the
highest precision, and the experimental
output was compared with the predictions
from the model. Fig. 9-26 shows the results
in the form of a dx/dt plot derived both 0.0
680 700 720
from the DSC output and from the fitted TEMPERATURE(K)

model, both for the as-quenched glass and Figure 9-26. Crystallization kinetics, dx/dt, deduced
for a sample preannealed at a constant from continuous DSC heating data, for Fe 80 B 20 glass
32 urn thick (solid curves), compared with fitted
temperature (which initiates crystallization curves derived from a model. The lower peak corre-
on preexisting nuclei). One adjustable pa- sponds to a preannealed sample. (After Greer, 1982.)
rameter, Ko, is adjusted to give the best fit
for both curves and it can be seen that a
very exact fit was obtainable for experi- rate increasing from zero to a steady state
mental peaks, except for a small unfitted value as the material is undercooled. (In
subsidiary peak at high temperatures. the case of Fe 8 0 B 2 0 Just discussed, the ob-
(This was shown to be due to a thin surface servations fit the hypothesis of transient
skin on the ribbons which was known to nucleation during the quench itself.) Fig.
contain no preexisting nuclei, so that crys- 9-27, taken from a review of nucleation
tallization of this skin was delayed until mechanisms (Greer, 1988) shows schemati-
new nuclei could form.) Greer showed that cally the different forms of nucleation
Ko is directly proportional to the nucleus
density for a fixed growth rate, and was
able to deduce a nucleus density (not af-
fected by the preanneal) of3.5xl0 1 8 m~ 3 .
This was checked against the grain concen-
tration in partly crystallized specimens as
determined by TEM, and fitted well. At
this stage, he could not be certain as to the
nucleation mechanism, but because of
the very high nucleus density he deduced
that it was very probably a homogeneous
mechanism. - He found that the nucleus
density was very sensitive to the thickness Time
of the ribbon and thus to the quench rate. Figure 9-27. Schematic variation in the number of
The next stage was to study both theo- nuclei with time in an isothermal anneal for the
following nucleation types: (a) steady-state homo-
retically and experimentally the phe- geneous; (b) transient homogeneous; (c) steady-
nomenon of transient homogeneous nucle- state heterogeneous; (d) transient heterogeneous;
ation; this term is applied to a nucleation (e) quenched-in active nuclei. (After Greer, 1988.)
534 9 Metallic Glasses
which can arise during crystallization of a
glass (and beforehand, during the quench).
Kelton and Greer (1986) published a de-
tailed analysis of the role of transient ho-
mogeneous nucleation in glass formation
and showed that a glass can sometimes
form only because nucleation was of the
transient rather than the steady-state type.
This is exemplified by Fig. 9-28, which
shows calculations, based on known mate-
rial parameters, for both types of nucle-
ation for Au 81 Si 19 . The dashed line in the
lower figure indicates the low level of vol-
ume fraction transformed which has usu-
ally been taken as the condition for form-
ing a metallic glass successfully; it can be
seen that this level is achieved with tran-
sient nucleation for a quench rate of
105 K s" 1 , whereas for steady-state nucle-
ation the unrealistic rate of 10 8 Ks~ 1
would be needed.
Au 81 Si 19
10 5 10 6 10 7
Quench r a t e in K / s
Figure 9-28. (a) The number of nuclei and (b) the
transformed crystal fraction calculated for quenching
molten Au 81 Si 19 at various rates, assuming either
steady-state or transient homogeneous nucleation.
(After Kelton and Greer, 1986.)
Homogeneous nucleation has been
firmly established in the much-studied
Fe 40 Ni 40 P 14 B 6 glass, by appeal to crystal-
lite counting (Morris, 1982) and a few other
metal-metalloid glasses. Other glasses in
which homogeneous nucleation is much
slower, notably Pd 4 0 Ni 4 0 B 2 0 (Drehman
and Greer, 1984) crystallize predominantly
heterogeneously, both from internal de-
fects and from defects at free surfaces. Even
for such alloys, homogeneous nucleation
with the concomitant fine grain size can be
achieved by first annealing close to the
temperature of maximum nucleation fre-
quency and then raising the temperature to
allow the nuclei thus formed to grow. Con-
trariwise, this same alloy can be formed
into large glassy volumes, « 1 cm3, by cool-
ing at a rate as low as 1 K s ~ 1 , if the surface
is cleared of local defects by immersing it in
a molten flux (Kui et al, 1984).
At the opposite extreme, it has recently
been shown (Sinning et al., 1991) that a
Co 33 Zr 67 glass containing a small amount
of hydrogen can be crystallized by fairly
fast heating to give a nanocrystalline struc-
ture (see Vol.15, Chap. 13). This is most
simply interpreted in terms of a very copi-
ous homogeneous nucleation, with a crys-
tal growth rate that slows down sharply at
higher temperatures.
Generally, heterogeneous nucleation is
most clearly demonstrated at free surfaces.
In some instances, the process is so domi-
nant that columnar grains grow in from
the surface while none grow in the interior
- i.e., the exact converse of what is ob-
served in Fe 8 0 B 2 0 , as we have seen above.
However, a glass of this type can crystallize
108 preferentially at the surface if the surface is
chemically or otherwise modified before or
during annealing. Thus, if Fe 8 0 B 2 0 is differ-
entially oxidized so that the boron content
is reduced at the surface (Koster, 1984),
preferential surface nucleation is found.

The related composition Fe 4 0 Ni 4 0 B 2 0 be-
haves similarly; here, iron is preferentially
removed. Recently, Wei and Cantor (1989)
made a detailed study of surface crystal-
lization of Fe 4 0 Ni 4 0 B 2 0 and found that it is
enhanced if the alloy is first phase-sepa-
rated by relaxation and then abraded at
the surface, or else the surface is enriched in
Ni by electroplating Ni and then annealing
the glass. Sometimes, surface oxidation can
have the opposite effect of inhibiting sur-
face crystallization; with Pd 4 0 Ni 4 0 P 2 0 , a
thin NiO layer protects the glass from local
loss of P; such loss is the prime cause of
preferential surface nucleation. - Removal
of the original surface can drastically mod-
ify crystallization behavior: thus, Ni 6 6 B 3 4
glass (which normally crystallizes from the
surface with a strong accompanying [100]
fiber texture, loses the quenched-in nuclei
responsible for this if the surface is etched
off (Koster and Schiinemann, 1991). Ac-
cording to the same authors, another way
of inhibiting surface crystallization is to
remelt the original surface by means of la-
ser pulses; the self-quenching resulting
from this seems to be fast enough to obvi-
ate quenched-in nuclei.
Clearly, the variegated phenomena sur-
rounding surface nucleation during the
crystallization of metallic glasses as yet
defy generalization, and it must be left to
future research to systematize and inter-
pret them, as homogeneous nucleation has
recently been interpreted. Certainly, there
is a practical interest in gaining such un-
derstanding, because preferential surface
nucleation can produce undesirable side-
effects, such as increased magnetic eddy
current losses in surface-crystallized soft
magnetic glass ribbons for high-frequency
applications (Datta et al., 1982).
9.5 Chemical Properties 535
9.5 Chemical Properties
A good deal of research has been done,
mostly in Japan, on the corrosion resis-
tance of metallic glasses, which can be
spectacularly good. Much more recently,
such research has extended also to the cat-
alytic and electrocatalytic properties of
suitable treated metallic glasses. A com-
bined overview of these fields of research
can be found in a recent conference pro-
ceedings (Diegle and Hashimoto, 1988)
and in review papers (Hashimoto, 1985,
1992). Here we have space only for a sum-
mary.
9.5.1 Corrosion Resistance
The wet corrosion resistance of metallic
glasses is greatly affected by their struc-
tural and chemical homogeneity. In partic-
ular, there are no grain boundaries with
their frequent forms of chemical hetero-
geneity; accordingly, no electrolytic micro-
circuits are set up with their bad effects on
corrosion resistance.
Most of the research which has been
done on iron-base glasses containing
metalloid addition, in various acids and
sodium chloride solutions, although very
recently, work has been extended to some
metal-metal glasses, for instance in the
Ni-Ta series. With respect to Fe-based
glasses, the following have been thor-
oughly established:
1) Most metallic solutes increase corro-
sion resistance; Cr and Mo are particularly
effective, most so in combination. By way
of example, a-Fe 72 Cr 8 P 13 C 7 passivates
spontaneously in 2 N HC1 (a very powerful
corrodant) at ambient temperature, while
some glasses containing both Cr and Mo
will passivate spontaneously even in hot
concentrated HC1.
536 9 Metallic Glasses
2) Metalloids accelerate passivation by
aiding the dissolution of all constituents
other than the passivating one from a thin
surface layer; P has been found to be par-
ticularly effective. Accordingly, even small
amounts of Cr, « 3 at.%, can lead to much
higher surface concentrations of Cr ion
than is found on crystalline stainless steels.
On Ni-Ta and N i - N b glasses, the
cations in the highly effective passive films
are almost pure Ta 5+ or N b 5 + . Ni-Ta
glass is more resistant to hot phosphoric
acid than pure Ta.
9.5.2 Heterogeneous Catalysis
and Electrocatalysis
Research has been concentrated on cata-
lysts for gas-phase reactions such as the
hydrogenation of CO or methanol synthe-
sis, and on electrocatalysts for electrodes
used in fuel cells and for electrowinning of
metals (see Sec. 9.6.4). The recent literature
makes one thing quite clear: while metal-
metal glasses often make excellent cata-
lysts, they do so only after treatments
which wholly or partly crystallize the sur-
face; unmodified glasses are not effective
catalysts. One must therefore think of
metallic glasses as precursors for catalysts,
although according to a quite recent re-
view (Schlogl, 1985) this was not yet clear
at that time.
The most comprehensive review, written
more with emphasis on the chemical reac-
tions which can be catalysed than on the
state of the catalysts, is by a Hungarian
group (Molnar et al, 1989); this cites 177
references.
Selective oxidation of, or the absorption
of hydrogen in, glasses such as Ni-Zr,
Cu-Zr or P d - Z r modifies their surface
(e.g., the early study by Spit et al., 1981). A
recent study by Vanini (1990), using Auger
electrons and X-ray diffraction, shows that
hydrogen absorption in various Cu-Zr
glasses generates a Cu-enriched surface
layers containing Cu microcrystals. A P d -
Zr glass, activated in CO, O 2 , CO 2 or H 2 ,
crumbles to a powder consisting of fine Pd
and ZrO 2 particles. The catalytic effective-
ness of such catalysts depends entirely on
the fineness of the crystalline metal parti-
cles produced during activation. In both
Cu-Zr (Vanini, 1990) and Ni-Zr (Spit
et al., 1981) the activity is enhanced be-
cause the Cu or Ni can diffuse to the sur-
face along the surface of cracks opened up
by the hydrogen activation. Selective oxi-
dation operates in much the same way to
provide an activation mechanism as does
hydrogen absorption (Schlapbach et al.,
1980).
Some experiments have also been done
with metal-metalloid glassy precursors.
Guczi and his coworkers (e.g., Kisfaludi
et al., 1987), who sought to catalyze the
hydrogenation of CO with Fe-B and
F e - N i - B glassy catalysts, found that par-
tially crystallized alloys were more effective
than wholly crystalline ones, primarily be-
cause in that state, very small iron particles
are stabilized.
The important Japanese work on acti-
vated electrode alloys is outlined in Section
9.6.4.
9.6 Applications
Up to the present, the only bulk use of
metallic glasses has exploited the soft mag-
netic properties of certain Fe-based glasses
in the form of transformer laminations.
However, other magnetic uses, and to a
lesser degree electrocatalytic uses, are in
the process of developing. The exploitation
of the great strength and good toughness of
some metallic glasses has, somewhat sur-
prisingly, lagged badly behind other cate-
gories of uses.

Since there is room here only for an out-
line of what has been done, especially with
regard to transformer applications (which
is a complex topic in its own right), we cite
three important overviews of applications
of metallic glasses. Luborsky (1983) has an
important overview chapter on applica-
tions-oriented magnetic properties, the
Proceedings of the Fifth Conference on
Rapidly Quenched Metals (Steeb and War-
limont, 1985) have over 200 pages of pa-
pers specifically devoted to various types of
application, mostly of metallic glasses, and
a book on metallic glasses (Anantharaman,
1984) has 4 chapters on applications.
9.6.1 Magnetic Applications
The growing use of wide sheets of Fe-
based metallic glass, made by planar flow-
casting, as transformer laminations, is
based essentially on two properties of the
best of such glasses: a more slender magne-
tization (hysteresis) loop than grain-ori-
ented Fe-Si sheet, the excellent material
used for over half a century for this pur-
pose, can achieve (Fig. 9-29); and a higher
electrical resistivity, which reduces induced
eddy currents in comparison to the crys-
talline Fe-Si alloy. The slenderer hys-
teresis loop is associated with a lower satu-
ration magnetization: this is an ines-
capable price, because intrinsically, no
glass can achieve as good a magnetization
as almost pure iron. The gradual recogni-
tion that a metallic glass could outperform
crystalline alloys which had been gradually
perfected over many years led to a progres-
sive improvement of glass compositions as
well as technical improvements in the eco-
nomic production of wide sheets, culminat-
ing in the glass composition Metglas®
2605 SC, Fe 81 B 13>5 Si 3 . 5 C 2 ("Metglas" is a
trademark of Allied-Signal Corporation);
an improved alternative is 2605 S2,
9.6 Applications 537
-1.0 -0.5 0 0.5
H in A/cm
Figure 9-29. Comparison of the hysteresis loops at
mains frequency for Metglas 2605 SC (0.4 mm thick)
and crystalline Fe-3 wt.% Si sheet (0.3 mm thick). (Af-
ter Hilzinger, reproduced by Anantharaman, 1984.)
Fe 78 B 13 Si 9 . In a classical episode of chal-
lenge-and-response, the steel community
has set about improving crystalline Fe-Si
alloys by increasing the Si content from
« 3 to « 6 at.% (with concomitant en-
hanced resistivity and reduced magneto-
striction) by using rapid quenching meth-
ods to obviate extreme brittleness, but they
have not caught up with the best metallic
glasses yet, except for the fact that Fe-Si is
still cheaper than metallic glass.
Fig. 9-30 shows, on a logarithmic scale,
comparative values for the core loss (hys-
teretic and eddy currents) and the exciting
power in watts per kg of core, for oriented
and unoriented Fe-Si and for the best
metallic glass. The superiority of the glass
is very clear. Once the problems of cutting,
coating and winding metallic glass sheet on
an industrial scale had been solved, a large
number of experimental distribution trans-
formers (used in the U.S.A. and Japan to
transform supplies down to the domestic
voltage of 110 V) were successfully made
and evaluated (Natasingh and Lieber-
mann, 1987). Competing designs have also
been described (e.g., Schulz et al., 1988).
The economics of glass-wound transform-
ers well as a critical comparison with those
538 9 Metallic Glasses
M-19 (non-oriented)
(0.36mm thick) />'
6.5wt%Si-Fe-
(0.06 mm thick) -
MetglasR2605S2
(0.03 mm thick)
Exciting power
Core loss
0.01
0.6 0.8 1.0 1.2 U 1.6 1.8 2.0
Induction, B in T
Figure 9-30. Core loss and exciting power vs. induc-
tion at 60 Hz for annealed grain-oriented Fe-
6.5 wt.% Si, non-oriented Fe-3.5 wt.% Si alloy M19
and Metglas 2605 S2. (After Das et al., 1985 a.)
using silicon-iron were discussed by Bailey
and Lowdermilk (1985).
It should be noted that metallic glasses
have not yet been used for large power
transformers (presumably because sheets
cannot be made sufficiently wide). Metallic
glasses are only just beginning to make
inroads into the high-frequency (kHz)
regime, though suitable glasses have been
developed. Datta et al. (1982) have re-
ported on Metglas® 2605 S3, Fe 70 B 16 Si 5 ,
which at up to 100 kHz shows core losses
below those for supermalloy and a high-
frequency ferrite. It seems also that very
small fractions of a-iron precipitates in the
glass help to reduce losses. Glasses do not
as yet seem particularly promising for mo-
tor windings, which is a very large and
lucrative market; this market is particu-
larly sensitive to price, and this may well be
the principal reason.
Metallic glasses have, however, been
used for a range of small-scale applica-
tions, many developed in Japan and Ger-
many; these include sensors and transduc-
ers (exploiting magnetostrictive proper-
10 ties), recording heads, saturable cores,
magnetic switches, magnetometers and
<
other devices used in light electrical engi-
C
1.0 a. neering. These are well reviewed by War-
limont (1985,1988). Magnetic shielding us-
o
a. ing woven tubes or sheet made of narrow
magnetic glass ribbon (Dismukes and Sel-
0.1 o lers, 1978) is another important applica-
tion, bypassing the sensitivity of permalloy
sheet (the crystalline competitor) to even
the slightest deformation: the shielding
0.01 achieved by a glass ribbon is not affected
by elastic bending. Indeed, Fe-based
metallic glasses have the unique distinction
of combining magnetic softness with me-
chanical hardness.
9.6.2 Brazing Foils
One of the less obvious commercial ap-
plications of metallic glasses is for brazing
(DeCristofaro and Bose, 1986; Lieber-
mann and Rabinkin, 1988). Until recently,
furnace brazing of complex assemblies was
performed by placing low-melting brazing
alloy in powder form, as a paste, between
the components to be joined. Most of the
crystalline alloys used are brittle and there-
fore cannot be shaped as sheet. The use of
powder is messy and impossible to dose
accurately. It has been found that brazing
alloys can also be made by melt-quenching
in the form of amorphous sheets. Examples
of such glass sheets are: Cu-P, Ni-Si (B, P),
C o - S i - P , Cu-Ti-Ni. (Other combina-
tions have been melt-quenched in the form
of microcrystalline sheets.) Such sheets are
ductile even when crystalline alloys of the
same compositions are highly brittle, so
that preforms can be stamped out in elabo-
rate shapes to fit precisely between the
components in a brazing operation. - The
alloy compositions are chosen by criteria
such as good GFA, low melting tempera-
ture, low surface tension and constituents
 9.6 Applications 539

Table 9-3. Tensile properties of various continuous filaments and ribbons.

Material Yield Relative Young's

stress density modulus
<iy(GPa) d ffytT^GPa) E(GPa) Ed-^GPa)

S-glass (SiO 2 -Al 2 O 3 -MgO) 5.0 2.5 2.0 85 34

C fibre (high-yield PAN type)a 3.2 2.6 1.7 490 153
B filament (on W core)a 2.5-4.5 2.6 1.0-1.7 380 146
SiC microcrystalline filament3 3.5 2.6 1.4 200 77
Kevlar fibre (organic polymer)b 2.8 1.5 1.9 135 90
High-C steel wire 4.2 7.9 0.55 210 27
Fe 80 B 20 met glass b 3.6 7.4 0.5 170 23
Ti
5oBe4oZrio met
- Slassb 2.3 4.1 0.55 105 26
Ti6OBe35Si5 met glassb 2.5 3.9 0.65 -110 -28
Cu 50 Zr 50 met glass b 1.8 7.3 0.25 85 12
Al87Y8Ni5 met glassb ~1.1 -3.0 0.38 71 24
a
Indicates heat-resistant materials.
b
Indicates materials with some ductility.

which reduce surface oxides on the compo-
nents to be joined.
9.6.3 Mechanical Properties
The high strength and toughness of a
number of metallic glasses, combined with
adequate stiffness, has often been re-
marked, and the natural assumption has
been made that such glasses should be use-
ful for applications such as reinforcement
in composites and cutting utensils. How-
ever, no signs of such uses have appeared in
the market-place. For some years, repre-
sentatives of razor blade manufacturers
haunted conferences at which metallic
glasses were being discussed, but this has
ceased and no glassy razor blades have ap-
peared yet. (One can have an enjoyable
time speculating on advertisement strate-
gies for such blades, were they ever to be
marketed!) Perhaps it is impossible to
grind an edge on a metallic glass without
local crystallization? - Exceedingly sharply
pointed metallic glass needles for eye
surgery have been developed and are now
in use (J. V. Wood, priv. comm.). It has not
been revealed whether the point was cre-
ated by mechanical means or by an elec-
trolytic process. - It has been pointed out
(Warlimont, 1980) that some metallic
glasses have exceptionally high bend fa-
tigue resistance, and this suggests use of
glass ribbons for springs exposed to nu-
merous alternating loads.
Table 9-3 (Cahn, R.W., 1980) compares
mechanical properties of a number of po-
tential and actual reinforcing fibers and
ribbons, with special attention to density-
compensated strength and stiffness. It can
be seen that most metallic glasses are let
down by their high densities, compared
with materials such as graphite and
Kevlar. The Be-containing glasses were at
one time considered very promising but
have never been put into production be-
cause of the health hazards associated with
beryllium. Much interest attaches to the
new Al-bearing glasses (see Sec. 9.3.1); one
of the strongest representatives of this fam-
ily is included in Table 9-3. It has been
pointed out (Bechet et al, 1989) that the
best Al-base glasses are twice as strong as
the strongest commercial crystalline Al-
540 9 Metallic Glasses
base alloys, and that their corrosion resis-
tance is very much better than that of any
commercial aluminum alloys.
Experiments were done some years ago
on polymer matrix composites reinforced
with metallic glass ribbons (Fels et al.,
1984) and reasonable reinforcement was
observed. Recently, this approach has been
taken to the next stage in experiments to
reinforce glass ceramics with small volume
fractions of metallic glass ribbons (Vaidya
and Subramanian, 1990). Both 2605 SC
and a N i - C o - M o - F e - B glass, each a
commercial product, were tried; the latter
is the stronger (1300 MPa yield strength)
and has a high crystallization temperature
( « 605 °C). The glass precursor in the form
of powder is assembled with parallel rib-
bons and heated to 400-450 °C, at which
temperature the glass first sinters and then
crystallizes, to give a porosity-free matrix,
without crystallizing the metallic glass rib-
bons. The modulus of rupture was doubled
by as little as ^ 1 vol.% of glass ribbon,
and the fracture toughness enhanced more
than 3-fold. - It has been suggested that
instead of using ribbons, fine wires made
by the in-rotating-water melt-quenching
approach could be used, and Hagiwara
etal. (1985) have shown that Fe-based
glass wires, strengthened by additions of
Nb, Ta, Cr or Mo, can combine high yield
strengths with exceptionally high fatigue
strengths.
A further possible use of such wires is as
reinforcement for motor tires, another very
large market. This was first suggested by
Ohnaka (1985), who developed the in-ro-
tating-water melt-quenching process to
make wires of ^0.1 mm diameter, and sub-
sequently it was shown by an American
company that Fe-Si-B amorphous wires,
with a suitable coating, fulfilled the re-
quirements of tire reinforcement, which
are: a high tensile strength, good adhesion
to rubber, and excellent resistance to fa-
tigue and corrosion (Ogino, 1986). Japa-
nese investigators are also pursuing this
application.
Reinforcement in composites, as in the
pioneering experiments just described,
would seem the most likely applications
exploiting the mechanical properties of
metallic glasses, but it is also possible that
pieces of substantial dimensions might be
made by consolidating metallic glass pow-
ders; this can be done by warm isostatic
pressing or explosive compaction without
crystallizing the powder. Bechet et al. (1989)
pointed out that Al-base glasses can read-
ily be made in the form of powders. How-
ever, applications for Al-based glasses are
at this stage still speculative.
A number of experiments on the wear
and frictional properties of metallic glasses
have been reported, but at this stage
no clear generalizations have emerged.
Some amorphous coatings, notably
(W 06 Re 0 4 ) 7 6 B 2 4 , have proved to give very
large improvements in wear resistance over
uncoated steel (Thakoor et al., 1985).
9.6.4 Chemical Properties
The excellent corrosion resistance of a
number of metallic glasses suggests their
use as a protection in aggressive environ-
ments. The problem is that objects such as
containers can scarcely be made entirely of
metallic glass, and so for some uses it is
essential to think in terms of glassy coat-
ings. This has been done successfully by
laser-amorphization (Vol. 15, Chap. 3) of
coatings of suitable composition on con-
ventional substrates, for instance mild
steel. The composition must be carefully
chosen because, with laser amorphization,
the overlap between successive passes of
the focused laser beam across the surface
can lead to localized crystallization. How-

ever, by the use of suitable optics, a laser
can be used to amorphize difficult surfaces,
for instance, the inside of a vessel. Fig. 9-31
shows the electrochemical characteristics
of a Cr-rich metallic glass made in situ and
compares it with the same glass made by a
conventional melt-spinning process and
with the corresponding crystalline alloy.
An alternative process, which allows
coating and amorphization to be achieved
in one step, is sputtering. A number of
amorphous layers have been produced in
this way and some have been found to
evince remarkable corrosion protection
(Hashimoto, 1992; Diegle and Hashimoto,
1988). The technique has the incidental
advantage, as we saw earlier, that amor-
phous alloys can be made over a wide com-
position range. Amorphous Cu-Ta (20-
80at.%Ta) has been found to passivate
spontaneously even in 12 N HC1; it be-
haves much better than crystalline Ta, itself
notably resistant to acids.
Some applications can use melt-spun
glasses directly, without any coating stage.
Thus, a - F e - C r - P - C ribbons were used as
the active element in electromagnetic filters
to remove rust from water (Kawashima
et al., 1985). Since the field is strongest at
the edges of ribbons, narrow ribbons were
used. Their high corrosion resistance en-
sured a long life for the filter elements.
The Japanese group which has made
much of the running in corrosion and elec-
trochemical research concerned with
metallic glasses has also developed amor-
phous materials for electrocatalytically ac-
tive electrodes (Hashimoto, 1992). The aim
is to make electrodes highly active for
specific electrochemical reactions. Thus,
for example, chlorine is made by electroly-
sis of hot concentrated sodium chloride so-
lutions, and anodes are needed with a high
electrocatalytic activity for Cl2 evolution
and a low activity for O 2 evolution, a par-
9.6 Applications 541
Ni-15Cr-16P-4B
10:
1N HCl 30°C
c
CD
XJ
10"
-0.5 0 0.5
Potential in V
Figure9-31. Electrochemical characteristics in I N
HCl of a N i - C r - P - B metallic glass prepared by
melt-spinning or surface laser-amorphization, com-
pared with the same alloy before amorphization. (Af-
ter Yoshioka et al., 1987.)
asitic process. None of the platinum group
metals combine the required activity with
good corrosion resistance, but Pd-based
glasses have been found to have the neces-
sary combination of properties. - These al-
loys however were found not to be good
enough for the electrolysis of seawater,
which is much more dilute than the normal
industrial brines. The answer to this was
found to be the introduction, by low-tem-
perature diffusion, of zinc into the surface
layers of a glassy electrode followed by a
leaching process in hot alkali solution to
remove the zinc again. In this way, the
specific surface area is greatly increased,
enhancing the electrocatalytic activity. -
Because of the high resistivity of metallic
glasses, which is a disadvantage in elec-
trodes, the Japanese group has developed
ways of coating glassy surface layers on
normal high-conductivity metals.
The electrodes used in extractive metal-
lurgy to produce metals electrolytically
have also been improved by exploiting
metallic glasses. Here, surfaces combining
electrode activity with corrosion resistance
have been made by combining glasses such
542 9 Metallic Glasses
as N i - N b and Ni-Ta with a few per cent
of platinum group elements (Diegle and
Hashimoto, 1988).
9.6.5 Diffusion Barriers
In the manufacture of complex multi-
level integrated circuits, diffusion barriers
are necessary between Si and the Al metal-
lization applied to make interconnections
between circuit elements, because Si and Al
would react at high temperatures, either
during the later stages of circuit manufac-
ture or (for some circuits) during high-tem-
perature service. Many crystalline barriers
have been tried, but in 1981, at the First
High-Temperature Electronics Confer-
ence, the use of a metallic glass was pro-
posed, and a variety of metal-metal binary
glasses were soon shown to be effective.
(The early history of this concept, with its
advantages and difficulties, is surveyed by
Cahn (1986 b).) The underlying principle is
shown in Fig. 9-32. Gold (used as a model
diffusant) diffuses much more slowly in a-
Ni 5 5 Nb 4 5 than it does in the same alloy in
crystalline form, at relatively low tempera-
tures, because in this temperature range,
T in
_ 70Q 600 500 400 300
10 u
10 urn
\ Amorphous ^
10-'
^B Polycrystal
\ 1um
10"
0.1 urn ~
; \
10r 20
Diffusion of \ 100 A
- Au in NiNb \
" \ , , - 10 A
1.0 1.2 U 1.6
1000/ T in K
Figure 9-32. Diffusivity of gold in amorphous and
polycrystalline Ni 5 5 Nb 4 5 . The righthand ordinate
shows the diffusion distance in a period of one year.
(After Doyle et al., 1982.)
diffusion in polycrystals is dominated by
grain-boundary transport, which is en-
tirely excluded in a glass. As can be seen in
the figure, at 400 °C the difference in diffu-
sivity is seven orders of magnitude! Ap-
proximately equiatomic Ta-Ir glasses, the
most resistant to crystallization known
(and therefore also particularly resistant to
diffusion), with T cryst «900 °C, were sug-
gested to be the best material to use for
diffusion barriers. The most recent studies
of this glass (de Reus, 1990) has shown neg-
ligible interdiffusion up to 800 °C. Never-
theless, such glasses can give problems at
the higher temperatures owing to chemical
reaction with either Si or Al, and this may
be the factor that effectively limits the max-
imum temperature of use. Another reputed
problem with Ta-Ir diffusion barriers is
that the glass is so very stable that it resists
all etching processes associated with litho-
graphic circuit-shaping procedures.
Ta-Ir glassy alloy has been used to
make effective diffusion barriers between Si
substrates and Y - B a - C u - O ceramic su-
perconductor layers (de Reus et al., 1988).
9.6.6 Metallic Precursors
for Devitrification
The use of highly alloyed metal glasses
as precursors for the production of fine-
grained crystalline alloys has received
g
>
some attention, although very little by
comparison with the effort which has gone
into the design of glass-ceramics. The first
serious research was by Ray (1981): his al-
loys were based on Fe, Ni, Al, Cr, Mo, Co
and W in multiple combinations, with 5 -
12 at.% of B or other metalloids as glass-
forming aids. This interesting work has not
received any follow-up until very recently,
when Arnberg et al. have developed a
range of tool steels by devitrification of
glassy F e - C r - M o - C - B or F e - C r - M o -

C-V glasses (Arnberg, 1991). Subsequent
to Ray's work, alloy developments along
similar lines were by Das et al. (1985 b) and
by Vineberg et al. (1985). Das et al. devel-
oped N i - M o - B and N i - A l - T i - X - B al-
loys, and later other N i - M o - B alloys with
added Cr. These alloys were made by melt-
quenching, comminution and consolida-
tion by extrusion or HIPping (Vol. 15,
Chap. 4). During the processing, ordered
phases including Ni 4 Mo, Ni 3 Mo, Ni 2 Mo
and Ni3(Al,Ti) are precipitated from the
crystallized matrix, together with stable
boride precipitates. This family of alloys is
now manufactured commercially under
the trade name Devitrium® (Vineberg,
1985). The best of these alloys have very
impressive high-temperature properties,
exceeding high-grade tool steels.
By far the most industrially important
development of this kind is connected with
rare-earth permanent magnets. The mod-
ern family of magnets based on the high-
coercivity phase Nd 2 Fe 14 B can be made
either by sintering an alloy powder or by
melt-spinning the alloy to form a glass
which is then devitrified (or, alternatively,
quenching direct to a microcrystalline
structure). The melt-quenching method
was introduced by Croat et al. (1984) and
culminated in a full-scale industrial process
for making magnets. The various compli-
cations and improvements along the way
are surveyed in a major review by Buschow
(1986). Fig. 9-33 shows diagrammatically
why there is an optimum quenching rate
for this process, whether by direct quench-
ing to a microcrystalline phase or by for-
mation of a glass followed by reheating.
The hard magnetic phase is desired, the
alternative soft magnetic phase must be
completely avoided, and a fine grain size
is desirable for high coercivity. The pro-
cess of devitrifying glass precursors in the
N d - F e - B system is still receiving exten-
9.8 References 543
continuous cooling
quenching and annealing
onset of crystallization
soft magnetic phase
O \ — hard magnetic phase
I decreasing
Tgrain size
W
Time
Figure 9-33. Schematic time-temperature-transfor-
mation diagram to rationalize optimum conditions
for producing N d - F e - B permanent magnets. (After
Warlimont, 1985.)
sive attention: thus Jha et al. (1991) have
established the formation of a metastable
intermediate phase during the devitrifica-
tion; the nature of the Nd 2 Fe 14 B phase
itself was found to change progressively
during the anneal, as indicated by a grad-
ual change in the Curie temperature.
A beginning has now also been made in
using the devitrification approach for mak-
ing nanocrystalline soft magnetic alloys, for
instance a series of Fe-Cu-Nb-Si-B com-
positions (Herzer, 1991). Nanocrystallinity
in such alloys presumably derives from ex-
ceedingly copious homogeneous nucle-
ation during crystallization.
9.7 Acknowledgement
I am greatly indebted to Dr. A. L. Greer
for a critical reading of this chapter.
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Alloys: Das, S.K., Kear, B. H., Adam, C M .
(Eds.). Warrendale: The Metallurgical Society,
306.
Volkert, C. A., Spaepen, F. (1990), Scripta Metall. 24,
463.
Vredenburg, A. M., Westendorp, J. F. M., Saris, F. W,
van der Pers, N. M., Keijser, Th. D. (1986), /. Ma-
ter. Res. 1, 775.
Wagner, C.N.J. (1986), in: Amorphous Metals and
Semiconductors: Haase, P., Jaffee, R. I. (Eds.). Ox-
ford: Pergamon, pp. 54-69.
Walter, XL., Bacon, F , Luborsky, F.E. (1976), Ma-
ter. Sci. Eng. 24, 239.
Warburton, W.K., Turnbull, D. (1975), Diffusion in
Solids: Recent Developments. Nowick, A. S., Bur-
ton, X X (Eds.). New York: Academic Press, p. 171.
Warlimont, H. (1980), Physics in Technology 11, 28.
Warlimont, H. (1985), in: Rapidly Quenched Metals
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Amsterdam: North-Holland, pp. 1599-1609.
Warlimont, H. (1988), Mater. Sci. Eng. 99, 1.
Weeber, A.W., Bakker, H. (1988), X Phys. F: Met.
Phys. 18, 1359.
Weeber, A.W, Haag, W.X, Wester, A.J.H., Bakker,
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Wei, Gao, Cantor, B. (1989), Acta Metall. 37, 3409.
Whang, S.H. (1983), Mater. Sci. Eng. 57, 87.
Wolf, D., Okamoto, P. R., Yip, S., Lutsko, J.F.,
Kluge, M. (1990), J. Mater. Res. 5, 286.
Wu, T. W, Spaepen, F. (1986), in: Mechanical Behav-
ior of Rapidly Solidified Materials: Sastry, S. M. L.,
MacDonald, B.A. (Eds.). Warrendale: TMS-
AIME, p. 293.
Yamasaki, T, Takahashi, M., Ogino, Y. (1985), in:
Rapidly Quenched Metals (V): Steeb, S., Warli-
mont, H. (Eds.). Amsterdam: North-Holland, pp.
1381-1384.
Yater, J.A., Thompson, M.O. (1989), Phys. Rev.
Lett. 63, 2088.
Yavari, A.R. (1986), J. Mater. Res. 1, 746.
Yavari, A.R., Hicter, P., Desre, P. (1983), J. Chim.
Physique 79, 572.
Yeh, X.L., Samwer, K., Johnson, WL. (1983), Appl.
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Yermakov, A. Ye., Barinov, V.A., Yurchikov, Ye. Ye.
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(1982), Phys. Met. Metall. 52, 50.
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General Reading
Anantharaman, T. R. (Ed.) (1984) Metallic Glasses -
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Cahn, R. W. (1980), Metallic Glasses. Contemp. Phys.
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Giintherodt, H.-X, Beck, H. (Eds.) (1981, 1983),
Glassy Metals I and II. Berlin: Springer.
Haasen, P., Jaffee, R.I. (Eds.) (1986), Amorphous
Metals and Semiconductors. Oxford: Pergamon.
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loys. London: Butterworth.
10 Glass-Like Carbons
Sugio Otani and Asao Oya

Department of Materials Science, Gunma University, Gunma, Japan

List of Symbols and Abbreviations 550

10.1 Introduction 551
10.2 A Short History of Glass-Like Carbon 551
10.3 Preparation Procedures of Glass-Like Carbon 553
10.3.1 Preparation from Cellulose 553
10.3.2 Preparation from Thermosetting Resin 554
10.3.3 Preparation by Use of Filler Material 555
10.3.4 Porous Glass-Like Carbon 555
10.3.5 Fine Glass-Like Carbon Particles 556
10.3.6 Glass-Like Carbon Coating and Film 556
10.3.7 Glass-Like Carbon Fiber 556
10.4 Structure of Glass-Like Carbon 557
10.4.1 Structural Models of Glass-Like Carbon 557
10.4.2 Structural Change on Hardening and Initial Carbonization Processes .. . 558
10.4.2.1 Cellulose 558
10.4.2.2 Phenol-Formaldehyde Resin 559
10.4.2.3 Furfuryl-Alcohol Resin 562
10.4.3 Structural Change During the Carbonization Process 562
10.5 Properties of Glass-Like Carbon 563
10.5.1 Normal Glass-Like Carbon 563
10.5.1.1 Density, Porosity and Gas Permeability 564
10.5.1.2 Mechanical Properties 564
10.5.1.3 Electrical Properties 565
10.5.1.4 Thermal Properties 565
10.5.1.5 Chemical Properties 565
10.5.1.6 Purity 565
10.5.1.7 Comparison with other Materials 566
10.5.2 Properties of Composite Glass-Like Carbon
and Porous Glass-Like Carbon 566
10.6 Applications of Glass-Like Carbon 566
10.6.1 Electronic and Magnetic Applications 566
10.6.2 Applications in Analytical Chemistry 569
10.6.3 Metallurgical Applications 569
10.6.4 Applications to Biomaterials 569
10.6.5 Applications to Fuel Cells 569
10.6.6 Other Applications 571
10.7 Acknowledgements . 571
10.8 References 571

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
550 10 Glass-Like Carbons

List of Symbols and Abbreviations

d002 interlayer distance
Lc crystallite thickness parallel to the c axis
La crystallite size normal to the c axis
CVD chemical vapor deposition
HHT heat-treatment temperature
PAN polyacrylonitrile
RVC Reticulated Vitreous Carbon
 10.2 A Short History of Glass-Like Carbon
10.1 Introduction
Carbon atoms have three valence states,
sp, sp 2 and sp3, from which three allotropic
forms are derived: carbyne (Sladkov et al.,
1968; Heimann et al., 1983), graphite and
diamond. Carbon materials such as coke,
carbon black and graphite electrodes,
however, have complex structures of sp 2
and sp 3 as well as small amounts of sp
carbon atoms. Despite containing only one
element, carbon materials therefore have a
wide range of structures and properties.
Glass-like carbon is a unique carbon
material because it consists of an amor-
phous-like and isotropic structure includ-
ing a large amount of tetrahedral sp 3 car-
bon. It has several characteristic proper-
ties resulting from its structure in addition
to its glass-like appearance. When glass-
like carbon was developed around 1960,
many practical applications were expected,
but were not realized because of some dis-
advantages described at a later date. In-
stead, this material served to increase fun-
damental and academic knowledge of
carbon materials and just recently some
potential applications have appeared. For
successful applications, the preparation
procedure as well as the structure and
properties of glass-like carbon have been
diversified remarkably, once again stimu-
lating interest in this material and raising
expectations of future development.
Since many of the preparations and ap-
plications are described in patents, many
are cited, especially from Japan where the
most active development is now in pro-
gress.
10.2 A Short History
of Glass-Like Carbon
A short history of this material is shown
in Table 10-1. The initial purpose of the
551
Table 10-1. A short history of glass-like carbon.
Year Event
1957 First glass-like carbon Cellulose Carbon
by General Electric Company (UK).
1961 Vitreous Carbon derived from phenol-
aldehyde resin by Plessey Company (UK).
1962 Glassy Carbon derived from furfuryl
alcohol by Tokai Carbon Company.
1964 Microporous glass-like carbon by Societe
le Carbone-Lorraine (Development year of
Carbone Vitreux is not clear).
1964- Proposal of some structural models of glass-
1965 like carbon using X-ray diffraction technique
by Noda et al.
1966 Vitro Carbon derived from acetone-
furfuryl resin by Nippon Carbon Company.
1967 Glass-like carbon fiber
by Tokai Carbon Company.
1969 Composite glass-like carbon using filler
by Lockheed.
1969 Formation mechanism of glass-like carbon
by Fitzer's group.
1971 Structural model of "network of ribbon
stacking" for glass-like carbon by Jenkins
and Kawamura.
1974 Glass-like carbon containing the finely
dispersed iron particles by Walker et al.
and Yajima et al.
1975 Fine porous glass-like carbon by Hucke.
1980 Reticulated Vitreous Carbon by Chemo-
tronics International. Glass-like carbon
coating by The Aerospace Corp.
1981 Activation of study on the fuel cell.
1983 A high quality glass-like carbon (Glahard)
derived from a hydrophilic resin by Kao
Company.
1983 Composite glass-like carbon
by Showa Denko.
1984 Development of a large-sized composite
glass-like carbon by Showa Denko.
New model of glass-like carbon by Shiraishi.
glass-like carbon was to develop a compo-
nent of nuclear fuel. For this application,
the carbon material must be gas-imperme-
able and of high purity. Davidson (1957) of
the General Electric Company (UK) suc-
ceeded in developing the first glass-like
carbon, Cellulose Carbon, from cellulose
slurry. The products were small pipes. This
552 10 Glass-Like Carbons
company developed the preparation pro-
cedure of glass-like carbon from thermo-
setting resins in 1960 (Rivington, 1960).
With this as a trigger, the race for the de-
velopment of glass-like carbon had begun.
Plessey in England (Redfern, 1961; Red-
fern and Floyd, 1962; Cowlard and Lewis,
1967) developed Vitreous Carbon from
phenol-aldehyde resin. A glass-like carbon
boat, disc and rod in addition to pipes were
prepared. The glass-like carbon was gradu-
ally shown to have some additional attrac-
tive properties, e.g. high chemical durabil-
ity, and was expected to have practical
applications in the use of chemical vessels
and electrodes for electroanalysis (Zittel
and Miller, 1965; Yoshimori et al., 1965).
These applications were later industrial-
ized but their production quantities were
quite small. At almost the same time, Tokai
Electrode (at present Tokai Carbon)
derived Glassy Carbon from furfuryl-alco-
hol resin (Yamada and Sato, 1962; Yamada
and Takada, 1963 a, 1963 b). Here new
techniques were developed, e.g., using a
powder filler and making a mold by re-
peatedly coating the resin on a substrate.
In 1964, the Societe Carbone-Lorraine de-
veloped porous glass-like carbon. This
company also distributed a catalog for a
dense glass-like carbon called Carbone
Vitreux but the preparation procedure has
not been published as far as we know. Nip-
pon Carbon subsequently developed Vitro
Carbon by using an acetone-furfural resin
(Honda et al., 1966; Teranishi et al., 1967).
In addition, Sigri GmbH (FRG) developed
Sigradur (the preparation procedure is not
clear, however).
A unique glass-like appearance and
some attractive properties of this material
led to active interest in its structure, begin-
ning around 1964. Some structural models
for glass-like carbon were proposed on the
basis of X-ray diffraction analysis as de-
scribed in Sec. 10.4.1. In 1971, Jenkins and
Kawamura proposed a novel "network of
ribbon stacking" model (sometimes called
the "Jenkins nightmare" model) on the ba-
sis of high-resolution electron microscopic
observations in 1971. Such fundamental
work contributed favorably to the under-
standing of the structure of not only glass-
like carbon but also other carbon materi-
als.
The pitch-based carbon fiber developed
by Otani (1965, 1966) had a similar struc-
ture. Stimulated by this invention, a glass-
like carbon fiber was developed by Ya-
mada et al. (Yamada and Nakamura, 1966;
Yamada and Yamamoto, 1968). However,
the resulting fiber was mechanically weak
compared with fibers derived from pitch
material and polyacrylonitrile (PAN). It
was not until around 1980 that carbon fi-
ber from phenol resin was industrialized
on the basis of its high flexibility (Kawa-
mura and Jenkins, 1970) or because of the
large specific surface area achieved through
activation treatment (Miyashita, 1983).
Research and development on new ap-
plications of glass-like carbon were contin-
ued. Walker's group endeavored to apply
the glass-like carbon, with or without fine
metals, as a catalyst (Jung et al., 1979) and
as a catalyst support and molecular sieve
(Walker et al., 1977). Its potential use as
biomaterial was examined by Fitzer's
group (1978). None of these results, how-
ever, were industrialized. The uniform dis-
persion of fine iron metals in glass-like car-
bon has been achieved by some researchers
(Yajima and Omori, 1972; Kammereck
et al., 1974). Recently, fine glass-like car-
bon particles containing dispersed fine
metals have again attracted much atten-
tion as electromagnetic material, catalyst,
etc. (Hirano et al., 1983; Yogo et al., 1986).
However, practical applications for
glass-like carbon were not developed as ex-
 10.3 Preparation Procedures of Glass-Like Carbon
tensively as expected initially because of
the low productivity and high price. But
then again, in those days there were no
high technology application fields in which
the unique properties of this material
would be required.
Around 1980, some potential applica-
tions appeared, among which the most at-
tractive ones were as parts of fuel cells and
magnetic recording equipment. Both ap-
plications required a low priced, large and
thin glass-like carbon plate; however,
somewhat lower gas impermeability and
structural homogeneity were needed in the
first case and a high quality glass-like car-
bon was required in the second. Some
companies entered the field of glass-like
carbon and made extensive contributions
to accomplish these requirements. The first
was achieved successfully by the use of
filler material (Saura et al, 1987; Fukuda
et al., 1988). In connection with the second
application, on the other hand, the chemi-
cal structure of the starting thermosetting
resin itself was reconsidered, and a hy-
drophilic resin was developed by a struc-
tural modification technique or blending
technique of the resins to result in a high
quality glass-like carbon (Yamauchi et al.,
1985). These materials are now undergoing
extensive trials for practical uses. Also, the
conventional glass-like carbon has pene-
trated somewhat into the semiconductor
as well as other industries (Yasuda and
Nakamura, 1975).
10.3 Preparation Procedures
of Glass-Like Carbon
10.3.1 Preparation from Cellulose
There are three typical carbonization
processes, called the liquid-phase, gas-
phase and solid-phase carbonizations. The
553
typical carbon materials resulting from
these processes are coke, pyrolytic graphite
and charcoal (or carbon fiber), respectively.
Glass-like carbon is prepared through the
solid-carbonization process. As seen in the
case of charcoal, the carbon resulting from
solid-phase carbonization tends to become
porous in nature. In the preparation of
glass-like carbon, therefore, the key point
is the removal of the pores from the mate-
rial. Many preparation procedures are dis-
closed in patents but expert knowledge is
essential for practical production.
Cellulose Carbon is prepared according
to the processes shown in Fig. 10-1 a
(Davidson, 1957, 1959). The fibrous struc-
ture of the cellulose is mechanically and/or
chemically beaten in an aqueous medium
to prepare the cellulose slurry. It is impor-
tant to prepare a fine and homogeneous
dispersion of the cellulose because the state
of the cellulose slurry is intimately related
to the cross-linking reaction in the subse-
quent heating process and to the properties
of the final product. The close cross-link-
ages result in a dense and homogeneous
glass-like carbon. The addition of a disper-
sion agent such as zinc chloride is effective
in forming the homogeneous slurry.
The slurry is fed into the bowl of a cen-
trifuge, and, while the water is continu-
ously removed, the beaten cellulose is au-
tomatically pressed against the centrifuge
wall to form a long hollow tube. The moist
cellulose tube is carefully and slowly dried
at room temperature and, if necessary, un-
der controlled humidity. The tube under-
goes a 50% volume shrinkage. After ma-
chining to the desired size and shape, the
regenerated cellulose tube is slowly car-
bonized under an inert atmosphere for sev-
eral days and then graphitized above
2500 °C. The carbonized tube is micropo-
rous in nature, the pore size being approx-
imately 2 nm. Graphitization results in clo-
554 10 Glass-Like Carbons
(a) (b)
Cellulose slurry Thermosetting Thermosetting
resin
Molding Molding
Drying Hardening
Machining Machining
Carbonization Carbonization
I I
Graphitization Graphitization
sure of the ends of the pores, achieving gas
impermeability. The products are small
tubes, as suggested by the preparation
method.
Glass-like carbon formation from lignin
was later attempted by Tormala and
Romppanen (1981) using a different proce-
dure from that of Cellulose Carbon, but
the resulting product did not exhibit high
mechanical strength.
10.3.2 Preparation
from Thermosetting Resin
Many kinds of thermosetting resins such
as phenol resin and furfuryl-alcohol resin
are used as raw materials for glass-like car-
bon (Rivington, 1960; Redfern, 1961), but
the fundamental preparation procedure is
almost the same. As shown in Fig. 10-1 b, a
thermosetting resin is first shaped. Here
the resin is usually poured into a mold and
thereafter hardened through polymeriza-
tion. In practical operations, an organic
hardener such as benzoic peroxide or ani-
line sulfate is sometimes used (Yamada and
Takada, 1963 a, 1963 b). When a tube is
desired, the resin is poured into a cylindri-
(c)
resin
I
Kneading
I
Molding
Hardening
Machining
Figure 10-1. Preparation proce-
dures for glass-like carbons from
Carbonization
(a) cellulose, (b) thermosetting
Graphitization
resin, and (c) thermosetting resin/
filler particle.
cal mold and rotated at high speed (in or-
der to form the resin into a tubular shape
by centrifugal force), followed by harden-
ing treatment.
The product after hardening is dehy-
drated slowly by heating under pressure or
at a very low heating rate (1 °C h~ x ) under
reduced pressure (Redfern, 1961); the re-
sulting product breaks easily since the
moisture evolved is not easily released
from the mold, which shrinks extensively.
This is the most substantial cause of low
productivity of this material. A glass-like
carbon product of >10mm in thickness
is difficult to prepare. According to the
patents applied for by Tokai Carbon Com-
pany (Yamada and Takada, 1963 a, 1963 b),
a shaped substrate is repeatedly coated
with resin and then hardened, to form the
product. The moisture is easily released
from the mold and the resulting product is
strong because of the layered structure.
The product is carbonized to 1000-
1500°C with a heating rate of about 5°C
min" 1 and subsequently graphitized. The
largest products attained by this method
were a rod of 6.25 mm diameter x 300 mm
length and a tube of 23 mm diameter
 10.3 Preparation Procedures of Glass-Like Carbon
(thickness 6 mm) x 165 mm length, etc.
(Redfern, 1961).
10.3.3 Preparation by Use
of Filler Material
Attention has concentrated recently on
glass-like carbon containing filler material
(here, this type of glass-like carbon is re-
ferred to as composite glass-like carbon).
The addition of filler is effective in decreas-
ing the weight loss and the shrinkage of the
product, and in facilitating the release of
the evolving gas during the hardening and
carbonization processes. This method is
used to prepare a large-sized inexpensive
glass-like carbon with a lowering of gas
impermeability and structural homogene-
ity. In the initial patent describing this
method, the thermosetting resin powder
after hardening was used as a filler to pre-
pare the final product consisting of the
same glass-like carbon component. Natu-
ral graphite has also been used (Bradshaw
et al., 1969); and fine graphite powder of
less than several microns has again at-
tracted much attention recently (Saura
et al., 1987; Fukuda et al., 1988).
As shown in Fig. 10-1 c, the thermoset-
ting resin and the filler particles are first
kneaded under a vacuum to remove
trapped gas. Several effective shaping tech-
niques such as extrusion, pressing and
roller forming can be used. The productiv-
ity of these methods is far higher compared
with the methods without the filler (Saura
et al., 1987). A plate as large as 100 x 100 cm
and several millimeters in thickness is pre-
pared commercially by using graphite
powder filler.
In the preparation of the glass-like car-
bon Strux by the Fudow Chemical Com-
pany, a woven fabric of the thermosetting
resin fiber is used as a filler. The filler is first
impregnated with the resin and stacked,
555
then pressed. The resulting product con-
sists completely of the glass-like carbon
component. According to a patent by Sa-
kaguchi (1988), some kinds of ceramic
powder (A12O3, SiC, etc.) are used to im-
prove the abrasion resistance of the prod-
uct. It is well known that the thermosetting
resin is used as a matrix for fiber-reinforced
carbon composites, further details of which
can be found elsewhere (Fitzer, 1987).
10.3.4 Porous Glass-Like Carbon
Porous glass-like carbon can be pre-
pared more easily without damage than
the products described in 10.3.2 and 10.3.3.
In some cases, therefore, porous glass-like
carbon is first prepared and then subjected
to impregnation by the resin (Johnson
et al., 1979) or chemical vapor deposition
(CVD) (Nagle and Walker, 1973) to obtain
a dense glass-like carbon.
There are four fundamental methods for
preparing porous glass-like carbon:
(i) Polyurethane foam or non-woven
fabric of carbon fiber, cellulose, etc., is im-
pregnated with thermosetting resin, fol-
lowed by removal of the excess resin which
then remains on the fiber surface alone.
Subsequently, the resulting skeleton is sub-
jected to the usual preparation procedures
of glass-like carbon (Franklin, 1980).
(ii) The pore former, such as water or
polyethyleneglycol, is added to the raw
thermosetting resin (Hucke, 1975; Walker
Jr. etal., 1977; Yata et al., 1986). It is re-
leased from the resin after hardening, leav-
ing the pores, because it is not a compo-
nent forming the glass-like carbon. The
pore size is controlled by additional
amounts of both the surface-active agent
and the pore former. The procedure in-
volving the replication of a porous sacrifi-
cial substrate, i.e., sodium chloride, is used
for glass-like foam (Pekala and Hopper,
556 10 Glass-Like Carbons
1987). This technique is suitable for prepar-
ing glass-like carbons with relatively large
pores.
(iii) Glass-like carbon particles are
shaped with a binder by pressing. The pore
remains at the particle boundary. It is diffi-
cult, using this method, to prepare porous
material with a large pore volume without
lowering the mechanical strength.
(iv) A chemical foaming agent such as a
halogenated hydrocarbon is used (Mu-
rakami etal., 1985; Katsura and Shiraki,
1987).
The graphite powder is added to prepare
the composite glass-like carbon as stated in
Sec. 10.3.3. However, when the exfoliated
graphite is used instead of the graphite
powder, a unique, porous glass-like carbon
is obtained (Kikuchi et al., 1985).
10.3.5 Fine Glass-Like Carbon Particles
Fine glass-like carbon particles have
several specific applications. So far, parti-
cles have been prepared by crushing mas-
sive glass-like carbon. Recently, some new
practical preparation procedures have
been developed:
(i) The polymer precursor is subjected to
controlled atomization, followed by hard-
ening and heat treatment (Levendis and
Flagan, 1989).
(ii) A suitable viscous thermosetting
resin with a hardener is added dropwise
into sulfuric acid and hardened in situ. The
fine particles obtained after washing are
carbonized and then graphitized.
(iii) An aqueous solution of phenol is
dropped into a hydrochloric acid/formal-
dehyde mixture, stirred to convert the mix-
ture into a slurry or resinous state and then
hardened by heating. The resulting fine
spheres of several tens of microns in diame-
ter are subjected to the subsequent heat
treatments (Koyama et al., 1988).
10.3.6 Glass-Like Carbon Coating
and Film
To avoid the difficulties involved in
preparing a large-sized glass-like carbon
product, the conventional artificial graph-
ite products can be coated with glass-like
carbon. Initially, a diluted thermosetting
resin was used for the coating but the tech-
nique developed recently (Murata et al.,
1988) is as follows: After initial carboniza-
tion, the resin is subjected to extraction
with an organic solvent. The solution is
concentrated to about 20 wt.%, then used
to coat the conventional graphite product
- mainly high-density isotropic graphite -
followed by hardening, carbonization and
graphitization. The resulting product is
substantially gas-impermeable.
When the glass-like carbon is coated on
a quartz glass plate coated with a release
agent, a glass-like carbon film is obtained
by peeling (Ogata et al., 1987).
10.3.7 Glass-Like Carbon Fiber
The thermosetting resin is subjected to
continuous melt-spinning, hardening, car-
bonization and then graphitization, just as
the usual pitch-based carbon fiber. The
preparation using Kynol-type phenol resin
has already been industrialized (Miyashita,
1983). The carbon fiber has low mechanical
strength on the one hand, reflecting its
amorphous-like structure, but high flexi-
bility on the other. These inherent proper-
ties of the fiber are suitable for several
applications as explained later. The me-
chanical properties can be improved by
hot stretching carbonization but this tech-
nique is not practical (Economy and Lin,
1971). The carbon fiber can be converted
into an excellent active carbon fiber
through activation treatment (Miyashita,
1983).

10.4 Structure
of Glass-Like Carbon
10.4.1 Structural Models
of Glass-Like Carbon
Figure 10-2 shows changes in the X-ray
parameters of two typical kinds of carbons
with heat-treatment temperature. Normal
pitch coke shows a decrease of interlayer
distance (d002) an<^ a n increase of crystal-
lite thickness parallel to the c axis (Lc) with
increasing heat-treatment temperature, as
shown by the lines in Fig. 10-2. The crys-
tallite size normal to the c axis (La), though
not presented, is almost proportional to
L c . A carbon exhibiting such excellent
crystal growth is called graphitizable or
soft carbon. On the contrary, the glass-like
carbon Glassy Carbon shows a far smaller
decrease of d002 and smaller increase of L c
with increasing temperature (Noda et al.,
1969) compared with graphitizable carbon.
Such a carbon is called a non-graphitizable
or hard carbon. This structural behavior is
the most substantial characteristic of glass-
like carbon. When a hard carbon is heated
to high temperature, it exhibits multi-
phase graphitization in which the graphite
component suddenly appears within the
low crystalline matrix (Kamiya and Su-
zuki, 1975).
The structure of the glass-like carbon
was initially studied by using the X-ray
diffraction technique, including the radial
distribution analysis because of its low
crystalline structure. Noda and Inagaki
(1964) proposed the presence of two types
of carbon atoms, one having a tetrahedral
(sp3) relationship, and the other a trigonal
(sp2) relationship to the nearest carbon
atoms in the glass-like carbon. The unique
characteristic was that the presence of a
fairly large amount of tetrahedral sp 3 car-
bon was proposed. Their model has trigo-
10.4 Structure of Glass-Like Carbon 557
80
70
60
50-
40 .
30
20
10
0
5 10 15 20 25 30
Heat-treatment temperature (x 102 °C)
Figure 10-2. Changes of X-ray parameters of Glassy
Carbon and a typical graphitizable carbon as a func-
tion of the heat treatment temperature.
nally bound carbon atoms forming small
domains of two-dimensional graphite-like
arrangements and these domains are cross-
linked by tetrahedrally bound carbon
atoms.
Furukawa (1964) criticized this model
by Noda and Inagaki in the following two
points: (i) their results are questionable in
view of the shape of the radial-distribution
curve, and (ii) if a large amount of sp 3 car-
bon exists, as they proposed, the density of
the glass-like carbon should be larger in
view of the density of diamond (3520 kg
m~ 3 ). He proposed a three-dimensional
irregular network configuration model
which contains all kinds of C - C bonds,
i.e., tetrahedral, planar double, linear triple
and also conjugated bonds. Whittaker and
Tooper (1974) revealed that Vitreous Car-
bon gives some kinds of electron diffrac-
tion patterns including a single-crystal pat-
tern, of which further details are unclear.
Based on a paper describing an oxygen
content of 5-6% in Glassy Carbon, Kaki-
558 10 Glass-Like Carbons
noki (1965) proposed a model which con-
sists of two kinds of domains, each of
which is composed of tetrahedral carbon
atoms and trigonal carbon atoms, respec-
tively, linked by oxygen bridges. The low
density of the glass-like carbon is explained
by the oxygen bridges. Later, it was shown
that the oxygen content of Glassy Car-
bons, after heating to 900 and 1200°C, are
1.2 and 0.9%, respectively (Noda et al.,
1969), so that his model became ground-
less. Takahashi and Westrum, Jr. et al.
(1970) reported that the specific heat of
Glassy Carbon is proportional to the
square of the absolute temperature, sug-
gesting that this carbon consists mainly of
two-dimensional layers.
The controversy was ended in 1971 by
high resolution electron microscope ob-
servations. Figures 10-3 a and 10-3 b are
high resolution electron micrographs of
a)
b)
Figure 10-3. High resolution electron microphoto-
graphs and electron diffraction patterns of phenol
resin carbons after heating to (a) 1200°C and (b)
2800°C.
the phenol resins after heating to 1200 and
2800 °C. The former sample consists of a
random configuration of small crystallites
with stacks of several layers, 2-3 nm in
size. After heating to 2800 °C, however, the
crystallites grew to stacks of about 10 lay-
ers, 6-7 nm in size, and were entangled
with each other. Based on these photo-
graphs, Jenkins and Kawamura (1971) and
Jenkins et al. (1972) proposed a "network
of ribbon stacking" model for the glass-like
carbon after heating to a high temperature
as shown in Fig. 10-4 a, in which only small
amount of sp 3 carbons exist. D'Antonio
and Konnert (1981) later supported this
model by the use of X-ray radial distribu-
tion analysis.
The network of ribbon stacking model
provides a reasonable explanation for the
behavior and properties of glass-like car-
bon: (i) an isotropic structure, (ii) gas-im-
permeability in spite of its low density, and
(hi) less crystalline growth by heating to
high temperatures. This model was also
supported by the use of electron micro-
scopic observations (Bose et al., 1978) and
has gained wide acceptance. Shiraishi
(1984), however, had doubts about the gas-
impermeability predicted by this structural
model. He pointed out that glass-like car-
bon has a low He density (1500 kg m~ 3 ),
determined by He pyknometry, and small
CO 2 absorption capacity (2 10" 3 m 3
kg" 1 ), which means that it consists of a
large proportion of closed pores. He pro-
posed the model shown in Fig. 10-4 b.
10.4.2 Structural Change on Hardening
and Initial Carbonization Processes
10.4.2.1 Cellulose
The properties and structure of the car-
bon material are strongly dependent on the
structure of the raw material and the car-
bonization process. Such relationships are

La: Crystallite size
Z.c: Crystallite thickness
especially retained in solid-phase car-
bonization because of the difficulty of re-
arranging the constituents during the car-
bonization process. It is important to
understand the initial thermal degradation
process of some raw materials of the glass-
like carbon (Fitzer et al., 1971).
As shown in Fig. 10-5 cellulose (I) under-
goes changes when heated slowly (Tang
and Bacon, 1964). After removal of the ab-
sorbed water below 150°C, a dehydration
reaction starts to form keto groups (II)
which have a keto-enol tautomer (III).
Glucose bonds are broken at 240-400 °C,
resulting in fragments (IV) and (V) together
with the evolution of CO, CO 2 , H 2 O and
a residue of tarry matter. As the reaction
proceeds further, the volatile material (VI)
is formed to a slight extent. By dehydration
around 400 °C, compound (V) also changes
into compound (VII) of which the carbon
skeleton model is shown in (VIII). This
compound converts into C 4 fragments as
shown by the flame with removals of H 2 O,
CO 2 and CO. The fragments slowly grow
into the carbon crystal with increasing heat
treatment. The structural changes involved
in the carbonization of cellulose fiber were
examined in detail (Tang and Bacon, 1964;
Bacon and Tang, 1964).
10.4 Structure of Glass-Like Carbon 559
(b)
Figure 10-4. Two structural
models of glass-like carbon
heated to high temperature;
(a) network of ribbon
stacking model by Jenkins
and Kawamura, (b) Shi-
raishi model.
10.4.2.2 Phenol-Formaldehyde Resin
There are many reports on the initial
carbonization process of phenol-formalde-
hyde resin (Yamashita and Ouchi, 1981).
As shown in Fig. 10-6 (Fitzer and Schaefer,
1970), phenol-formaldehyde resin (II) is
first subjected to dehydration polymeriza-
tion by heating, leading to the formation of
ether cross-linkages (III) and the triphenyl-
methane structure (IV) with methylene
bridges. The cyclization as shown by the
formation of diphenylpyran (V) also occurs
at temperatures somewhat lower than
400 °C. The reaction becomes most active
around 400 °C and the pyran ring is bro-
ken to change into the furan ring (VI). By
heating to 450 °C or higher, the methylene
bridge (VII) derived from the raw material
(II) is oxidized by the resulting H 2 O and
changes into the keto radical (VIII) which
is finally converted into the biphenyl struc-
ture (IX), evolving CO gas. The structural
model (XI) of Ouchi and Honda (1959) of
phenol-formaldehyde resin after heating to
600 °C consists of a three-dimensional dis-
ordered structure. This structure remains
as a memory after carbonization, leading
to a homogeneous and amorphous-like
structure.
560 10 Glass-Like Carbons
o
o
o
o
CO
O'
i
 OH H2 OH /-H2O

Figure 10-6. Initial thermal degradation mechanisms of phenol resin.

CO
C
.°2
CH,

H2O
I
130
°C
200 300 400 500 o
100 600
- H 2 0 ( -CH 4 1 1 1
CH 2 -0H j^ 1
1 r^
-C0 2 , - C O c
<A50°C 1 1 1 1 o
o
>450»C =3

- H 2 |>H 2 < IV

I I I
-co O1
-C
l
"C
i l
C
t
^C >460°C •c* V Y c V
c c
I I I 1

Figure 10-7. Initial thermal degradation mechanisms of furfuryl-alcohol resin. Ill

562 10 Glass-Like Carbons
Bhatia et al. (1984) and Aggarwal et al.
(1988) examined in detail the carboniza-
tion processes of phenol-formaldehyde
resins relevant to the number of OH in
phenol and to the molar ratio between
phenol and formaldehyde, and pointed out
that the quality of glass-like carbon de-
pends strongly on both factors. Kobayashi
et al. (1968) reported that the phenol-form-
aldehyde resin fuses during the carboniza-
tion process, with increasing numbers of
methyl radicals in the phenol molecule. As
shown by these observations, the proper-
ties of glass-like carbon can be sensitively
controlled by changing the starting
molecules.
10.4.2.3 Furfuryl-Alcohol Resin
As shown in Fig. 10-7 (Fitzer and Schae-
fer, 1970), methylene bridges (I) are formed
in furfuryl-alcohol resin by dehydration at
the initial stage. Above 150°C the methy-
lene bridge is broken to evolve methane, of
which the intermediates are not clear. The
furan ring itself is broken to evolve CO 2
and H 2 O. Around 450 °C a part of the
methylene bridge is oxidized by the result-
ing H 2 O to change into a chain polymer
(III). During heating above 460 °C, CO
evolves from the carbonyl bond, leading
first to an unsaturated conjugated system
(IV) and then to the carbon crystallite.
Jenkins et al. (1972) proposed a clear path-
way from phenol-hexamine resin carbon to
the network of ribbon stacking model.
10.4.3 Structural Change During
the Carbonization Process
In contrast to the hardening and initial
carbonization processes, the structural
change in the carbonization process is not
well known because the usual chemical
analyses cannot be used. By using other
structural parameters, the carbonization
process of Glassy Carbon derived from fur-
furyl alcohol was clarified, but there are
few data on other resins. According to op-
tical microscopic observations on the pol-
ished surfaces of Glassy Carbon, the pores
appear at approximately 500 °C, below
which no pore exists (Fitzer et al., 1969).
The most abundant pores of 0.2-2 nm in
diameter are observed after heating to
800 °C. Heating to even higher tempera-
tures causes the pores to shrink and de-
crease and to disappear completely after
heating to 1600°C. Some techniques of
burying the pores are also available (Nagle
and Walker, Jr., 1973; Edelson and
Glaeser, 1986).
Figure 10-8 shows some structural pa-
rameters of Glassy Carbon as influenced
by the carbonization process (Fitzer et al.,
1969). The amount of water absorbed and
the specific surface area correspond to the
appearance of the carbon surfaces stated
above, i.e., both parameters increase up to
800 °C and then decrease to reach constant
O BET surface area
• Water adsorption
1? a n l A \ A Volume change
Q) "U \ \
• Weight change
£00 800 ~12OOW 1600 2000
Heat-treatment temperature (°C)
Figure 10-8. Changes of some structural parameters
of Glassy Carbon with heat-treatment temperature.

ill!
Glahard
Figure 10-9. Polished surface appearance of conventional glass-like carbon and high-quality glass-like carbon
Glahard.
values at 1000-1100 °C. The weight de-
crease of Glassy Carbon almost finishes by
800 °C. The bulk shrinkage, on the other
hand, continues strongly up to 800 °C and
then decreases at higher temperatures.
During carbonization below 800 °C the
weight loss is more substantial than the
shrinkage, leading to formation of pores.
Since the main change at higher tempera-
ture is shrinkage rather than weight loss,
the resulting pores gradually disappear.
The pores present during the carboniza-
tion process are so-called closed pores,
which do not affect gas permeability but
do result in some problems in applications
which depend on the surface smoothness of
the glass-like carbon.
The behavior stated above can be some-
what changed, depending on the kind of
resin used and the heat-treatment condi-
tions. With some resins, pores are never
formed during the preparation processes.
The hardening treatment must be carried
out carefully because it is intimately re-
lated to the subsequent thermal degrada-
tion behavior and, furthermore, to the
properties of the final glass-like carbon
10.5 Properties of Glass-Like Carbon 563
Conventional glass-like carbon
product. The pore-free glass-like carbon
Glahard was developed recently by using a
hydrophilic resin (Yamauchi et al., 1985).
The water which is formed during the
hardening and initial carbonization pro-
cesses tends to coagulate to form fine
drops, leading to pores after removal at a
subsequent stage. A hydrophilic resin is so
effective in dispersing the resulting water
that no pores remain. The polished surface
of such a glass-like carbon, after heating to
1200 °C, is shown together with that of the
conventional material in Fig. 10-9. Hot
isostatic pressing (HIP) is also effective in
removing pores. The UDAC Carbon of the
Kobe Steel Company, produced by this
technique, has a surface smoothness of
< 0.01 jam without pores.
10,5 Properties
of Glass-Like Carbon
10.5.1 Normal Glass-Like Carbon
The properties summarized in Table 10-2
are quoted from the catalogs of three com-
564 10 Glass-Like Carbons

Table 10-2. The properties of commercially available glass-like carbon products (manufacturers are listed in
parentheses beside each product).

Property Celluose Glassy Carbon (Tokai) Glahard (Kao)

Carbon (G.E.)
GC-10 GC-20 GC-30 S-100

HTT (°C) >1700 1300 2000 3000 1200

Bulk density (103 kg m" 3 ) 1.55 1.47-1.51 1.46-1.50 1.43-1.47 1.45
Apparent porosity (%) 1-3 1-3 3-5
Gas permeability (cm2 s"1) io- 1 2 l O - ^ - l O " 1 2 1Cr i o _ 1 0 - i 2 1 0 -7_ 1 ( ) -9

Bending strength (MPa) 176.5 88.3-98.1 98.1-117.7 49-58.8 98.1

Young's modulus (GPa) 27.4 29.4-32.37 29.4-32.37 21.6-24.5 19.6
Shore hardness 95 100-120 100-110 70-80 120
Electrical resistivity (10" 6 Om) 40 45-65 40-45 35-40 45
Thermal conductivity 4.18-16.72 3.76-4.6 8.36-9.19 15.0-17.55 3.34-3.76
y W Hi Jv )
Thermal expansion coefficient 3.4 2.0-2.2 2.0-2.2 2.0-2.2 3.5
.(lO-^CT 1 )

mercially available glass-like carbons: Cel-
lulose Carbon is characterized by its
unique raw material; Glassy Carbon has
been the most comprehensively examined
carbon until now (Yamada et al., 1964;
Metrotra et al., 1983); Glahard is a high
quality glass-like carbon derived from a
hydrophilic thermosetting resin (Yamauchi
etal., 1985).
10.5.1.1 Density, Porosity
and Gas Permeability
The density of many glass-like carbons is
around 1500 kg m~ 3 . These values are far
smaller than the 3520 kg m~ 3 of diamond
and 2250 kg m~~3 of graphite but glass-like
carbon is gas-impermeable because of the
characteristic structure shown in Fig. 10-9.
The porosity of Glahard, though not dis-
closed, must be zero in view of the pho-
tograph shown in Fig. 10-9. With increased
heat-treatment temperature, Glassy Car-
bon shows a decrease in density and an
increase in porosity as well as gas perme-
ability. Such behavior is not necessarily
common to all glass-like carbons; for in-
stance, there are glass-like carbons that ex-
hibit the opposite behavior, or almost no
change, with heat treatment.
Craievich et al. (1973) and Jenkins and
Walker, Jr. (1976) used the small-angle X-
ray scattering technique to examine the
pores in glass-like carbon. Both results
agree well: glass-like carbon contains
pores of 1-2 nm (mean diameter), and
their shape is possibly that of oblate ellip-
soids.
10.5.1.2 Mechanical Properties
The bending strength of glass-like car-
bon is 196.2 MPa at maximum but usually
around 98.1 MPa as shown in Table 10-2.
This material has a large Young's modulus
of 19.6-29.4 GPa. These mechanical prop-
erties, in general, decrease with increased
heat-treatment temperature. The disper-
sion of the fine iron particles is effective in
improving the bending strength of glass-
like carbon after carbonization but not
after graphitization (Kammereck et al.,
1974).
As shown by the Shore hardness of 100
or higher, glass-like carbon is very hard
and brittle. It retains a Shore hardness of

70-80 even after graphitization. The ma-
chining of this material is so difficult that
the shape and size of the product are con-
trolled at the hardening stage. Because of
the extended shrinkage during subsequent
heating, however, it is also not easy to pre-
pare a product with a close tolerance. As
suggested from its characteristic structure,
glass-like carbon is different from conven-
tional artificial graphite because it has low
self-lubricity and high abrasion resistance.
10.5.1.3 Electrical Properties
The specific resistivity of glass-like car-
bon is around 40 • 10~ 6 Qm, which is the
smallest among carbon materials. The
change of resistance with heat-treatment is
small as a result of minor structural
changes caused by heating to high temper-
atures (as shown in Fig. 10-2). This level of
resistivity is suitable for use as a heater. In
addition, isothermal heating is possible
throughout the glass-like carbon heater
because of its homogeneous structure. This
is another reason for using it as a heater in
semi-conductor technology.
10.5.1.4 Thermal Properties
There is no difference in the thermal ex-
pansion coefficients between glass-like car-
bon and conventional artificial graphite.
The thermal conductivity of glass-like car-
bon is relatively small. The thermal shock
resistance of this material is only one tenth
of that of conventional artificial graphite
because of its low thermal conductivity in
addition to its high degree of hardness and
high modulus. Enhancement of the ther-
mal conductivity was an important prob-
lem from the practical point of view, and
was solved later by adding a filler with high
thermal conductivity such as natural
graphite (Fukuda et al., 1988; Saura et al.,
1987).
10.5 Properties of Glass-Like Carbon 565
10.5.1.5 Chemical Properties
Glass-like carbon has outstanding
chemical properties. Both the glass-like
carbon and the conventional artificial
graphite, for example, begin to react with
an oxidizing gas at the same temperature;
thereafter, however, the former reacts far
more slowly. The reason was initially con-
sidered to be the low specific surface area
of this material, but later it was attributed
to its characteristic structure, as shown in
Fig. 10-4a, i.e., relatively little of the reac-
tive edge of the carbon crystallite is present
in glass-like carbon. The chemical reactiv-
ity decreases with increasing heat-treat-
ment because of the development of the
crystal structure and removal of impurities
which act as catalysts (Tingey, 1975).
Conventional graphite reacts with
H 2 SO 4 :HNO 3 (1:1) mixed acids and
breaks down into powder after 40 h, but no
weight loss of Glassy Carbon was observed
after 150 days under these conditions (Ya-
mada et al., 1964). Glass-like carbon can
also withstand hydrofluoric acid and
chromic acid but is not as stable against
alkaline reagents. Glass-like carbon is far
more stable toward metals at high temper-
atures than conventional carbon materials,
leading to electrical and metallurgical ap-
plications.
10.5.1.6 Purity
For the applications described in
Sec. 10.6, the purity of glass-like carbon is
one of the most important factors. In con-
trast to the artificial graphite electrode us-
ing pitch and coke derived from natural
products, glass-like carbon has a high
grade of purity because of its derivation
from artificial thermosetting resin. The im-
purity (ash) content of this class of materi-
als - without treatment - is 0.1 to 0.5%.
After specific purification treatment, how-
566 10 Glass-Like Carbons

Table 10-3. Impurity (ash) analyses of Glassy Carbon products a after purification treatment (results given in ppm;
ND: not detected).

Product Total Al B Ca Co Cr Fe Mg Mn Ni Cu Si V

GC-20S <200 3 <1 10 ND 2 20 <1 ND 1 <1 7 15

GC-20SS <10 ND <1 ND ND ND <1 <1 ND ND ND <1 ND
GC-30S <100 4 <1 ND ND ND 5 <1 ND ND <1 20 ND

Heat treatment temperatures: 2000°C for GC-20S, GC-20SS; 3000°C for GC-30S.

ever, it decreases remarkably: the results of
ash analysis of some Glassy Carbon prod-
ucts show that the product with the highest
purity contains < 10 ppm impurities (Table
10-3).
10.5.1.7 Comparison with other Materials
Table 10-4 shows the properties of three
materials: Pyrex glass, glass-like carbon
(Glassy Carbon-20) in Table 10-2 and the
artificial graphite electrode without im-
pregnation. Glass-like carbon is similar to
Pyrex glass in its gas impermeability, me-
chanical properties and appearance, but
similar to the graphite electrode in electri-
cal and thermal properties. Glass-like car-
bon is therefore an intermediate material
between the other two.
10.5.2 Properties of Composite Glass-Like
Carbon and Porous Glass-Like Carbon
Table 10-5 shows the properties of com-
posite glass-like carbons (SG-1 and SG-3)
and porous glass-like carbons, e.g., SG-
200, GGC-composite and Reticulated Vit-
reous Carbon (RVC) (Franklin, 1980;
Wang, 1981). SG-3 carbon contains a
larger amount of fine natural graphite filler
than SG-1. In general, gas permeability
and bending strength are lower after
adding the filler (see Table 10-5), but such
decreases are not serious problems in some
applications. The reinforcing effects of the
filler are preferable, e.g., the graphite pow-
der decreases the thermal expansion coeffi-
cient and increases thermal conductivity,
leading to improvements in thermal shock
resistance. The lowering of electrical resis-
tivity is also favorable for some applica-
tions.
The porous glass-like carbons SG-200
and GGC-composite were prepared by us-
ing non-woven fabric and exfoliated
graphite as a filler; their pore structures
differ from each other. GGC-202 contains
a larger amount of filler than GGC-201.
The gas permeability of GGC-202 is 100
times larger than that of GGC-201, but the
other properties do not have such extreme
differences. The applications of such po-
rous materials depend on gas permeability;
the control of this property is therefore im-
portant. RVC (Wang, 1981) has an entan-
gled porous structure different from other
porous carbons. Its bulk density and ap-
parent porosity are 0.048 and 97%, respec-
tively. The application target of this mate-
rial is, of course, different from other po-
rous carbons, as explained below.
10.6 Applications of Glass-Like
Carbon
10.6.1 Electronic
and Magnetic Applications
Some glass-like carbon products are
shown in Fig. 10-10. The best known appli-
cation is for a susceptor (heater) for the
vapor phase growth of semi-conductor sili-
 10.6 Applications of Glass-Like Carbon 567

Table 10-4. Comparisons of the properties of Glassy Carbon GC-20, conventional artificial graphite and Pyrex
glass.

Property GC-20 Graphite Pyrex glass

3 3
Bulk density (10 kg m~ ) 1.46-1.50 1.5-1.7 2.23
Apparent porosity (%) 1-3 20-30 0
Gas permeability (cm2 s"1) 10-10-10'12 lO0-^"1 IO-^-IO- 1 2
Bending strength (MPa) 98.1-117.7 19.6 39.2-68.6
Young's modulus (GPa) 29.4-32.4 4.9-11.7 62.8
Shore hardness 100-110 30
Electrical resistivity (10 ~6 Qm) 40-45 5-12 1015
Thermal conductivity ( W m ^ K " 1 ) 8.36-9.19 104.5-242.4 1.08
Thermal expansion coefficient (10~ 6o C~ 1 ) 2.0-2.2 1-3.5 3.25

Table 10-5. Properties of the commercially available composite glass-like carbons (SG-1, SG-3) and porous
glass-like carbons (SG-200, GGC-201, GGC-202, RVC) (manufacturers are listed in parentheses beside each
product).

Property SG carbon GGC composite RVC

(Showa Denko) (Kobe Steel) (ERG)

1 3 200 201 202

HTT (°C) 1000 1000 1000

Bulk density (103 kg m~ 3 ) 1.55 1.60 0.55 0.6 0.6 0.048
Apparent porosity (%) 1.5 1.6 70 65 70 97
Gas permeability (cm2 s" 1 ) <10" ( 3 <10~4 0.2 0.3 30
Bending strength (MPa) 176.5 132.4 22.6 16.5 14.7 0.3-1.17 a
Young's modulus (GPa) 29.4 24.5 0.098
Shore hardness 100 80 6-7b
Electrical resistivity (10" 6 Qm) 47 26 20 45 45 4700
Thermal conductivity (Wm" 1 K" 1 ) 3.34 91.9 1.25 4.18 4.18
Thermal expansion coefficient (10~ 6o C 2.4 0.8
a b
Tensile; Mors

con wafers (Yasuda and Nakamura, 1975).
Since the glass-like carbon is of high purity
without adsorbed gas, it is possible to put
this material directly into the reaction
chamber. Other characteristics are: (i) mod-
erate electrical resistance suitable for a
heater, (ii) homogeneous structure (ensur-
ing a uniform heating action), (iii) high ox-
idation resistance, (iv) resistance to hy-
drofluoric acid (the cleaning solution), etc.
On the basis of its dense structure and high
oxidation resistance, glass-like carbon is
used for crucibles and boats to synthesize
compound semiconductors such as GaAs,
which is very corrosive. Also, glass-like
carbon is used for crucibles to grow single
crystals - with a corrosive flux such as
CaF2 (Lewis, 1963) instead of a platinum
crucible. Properties required for jigs used
in transistor preparation are high purity,
high precision machinability, moderate
electric resistance and low reactivity with
metals.
A perpendicular magnetic recording sys-
tem now being developed has achieved
higher density recording than the present
568 10 Glass-Like Carbons
Figure 10-10. Some products of glass-like carbons, (a)
Glassy Carbon; (b) Glahard.
systems (Iwasaki and Nakamura, 1977). A
serious problem was the development of
material with high lubricity and high abra-
sion resistance for the magnetic head
(Wakasa et al., 1987), because the magnetic
head slides on the magnetic recording me-
Time (min)
dia in this system. Glass-like carbon was
selected as the material of choice, but the
surface of the conventional glass-like car-
bon was too rough for this purpose. There-
fore a glass-like carbon with a more homo-
geneous structure was developed by using
a hydrophilic thermosetting furan resin.
Fig. 10-11 shows changes in the coefficient
of friction with time when some samples
were rubbed against Co-Cr-sputtered
metal film. With the lubricants presently
being used, no change in the friction coeffi-
cient with time was observed in the glass-
like carbon (Glahard-1000) in contrast
with the glass Neoceram.
At present, aluminum is used as the sub-
strate material of the so-called hard mag-
netic disc. In order to make a smooth sur-
face, an aluminum plate is subjected to
Ni/P chemical plating or anodic oxidation
in a chromic solution, followed by polish-
ing to attain a surface with a smoothness of
better than < 0.02 fim. Conventional glass-
like carbon is too rough to use as substrate
material. The application of Glahard to
this purpose is now under development.
This glass-like carbon has a low productiv-
ity, but this is not such a serious problem
in high-value applications.
Glass-like carbon was to be applied to
the type-wheel of high-speed printers but
Neoceram
Neocream
+ Lubricant A
Figure 10-11. Changes of
Neoceram friction coefficient of glass-
Lubricant B like carbon Glahard and
Glahard
commercially available
Neoceram with rubbing
time.
 10.6 Applications of Glass-Like Carbon
its brittleness prevented its successful ap-
plication.
10.6.2 Applications
in Analytical Chemistry
Glass-like carbon is used in special elec-
trodes for emission spectral analysis, polar-
ography, potentiometry, etc. (de Galan
etal., 1983; Linden and Dieker, 1980).
Here, low reactivity and electric conductiv-
ity are mainly required. There are many
reports on the electrochemical corrosion of
glass-like carbon in chemical reagents
(Neffe, 1988). In the case of emission spec-
tral analysis, the usual artificial graphite
electrode is used one to three times and is
then thrown away. However, glass-like
carbon electrodes can be used 100 times
and, furthermore, they are highly sensitive
and reproducible.
Another application is packing for the
various chromatography techniques (Fuji-
naga etal., 1967; Tanaka etal., 1976) be-
cause glass-like carbon can be used at a
high temperature, can be packed easily and
causes no tailing of chromatographic
peaks. This application might be extended
because of the development of new proce-
dures to prepare the fine glass-like carbon
particles stated above. Fine porous glass-
like carbon particles may be used as a
molecular sieve.
10.6.3 Metallurgical Applications
Glass-like carbon crucibles are used as
containers for molten salt electrolysis in
the production of corrosive metals. Also,
glass-like carbon tubes are used to blow
chlorine gas to remove hydrogen from alu-
minum ingots. Since glass-like carbon is
gas-impermeable and unreactive with
metals at high temperatures, this applica-
tion is expected to be extended if the cost
can be lowered. There have been some tri-
569
als to replace the usual glass-like carbon
with a composite glass-like carbon able to
produce high yields.
10.6.4 Applications to Biomaterials
Carbon material has a high biocompati-
bility (Bokros etal., 1973), but problems
are caused by its low moldability and diffu-
sion of the fine carbon particles into tissue.
In general, carbon materials for use as bio-
materials are subjected to a hardening
treatment of the surface, but glass-like car-
bon can be used without such treatment
because of its hard and dense structure
with no pores. Wear resistance, one of the
most important properties, is improved by
ion implantation (Pollock et al, 1987). An
application has been attempted for dental
implants, with unsuccessful results (Greno-
ble and Kim, 1973). It was difficult to pre-
pare a thin rod with sufficient mechanical
strength. Applications to joints in various
parts of the body (Jenkins, 1980; Fitzer,
1980) and replacement of broken bones
(Itoh et al., 1985) were reported; however,
the subsequent results have not yet been
reported.
A well-known biocarbon material is py-
rolytic carbon which is widely used as a
heart valve (Bokros et al., 1973). Fitzer et
al. (1978) reported that the lower-priced
glass-like carbon can be used successfully,
instead of pyrolytic carbon, as the valve
material.
10.6.5 Applications to Fuel Cells
As shown in Fig. 10-12, separators used
for fuel cells are large (60 x 60 cm-
100 x 100 cm, 0.5-1 mm in thickness). The
phosphoric acid fuel cell (or first genera-
tion fuel cell) using a concentrated phos-
phoric acid electrolyte (Fig. 10-13) oper-
ates at 200 °C for long periods of time. The
constituent material must have high oxida-
570 10 Glass-Like Carbons

Figure 10-12. The fuel cell

separator.

tion as well as high thermal resistance. Ad-
ditional properties required are as follows:
(i) high mechanical strength to be handled
in thin plates and to resist multiple stack-
ing, (ii) gas impermeability, (iii) a small co-
efficient of thermal expansion, (iv) high
electrical and thermal conductivities. Only
noble metals and the carbon materials pos-
sess such properties.
Initially, carbon plate separators were
prepared by cutting artificial graphite out
of normal bulk and subsequent impregna-
tion with thermosetting resin. Such a
method of low production yield resulted in
an increase of the price of plates. The glass-
like carbon plate was selected instead, but
it has too small a thermal conductivity and
low production yield. As a result, com-
posite glass-like carbon with graphite pow-
der as a filler was developed and is now
being tested. The use of the graphite filler
results in an improvement of mechanical
strength and flexibility as well as signifi-
cant increases in electrical and thermal
conductivities.
Porous carbon is used as an electrode of
the fuel cell (Stonehart, 1984). Here, the
homogeneous sizes and uniform distribu-
tion of pores are required, in addition to
the properties required in the separator.
An electric capacitor using the active
carbon fiber derived from Kynol-type phe-
nol resin has already been industrialized in
Japan; details have been reported else-
where (Nishino et al, 1985).

Residual
hydrogen
Hydrogen

uri A electrode
.— Separator

^ Oxygen electrode
• Electrolyte. (with catalysis)
„ Electrolyte
(Phosphoric acid)
-*—Hydrogen electrode
^ Oxygen (with catalysis)
Natural.
gas
V Water
Air
electrode
• Hydrogen
o Oxygen
-— Separator
Hydrogen

vapor • o Water

Figure 10-13. Schematic model of the phosphoric acid fuel cell and assembly of the electrodes.

10.6.6 Other Applications
In aerospace applications, glass-like car-
bon is used as a rocket nozzle. Applica-
tions of the porous glass-like carbon to
make heat-insulators, filters and catalyst
supports are now under development. At-
tempts were made some years ago to use a
light-weight glass-like carbon mirror in ad-
vanced optical systems (Pinoli and Brad-
shaw, 1975). Composite glass-like carbon
with a high production yield is being con-
sidered for use as a tube for the heat ex-
changer. Glass-like carbon fibers are so
flexible, though with poor mechanical
properties, that they are used as a packing
material, abrasion material, and wear-re-
sistant material (Miyashita, 1983).
A high-quality glass-like carbon may be
used as a cast for optical lens preparation
and as a laser mirror.
10.7 Acknowledgements
The authors express their appreciation
to Dr. M. Shiraishi of the National Re-
search Institute for Pollution and Re-
sources for useful discussions and lending
of high resolution photomicrographs.
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11 Organic Glasses and Polymers
Ernst Rossler
Institut fur Atom- und Festkorperphysik, Freie Universitat Berlin,
Berlin, Federal Republic of Germany

Hans Sillescu
Institut fur Physikalische Chemie, Universitat Mainz,
Mainz, Federal Republic of Germany

List of Symbols and Abbreviations 574

11.1 Introduction 577
11.2 General Considerations 579
11.2.1 Typical Properties of Organic Glasses 579
11.2.2 Different Types of Glasses 582
11.2.3 Experimental Methods . 585
11.2.3.1 Thermal Methods 586
11.2.3.2 Viscosity, Mechanical and Dielectric Relaxation 586
11.2.3.3 Optical Methods 587
11.2.3.4 Neutron Scattering 588
11.2.3.5 NMR Methods 588
11.2.4 Theoretical Treatment 593
11.2.4.1 Free-Volume Theory 593
11.2.4.2 Thermodynamic Theories 595
11.2.4.3 Mode-Coupling Theory 596
11.2.4.4 Energy Landscapes 597
11.3 Typical Examples and Recent Applications 598
11.3.1 Simple Liquids 598
11.3.1.1 a Process 598
11.3.1.2 p Process 605
11.3.2 Polymeric Liquids 607
11.3.3 The Glassy State 608
11.4 References 615

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
574 11 Organic Glasses and Polymers

List of Symbols and Abbreviations

B molecular-size parameter
C effective coupling constant
cP heat capacity
complex heat capacity
D translational diffusion coefficient
E electric field
E activation energy
EP most probable activation energy
f mean fractional free volume
h Debye-Waller factor
non-ergodicity parameter
f(Td distribution of spin-lattice relaxation times
F field
FA(t) motional correlation function
F{x1,x2, t 2 correlation function of spin alignment experiment
)
g(E) distribution of activation energies
G(t) Fourier transform of G (co)
GA*,t) van Hove's autocorrelation function
G(lnr) distribution of correlation times
G'(co) storage modulus
G"((o) loss modulus
/(CO) powder spectrum
I(co,T) solid echo spectrum
7
fast(<») fast exchange spectrum
I slow (<») slow exchange spectrum
J(t) shear compliance
J((O0) spectral density function
Ks(co) adiabatic compressibility
M(q,t) mode-coupling memory function
PA(?) distribution of correlation times
) conditional probabilities
position of a scatterer j
rk(t) position of a scatterer k at time t
solid echo time signal
sc configurational entropy
coherent dynamic structure factor
Sine (9, <») incoherent dynamic structure factor
TltT2 spin-lattice and spin-spin relaxation times
T* transversal relaxation time
Tc critical temperature of mode coupling theory
Ts glass transition temperature
Tk Kauzmann temperature
Tm melting point
 List of Symbols and Abbreviations 575

Vogel temperature
corrected glass transition temperature (reference temperature)
cell volumes
critical volume
average free volume
% free volume
constant molecular volume
V volume
V(q,q') vertex function
wtj transition rate
W(T) weight factor
XA(co) dynamic complex susceptibility
X'D(CO) dielectric loss curve
a thermal expansion coefficient
Of differences of thermal expansion coefficients above and below Tg
r gamma function
8 activation energy
£*((L>) complex dielectric constant
n shear viscosity
complex viscosity
bulk viscosity
compressibility
X coupling constant
temperature-independent coupling parameter
n Prigogine-Defay ratio
n
kj rate of the transitions Qt Qk
Q>Qo density
u cs u cs u cs anisotropic chemical shift tensor
zz yy xx
motional correlation time
cut-off time of the CD distribution
response function
density correlation function
intermediate-scattering function
excitation frequency
C0 0 Larmor frequencies
adjustable parameters
BMO 1,1 -bis (4-methoxyphenyl) cyclohexane
BPP Bloembergen Purcell Pound
CD Cole-Davidson
DSC differential scanning calorimetry
FID free-induction decay
FRS forced Rayleigh scattering
HMB hexamethyl benzene
LCPS liquid crystal side chain polysiloxane
576 11 Organic Glasses and Polymers

KWW Kohlrausch-Williams-Watts
OTP o-terphenyl
PCS photon correlation spectroscopy
PS polystyrene
PDB phthalic acid di-n-butylester
PMMA polymethylmethacrylate
RBS Rayleigh-Brillouin spectra
TLS two-level system
TNB 1,3,5-tri-oc-naphthyl benzene
TTI thiophene indigo derivative
VFT Vogel-Fulcher-Tammann
WLF Williams-Landel-Ferry

11.1 Introduction
Transparency and the capability of glass
blowing are the most prominent features
that a layman attributes to glassy materi-
als. Transparency, specifically optical iso-
tropy, corresponds to disorder. The simi-
larity to a liquid is stressed by the term
frozen liquid, which characterizes the struc-
ture of the glassy state. All microscopic
theories introducing the concept of micro-
crystalline structure have failed thus far to
describe the structure of glass. A glass is
instead described by the predominance of
local order; no translational symmetry,
that is, long-range order, is observed. To-
pological disorder leads to a distribution of
intermolecular distances, orientations, and
bond angles. Many physical properties of a
glass are not completely characterized by
an average value; the corresponding distri-
bution function is also of major interest.
A necessary precondition of glass blow-
ing and an important technical processing
advantage as compared to crystalline ma-
terials is the possibility of controlling the
viscosity of molten glass. The viscosity of a
glass, or more precisely, that of a super-
cooled liquid, may be changed over some
orders of magnitude within a narrow, but
of course, temperature range. In contrast
to the liquid-crystal transition, the viscos-
ity increases continuously for the liquid-
glass transition. Above 1012 Pa s the super-
cooled liquid is conventionally called a
glass. Every liquid may be solidified as a
glass provided crystallization is bypassed.
The competition between crystallization
and vitrification may be decided in favor of
the latter when sufficient high cooling rates
are applied. Hence speed is the important
ingredient of glass formation. Supercooled
metallic melts with their high tendency of
crystallization may be vitrified by quench-
ing the melt with cooling rates of about
11.1 Introduction 577
10 6 K/s (see Chap. 9). On the other hand,
polymer glass forming systems- like win-
dow glass melts already have high viscosi-
ties near their melting point, and thus the
tendency to crystallize is small. Molecular
liquids form stable supercooled liquids
only in favorable cases; however, these rare
liquids are of major interest for experimen-
talists concerned with checking theoretical
predictions.
The technology of glass handicraft was
already being applied in Phoenician times
(see Chap. 1). Oxide glasses containing
SiO 2 , Na 2 O and several further additives
are nowadays used to yield high-perfor-
mance window or technical glasses. Ex-
tremely high transparency glass is necessary
for fiber-optical communications. Here,
typical materials are SiO 2 /GeO 2 mixtures
(see Chap. 15). Glass-forming composi-
tions of particular halides work to shift the
IR edge of standard glass to longer wave-
lengths (see Chap. 8). Chalcogenide glasses
like Se or AsSe exhibiting high photocon-
ductivity are applied in xerography. The
glass-crystal transition is exploited in
amorphous semiconductor memory ele-
ments like Te0 8 Ge 0 2 (see Chap. 7). Amor-
phous silicon containing hydrogen for
photoreceptor films plays an important
role in solar cell technology, and rapidly
quenched metallic glasses find their appli-
cation in transformer cores (see Chap. 9).
All materials mentioned here consist of in-
organic glasses. In many cases large area
films are necessary for application, which
may easily be achieved by technical control
of the viscous flow. On the other hand,
many new materials in daily life are made
from organic polymers, in the simplest case
from linear chain molecules of high molec-
ular weight. Low specific weight, low cost
and easy processing are prominent features
of this class. All together, the amorphous
state, as an alternative solid state to the
578 11 Organic Glasses and Polymers
crystalline state, offers a variety of excep-
tional properties.
Two important questions may be ad-
dressed to the physics of amorphous solids.
First, what structural principles character-
ize the glassy state, and what are the rules
determining the distribution of local or-
der? Here, the random-close-packing
structure advanced by Bernal (1965), Scott
and Kilgour (1969), and Finney (1970) as a
model for metallic glasses is a starting
point. The concept of a continuous ran-
dom network proposed by Zachariasen
(1932) and further developed by Polk
(1971), has been used as a guide describing
covalently bonded glasses, e.g., fused silica.
Although long-range order is missing in a
glass, intermediate-range order might play
a role. In addition, the importance of struc-
tural heterogeneities or cluster formation
in amorphous systems has to be clarified.
Answers may be presented, for example, by
X-ray, neutron, or electron scattering, by
extended X-ray absorption fine structure,
and by Mossbauer, IR and NMR spectros-
copy. Reviews are given by Zallen (1983)
and Elliot (1990) (see Chap. 4).
The second challenging question for a
theory on amorphous solids, which is re-
lated to the first question, involves the
glass transition itself. What microscopic
mechanism controls the sudden increase of
viscosity below the melting point of a liq-
uid? Many concepts have been proposed
thus far. The most important ones are
found in free-volume and thermodynamic
theories, respectively. In particular, the
widely applied Vogel-Fulcher-Tammann
(VFT) equation describing the divergence
of the viscosity below the melting point
may be derived from both theories. The
decrease of free volume and excess entropy,
respectively, is related with the slowing-
down of the dynamics. The free-volume
theories are related to the work of Fox and
Flory (1950), Cohen and Turnbull (1959),
and Williams, Landel, Ferry (1955), who
proposed their famous WLF equation, a
version of the VFT equation. The thermo-
dynamic theories were first formulated by
Gibbs and Di-Marzio (1958) and Adam
and Gibbs (1965). Within these theories, a
second-order phase transition is assumed
to account for the Kauzmann paradox
(1948); that is, extrapolating the entropy of
a supercooled liquid should lead to lower
entropies as compared to the correspond-
ing crystal. However, the failure of the
VFT equation to describe the viscosity
over the entire supercooled region of sim-
ple liquids is emphasized in many publica-
tions (see Chap. 3).
Not only has the divergence of viscosity
or molecular time constants to be ex-
plained by a proper theory but also the
appearance of a secondary relaxation pro-
cess in the supercooled region, namely, the
P-process. In addition, the striking anoma-
lies of glasses at low temperatures have at-
tracted many scientists in the last years.
Heat capacity, thermal conductivity, and
acoustic and dielectric absorption show
peculiarities when investigated below 10K.
So-called two-level systems have been in-
troduced by Anderson et al. (1972) and
Phillips (1972, 1981, 1987) to explain the
anomalies; however, the physical origin of
such tunneling modes is still a matter of
controversy.
An increasing number of publications
attack the physics of the amorphous state
by computer simulations, in particular,
Monte Carlo and molecular dynamics sim-
ulations. Lennard Jones liquids and hard-
and soft-sphere systems are modeled; high
quenching rates may be applied which can-
not be reached by any experiment. (A re-
view is given by Angell et al., 1981.) Poly-
mer dynamics of systems confined to a
lattice structure have shown similarities

with percolation phenomena, and dynamic
non-uniformities have been observed (De
la Batie et al., 1984). Computer models of
the random-close-packing structure (Fin-
ney, 1970) and the continuous random net-
work (Polk and Boudreux, 1973) have also
been carried out.
The question of the nature of the glass
transition has been raised anew by recent
extensions of the mode-coupling approach,
which is known from the dynamics of sim-
ple liquids, and which explains the glass
transition on a molecular scale. Contribu-
tions by Leutheusser (1984), Bengtzelius
et al. (1984), and Sjogren and Gotze (1989)
have postulated the existence of a distin-
guishable temperature above Tg, where
traces of a dynamic phase transition may
be observed. This marks the first time that
a phenomenon like the glass transition has
been predicted by an ab initio type theory.
Indications for such a transition are sub-
stantiated by recent neutron-scattering ex-
periments. The promising concept has in-
spired many new experiments, and once
again, an exciting discussion concering the
dynamics of the glass transition has begun.
This chapter provides a review of recent
applications of new methods mainly on
simple supercooled liquids. The class of
Van der Waals liquids is well suited to
provide model systems for investigating
new theoretical concepts of the glass tran-
sition. The investigations are not ham-
pered by additional relaxation processes or
structural peculiarities. Emphasis is on re-
sults from several relaxation methods, e. g.,
neutron and light scattering, dielectric re-
laxation, diffusion measurements, and, in
particular, NMR studies. The survey in-
cludes relaxation studies of the glassy state
of organic glasses. For comparison, results
on polymers will be recalled, especially
polymers with low-molecular-weight addi-
tives, as models for polymer plasticizer sys-
11.2 General Considerations 579
tems. The experimental picture is com-
pleted by reviewing the most influential
theoretical concepts which provide a tool
for understanding the experimental find-
ings.
11.2 General Considerations
11.2.1 Typical Properties
of Organic Glasses
A prominent feature of a supercooled
liquid is its dramatic increase in viscosity
directly below the melting point Tm. This is
demonstrated in Fig. 11-1 for two organic
liquids, where data for an organic and an
inorganic polymer liquid are included for
comparison. While viscosities of the order
oflO~ 3 -10~ 2 Pas are typical for non-as-
sociated liquids above Tm, the viscosity
rises continuously up to values of the order
of 10 1 3 Pas within a narrow temperature
range. Several approaches describing the
strong non-Arrhenius temperature depen-
dence of viscosity have been proposed, but
none of them is able to fit the data over the
whole supercooled region. In particular,
the often-applied Vogel-Fulcher-Tammann
equation, lg(rj/f]0) =D/(T- TJ (T^ < Tg),
fails for viscosities below 10 2 Pas (Placzek
and Magill, 1968). Recently, the equation
lg(^/^ 0 ) = (T0/T)2, has been proposed by
Bassler (1987), extending energy-transport
kinetics in disordered solids to supercooled
liquids. In the framework of the mode-cou-
pling theory, a power law, rj =A(T— Tc)~y
(Tc > Tg), is predicted for the onset of the
glass transition (Sjogren and Gotze, 1989).
All three fits are included in Fig. 11-1,
demonstrating that only part of the dy-
namics is described by a single approach.
The situation is even more confusing when
polymer liquids are considered; the tem-
perature dependence is much smaller as
580 11 Organic Glasses and Polymers
Igl^in Pa s)
12
300 400 500
compared to simple liquids. On the other
hand, the specific temperature dependence
of the viscosity may be used to classify dif-
ferent types of liquids (see Sec. 11.2.2).
When measuring the heat capacity of a
supercooled liquid as a function of temper-
ature one will notice a significant change
occurring at a temperature Tg. A similar
effect is observed for the thermal expansion
coefficient. Although these features are
characteristics of a second-order phase
transition, Tg cannot be related unambigu-
ously to an equilibrium function, such as
free energy. In particular, the position and
the sharpness of the transition near Tg de-
pends on the cooling rate at which the heat
capacity is monitored. Conventionally,
cooling rates of about 10 K/min are used to
determine Tg. Determined in this way, the
glass transition temperature Tg can be used
to compare different glasses. Isodynamic
points are probed, as will be shown below.
The interpretation of Tg as a kinetically
controlled temperature is also supported
by deviations from unity for the so-called
Prigogine-Defay ratio, which is unity for a
second-order phase transition, or more
generally, when only one order parameter
determines the system (see Sec. 11.2.4.2).
Figure 11-1. Viscosity as a
function of temperature:
o-terphenyl (OTP) (O),
1,3,5-tri-oc-naphthyl benzene
(TNB) (•), polystyrene
(PS) (0), and borone triox-
ide (B2O3) (#•). Solid line:
Vogel-Fulcher-Tammann
fit; dashed line: 1/T2 fit;
dotted line: power-law fit.
600 700
TinK
Viscosity as well as correlation times
provided by different relaxation methods
yield information on the slowing down of
the dynamics. In particular, the dynamic
complex susceptibility XA(co) for a given
observable, A, is of major interest. Gener-
ally, XA (to) is measured when some alter-
nating field F is applied and the response A
of the systems is detected. For the linear-
response region, both are related by
A = XA(co)F (11-1)
For the case of dielectric relaxation mea-
surements, A is identified with the polar-
ization P, and F with the electric field E.
The response of the system may be ob-
served in the frequency domain or in the
time domain. The response function <PA (t)
measured in the time domain is related
with the response in the frequency domain
by
with
&'X{co) = ]cos(tot)<PA(t)dt
o
On the other hand, &A (t) characterizes the
correlation loss of the equilibrium flue-

tuations of the quantity A. <t>A(t) is related
to the normalized correlation function
(A(0) A(t)}KA(0)2} = FA(t) by <PA(t) =
XA FA(t), where XA is the static susceptibil-
ity. The correlation time xA is defined by
the integral over the correlation function
FA®:
00
xA = lFA(t)dt (11-3)
0
Different relaxation methods report differ-
ent correlation times corresponding to dif-
ferent dynamic windows of the dynamics
typical for the glass transition. An impor-
tant task is to relate these quantities to
each other in order to obtain a consistent
picture. In many different experiments in
the supercooled region, FA (t) cannot be de-
scribed by a simple exponential decay
which is implied by the so-called Debye
model (Debye, 1929). Non-diffusional dy-
namics determine the motion of the
molecules. In many cases, the non-expo-
nential correlation function may be ap-
proximated by a stretched exponential,
namely, the Kohlrausch-Williams-Watts
function (Kohlrausch, 1847; Williams and
Watts, 1970)
FA(t) = exp(-t/Ty (11-4)
An alternative description is the introduc-
tion of a distribution of correlation times
pA (T). The correlation function is given by
a convolution of exponential decays with a
distribution pA (T).
(11-5)
Distribution functions proposed by Cole
and Davidson, Cole and Cole, or Fuoss
and Kirkwood have been widely applied.
(A review is given by Bottcher and Bor-
dewijk, 1978.) In many cases analytical
expressions for FA (t) cannot be given, but
the corresponding expressions in the fre-
11.2 General Considerations 581
quency domain, that is, XA (co), are analyti-
cal. Taking the concept of a distribution of
correlation times literally and not only as
a formal way to account for non-exponen-
tial correlation loss, the question arises
whether a distribution of correlation times
is a realistic picture for a supercooled liq-
uid. Different molecules perform reorienta-
tion with different time constants and relax
independently with an exponential corre-
lation function. The alternative picture de-
scribes highly coupled molecules which re-
lax collectively with a non-exponential
correlation function. In the last case the
cooperative nature of the glass transition
is emphasized. We will come back to this
question.
When X"A (co) is measured in the super-
cooled region, pronounced asymmetric
curves are found for the main a peak and
its maximum shifts to lower frequencies
when the temperature is lowered. In many
cases the frequency-temperature super-
position principle holds. The individual
XA(CD, 7j) are superimposed to a master
curve X"A as the frequency co is scaled by
com, where com is taken from each maxi-
mum of XA(a>, Tt). Thus, we write
X'JL(co9T) = X'JL(ca) (11-6)
with co = co/com. These experimental find-
ings imply a scaling law for the correlation
function FA (t), namely
FA(t,T) = FA(t/z{T)) (11-7)
Changes in temperature do not affect the
shape of the correlation function but only
the time scale. Applying this important re-
sult to the distribution of correlation times
pA (T), all correlation times have to change
by a constant factor for a given change of
temperature. This implies that a distribu-
tion of correlation times originating from a
distribution of activation energies violates
the scaling law (Eq. 11-7). Thus, such an
582 11 Organic Glasses and Polymers
interpretation of pA (T) is not suited to de-
scribe the cooperativeness of the a process.
However, the concept of a distribution of
activation energies might be suited to ac-
count for motional non-uniformities of
guest molecules in a glass below Tg (see Sec.
11.3.3).
The temperature range for the appli-
cability of the stretched exponential scaling
law, (Eq. 11-4), is not well understood. One
can argue that at the highest temperatures
above the melting point, the exponent of
the KWW function should return to unity
(Grimsditch and Torell, 1989), and a Debye
process might be a proper mechanism for
the reorientation of liquid molecules at low
viscosities.
Returning to the operational definition
of Tg by the center of the temperature range
AT of the large change in heat capacity in
a DSC run with cooling rate T, we note
that the glass transition is related with a
low-frequency excitation. For a typical
rate of 10 K/min = 0.02 K/s and AT= 10 K,
the excitation frequency is co = f/AT =
0.02 s" 1 , thus probing correlation times of
about 50 s. The glass transition tempera-
ture defined in this manner can be under-
stood as an isodynamical point which
allows for comparing different glasses
at temperature Tg. The question arises
whether the different correlation times
sampled by different methods have the
same order of magnitude at Tg, or whether
some decoupling of different motional
modes may be observed. Experimental re-
sults which support a decoupling will be
presented below (see Sec. 11.3.1.1).
A further important feature of a super-
cooled liquid is the appearance of the fi
process. Inspecting mechanical and dielec-
tric susceptibility, one finds in addition to
the large a peak a second smaller /? peak
(McCrum et al., 1967; Johari and Gold-
stein, 1970, 1971; Williams and Watts,
1971). Its maximum shifts with tempera-
ture according to an Arrhenius law, where-
as the a peak shifts in the typical non-
Arrhenius way. Relative to the a process,
a faster process is responsible for the /?
peak. The mean correlation times of the a
and p processes merge for high tempera-
tures. Whereas the a process is clearly at-
tributable to the overall reorientation of
the molecules, the origin of the (3 relaxation
is not yet clarified. Loosely packed regions
or islands of mobility (Johari, 1976, 1987),
i.e., heterogeneities in the glass, might be
responsible for this additional relaxation.
Local vibrational modes of some kind have
also been considered (Goldstein, 1969).
The /? process persists in the glassy state
below Tg; however, the total polarization
decreases rapidly (Johari, 1976,1987). As a
consequence only a few correlation times
are reported for supercooled liquids. The /?
process is believed to be an intrinsic feature
of the glass transition, but it is not ob-
served by all relaxation methods. In Sec-
tion 11.3.1.2 recent NMR experiments are
described which also provide a hint for
such an additional process.
The appearance of a (S process implies a
more involved structure for the correlation
function FA (t). For the limit of very short
times (10~ 13 s), it starts with zero slope in
the form of a Gauss function for free flight
of liquid molecules. The development in the
picosecond time domain has recently been
studied by neutron-scattering techniques
(Bartsch et al., 1989) and will be discussed
further in Section 11.3.1.2. The traditional
p process seen in dielectric and mechanical
relaxation occurs on a much slower time
scale merging with that of the a process at
temperatures above Tg.
11.2.2 Different Types of Glasses
Metallic glasses, ionic glasses, Van der
Waals glasses, hydrogen-bonded glasses,

and covalently bonded glasses are distin-
guished from one another according to dif-
ferent kinds of intermolecular or inter-
atomic interactions. To study the dynamics
below Tm, Van der Waals liquids, ionic liq-
uids, and hydrogen-bonded liquids may be
supercooled slowly in favorable cases.
Lowering the symmetry of the molecular
shape by introducing bulky side groups
slows down the tendency of a liquid to
crystallize, and investigations might thus
be facilitated. However, this introduces ad-
ditional problems; i.e., the role of internal
motional freedom, which gives rise to addi-
tional relaxation effects, has to be singled
out from normal glassy behavior. The class
of covalently bonded glasses, which in-
cludes inorganic and organic polymers, is
somewhat special. Because of polymer-
entanglement effects, the viscosity of such
polymer liquids near the melting point is
much higher than that of Van der Waals
liquids. Consequently, crystallization is
slowed down, and the amorphous state is
favored for these systems. However, with
respect to dynamics, many properties are
controlled by typical polymer properties,
e.g., entanglement effects, decoupled
molecular processes, or molecular-weight
dependencies. Compared to polymer liq-
uids, hydrogen-bridged liquids may be re-
garded as temporary polymers; the con-
nectivity of the subunits is not permanent.
The temperature dependence of viscos-
ity helps to discriminate different classes of
liquids. In particular, the question of uni-
versality within one class is often discussed.
In 1972, Laughlin and Uhlmann proposed
the use of the glass transition temperature
for reducing the data. The authors extrap-
olated their data to a temperature corre-
sponding to a viscosity of 10 14 Pa s. Later,
Wong and Angell (1976) rescaled the data
mainly for inorganic glass-forming systems
by defining a glass transition temperature
11.2 General Considerations 583
as Tg = T{rj = 1012 Pa s). In the first case a
reasonable master plot was provided for
organic liquids, whereas in the second case
different curves were obtained which were
distinguished in terms of strong and fragile
network glass formers. A different scaling
procedure has been proposed recently by
Rossler (Rossler, 1990 a, b) which is more
in the spirit of Laughlin and Uhlmann.
A better correlation was observed when
minor corrections for the calorimetric Tg
were carried out. The viscosity data of non-
associated liquids was rescaled in order to
provide the best agreement in the range
10 2 -10 1 0 Pas. Furthermore, a reference
liquid, 1,3,5-tri-a-naphthyl benzene, is in-
troduced, where Tg = Tr is used for defining
a reduced temperature scale. The result is
shown in Fig. 11-2. Table 11-1 compiles Tg
and Tr, and a high correlation is found
among these quantities. The fundamental
and experimental uncertainties in measur-
ing Tg are minimized, and extrapolation
errors are avoided by applying this reduc-
tion procedure. The isodynamic point Tg
with a minor correction is taken to rescale
the viscosity data of different glass-forming
liquids.
Three features are discovered from such
a corresponding states analysis for non-as-
sociated organic liquids, (i) Universal be-
havior is revealed for organic liquids above
10 2 Pas. (ii) Below 10 2 Pas individual
curves separate from the master curve,
(iii) The viscosity at Tg is of the order of
1010 Pa s. Thus, a correlation time for heat
flow of about 50 s corresponds to a viscos-
ity of 10 10 Pa s. Judging from these results,
it is believed that two dynamic regions
have to be distinguished at least for simple
organic liquids-namely, above and below
10 2 Pas - and have to be described sepa-
rately. It has been shown that the VFT
equation yields the best fit for the compiled
data only above 10 2 Pas (see Fig. 11-2),
584 11 Organic Glasses and Polymers

Table 11-1. Glass transition temperatures Tg reported and reference temperatures TT given by the corresponding
states analysis.

Glass forming system Tg(K) T r (K) Symbols in References

Fig. 11-2

Non-associated organic and ionic liquids

n-butyl benzene 125 132.5 + 1, 2 | 3
sec-butyl benzene 127 138 A 1 |3
di-n-butyl phthalate 176/193/181 185 •V 1 1 3, 4, 5
3-methyl pentane 77 86.4 6|7
o-terphenyl 242/243/244 244.2 o• 8,9 | 10, 11, 12
a-phenyl-o-cresol 221/230 215.3 8,9 5, 10
phenyl salicylate 220/230/225 218.8 8,9 5,10
n-propyl benzene 122 131 O 1 |3
i-propyl-benzene 125/127 131.7 X 1,2 3,12
1,3,5-tri-a-naphthyl benzene 342/345 345 • 13 | 14, 13
Hydrogen bonded
propanol 98 98 O 15 | 3
Polymers
oligostyrene (M = 550) 251 258.4 1— 16 | 17
polystyrene (M = 4000) 353/350 343.6 2— 18 | 19, 17
polystyrene (M = 37OOO) 378/370 370.1 3— 18 | 19, 17
polystyrene (M = 390000) 380/373 373 4— 18 | 19, 17
B2O3 526/530/539 532 20 | 21, 22, 10
BeF2 598/570 584 O 23 | 24, 25
BSC (Oxide-glass) — 816 15 | —
GeO 2 853/820/810 810 26 | 24, 25, 26
NBS-711 — 694 o 15 | —
SiO2 1430/1453 1430 26 | 24, 22
Soda lime — 781 27|-

References: 1) Barlow, A. I, Lamb, J., Matheson, A. J. (1966), Proc. Roy. Soc, London Ser. A 293, 322. 2) Ling, A. C,
Willard, J. E. (1968), J. Phys. Chem. 72,1918. 3) Carpenter, M. R, Davies, D. B., Matheson, A. J. (1967), J. Chem.
Phys. 46, 2451. 4) Hains, P. J., Williams, G. (1975), Polymer 16, 725. 5) Rossler, E. (1990), Ber. Bunsenges. Phys.
Chem. 94, 392. 6) Von Salis, G.A., Labhart, H. (1968), J. Phys. Chem. 72, 752. 7) Johari, G.P., Goldstein, M.
(1971), J. Chem. Phys. 55, 4245. 8) Laughlin, W.T., Uhlmann, D.R. (1972), J. Phys. Chem. 16, 2317. 9) Cukier-
mann, M., Lane, J. W., Uhlmann, D. R. (1973), J. Chem. Phys. 59, 3639. 10) Grest, G. S., Cohen, M. H. (1981), Adv.
Chem. Phys. 48, 455. 11) Greet, R. I, Turnbull, D. (1967), J. Chem. Phys. 47, 2185. 12) Johari, G.P., Goldstein,
M. (1970), J. Chem. Phys. 53, 2372. 13) Plazek, D. J., Macgill, J. H. (1968), J. Chem. Phys. 45, 3038. 14) Ehlich, D.,
Sillescu, H. (1990), Macromolecules 23, 1600. 15) Tweer, H., Simons, J.H., Macedo, P.B. (1971), J. Chem. Phys.
54, 1952. 16) Allen, V.R., Fox, T.G. (1964), J. Chem. Phys. 41, 337. 17) Fox, T.G., Loshaek, S. (1955), J. Polym.
Sci. 15, 371. 18) Otsuka, S, Ueno, H., Kishimoto, A. (1979), Angew. Makromol. Chemie 80, 69. 19) Claudy, P.,
Letoffe, J. M., Camberlain, Y, Pascault, J. P. (1983), Polym. Bull 9, 208. 20) Macedo, P. B., Napolitano, A. (1968),
J. Chem. Phys. 49,1887. 21) Grimsditch, M., Torell, L. M. (1989), Springer Proceedings in Physics, Vol. 37: Richter,
D., Dianoux, A. J., Petry, W., Teixeira, J. (Eds.). Heidelberg: Springer, p. 196. 22) Van Uitert, L. G. (1979), J. Appl.
Phys. 50, 8052. 23) Moynihan, C. X, Cantor, S. (1967), J. Chem. Phys. 48,115. 24) Wright, A. C, Etherington, G.,
Desa, J. A. E., Sinclair, R. N., Connell, G. A. N., Mikkelson, J. C. (1982), J. Non-Crystal. Solids 49, 63. 25) Zallen,
R. (1983), The Physics of Amorphous Solids. New York: J. Wiley. 26) Wong, J., Angell, C. A. (1976), Glass Structure
by Spectroscopy. New York: Marcel Dekker. 27) Doremus, R. H. (1973), Glass Science. New York: J. Wiley.

13 -
11 -
I/)
9 inorganic
o
CL polymer liquids
7 /
0
5
° *
I ~$* • *®
a
3 organic
1 &"- " %"*
2.
-1
1 • /
A—VFT Fit
i 1
0.6 0.7 0.8
T r /T
whereas below 10 2 Pas a power law,
rj =A(T— Tc)~y, as predicted by mode-
coupling theory, is well suited to fit the
onset of the glass transition, where the
highest curvature of r\ (T) occurs. Tc —
1.18 Tr provides a reasonable description
for all liquids (Rossler, 1990 a, b).
Extending the scaling procedure to inor-
ganic polymer liquids does not allow the
data to be rescaled to coincide with the
master curve of simple liquids. However,
we chose B 2 O 3 as a reference system with
Tr = Tg and superimposed all data at
highest viscosities (Rossler, 1991). Again,
some degree of universality was found and
the relation between Tg and Tr is satisfying
(compare Fig. 11-2 and Table 11-1). Tg cor-
responds to 10 13 Pa s which is a consider-
ably higher value compared to simple liq-
uids.
The two types of rescaled viscosity
curves in Fig. 11-2 may be related to each
other if the viscosity of organic polymers
with different molecular weights are
rescaled. Data for different molecular
weights of polystyrene are included in Fig.
11-2 (Allen and Fox, 1964; Otsuka et al.,
11.2 General Considerations 585
X
simple
-•if
liquids
T
TC
Figure 11-2. Rescaled Arrhenius
plot for different types of liquids.
i i For symbols see Table 11-1.
0.9 1.0
1979). The polystyrene with the lowest
molecular weight behaves like a typical
simple liquid, whereas the data of high
molecular weight do not at all coincide
with the curves of simple organic liquids.
Instead, the multitude of inorganic glass-
forming polymers is approached. Hence,
we conclude that the differences between
the class of low- and high-molecular-
weight liquids mainly involve a polymer
effect, namely, an entanglement effect (De-
Gennes, 1979); the chemical character of
the polymer liquid is of minor importance.
The viscosity curves of hydrogen-bonded
liquids lie between the two limiting curves,
as demonstrated for propanol in Fig. 11-2.
11.2.3 Experimental Methods
In this Section, experimental methods
for investigating physical properties of su-
percooled liquids and amorphous materi-
als are briefly described. More details are
given on recent NMR techniques, since
most examples in Section 11.3 are related
to NMR applications.
586 11 Organic Glasses and Polymers

11.2.3.1 Thermal Methods capillary techniques are only applicable to

normal liquids, rotation viscosimetry can
The calorimetric techniques used for be used in the viscous range up to about
measuring the heat capacity Cp of glasses 10 3 Pas, and sphere drag methods are
are the same as used for other solid materi- applicable up to ~ 1 0 8 P a s . Since super-
als (see Vol. 2). In particular, differential cooled liquids and molten polymers are vis-
scanning calorimetry (DSC) is used for de- coelastic, a frequency-dependent complex
termining the glass transition temperature shear viscosity (Ferry, 1980) is defined as
Tg. Here, it is important to note the depen-
dence of Cp and Tg on the cooling and
heating rates, which has led to particular
techniques for investigating the dynamics = co
-l [G"(co)-iGf(co)]
of enthalpy relaxation.
where Gf(co) is the storage modulus, and
Thus, one can analyze the hysteresis in
G" (co) the loss modules. The real viscosity
heating and cooling cycles or the enthalpy
is then obtained as the zero frequency limit
relaxation after temperature jumps in
of Gff(co)/co. Since G(co) is perhaps the
terms of an order-parameter formalism
most important quantity for characterizing
that takes account of the time-dependent
the internal dynamics of polymeric materi-
non-equilibrium states at and below Tg
als and rubbers, rather sophisticated tech-
(Jackie, 1986; Kovacs, 1981). Recently, a
niques have been developed for its mea-
very elegant technique has been developed
surement and analysis, mostly by applying
which in effect allows for the determination
small oscillations in plate-plate or cone-
of a complex heat capacity C* (co) at tem-
plate geometry. It is clear that the Fourier
peratures T>Tg (Birge and Nagel, 1985).
transform of G(co) is the shear relaxation
Here, the temperature can be modulated at
function G (t) which is related to the shear
frequencies up to the kHz region, with
compliance J(t). Other mechanical relax-
small amplitudes (~0.1K) around some
ation functions are related to extension
temperature T where the system is in
and compression experiments yielding the
quasi-equilibrium. C* (co) has a frequency
bulk viscosity in the zero frequency limit.
and temperature dependence which is sim-
We refer the reader to the monograph of
ilar to the complex viscosity rj*(co) and
Ferry (1980) for a detailed description of
dielectric constant s* (co) (see below). How-
these techniques. Recent applications to
ever, whereas the latter may only couple to
polymer glass formers have been reviewed
part of the glass process, C* (co) depends on
by Pearson (1987) and to low-molecular-
all motional degrees of freedom. This has
weight glass formers by Angell (1988).
important consequences for analyzing the
dependence of the a process on time and Dielectric relaxation is one of the most
temperature (Angell, 1988). important observables for studying the a
and /? processes in glass formers (McCrum
etal., 1967; Johari, 1970, 1971). Although
11.2.3.2 Viscosity, Mechanical
the relation between the complex dielectric
and Dielectric Relaxation
constant 8 (co) and the motion of molecular
The shear viscosity of supercooled liq- dipoles is complex due to interdipole cross-
uids varies over a dynamic range of about correlations, one can often obtain approxi-
15 decades between the liquid region and mate correlation functions for molecular
the glass transition temperature. Whereas reorientation over a wide time and temper-

ature range extending from the liquid state,
through the glass transition, to the solid
glass. Recent technical advances have
made it possible to build measuring sys-
tems from mostly commercial components,
where a frequency range from 10 4 -10 9 Hz
can be scanned in 3 stages essentially auto-
matically as a function of frequency and
temperature (Kremer etal, 1989). An ex-
cellent monograph on dielectric relaxation,
which includes IR and optical frequencies
as well as the dynamic Kerr effect, was
published by Bottcher and Bordewijk
(1978). Applications to supercooled liquids
and glasses have been reviewed by Johari
(1976 and 1987).
11.23.3 Optical Methods
Dynamic light-scattering techniques
have recently been applied very success-
fully to the dynamics in polymers and
glass-forming liquids. At high frequencies
(~ 10 * ° Hz), Rayleigh-Brillouin spectra
(RBS) can be analyzed in terms of the fre-
quency-dependent bulk viscosity rjv (co) and
adiabatic compressibility Ks (co) which can
be related with the dynamics of density
fluctuations (Berne and Pecora, 1976). In a
temperature range of up to 150 K above
Tg, one observes excess scattering in the
central Rayleigh line which has been at-
tributed to clusters. These clusters are also
detected in static light scattering, which be-
comes wave vector dependent in the glass
transition region, and in photon correla-
tion spectroscopy (PCS). A first account of
these findings was given by Fischer (1989)
and Gerharz et al. (1990), where references
to literature on the applied light-scattering
techniques can also be found. PCS has
mostly been used for studying the slow dy-
namics of density fluctuations at the glass
transition (Patterson, 1983). However, the
Fischer group has also analyzed the dy-
11.2 General Considerations 587
namics of concentration fluctuations in
mixed systems where a slow mode has been
detected in addition to the expected inter-
diffusion mode. The former can be related
to a diffusional motion of clusters of ap-
proximately 100 nm in size, which must be
related to the structure of the supercooled
liquid close to the glass transition (Gerharz
et al., 1990). These interesting new results
will probably stimulate further applica-
tions of dynamic light scattering to glass-
forming systems.
Translational diffusion at the glass tran-
sition was previously restricted to rela-
tively rapid motions of small molecules
permeating through polymer films. Re-
cently, the application of forced Rayleigh
scattering (FRS) has extended the dynamic
range to diffusion coefficients D > 1 0 ~ 1 7
cm2 s" 1 (Sillescu and Ehlich, 1990). In this
technique, photoreactive dye molecules
serve as diffusional tracers. A holographic
grating is formed in the sample exposed to
two interfering laser beams, and the diffu-
sive decay of this hologram is subsequently
monitored by forced Rayleigh scattering.
An example is discussed in Section 11.3.1.1
(Fig. 11-10).
Photochemical hole burning has been
successfully applied to the slow dynamics
in glasses at low temperatures. Here, the
photoreactive probe molecule is irradiated
by a laser in a narrow band of the optical
spectrum. Subsequently, the spectrum is
recorded and the broadening of the hole is
measured as a function of observation
time. Eventually, the sample is annealed at
higher temperatures, and the dynamics is
studied as a function of temperature
(Kohler and Friedrich, 1987). A review of
the hole-burning technique has been given
by Friedrich and Haarer (1984). Recent ap-
plications of optical spectroscopy to
glasses can be found in a book edited by
Zschogge (1986).
588 11 Organic Glasses and Polymers
11.2.3.4 Neutron Scattering
Neutron-scattering methods have be-
come of particular interest recently, since
they appear to be most appropriate for
testing the predictions of mode-coupling
theories of the glass transition (see Sec.
11.2.4.3). Whereas the structure of a super-
cooled liquid shows no significant change
at the transition to a solid glass, the dy-
namics freezes in a very complex way, and
dynamic neutron scattering provides infor-
mation on the short-time behavior. The
techniques available cover a q range of
~10~2__l nm" 1 a n c j a time range of
~10~ 8 -10~ 1 2 s. Neutron backscattering,
time of flight, and spin-echo techniques are
used to provide optimum conditions in the
different q and t ranges. In organic glasses,
neutron scattering by the protons of the
organic molecules yields an incoherent dy-
namic structure factor Sinc (</, co) or its fre-
quency Fourier transform, the intermedi-
ate-scattering function # s (q, t\ which is the
space Fourier transform of van Hove's au-
tocorrelation function Gs(r,t). The latter
provides a measure of the displacement of
the scattering centers, the protons, in space
and time. Thus, it decays to zero in liquids
where the molecules perform diffusive mo-
tions over distances of < 1 nm within the
time scale of < 10" 8 s covered by neutron
scattering. In a solid glass, there is a fast
initial decay due to vibrational or libra-
tional displacements; however, Gs (r, t) will
not decay to zero since the protons can
only move within a small spacial region.
The height of the long-time plateau deter-
mines the elastic peak height of the neu-
tron-scattering spectrum and thus the De-
bye-Waller factor, or the non-ergodicity
parameter fs (q% of the mode-coupling the-
ory. The increased amplitudes of the local
motions due to the fast ft process (see Sec.
11.3.1.2) predicted by the mode-coupling
theory cause a decrease of fs(q) with in-
creasing temperature, which is measured at
different q values in neutron-scattering ex-
periments and allows for testing of particu-
lar scaling predictions (Eq. 11-29). At still
higher temperatures, where the a process
enters the neutron-scattering time window,
a broadening of the elastic peak is observed
and used for testing the von Schweidler law
(Eq. 11-33).
Neutron scattering can also provide
the coherent dynamic structure factor
Scoh (q, co) in deuterated organic glass form-
ers, since the deuteron is a strong coherent
scatterer. Here, the collective motion of nu-
clei within the scattering volume is moni-
tored since the corresponding van Hove
correlation function relates the position
Vj (0) of a scatterer j with vk (t) of a neigh-
boring scatterer k at time t. The scaling
predictions of the mode-coupling theory
(see Eqs. 11-29 to 11-34) are rather similar
to those for incoherent neutron scattering
and are currently being tested in different
glass formers (see Sec. 11.3.1.2). For details
of the technique, we refer to monographs
on neutron scattering (Springer, 1972;
Lovesey, 1986; Bee, 1988).
It should be noted that neutron scatter-
ing yields information on the type or mech-
anism of molecular motion that is inacces-
sible to the relaxation and light-scattering
techniques described above (see Sec. 11.2.3.2
and 11.2.3.3). This is demonstrated in Fig.
11-3, where the elastic incoherent structure
factor that corresponds to / s (q) (see above)
is drawn as a function of q for several
motional models (Fujara et al., 1986). Sim-
ilar information is available by particular
NMR techniques discussed below but on a
much slower time scale, 1 0 ~ 3 S < T < 1 0 2 S .
11.2.3.5 NMR Methods
As early as 1948, Bloembergen carried
out a thesis together with Purcell and
 11.2 General Considerations 589

Quasieiastic neutron scattering Deuteron spin alignment

l.rir
0
nr7\
A 0 (q)
1

0.75 -
0.5 —'- .>_
0.25
"X*\ ._ — —-~^.- ._
A- •••
J V7TV- ^^. -,
0 10 20 30
Figure 11-3. Elastic incoherent structure factor A0(q) and normalized spin-alignment echo amplitude F^Tj)
calculated for various molecular reorientation models. Dashed line: two-site jump; dotted dashed line: four-site
jump; dotted line: rotational diffusion on a circle; solid line: isotropic rotational diffusion, a defines the position
of the scatterer of neutron scattering; SQ is 3/4 of the quadrupole coupling constant (Fujara et al, 1986).

Pound by investigating viscous glycerol, lar time scale was significantly extended by
thus demonstrating that spin-lattice relax- the advent of pulse techniques for studying
ation is most effective when a motional slow chemical and, in particular, motional
correlation time x obeys the condition exchange in liquids and in the solid state.
co0 T ~ 1 (Bloembergen et al., 1948). Apply- Here, two-dimensional NMR techniques
ing magnetic fields of the order of 1 tesla are of major importance. A review of the
results in proton Larmor frequencies coo of application to solids is given by Fyfe
about 50 MHz; the relaxation is shortest if (1984). 2 H N M R applied specifically to
correlation times are of the order of 10 ~9 s. polymers is reviewed by Spiess (1984 and
For a simple liquid, such correlation times 1985).
are reached only below Tm, i.e., in the su-
percooled region. The first NMR applica-
tion to molecular motions was concerned Spin-Lattice and Spin-Spin Relaxation
with the glass transition. Motional nar-
The exponential spin-lattice relaxation
rowing of NMR line shapes provides fur-
of a liquid is characterized by the time con-
ther information on an even slower time
stant T±, which is related to a spectral den-
scale. Introducing high magnetic fields in
sity function J(co) given by the Fourier
combination with Fourier transform tech-
transform of a motional correlation func-
niques has increased the effective signal in-
tion FA(t) (see Sec. 11.2.1). Corresponding
tensity considerably and has almost com-
relations hold for the spin-spin relaxation
pletely pushed aside the old continuous
time T2, which determines the line shape in
wave methods. Measurements of 2 H, 13 C,
31 a liquid (Abragam, 1961).
P nuclei have become attractive and
yield information on many problems of
physical chemistry. In particular, high-res-
l/T2 = C/2[3J{0) + 5J{(o0) + 2J(2co0)]
olution solid-state NMR has gained more
and more interest. The accessible molecu- (11-8)
590 11 Organic Glasses and Polymers
C represents an effective coupling constant,
depending on the nuclei under investiga-
tion. For standard NMR, it is not possible
to vary the Larmor frequency co0 over a
broad range. Thus, in order to extract mo-
tional information from T± or T2, the func-
tional time dependence of FA (t) has to be
given. For XH NMR, FA(t) is governed by
intra and intermolecular contributions of
the dominant dipole-dipole interaction
(i.e., by rotational and translational contri-
butions), which are not easily handled.
A separation of both contributions is
possible by application of the deuteron di-
lution technique (Eisner and Mitchell,
1961; Zeidler, 1965; Lindner et al, 1981).
High-resolution NMR in solids and in su-
percooled liquids (Mehring, 1976; Haeber-
len, 1976) is achieved by systematic sup-
pression of the dipolar coupling. Only
chemical-shift anisotropy or quadrupolar
interaction remain. The solid-state spectra
are no longer smeared out by a dipolar
broadening, and high-resolution spectra
result. With respect to relaxation, only cor-
relation functions related to rotation of the
chemical-shift anisotropy or electric-field
gradient are probed. The dipole-dipole in-
teraction is eliminated most effectively by
isotopic substitution. For deuterons (qua-
drupole coupling, 7 = 1) or for phospho-
rous nuclei (chemical-shift anisotropy,
I = 1/2), FA (t) is given in good approxima-
tion by the normalized correlation func-
tion of the second-order Legendre poly-
nomial
(11-9)
<(3 cos2 & (0) - 1 ) (3 cos2 $ (t) -1)>
FA(f) =
<(3cos3(0)-l) 2 >
where S is the angle between the direction
of the z component of the diagonalized
coupling tensor and the magnetic field B.
In the case of 2 H NMR, the angle is given
by the direction of the a bond and B.
Hence, the reorientation of the C- 2 H
bond is probed directly.
For the simplest case of a Debye process,
where % defines the time scale of molecular
rotation. A major property of molecular
reorientation in a supercooled liquid is
its non-exponential correlation function,
which might be modeled by a distribution
of correlation times adapted to NMR
(Connor, 1963; Noack, 1971). Studying Tx
and T2 renders the choice of a proper dis-
tribution function less ambiguous. Both re-
laxation times depend differently on the
correlation function. In particular, for
co0 r ^> 1 the relaxation rate 1/T2 is directly
proportional to the mean correlation time
<T>, which is given by the integral over the
correlation function. Hence, the tempera-
ture dependence of 7\ and T2 are generally
different and can be used to unravel the
type of non-exponential correlation func-
tions.
Line Shape Analysis
In addition to spin relaxation measure-
ments, motional narrowing of NMR line
shapes yields information on molecular
motion. Consider a proton which can be
exchanged by molecular motion, located
between two sites with the NMR frequen-
cies co and co'. The two-line spectrum col-
lapses into one line if the exchange fre-
quency 1/T is larger than the spectral
splitting \CO — (D'\. This basic phenomenon
can be exploited for studying the molecular
motion in the solid state or in the super-
cooled liquid, since the NMR frequency
co oc 3 cos2 $ — 1 changes as # varies
through molecular reorientation. The
powder line shape depends upon the mech-
anism of rotational motion in the slow-
motion region, where 1/T is of the order of
the width of the powder spectrum. Thus,

rotational jumps have been confirmed as a
mechanism of molecular reorientation in
crystalline solids (Spiess, 1974; Alexander
etal., 1974; Pschorn and Spiess, 1980;
Wemmer et al., 1981).
Discarding any dipolar broadening, the
NMR frequency co + cocs of spin 1/2 nuclei
like 13 C and 3 1 P is determined by the
chemical-shift anisotropy which is de-
scribed by a second-rank tensor with prin-
cipal components o^, °"yy a n d ^S
cocs = A cs (3 cos2 $ — 1 — rjcs sin2 S cos <p)
^ = (a;; - o/(*2 - O (u-io)
The angles 5 and cp characterize the orien-
tation of the principal axes of the interac-
tion tensor with respect to the magnetic
field B. For deuterons with / = 1, two tran-
sitions are observed resulting in a doublet
splitting with the frequency shifts + Q ) Q
and — coQ. Here, the interaction of the elec-
tric quadrupole moment e Q and the elec-
tric-field-gradient EFG tensor aQ deter-
mines the line shape. Thus the constant in
Eq. 11-10 is AQ = 3/&(eQag/h). In good
approximation f7Q = 0 holds for deuterons
in organic compounds. In a glass or a poly-
crystalline powder the orientation of the
tensor is randomly distributed and typical
powder spectra with distinct edges and
peaks are observed. For deuterons the
well-known Pake spectrum is found.
According to a spectral width of the or-
der of 100 kHz, motional correlation times
of a supercooled liquid smaller than 10 ~5 s
lead to a complete collapse of the broad
solid-state spectrum, and for T < 1 0 ~ 6 S a
Lorentzian line shape is found. Typically,
such a collapse is observed 20-30 K above
Tg. In the intermediate range ( 1 / T ~ 1 0 0
kHz), information on the type of molecular
reorientation is accessible. The line shape
is given by the Fourier transform of the
11.2 General Considerations 591
free-induction decay (FID), which is usu-
ally measured by standard NMR. The FID
can be expressed as
» = (exp i $coQ(t')dt' (11-11)
o
where the average is over all orientations
at t = 0 (powder average) and the stochas-
tic process. The latter is modeled by solv-
ing the set of rate equations
(11-12)
(d/dt)P(Qi/Qj9t)='EP(Qi/Qk9t)nkj
k
where P(Qi/Qj9t) represents conditional
probabilities, and IJkj rates of the transi-
tions Qk -> Qj where Qj represents the ori-
entation j of the EFG tensor. For a well-
defined rotational jump process, these
equations can be solved in a straightfor-
ward way.
For a 2 H NMR spectrum of width 100-
200 kHz, Eq. 11-11 can not be evaluated,
because the fast time signal is partially lost
in the dead time of the receiver system, and
severe distortions of the spectrum occur as
a Fourier transform of the time signal is
performed. These problems can be over-
come by applying a solid echo sequence, as
depicted in Fig. 11-3. Now the time scale
can be extended to a few hundred micro-
seconds, because the dynamical range of
the solid echo technique is limited only by
the transversal relaxation time T2*. Beyond
a time of the order of T2*, no echo is ob-
served. The solid echo time signal starting
at the echo maximum can be formulated as
(Spiess and Sillescu, 1981)
= ( exp i J coQ ( 0 df -i]coQ (tr) dtf
\ L o *i J
where x1 is the distance between the two
pulses. Again (Eq. 11-12) is applied to de-
scribe S1 if a proper motional model is
given. The FID So and the solid echo time
592 11 Organic Glasses and Polymers
signal St become equal in the rigid solid
limit. In the case of fast isotropic reorienta-
tion of the molecules, the solid echo spec-
trum disappears, and the FID spectrum
shows a sharp Lorentzian line. However,
fast, but anisotropic, reorientation results
in a motionally averaged powder spectrum
where A and rj have to be replaced by the
averaged values of the tensor components
(i.e., A and fj in Eq. 11-10). A typical exam-
ple is the fast methyl rotation which results
in a Pake spectrum reduced by a factor of
three. For a fast anisotropic reorientation
with a symmetry higher than C 2 , the spec-
tral reduction is generally given by
2
A=A/2(3cos y-l) (11-14)
where y is the angle direction of the C - 2 H
bond with respect to the axis of rotation.
For a lower symmetry, a characteristic
nonzero fj is found which is related to the
type of reorientation.
Three Pulse Techniques
Ultra-slow motions with correlation
times T < Tt can be probed by applying a
spin-alignment echo sequence (Spiess,
1980) or a stimulated echo sequence (Gul-
lion and Conradi, 1984; Rossler, 1986) as
sketched in Fig. 11-3. In contrast to the
methods mentioned above, the correlation
function can now be mapped directly in the
time domain. For spins I = 1 or 1/2, differ-
ent pulse lengths are used; however, the
same correlation function is monitored,
namely
"2^2) (11-15)
= <sin(Q)Q(O)T1)sin(coQ(T2)t2)>
In this case three time variables control the
correlation loss: t2 is the running time for
the second echo maximum; the mixing
time T2 probes the exchange of the frequen-
cies for a time T 2 2. The significance
of the correlation function is easily realized
if, e.g., the condition COQT1<^1 is consid-
ered, and only the echo maximum as a
function of T 2 is monitored, i.e., t2 = zl.
Then, SHICOQT! can be expanded, and the
second Legendre polynomial P2 can be
measured directly.
lim F(T 1 ,T 2 )OC<G)(0)CD(T 2 )>X
OC<P2(0)P2(T2)> (11-16)
Furthermore, investigating the function
F ( T 1 ? T 2 ) for t2->oo the quantity ^ ( T J
can be defined ... .~
F 0 0 ( T 1 ) = F ( T 1 , T 2 - O O ) / F ( T 1 , T 2 = 0)
F^iti) is a characteristic oscillating func-
tion highly sensitive to the type of motion.
This is demonstrated in Fig. 11-3 for sev-
eral examples. In particular, Fo0(x1^>co) =
1/n, where n is the number of frequencies
which are exchanged for a given reorienta-
tional process. As an analogy to the elastic
incoherent structure factor measured by
incoherent neutron scattering, F^ (T±) may
be considered to represent the static struc-
ture of the motional process (Fujara et al,
1986).
Details on the path followed by the ori-
entation of a given C - 2 H bond are re-
vealed as the spin-alignment spectrum is
analyzed. Based on the ideas of two-dimen-
sional NMR introduced by Ernst and
Jeneer (Jeneer, 1971; Aue et al., 1976), a
Fourier transform of Eq. 11-15 can be car-
ried out with respect to TX and t2. The
mixing time T 2 is kept as a parameter. Two-
dimensional exchange patterns with char-
acteristic ridges result for powder spectra
which have been used to describe motional
processes in molecular crystals and poly-
mers by Spiess and co-workers (Schmidt
et al., 1986; Schaefer et al., 1990). In partic-
ular, a model-free inversion of the two-di-
mensional spectrum to a distribution of ro-

tation angles which has evolved after a
given mixing time T2 was recently carried
out (Hagemeyer et al., 1990).
11.2.4 Theoretical Treatment
There is hardly another single phe-
nomenon in physics which has been
treated by as many different theoretical ap-
proaches as the glass transition. In the fol-
lowing, we shall try to give an overview of
the most important (or most influential)
treatments. Only the basic ideas are re-
viewed, and the results are described in
close relation to experiments relevant to
the glass transition in supercooled, mostly
organic liquids. We refer to a recent review
(Binder and Young, 1986) of the theories of
spin glasses; this topic is beyond the scope
of this chapter. The structure of amor-
phous solids below the glass transition is
somewhat similar to that of the corre-
sponding liquids. However, the dynamics
differs from that in liquids and in crys-
talline solids as well. We confine our review
of the T<Tg region to some aspects related
to /? processes, energy landscapes, and the
formalism for the two-level system (TLS),
which accounts for most low-temperature
phenomena.
11.2.4.1 Free-Volume Theory
The first derivation of the Vogel-
Fulcher-Tammann law (see Eq. 11-20)
from free-volume assumptions was given in
1959, although free-volume ideas are much
older than this (Cohen and Turnbull, 1959;
Ferry, 1980). They associate a different
free volume with each of N molecules in
the total volume V and determine the
most probable free-volume distribution for
the boundary conditions ^Nt=N and
Z JVf % = V— Nvm, where vm is some essen-
tially constant molecular volume, and Nt
represents molecules with the free volume
11.2 General Considerations 593
vn. The result NJN ocexp( — yvfi) is
analogous to the Boltzmann distribution
NJN ocexp( —/Jef) since the condition of
constant energy, X Nt ef = £, has been re-
placed by that of constant total free vol-
ume V—Nvm. Similarly, the parameter y
is related to the average free volume v{ in
analogy with the relation of /? = l/feB T and
the average thermal energy kB Tper molec-
ular degree of freedom. In the simplest ver-
sion of free-volume theory, a molecule
jumps into a hole of its own size (~v^3)
whenever it has a free volume vn <v*~vm.
(No activation energy is assumed!) Thus,
the jump frequency, which is proportional
to the diffusion coefficient D for transla-
tional displacement, is proportional to the
fraction of molecules having a free volume
larger than v* (Doolittle, 1951):
00
Doc Jexp(~t;/t;f)dt;xexp(-t;*/^f)(ll-18)
It is now assumed that the mean fractional
free volume f=Nvf/V has a linear temper-
ature dependence above Tg,
f=fg + af(T-Tg) (11-19)
where af is the difference of the thermal
expansion coefficients above and below Tg.
By combining Equations 11-18 and 11-19
one readily obtains the Vogel-Fulcher-
Tammann (VFT) law
^71 (11-20)
where T^ = Tg- is the Vogel tempera-
ture, and Do T^ = B/af relates the parame-
ter Do with a molecular size parameter
B ~ 1 which can be determined by compar-
ison with thermal-expansion experiments
(Ferry, 1980). It is plausible (Stokes-Ein-
stein relation) that D ~* is proportional to
the shear viscosity rj and the related relax-
ation time %n (see, however, Sec. 11.3.1.1).
The Williams-Landel-Ferry (WLF) equa-
594 11 Organic Glasses and Polymers
tion, which is readily obtained by reformu-
lation of the VFT equation, is often used to
express this temperature dependence:
Clg(T-Tg)
log aT = (11-21)
C2g + T-Tg
c 2g =/ g K
Applications of the free-volume theory to
amorphous polymers have been reviewed
by Ferry (1980). Polymer diluent systems
were treated most extensively by Vrentas
etal. (1985). A more sophisticated treat-
ment of the free-volume theory was given
by Cohen and Grest in 1979 (Cohen and
Grest, 1979; Grest and Cohen, 1981).
Within the framework of a cell model they
assume a local free energy that differs for
cell volumes v above and below a critical
value vc. It contains a term proportional to
v — vc for liquid-like cells having v > vc. For
solid-like cells (v<vc) it is proportional to
(v — v0)2, where v0 is the cell volume at the
free energy minimum. From these assump-
tions, a particular intermolecular potential
can be modeled and one obtains an aver-
age free volume of the form
vt = a{T-TJ + b[{T-Tm)2 + cT] (11-22)
where a, b, c and T^ can be estimated from
the details of the model and are interre-
lated, yielding vf oc (T- TJ for 7 > T^ and
vf oc T for T^T^. The glass transition fol-
lows from the assumption that molecular
displacement is only possible in liquid-like
clusters of liquid-like cells having a total
free volume X (^i — vc) > vc • The size of the
liquid-like clusters increases with increas-
ing temperature, and Tg is associated with
the percolation temperature where the crit-
ical cluster is attained. Thus, molecular dis-
placement over macroscopic distances is
only possible at T >Tg. An essential point
is the behavior of the communal entropy,
which is zero if only solid like cells are
present and becomes N kB at the high-tem-
perature limit, where the full volume, V9 is
accessable to all N molecules. Clearly, the
communal entropy rises sharply at the per-
colation transition, thus modeling the
jump of the heat capacity at Tg. Additional
assumptions are necessary for taking ac-
count of the cooling-rate dependence of Tg
(Cohen and Grest, 1979), which otherwise
should be identified with the quasistatic
limit of very slow cooling, where Tg attains
a value of the order of the Vogel tempera-
ture 7^. We should also note that the huge
temperature dependence of transport coef-
ficients and relaxation times (D, r\, zn,...) is
essentially given by Eq. 11-22, which corre-
sponds to Eq. 11-19 of the Cohen-Turnbull
theory, and Eq. 11-18, the Doolittle equa-
tion. The main contribution to the temper-
ature dependence above Tg is given by the
slope of the linear term in the local free
energy, which is a local quantity.
Thus, the large apparent activation en-
ergy close to Tg is related to the cooperativ-
ity of molecular motion, not directly but
rather via more or less ad hoc assumptions
about free-volume properties. This is also
typical of the old Cohen-Turnbull ap-
proach. It should also be noted that solid-
like clusters at T>Tg correspond to the
liquid-like clusters in a percolation model.
Cluster-like heterogeneities have recently
been detected by dynamic light-scattering
experiments in supercooled liquids above
Tg (Gerharz et al., 1990).
In summary, the basis of the free-volume
theory is given by the Doolittle equation,
Eq. 11-18, which originally was formulated
as a phenomenological equation but can
be justified within different theoretical
frameworks. Various assumptions about
the dependence of v{ on temperature, pres-
sure (Ferry, 1980), composition (Ferry,
1980; Doolittle, 1951), and time (physical

aging, Struik, 1980) allow for broad appli-
cability to describing experimental results
at T>Tg.
11.2.4.2 Thermodynamic Theories
The origin of the thermodynamic ap-
proaches to the glass transition lies in the
observation that a straightforward extrap-
olation of the entropy of supercooled liq-
uids to a lower temperature leads to values
below the entropy of the crystalline solid at
a temperature Tk > 0 K (Kauzmann para-
dox). Therefore, a phase transition at
T2 > Tk is postulated for experiments in the
limit of infinitely slow cooling rates. There
is still no agreement about the nature of
this transition, which is experimentally in-
accessible (DiMarzio, 1981; Jackie, 1986;
Fredrickson, 1988). It is noteworthy, that
the Prigogine-Defay ratio
n = VTaAa2 (11-23)
is larger than one for any experimental
temperature Tg>T2. In Eq. 11-23, Ax,
ACp, and Aa are the changes at Tg of the
compressibility, the heat capacity, and the
thermal expansion coefficient, respectively.
It can be shown that U = 1 for a second-or-
der phase transition (Jackie, 1986). We note
further that a first-order transition is ob-
tained if T2 is associated with the percola-
tion transition of the Cohen-Grest theory
(1979).
Gibbs and DiMarzio (1958; DiMarzio,
1981) have devised a lattice model where
the configurational entropy Sc of model
chains can be calculated as a function of
some energy difference between flexible
and stiff segments and the fraction of
empty cells. Thermodynamic quantities
can be described within this model as a
function of temperature (Sc = 0 at T2),
pressure, and chain length. The model can
11.2 General Considerations 595
also be adapted to copolymer and polymer
plasticizer systems (DiMarzio, 1981). Dy-
namic properties are modeled in a theory
of Adam and Gibbs (1965; Jackie, 1986),
where it is assumed that the supercooled
liquid consists of cooperatively rearranging
regions which grow to infinite size at T2.
The fraction of regions where cooperative
rearrangement is possible is then propor-
tional to the transport coefficients D, rj~1,
and T" 1 . The analogue of the VFT equa-
tion, Eq. 11-20 (Ferry, 1980), then becomes
D^exp - (11-24)
where the configurational entropy Sc is re-
lated with the Cp jump at Tg by
Sc= J(AC p /T)dT (11-25)
T2
which yields the VFT equation if one as-
sumes T2 — T^ and ACp oc T ~x (Angell,
1988). However, the assumption of con-
stant ACp also results in a dependence on
T which is indistinguishable from the VFT
equation within the accuracy of most ex-
periments. Although, the Adam-Gibbs
equation is conceptually rather different
from the VFT equation, the physics is not
so different if the free volume is viewed as
a dynamic quantity which somehow trig-
gers cooperative rearrangements. This im-
plies, for example, that the elementary pro-
cess of the Cohen-Turnbull theory, where a
molecule jumps into a hole of its own size,
is fictitious, and no real holes exist in liq-
uids. We should also mention the applica-
tion of the coupling model of Ngai et al.
(1986) to the Adam-Gibbs theory (Ngai
et al., preprint). Here, a dynamic coupling
is introduced between the cooperatively re-
arranging regions according to a coupling
scheme which has been successfully ap-
plied to many types of relaxations in com-
plex systems (Ngai et al., 1986). In contrast
596 11 Organic Glasses and Polymers
to the Adam-Gibbs theory, which predict
exponential relaxation, one obtains a
stretched exponential relaxation function:
T* is related to T O (T) by T* = (fizo)1/P'
• co~(1~1//?). The time T 0 describes relax-
ation within an individual cooperatively re-
arranging region, whereas the tightness of
coupling and the number n of coupled
units are characterized by the adjustable
parameters coc and /? = 1 — n, respectively.
11.2.4.3 Mode-Coupling Theory
The mode-coupling theory of the liquid-
glass transition has emerged from treat-
ments of dynamics in liquids. Leutheusser
(1984) and Bengtzelius, Gotze, and Sjolan-
der (1984) have proposed a mode-coupling
assumption which introduces a nonlinear-
ity into the equation of motion for the den-
sity correlation function, resulting in a sin-
gularity with properties resembling a glass
transition. Thus, the q mode (q = (4n/X)-
• sin 0 is the wave vector) of the density
correlation function
(11-26)
<P (q, t) = J <e (0,0) Q (r, t)> exp (i q r) dr
is assumed to follow the kinetic equation
J
dt'M(q,t-t') — <P(q,t') = O (11-27)
o or
with a memory term subject to the mode-
coupling assumption
(11-28)
M (q91) = J dq' V(q, qf) $ (q, t)<P(q- q', t)
which introduces a quadratic nonlinearity
into Eq. 11-27. The discussion of numerical
results often refers to the simpler case
where the vertex function V(q,q') is re-
placed by a single coupling constant k
(Bengtzelius et al., 1984; Sjogren and
Gotze, 1989), or the dependence on q is
totally eliminated (Leutheusser, 1984). In
Eq. 11-27 y is a damping coefficient, and co0
an oscillator frequency. The most interest-
ing feature, which is obtained in the sim-
plest version (Leutheusser, 1984), is a char-
acteristic slowing down of $(q,t) in the
vicinity of a particular value lc of the cou-
pling constant. One can then associate
E = (XC- X)/kc with the distance (Tc - T)/Tc
from the glass transition temperature or
r
(QC~Q)/QC f° ^ e macroscopic density.
The slowing down at lc is not accompa-
nied by marked structural changes, thus
describing a purely dynamical transition.
Some of the most important predictions of
the mode coupling theory can be sum-
marized as follows: The long time limit
<P(q,t^KX))=f(q\ termed non-ergodicity
parameter by Sjogren and Gotze (1989)
and measurable from the amplitude of the
elastic peak in neutron scattering (Debye-
Waller factor or Mossbauer-Lamb factor),
reaches a plateau in the vicinity of Xc with
a square root dependence on Tc — T at
T<TC and a very weak T dependence at
T>TC: (H-29)
(7zaV/£ + O(T), for T<TC
/ ( ) = / +
« « | OiT), for T>TC
e = \(Tc-T)/TJ (11-30)
The remainder of $ (q, t) is found in a very
fast fi process; (11-31)
for
(11-32)
and a slower a process
(11-33)
for
<x>~1 < t < co'e ~1 oc (<oeef'2 (11-34)
 11.2 General Considerations 597

A, a, b, cog, and co'E are parameters which

can be determined in numerical solutions
of Eq. 11-27. The dependence of the power
law on time for the a process (Eq. 11-33)
was proposed long ago (von Schweidler,
1907) and is usually quoted as the von
Schweidler law (Gotze, 1990). It is in agree-
ment with the short-time limit of the
stretched exponential (see Sec. 11.2.4.2),
exp [ - {t/xY} = 1 - (t/xY + - . . . , which
applies in many experiments. In Fig. 11-4,
the density correlation function is shown
Figure 11-4. Two-step correlation function as given
for a model calculation (Gotze and
by the mode-coupling theory. The dashed curve
Sjogren, 1989) where the glass transition is labeled a gives the asymptotic function f+A/ta,
approached in the series A, B, C, .... The and the dashed curve labeled b gives the function
scaling laws for the fast (3 process (curve a) f-B(t/T)b (Gotze and Sjogren, 1989).
and the von Schweidler law (curve b) are
also shown.
A scaling law is also predicted for the
havior. In most treatments of dynamics in
shear viscosity
amorphous solids, a Gaussian barrier dis-
tribution is assumed or obtained from par-
Y\ GC8~ (11-35)
ticular model assumptions (Wagner, 1913;
Tweer et al., 1971; Griinewald et al., 1984;
The scaling predictions (Eqs. 11-29 to
Bassler, 1987; Richert and Bassler, 1990;
11-35) have stimulated a number of experi-
Phillips, 1987; Sethna and Chow, 1985;
mental tests, in particular, with neutron-
Movaghar et al., 1986; Schirmacher and
scattering techniques, which are discussed
Wagener, 1989). The old proposal of a log-
further in Sec. 11.3.1.2. Mode-coupling as-
Gauss distribution of correlation times
sumptions have also been introduced in
(Wagner, 1913) implies a Gaussian distri-
hydrodynamic equations and cause non-
bution of activation energies s if
linearities which, however, do not result in
a sharp glass transition but rather in a kBT) (11-36)
broader transition region (Das, 1987).
is assumed:
G (s) de = g (lnr) (d In x/d&) ds (11-37)
11.2.4.4 Energy Landscapes
Rotational and translation motion in
crystalline solids is usually characterized results from .
by a few well-defined processes, with expo- (11-35)
nential correlation functions and correla- g (In T) = (2 n <72)~1 exp { - [In (T/T O )] 2 /2 a 2 }
tion times following an Arrhenius tempera-
where the respective widths are related by
ture dependence. Clearly, the amorphous
structure of a glass is related with some <jx = ae/kBT (11-39)
random distribution of energy barriers The mean energy s0 of the & distribution is
leading to rather complex dynamical be- related to x0 via Eq. 11-36 (Tweer et al.,
598 11 Organic Glasses and Polymers
1971) but is different from the activation
energy £A, which is related to the mean
correlation time <T>. One obtains
= Tooexp(fiA/feBT) (11-40)
eA = e0 + at/2kBT (11-41)
from Eqs. 11-36 to 11-39.
Macroscopic transport coefficients
should have a temperature dependence
given by Eq. 11-41 which results in a T2
law (Griinewald et al., 1984) at low temper-
atures (2kBTs0<a2):
T2/T2) (11-42)
(11-43)
The T2 law has also been assumed to apply
to shear viscosity, and agreement was
found in some supercooled liquids in a cer-
tain range above Tg (Bassler, 1987). Below
Tg, sA is assumed to be fixed by setting
T= Tg in Eq. 11-41 which results in Arrhe-
nius behavior of the temperature depen-
dence (Richert and Bassler, 1990).
At very low temperatures, activated
hopping over the barriers of the distribu-
tion, Eq. 11-37, becomes negligible. How-
ever, the low-energy tail should contain
isolated double-well potentials with suffi-
ciently low barriers allowing for tunneling
processes. Thus, the concept of energy
landscapes is closely related to the descrip-
tion provided by the two-level system
(TLS) theory for low-temperature anoma-
lies in amorphous solids (Phillips, 1987).
This has been confirmed quantitatively
for the orientational glass of KBr1 _x (CN)X
where a jS process with a Gaussian barrier
height distribution was associated with
180° jumps of CN groups by dielectric re-
laxation experiments. Model calculations
yielded ~O.35% of CN groups tunneling
through low-energy barriers, thus account-
ing for the specific-heat anomaly at T< 1K
(Sethnaetal, 1985).
The concept of activated hopping over
barriers in an energy landscape is only one
aspect of more general treatments dealing
with the transport of charges or excitons in
amorphous solids (Griinewald et al., 1984;
Movaghar et al., 1986; Klinger, 1988).
First, a specific set of quantum states local-
ized at randomly distributed sites is as-
sumed. Then a master equation is solved
with transition rates Wtj that depend upon
the distance rtj between the sites and their
energy difference Sj — st (note that W^^
Wjt in general). These models, which start
from localized quantum states and intro-
duce dynamic couplings in order to ac-
count for delocalization, should be con-
trasted with phonon models where anhar-
monicities and/or interactions with defects
result in localization due to short phonon
lifetimes (Buchenau, 1989).
11.3 Typical Examples
and Recent Applications
The examples discussed below include
different experimental techniques applied
to supercooled liquids, namely, simple
non-associated organic liquids (see Sec.
11.3.1) and polymeric liquids, especially
molten polystyrene (see Sec. 11.3.2). In Sec-
tion 11.3.3, relaxation studies of the glassy
state (i.e., below the glass transition tem-
perature Tg) are reported. Here, different
phenomena are addressed by the experi-
ments.
11.3.1 Simple Liquids
11.3.1.1 a Process
The drastic change of the NMR line
shape as the reorientational correlation
time of a supercooled liquid passes through
 11.3 Typical Examples and Recent Applications 599

the NMR time window (10~5 > T > 10" 7 s) Tj in S . « %

is shown in Fig. 11-5. Tricresyl phosphate [ 2H NMR
was measured by 3 1 P NMR (Rossler, 101 r
1989), and 2.9% deuterated hexamethyl
benzene (HMB) dissolved in phthalic acid 10° r
di-n-butylester (PDB) by 2 H NMR (Bor- /
•N-1 - ^
ner and Rossler, to be published). A typical 10"' r
chemical-shift spectrum is found for tri- r >k #f
cresyl phosphate at low temperatures, 10 - 2
whereas at higher temperatures the spec- o-terphenyl
trum collapses to a narrow single line. Sim- 10 - 3 • % ^ f f l

ilar behavior is found for HMB in PDB; -4 o

10 =- : o
however, the characteristic Pake spectrum : o
°o
is found at low temperatures correspond- - 5 Tg"1
10 — @

1 , 1-.
ing to the two transitions of a nucleus with I
" > 1 !
* 11 , 1 , 1 , 1 ,
spin 1 = 1. 2.5 3.0 3.5 4.0 4.5 5.0 5.5
1/T in 1O'3K"1
Figure 11-6. 2 H NMR spin-lattice relaxation times
(7^) and spin-spin relaxation times (T2) of o-terphenyl:
31
P NMR
T; at 2n 15 MHz (El); Tx at 2TT 33 MHz (x); T, (#)
222
and T 2 (O)at 2n 55 MHz.

At temperatures higher than those of the

line-shape changes, measurements of Tt
4-
K
241

243
and T2 provide information on the dynam-
ics, whereas at lower temperatures mainly
three pulse techniques in connection with
40 20 0
kHz
-20 -40
measurements of Tt may be applied. 2 H
2
spin-lattice relaxation times (T±) and spin-
HNMR
spin relaxation times (T2) as a function of
188 reciprocal temperature are given in Fig.
11-6 for the system o-terphenyl (Dries
etal., 1988). Tx passes through an asym-
metric minimum, whereas T2 decreases
continuously. At temperatures below the
Tx minimum, a shoulder appears for the Tx
data. At even lower temperatures (i.e., be-
low jTg) another relaxation process with
a much weaker temperature dependence
takes over, indicating almost rigid mole-
0
cules in the glassy state.
kHz
Figure 11-5. NMR line shapes in the supercooled re-
In order to extract correlation times
gion: neat tricresyl phosphate (top); 2.9% HMB-d18 from T± and T2 data, the spectral density is
in phthalic acid di-n-butyl ester (bottom). approximated by a Cole-Davidson (CD)
 600 11 Organic Glasses and Polymers
distribution function yielding
J(co) = sin (/?CD arctan (co TO) •
(11-44)
where TO characterizes the cut-off time of
the CD distribution. The distribution pa-
rameter PCD is the only free-fit parameter
because the coupling constant C in Eq.
11-8 is determined from the low tempera-
ture width of the powder spectrum. The
mean correlation times <T> for o-terphenyl
are drawn in Fig. 11-7. Below 10 ~ 6 s, T±
and T2 yield the same correlation time, and
a temperature-independent width parame-
ter j8CD = 0.50 is found. This corresponds
to /? = 0.63 of a Kohlrausch-Williams-
Watts (KWW) distribution if the relation
- 0.97 jSCD + 0.144,
for 0.2 S £CD ^ 0-6 (11-45)
Igd in s)
0
oc process ; a'
n
e*ir B process
o-terphenyl
-12
2.4 2.8 3.2 3.6 4.0 4.4 4.8
1/T in 1O"3K"1
Figure 11-7. Correlation times of o-terphenyl from 7^
( • ) , T2 (O), spin alignment (2H NMR) ( • ) , dielectric
relaxation (+), dynamic Kerr effect ( x ) (Beevers
etal., 1976), light scattering (©) (Fytas et al., 1981)
and dielectric relaxation, /? process (#) (Johari and
Goldstein, 1970), dashed line: guide for the eye.
obtained by Lindsey and Patterson (1980)
in a numerical comparison of both distri-
butions is used. For <T> > 1 0 ~ 7 S , there is
no straightforward analysis of T2 (Dries
et al., 1988), and T± yields correlation times
considerably below the values obtained for
the a process from other experiments. This
indicates the influence of a )S process, dis-
cussed further in Section 11.3.1.2.
The analysis of the spin-alignment data
yields the correct correlation times for the
a process (Fig. 11-7) and in addition pro-
vides information on the type of slow
molecular reorientation close to Tg. Al-
though the analysis of the spin-alignment
results by Eq. 11-15 is rather complex
(Dries etal., 1988; Erratum, 1989; Diehl
etal., 1990), reorientations by only small
angular step rotational diffusion can clear-
ly be excluded, and some distribution of
larger jump angles is in concordance with
the experimental results.
For tricresyl phosphate the condition
cocs TX <§ 1 is more easily reached because of
the smaller width of the powder spectrum
which is governed by the chemical-shift
anisotropy. Thus, the rotational correla-
tion function can be obtained directly by
analyzing Eq. 11-16 in the time domain
(Rossler, 1989, 1990 a). In Fig. 11-8 the de-
cay curves are shown in a presentation
suited to demonstrate the stretched expo-
nential behavior. Straight lines with tem-
perature-independent slopes /?KWW are
found. These results demonstrate nicely the
scaling property of the correlation func-
tion: a shift of the time scale leads to a
master plot for all temperatures. From
these decay curves a mean correlation time
<T> = r KWW r(l//? KWW )//? KWW is defined,
where F represents the gamma function
(Lindsay and Patterson, 1980). The corre-
lation times, together with those given by a
CD analysis, are shown in Fig. 11-9. Now,
ten orders of magnitude are covered by
 11.3 Typical Examples and Recent Applications 601

lg[-lnFA(t)]

tricresyl phosphate
31
PNMR
T/K 226 225 223 221 220 219 217 215

Figure 11-8. 31 P stimulated

echo decays of tricresyl
phosphate demonstrating
stretched exponential scal-
ing law behavior.
lg (t in s)

correlation times provided by NMR meth-
ods. The corresponding exponents j8KWW
from the stimulated echo and the 7\ and T2
analysis are 0.55 and 0.60, respectively. In-
cluded in Fig. 11-9 are the NMR correla-
tion times for toluene-d3 and toluene-d5
for comparison, where the correlation
times are extracted from T1 and T2 only
(Rossler and Sillescu, 1984).
o-Terphenyl and tricresyl phosphate
have also been investigated by dielectric
relaxation (Johari and Goldstein, 1970;
Beevers et al., 1977), by the dynamic Kerr
effect (Beevers et al., 1977), and by photon
correlation spectroscopy (Fytas et al.,
1981). The correlation times are obtained
directly from the maximum of the dielectric
loss curve, and X'^{co) is analyzed as a
function of temperature. The maximum
frequency fm is related to the correlation
time by T = 1/(2 n fm). In the case of photon
correlation spectroscopy, the correlation

Igd in s)
0 * tricresyl phosphate
a process
-2

-4 # B process
Figure 11-9. Correlation times of
tricresyl phosphate from Tx ( • ) ,
-6 T2 (O), stimulated echo <•) at 2TT
toluene
121 MHz, and from dielectric re-
laxation (+) and dynamic Kerr ef-
fect (x) (Beevers et al., 1976).
Dashed line: guide for the eye.
-10 Correlation times of toluene from
7; and T2 at 2n 55 MHz: toluene-
-12 d 3 (O), toluene-d5 (#).
3.0 4.0 5.0 6.0 7.0
3 1
1/T in 1O" K"
602 11 Organic Glasses and Polymers
function of depolarized scattering can be
fitted by a KWW function revealing a
slight temperature dependence of the expo-
nent j8KWW. Similar behavior is found for
the correlation function of polarized light
scattering. A mean correlation time is de-
fined by the integral of the correlation
functions. A similar analysis is carried out
for the non-exponential Kerr effect rise and
decay functions. Here, the /?Kww exponent
also shows some temperature dependence.
Correlation times from these methods are
included in Figs. 11-7 and 11-9. Qualita-
tively, the different correlation times show
the same non-Arrhenius temperature de-
pendence. However, some scatter for the
different data is found; in particular, dielec-
tric and dynamic Kerr effect correlation
times for o-terphenyl are systematically
shorter than those from light scattering. In
the case of tricresyl phosphate, some dis-
crepancies are found for both the NMR
correlation time and the Kerr effect corre-
lation times for intermediate temperatures.
The high temperature coefficient of the
correlation times in the supercooled region
might give rise to some experimental un-
certainties when comparing correlation
times provided by different methods.
In summary, the reorientational correla-
tion function is described by a KWW func-
tion at least for correlation times longer
than 10 ~ 9 s, which clearly exhibits the fea-
tures of a scaling law. For T < 1 0 ~ 9 S ,
T± = T2 and the relaxation data are not sen-
sitive to the non-exponential character of
the correlation function. Thus, NMR tech-
niques are not able to probe a possible
Table 11-2. £ K W W as reported by different relaxation methods.
NMR
o-terphenyl 0.63
tricresyl phosphate 0.55-0.60
crossover to Debye relaxation in the fluid
region (Grimditch and Torrel, 1989). The
j8KWW values reported for the different sys-
tems are compiled in Table 11-2. Correla-
tion times of the first and second Legendre
polynomial as given by dielectric relax-
ation and the other relaxation methods,
respectively, are similar in favoring a rota-
tional jump process. This is emphasized by
Beevers et al. (1977).
Besides viscosity and correlation time,
the translational diffusion coefficient, D, is
another transport coefficient that reveals
information on the dynamics of a liquid.
However, the very slow diffusion in the su-
percooled region is not accessible by most
standard methods. Diffusion coefficients of
dye molecules in organic liquids have re-
cently become available through applica-
tion of a holographic grating technique
(forced Rayleigh scattering, see Sec. 11.2.3.3)
(Eichler et al., 1986; Sillescu and Ehlich,
1990). The diffusion of dye molecules can
be studied at low concentrations of ap-
proximately 0.1%. The results for a thio-
phene indigo derivative, namely, 2,2'-
bis(4,4'-dimethylthiolan-3-one) (TTI), dis-
solved in polystyrene, 1,3,5-tri-a-naphthyl
benzene, o-terphenyl, and l,l-bis(4-meth-
oxyphenyl)cyclohexane (BMC) are pre-
sented in Fig. 11-10. For comparison, we
have included the inverse viscosity (Laugh-
lin and Uhlmann, 1972) and the self-dif-
fusion data of o-terphenyl (McCall et al.,
1969).
Again, typical non-Arrhenius behavior
is observed. It is apparent that the experi-
mental D values bend over to an Arrhenius
Kerr effect Dielectric Light scattering
0.56-0.71 0.67-0.69 0.54-0.61
0.70-0.88 0.73-0.77
 11.3 Typical Examples and Recent Applications
1
in cm 2 s~ 1
10
10
-16
10
0.70 0.80 0.90 1.00
Tg/T
behavior with lower apparent activation
energy at a temperature close to Tg. Here,
the glassy state is reached, and the system
is trapped in a state which is unstable with
respect to the supercooled liquid; however,
it is kinetically blocked. Tempering the ma-
trix leads to a further decrease of D. Com-
parison of high- and low-molecular-weight
matrices in Fig. 11-10 shows that tracer dif-
fusion in a polymer is characterized by a
higher diffusion coefficient near Tg, but
similar slopes are observed. This behavior
is in contrast to viscosity behavior, where
a smaller slope is found for the polymer
liquids in the Arrhenius plot near Tg (cf.
Fig. 11-2). Hence, some degree of decou-
pling is observed if the temperature depen-
dence of the diffusion coefficient is com-
pared with that of the matrix viscosity rj
(Fig. 11-10). The VFT equation can be ap-
plied in the form
D(T)=Doexp(-fB/(r-TJ) (11-46)
The parameters B and T^ are identical
with those provided by the analysis of the
viscosity data of the matrix assuming £ = 1
603
_ 4" in (Pas)"1
Figure 11-10. Reduced Arrhenius
plot of tracer diffusion data (Eh-
lich and Sillescu, 1990; Lohfink
et al., 1991) and self-diffusion data:
tracer diffusion (O) and self diffu-
sion (0) (McCall et al., 1969) in
o-terphenyl; tracer diffusion (El)
in 1,3,5-tri-a-naphthyl benzene,
tracer diffusion (A) in BMC;
tracer diffusion (0) in polysty-
rene; inverse viscosity of o-ter-
phenyl (solid line) (Laughlin and
Uhlmann, 1972). Dashed line:
guide for the eye.
in the corresponding VFT equation. The
temperature-independent coupling param-
eter £ has been introduced in a free-volume
treatment of polymer liquids (Fujita, 1971;
Vrentas et al., 1985) in order to account for
motional decoupling of D and rj. Typically,
a range of 0.8-0.9 is found for £ unless
further decoupling is provided by internal
matrix motions (Ehlich and Sillescu, 1990).
Eq. 11-46 implies that Docrj~^ which is at
variance with the classical Stokes-Einstein
relation unless £ — 1. The Stokes-Einstein
relation for translational diffusion and the
corresponding Debye eqation for rota-
tional diffusion can be formulated as
-kBT/(fri)
(11-47)
vrj/(kBT)
where / is proportional to the size and v to
the volume of a molecule dissolved in a
liquid of viscosity r\. Both equations are
well established for the fluid region. Hence,
some crossover from £ = 1 to £ < 1 has to
be observed as the temperature is lowered.
In particular, the following relations may
604 11 Organic Glasses and Polymers
in Pa
10 r 0.38 KNO 3 0.62Ca(NO3)2.
.5 0.6 0.7 0.8 0.9 1.0
T g /T
be checked (Rossler, 1990 c):
T/TJccl/T fluid regime
>0 (11-48 a)
8(1/T)
viscous regime
<0 (11-48 b)
6(1/T)
A similar relation holds for the transla-
tional diffusion if we set T = r trans oc 1/D.
In Fig. 11-11 reorientational correlation
times of 1,3,5-tri-a-naphthyl benzene (Fu-
jara, 1990) and o-terphenyl, as given by
T± and T2, respectively, as well as by de-
polarized light scattering (Ma et al., 1988),
are used to plot T/TJ as a function of
the reduced temperature Tg/T. In addition,
1/(D rj), as given by forced Rayleigh scatter-
ing of TTI (see above) as a dye molecule
and by self-diffusion data, is included. In
fact, although some scatter shows up in the
data, a crossover in the temperature coeffi-
cient can clearly be identified. For high
temperatures a positive temperature coef-
V(D^)inPa" 1 cm -2
Figure 11-11. Test of the Stokes-
Einstein relations (see Eq. 11-48):
71 (D), light scattering ( • ) (Ma
et al., 1988) and tracer diffusion
( • ) in 1,3,5-tri-a-naphthyl ben-
zene; T2 (O), tracer diffusion (#),
and self diffusion (0) (McCall
et al., 1969) in o-terphenyl; electri-
cal conductivity (O) in 0.4 KNO 3
0.6 Ca(NO 3 ) 2 (Howell et al., 1974;
Bose et al., 1970); electrical con-
ductivity (A) (Angell et al., 1969)
and dielectric relaxation ( • )
(Rhodes et al., 1966) of
Dashed line: guide for the eye.
ficient in accordance with the hydrody-
namic equations is found, but a negative
coefficient is revealed at low temperatures.
It has been known for a long time from
studies of supercooled ionic liquids that a
decoupling of correlation times from elec-
tric conductivity and other correlation
times occurs (Moynihan et al., 1971; An-
gell, 1990). A comparably high conductiv-
ity is observed near Tg. This phenomenon
might have the same origin as the decou-
pling found in supercooled organic liquids.
For the system xKNO 3 (l - x)Ca(NO 3 ) 2 ,
the corresponding ratios T/TJ are included
in Fig. 11-13 (Rhodes et al., 1966; Angell
et al., 1969; Bose et al., 1970; Howell et al.,
1974). Again, a crossover is observed at
comparable reduced temperatures. The
degree of decoupling is much higher. The
Stokes-Einstein relation does not even
hold at the highest temperatures. Accord-
ingly, the crossover is less sharp.
In summary, indications are given which
demonstrate a breakdown of the Stokes-
Einstein relation at some temperature be-
tween Tm and 71. A change in the diffusion
 11.3 Typical Examples and Recent Applications
mechanism occurs. In view of predictions
of the mode-coupling theory, this cross-
over might be related with traces of a dy-
namic phase transition at a temperature
Tc. For T>TC, correlation times provided
by different methods as well as the transla-
tional diffusion coefficient show approxi-
mately the same temperature dependence
as that of viscosity, whereas below Tc some
degree of decoupling is observed, which
is different in different systems (Rossler,
1990 c).
11.3.1.2 p Process
Correlation times derived from 2\ mea-
surements in the low-temperature region
are consistently shorter than those of the a
process. This is clearly seen in Figs. 11-7
and 11-9. The only additional process dis-
cussed for simple liquids is the /? process as
reported, e.g., by dielectric relaxation (Mc-
Grum et al., 1967; Johari and Goldstein,
1970, 1971; Williams and Watts, 1971),
where an additional small maximum at
high frequencies is observed for X^(co). The
corresponding dielectric relaxation times
for o-terphenyl are also plotted in Fig.
11-7. Obviously, the apparent activation
energies are different. However, extrapo-
lating the data to higher temperatures
shows the relaxation times of the /? process
intersecting those of the a process at the
same temperature. Here, the correlation
times are of the order of 10~ 7 s and the
reduced temperature is T r /T^0.85. It is
believed that the CD distribution is not
appropriate for analyzing Tx data at tem-
peratures where the /? process predomi-
nates, and a different analysis leads to dif-
ferent mean correlation times, perhaps
closer to those from dielectric relaxation.
On the other hand, the dielectric loss max-
imum is very broad, inferring formally a
broad distribution of correlation times.
605
Different methods yield rather different
mean correlation times for this complex
process. Nevertheless, a two step correla-
tion function appears in the supercooled
region, which at least shows up in dielectric
and NMR experiments. Since the NMR
line shape is not altered by the /? process, it
may be related to slow low-amplitude li-
brations. It is worthwhile to emphasize
that the /? process does not always show
the same temperature dependence as the
high-temperature end of the a process. At
least for simple organic liquids, a and /?
processes merge within the supercooled re-
gion, and the bifurcation is close to the
temperature Tc given by the power-law
analysis of the viscosity data and also by
the failure of the Stokes-Einstein descrip-
tion (see Fig. 11-2 and Fig. 11-11). Hence, it
might be related to traces of the predicted
dynamic phase transition. However, the
crossover predicted by the mode-coupling
theory refers to a much faster process. Be-
fore discussing this difference, we shall re-
port some recent results which substanti-
ate predictions from the mode-coupling
theory.
The first indications for a critical tem-
perature above Tg have been reported
by neutron-scattering experiments; an
anomaly of the Debye-Waller factor, / q ,
determined from elastic scattering (see Sec.
11.2.4.3), is observed. / q drops significantly
within a narrow temperature range. An ad-
ditional softening appears which starts al-
ready below Tg and increases its amplitude
as the temperature is raised. This is not
caused by the a relaxation but due to some
very fast process. In the frame of the mode-
coupling theory, such a process yields a
correlation loss for the density-density cor-
relation function and shifts the plateau / q
of the a process to lower values. Because of
some similarities with the conventional /J
process, it has also been called a jS process.
606 11 Organic Glasses and Polymers

o. - A &--A... . A
"•MM
n finc ( q )

-. 5 •
\
Figure 11-12. Debye-Waller
-
factor, fmc (q), determined
from neutron scattering in
A o-terphenyl at q = 1.39 A" 1 .
-1.0- (See text for explanation
Tc of solid triangles.) (Bartsch
i i 1, et al, 1989).
100 200 300
T in K

In Fig. 11-12, the logarithm of the De- butadiene (Frick and Richter, 1989). It is
bye-Waller factor is shown as a function of rather remarkable that Tc values obtained
temperature (Bartsch et al., 1989). The fit from neutron scattering, from a power-law
included is provided by predictions of the fit of viscosity, and from the breakdown of
theory. For the additional drop of the De- Stokes-Einstein relations are in agreement
bye-Waller factor, the theory yields (see to within a few degrees, as demonstrated in
Sec. 11.2.4.3) Figs. 11-11 and 11-12.
(11-49) The mode-coupling theory in its present
from accounts for only part of the dynam-
; + O(T) T>TC ics and makes no predictions about the
dynamics of the a process below Tc. In par-
Hence, a discontinuity of / q is predicted at ticular, no singularity of the viscosity is
a temperature Tc, whereas for T^TC the observed at Tc. Only the highest curvature
typical behavior of solids is observed, shows up in the data. The assumption that
namely, In / q oc — T. At temperatures above activated-hopping processes govern the
Tc, quasielastic neutron scattering can be slow dynamics below Tc leads to a smear-
analyzed in terms of a two-step function ing out of the dynamic phase transition
where the long-time behavior is attributed anticipated in the idealized form of the the-
to the a process, and the short-time portion ory. However, traces of the transition
(t ^ 10 ~1X s) can be separated and is repre- should survive in real supercooled liquids,
sented by the solid triangles in Fig. 11-12. and judging from the experiments, Tc lies
No indications of the conventional /? well above Tg.
process are seen. Apparently, it has The question has been raised whether
merged with the a process at T>TG. The the fast (I process observed by neutron-
discontinuity of fq at Tc has also been ob- scattering experiments is related to the
served in coherent neutron scattering of slow P process reported by NMR and
deuterated o-terphenyl (Petry et al., 1991) dielectric relaxation. At a first glance, the
and is indicated in neutron-scattering re- corresponding time scales are completely
sults obtained in supercooled 0.6 KNO 3 • different. Typical times for the fast p pro-
0.4Ca(NO 3 ) 2 (Mezei, 1989) and in poly- cess are of the order of 10" 13 -10"" 11 s,
 11.3 Typical Examples and Recent Applications
whereas for the same temperatures, dielec-
tric and NMR correlation times are in
range oflO~ 2 -10~ 7 s. However, there are
indications (Rossler and Schnauss, 1990)
that the slow and fast ft processes have the
same origin and can be understood within
the framework of mode-coupling theory. It
should be noted that activated "hopping"
processes that account for the finite shear
viscosity at T< Tc (Fig. 11-11) are also re-
lated to the /? process (Gotze and Sjogren,
1987; Sjogren, 1990). Finally, we mention
that the fast process can be related with a
softening of the low-frequency phonons, as
discussed by Buchenau (1989).
11.3.2 Polymeric Liquids
The dynamic behavior of polymeric liq-
uids above the glass transition was already
discussed in Section 11.2.2, where we noted
that the connectivity along the chain places
polymer glass formers between inorganic
networks (window glass) and supercooled
van der Waals liquids (Fig. 11-2). This is
also true for the transition from Arrhenius
behavior at low viscosities to the VFT be-
havior close to Tg where the characteristic
temperature Tc has been identified in
polybutadiene by neutron scattering (Frick
and Richter, 1989), but the changes are less
pronounced than in o-terphenyl (Bartsch
et al., 1989). The chain connectivity also
results in large density (free-volume) fluctu-
ations due to the problem of reconciling
the random coil shape with the dense pack-
ing of the chains. As a consequence, the
motion of low-molecular-weight additives
is less coupled to matrix motion in polymer
glasses than it is in monomer glasses, as
was shown in Fig. 11-10 for translational
diffusion of probe molecules. The rota-
tional motion was studied by 2 H NMR of
deuterated toluene added to polystyrene
(PS) (Rossler, 1987). The rotational corre-
607
lation times were found to be significantly
shorter than those characterizing PS seg-
ment motion, which also indicates decou-
pling from the a process.
The various NMR techniques described
in Sec. 11.2.3.5 have been extensively ap-
plied to the segmental motion in chain-
deuterated PS-d3 and phenyl-group-
deuterated PS-d5 (Lindner et al., 1981;
Rossler et al., 1985; Wefing et al., 1988;
Kaufmann et al., 1990; Pschorn et al.,
1990). The results can be summarized as
follows: At temperatures above Tg, chain
reorientation via small angular steps can
be clearly identified in the shapes of
deuteron ID- and 2D-spectra and fitted by
a rotational diffusion model allowing for
a distribution of correlation times. The
width of the distribution - as seen by C- 2 H
reorientation of PS-d3 chains - increases
from about 1 decade at T>T g + 50K to
about 5 decades a few K above Tg. This is
different from the results of other relax-
ation techniques which detect fluctuations
of larger volume elements (Patterson,
1983). Nevertheless, the mean rotational
correlation time detected by 2 H NMR has
the temperature dependence as mechanical
relaxation. This is shown in Fig. 11-13
where the NMR results are fitted by a
WLF equation with almost the same
parameters as obtained for viscoelastic be-
havior. Thus, local chain dynamics must be
closely linked to the collective dynamics of
the a process. It is remarkable that reorien-
tation by small angular steps predominates
in PS, whereas larger angular rotational
jumps are seen in supercooled o-terphenyl
(see above). Although we cannot exclude
the additional occurrence of rare rota-
tional jumps in PS, we have to conclude
that motion in different glass formers can
indeed differ on a local scale.
Due to the faster time window of Tx
measurements, which are most sensitive at
608 11 Organic Glasses and Polymers
T I IK]
KI
650 UP A30 £20 £10 Z.00
1-10
1-10
the Larmor frequency, the correlation
times extracted from Tt data are related to
the /? process. This parallels our findings in
supercooled o-terphenyl (compare Figs.
11-7 and 11-13). It should be noted, how-
ever, that T± provides little information on
the type of molecular motion. We expect
that the amplitude of the /? process de-
creases on approaching Tg from above.
This is not properly taken into account in
the conventional analysis of Tx data and
may imply large errors in the correlation
times shown for the /? process in Figs. 11-7
and 11-13.
11.3.3 The Glassy State
The glassy state of simple organic sys-
tems is characterized by the absence of
large-scale motion. Because of the struc-
tural arrest, the liquid-like short-range or-
der is frozen. The dielectric absorption
maximum attributed to the /? process de-
creases and is finally lost in the experimen-
tal background as the temperature is low-
'9
390 380 J370 360
Figure 11-13. Average rota-
tional correlation times TC
for C - 2 H bond reorienta-
tion in chain-deuterated
polystyrene, determined
from 2D-spectra (O), solid
echo spectra (O), broad
line spectra (•), and spin-
lattice relaxation times
(A,A).(C l g =15.9,
C2g = 49.9, see Eq. 11-21
and Pschorn et al, 1991).
2.7
ered. Thus, the remaining dynamics of the
glassy state is determined by vibrational
and electronic excitations only. Due to the
absence of periodicity, Bloch states can not
be introduced in order to simplify the theo-
retical treatment. As a consequence, the
density of states is smeared out. For non-
metallic solids, observables such as heat
capacity and thermal conductivity are de-
termined by the phonon spectrum, where
in amorphous solids pronounced peculiar-
ities show up at low temperatures, i.e., be-
low 10 K. These properties are attributed
to low-frequency modes which are mod-
eled by assuming two-level systems. A re-
view is given by Phillips (1987). At present,
it is not clear whether these two-level sys-
tems also account for properties of amor-
phous solids above 10 K.
Regarding NMR studies, only a few ex-
periments have been reported on the glassy
state. In most cases inorganic glasses have
been studied. It is a common feature that
the spin-lattice relaxation is faster than the
corresponding relaxation in the crystalline
 11.3 Typical Examples and Recent Applications
solid. At low temperatures (T<100K),
power-law behavior characterized by Tx oc
T~y(y = 1.1-1.5) is usually observed and
can be related to the two-level system (TLS)
theory (Szeftel and Alloul, 1978; Balzer-
Jollenbeck et al., 1988). At temperatures
closer to Tg, activated processes lead to
further reduction of T±. In spin 1/2 sys-
tems, the mechanism of spin diffusion
causes a common spin temperature, and it
then becomes difficult to identify the pro-
cesses determining the experimental T±
(Miiller-Warmuth and Eckert, 1982). Spin
diffusion plays a minor role in 2 H NMR
(/ = 1) where non-exponential spin-lattice
relaxation was found for several organic
glasses. Interestingly, the spin relaxation
function becomes exponential at about
20 K above Tg, where Tx becomes larger
than the structural relaxation time (a pro-
cess). Thus, non-exponential 2 H spin-lat-
tice relaxation can be looked upon as a
signature of the glassy state, and it contains
information on the spatial heterogeneity
frozen within the glass (Schnauss et al.,
1990).
The problem of long relaxation times for
Tx in solid glasses can be circumvented by
using deuterated guest molecules, which
are characterized by fast intrinsic rota-
tional motion in a protonated glassy ma-
trix. The molecular rotation, e.g., C6-rota-
tion in benzene, persists also in the glassy
state (Miiller-Warmuth and Otte, 1979).
In contrast to investigations of the pure
matrix, a well-known relaxation mecha-
nism, namely, the molecular reorientation
around the symmetry axis, simplifies the
interpretation, resulting in comparatively
fast relaxation. The rotational correlation
times T of the individual guest molecules
reflect the local structure. In particular, the
activation energy E depends on the local
arrangements of the molecules. According
to a distribution of local environments in
609
the glass, the guest molecules probe a dis-
tribution of activation energies g (E), Here,
the concept of a distribution of correlation
times is well suited to account for the guest
dynamics, as will be demonstrated. Al-
though 2 H NMR is not sensitive to spa-
tial heterogeneities, the corresponding mo-
tional non-uniformities should be observ-
able in an NMR experiment.
Again, absence of spin diffusion leads to
a non-averaged spin-lattice relaxation.
Further results are provided by 2 H NMR
line shape studies. Hence, we believe that
structural information may be obtained by
studying the dynamics of small, mobile
probes in disordered systems (Jansen-
Glaw et al., 1989; Rossler et al., 1989 a).
In Fig. 11-14, highly non-exponential
spin-lattice relaxation curves are shown for
two systems, namely, benzene-d6 in a liq-
uid crystal side chain polysiloxane (LCPS)
(Rossler et al., 1991) and adamantane-d 16
in phthalic acid di-n-butyl ester (PDB)
(Rossler et al., unpublished data). The
shapes of the curves can be understood in
terms of a superposition of exponentials
= [M0-M(t)]/M0
(11-50)
where /(T x ) is a distribution of spin-lattice
relaxation times. It is now assumed that
each individual 7\ is related with a rota-
tional correlation time of the deuterated
probe molecule at one particular site by
applying the Bloembergen-Purcell-Pound
(BPP) equation (see Eq. 11-8)
T 4l
+ K)T) 2 +
1 + (2COOT)
Since / ( 7 \ ) can extend over many de-
cades from the high-temperature branch
(co0 r <g 1, T± oc T~ *) to the low-temperature
branch (COOT ^>1, 7\OCT) of Eq. 11-51, it is
610 11 Organic Glasses and Polymers

H EBEBBBEEB fflEBEBfflEBffleiBfflESBHlBmai

•
a 20 K OQ S3 ffl

• 32 *°0D \
l O ' 1 r~ o 49
• ^ ^ 7 O •

a n
I 60
O % 03
o 69 ^ O

88 T O O

96 V no
D
•
• 105 " O o°
• 156 ^ . •
v v o
-2 ,,,1 i i # l A ,,„•• , ^ ,n 1 ,
10 t 1 M M l i

3 2 1 1
A1I1I

2
10~ 10" 10" 10° 10 10
t in s
<D(t) 1

Figure 11-14. Non-expo-

nential 2H NMR spin-lat-
tice relaxation. 10.0% ben-
zene-d6 in a liquid crystal
polysiloxane (top); 4.1%
adamantane-d16 in phthalic
acid di-n-butyl ester (bot-
tom).
10"1 101 102
•,-2
10" 10°
t in s

not surprising that rather unusual shapes Arrhenius temperature dependence for % is
result (Fig. 11-14) which allow for the de- assumed for the molecular probe reorien-
termination of the distribution of correla- tation, where
tion times G(lnt) corresponding to / ( T J .
r = zoexp(E/RT) (11-52)
In particular, NMR relaxation is sensitive
to asymmetric G (In T) (Rossler et al., The width of G (In T) is found to be propor-
1989 b). A detailed analysis of the curves tional to 1/T, a behavior completely differ-
shown in Fig. 11-14 (Rossler et al., 1989 a; ent from features of a scaling law, discussed
Rossler et al., 1990 b) has revealed that the for the dynamics of the a process and often
distribution of correlation times G(lnt) described by a distribution of correlation
has a temperature dependence which re- times (see Sec. 11.2.1). Since g(E) reflects
sults in a temperature-independent distri- the probe environment of many different
bution of activation energies g(E) if an sites, it should provide an excellent picture
 11.3 Typical Examples and Recent Applications
of the energy landscape (see Sec. 11.2.4.4)
within a glass. Furthermore, studying the
reorientation of mobile guest molecules in
a glass may be useful for checking conse-
quences of the energy landscape models,
which are also applied to explain the tem-
perature dependence of the dynamics
above Tg (see Sec. 11.2.4.4).
The relaxation can be fitted by a Gaus-
sian distribution in the high-temperature
region. However, at low temperatures the
linear portion of the double logarithmic
plot can only be accounted for by assum-
ing that g (E) is asymmetric with its maxi-
mum on the low E side. From model calcu-
lations shown in Fig. 11-15 it is seen that
the power-law behavior observed at low
temperatures is in agreement with g (E) oc
ocexp[ — (Eo — E)/e], whereas Gaussian E
distributions provide $ (t) curves with only
positive curvature not in agreement with
Fig. 11-14 (Taupitz et al, 1990). Unraveling
the exact shape of g (E) is difficult, due to
the stringent requirement that allows only
one g (E) to fit all relaxation curves over a
wide temperature range. In particular, the
role of spin diffusion, which leads back to
a more exponential relaxation and is rec-
ognized by a bending off of the relaxation
for t ^ 10 s (see Fig. 11-14) has to be incor-
porated in the relaxation theory. However,
an exponential E distribution with some
Gaussian broadening yields a fair interpo-
lation of the relaxation data over a large
temperature range (Rossler et al., 1990 b,
1991).
Information on g (E) is also povided by
line shape analysis of the deuterated guest
molecules. Fig. 11-16 shows 2 H NMR
spectra of benzene in LCPS (Rossler et al.,
1990 a). A motional-averaged Pake spec-
trum is found at high temperatures accord-
ing to fast rotating molecules (T < 10" 7 s),
whereas at low temperatures a broader
spectrum is found corresponding to
611
10" 3 10" 2 10"1 10° 101 102 10
icr q(E) Exponential
\ distribution
10"
10"
\^051^\90K
- I/SKUX
10 10" 10" 10u 101
t in s
Figure 11-15. Simulated spin-lattice relaxation for a
Gaussian distribution (top); an exponential distribu-
tion of activation energy (bottom).
molecules in the limit of slow rotation
( T > 1 0 ~ 5 S ) . In the intermediate tempera-
ture range, the line shapes can be described
by a superposition of only two sub-spectra
corresponding to molecules in the limit of
fast and slow reorientation with tempera-
ture-dependent fractions. No contribution
from intermediate exchange spectra is
observed where the correlation time is of
the order of the reciprocal spectral width.
These results confirm the existence of a
very broad distribution of correlation
times. The spectra have to be compared
with those in Fig. 11-5, where no such two-
phase spectra are observed for the slowing
down of the a process. Hence, a compara-
tively uniform motional process governs
the a process above Tg in contrast to the
612 11 Organic Glasses and Polymers
150 100 50 0 -50 -100 -150 150
kHz
Figure 11-16. 2 H NMR line shapes of 10.0% benzene-d6 in a liquid crystal polysiloxane (bottom, left) and
corresponding simulations (bottom, right).
dynamics of mobile guest molecules below
Tg. We should mention that similar spectra
have been reported for gas hydrates by
Ripmeester and co-workers (Davidson and
Ripmeester, 1984). The disorder of the
cage is reflected by the dynamics of mobile
guests.
The spectra can be explained by a distri-
bution of correlation times which passes
through the NMR spectral window as the
temperature is lowered. It can be shown
that in the case of a broad distribution the
solid echo spectrum is given by the
weighted sum of the fast and the slow ex-
100 50 0 -50 -100 -150
kHz
change spectrum (Rossler et al., 1990 a)
/ (Q), T) = Itast M 7 G (In T) d In T +
(11-53)
+ / sIOW M J G(lnT)dlnz
lnt*
It is apparent from the example of Fig.
11-16 that the distribution of correlation
times G(lni) can be determined by mea-
suring the weight factor W(T) given by the
first integral in Eq. 11-53, where the second
integral is i — W(T). It has also been
shown that the distribution of activation
energies, g(E) is equal to (d/dT) W(T) up
 11.3 Typical Examples and Recent Applications
to a constant factor / = R In (T*/TO)> which
is 133 Jmol" 1 K " 1 if one assumes T* =
= 10~ 5 s and TO = 1 0 ~ 1 2 S , where T* is
roughly the inverse width of the powder
spectrum I(co) (Rossler etal., 1990 a). The
factor / relates the E scale with the T
scale used for evaluating the experimental
weight factor W{T\ see Fig. 11-17. (This T
scale should not be confused with the en-
ergy scale E/R often used in the literature.)
In Fig. 11-17, the E distributions obtained
by analyzing the 2 H NMR line shapes of
the two probe molecules in some monomer
and polymer glasses are shown (Rossler
et al., 1990 a). For all systems, the shape of
g(E) is asymmetric. The main difference
among the systems is the position of the
most probable activation energy E p . For
benzene as guest molecule, g(E) is shifted
to lower activation energies compared to
HMB. This reflects the smaller molecular
size and mass of benzene relative to HMB.
Comparing high and low-molecular-weight
matrices for the same guest molecule, one
finds that £ p is lower for the high-molecu-
lar-weight matrix, indicating a higher de-
gree of local free volume in the polymer
systems. For HMB in PDB with the
highest £ p , the asymmetric character of the
distribution is almost lost.
Both NMR methods yield comparable
results; asymmetric distribution functions
determine the dynamics of mobile guest
molecules in glassy systems. A Gauss dis-
tribution, as often discussed for the glassy
state, does not fully describe the experi-
mental results. The method is well suited to
characterize disordered systems; the local
packing of the molecules is probed. Differ-
ent types of disordered systems may be in-
vestigated and a relation to mechanical
properties of a matrix may be attempted.
Although a quantitative correlation be-
tween structural and motional properties
is not yet known, we think that this
613
g(E)
/-x P D B
0.02 LCPS//
x\ \PDB
V \ \> \\
* \
0.01
i i
10 15 20
E in kJmol'1
Figure 11-17. Activation energy distribution g(E) in
different glasses as given by 2 H NMR lineshape anal-
ysis. Solid line: benzene, dashed line: HMB as probes;
PS: polystyrene; LCPS: liquid crystal side chain
polysiloxane; PDB: phthalic acid di-n-butyl ester.
method yields information on the first co-
ordination shell of a given guest molecule.
In favorable cases guest concentrations of
2% are sufficient to provide a reasonable
signal-to-noise ratio.
We should mention that distributions of
correlation times have also been observed
for side group motion in polymers
(Schmidt etal., 1985; Wehrle etal., 1988).
The distributions found are less broad as
compared to those reported here. Large
intramolecular contributions to the rota-
tional potential have to be expected for
such internal motions which result in a
high mean activation energy and less sensi-
tivity to the disorder of the environment.
Broad distributions of the equilibrium
constants of isolated bistable dye mole-
cules inbedded in glassy solids have also
been reported by 15 N NMR (B. Wehrle
et al., 1987). On the other hand, the asym-
metric distribution functions are similar to
distribution functions found by Frauen-
felder (1984) for the recombination kinetics
of CO in proteins. This supports the as-
sumption that a single protein resembles a
glassy state. The distribution revealed by
optical hole-burning experiments is also
asymmetric with Ep on the low E side
614 11 Organic Glasses and Polymers
(Kohler and Friedrich, 1987). A distribu-
tion g(E)ocl/y/E is observed which is ex-
plained within the framework of the two-
level system theory.
Two-phase spectra are also observed
when deuterated low-molecular-weight
additives in polymers are investigated by
2
H NMR. Fig. 11-18 shows typical spectra
for 3% HMB in polymethylmethacrylate
(PMMA) indicating that in addition to C 6 -
rotational jumps of HMB, isotropic reori-
entation is observed in the polymer glass
(Borner and Rossler, to be published). Sim-
ilar spectra are observed in the system
toluene-polystyrene (Rossler et al., 1985
and Rossler 1987). On top of the broad
Pake spectrum a narrow line is observed
representing liquid-like molecules. Its rela-
tive intensity increases as the temperature
is raised. The solid-like spectrum disap-
Figure 11-18. Spectra of 3.0% HMB-d 18 in PMMA
demonstrating two-phase spectra.
pears completely above Tg. The tempera-
ture dependence of the fraction of the liq-
uid-like molecules is plotted in Fig. 11-19.
Clearly, there is fast molecular motion in
the mixed PS-toluene glasses well below Tg
as determined by DSC. The temperature
interval for a coexistence of liquid-like and
solid-like molecules becomes narrower as
more toluene is added, and the thermal Tg
lowered. Apparently, the mixed system be-
comes a rigid glass at the glass transition of
the additive, Tg = 117K. This is also ob-
served for HMB motion in PMMA, where
Tg of HMB should be around 260 K if we
apply the rule of thumb T g =0.6T m with
Tm = 439K. In Fig. 11-18 the two-phase
behavior of HMB starts above 280 K and
extends to temperatures above the thermal
T g =378K of neat PMMA. Of course,
HMB motion is never slower than that of
PMMA; however, the rigid Pake spectrum
is already obtained for relatively short cor-
relation times T ^ 10 ~5 s.
It is tempting to perform the same anal-
ysis as described above. Consequently, the
NMR behavior would be explained in
terms of a distribution of correlation times
related with a distribution of activation en-
ergies for liquid-like motion in the rigid
polymer matrix (Rossler etal., 1990 a).
Rigid polymer molecules have been con-
firmed by investigating the matrix of
polystyrene itself. According to Fig. 11-19
the distribution of activation energies
should become narrower if more toluene is
added to polystyrene, and a correspond-
ingly greater intensity from intermediate
spectra should appear where the correla-
tion time is of the order of the reciprocal
spectral width. However, the opposite be-
havior is observed. Hence, the precondi-
tion of line shape analysis, namely the pres-
ence of an activated process which governs
the slowing down of the molecular motion,
is not given for the isotropic motion in

W(T)
0.0 -
120 160 200 240 280 320 360 400
T in K
these mixed systems. We find instead that
the motion of a probe molecule at a partic-
ular site has a temperature dependence re-
sembling that of the a process, but with the
local Tg differing from the macroscopic
glass transition. It is not possible to quan-
tify this scenario, which characterizes a
motional non-uniformity within the mixed
glass and could also be looked upon as a
spatial distribution of free-volume aggre-
gates, each related to molecular motion by
the Doolittle equation (see Sec. 11.2.4.1).
Summarizing the experimental findings
of the last section, polymer glasses, in con-
trast to low-molecular-weight glasses, are
characterized by a higher fraction of local
free volume. Static density fluctuations are
considerably larger. Local motion of guest
molecules is facilitated. The distribution
of activation energies of mobile guest
molecules acting as a probe, e.g., by the C 6
rotation of benzene, is shifted to lower en-
ergies. In addition, motional decoupling is
observed for low molecular additives; i.e.,
the guest molecules perform liquid-like iso-
topic reorientation in a rigid polymer ma-
trix.
11.4 References 615
Figure 11-19. Fraction of
liquid-like spectra as a
3% HMB function of temperature for
in PMMA the systems toluene/poly-
styrene and HMB/PMMA.
Concentration in mass per-
cent.
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12 Optical Properties of Glasses
Marvin J. Weber

Lawrence Livermore National Laboratory, University of California,

Livermore, CA, U.S.A.

List of Symbols and Abbreviations 620

12.1 Introduction 622
12.2 Fundamental Optical Phenomena 622
12.2.1 Absorption 623
12.2.2 Refraction 625
12.2.3 Reflection 627
12.2.4 Scattering 629
12.2.5 Photoelastic Properties 630
12.2.6 Thermal-Optical Properties 631
12.2.7 Magneto-Optical Properties 632
12.2.8 Nonlinear Optical Properties 634
12.2.9 Luminescence and Stimulated Emission 637
12.2.10 Optical Damage 639
12.3 Optical Glasses 639
12.3.1 Classification and Designation 639
12.3.2 Transmission 641
12.3.3 Refractive Index and Dispersion 642
12.3.4 Thermal Properties 644
12.3.5 Mechanical Properties 646
12.3.6 Chemical Durability 647
12.3.7 Quality and Forms 648
12.4 Special Glasses 649
12.4.1 Abnormal Dispersion Glass 649
12.4.2 Gradient Index Glass . . . . 649
12.4.3 Mirror Substrate Glass . 650
12.4.4 Optical Filter Glass 651
12.4.5 Nonlinear Glass 652
12.4.6 Laser Glass 654
12.4.7 Faraday Rotator Glass 657
12.4.8 Acoustooptic Glass 658
12.4.9 Radiation Detection Glass 659
12.4.10 Radiation Shielding Glass 660
12.4.11 Photosensitive Glass 661
12.5 Future 661
12.6 Acknowledgements 662
12.7 References 662

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
620 12 Optical Properties of Glasses

List of Symbols and Abbreviations

B bulk modulus
B Kerr constant
c velocity of light in vacuum
c elastic stiffness constant
a
C
P
specific heat at constant pressure
e electron charge
E electric field
E Young's modulus
energy gap
f oscillator strength
F force constant
9 Lande g factor
G modulus of rigidity
h Planck's constant
H magnetic field
I intensity
J angular momentum quantum number
Kc fracture toughness
K stress-optical coefficient
kB Boltzmann's constant
k extinction coefficient
I length
m electron mass
M figure of merit
n, n* index of refraction, complex index of refraction
n0 linear index of refraction
n2 nonlinear index of refraction coefficient
OD optical density
P elastic-optic constant
P(co) polarization
P, acoustic power
P*y partial dispersion
P thermo-optic coefficient
P pressure
q piezo-optic constant
Q thermo-optic coefficient
r reflectivity
R reflection factor
Landau-Placzek ratio
RT thermochemical figure of merit
S optical path length
T temperature
V Verdet constant
 List of Symbols and Abbreviations 621

w thermo-optic coefficient
V velocity
longitudinal sound velocity

a coefficient of thermal expansion

a linear absorption coefficient
aB Brillouin loss coefficient
as scattering loss coefficient
P Bohr magneton
P cubic coefficient of thermal expansion
P two-photon absorption coefficient
y damping factor
y linewidth
s stress
8 dielectric constant
complex dielectric constant
permittivity
flux
oB Bragg angle
Brewster angle
X susceptibility
X thermal conductivity
I wavelength
\i Poisson's ratio
fi reduced mass
V Abbe number
V frequency
Q density
G stress
CO angular frequency
Faraday rotation angle
0L magnetic linear birefringence
magnetic linear dichroism
ll/F Faraday ellipticity

AO acousto-optic glass
ESCA electron spectroscopy for chemical analysis
FR Faraday rotator glass
GRIN gradient index
LG laser glass
MCD magnetic circular dichroism
622 12 Optical Properties of Glasses
12.1 Introduction
Of the properties of glass, none com-
bines science, technology, and aesthetics to
the extent exhibited by optical properties.
Glass has enabled mankind to observe na-
ture from the minuscule to the vastness of
space, yet understanding its linear and
nonlinear optical behavior and their de-
pendence on glass structure and composi-
tion remains a scientific challenge. Techno-
logically, the benefits of glass transparency
range from simple windows for buildings
to optical fibers for ultra-long-distance
communications. And the beauty of glass -
its clarity, color, and art forms - is one of
the most appealing features of its optical
properties.
Optical glass epitomizes an engineered
material (Stokowski, 1987). In contrast to a
crystal which has a specific chemical com-
position, glass has a variable chemical
composition (Kreidl, 1983). This composi-
tional versatility has been exploited to tai-
lor glasses to achieve an optimal compro-
mise of properties for specific applications.
Hundreds of optical glasses now exist with
extremely well characterized and repro-
ducible properties for numerous optical
components and systems. These include
glasses for passive applications such as
lenses, windows, prisms, and substrates,
and for active applications such as laser
sources and magnetooptic and acoustoop-
tic modulators.
Today, optics encompasses not only the
visible spectral region but extends from the
vacuum ultraviolet through the mid-infra-
red. Optical glasses of high quality are
available for use throughout this spectral
range.
Compared to window glass, optical glass
is distinguished by demands for quality
(high homogeneity, transparency, and the
absence of imperfections), for varied sizes
and forms (from disks measured in meters
to fibers measured in microns), and for a
multitude of special properties (linear, non-
linear, electrooptic, magnetooptic, acous-
tooptic, etc.). Over one hundred and fifty
years ago Michael Faraday (1830) in his
Bakerian lecture noted that "Perfect as is
the manufacture of glass for all ordinary
purposes, and extensive the scale upon
which its production is carried on, yet
there is scarcely any artificial substance in
which it is so difficult to unite what is re-
quired to satisfy the wants of science." To
the glass technologist of today, his com-
ments are still apropos.
In this chapter we begin with a brief re-
view of fundamental optical phenomena
and properties characteristic of optical
glasses. Oxide glasses are by far the most
advanced of the optical glasses and their
properties are discussed in detail. These
glasses were developed mainly for the visi-
ble portion of the spectrum, but present
science and technology require materials
with optical properties covering a wider
spectral range than can be satisfied by ox-
ide glasses. Hence considerable current re-
search and development are devoted to
non-oxide glasses. A number of the optical
properties of these glasses are covered in
the earlier chapters in this volume on ha-
lide and chalcogenide glasses. Here we em-
phasize the characteristics of oxide glasses
but also present data for other glasses to
display the range of physical properties
available. We conclude with descriptions of
a number of glasses having special optical
properties for special applications.
12.2 Fundamental Optical
Phenomena
The interaction of light with a solid can
be specified by various optical response
 12.2 Fundamental Optical Phenomena 623

functions. To describe the amplitude and
phase of the response, these functions are
generally frequency-dependent complex
quantities. The complex dielectric constant
£*, for example, relates the amplitude of an
optical electric field E of frequency co to the
polarization wave P(co) induced in the ma-
terial. It is related to the complex index of
refraction /i* (co) by s* (co) = /i*2 (co). The in-
dex of refraction, in turn, can be related to
the amplitude and phase of the reflectivity.
For each of these complex quantities the
real and imaginary components are related
by Kramers-Kronig integral equations
(Kittel, 1976). Thus if one of the compo-
nents is known over a sufficiently large fre-
quency range, the other component can be
obtained from an integral transform. Be-
cause glass is a disordered medium, it is
isotropic on a macroscopic scale and does
not exhibit sharp spectral features charac-
teristic of crystalline materials. This simpli-
fies the treatment of most optical properties.
12.2.1 Absorption
Optical glass absorbs strongly in the in-
frared and the ultraviolet spectral regions.
The former is associated with the interac-
tion of light and molecular vibrations giv-
ing rise to multiphonon absorption pro-
cesses; the latter is associated with elec-
tronic transitions between the valence
band and the conduction band or exciton
levels. The absorption spectrum for a soda-
lime-silicate glass (Bagley et al., 1976)
shown in Fig. 12-1 illustrates the region of
transparency and of strong infrared (IR)

Wavelength (nm)
12398 1240 124
10 8
Visible

Infrared l • i Ultrai/iolet w

6
10

104 /

A
i

1
S10 2
o
"5
8
.1
fr o
O

\J
10- 2

10" 4
0.01 0.10 1.0 10 100
Energy (eV)

Figure 12-1. Absorption spectrum of a soda-lime-silicate glass [see Bagley et al. (1976)].
624 12 Optical Properties of Glasses
and ultraviolet (UV) absorption typical of
an optical glass. The positions of both the
long- and short-wavelength absorption
edges depend on the glass composition and
can be varied by the choice of glass net-
work former and network modifier ions.
The region of transparency is shifted into
the mid-infrared for chalcogenide glasses
and into the ultraviolet for fluoride glasses.
Oxide glasses typically have a broad trans-
mission window in the visible and near in-
frared; fluoride-containing glasses can
have a more extended range of transpar-
ency.
The intensity / of light transmitted
through a sample of length / is given by the
Lambert-Beer law as
= Io exp( — a I (12-1)
where J o is the incident intensity and a is
the absorption coefficient. As evident from
Fig. 12-1, the range of absorption coeffi-
cients for glass over the entire spectrum
covers many orders of magnitude, from
106 cm" 1 in the UV to less than 1(T 4 cm" 1
in the near IR for ultrapure glass.
The fundamental absorption edge at
short wavelengths in Fig. 12-1 can be de-
scribed by an absorption coefficient
<xl]y(co) =
= a0exp{-G[Eg(T)-hco]/kBT} (12-2)
where ao, a and the temperature-depen-
dent energy gap Eg are fitting parameters
independent of the frequency co. This em-
pirical relation, known as Urbach's rule
(Urbach, 1953), has been well verified ex-
perimentally (see, for example, Mohler and
Thomas, 1980). The UV absorption edges
of many different glasses and the depen-
dence of the edge on composition have
been reviewed by Sigel (1977). In oxide
glasses the excitation of non-bridging ox-
ides requires less energy than the excitation
of bridging oxygens, thus the absorption
edge occurs at longer wavelengths for
multi-component silicate glasses than for
simple fused silica. From photoelectron
spectra it is possible to distinguish between
bridging and non-bridging oxygen atoms
and, in the case of phosphate glasses, dou-
ble-bonded oxygen atoms (Bruckner et al,
1980). Studies of silica, alkali silicate, and
aluminosilicate glasses show a clear shift of
the non-bridging oxygen 1 s line corre-
sponding to progressively lower bonding
energies in the series Li-Na-K-Rb-Cs. This,
in turn, shifts the UV absorption edge to
longer wavelengths (Smith and Cohen,
1963).
The long-wavelength absorption edge in
solids arises from multiphonon excitation
of overtone and combination bands of fun-
damental vibrational modes and can also
be fitted to an exponential dependence on
energy similar to Eq. (12-2) of the form
(Bendow, 1973, 1977)
(12-3)
where N(co) = [exp (h co/kB T) — 1] ~ x , coo is
an average optical phonon frequency, and
C is a material constant characterizing
the vibrational anharmonicity. The highest
frequency vibrations in glass are usually
associated with the network former, such
as the silicon-oxygen SiO4 tetrahedron.
The frequency varies with the strength of
the force constant F and inversely with the
reduced mass fi = m1rn2/(m1 + m2) of the
component ions and is found empirically
to obey the Szigeti equation (Szigeti, 1950)
co = (F/n)1/2/2nc (12-4)
Thus with respect to silicate glasses the IR
absorption moves to long wavelengths for
germanate or tellurite glasses or for heavy
metal (Zr, Hf) fluoride glasses due to the
changes in bond strength and reduced mass.
Similarly, the absorption edge moves to

longer wavelengths for chalcogenide glasses
in the series As-S<As-Se<As-Te.
The extremely low absorption in the re-
gion between the UV and IR absorption
edges in Fig. 12-1 is obtained only in ultra-
pure glasses. Absorption in this region is
dominated by the presence of trace
(< parts per million) iron and other transi-
tion or post-transition group impurities in
the raw materials, by color centers due to
vacancies or electron traps, and by higher-
order harmonics of the glass network vibra-
tions. Water is frequently present in glasses
in the form of OH ~ groups. This gives rise
to a strong fundamental absorption near
3 pm and other weaker overtone and com-
bination absorption bands throughout the
near infrared (Bartholomew, 1982). Glasses
melted in platinum may also incorporate
ionic platinum which has an absorption
band extending into the visible.
For most optical glasses, an absorption
coefficient of <10~ 2 cm~ 1 in the wave-
length region of interest is sufficient. For
laser glasses, absorption due to impurities
is usually kept to less than 10~ 3 cm~ 1 at
the lasing wavelength. In comparison, for
ultralow-loss glass fibers for optical com-
munications (see Chapter 15), losses of less
than 1 dB/km have been achieved in the
near infrared corresponding to an absorp-
tion coefficient of ~10~ 6 cm~ 1 .
12.2.2 Refraction
The index of refraction n for monochro-
matic radiation is the ratio of the velocity
of light in vacuum to the velocity of light in
the medium, that is, n — c/v. For an ab-
sorbing dielectric medium, the index of re-
fraction at wavelength X is complex and
given by
n* = n-ik (12-5)
where the extinction coefficient k is related
to the absorption coefficient by k = a X/4 n.
12.2 Fundamental Optical Phenomena 625
In vacuum the propagation velocity is the
same for all wavelengths, but in a transmit-
ting medium the velocity and refractive in-
dex vary with wavelength. Using a classical
oscillator model, the refractive index due
to absorption of a system of N atoms per
unit volume is described by
Ne
/; (12-6)
/r -1 = JflSn co2 — co2
where e0 is the electric permittivity, / is a
dimensionless oscillator strength, and the
summation is over all oscillators of fre-
quency ojj and linewidth y^ contributing to
the absorption (Born and Wolf, 1980). Sep-
arating Eq. (12-6) into its real and imagi-
nary parts yields
/JK-M2)
and (12-7)
(12-8)
msn
Figure 12-2 illustrates the general wave-
length dispersion of the refractive index for
a simple case where X± and X2 are the wave-
lengths of two effective oscillators corre-
sponding to the ultraviolet and infrared
absorption bands, respectively.
In regions far removed from absorption,
wherefc^O,Eq. (12-7) reduces to
(12-9)
men
The wavelength dependence of the refrac-
tive index in this case is frequently ex-
pressed by the Sellmeier relationship
m 4 22
2
n (A)-l=Z^rr (12-10)
where Aj and Xj are the effective strength
and mean wavelength of the jth absorption
band and the summation is over all infra-
red and ultraviolet bands. The static dielec-
626 12 Optical Properties of Glasses
•Ultraviolet -j Visible | - Infrared-
/
*1/
Wavelength •
Figure 12-2. Schematic dispersion curve for an optical glass. Dashed portions correspond to regions of strong
absorption.
trie constant 8 of the material is equal to n2,
where n is given by Eq. (12-9) for co = 0
(* = oo).
Other simplified models involving more
physically meaningful phenomenological
parameters can be used to describe the
wavelength dependence of n. A two-param-
eter Sellmeier expression for the electronic
contribution and a single-parameter
asymptotic expression for the lattice con-
tribution of the form
'<-l = EdE0/(E2-h2co2)-
-Ef/h2co2
where Eo is an average electronic energy
gap, Ed is the electron oscillator strength or
dispersion energy, and El is the lattice os-
cillator strength fits refractive index data
satisfactorily for a wide range of crystalline
and amorphous materials (Wemple, 1973,
1977). Eo scales with the fundamental en-
ergy gap and is a strong function of bond
length d, that is, Eoccd~s, where 2 < s < 3 .
The macroscopic oscillator strength Ed is
related to the cation coordination number,
anion valency, and ionicity by
Ed=fncZa(NAd3)
>
where ne is the number of valence electrons
per anion (usually ne = 8), Z a is the anion
valence (2 for oxides, 1 for fluorides), and
iVA is the anion number density. The nor-
malized oscillator strength / for crystals
and glasses is unaffected by disorder. This
indicates that the bond lengths remain es-
sentially unaltered and illustrates the in-
sensitivity of bond-dependent optical
properties to the absence of long-range or-
der. This is consistent with a picture of a
glass as a loosely-packed version of a crys-
tal in which no significant bonding changes
(12-11) occur within the basic molecular unit (SiO4,
PO 4 , BO 3 , etc.). Ed is also nearly indepen-
dent of £ 0 . The lattice energy El in Eq.
(12-11) is ~0.1 eV and in the short wave-
length regime its contribution is negligible.
In the simple formalism of Eq. (12-11),
EQ and Ed represent weighted averages of
the absorption band energies and oscilla-
tor strengths. For selected optical glasses
(n values ranging from 1.46 to 1.81),
changes in n correlate with changes in the
band gap energy Eo (DiDomenico, 1972).
There is little change in Ed with com-
position. For most binary, ternary, and
more complex lanthanide silicate glasses,
(12-12) £ d ^ 1 5 e V ± 1 0 % (Wemple, 1973). Larger

values of Ed for lanthanide and mixed ox-
ide glasses are attributed to changes of co-
ordination number.
Compositional Dependence; Additivity
Physical properties of solids may be di-
vided into two groups: (1) structure sensi-
tive - those dependent on long-range order
and only weakly dependent on composi-
tion, and (2) bond sensitive - those depen-
dent on the nature, local arrangement, and
interactions of neighboring constituent
ions but not dependent on long-range
structural order. Examples of structure-
sensitive properties are thermal and electri-
cal conductivity, fracture characteristics
such as breaking strength and yield point,
acoustic attenuation, and dielectric, ferro-
magnetic and other losses. These proper-
ties can differ greatly for crystalline versus
amorphous solids. Bond-sensitive proper-
ties such as thermal expansion, specific
heat, specific volume, elastic and photo-
elastic coefficients, band gap, and refractive
index depend strongly on composition;
however the values of these properties for
crystalline and amorphous solids exhibit
only small differences.
Structure-insensitive properties of glass
can, within limits, be represented by re-
garding the material as a simple mixture of
components each of which contributes in-
dependently to the overall effect. Therefore
a glass property P can be described by an
additive relation of the form
'=a+ btxt (12-13)
where a is a constant dependent on some
other property or procedure, N is the num-
ber of constituents, xt is the weight or mole
fraction of each component, and the bt are
experimentally determined factors for each
12.2 Fundamental Optical Phenomena 627
component z. The b{ vary within a given
glass former and for different formers.
Over the region where this simple linear
relationship has validity, if sufficient mea-
surements are made to determine the bi
accurately, Eq. (12-13) provides a valuable
method for selecting and adjusting glass
compositions to obtain desired property
values (Volf, 1988). An early and classic
example of this approach is the work of
Winkelmann and Schott (1894) on glass
density. For large compositional variations,
Eq. (12-13) can be extended to include non-
linear terms (Huff and Call, 1973).
The refraction and dispersion of glasses
can be expressed by additivity relations of
the form in Eq. (12-13) (Huggins and Sun,
1943; Goldstein and Sun, 1979). This is a
useful procedure for finding approximate
values of the refractive index and disper-
sion of a glass from its chemical composi-
tion. Morey (1954) cites many experimen-
tal investigations of refractive index versus
composition.
Glass properties such as density and re-
fractive index have also been expressed in
terms of the bridging oxygen to non-bridg-
ing oxygen ratio derived from ESCA stud-
ies (Jen and Kalinowski, 1980). This ratio
has direct implications for glass structure
and therefore is more physically meaning-
ful than simple glass composition.
12.2.3 Reflection
When a flux of light $ traversing a
medium of refractive index nf is incident on
a glass of index n, it is partially reflected
and partially refracted as shown in Fig.
12-3. By Snell's laws, 9r1 = 91 on reflection
and n sin 62 = n'sind1 on refraction (Born
and Wolf, 1980). The amount of light re-
flected is a function of the angle of inci-
dence. For light incident from a less dense
to a more dense medium, the reflectivity
628 12 Optical Properties of Glasses
° incident
nf
Figure 12-3. Reflection, refraction, and transmission of light at material boundaries (n' < n).
becomes very large as 61 approaches graz-
ing incidence. If n>n\ 62<0l and light is
refracted toward the normal. If n! > n, at a
critical angle determined by sin 6C = n/ri,
light is totally reflected.
Light becomes polarized due to reflec-
tion, refraction, absorption, and scattering.
At Brewster angle 9V, given by ri/n = tan 6p,
only the component of light polarized per-
pendicular to the plane of incidence is re-
flected and the intensity is plane polarized;
at other angles of incidence the reflected
light has mixed polarization. If the glass
surface is oriented at Brewster's angle with
respect to the direction of propagation of a
plane-polarized beam, light is propagated
through the glass with no reflective losses.
The dependence of the reflectivity on
wavelength and angle of incidence (Fresnel
transmitted
laws) is complex, especially near an ab-
sorption band (Born and Wolf, 1980). The
index of refraction and the absorption co-
efficient of a material can be derived from
reflectivity data integrated over a broad
range of wavelengths beyond the IR and
UV absorption edges using a Kramers-
Kronig analysis (Powell and Spicer, 1970).
The fraction of light reflected by a glass
in air (nf«1) for normal incidence is given
by the Fresnel reflectivity
In the transparent region where k w 0, this
reduces to r = 4% for a glass of refractive
index 7? = 1.5. The fraction of light trans-
mitted when multiple reflections at both
entrance and exit surfaces are considered is

given by the reflection factor
2n
R- (12-15)
For high-index glasses, Fresnel reflective
losses become very large.
In addition to spectral reflection de-
picted by Fig. 12-3, the transmitted flux
may also be reduced by diffuse reflection
from rough or irregular entrance and exit
surfaces and imperfections in the interior
of the glass.
12.2.4 Scattering
The flux transmitted in Fig. 12-3 is re-
duced from the incident flux by a combina-
tion of losses due to absorption, reflection,
and scattering. Scattering of light in glass
may be due to extrinsic causes or it may be
intrinsic in nature. The former include dis-
crete scattering centers such as bubbles, in-
clusions, impurities or flaws introduced
during production. The latter includes
Rayleigh scattering caused by stationary
density, temperature, and compositional
fluctuations, and Brillouin scattering
caused by propagating fluctuations in the
dielectric constant. Spontaneous and stim-
ulated Raman and Brillouin scattering in-
volve optic and acoustic phonons and non-
linear optical processes (Shen, 1984).
Scattering processes may also be distin-
guished by the size and absorptivity of the
active centers (Van de Hulst, 1957). Ray-
leigh scattering is caused by scattering cen-
ters that are small compared to the wave-
length of light and exhibits a characteristic
A~4 dependence on wavelength. As the
particle size increases, scattering occurs in-
creasingly in the forward direction and ex-
hibits a l " 2 dependence (Rayleigh-Gan
scattering). Mie scattering occurs when the
scattering centers have a size comparable
to the wavelength of light. Scattering in
12.2 Fundamental Optical Phenomena 629
glass begins to be visible for centers
> lOnm in size. For large numbers of cen-
ters of dimensions ~100nm, glass appears
cloudy. For high densities of centers hav-
ing dimensions >1000nm, glass is usually
opaque.
Colloidal particles (crystals) that diffract
light - the Tyndall effect - also contribute
to light scattering. The color of the scat-
tered light changes with the size of the col-
loidal particles. This particle size property
is used to obtain optimum color character-
istics, for example, in gold ruby glass.
The spectrum of intrinsically scattered
light consists of an unshifted central Ray-
leigh line and frequency-shifted Brillouin
lines, the theoretical and experimental as-
pects of which are reviewed by Schroeder
(1977). The ratio of the intensities of the
central component to the total Brillouin
components is given by the Landau-
Placzek ratio RhP. The scattering loss coef-
ficient as at wavelength X and temperature
T is given by
(12-16)
where
8TI 3 kBT n8p212
(12-17)
QV\
In Eq. (12-17), p12 is the longitudinal elas-
tooptic constant (see Sec. 12.2.5), and vl is
the longitudinal sound velocity (Pinnow
et al., 1973). A similar expression applies to
Rayleigh scattering where the temperature
T is now the fictive temperature Tf at
which density fluctuations are frozen in
(near the glass transition temperature Tg).
Light scattering losses in single-compo-
nent glasses such as SiO2 are small and
limited by microscopic density fluctuations
associated with the random molecular
structure. Losses in multi-component
glasses and mixtures are generally larger
because of additional concentration fluctu-
630 12 Optical Properties of Glasses
ations. Compositional studies of scattering
losses show, for example, that for simple
binary alkali silicate glasses, density fluctu-
ations decrease with decreasing molecular
weight of the alkali oxide. Thus glasses
composed of low-atomic-number cations
have reduced scattering losses. Since
Tf > T, Rayleigh scattering is greater than
Brillouin scattering. For single-component
glasses, RLP~ 20.
Scattering losses in optical fibers (Chap.
15), where ultralow losses are important,
have been investigated extensively. For
these materials, scattering is the major loss
mechanism when absorption is success-
fully reduced. For most bulk optical and
laser glasses, losses due to extrinsic imper-
fections and impurity absorptions are usu-
ally larger than intrinsic scattering losses.
12.2.5 Photoelastic Properties
While glass is normally considered to be
an isotropic material, it becomes birefrin-
gent under stress. Photoelastic properties
describe the effects of elastic deformation
on the refractive index; these result in dis-
tortions of the optical wavefront. The
piezo-optic and elasto-optic coefficients
determine the effects of stress and strain,
respectively. In general a material may
possess 36 independent piezo-optic or elas-
to-optic constants, but because glass is iso-
tropic, there are only two independent co-
efficients for each.
The change in refractive index An caused
by a change in stress o for light polarized
parallel or perpendicular to the line of
stress is given by
n3
An = Anl]-An1= — (q11-q12)a (12-18)
where the g's are the piezo-optic constants
and ^44 = ^ii — ^i2- The change in refrac-
tive index for uniform hydrostatic pressure
P i s An = n3(q11+q12)P/2.
Corresponding relations involving elas-
tic-optic constants p (Pockels coefficients)
describe changes in refractive index and
the state of strain in the glass. The p's and
g's are related by
Pn = (12-19 a)
and
P12 = Cn «i2 + cii(«n +«i2> (12-19b)
where the c's are elastic stiffness constants.
Also, p 4 4 = (p 11 ~p 12 )/2.
Photoelastic constants have been mea-
sured for many optical glasses (Schaefer,
1953; Waxier, 1971) and studied as a func-
tion of glass composition. The dependence
of the elastic-optic coefficients (measured
from Brillouin line shifts) on composition
for binary and ternary silicate glasses have
been correlated with the degree of ion
overlap and covalent bonding as the
amount of alkali oxide in the base glass
was varied (Schroeder, 1980).
Stress-Optical Coefficient
Mechanical stress, either developed in-
ternally during production, applied exter-
nally, or as a consequence of fluctuating
temperature, changes the refractive index.
The resulting change in optical path length
S for a sample of length / caused by stress
birefringence is
AS = Anl = Kla (12-20)
where, from Eq. (12-18), the stress-optical
coefficient K is defined by
K = Y(<h2-«n) (12-21)
Pockels (1903) was the first person to study
the stress-optical effect, including the vari-
ations of K with PbO content in a lead
silicate glass. K was found to decrease with
increasing PbO content, was zero at

«75wt.%, and became negative at higher
PbO concentrations.
Several studies have been made to re-
duce the stress-optical coefficients of oxide
and oxyfluoride glasses (Tashiro, 1956;
Galant, 1979) with the result that to reduce
K the glass composition should contain
strongly polarizable cations (e.g., Cs + , Tl + ,
Ba 2+ , Pb 2 + , La 3+ ) and weakly polarizable
anions (F~). Additivity relations have been
applied (Nissle and Babcock, 1973) which
are useful for estimating K for contiguous
fields in the glass compositional space.
Partial stress-optical coefficients have been
tabulated for alkali, alkaline earth, and
other oxide components in silicate and
phosphate glasses (Shchavelev et al., 1978).
The birefringence varies with both tem-
perature and wavelength. The wavelength
dispersion of K over a large wavelength
range can be fitted using an empirical ex-
pression involving ultraviolet and infrared
absorption frequencies (Sinka, 1978).
12.2.6 Thermal-Optical Properties
Partial absorption of intense light
traversing a glass or, in the case of laser
glass, optical pumping lead to the forma-
tion of temperature gradients and stress in
the glass. Thermally-induced optical dis-
tortions in laser materials have been the
subject of many theoretical and experimen-
tal studies (see Quelle, 1966; Riedel and
Baldwin, 1967). The optical path length of
light passing through a glass varies with
temperature owing to thermal expansion
and to changes in the refractive index and
is given by
dS/dT = (n - 1 ) a + dn/dT = W (12-22)
where a is the linear coefficient of thermal
expansion and W is one of three coeffi-
cients used to define the thermo-optic ef-
12.2 Fundamental Optical Phenomena 631
fects. At a given wavelength, the change in
refractive index resulting from the temper-
ature-dependent shift in absorption and
thermal expansion is given by
dn/dT = dn/dT -0Q dn/dg (12-23)
where dn/dT is the change in refractive in-
dex at constant density Q and /? is the cubic
expansion coefficient. Because both dn/dT
and dn/dg are always positive, dn/dT can
be either positive or negative. By adjusting
the glass composition so that the change
in path length change due to thermal ex-
pansion is compensated by a negative
value of dn/d7^ the thermo-optic coeffi-
cient can be positive, negative or zero
(Shchavelev and Babkina, 1970).
Pump-induced optical distortions in
laser rods affect both radially and tangen-
tially polarized light propagating along the
axis. For a rod of radius r0 at a tempera-
ture To, refractive index fluctuations for
light polarized parallel or perpendicular to
the radius are
dnr(r) = (P + Q/2) To [1 - (r/r0)2] (12-24 a)
and
6n& (r) = (P- 2/2) To [1 - (r/r0)2] (12-24 b)
where the two additional thermo-optic co-
efficients P and Q are defined by
dn n3aE
L + 3<?12) (12-25)
dT 4(1-^
and
(12-26)
4(1-/ 2(1-A*)
The coefficient P can be positive or nega-
tive. Studies (Shchavelev et al., 1976) of sil-
icate, phosphate and fluorophosphate
glasses show that P can range from approx-
imately 40x 10" 1K'1 to - 2 5 x l O ~ 7 K - 1 .
Since E and \x in Eq. (12-26) are positive,
the sign of Q is generally determined by the
632 12 Optical Properties of Glasses
stress-optical coefficient K. As discussed in
Sec. 12.2.5.1, by compositional variations
K, and hence Q, can be made equal to zero
for some glasses.
All coefficients and moduli that enter
into W9 P and Q are, in varying degrees,
dependent on the glass composition and
the temperature. In principle, with the
proper combination of glass properties, no
optical distortions would appear in the
presence of a nonuniform temperature dis-
tribution. Even if this ideal athermal glass
is not achieved, thermo-optic distortions in
optical glass can be reduced by composi-
tional tailoring.
12.2.7 Magneto-Optical Properties
Optical rotation occurs in a medium
when the refractive indices n+ and n_ for
right and left circularly-polarized light are
unequal. The microscopic origin of mag-
netic optical rotation is the inequality that
is created by the splitting of the ground or
excited-state energy levels due to an ap-
plied magnetic field or magnetization.
Magneto-optical effects are described by
the dielectric tensor elements (Zeiger and
Pratt, 1973). When the magnetic vector is
parallel to the light propagation vector,
measurable optical qualities are
(12-27)
and
71
(12-28)
where <9F is the angle of Faraday rotation
(also called magnetic optical rotation and
magnetic circular birefringence) and \j/¥ is
the Faraday ellipticity or the magnetic cir-
cular dichroism (MCD). The sense of rota-
tion is positive if the rotation is in the di-
rection of the positive current in the coil
that produces the magnetic field. When the
magnetization vector is perpendicular to
the light propagation vector, measurable
optical quantities are
271
(12-29)
and
(12-30)
where @L is the magnetic linear birefrin-
gence (also called the Voigt or Cotton-
Mouton effect) and \/JL is the magnetic linear
dichroism.
The four quantities <9F, \j/F, 0 L , i/fL are
usually measured in transmission experi-
ments. Although Faraday rotation occurs
in both nonabsorbing and absorbing re-
gions, magnetic circular dichroism occurs
only in absorbing regions. In regions of
strong absorption, reflection measure-
ments are possible using magnetization
Kerr effects (Sec. 12.2.8). The real and
imaginary parts of the off-diagonal dielec-
tric tensor elements are again related by
a Kramers-Kronig transform. Therefore
Faraday rotation can be calculated from
magnetic circular dichroism measure-
ments. Measurements of Faraday rotation
and magnetic circular dichroism in the
vicinity of absorption yield information
about ground and excited states of para-
magnetic ions and about intra- and inter-
band transitions (Buckingham and Ste-
phens, 1966).
For the Faraday effect the rotation of
the plane of polarization of light is given by
0F = VlHs (12-31)
where H is the strength of the applied field,
£ is a unit vector in the direction of light
propagation, and the constant of propor-
tionality V is the Verdet constant. In terms
of the electric susceptibility x for right and

left circularly-polarized light,
(12-32)
The term in brackets in Eq. (12-32) is the
local field correction derived from the
Lorentz-Lorenz model. For a system of N
atoms per unit volume, the susceptibilities
are given by the Kramers-Heisenberg dis-
persion relation (Zeiger and Pratt, 1973)
Qa
(Ea-Eb) (12-33)
where the summation is over transitions
between all ground states a and excited
states b (E^>kB T). The transitions are
weighted by the Boltzmann factor Qa. Al-
though Eq. (12-33) involves electric-dipole
transition matrix elements, it can be gener-
alized to include all types of transitions.
Combining Eqs. (12-32) and (12-33) the
quantum mechanical expression for Fara-
day rotation is
ACD2N [>2 + 2)2~|
exp(-hcoa/kBT)
Zexp(-ftcofl/feBTV
a,b 0) —CO a,b
where coa is the ground state splitting, co is
the light frequency, coab is the frequency
difference of the ground and excited states,
and X and Y are components of the elec-
tric-dipole moment. The frequency wa is
dependent on the magnetic field. Therefore
in the small-field limit where ® F depends
linearly on if, the Verdet constant is a func-
tion of co, T9 and n.
The classical formula for the Verdet con-
stant of diamagnetic materials derived by
12.2 Fundamental Optical Phenomena 633
Becquerel (1897) is
eX dn
V = (12-35)
dia 2
2 m c dX
This expression holds for most materials if
a multiplicative factor y, the magneto-optic
anomaly, is introduced (Serber, 1932). This
factor varies with the nature of the bonding
in the material and ranges from near unity
for predominantly ionic bonding to 0.28
for strongly covalently bonded diamond.
Generally, the larger the refractive index
of a material, the larger the diamagnetic
Verdet constant; however, a better correla-
tion is obtained if V is plotted as a function
of the Abbe number (Cole, 1950). Plots of
V for similar glasses as a function of other
partial dispersions also yield satisfactory
predictions of Verdet constants at a given
wavelength.
Because of the wavelength dependence
of the dispersion dn/dX and the magneto-
optic anomaly y, Fdia increases as the wave-
length approaches the fundamental ab-
sorption edge. The frequency dependence
of the diamagnetic term derived from the
quantum mechanical expression in Eq.
(12-34) has the form
where C (a, b) is a function of the transition
moments between the ground state and ex-
cited states. The Verdet constant of dia-
magnetic materials exhibits only a small
temperature dependence and in the long-
wavelength limit (X^>Xab) varies as 1/X2.
When paramagnetic ions are present in
a material, their contribution to the Fara-
day rotation is given by Eq. (12-34), where
now N is the number of paramagnetic ions
and coab is the frequency of electronic tran-
sitions of the ions. Magnetic optical rota-
tion occurs for ions from various transition
metal groups, ions of the iron transition
634 12 Optical Properties of Glasses

group and lanthanide series being the most frequency co can be expressed by the power
thoroughly studied (Buckingham and Ste- series
phens, 1966). The paramagnetic Verdet con-
stant is given
<}1)(co)E{(o) +
C(a,b) E(coi)E(co2)
V =
para
3ch kBT a,b
(12-37) E((D1)E(co2)E(co3) (12-38)
where g is the Lande factor, J is the total
where the complex dielectric susceptibilities
angular momentum quantum number of
X(n) are tensors of rank (rc + 1) and are re-
the ground state, and p is the Bohr magne-
lated to the microscopic (electronic and
ton. In the long wavelength limit, Fpara
nuclear) structure of the material (Bloem-
again varies as I/A2 and, except for ex-
bergen, 1965; Shen, 1984). Classical or lin-
tremely low temperatures, is inversely pro-
ear optics is concerned with the first-order
portional to temperature.
term x(1). The linear refractive index n0 and
All glasses exhibit diamagnetic Faraday
the linear absorption coefficient k are pro-
rotation; however, when paramagnetic
portional to the real and imaginary parts
ions are present in sufficient quantities,
of x(1) (Born and Wolf, 1980). In regions of
paramagnetic Faraday rotation can domi-
no absorption, n2 — 1 = 4TT %(1).
nate. Because the diamagnetic and para-
Second-harmonic generation and the
magnetic effects produce opposite rota-
electro-optic effect are both described by
tions, the sign of the net Verdet constant
the second-order nonlinear susceptibility
can change with paramagnetic ion content.
y(2) j n gq (12-36). In the first process an
The wavelength and concentration depen-
optical signal is generated at twice the fre-
dences of the Verdet constant for a rare-
quency of the incident optical field, that is,
earth doped silicate glass are illustrated in
co1=(o2 and co = 2(o1. In the second pro-
Fig. 12-4.
cess, an optical signal is changed by the
application of the strong DC field. The
12.2.8 Nonlinear Optical Properties
generated signal is at the same frequency as
The polarization P induced in a medium the incident optical signal and a)2 = 0 and
by an external optical electric field E of co = co1. This latter process can also be de-

40

20
2.

8
8
-20
Figure 12-4. Faraday rotation of a sodium silicate
glass at 4.2 K for several concentrations of Ho 2 O 3
-40 (wt.%) [from Collocott and Taylor (1978)].

scribed in terms of a DC-field-dependent
change of the refractive index. The second-
order nonlinearity term x(2) is important in
materials having no center of inversion. In
isotropic materials that possess inversion
symmetry such as glasses, the second-order
contributions are ruled out although elec-
tric quadrupole, magnetic dipole and sur-
face terms can produce weak harmonic
generation even in centrosymmetric mate-
rials.
The third-order contributions to the po-
larization are given by
jkl
(12-39)
where Ej9 Ek, Ex are three separately ap-
plied electric fields each having its own fre-
quency (co1? co2, co3) and polarization direc-
tion. Many different third-order nonlinear
processes are possible because three incom-
ing electric fields are involved (Hellwarth,
1977). Processes involving x(3) are third-
harmonic generation, Raman and Bril-
louin scattering, self focusing, optical phase
conjugation, and a large number of four-
wave mixing processes. The optical (AC)
Kerr effect is a four-wave mixing process
involving optical frequency fields. In the
DC Kerr effect, the modifying electric field
is at microwave or lower frequencies. Ra-
man and Brillouin scattering arise from the
imaginary part of x(3) and involve interac-
tions with optical and acoustic vibrations
of the material.
Nonlinear optical properties also depend
upon whether the frequency co is resonant
or nonresonant with an electronic transi-
tion in the material (Borrelli and Hall,
1991). The resonant case applies when the
operating wavelength is near a fundamen-
tal absorption. Near resonance part of the
light beam is absorbed which can lead to
redistribution of electron energies, shifts in
12.2 Fundamental Optical Phenomena 635
the absorption frequency, and changes in
the refractive index. The response time de-
pends on the relaxation time of the carriers
that are excited by the optical field. Ther-
mally-induced nonlinearies associated with
absorption generally have much longer re-
laxation times. The nonresonant case ap-
plies for wavelengths far removed from any
fundamental absorption in the glass. Non-
resonant optical nonlinearities are pre-
dominantly of electronic origin and exhibit
subpicosecond response times with mini-
mal heating; however, the nonlinearities
are much smaller than for the resonant
case (Vogel et al., 1991).
When the optical Kerr effect is included,
the refractive index becomes intensity-de-
pendent and is given by
n = n0 + n21 (12-40)
where n0 is the linear index of refraction, /
is the time averaged-intensity of the inci-
dent optical beam, and n2 is the nonlinear
refractive index coefficient. n2 is derived
from the real part of / (3) . For an isotropic
medium and a linearly-polarized mono-
chromatic beam of frequency co,
(12 41)
480** "
If a high-intensity beam propagating
through a glass has a non-uniform spatial
profile, the spatial variation of the induced
refractive index will lead to whole-beam
or small-scale self-focusing (or defocusing
depending on the sign of n2) (Bliss et al.,
1974). The intensity-dependent refractive
index also causes the phase at the peak of
an optical pulse to be retarded with respect
to its leading or trailing edges. This self-
phase modulation produces a frequency
chirp and spectral broadening of the pulse
(Stolen and Lin, 1978). Depending upon
the sign of the dispersion, the pulse may
expand or contract. In addition, certain so-
636 12 Optical Properties of Glasses
lutions of the nonlinear wave equation,
called solitons, propagate without any
change in shape (Tomlinson, 1988). The
above nonlinear optical phenomena are
observed in optical fibers at more modest
power levels than in pulsed high-power
lasers because of the longer path length
possible due to the beam confinement and
low-loss propagation.
Four physical processes contribute to
self focusing (Feldman et al., 1973): elec-
tronic-arising from induced distortions of
the electron orbit about the nuclei (re-
sponse time 10" 1 4 -10~ 1 6 s), nuclear-op-
tical induced changes in the motion of the
nuclei (response time ~ 10~ 12 s), electro-
striction-electric-field induced strains (re-
sponse time 10~ 7 -10~ 9 s), and thermal-
resulting from absorption (response time
~ 10 ~1 s). The nuclear contribution can be
determined from Raman scattering spectra
and is only about one-third of the total n2
for many glasses (Heiman et al., 1978).
In the DC Kerr effect, an applied field
induces a birefringence
An n — . (12-42)
where B is the Kerr constant and <£2> is
the time-averaged square of the modifying
electric field amplitude. B is proportional
to the difference of two components of x(3)
and is given by
n
B= [X(i3Ai(- a, co, Q,-Q)
3Xn0
-co,co,Q,-Q)] (12-43)
where the frequency Q <^co (Borrelli and
Hall, 1991).
The imaginary part of %(3) contributes
to two-photon absorption. For the case
above, a beam of intensity / propagating in
the z-direction is attenuated as
^ = al-pi2 (12-44)
where a is the linear absorption coefficient
and P is the two-photon absorption coeffi-
cient given by
(12-45)
I m
P= — T ^ T Xuii (~co, co, co, - co)
The specific linear combinations of x (3)
components that define n2 and (3 are de-
pendent on the geometry.
In the same way that the linear refractive
index exhibits dispersion as a fundamental
absorption is approached, the nonlinear
refractive index exhibits dispersion and
changes sign as one transverses a two-pho-
ton absorption (Sheik-Bahne et al., 1990).
The linear absorption coefficient and re-
fractive index are related by a Kramers-
Kronig transformation, therefore a change
in the absorption coefficient due to nonlin-
ear effects can be correlated with a change
in refractive index via the relationship (Ol-
bright and Peyghanbarian, 1986)
Aa(cof)
An(co) = da/ (12-46)
n I co'2 - co2
Photoinduced Nonlinearities
Several nonlinear optical effects are ob-
served after a glass has been exposed to
light for periods of time varying from min-
utes to hours. Photoinduced nonlinearities
include refractive index gratings and sec-
- ond harmonic generation in fibers. In the
first effect, when a laser beam is injected
into an optical fiber, a standing wave pat-
tern is set up by the transmitted beam and
the counterpropagating beam reflected
from the fiber end. This intensity grating
leads to a permanent photoinduced modu-
lation of the refractive index which acts as
a Bragg grating for the incident light (Hill
et al., 1978). Gratings can also be formed
by side illumination using the interference
pattern generated by two coherent, over-

lapping laser beams. These so-called Hill
gratings are extremely wavelength specific
and can be used as narrowband filters.
Laser-induced refractive index gratings
have also been produced in bulk glasses
doped with trivalent rare-earth ions using
four-wave mixing geometries (Behrens
et al., 1990). Permanent gratings are attrib-
uted to a change in the local structure of
the glass at the rare-earth site caused by
vibrational energy released by the nonra-
diative relaxation of the rare earth follow-
ing optical excitation.
Glass is macroscopically isotropic, there-
fore it is not expected to exhibit second
harmonic generation due to the second-or-
der nonlinear susceptibility x(2)- Osterberg
and Margulis (1986) found, however, that a
fiber that had been irradiated for several
hours with a very intense laser beam at
1.06 |im showed a strong second-harmonic
signal which grew exponentially with the
time of the irradiation. Moderately high
conversion efficiencies are obtained be-
cause the second harmonic beam can be
phase-matched to the input beam by a
periodic variation of y}2) (Stolen and Tom,
1987). Both photoinduced refractive index
gratings and second harmonic generation
have only been reported for Ge-P or Ge
doped silica fibers. Germanium-related de-
fects are believed to play an important role
in the processes, although the origins of the
phenomena are not understood in detail
(Vogel et al., 1991).
12.2.9 Luminescence and Stimulated
Emission
Luminescence from glass can arise from
the presence of various transition metal
ions (principally iron group and lantha-
nide series elements having partially filled
electron shells), filled shell and post-transi-
tion group elements, semiconductor clus-
12.2 Fundamental Optical Phenomena 637
ters, molecular complexes, organic dyes,
and defect or color centers (Bamforth,
1977; Hiifner, 1978; Nassau, 1986). While
many of the general features of the lumi-
nescence from a given species are similar
whether the host is a glass or an insulating
crystal, site-to-site variations in the local
environments in glass result in a distribu-
tion of energy levels and radiative and non-
radiative transition probabilities. This ap-
pears spectrally as inhomogeneous line
broadening and in the time domain as non-
single-exponential excited state relaxation
(Weber, 1981). High frequency vibrations
associated with the glass network former
determine the probability of nonradiative
decay of excited ions by multiphonon
emission, hence the radiative quantum effi-
ciency and number of fluorescing states are
generally smaller for a borate or silicate
glass than for a heavy metal fluoride glass
(Layneetal, 1977).
Stimulated emission (laser action) re-
quires an inverted ion population. The es-
sential features necessary to achieve this
condition are illustrated in the energy level
scheme in Fig. 12-5. The laser ion is excited
by optically pumping the 1 -> 4 transition
with a flashlamp or another laser. This is
followed by rapid relaxation to a metasta-
ble level 3, thereby creating a population
inversion AN = N3 — N2 with respect to
level 2. The gain coefficient for the 3 -• 2
transition is given by a AN, where a is
the stimulated emission cross-section. If
the probability for stimulated emission is
greater than that for excited-state absorp-
tion 3 -> 4 and if the resulting gain is greater
than losses due to absorption and scatter-
ing at the lasing wavelength and losses in
the optical resonator, laser oscillation will
be obtained.
The electronic states of the unfilled 4f"
shell of the trivalent lanthanide ions
provide many energy level schemes suit-
638 12 Optical Properties of Glasses
i
Pump Laser
transition transition
Figure 12-5. Schematic diagram of energy levels and transitions important for four-level laser action. Wavy lines
denote nonradiative transitions.
able for laser action. Lasing has been ob-
tained for all ions of the 4P1 series in either
crystals or glasses, in many cases involving
several different transitions (Weber, 1991).
Lanthanide ions are readily incorporated
into most glasses in concentrations of up to
~ 1 mol% needed for flashlamp-pumped
lasers. Other ions with complementary ab-
Excited state
absorption
sorption band may also be added to the
glass as fluorescence sensitizers to increase
the optical pumping efficiency. Host glass
requirements include transparency at the
pump and lasing wavelengths.
The overall performance of glass lasers
depends upon the efficiency and limita-
tions of energy storage and energy extrac-

tion. The energy storage is affected by the
spectral match of the laser ion absorption
bands to the pump source, excited-state
absorption of pump radiation, and the life-
time and efficiency of decay to the upper
laser level. The rate of energy extraction is
proportional to a 1/Pico and thus is limited
by the effective stimulated emission cross
section a and the beam intensity / that can
be propagated in the glass without self fo-
cusing or optical damage. Because energy
is extracted only from those ions resonant
with the lasing wavelength, in large-signal
or saturated gain operation a hole devel-
ops in the gain profile (spectral hole burn-
ing) which reduces the energy extraction
efficiency (Hall et al, 1983).
12.2.10 Optical Damage
The extremely large optical electric fields
associated with the high peak powers and
fluences of lasers can lead to damage of
reflecting and transmitting optical compo-
nents (Wood, 1990). Owing to the intensity-
dependent index of refraction, a light beam
having a non-uniform spatial profile will
self-focus as it traverses a glass. If uncon-
trolled, whole beam or small-scale self-fo-
cusing will lead to catastrophic damage in
the form of bubbles or tracking along the
light path. Self-focusing is minimized by
using glasses with small nonlinear refrac-
tive index coefficients n2 and by controlling
spatial nonuniformities in the beam profile.
Interaction of intense light with struc-
tural or chemical imperfections in the sur-
face leads to damage in the form of pitting
of the glass. Because the ratio of the optical
intensities at the exit and entrance faces of
a glass of refractive index n is 4n2/(n +1) 2
(Crisp et al., 1972), the threshold for dam-
age is lower at the exit face. Accumulation
of surface damage may eventually render
the optical component useless.
12.3 Optical Glasses 639
Laser-induced damage usually arises
from extrinsic rather than intrinsic glass
properties. Glasses melted in platinum, for
example, have the potential problem of
metallic platinum inclusions which, if pres-
ent, are heated by the absorption of light.
At high fluences, absorbing inclusions va-
porize and cause internal cracking in the
glass. Most of the platinum in glass is in-
troduced in the early stages of the melt
cycle, the primary source being the reduc-
tion of PtO 2 vapor to metallic Pt on the
melt surface due to thermal gradients or
other nonequilibrium conditions. By using
strongly oxidizing conditions, small metal-
lic Pt particles are oxidized and dissolved
in the melt. Although the resulting ionic Pt
introduces a near-ultraviolet absorption
band in glass, this is usually more tolerable
than damaging metallic Pt inclusions.
12.3 Optical Glasses
Commercially available glasses for opti-
cal components and ophthalmic use are
principally colorless oxide glasses. They
provide a wide range of refraction, disper-
sion, specific gravity, and other optical,
thermal, and mechanical properties.
12.3.1 Classification and Designation
Optical glasses are characterized and
designated by their refractive index and
dispersion. The most common measure is
the refractive index at the wavelength of
the He d line (587.6 nm) or the Hg e line
(546.1 nm). The difference in the refractive
index at the hydrogen F (486.1 nm) and
C (656.3 nm) lines, nF — nc, is called the
average or principal dispersion. The ratio
(nF — nc)/(nd — 1) is called the relative dis-
persion; the reciprocal of this quantity is
the Abbe number vd. A six-digit number is
used to specify optical glasses, where the
640 12 Optical Properties of Glasses

Table 12-1. Designation, type, and major compositional components of optical glasses.

Designation Glass type Compositiona

FB Fluoroberyllate BeF2-AF3-RF-MF2
FA Fluoroaluminate AlF 3 -RF-MF 2 -(Y,La)F 3
FP (FK) Fluorophosphate P2O5-A1F3-RF-MF2
FZ Fluorozirconate ZrF 4 -RF-MF 2 -(Al,La)F 3
FK (FC) Fluorocrown SiO2-B2O3-K2O-KF
BK (BSC) Borosilicate crown
SiO 2 (P 2 O 5 )-B 2 O 3 R 2 O BaO
PK (PC) Phosphate crown
PSK (DPC, PCD) Dense phosphate crown P 2 O 5 ~(B,A1) 2 O 3 -R 2 O MO
K(C) Crown SiO 2 -R 2 O-(Ca,Ba)O
ZK (ZC, ZnC) Zinc crown SiO 2 (B 2 O 3 )-ZnO
BaK (BaC, LBC) Barium crown SiO 2 (B 2 O 3 )-BaO-R 2 O
SK (DBC, BCD) Dense barium crown
SiO 2 -B 2 O 3 -BaO
SSK (EDBC, BCDD) Extra dense barium crown
LaK (LaC, LaCL) Lanthanum crown
Dense lanthanum crown B 2 O 3 (SiO 2 )-La 2 O 3 -ZnO MO
LaSK
LgSK Special long crown B 2 O 3 -A1 2 O 3 -MF 2
TiK Titanium crown "J
TiF Titanium flint v SiO 2 (B 2 O 3 )-TiO 2 -Al 2 O 3 -KF
TiSF (FF) Dense titanium flint J
KzF (CHD, SbF) Short flint SiO 2 -B 2 O 3 -R 2 O-Sb 2 O 3
KzFS (ADF) Dense short flint B 2 O 3 (Al 2 O 3 )-PbO-MO
KF (CF, CHD) Crown flint
LLF (BLF, FEL) Extra light flint
LF (FL) Light flint SiO7-R9O-PbO-MO
F (DF, FD) Flint
SF (EDF, FDS) Dense flint
SFS Special dense flint SiO3-R?O-MO-TiO?
BaLF (LBC, BCL) Light barium flint ^
BaF (BF, FB) Barium flint > SiO2-B2O3-BaO-PbO-R2O
BaSF (DBF, FBD) Dense barium flint J
LaF (LaFL) Lanthanum flint
B 2 O 3 (SiO 2 )-La 2 O 3 -MO-PbO
LaSF Dense lanthanum flint
TaK Tantalum crown "1
TaF Tantalum flint / B 2 O 3 -La 2 O 3 -(Gd,Y) 2 O 3 -(Ta,Nb) 2 O 5
TaSF Dense tantalum flint J
NbF Niobium flint B2O3-La2O3-ZnO-Nb2O5
NbSF Dense niobium flint B 2 O 3 (SiO 2 )-La 2 O 3 -ZnO-(Ti,Zr)O 2

R and M denote one or more alkali or alkaline earth elements, respectively.

first three digits designate the refractive in-
dex nd with the preceding " 1 " omitted and
the last three digits designate the Abbe
number vd with the decimal point omitted.
Thus a borosilicate glass BK 7 having an
nd = 1.51680 and vd = 64.17 has a designa-
tion 517-642. This six-digit refraction in-
dex-Abbe number code is the most univer-
sally useful way of designating optical
glasses.
Glasses having nd > 1.60, vd > 50 or
nd < 1.60, vd > 55 are called "crown" (K)
glass; other glasses are called "flint" (F).
These letters, plus others, are usually con-
 12.3 Optical Glasses 641
2.0 I 1
1 1 1
1
/
1.9 - - TaSF
//
1.8 - LaSK TaF
LaSF

LaF
1
NbF ^
BaSFy/
7/SFS_
- LaK
BaF /TiSF
.1 1.6 - - SK
SSK A/
KzFS -
PSK 8aLF
<D
DC 'BaK
FZ PK / _
1.5 - XBK
FP FK #
[TiKl
SiO2

1.4 - - FA -

FB
1.3 ; -
B e F 2 (
1 1
100 80 60 40 20
Abbe number vH

Figure 12-6. Location of the optical glasses in Table 12-1 in a refractive index-Abbe number diagram.

tained in the manufacturer's designation of are specified by the manufacturer's name

optical glasses. Representative manufac-
turer's designations, descriptive names,
and principal compositional components
of commercial optical glasses are given in
Table 12-1 (Fig. 12-6) (Gliemeroth, 1983;
Izumitani, 1986; Marker and Scheller,
1988). (Designations vary with the country
of origin and some alternate designations
are given in parentheses.) "Light" or
"dense" indicate the relative amounts of
heavy metal oxides such as PbO or La 2 O 3 .
Glasses with prefixes U or IR denote ex-
tended ultraviolet or infrared transmitting
glasses. Other designators are used for
glasses for special applications such as
LG-laser glass, FR-Faraday rotator glass,
and AO-acousto-optic glass.
Only a few non-oxide optical glasses
such as heavy metal fluorides and chalco-
genides are available commercially. These
or by the composition if it is simple.
12.3.2 Transmission
Glasses exist that are optically transpar-
ent in the vacuum ultraviolet and in the
mid-infrared. Figures 12-7 and 12-8 illus-
trate the variation of the ultraviolet and
infrared absorption edges of representative
optical glasses. The optical transmission in
these figures depends on the wavelength
dependence of the absorption, reflection,
and scattering of the glass. The transmis-
sion of optical glasses is frequently given in
terms of the internal transmission Tt after
correction for reflective losses, that is,
7] - T/R, where R is the reflection factor
given by Eq. (12-15). The deviation of Tt
from 100% is a measure of absorption due
to impurities and scattering due to defects.
642 12 Optical Properties of Glasses

100
Fused
silica^- /^Pluoropho sohate -— - '
80
' (LG-810JL.—"*^
/Borosilicsrte /

f
60
• ( / / (BK7)

; 40
- / / /

1 i /Lead
20

150
/

200
1 250
1
300
Wavelength (nm)
350
/ silicate
/ (SF6)

400

Figure 12-7. Ultraviolet absorption edge of representative optical glasses. Sample thickness: 5 mm except for
SiO2 and LG 810 which are 2 mm [from Cook and Mader (1982); Schott (1982)].

The internal transmittance is usually re-
ported at a number of standard wave-
lengths from the ultraviolet to the infrared.
Transmittances of near unity for millimeter
thick samples attests to the high quality of
most optical glasses.
The transmission (I/Io) and the absorp-
tion coefficient a for a sample of length / are
related by
ln(/ 0 /J) 2.303 OD
a=- I
I the lines divide the main compositional
where OD = log 10 (/ 0 //) is the absorbance
or optical density. The absorption cross
section a is derived from a = oN, where N
is the number of absorbing centers to unit
volume.
12.3.3 Refractive Index and Dispersion
Optical glasses cover a general range of
refractive indices nd = 1.4 to 2.0 and recip-
rocal dispersions vd = 20 to 90. These are
almost exclusively oxide glasses. The loca-
tion of the glasses in Table 12-1 on an
(12-47) nd — vd map is shown in Fig. 12-6, where
types. Optical glass companies supply such
a figure with dots scattered throughout
this parameter space representing avail-

2 4 6 8 10 12
Wavelength (jam)

Figure 12-8. Infrared absorption edge of representative optical glasses. Sample thickness: 2 mm [from Dumbaugh
(1985)].
 12.3 Optical Glasses 643

able glasses. The range of nd — vd in Fig. Table 12-2. Wavelengths of spectral lines used for re-
12-6 is larger than that given in the ordi- fractive index measurements.
nary glass catalog so as to include low-in- Wavelength Spectral line Element
dex, low-dispersion fluoride glasses. Amor- (nm)
phous SiO2 and BeF2 are added in Fig.
365.0 i Hg
12-6 to indicate the extrema for oxide and
404.7 n Hg
fluoride glasses. 435.8 Hg
g
Higher index chalcogenide glasses can- 480.0 F Cd
not be located in an nd — vd plot because 486.1 F H
the absorption edge extends into the visible 546.1 e Hg
587.6 d He
and it is not always possible to measure vd.
589.3 D Na
Therefore, for infrared materials, plots are 643.8 C Cd
made using a reciprocal dispersion based 656.3 C H
on measurements of refractive index at 706.6 r He
longer wavelengths. For example, for the 768.2 A' K
atmospheric window at 8-13 jim, a rela- 852.1 s Cs
1014.0 t Hg
tive dispersion v l o = (n lo — l)/(ns 0 — n12) is
used, where the wavelengths are in microns
(Feltz et al, 1991). Similarly, for more ultra- tal band gap, the greater the refractive in-
violet-transmitting glasses, relative disper- dex and dispersion at a given wavelength.
sions such as v313 = (n 3 1 3-l)/(n 2 6 5 -n 4 0 5 ) For interpolating values of the refractive
have been used, where here the wave- index at the other wavelengths, glass man-
lengths are in nanometers (Gerth et al., ufacturers use an approximate dispersion
1991). formula derived from a power series ex-
Data sheets usually report the refractive pansion of Eq. (12-10) of the form
index (the mean value for a number of
melts) at a number of specific wavelengths. n2 = Ao r i ^ 2 •A3X~4
Wavelengths of a number of commonly (12-48)
used spectral lines are given in Table 12-2.
where the constants At are determined
Refractive indices may also be given for
from a least squared fit of the measured
common laser wavelengths, e.g., the He-Ne
values. Using this equation, refractive in-
gas laser at 632.8 nm and the N d : YAG
dices in the wavelength range 365-1014 nm
laser at 1064 nm. Hg lines at 1530, 1970,
can be calculated to an accuracy of ± 5 x
and 2325 nm are frequently used to report
10" 6 or better.
values in the infrared.
Various relative partial dispersions
The wavelength dependence of the re-
fractive index of a number of representa- _nx-ny (12-49)
tive optical glasses is shown in Fig. 12-9 to
illustrate the range of values and disper-
are defined for other wavelengths x and y.
sions obtainable. These depend upon the
A century ago Abbe found an empirical
relative positions of the intrinsic absorp-
rule that the relative partial dispersion of
tion bands in the ultraviolet and infrared.
most glasses obeyed a linear relationship
Figure 12-9 represents only a small portion
on vd of the form
of the overall dispersion indicated in Fig.
12-2. In general, the smaller the fundamen- L
x,y
(12-50)
 12 Optical Properties of Glasses
400 600
Wavelength (nm)
Figure 12-9. Dispersion of the refractive index of representative optical glasses [from Schott (1982)].
where a and b are constants. As discussed
later in Section 12.4.1, it is not possible to
correct for second-order chromatic aberra-
tions using so-called "normal" glasses that
satisfy Eq. (12-50). Optical glass catalogs
therefore list deviations of the relative par-
tial dispersions from the normal for glasses
covering a wide range of vd values.
12.3.4 Thermal Properties
The temperature range in which a glass
transforms from its solid state into a "plas-
tic" state is called the transformation re-
gion. A (glass) transformation temperature
Tg is used to define this region and is deter-
mined from a standard thermal expansion
measurement. The viscosity of the melt at
Tg is approximately 10 13 poise. The soften-
ing temperature is that temperature at
which in a standard test the glass deforms
under its own weight and corresponds to a
melt viscosity of 10 7 6 poise. A low Tg is
important for molded optical elements.
800 1000
Thermal expansion varies the dimen-
sions of glass and affects refractive optics
subject to either uniform or gradient tem-
perature variations. The coefficient of ther-
mal expansion, a, of glass ranges from near
zero for special low expansion glasses such
as titania-doped SiO2 and tailored glass
ceramics to values greater than 20 x 10~ 6 /
K. For optical glasses a ranges from about
4 to 16 x 10" 6 /K. The thermal expansion
coefficient increases with increasing tem-
perature, exhibiting a nonlinear increase
up to about room temperature, followed
by an approximately linear range until the
glass begins to exhibit plastic behavior,
and then a rapid increase with increasing
structural mobility in the glass. Therefore
mean thermal expansion coefficients are
given for a specific temperature range.
Some representative values around room
temperature are listed in Table 12-3.
The thermal coefficient of refractive in-
dex depends on the wavelength, tempera-
ture, and pressure. Examples of the varia-
 12.3 Optical Glasses 645

Table 12-3. Thermal properties of optical glasses.

Glass type x(W/mK) c p (J/gK) T<°C)

Fused silica (SiO2) 0.55 1.38 0.75 1175

Fluorophosphate (FK 54-487 865) 16.9 1.06 0.71 403
Fluorosilicate (FK 5-487 704) 10.0 0.92 0.81 464
Fluorozirconate (ZBLAN) 17.2 -0.6 0.62 265
Borosilicate (BK 7-517 642) 8.3 1.11 0.85 559
Barium silicate (SK 14-603606) 7.0 0.85 0.64 649
Alkali lead silicate (F 2-620 364) 9.3 0.78 0.56 432
Barium alkali silicate (BaFNlO-670471) 7.9 0.80 0.59 630
Lanthanum borate (LaFN2-744448) 9.1 0.67 0.48 616
Lanthanum silicoborate (LaK 9-691547) 7.6 0.91 0.65 650
Lead silicate (SF 2-648 339) 9.2 0.73 0.50 441
Lead silicate (SF 6-805 254) 9.0 0.67 0.39 423
Lead silicate (SF 59-953 204) 10.3 0.51 0.31 362
Arsenic trisulfide (As2S2) 2.6 0.17 - 163
a
Temperature range: 20-300°C.

tions with wavelength and temperature for
representative optical glasses are shown in
Figs. 12-10 and 12-11. Both positive and
negative values of dn/dT are included. In
the pressure range 0-10 5 Pa, the thermal
coefficient of refraction for a borosilicate
glass (BK 7) glass changes by «1.3 x 10~ 6 /
K at 546 nm and temperatures of 20-40 °C.
Because of its disordered atomic struc-
ture, the thermal conductivity of glass is

20

10

^ - — _
.
SF6

" —

— —
PK3

-10

I I i

400 600 800 1000 1200

Wavelength (nm)
Figure 12-10. Absolute thermal coefficient of refractive index for representative optical glasses as a function of
wavelength [from Schott (1982)].
646 12 Optical Properties of Glasses

20
I I I I

^ ^

^ ^

10

LaK10

I
•o
• — '

- — • — "
—

_
— - —
—

—_
—

—
"
BK7

"
, — - —

___ PK51
-10
I —r—" I I
-40 0 40 80
Temperature (°C)

Figure 12-11. Absolute thermal coefficient of refractive index for representative optical glasses as a function of
temperature [from Schott (1982)].

much lower than that for crystalline mate- 12.3.5 Mechanical Properties
rials. This limits its use as an optical mate-
The mechanical response of a glass to an
rial for high average power applications
applied force is described by various mod-
where linear or nonlinear absorption is
uli. Optical glass catalogs usually list mod-
present to cause heating. The thermal con-
uli such as Young's modulus E (extension
ductivity of optical glasses ranges from
in tension) and the modulus of rigidity or
about 0.5 to 1.5 W/m • K, being high for
shear G which are important for thermal
silica and low for glasses containing large
and mechanical stress determinations.
quantities of heavy elements such as lead,
These are related to Poisson's ratio pt (ratio
tantalum, barium and lanthanum. The
of lateral to longitudinal strain under uni-
thermal conductivity of glass increases with
lateral stress) by
temperature but only slightly above 300 K.
Representative values of the thermal con-
ductivity, %, and specific heat at constant (12-51)
"-SO"1
pressure and room temperature of optical
glasses are included in Table 12-3. The bulk modulus B (1/isothermal com-
pressibility) is related to the above moduli
by
-H) (12-52)
 12.3 Optical Glasses 647

Values of E and jn for glasses at room tem-
perature are included in Table 12-4.
Elastic moduli can also be expressed in
terms of the longitudinal and transverse
sound velocities and the density. Ultra-
sonic pulse-echo, Brillouin scattering, and
other methods are used to measure sound
velocities to determine elastic and photo-
elastic constants.
The hardness of a glass is an indication
of its vulnerability to surface damage and
the ease with which the glass can be pol-
ished. It is usually measured from the in-
dentation of Knoop or Vickers penetrators.
Values (Knoop) for oxide glasses range
from ~ 250 for high-lead-content glasses to
> 600 for lanthanum crown glasses. Repre-
sentative values for a variety of glass types
are summarized in Table 12-4. The Knoop
hardness generally correlates with Young's
modulus.
The stress-optical coefficient K varies
with glass type and wavelength. It is usu-
ally positive, although it can become nega-
tive (so called Pockets glasses) for silicate
glasses having a high lead content. The
stress-optical coefficient is measured in
units of 1 Brewster = (TPa)" 1 = 10~ 12 m 2 /
N. Values of K are included in Table 12-4
and generally range from —2<K<
4 T P a " 1 for oxide glasses to — 40 < K <
20 TPa" 1 for chalcogenide glasses. For
high-quality optical glass, distortions due
to stress-induced birefringence are mini-
mized by careful annealing.
12.3.6 Chemical Durability
An important consideration for many
optical glasses is their chemical reactivity
with slurries during cutting and polishing
of components such as lenses, windows,
and prisms and with its environment where
it may be subject to chemical attack by
water, water vapor, gases, acids, etc. In the
presence of water, there is dissolution of
glass and a coating develops as hydrogen
from the solution exchanges with alkali
ions in the glass. This and other forms of
corrosion, dimming, and straining occur
and vary greatly depending on the chem-
ical composition of the glass. Whereas
SiO2, A12O3, TiO 2 and La 2 O 3 resist leach-
ing by aqueous or acid solutions, alkali

Table 12-4. Mechanical properties and stress-optical coefficients at 589 nm for representative optical glasses.

Glass type (designation) Knoop hardness Stress-optical Young's modulus Poisson's ratio
(N/mm2) coefficient (103 N/mm2)
(TPa)" 1

Fused silica (SiO2) 450 3.5 70 0.170

Fluorophosphate (FK 54-487 865) 320 0.01 76 0.286
Fluorosilicate (FK 5-487 704) 450 2.91 62 0.205
Fluorozirconate (ZBLAN) 250 - 54 0.31
Borosilicate (BK 7-517642) 520 2.74 81 0.208
Barium silicate (SK 14-603606) 490 2.00 86 0.261
Alkali lead silicate (F 2-620 364) 370 2.81 58 0.225
Lanthanum borate (LaFN2-744448) 450 1.65 87 0.294
Lead silicate (SF 2-648 339) 350 2.65 55 0.231
Lead silicate (SF 6-805 254) 310 0.63 56 0.248
Lead silicate (SF 59-953 204) 250 -1.46 51 0.269
Arsenic trisulfide (As2S3) 180 -1.1 16 0.240
648 12 Optical Properties of Glasses
and alkaline earth oxides do not. Also,
B 2 O 3 and P 2 O 5 are more soluble glass net-
work formers than SiO2.
No simple test and parameter is suffi-
cient to characterize chemical reactivity
under all conditions. Thus many terms and
tests are used to rank glasses with respect
to their resistance to acids, straining, cli-
mate, weathering, etc. Glasses may be de-
scribed by several grades ranging from
those exhibiting no surface deterioration in
normal humidity conditions to those ex-
hibiting increased surface scattering within
a few hours and for which protective coat-
ings are recommended after polishing and
before storage.
Ion-exchange reactions create a surface
layer of lower refractive index. This ap-
pears as colors when the product of n and
the optical thickness becomes a multiple of
1/4 and interference occurs between the in-
cident and reflected light. Staining is a sur-
face change resulting from contact with
acidic conditions or small quantities of
slightly acidic water (e.g., perspiration). It
appears as a coloration for standard ace-
tate (pH = 4.6). Glasses range in their resis-
tance to staining from those showing virtu-
ally no interference coloring after many
days exposure to those that change color in
minutes in sodium acetate buffer (pH = 5.6).
The latter glasses require special care in
processing.
Acidic or alkali aqueous solutions also
cause decomposition of glass surfaces. The
time lapse before a layer of 0.1 jam is dis-
solved is used as a measure of acid resis-
tance. For optical glasses in 0.5 N nitric
acid this time can range from more than
100 h to only a few minutes. In sodium
hydroxide, pH 10 at 90 °C, some glasses
show no visible effects in hours whereas
other glasses show color or whitish strains
and develop coatings in a few minutes.
Manufacturers typically list several cate-
gories of acid and alkali resistance to cover
the above ranges.
12.3.7 Quality and Forms
By careful batching, processing, and an-
nealing, optical glasses can be made with
very reproducible properties. The refrac-
tive index is controlled by the rate of an-
nealing in the transformation range. Toler-
ances for nd of ±0.001-0.002 and for vd of
±0.8% are standard. Closer tolerances for
nd and vd of ±0.0002 and ±0.2% can usu-
ally be obtained by precision annealing.
The homogeneity of the refractive index is
important for imaging systems and is doc-
umented interferometrically. From select-
ed melts or selected blanks, homogeneities
of ± 1 0 " 5 - 1 0 ~ 6 are possible. At 633 nm,
the wavefront distortion after transmission
through 100 mm of a glass of index homo-
geneity 10" 6 is only 0.3 wave.
Residual stress birefringence varies with
glass size and type. For some glasses values
of < 20 nm/cm are achievable for large
( ^ l m ) diameter blanks. For smaller pieces
(~ 100 mm), values of ^ 4 nm/cm are pos-
sible by special annealing.
Striae (cords) are localized regions of
glass that differ slightly in chemical com-
position from that of the base glass. If pres-
ent, they can be observed by examining the
glass in one or more directions, depending
upon the intended use, in a shadowgraph
or Foucault knife-edge test. Other macro-
scopic defects such as bubbles or inclusions
may also be present. The total content of
inclusions above a specific dimension, e.g.,
those measuring ^ 0.05 mm, is specified by
giving their measured cross section area in
mm 2 per 100 cm3 of glass. Most glasses can
be produced virtually striae and inclusion
(bubble) free.
Optical glass is available in many forms
including (1) slabs and blocks with two or

more machined and polished faces used for
test purposes, (2) strips, rods and rolled
glass with unfinished surfaces, (3) semi-fin-
ished and pressings of some required form,
and (4) simple gobs.
Several hundred optical glass types are
available commercially. These are multi-
components glasses whose chemical com-
positions have been tailored to achieve the
range of refractive indices and other physi-
cal properties discussed above. All glass
types cannot be produced in the same sizes
or with the same quality, however. Manu-
facturers may indicate "preferred" glass
types which can be melted more easily and
obtained in the size and quality required.
12.4 Special Glasses
12.4.1 Abnormal Dispersion Glass
The partial dispersions of optical glass
are important in the design of compound
lenses. By combining a positive lens of a
crown glass with a negative lens of a flint
glass, chromatic aberration can be avoided
at two wavelengths. For such an achro-
matic lens composed of different glasses of
local lengths f1 and f2 to have the same
focal length at the wavelengths of the C
and F lines, the condition
Vid/id + v 2 d / 2 d = 0 (12-53)
must be satisfied. There will, however, be a
residual error in the intermediate wave-
length range. The difference in the focal
length of the compound lens at wave-
lengths x and y is given by the relationship
(Rawson, 1980)
, < < ( 12 " 54 )
l-V2d)
L fy
Because of the linear relationship between
the relative partial dispersions and Abbe
12.4 Special Glasses 649
number in Eq. (12-50), the difference in
partial dispersion will always be the same
for normal glasses.
Correction for second-order chromatic
aberration (secondary spectrum) is accom-
plished using glasses with equal partial dis-
persions for different Abbe values. The cor-
rected systems are called apochromats. So-
called abnormal dispersion glasses depart
from the "normal line" and the linear rela-
tionship in Eq. (12-50). Figure 12-12 plots
the relative dispersion (ng — nF)/(nF — nc) of
optical glasses and shows the magnitude of
the deviations from the normal line that
are possible. The deviations can be either
positive or negative. A glass with the same
nd and nx as a flint glass, but for which the
increase in refractive index from the blue to
the ultraviolet is steeper, is called a "short"
flint. Abnormal dispersion glasses are pro-
duced by tailoring the chemical composi-
tion of the glass so as to alter the relative
strength and positions of the ultraviolet
and infrared absorption bands of the con-
stituents and thereby change the disper-
sion.
12.4.2 Gradient Index Glass
A conventional glass lens consists of a
homogeneous material with a single index
of refraction. Imaging occurs by means of
discrete refraction at the lens surfaces. In
the design of a compound lens, the curva-
ture, thickness, and refractive index of each
element are varied to control aberrations
and curvature of the imaging field. Glass
elements, however, can also be manufac-
tured in which the index of refraction var-
ies continuously within the material. These
are called gradient index or GRIN mate-
rials. The refractive index gradient may be
axial (varying along the optical axis), radial
(varying outwardly from the optical axis),
or spherical (varying symmetrically from a
650 12 Optical Properties of Glasses
0.65
0.60
•
•
0.55
• •
•
0.50
100 80 60
v
d
Figure 12-12. Absolute thermal coefficient of refractive index for representative optical glasses as a function of
temperature [from Schott (1982)].
point) (Moore, 1980). For imaging systems,
gradient index glass provides an alterna-
tive to the generation of complex aspheric
lens surfaces to control aberrations. Gradi-
ent-index rods and fibers are used in mi-
crooptics, imaging optics, and optical fiber
communication systems (Iga et al., 1984).
In a rod or fiber having a radial index gra-
dient, light propagates in a sinusoidal fash-
ion because rays passing through the cen-
ter travel more slowly than those further
away from the optical axis.
Several techniques have been developed
to create refractive index variations in
glass. These include neutron irradiation of
boron-rich glasses such as borosilicates,
chemical vapor deposition of layers of
glass of slightly different refractive indices,
and ion exchange by immersing the glass in
an appropriate solution. These methods
differ in the size of components that can be
treated and the magnitude and gradient of
the index that can be produced. Changes in
refractive indices of An < 0.04 are achiev-
able by the above techniques (Moore, 1980).
Ion stuffing in porous glass and sol gel
•
40 20
techniques can also be used to create gradi-
ent index glass.
Production of large pieces of glass hav-
ing index variations of An ~ 0.5 has been
demonstrated (Blankenbecker et al., 1991).
The process is based on controlled fusion
of glass layers of different physical proper-
ties. Diffusion within and between layers
creates a gradual change of properties. The
smoothness of the gradient profile is a
function of the concentration gradient and
the diffusion rate of the major index deter-
mining components. In practice, powders
of different glasses are mixed in varying
proportions and layered in a mold or ho-
mogenous plates of different glasses are
fabricated and stacked together; the com-
posite material is then fused together in a
furnace to produce the gradient index ma-
terial.
12.4.3 Mirror Substrate Glass
The selection of glass for mirror sub-
strates involves many factors. For front
surface mirrors where retention of the opti-

cal figure is important, the thermal stabil-
ity of the environment is a major consid-
eration. In a temperature-controlled envi-
ronment, low-cost borosilicate glasses can
be used. If, however, the substrate is sub-
ject to temperature variations, materials
with the lowest possible coefficient of ther-
mal expansion are needed. Silica contain-
ing small quantities of titanium dioxide or
other heavy metal oxides and transparent
glass ceramics can be produced which have
extremely small, near-zero coefficients of
thermal expansion. The latter materials
(such as lithium-aluminum silicates) are
solid solutions in which the very small or
even negative thermal expansion coeffi-
cient of the crystalline phase compensates
for the positive expansion coefficient of the
remaining glass matrix. Glass ceramic mir-
ror blanks with diameters of more than
eight meters have been produced for tele-
scope mirrors, (see also Vol. 11, Chap. 5).
Because optical coatings are not 100%
reflective, some light is always transmitted
to the substrate. Thus UV-transmitting sil-
ica is used for mirrors intended for high-
power ultraviolet applications. Homoge-
neity of the glass is a consideration for
substrates for partially reflecting elements.
Variations in the chemical composition of
the glass and the presence of striae produce
spatial variations in the thermal expansion
that can result in optical distortions. Bub-
Table 12-5. Common mirror substrate glasses.
Material (supplier) Density
(g/cm3)
Fused silica (various) 2.20
ULE (Corning) 2.21
Zerodur (Schott) 2.53
Pyrex (Corning) 2.23
BK 7 (various) 2.51
12.4 Special Glasses 651
bles, if at the surface, cause coating prob-
lems. For airborne or space applications,
weight of the substrate is a factor. In all
cases, fabrication - the ease of grinding and
polishing the mirror - is an additional con-
sideration.
Properties of several low-expansion
glasses used for mirror substrates are listed
in Table 12-5. Barnes (1979) gives more de-
tailed descriptions of the properties of sub-
strate glasses and compares them with
other insulating materials and metals.
12.4.4 Optical Filter Glass
Transmitting filter glasses change the
spectral properties of optical radiation and
provide selective filtering for scientific and
technological applications, for color en-
hancement in ophthalmic lenses, and for
contrast enhancement in displays. Filters
are categorized as band passing and band
blocking filters, short-wavelength and long-
wavelength cutoff filters, and neutral den-
sity and color conversion filters. The trans-
mission characteristics are determined by
a combination of the base glass and ion
doping or colloidal coloration (Cook and
Stokowski, 1986).
As can be seen from Figs. 12-7 and 12-8,
the UV and IR cutoff wavelengths vary
greatly depending on the glass composi-
tion; thus the composition can be tailored
Thermal expansion Hardness Stress-optical
coefficient (Knoop) coefficient
(KTVKT 1 ) (TPa" 1 )
0.55 450 3.5
0.03 460 4.0
0.10 630 3.0
3.2 418 3.9
8.3 520 2.7
652 12 Optical Properties of Glasses
to achieve selected transmission character-
istics. Other cutoff and bandpass filters are
produced by doping with transition metals
(Ti3 + ' 4 + , V3 + , Cr 3 + , Mn 3 + , Fe 2 + ' 3 + ,
Co 2 + , Ni 2 + , Cu 2 + ), rare-earths (Ce3 + ' 4 + ,
Pr 3 + ,Nd 3 + ,Sm 3 + ,Eu 2 + ,Ho 3 + ), and ura-
nium (U6 + , [UO 2 ] 2+ ). The 3 d - 3 d transi-
tions of iron group ions generally produce
broad absorption bands. The 4f-5d tran-
sitions of the rare-earths are also broad,
whereas the 4f-4f transitions are nar-
rower and provide more selective filtering
(Bamforth, 1977).
The fundamental absorption edge of
semiconductor-doped glasses depends on
the size and absorption characteristics of
the colloidal particles. By careful heat
treatment and processing of Cd(S, Se) and
CdTe doped silicate and borosilicate
glasses, a series of long pass filters can be
manufactured with sharp cutoff wave-
lengths varying over a wide spectral range
in the visible and near infrared. The wave-
length Xc of the absorption edge of these
colloidally-colored filters increases with
temperature; values of d/l c /dT<0.4nm/K
are typical.
Glass can also be colored by the incor-
poration of metallic particles, such as the
~ 5 nm gold spheres in ruby glass. Metal-
doped glasses are much more limited in
their use as optical filters.
Optical filter glass, like other optical
glasses, is manufactured in high optical
quality, free of striae and inclusions, and in
a variety of forms. Transmission is carefully
controlled. Filter glass catalogs present ex-
tensive data on transmittance; data on re-
fractive index and other thermal and me-
chanical properties and chemical durabil-
ity are also listed. To define the color, the
chromaticity coordinates x and y of the
color focus, the dominant wavelength 2 d ,
the color saturation Pe, and the photooptic
transmission Y are specified for three light
types: a Planck black body at 2856 K (light
from an incandescent bulb), a Planck black
body at 3200 K (halogen lamp light), and
standard daylight (D 65). These conform to
the Commission Internationale d'Eclairage
(CIE) standard colorimetric system (Fan-
derlik, 1983).
Under prolonged exposure to high-in-
tensity ultraviolet radiation, some filter
glass may solarize and exhibit reduced
transmission, particularly at shorter wave-
lengths. Some ionically or colloidally col-
ored glasses also exhibit photolumines-
cence (Turner, 1973).
12.4.5 Nonlinear Glass
Optical nonlinearities in glass arising
from the Kerr effect are of interest in two
extremes: in high power lasers where glass
with a small nonlinear refractive index n2
is desired to reduce self-focusing and opti-
cal damage, and in all optical switching
devices where glass with a large n2 is de-
sired to minimize the optical power re-
quirements. The magnitude of the optical
Kerr effect is known for a wide range of
undoped and doped glasses (Borrelli and,
Hall, 1991; Vogel et al., 1991) and, given a
glass composition, reasonable estimates of
the nonresonant n2 can be made. Although
there is a wavelength dispersion of n2, most
measurements have been made in the long-
wavelength limit where hcop Eg.
Nonlinear Refractive Index
Glasses with small values of linear re-
fractive index and dispersion generally
have small n2 values (Adair et al., 1987).
Accurate first-principles calculations of
nonlinear indices of glasses are not possi-
ble; however, estimates of the nonresonant
n2 can be obtained from the linear index
 12.4 Special Glasses 653

1
I ' i ' 1 1 i

-
Oxide
glasses^
\ X \
\
\\
/

1.8 -

-
\

X
/
\\ /
\
20 "
Fluoride /
V
glasses -
1.6 - -
\
\ \ ^ / \
N
10
X^^+
N \

X
X \
y C sio2 N
5
N
1.4 — —
X ^ ^ 3

- / ^
x -
^ 1 n 2 (i<r 2 °m 2 /W)
BeF2
1 0 i I 1 I
100 80 60 40 20
Abbe number ud
Figure 12-13. Oxide and fluoride glasses on an nd — vd diagram with lines of constant nonlinear refractive index
coefficient n2 predicted from Eq. (12-55).

and dispersion via the expression (Boling
et al, 1978)
K(nd-l)(nj
n1 =-
where K is an empirical constant obtained
from a fit to experimental data (Weber
etal., 1978 a; Adair et al, 1987). Lines of
constant n2 predicted from Eq. (12-55) are
plotted as a function of nd and vd in Fig.
12-13 and are superimposed on regions
of known oxide and fluoride glasses. For
these glasses n2 can be estimated from Eq.
(12-55) with an accuracy of ~ 10-20%.
The equation is not generally applicable to
chalcogenide glasses.
The smallest linear and nonlinear refrac-
tive indices for glass occur for simple BeF2
(Weber et al, 1978 b). The addition of alkali,
alkaline earth, and aluminum fluorides pro-
duces durable fluoroberyllate glasses with
only a small increase in n2 and with excel-
lent ultraviolet transmission (Dumbaugh
and Morgan, 1980). Comparing Figs. 12-6
(12-55)
+ 2] and 12-13, fluorozirconate glasses have
significantly larger n2 values than fluoro-
beryllate glasses and overlap the lower in-
dex region of oxide glasses. The refractive
indices of halide glasses increase when the
network former anion is changed in the
series F < Cl < Br < I.
Simple SiO 2 has the smallest linear and
nonlinear refractive indices of the oxide
glasses. These values increase as modifier
ions are added. For laser applications
where lower n2 values are needed, oxygen
can be replaced in part by fluorine to re-
duce n2 (e.g., in fluorophosphate glass).
For all-optical switching devices, mate-
rials are sought having a large n2 and a
small absorption loss coefficient at the
operating wavelength. Hall et al. (1989)
has established an upper limit of n2 ~
10~ 1 8 m 2 /W for oxide glasses containing
654 12 Optical Properties of Glasses
heavy metal ions (Pb, Bi). Although high
purity silica has a much lower n2 value, it
has the best overall figure of merit for this
application due to its extremely low ab-
sorption (Vogel, 1989).
Doped Glass
Very large resonant optical nonlineari-
ties are observed in doped glasses. Jain and
Lind (1983) showed that enhanced reso-
nant third-order optical nonlinearities
could be obtained in semiconductor-doped
glasses (colloidally-colored filter glass),
where n 2 - 1 0 ~ 1 4 m 2 / W , x ( 3 ) - 1 0 - 8 - 1 0 - 9
esu, and response times were <10~ 1 1 s.
The nonlinear behavior appears as intensi-
ty-dependent changes in absorption and
refractive index originating from the gener-
ation of a short-lived free electron plasma
and band filling effects. The size of the
semiconductor microcrystals in the glass
affects the linear and nonlinear optical
properties due to quantum confinement ef-
fects (Borrelli et al., 1987; Potter and Sim-
mons, 1988). Very strong dispersion and a
change in sign of n2 are observed in the
vicinity of the band gap of these materials
(Olbright and Peyghambarian, 1986). Semi-
conductor doped glasses have included
I-VII [CuCl, CuBr, Ag(Cl,Br,I)] com-
pounds, II-VI [CdS, CdSe, C d S ^ S e ^ ,
CdTe] compounds, and III-V compounds
(Vogel etal., 1991).
Organic dye molecules have intense
singlet-singlet transitions and have been
added to low-melting-point glasses such as
boric-acid glass (Kramer et al., 1986) and
lead-tin fluorophosphate glass (Tompkin
etal., 1987) without decomposition. Satu-
ration of the ground state absorption of the
dye produces optical nonlinearities with
very large effective x(3) ~ 1 esu. Because the
response time is governed by the relaxation
time of the triplet state of the dye, recovery
of the saturated nonlinearity is very slow
compared to that of nonresonant elec-
tronic nonlinearities.
Glasses containing very small metallic
particles also exhibit an efficient, fast opti-
cal Kerr effect with x(3) ~ 10" 8 esu. A large
enhancement of the intrinsic x(3) of the
metal arises from a surface-mediated plas-
mon resonance effect analogous to surface-
enhanced Raman scattering (Hache et al.,
1986).
12.4.6 Laser Glass
A large number of different lasing ions
and host glasses have been used for glass
lasers (Patek, 1970). Table 12-6 summa-
rizes the dopant ions, representative of
lasing wavelengths (the exact wavelength
varies with host), and host glasses that
have been reported (Hall and Weber, 1991).
Fluorescence sensitizing ions are some-
times added to the glass to improve the
optical pumping efficiency. The forms used
for laser glasses include bulk, fibers, and
planar waveguides.
Thus far all glass lasers have used triva-
lent lanthanides as the active ion. Figure
12-14 shows the 4 f electronic energy levels
and transitions for which stimulated emis-
sion has been observed. The spectral range
of glass lasers extends from ~ 0.5 to 3.0 }im;
this is smaller than the ~ 0.2-5.0 |im range
of crystalline lasers (Weber, 1991). The
spectral range of glass lasers can undoubt-
edly be expanded by the use of appropriate
ions and transitions in wide-band-gap
fluoride glasses or fused silica as hosts
for the ultraviolet and in heavy metal ha-
lide or chalcogenide glasses as hosts for
the infrared. Because the optical spectra of
ions in glass are inhomogenously broaden-
ing, glass lasers provide some tunability
(<10%) that is not possible in crystalline
hosts.

Table 12-6. Rare-earth glass lasers and representative lasing wavelengths (from Hall and Weber, 1991).
Ion Wavelength (um)
Cu+b 0.56-0.58, 0.63
Pr 3 + 0.61, 0.64, 0.70, 0.72, 0.91, 0.89, 1.08, 1.31
Nd 3 + 0.93, 1.06, 1.34
Pm 3 + 0.93, 1.10
Sm3 + 0.65
Tb 3 + 0.54
Ho 3 + 0.55, 0.75, 1.38, 2.05, 2.9
Er 3 + 0.85, 0.99, 1.55, 1.66, 1.72, 2.75
Tm3 + 0.46, 0.48, 0.82, 1.48, 1.51, 1.88, 2.25
Yb 3 + 1.03
Organic dyes b -0.53-0.65
a
Form of the laser glass: b - bulk, f - fiber, w - planar waveguide.
b
Optical gain rather than laser oscillation was observed.
The spectroscopic properties important
for laser action vary with the chemical
composition of the host (Jacobs and We-
ber, 1976). These include absorption and
stimulated emission cross sections, ho-
mogeneous (natural) and inhomogeneous
linewidths, and radiative and nonradiative
transition probabilities. An extensive data-
base exists of spectroscopic properties as-
sociated with the 4 F 3/2 -> 4 Iii/2 transition
of Nd 3 + (Weber, 1990). The stimulated
emission cross section, for example, can
vary by one order of magnitude depending
upon the host glass. This arises from com-
bined changes in the oscillator strength of
the transition, the linewidth, and the re-
fractive index of the host. From systematic
compositional studies, rules can be derived
for tailoring laser parameters. The varia-
tions in spectroscopic properties observed
for Nd 3 + usually also apply to other triva-
lent rare-earth ions.
In contrast to the large number of exper-
imental laser glasses listed in Table 12-6,
12.4 Special Glasses 655
Host glassa
Aluminoborosilicate (b), fluorohafnate (b)
Silica (i), fluorozirconate (f)
Silica (b, f), silicate (b, f, w), borosilicate (w),
phosphate (b, f, w), germanate (b), tellurite (b),
fluoroberyllate (b), fluorophosphate (b),
fluorozirconate (f)
Phosphate (b)
Silica (f)
Borate (b)
Silica (f), silicate (b), fluorozirconate (f)
Silica (f, w), silicate (b), phosphate (b, f),
fluorophosphate (b), fluoroaluminate (b),
fluorozirconate (b, f)
Silica (f), silicate (b), fluorozirconate (b, f)
Silica (f), silicate (b), borate (b)
Silica (b)
commercial laser glasses are almost exclu-
sively silicates and phosphates. Fluoro-
phosphate glasses have also been devel-
oped for applications requiring low n2
values (Neuroth, 1987). Phosphate glasses
generally have narrower linewidths and
for ultraphosphates have less fluorescence
concentration quenching than for silicate
glasses, thus they are more appropriate for
applications requiring high gain and effi-
cient energy extraction (Marion and We-
ber, 1991).
Laser glass shares with optical glass the
requirements of refractive index homoge-
neity (variations <10~ 6 ), high purity (ab-
sorption coefficient at the lasing wave-
length of <10" 3 cm~ 1 ), freedom from
bubbles and striae, low birefringence
(< 5 nm/cm), good chemical durability,
and capacity of being finished to high opti-
cal tolerances (A/20). High-quality phos-
phate laser glasses satisfying these require-
ments have been produced with dimen-
sions greater than 0.5 m.
 30

1.51
25

_ ~ 20
W O

1.38 11

1.66 II

0.46
0.85 I
1.72 I

0.48
u

0.75

ess
2
• H,
o

|
X 15 o
1 \f u
f CD

2.25
10 f

2.75
f

1.48
V r^

2.9
f
f
F
4 5

0.99

1.55

1.88

0.82
2.05
}f f

| _
t

••H. \
^H6

Pr 3+ Nd 3 + Pm 3 + Sm3+ Tb 3 * Ho 3 + Er 3+ Tm 3 * Yb 3

Figure 12-14. Energy levels and transitions of trivalent rare earth glass lasers. Typical transition wavelengths are given in microns.

Thermooptic properties control the
beam quality of flashlamp-pumped, high-
average-power lasers. A thermal phosphate
glasses have been developed in which the
change of optical pathlength with tempera-
ture dS/dT^O (Izumitani, 1986). Fracture
of the laser glass from thermally induced
stress is a primary limitation on perfor-
mance (Marion, 1986). A thermomechani-
cal figure of merit for the fracture resis-
tance of a large plate of isotopic mate-
rial that absorbs light and is convectively
cooled on its major faces is
RT = Kcx(l~fi)/(xE (12-56)
where Kc is the fracture toughness (MPa/
m 1/2 ). The fracture toughness is a measure
of the inherent resistance of the glass to
crack propagation and is determined ei-
ther by direct crack measurements or from
the indentation produced by a microhard-
ness tester, but the accuracy is usually not
very high. As evident from Eq. (12-56), the
intrinsic resistance of a laser glass to frac-
ture can be increased by increasing the
thermal conductivity, decreasing Poisson's
ratio, and reducing the thermal expansion
coefficient and Young's modulus.
12.4.7 Faraday Rotator Glass
The rotation of the plane of polarization
of light propagating through a glass paral-
lel to an applied magnetic field, the Fara-
day effect, has been utilized in the construc-
tion of fast optical switches, modulators,
circulators, isolators, and sensors for mag-
netic fields and electric currents. Diamag-
netic and paramagnetic glasses have been
used in bulk and fiber forms for these ap-
plications. To minimize the magnetic field
and length of material needed to produce a
given rotation, the Verdet constant should
be as large as possible. For uniformity of
rotation and isolation, the Faraday rotator
12.4 Special Glasses 657
glass must also be optically homogeneous
and free of birefringence. In high-power la-
ser applications, the nonlinear refractive
index and optical damage threshold are
further considerations. Thus the stringent
requirements characteristic of optical and
laser glasses are usually also applicable to
Faraday rotator glasses.
The largest diamagnetic Verdet con-
stants are found for high-index, high-dis-
persion glasses located in the upper right-
hand corner of Fig. 12-6. Oxide glasses
containing cations with large, easily polar-
izable outer electron shells, such as Te4 + ,
Bi 3 + , and P b 2 + network formers and Tl + ,
In 3 + , Sb 3 + , La 3 + , Ti 4 + , Nb 5 + , and Ta5 +
network modifiers have large Verdet con-
stants (Borrelli, 1964). Of the nonoxide
glasses, beryllium and aluminum fluorides
exhibit little dispersion and hence have
corresponding small Verdet constants. At
the other extreme, chalcogenide glasses
have very high dispersion and large Verdet
constants and are appropriate for use in
the infrared (Stepanov, 1974). Since the
diamagnetic Verdet constant varies at I/A2
in the long wavelength limit hc/A<^Eg,
Vdia is increased by selecting materials for
which operation is nearer the fundamental
band gap energy. If, however, the material
figure of merit for the applications is VdiJa,
then the wavelength dependencies of both
Fdia and the absorption coefficient a must
be considered. The Verdet constants of
several representative glasses are given in
Table 12-7. The temperature dependence
of Fdia is very small which makes diamag-
netic glasses attractive for high-stability
Faraday effect sensors. Measured values
of (dV/dT)/V for SiO 2 , BK 7, and SF 57
glasses are approximately 10~4/K (Wil-
liams et al., 1991).
The magnitude and the wavelength and
temperature dependences of paramagnetic
Verdet constants vary depending upon the
658 12 Optical Properties of Glasses

Table 12-7. Verdet constants of glasses (at 633 nm and 300 K).

Diamagnetic Paramagnetic

Glass F(rad/Tm) Glass Ion F(rad/Tm)

Arsenic trisulfide _ 74 Borosilicate (FR-5) Tb 3 + -71

Lead-bismuth gallate - 42 Metaphosphate Tb 3 + -54
Lead silicate (SF 59) 20 29 Metaphosphate Pr 3 + -40
Alkali silicate (F2) 36 11 Fluorophosphate (FR-7) Tb 3 + -35
Borosilicate (BK 7) 64 4.1 Phosphate (FR-4) Ce3 + -31

choice of the paramagnetic ion. For lan-
thanide series ions Faraday rotation in-
volves 4P-4f"~ 1 5d electric-dipole tran-
sitions, therefore ions with low-lying 5d
states such as Ce 3 + , Tb 3 + , and Eu 2 + have
large F para . These ions also have large re-
gions of transparency in the visible-near
infrared region. Because Fdia and Fpara have
opposite signs, the best host glasses are
those having low dispersion (therefore
small Fdia) and capable of incorporating
large quantities of the paramagnetic ion.
Values of Fpara for several rare-earth con-
taining glasses are included in Table 12-7.
The wavelength dependence of Fpara is
also I/A2 at long wavelengths. Near sharp
resonances Vpara is enhanced and changes
sign as the wavelength of the incident light
passes through the resonance (Collocott
and Taylor, 1978). Except for very low tem-
peratures (T<20K), Fpara varies as 1/T
and hence is increased by operating at low
temperatures. A figure of merit for Faraday
rotator materials used in high power lasers
where self-focusing is important is V/n2. As
evident from Figs. 12-6 and 12-13, low-in-
dex fluoride glasses are attractive hosts for
paramagnetic ions for this application be-
cause both Fdia and n2 are small.
12.4.8 Acoustooptic Glass
Acoustic waves create a time-varying re-
fractive index grating in a material via the
photoelastic effect. The grating spacing is
equal to the acoustic wavelength; the grat-
ing depth is determined by the drive power
of the transducer. A light beam traversing
the medium is deflected by the grating at
the Bragg angle <9B from the normal to the
sound propagation direction given by
1 k
(12-57)
17
where X and A are the wavelengths of the
light and sound beams. This phenomenon
provides fast deflection or modulation of
light and is used in display technology.
The diffraction efficiency for a trans-
ducer of height H and interaction length L
is (see, for example, Gottlieb, 1986)
K2 L P, n6 2\l/2
(12-58)
7
V*J
where Pa is the acoustic power, p is the
photoelastic constant, Q is the density, and
v is the sound velocity. Thus an acousto-
optic material, in addition to having low
losses at the acoustic and optical wave-
lengths, should also have a large index of
refraction and small sound velocity. These
include materials containing heavy cations
such as lead silicate or tellurite glasses and
chalcogenide glasses. From Eq. (12-58), a
figure of merit for an acoustooptic mate-
rial is
n6p2
M = (12-59)
QV3

Table 12-8. Properties of acoustooptic glasses (from Gottlieb (1986) and Izumitani (1986)).
Material Transmission range Refractive index
(urn)
Fused silica (SiO2) 0.2 - 4.0
Lead silicate (SF 59) 0.46- 2.5
Tellurite(AOT5) 0.47- 2.7
TeO2 (crystal) 0.35- 5 2.26
Arsenic trisulfide (As2S3) 0.6 - 1 1
L - longitudinal wave, S - shear wave.
a
Figure of merit M = n6 P2/QVZ relative to that of SiO 2 .
Properties and figures of merit for several
glasses are compared in Table 12-8. The
selection of glass also depends upon the
operating wavelength. Compared to crys-
tals, glasses are attractive because they are
isotopic and can be prepared in large sizes
of excellent optical quality.
12.4.9 Radiation Detection Glass
Glass is used in two forms for detection
of high energy radiation and particles: as a
pure glass for the generation of Cerenkov
radiation by energetic particles and as a
doped glass for scintillation caused by X-
rays, gamma rays, charged particles, and
neutrons. If a particle travels through of
medium of refractive index n at a speed
greater than that of light (c/n\ Cerenkov
radiation is created. Since the Cerenkov
radiation is in the blue-violet, for the radi-
ation to be detected the glass must main-
tain good transparency in this spectral re-
gion. Large blocks of optical glass having a
high refractive index, rc^l.7 are used in
Cerenkov counters capable of detecting
particles traveling at 0.6 of the speed of
light in vacuum.
High energy particles and ionizing radi-
ation are detected by scintillation from
glass activated by a fluorescing species
12.4 Special Glasses 659
Sound velocity Relative
(0.633 urn) (km/s) Ma
1.46 5.96 1.0
1.95 3.20 12.6
2.09 3.40 21.5
4.20 (L) 22.8
0.616 (S) 525
2.61 2.6 256
(transition metal ion, organic dye, molecu-
lar group, etc.). Absorption causes core
level excitations followed by secondary ra-
diation and relaxation processes. These
lead to the creation of large numbers of
electron-hole pairs, subsequent excitation
of the activator, and fluorescence which is
detected by a photomultiplier tube or other
appropriate detector. Scintillation glasses
are available in bulk form for energy
calorimetry and in fiber form for particle
tracking.
Scintillation glass is produced by doping
glass with ions such as those used for phos-
phors and lasers. The fluorescence effi-
ciency for excitation by ionizing radiation,
however, is not the same as for optical radi-
ation. The development of scintillation
glass was pioneered by Ginther (Ginther
and Schulman, 1958; Ginther, 1960).
Among the glasses investigated were ce-
rium-activated lithium-magnesium-alu-
minum silicate glass. Variants of this glass
are still currently in use. The 5 d -> 4 f tran-
sition of Ce 3 + provides fluorescence at
~ 400 nm which is well matched to the
peak spectral sensitivity of photocathodes.
Because the absorption of Ce 4 + overlaps
the emission of Ce 3 + , the glasses are pre-
pared under reducing conditions to keep
the cerium in the trivalent state. The com-
660 12 Optical Properties of Glasses
position of the host glass affects the stop-
ping power and overall detection effi-
ciency. Cerium-activated glasses contain-
ing large quantities of BaO to increase the
density have been investigated for elec-
tronic and hadronic calorimetry (Bross,
1986).
Cerium-activated glass is also used for
neutron detection where 6 Li is the neutron
sensitive component (Spowart, 1976,1977).
6
Li interacts with a neutron to produce a
2.72 MeV triton and a 2.04 MeV alpha
particle; these lead to excitation of the
Ce 3 + fluorescence. Scintillation glasses are
produced with lithium present in its natu-
ral isotopic abundance, as enriched 6Li
(95%), or depleted (99.9% 7Li); weight per-
centages are in the range 2.5-7.5%. The
Ce 3 + fluorescence decay from these glasses
consists of a fast component (~ 20 ns) and
a slow component (~60ns). Longer life-
time decay(s) associated with trapping cen-
ters may also be present in scintillation
glass. The inertness of the glass to radia-
tion damage (color center formation) is im-
portant for use in high radiation intensity
environments.
Trajectories of highly ionizing charged
particles can be recorded in glass and re-
vealed by etching with concentrated hy-
drofluoric acid or sodium hydroxide to re-
move material selectively along the track.
The half-angle of the resulting cone-shaped
etchpit is a measure of the ionization rate
of the particle. Of the many glasses in-
vestigated for this application, phosphate
glasses provide the greatest sensitivity
(etching rate along the particle trajectory
to general etching rate) and the highest
charge resolution (Wang et al., 1988).
Among the uses of these glasses are identi-
fication of the mass and atomic number of
relativistic heavy cosmic rays and high res-
olution studies of relativistic heavy nuclei
at accelerators.
Phosphate glasses containing cobalt or
silver are used for personnel dosimeters.
When exposed to radiation, the cobalt
containing glass becomes colored due to
the formation of color centers. Irradiation
of silver phosphate glass produces silver
particles. The fluorescence stimulated by
ultraviolet radiation of the glass is then
used to measure the radiation dose.
12.4.10 Radiation Shielding Glass
Glass is used for remote viewing of radi-
ation environments such as X-ray facilities,
hot cells in nuclear research, irradiation
facilities for food preservation, and medical
sterilization and therapeutic installations.
In these applications the optical glass must
provide both adequate shielding and not
discolor during exposure to the radiation.
High-lead-content glasses are used for ra-
diation shielding glass. These glasses have
about one-half the absorption of lead of
comparable thickness.
When normal fused silica and multi-
component glasses are exposed to ionizing
radiation and high energy particles, charge
carriers and a variety of atomic defects are
produced. This results in electronic (charge
rearrangement) damage and, if the parti-
cles have sufficient momentum, atomic or
ionic displacement damage (Williams and
Friebele, 1986). Coloration (browning) of
optical glass begins at radiation doses
of ~10 2 Gy and becomes very dark at
~ 5 x l O 4 G y . Radiation-resistant glasses
have been developed to overcome this col-
oration. This is accomplished by the intro-
duction of a small quantity of polyvalent
ions that act as electron acceptors and re-
duce the probability for generating stable
color centers. A commonly used ion is
cerium which is added as CeO 2 in the
range of 0.3-3.0 wt.%.

12.4.11 Photosensitive Glass
Photosensitive glasses are a special class
of glasses whose optical properties are
changed by optical/thermal treatment.
Among these are photochromic glasses
that change color under ultraviolet or
short wavelength light, then revert back to
the original state when the light is reduced.
In ophthalmic and architectural applica-
tions, the transmission of such glasses in
the 400-700 nm region can be reduced by
more than 50% when exposed to bright
light.
Photochromism is observed in strongly
reduced alkali silicate and other multicom-
ponent silicate and borosilicate glasses, in
glasses containing suspensions of crystal-
lites, and in glasses colored by silver
halides (Araujo, 1977). Transparent pho-
tochromic glasses are produced by starting
with a homogenous glass containing dis-
solved silver and halide ions, then heating
it to precipitate the silver halide (Stookey
etal, 1978; Mauer, 1958). Many different
base glasses can be used; the choice of com-
position, especially the halide, and ther-
mal treatment influence the photochromic
properties. The large range of possible
compositional variations and careful con-
trol of the thermal treatment result in a
wide range of transmission spectra, rates of
color induction, and recovery times.
The mechanisms involved in pho-
tochromism are complex and include treat-
ment of precipitation kinetics and charge
carrier diffusion (Araujo, 1977). Using
small-particle scattering theory, the color
variation in polychromatic glasses are at-
tributed to the specific geometric shape of
the silver on the alkali halide monocrystal
(Borrelli et al., 1979).
Another example of a photosensitive
glass is lithium silicate glass containing
CeO 2 as an optical sensitizer and silver,
12.5 Future 661
gold, or palladium oxide as nucleating
agents. This glass photonucleates when
subjected to ultraviolet or ionizing ra-
diation via the process Ce 3 + +hv -*
Ce 4 + -f e~, followed by heating and diffu-
sion of the electron to a nearly silver ion
where Ag + +e~->Ag°. Upon further heat
treatment Ag° atoms agglomerate to form
silver colloids. These are dispersed through
the glass and act as nucleation sites for
crystal growth which proceeds upon heat-
ing at higher temperatures. Because crys-
tallization occurs only in areas exposed to
the ionizing radiation, spatially selective
chemical machining, photo engraving, and
photographs are possible, (see Vol.11,
Chap. 5).
As noted in Sec. 12.4.10, most glasses are
photosensitive in the negative sense that
they become colored (solarize) after expo-
sure to ultraviolet or ionizing radiation. To
prevent solarization in optically-pumped
laser glass and in glass used for UV lamps
(e.g., xenon and mercury lamps), small
quantities (<1%) of polyvalent ions such
as cerium, antimony, and molybdenum are
added. Solarization is also associated with
changes in the valence state of transition
metal ions. Examples of such reactions in-
clude Mn 2 + +/iv-+Mn 3 + +e~~, F e 3 + + e "
-> Fe 2 + , and Eu 2 + + T i 4 + -+ Eu 3 + +Ti 3 + .
12.5 Future
A history of the chemical composition of
optical glasses shows significant evolution
during the past century (Marker and
Scheller, 1988). Demands continue, how-
ever, for optical glasses with extended
transmission in the infrared or ultraviolet,
improved mechanical properties and ease
of fabrication, lighter weight, better chemi-
cal durability, and composed of less costly
or less hazardous raw materials. In recent
years, efforts have been devoted not only to
662 12 Optical Properties of Glasses
seeking new and improved optical glasses
with a wider range of properties, but
to maintaining existing glass properties.
Health and environmental concerns have
necessitated reformulating optical glass
compositions while still maintain their po-
sitions in the glass map. For example, ra-
dioactive thorium oxide has been replaced
by yttrium, gadolinium, and ytterbium ox-
ides and cadmium oxide by zinc and nio-
bium oxides. Elements such as beryllium,
which have several attractive properties for
glass, are not used commercially because of
the hazards associated with their use.
There are also concerns about heavy
metals such as lead, arsenic, antimony, and
mercury.
Although the compositional space of
glass-forming systems has been widely ex-
plored and exploited (Izumitani, 1986),
new glass compositions tailored to opti-
mize a property(s) for specific applications
continue to appear. These developments
occur empirically, guided by past investi-
gations and observations. Our ability to
perform reliable ab initio calculations of
physical and optical properties of simple
glasses, let alone complex, multi-compo-
nent compositions, is still very limited and
is expected to remain so for some time
(Weber, 1990).
Today the search for and selection of
optical glasses can be done using comput-
erized databases of glass compositions and
properties (Suzuki, 1991). With these, one
has ready access to the complete glass map,
partial dispersions, and numerous other
properties. As a further boon to the optical
designer, software is available to create new
glass maps composed of selected glasses
satisfying particular property criteria. Ex-
pert systems are also being used to derive
multicomponent compositions of glasses
having desired physical properties (Ma-
kishima, 1991).
12.6 Acknowledgement
Work performed under the auspices of
the U.S. Department of Energy by
Lawrence Livermore National Laboratory
under Contract W-7405-ENG-48. Refer-
ence herein to any specific commercial
products by trade name, trademark, manu-
facturer, or otherwise does not necessarily
constitute or imply its endorsement, rec-
ommendation, or favoring by the United
State Government or the University of
California.
12.7 References
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and Technology Vol. 12: Tomozawa, M., Doremus,
R. H. (Eds.). New York: Academic Press, p. 91.
Adair, R., Chase, L. L., Payne, S. A. (1987), J. Opt.
Soc. Am. B4, 875.
Bagley, B. G., Vogel, E. M., French, W. G., Pasteur,
G. A., Gan, J. N., Tauc, X (1976), /. Non-Cryst.
Solids 22, 423.
Bamforth, C. R. (1977), Color Generation and Control
in Glass. Amsterdam: Elsevier.
Barnes Jr., W. P. (1979), in: Applied Optics and Opti-
cal Engineering Vol. 7. New York: Academic Press,
p. 97.
Bartholomew, R. F. (1982), in: Treatise on Materials
Science and Technology Vol. 22: Tomozawa, M.,
Doremus, R. H. (Eds.). New York: Academic
Press, p. 75.
Becquerel, H. (1897), Compt. Rend. 125, 679.
Behrens, E. G., Powell, R. C , Blackburn, D. H.
(1990), /. Opt. Soc. Am. B 7, 1437.
Bendow, B. (1973), Appl. Phys. Lett. 23, 133.
Bendow, B. (1977), Ann. Rev. Mater. Sci. 7, 23.
Blankenbecker, R., Hagerty, J. X, Pulsifer, D. N.,
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13 Mechanical Properties of Glasses
Rolf Bruckner

Technische Universitat Berlin, Anorganische Werkstoffe, Berlin,

Federal Republic of Germany

List of Symbols and Abbreviations 667

13.1 Introduction 669
13.2 Glass as an Elastic Solid Material 669
13.2.1 Elastic Properties of Glasses 669
13.2.1.1 Fundamentals 669
13.2.1.2 Composition Dependence 670
13.2.1.3 Temperature Dependence 672
13.2.1.4 Dependence on Thermal and Mechanical Prehistories 673
13.2.2 Inelastic Properties of Glasses 675
13.2.2.1 Densification 675
13.2.2.2 Mechanical Losses 675
13.3 The Phenomenon of Uncontrolled Brittle Fracture 678
13.3.1 Theoretical and Practical Strength 679
13.3.1.1 Theoretical Strength 679
13.3.1.2 Real Strength: Griffith's Theory 679
13.3.2 Fracture Mechanics 681
13.3.2.1 Energy Balance 681
13.3.2.2 Fractography and Crack Velocity 683
13.3.3 The Phenomenon of the High Strength of Glass Fibers 686
13.4 Controlled Fracture Propagation and Time Dependent Phenomena 688
13.4.1 Subcritical Crack Propagation 690
13.4.2 Fatigue and Lifetime 691
13.4.2.1 Static Fatigue 691
13.4.2.2 Lifetime and Proof Test 693
13.4.2.3 Dynamic Fatigue 694
13.5 Techniques for Increasing Strength and Toughness of Glasses 694
13.5.1 Strengthening by Thermal Tempering 695
13.5.2 Chemical Strengthening 696
13.5.3 Fiber-Reinforcement of Glasses 697
13.6 Mechanical Behavior Above the Glass Transition Temperature 698
13.6.1 High-Temperature Strength 699
13.6.1.1 High-Temperature Strength as a Surface Property 699
13.6.1.2 High-Temperature Strength as a Volume Property 699
13.6.2 Non-Linear Relaxation Behavior 701
13.6.3 Non-Newtonian Flow Behavior 704

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
666 13 Mechanical Properties of Glasses

13.7 Further Properties 705

13.7.1 Microhardness 705
13.7.1.1 Indentation Process and Phenomena 705
13.7.1.2 Influence of Chemical Composition 706
13.7.1.3 Temperature Dependence and Thermal Prehistory 706
13.7.2 Stress-Optical Coefficient 707
13.7.2.1 Stress-Optical Coefficient within the Elastic Range of Glass 707
13.7.2.2 Stress-Optical Coefficient within the Viscoelastic Range 708
13.8 References 709
 List of Symbols and Abbreviations 667

List of Symbols and Abbreviations

a length
A crack propagation parameter
b broadness
c spring back value
C
P specific heat
C stress-optical coefficient
D relative distribution of the tensile strength
E Young's modulus
Et specific elastic factor for the i-th oxide
£(0 m ax relaxation modulus
/ factor
F load in Newtons
Fz drawing force
G shear modulus
Gi specific fracture energy
GSp specific fracture energy
h deformation rate
k Boltzmann constant
K compression modulus
Kad adiabatic compressive modulus
Kiso isothermal compressive modulus
Ki stress intensity factor for mode I
Klc critical stress intensity factor for mode I
I length
Mt molecular weights
m mass flow
An birefringence
N interference order
Pi content of z-th oxide in wt.% or in mol%
Q activation energy
r distance
r mean atomic distance
t time
T absolute temperature
% surface temperature
interior temperature
TD drawing temperature
Te glass transition temperature
U dissociation energy
*>\ longitudinal sound velocity
V{ fracture or crack velocity
v, specific factors calculated from the ionic radii
v, package density of the ions
668 13 Mechanical Properties of Glasses

p cubic thermal expansion

y shear or torsion angle
y surface energy
5 relative path difference
Kronecker symbol
£ deformation tensor
n viscosity
compressibility
X wavelength
Poisson ratio
V free surface energy
Q density of the glass
Q density
L stress tensor
o tensile or compressive stress
amplitudes
applied stress
pre-stress
working stress
strength under inert environment
^ax axial compressive stresses
T relaxation time
T shear stress
phase angle
CD frequency

ht high temperature
MH microhardness
MHK Knoop microhardness
MHV Vickers microhardness
 13.2 Glass as an Elastic Solid Material
13.1 Introduction
In this chapter the mechanical proper-
ties not only of glasses but also of their
melts will be treated, because there is a
continuous transition from the stable state
of the melt via the metastable state of the
undercooled melt to the thermodynami-
cally unstable state of the glass (vitreous
state) without significant change of struc-
ture and of phase. Therefore, the properties
of glasses are sometimes understood much
better if the stable and/or metastable state
is understood, even only partly, and vice
versa. Additionally, there are characteristic
differences in the properties of the rigid
glasses and their melts, particularly due to
the molecular dynamics. Following the
usual way of description of a material at
room temperature and of the most com-
mon and typical glasses, the silicate and
oxide glasses, the starting point will be the
vitreous state clearly below the glass tran-
sition temperature, Tg. Only then will the
temperature region around and above Tg
be treated when the mechanical properties
are altered and relaxation and flow phe-
nomena become more and more dominant.
13.2 Glass as an Elastic Solid
Material
13.2.1 Elastic Properties of Glasses
13.2.1.1 Fundamentals
If a solid body is deformed by a force,
both the deformation and the outer force
or the applied stresses on this body are
described by the components of the stress
tensor, E, and by the components of the
deformation tensor, 8. These usually con-
sist of nine components, for each of the
tensors. If no stresses are present within the
body, as for instance cooling stresses, the
669
tensors are symmetric if the structure of
the solid body is cubic or isotropic which is
the case for a slowly cooled glass. Thus, the
number of components are reduced to six
for each tensor. The relationship between
the two tensors are the so-called stress-
strain- and strain-stress-equations depend-
ing on which physical property is given
and which property is to be calculated. If
the strains are given and the stresses have
to be calculated the stress-strain-equations
are applied:
(13-1)
E
with Sik the Kronecker symbol = 1 for i = k
and = 0 for i ^ k. The indices i, k denote the
spatial directions x, y, z. Stress and strain
components with i = k are normal or or-
thogonal components, while components
with i 7^ k are shear components.
If the stresses are given, the strain-stress-
equations are applied:
1
E
Syy
~ E°yy'~E ^Gxx + °z^
(13-2)
£zz = T7 <*zz - 7T (°XX + °yy)
In these equations the elastic constants are
properties of the material used: E the
Young's modulus or elasticity modulus, G,
the shear modulus and \i the Poisson ratio.
If K is the compression modulus, the rela-
tionship between the elastic constants is
given by:
(13-3)
,-§-.
670 13 Mechanical Properties of Glasses
Methods for measuring these material
properties are described in many standard
books, such as those by Schreiber et al.
(1973), Davidge (1979) or Scholze (1988).
Since very early on measurements have
shown that glasses are excellent elastic ma-
terials for which Hooke's law is fulfilled:
E = G/S (13-4)
(j is the applied tensile or compressive
stress and e the deformation in the special
case of a glass rod, s = Al/l91 the length and
Al the elongation of the rod. Thus, glass is
usually an elastic body at room tempera-
ture. The larger its elastic modulus is, the
less it can be deformed by a certain stress.
Similar behavior shows the shear or tor-
sion modulus, G = i/y, where T is the shear
stress and y the shear or torsion angle. The
relationship to K and fi is given by Eq.
(13-3).
13.2.1.2 Composition Dependence
Silica glass with its three-dimensionally
connected network is expected to have a
large £-value £ = 72 GPa (Deeg, 1958).
If alkali oxide is introduced the network
is weakened and E decreases (Fig. 13-1).
At comparable alkali concentrations the
Young's modulus decreases with decreas-
ing field strength of the cations. In this way
E decreases from Li- to K-silicate glasses
(Deeg, 1958; Kozlovskaya, 1959; DeGuire
Figure 13-1. Young's modulus, E, of binary alkali sili-
cate glasses at room temperature from various au-
thors, composed by Scholze (1988).
and Brown, 1984). The introduction of
cations with still larger field strengths, such
as Ca2 + , leads to correspondingly higher
E-values, as do additions of A12O3 and
B 2 O 3 which reduce the number of non-
bridging oxygen atoms, B 2 O 3 by the so-
called boron oxide anomaly (Scholze,
1988) provided enough alkali oxide is pres-
ent to ensure a network-forming quality
for Al3 + and change to four-fold coordina-
tion for B 3 + . Livshits et al. (1982) showed
that E increases from 59 to 74 GPa with-
in the series 25Na 2 OxAl 2 O 3 (75-x)SiO 2
when x varies from zero to 25.
As in the case of many other properties
the borate glasses show a totally other de-
pendence on E with increasing alkali oxide
as compared with the silicate glasses. Start-
ing from the very low £-value of 17.5 GPa
for B 2 O 3 glass, the elastic modulus in-
creases with alkali oxide concentration up
to 60 GPa (Takahashi et al., 1983). Two
structural reasons are responsible for this
behavior. The B 2 O 3 glass has a very open
structure and the network is much less in-
terconnected than that of silica glass due to
the disc-like triangular BO 3 groups. If al-
kali oxide is added, the free volume is filled
at least partly by the alkali ions and the
BO3-groups are changed to BO4-tetrahe-
dra in proportion to the alkali oxide con-
tent, an effect which is well-known as
boron oxide anomaly (see Chap. 5).
A similar coordination change takes
place in alkali germanate glasses, from the
pure GeO 2 glass in which Ge 4 + is four-fold
coordinated to six-fold coordination in
proportion to the alkali oxide concentra-
tion up to about 12 to 17 mol% depending
on the type of alkali. In this way the
Young's modulus changes from 43 GPa for
GeO 2 glass to a maximum value of 73 GPa
at a Na 2 O content of 17 mol%. Above that
value the coordination is retrograde and
the ^-modulus is also (Osaka et al., 1985).
 13.2 Glass as an Elastic Solid Material 671
0.04
The shear modulus has been investi-
gated much less than the Young's modulus.
But the shear modulus can be discussed in
the same manner as the Young's modulus
because G « 0.4 to 0.3 £, as follows from
Eq. (13-3). 10 20 30 40 50
From its definition the Poisson ratio — R20 in mol % —

fi = (Ar/r)/(Al/l) theoretically exhibits val- Figure 13-2. Compressibility, x, of binary silicate

ues between 0 and 0.5. For many glasses \x glasses at 21 °C and at 1 GPa (Weir and Shartsis,
1955).
is between 0.2 and 0.3. A low /i-value indi-
cates that at a certain elongation Al/l the
radial contraction Ar/r is low. This is the 0.05

case for relatively rigid structures, e.g. for

silica glass with \i = 0.17. By the incorpora-
tion of network modifying cations, particu-
larly large ones, the /i-values increase (in-
creasing polarizability).
More relationships to structural aspects
may be deduced from the compressibility,
x, which is the reciprocal of the compres-
sion modulus K. Starting from silica
glass with its open structure and abundant
free volume, a large compressibility is
expected: x = 2.7 • 10" 1 1 Pa" 1 . The intro-
Ratio
duction of alkali oxide leads to a decrease number of oxygen ions
of free volume which is connected with a Figure 13-3. Compressibility of binary alkali and al-
decrease of compressibility, particularly for kaline earth borate glasses at 21 °C and extrapolated
small cations with a high field strength to 0.1 GPa (Weir and Shartsis, 1955).
(Li2O, see Fig. 13-2). However, for cations
with larger (ionic) radii and with a large
polarizability (K + , P b 2 + , Ba 2+ ), the com- tematic measurements:
pressibility is increased. These two coun- n
teracting effects are still more pronounced E= £ EiPi (13-5)
in binary R 2 O - B 2 O 3 and R O - B 2 O 3 sys-
tems (Fig. 13-3). Of special interest is one of where Et is the specific factor for the i-th
many anomalies of silica glass: in contrast oxide and pt the content of this i-th oxide
to nearly all other solids, x increases with in wt.% or in mol%, respectively, depend-
increasing compressive stress up to a max- ing on the authors who determined the
imum value at a compressive stress of specific factors. Similar treatments are
350 MPa. Above that value the compress- given for G, \i and K. Numerous authors
ibility decreases in the usual way (Bridg- have applied such treatments for various
man and Simon, 1953). homologous series: Appen et al. (1961),
Many attempts have been made to cal- Kozlovskaya (1959), Winkelmann and
culate the elastic constants by so-called Schott (1894), Makishima and Mackenzie
specific factors found empirically by sys- (1973, 1975). A useful and comprehensive
672 13 Mechanical Properties of Glasses

summary of these specific factors is given
by Scholze (1988).
Apart from the purely empirically eval-
uated specific factors, Makishima and
Mackenzie (1973,1975) calculated the elas-
tic properties using a physical background.
They regarded the Young's modulus as de-
pendent on the packing density of the ions,
Vt9 and on the dissociation energy, (7, re-
lated to the unit of volume. In this way they
obtained for single component glasses:
E = 2VtU (13-6)
For multi-component glasses, the sum
over all components must be calculated:
(13-7)
z
i =1
with Q the density of the glass, p{ portions
in mol%, Mt the molecular weights, and
V{ the specific factors which can be calcu-
lated from the ionic radii. Together with
the factors Ut in KJ/cm3, Makishima and
145 GPa is obtained (Williams and Scott,
1970). It is well known that a high Young's
modulus is usually connected to a high
strength, apart from or under comparable
surface conditions (see Sees. 13.3.1 and
13.3.2).
13.2.1.3 Temperature Dependence
Usually bonding forces decrease with in-
creasing temperature. This leads to a de-
crease of the elastic constants as was mea-
sured by Spinner (1956) and McGraw
(1952) for silicate glasses (Figs. 13-4 and
13-5). The increase of /a with temperature is
750
700-
650-
350
300-

Mackenzie obtained: 250

0.24
E = 0.2VtZUiPi
0.22-
= 0.2ZVipiZUipi/?1Mipi (13-8)
0.20
and in a similar manner they calculated the 100 200 300 400 500 600
T in °C —
compression modulus:
Figure 13-4. Elastic constants and Poisson ratio ver-
K = Vt2ZUiPi=l/x (13-9) sus temperature of a borosilicate glass below Tg (Spin-
ner, 1956).
and the Poisson ratio:
ju = 0.5-0A39/Vt (13-10)
The consequence of Makishima and
Mackenzie's considerations is that a glass
with a high Young's modulus should con-
tain components with high dissociation
energies and high package densities but
small molecular weights. Oxides with
cations of medium field strengths are
0 200 400 600 800
most advantageous in this respect. As an T in °C —
example for a glass with the composition Figure 13-5. Young's modulus of a sodium calcium
40.7 SiO 2 , 7.2A12O3, 26.7 MgO, 25.4 BeO silicate glass versus temperature below and above Tg
(in mol%) an extreme Young's modulus of (McGraw, 1952).
 13.2 Glass as an Elastic Solid Material
due to the fact that the glass structure ap-
proaches with increasing temperature the
value fi = 0.5 of melts and fluids. The de-
crease of E and G depends on the glass
composition. Increasing alkali oxide con-
centration leads to a steeper decrease of E
and G, the steepest decrease for Li 2 O-SiO 2
glasses following the series K 2 O -> Na 2 O
-• Li 2 O according to Galyant and Pri-
menko (1978). These authors also found
that A12O3 diminishes this effect drasti-
cally. One exception exists again for silica
glass: it shows an increase of E and G with
temperature by 9% for E at 900 °C which
might be due to its low thermal expansion
and other thermodynamical effects, such as
the entropy effect, based on an elastic an-
isotropy of the glass network (Coenen,
1983).
13.2.1.4 Dependence on Thermal
and Mechanical Prehistories
Most properties of glasses are dependent
on the prehistory. Among the various pre-
histories (Bruckner, 1990), the thermal and
the mechanical are the most important
ones. A typical consequence of the struc-
ture of glasses, with its failure of long range
order, is that the structure can be changed
continuously by thermal and mechanical
influences. If these influences are removed,
the properties will change back to their
previous values. This process takes time
depending on temperature and on the dis-
tance from the metastable state of the glass.
With respect to elasticity this phenomenon
is called elastic aftereffect and is closely re-
lated to relaxation effects (see Chap. 3 of
this volume). The fact that the Young's
modulus usually decreases with increasing
temperature makes plausible that very
quickly cooled glasses have lower E-values
than slowly cooled glasses. Stong (1937)
has found a change of the Young's modulus
673
from 74.5 and 71.5 GPa for a sodium cal-
cium silicate glass which had been cooled
normally and quenched. After having an-
nealed the same glass near Tg for several
hours they found E = 16 GPa. Similar re-
sults were obtained by Halleck et al. (1986).
Investigations on glass fibers have
shown very drastically the effects of ther-
mal and mechanical prehistory on the elas-
tic constants. Typical of these effects are the
two following examples for £-glass fibers
produced under different drawing condi-
tions (Pahler and Bruckner, 1985 a, b):
First, Figs. 13-6 a toe show that the
Young's and the shear moduli are decreas-
ing with decreasing fiber diameter. Since
the square of the fiber diameter is recipro-
cal to the fictive temperature of the fibers
(that temperature at which the glass struc-
ture is frozen-in), the fictive temperature
increases with decreasing diameter and the
moduli decrease. This tendency is indepen-
dent of the drawing temperature, TD, and
drawing force, but it depends on the mass
flow which is kept constant in Figs. 13-6 a
to c by variation of the pressure on the
nozzle. The strength, on the other hand,
increases with decreasing fiber diameter,
a phenomenon which will be discussed in
Sec. 13.3.3.
Second, if using the Young's and shear
moduli the Poisson ratios as a function of
the reciprocal radius at constant mass flow
are calculated, one gets values which are
not only near 0.5 but partly above 0.5
(Figs. 13-7 a to c). This indicates that these
Poisson ratios are apparent ones because
the formula fj* = E/G — 1 is only valid for
isotropic materials (Pahler and Bruckner,
1985 a, b). The fibers, however, are aniso-
tropic and show birefringence (see Sec.
13.3.3).
Thus, the first example indicates prefer-
entially the thermal prehistory, while the
second example shows both influences, the
674 13 Mechanical Properties of Glasses

33-
1L 30-
V
\
T D =1423K
m =5mg/s
TD = 1623K
m =5mg/s
\ T F 2 =3,8mN -x F z =1.2mN
8 f" 25- Q) ^"""""^--•^ c)
23:
80: \

75-
70-
s
x

^ ^ *——-—
66:
3500-

u 2500- /
T __5_ ?_

1500-
h
0 0.05 0,1 0,15 0,2 0 0.05 0,1 0,15 0,2 0 0,05 0.1 0,15 0,2
1
Reciprocal fiber radius in urn"

Figure 13-6. Shear and Young's moduli and strength of E-glass fibers versus the reciprocal of fiber radius under
various fiber drawing conditions (a to c) but at constant mass flow. Fz = drawing force, m = mass flow.

v
»w a) b) ; c)
11 T D =773K
0#4^
T D =1623K TD=1073K
0,2- m =5mg/s ffi =3mg/s m =243mg/s
D
E-Glass Fz = 1#2mN CaBa F 2 =0,8mN [ NaPoLi F z =0 f 8mN
a
0.6-
ent Poissor

TD = 673K
0,4- %—
TD=1023K
0.2- m =5mg/s m =3mg/s m =2.3m/s
F 2 =1.3mN F z =0,9mN Fz =2.45mN
%

a 0.6-
ex
^f
0A- ,/# T D =973K ^f^=648K
m =3mg/s m = 1.7mg/s
0,2- F z =3.0mN Fz =3,24mN

0 0,05 0,1 0.15 0.2 0 0.05 0.1 0J5 0.2 0 0.05 0.1 0.15 0,2
Reciprocal fiber radius in u.m~1
Figure 13-7. Apparent Poisson ratio of glass fibers versus the reciprocal of fiber radius under various drawing
conditions but at constant mass flow for a) £-glass, b) Ca-Ba-metaphosphate glass and c) Na-Li-metaphosphate
glass.

thermal and the mechanical prehistory, the It is plausible that time-dependent ef-
latter one produced by the stress during fects occur during phase-separation pro-
the fiber drawing process which causes the cesses. This because to the progress of
freezing-in of strains and, at least in the phase separation constitutes a kind of pre-
case of Na-Li-metaphosphate glass fibers, history for glasses which have composi-
also orientations of PO 4 -chains (Stock- tions within a solubility gap. Usually these
horst and Bruckner, 1982, 1986). effects are found to be low, within changes
 13.2 Glass as an Elastic Solid Material
of 2 to 5% (Pye etal., 1974; Shaw and
Uhlmann, 1969, 1971; Tille etal., 1978).
A common phenomenon which is not
only connected to the glassy but also to the
crystalline state is the dependence of the
elastic constants on thermodynamic prop-
erties, such as heat capacity, thermal con-
ductance and thermal expansion. There-
fore a distinction has to be made between
the isothermal and adiabatic elastic con-
stants. If the Young's modulus or the com-
pressibility is measured by static methods,
the isothermal moduli are obtained. When,
however, dynamic methods are applied,
the adiabatic moduli are measured, if the
frequency of the dynamic method is high
enough that no temperature equilibration
during torsional or tensile and compressive
stresses can take place. Therefore, if Kad is
the adiabatic compressive modulus, which
may be measured easily by ultrasonic ve-
locity and density, the isothermal modulus
can be calculated by the following equa-
tion and vice versa:
= Kis TH2/cp (13-11)
with T the absolute temperature, /? the
cubic thermal expansion coefficient, and cp
the specific heat.
The difference between the isothermal
and adiabatic compressibilities is about 5%.
13.2.2 Inelastic Properties of Glasses
13.2.2.1 Densification
Elastic deformations are by definition
reversible. At very high pressures, however,
the deformation can be irreversible; this
means that plastic flow takes place and the
result is an increase of density. This den-
sification can be reversed by annealing
around Tg as was shown first by Bridgman
and Simon (1953) and later by Cohen and
Roy (1961) and by Mackenzie (1963,1964).
The results indicate that the degree of den-
675
sification of silica glass (up to 16%) de-
pends strongly on the experimental condi-
tions of the compression process, specifi-
cally, on whether it is uniaxial or isostatic.
A uniaxial compression process provides
much higher shear stresses which act dur-
ing the compression experiment, and thus
a higher degree of permanent densification
compared with an isostatic compression
process. Seifert et al. (1983) showed by
means of Raman spectrocopy that this
process is accompanied by a decrease of
the mean S i - O - S i angle. The degree of
densification is, of course, also dependent
on the glass composition and on the start-
ing condition of the glass structure.
Uhlmann (1973/74) showed that the densi-
fication is increased with increasing tem-
perature and pressure, and no limit seems
to exist. The dependence on the composi-
tion is more complicated: in the systems
Na 2 O-SiO 2 and K 2 O-SiO 2 , densifica-
tion at 200 °C and 3 GPa increases with
R2O-concentration from pure silica glass
with 2.2% to R 2 O = 10 mol% up to 6.5%.
Above 10mol% R 2 O densification de-
creases again. Two effects are in conflict.
On the one hand the mobility of the glass
structure increases with increasing alkali
content, which increases the densification;
on the other hand, the free volume is filled
by the alkali ions which leads to a reduced
densification effect. Fig. 13-8 shows this
latter influence in comparable uniaxial
compression experiments as a function of
pressure and alkali concentration (Macken-
zie, 1963, 1964; Bridgman and Simon,
1953).
13.2.2.2 Mechanical Losses
Another inelasticity effect in glasses is
the internal friction. There are several act-
ing mechanisms which are responsible for
the internal friction or mechanical losses. If
676 13 Mechanical Properties of Glasses
0%NaoO-
10%Na20-
23%Na2Q
31%Na 2 CT
U 8 12 16 20
Pressure in GPa —m"
Figure 13-8. Densification of silica glass and sodium
silicate glass versus uniaxial compressive stress with
increasing Na 2 O content (composed from various au-
thors).
a sinusoidal stress (usually a torsional or a
bending one), a = a0 sin co t or a — a0 eicof,
is applied on a glass rod, the deformation,
8? lags behind the stress by the phase angle,
cp: a = e0 sin(cot — cp) or: s = 8 0 e l(wr ~^,
where a0 and e0 are the amplitudes,
co — 2 n v the frequency and t the time. If
mechanical energy is dissipated in the form
of heat in real materials, the phase angle cp
is identical with the loss angle. In ideal
elastic materials cp = 0, inelastic portions
give rise to cp ^ 0. As in the analogous case
of electrical vibration losses, the dynamic
shear modulus of torsional vibrations (or
in the case of longitudinal waves the dy-
namic elastic modulus) and the loss factor,
tan cp, depend on frequency, co, and on the
relaxation time, T, of that relaxation mech-
anism which causes the mechanical loss.
These relationships are given (Ferry, 1970;
Kirby, 1953 and 1954) for the simplest case
by:
G = G0-(G0-GJ(l + co2T2r1 (13-12)
COT
(13-13)
where G is the dynamic shear modulus, Go
that at co -+oo, and G^ that at co = 0.
The dynamic shear modulus, G, versus
frequency, co, is a typical dispersion curve
(a) and the curve of the loss factor (b) is a
typical absorption curve with a maximum
at the inflexion point of curve G (Fig. 13-9).
The maximum of a mechanical loss mecha-
nism with a relaxation time, T, occurs at a
frequency when COT = 1. This corresponds
to a loss factor of tan cp = (Go— G^)/2G0
and a modulus G = 0.5 (Go + G J .
The temperature dependence of the re-
laxation time, T, is given by the typical
Boltzmann equation T = ToeQ/fcT, from
which it follows for co x = 1 the tempera-
ture, 7^, at which the loss factor, tan cp, has
its maximum:
TM = Q//cln(l/coTo) (13-14)
where Q is the activation energy of the
relaxation process, k the Boltzmann con-
stant and T 0 the pre-exponential factor
(TO^10-13S).
From the logarithmic decrement of at-
tenuation, the loss factor can be obtained
by simple torsional or longitudinal vi-
brations as well. The relationship is:
tan cp = 8/n.
In order to study relaxation mechanisms
in glasses it is more convenient to vary the
temperature instead of frequency, because
from Eq. (13-14) it follows that a linear
alteration of temperature at constant fre-
quency is equivalent to an exponential al-
teration of frequency at constant tempera-
Figure 13-9. Typical dispersion curve for the dynamic
shear modulus G (curve a) and for the loss factor tan (p
versus frequency co• = 2 n v multiplied by the relax-
ation time r of a distinct relaxation or loss media-
 13.2 Glass as an Elastic Solid Material 677

ture. Therefore, most experiments were

made at constant frequency with variation
of temperature. In simple alkali and multi-
component silicate glasses three different
loss mechanisms are acting, as is shown in
Fig. 13-10 (Coenen and Amrhein, 1961).
With respect to a frequency of 5 cps the
low temperature maximum is caused by
the diffusion of alkali ions, the medium
temperature maximum is due to the mobil-
ity of non-bridging oxygen ions, connected
with a combined loss produced by the in-
teraction of two different mobile cations
(two different alkali and/or hydrogen ions).
The main loss maximum in the glass tran- 500 1000
sition range is related to the mobility of the - Temperature in
whole network. An interesting point in Fig. Figure 13-10. The logarithmic decrement of attenua-
13-10 is the existence of double maxima tion of binary sodium silicate glasses (Na2O-content
at medium and high temperatures for the from 20 to 40 mole%) versus temperature under tor-
sodium silicate glass with 24 mol% Na 2 O, sion vibrations with a frequency of 5 rps (Coenen and
Amrhein, 1961). Courtesy of flnstitut National du
indicating phase separation into high and Verre.
low silica portions with somewhat higher
and lower amounts of non-bridging oxy-
gen atoms and with higher and lower glass
transition temperatures, respectively.
All loss maxima show a shift to lower
temperatures with increasing Na 2 O con-
tent due to decreasing network strength.
Directly connected to the loss maxima are
step-wise decays of the shear modulus as
was shown by Coenen and Amrhein (1961)
in Fig. 13-11. 0 400
Further features of loss maxima mea- Temperature in °C •

sured by various authors (Fitzgerald, 1951;
Kirby 1953,1954,1957; Day and Rindone,
1962; Coenen and Amrhein, 1961) are as
follows. The height of the loss maxima in-
creases with increasing sodium oxide con-
tent and with increasing cooling rates of
the glass samples. The loss peak is shifted
at lower temperatures and the activation
energy is decreased from 21 kcal/mol (an-
nealed) to 16 kcal/mol (quenched glass)
as was shown by Fitzgerald (1951). This
author also demonstrated that the activa-
Figure 13-11. Logarithm of the shear modulus at con-
stant frequency of 5 rps for a sodium disilicate glass
versus temperature (Coenen and Amrhein, 1961).
Courtesy of l'lnstitut National du Verre.
tion energy for the alkali oxide loss peak
corresponds with that for the ionic conduc-
tivity, thus both processes are based on the
mobility of the alkali ions. The activation
energy decreases with decreasing field
strength, i.e. from Li + to K + .
678 13 Mechanical Properties of Glasses
It is of distinct interest that the medium
temperature loss maximum has no relation
to a conductivity effect, thus, it should be
electrically neutral. If A12O3 is added to a
silicate glass as a substitute for SiO 2 the
number of non-bridging oxygen ions de-
creases and the loss peak intensity should
decrease. This is confirmed by Kirby (1954)
and by Day and Rindone (1962), who
showed that the peak height decreases and
the peak is shifted towards higher tempera-
tures, indicating together with the shift of
Tg towards higher temperature a stronger
and more cross-linked network.
The method of internal friction has fre-
quently been applied to study the so-called
mixed alkali effect, an effect which is most
pronounced for alkali ion mobility in an
electric field by which the specific conduc-
tivity is decreased up to several orders of
magnitude if two alkali ions are exchanged
by molar fraction of 0.5. Also the mechan-
ical mobility in an alternating field of stress
is very pronounced as was shown by
Coenen (1961), Shelby and Day (1969,
1970), vanGemert et al. (1974), and in a
review by Zdaniewski et al. (1979).
13.3 The Phenomenon
of Uncontrolled Brittle Fracture
It is well known that glasses, particularly
oxide glasses, are highly brittle. The term
brittleness is related to the fracture behav-
ior and is closely connected to Hooke's
law: brittle fracture occurs at a certain
point on the elastic line without any indi-
cation or deviation from the stress-strain
straight line (Fig. 13-12, curve a). A ductile
polycrystalline metal, however, breaks af-
ter a significant deviation from linearity at
much higher strains and after a certain de-
formation which may be described as plas-
tic flow under a certain stress (Fig. 13-12,
Strain, relat. units —•-
Figure 13-12. Stress-strain straight line (Hooke's law)
with sudden (brittle) fracture of a bulk glass (curve a)
and with a ductile fracture (toughness) of a metal
(curve b).
curve b). This kind of fracture behavior is
called toughness and is explained by plas-
tic gliding of layers in crystalline lattices,
a phenomenon occurring particularly in
metals and for instance in graphite, which
has been shown experimentally. Therefore,
it was believed that the brittleness of oxide
glasses is due to their disordered network
without any long-range order where glid-
ing layers cannot be formed. However,
when the high ductility of metal glasses (see
Volume 6) was discovered, this explanation
could not be maintained any longer. The
main origin of ductility of a material seems
to lie in metallic bonding and that of
brittleness seems to be in an ionic and
covalent or mixed bonding character and
not (or at least not only) the ordered or
disordered structure of a material. In this
way it becomes plausible that not only are
glasses brittle materials but also ceramic
materials with and without glass phase,
quartz and even diamond and silicon car-
bide with their dominant covalent bonding
character.
Another point connected with the term
"brittleness" is the question: is the be-
havior of a glass as a brittle material really
characterized by curve a in Fig. 13-12 or is
this produced by effects which reduce only
the strength of the glass, e.g., by surface or
internal cracks?
 13.3 The Phenomenon of Uncontrolled Brittle Fracture 679

It is a very long-established fact, recog- 13.3.1 Theoretical and Practical Strength

nized since the key work by Griffith (1920),
Strength is not a material constant such
that the strength of glass fibers is two or
as the elastic constants, thermal expansion,
three orders of magnitude larger than that
density, etc. which can be determined with
of bulk glass. Only this fact has the conse-
an error of less than 3%. Strength depends
quence that the stress-strain curves of glass
on various influences, e.g. the size of the
fibers and bulk differ from each other not
specimen, the sample preparation, dura-
only by magnitude of stress, <x, and strain,
tion of load, surrounding media etc. There-
s, but also by the character of the curves
fore a scatter of strength values of 15 to
(see Fig. 13-32 in Sec. 13.5.3). A compari-
25% is normal. This indicates that fracture
son of curve 1 for bulk glass to curve 2 for
is broadly connected to statistics.
glass fibers shows a curvature at stresses
which are clearly beyond the strength val-
ues of bulk glass. Thus, the non-linear part 13.3.1.1 Theoretical Strength
of curve 2 cannot be measured for bulk The ultimate strength of a material is
glass because fracture occurs before these determined by the mutual bonding forces
stress-strain values are reached. of its atoms, ions or molecules and can be
As will be shown later (in Sec. 13.3.3) this calculated in various ways. Usually that
non-linearity is reversible at least within energy which is necessary to produce a new
the experimental error of one cycle of the surface is considered. Supposing a planary
stress-strain curve, as a result of the non- stress strain state, this leads to the theoret-
linear interaction potential between the ical strength (Griffith, 1920):
stressed and strained atoms which is obvi-
ously induced to a certain degree (Pahler (13-15)
and Bruckner, 1985 b). If such high stresses where E is the Young's modulus, y the free
are repeated numerous times, bondings surface energy and a the atomic distance. A
may be broken more and more, micro- rough estimation with the help of mean
cracks will be produced and finally the values for silicate glasses, E = 70 GPa,
stress-strain curve will no longer be re- y = 0.3 N/m and a = 1.6 • 10" 1 0 m, leads
versible, indicating that deviation from to a value for <7theOr.~ 13 GPa. Other esti-
ideal elasticity occurs, if fracture can be mations are within the same order of mag-
prevented during the stress-strain cycles. nitude, e.g. the so-called Orowanian rule
If any deviation from Hooke's straight leads to <7 theor ^£/10 = 7GPa. A some-
line indicates toughness, at least a very what modified estimation (Bartenev and
slight one, the non-linear part of curve 2 in Sanditov, 1982) is: <7theor. = (l -2/x)£/(l + pi)
Fig. 13-32 characterizes such a property with fi the Poisson number.
and this property should be dependent on
the composition of the glass. However, as
13.3.1.2 Real Strength: Griffith's Theory
will be shown in the next sections, the
strength of glasses below Tg is usually not The experimentally measured real
a volume, but primarily a surface property. strength values of glasses are usually lower
Above Tg, however, strength becomes a than the theoretical strength values by sev-
volume property (see Sec. 13.6.1). eral orders of magnitude. The origin of this
discrepancy is that real bulk glasses and
real materials all contain faults, micro-
680 13 Mechanical Properties of Glasses
f theoret. strength
10*- structural
> glass fibers defects
surface defects
I pristine and acid- and
| polished glasses microcracks
normal glass
products heavy surface
> scratched glasses
defects
macrocracks
Figure 13-13. Overview of the strength of glasses
(Kruithof and Zijlstra, 1959).
cracks and cracks, of which those at the
surface diminish the strength in the most
drastic manner. Figure 13-13 gives an
overview of the strength of glasses and the
origin of the reduced values (Kruithof and
Zijlstra, 1959).
Most interesting are the strength values
of glass fibers which are close below that of
the theoretical strength. This was recog-
nized already by Griffith (1920), who ob-
served a drastic increase of strength with
decreasing fiber diameter. After having ex-
plained the difference between theoretical
and experimental strength with his famous
equation:
(13-16)
where / is the length of that crack which
leads to fracture, Griffith interpreted the
high strength of glass fibers as being due to
very short crack lengths in pristine fibers.
An important point is the size of a sam-
ple, because the probability for the occur-
rence of voids and cracks increases with
the size of a specimen. Thus, the strength of
fibers decreases with increasing fiber length
at comparable diameters (Anderegg, 1939)
and the strength of a bulk glass with a
much larger volume than that of a fiber is
much lower. This size effect is also well-
known for the strength of sheet glass
(Blank et al., 1990; Struck and Briinner,
1989). The reason that cracks at the surface
influence positively the strength of glass as
compared with cracks in the interior may
be seen in the fact that the tensile strength
is about one order of magnitude less than
the compressive strength; the flexural
strength is in between because one side is
under compressive, the other one under
tensile stress before fracture. Thus if sur-
face cracks are removed by etching with
HF or by flame polishing, the strength of a
glass sample is increased.
The real strength is influenced not only
by the size of the specimen but also by
corrosion phenomena. Norville and Minor
(1985) have investigated 20-year-old win-
dow panes and have found clearly higher
strength values on the inner side compared
to the outer side. Still higher strength val-
ues resulted for the inner surfaces of insu-
lating double glazed windows.
Very large surface cracks are created by
collisions with small particles or stones.
The loss of strength is dependent on the
impact of the projectile (Wiederhorn et al.,
1979).
Smaller cracks can be observed by elec-
tron microscope, as was done by Varner
and Oel (1975), in order to attribute the
strength to certain faults and to study the
action of HF-etching of the surface. A
combination of electron microscope and
strength measurements was also applied
by Pavelchek and Doremus (1974), who
were able to show that the cracks produced
by grinding the surface with SiC paper,
which determines the strength of the glass,
have a depth of 6 jam, a value which
Griffith (1920) had already found by his
estimates from real strength values of bulk
glasses.
The reason for the difference between
the theoretical strength (10 to 30 GPa) and
the strength of glasses with crack-free sur-
faces (about 4 GPa) is a question of special
 13.3 The Phenomenon of Uncontrolled Brittle Fracture
interest. Rawson (1953) and Dietzel (1981)
explain this discrepancy by inhomogenei-
ties within atomic regions where stresses
occur by phase separation tendency or by
formation of swarms of alkali-rich regions.
In glasses with real phase separation small
cracks at the phase boundaries were found
by Vogel (1964). In normal glasses without
phase separation, Hillig (1962) explained
the low strength values of bulk glasses with
thermal motions within atomic regions
(fluctuations). It has also been discussed
that fluctuations at the surface may lead to
a kind of surface roughness which might
act as cracks in the sense of fracture me-
chanics (see Sec. 13.3.2). These small sur-
face cracks are not detectable, not even by
electron microscope. Therefore attempts
have been made to enlarge these surface
faults in order to convert them to visible
cracks. This was done by evaporation of
gold (Adams and McMillan, 1977) or
sodium vapor (Andrade and Tsien, 1937),
or by ion exchange (Acloque et al., 1960;
Ernsberger, 1962). The latter method was
the most successful one. Ernsberger pro-
duced tensile stresses in the surface by ion
exchange Na-»Li + (15 min. at 250 °C) and
counted the cracks which became visible as
a result of these surface tensile stresses. The
results for normal sheet glass was 50000
cracks/cm2. He could show that the cracks
originated from surface damages or sur-
face decompositions already produced by
small amounts of impurities. Rauschen-
bach (1981, 1983) has applied the method
of implantation of noble gas ions. A ther-
mal treatment after implantation leads to
formation of small bubbles which make
visible the finest defects at the glass surface.
Defect densities up to 10 11 cm" 2 are mea-
surable by this method.
681
13.3.2 Fracture Mechanics
13.3.2.1 Energy Balance
In order to produce glasses with higher
mechanical strength and to understand
brittle fracture behavior it is necessary to
investigate the processes that occur during
the fracture. Since about 1960, fracture
phenomena have been treated by the in-
creasingly developed discipline of fracture
mechanics (see also Vol. 6). Kerkhof (1970)
has summarized the knowledge in a book.
Conference proceedings were published by
Bradt et al. (1974, 1986) and by Kurkjian
(1985), and a long series of review articles
appeared, such as Charles (1961), Cher-
mant et al. (1979), Cottrell (1964), Doremus
(1982), Ernsberger (1977), Evans (1974,
1978), Freiman (1980), Hillig (1962), Hol-
loway (1986), LaCourse (1972), Lawn and
Wilshaw (1975), Lawn (1983) and Wieder-
horn (1974). The development of fracture
mechanics is closely linked with the names
of Inglis, Griffith and Irwin. In contrast to
the more statistical treatment of fracture
strength, the behavior of a single crack (or
flaw) is treated within a homogeneous and
isotropic continuum. If linear elastic be-
havior can be presupposed, the term linear
elastic fracture mechanics is also used.
As in the case of Griffith's theory, the
origins of fracture mechanics are located in
continuum mechanics and the difficulty is
the transformation to atomic scales if the
stress field at the flaw tip is treated during
the fracture process. This is the main task
of fracture mechanics. The stress fields
around a crack tip are complex and are
dependent on the kind of loading. Accord-
ing to Irwin (1958), one has to distinguish
between three fundamental types (modes)
of crack loadings which are characterized
by the relative shifts of the crack tips (Fig.
13-14). The first mode (I) is the most impor-
tant and is the typical crack opening mode.
682 13 Mechanical Properties of Glasses

Figure 13-14 The three

modes of crack loading
II III (Kerkhof, 1970).

Mode II is the first shear mode or the edge where KY is the stress intensity factor for
mode, and mode III is called the second mode I by which the stresses before the
shear mode or the tearing mode. Mode I is crack tip, r, can be easily calculated. For a
best realized if the fracture is a brittle one, crack with the length of 2 a which is under
which again is best realized for glasses. The an overall tensile stress, cr, the stress inten-
stresses for mode I before the crack tip are sity factor is given by:
(see Fig. 13-15):
x,= na (13-18)
Kr <p
G = cos For the special case of a long plane plate
' «xx ~—
2nr ~~ (1 ~ s i n <P/2 ' s i n 3 (p/2)
(13-17a) with a broadness b and with a crack at one
side of depth a which is under tensile stress,
u
yy
cos — (1 + sin cp/2 • sin 3 (p/2) cr, perpendicular to the crack, the stress
(13-17b) directly before the sharp crack tip, ar9 at
the distance r is given (see, e.g. Kerkhof,
(13-17c) 1970 or Paris and Sih, 1965) by:
sin (p/2 • cos (p/2 • cos 3 (p/2 or = 2o« (13-19)
2nr
(13-17d) !f t he condition a<b is not fulfilled, Eq.
= (7™ = 0 (13-17e) (13-18) must be multiplied by a certain
factor on the right side, e.g. f{a/b) =
1.99 - 0.41 (a/b) + 18.7 (a/b)2 - 38.48 {a/b)3
+ 53.85 (a/b)4. Equation (13-19) shows that
the stress, or, at the crack tip is much
zy higher than the outer tensile stress, o. For
example, at a distance of several atomic
spaces, say r = 10A = 10~ 9 m, and for a
crack depth of a = 1 mm, the stress or is:
or = 2000 o. \ior > <TC, with oc the strength
of the glass plate, the fracture is sure. For
the special case or = oc the critical value
for the stress intensity factor KY is reached
and this is called the critical stress intensity
Figure 13-15. The crack tip front with the correspond- factor, Klc, or the fracture toughness:
ing coordinates and the components of stresses in the
advanced field of the crack (Kerkhof, 1970). Tea (13-20)
 13.3 The Phenomenon of Uncontrolled Brittle Fracture 683

This is a material-specific property and is
important as a fracture criterium. From
the energy balance, the specific fracture en-
ergy, GI? is obtained for the plane stress
condition:
G, = Kf/E (13-21)
If the critical stress is exceeded, the crack
propagation becomes unstable and GY be-
comes the critical specific fracture energy,
GIC = K2C/E. For an ideal brittle material
Gj = 2y (y the surface energy) which leads,
together with Eq. (13-18) to
a) (13-22)
which is equivalent with Eq. (13-16), if
a = 1/2. This equation leads to an unstable
equilibrium, because, if 2 y > a2 n a/E the
crack would be closed and if 2 y < a2 n a/E
the crack would be opened, an effect which
was realized by Stavrinidis and Holloway
(1983) in load-changing experiments where
fracture has to be prevented.
In real fracture experiments with glasses
it was found that the fracture energy is
clearly higher than that for ideal elasticity.
Marsh (1964) interpreted this problem to
mean that something other than elastic en-
ergy still has to be considered, such as plas-
tic deformation at the crack tip. Irre-
versible chemical reactions may also take
place (Wiederhorn and Townsend, 1970).
This is the reason why today the critical
specific fracture energy, GIC, is measured
indirectly by the determination of the criti-
cal stress intensity factor, Klc. It must be
emphasized, however, that the fracture
criterion, <rc «J% a = Klc, is no theoreti-
cally founded law, but an experimentally
based fact. Klc is also defined as that stress
intensity factor at which a rapid crack
propagation occurs. Rapid is understood,
for practical reasons, to be a crack propa-
gation larger than about 10 mm/s. The in-
formation derived from Klc is the permissi-
ble stress and crack length which ensure
that no fracture takes place immediately.
KIC-values for silicate glasses do not dif-
fer much with composition. Typical values
are given in Table 13-1 (Wiederhorn, 1969).
This table also shows the above-mentioned
discrepancy between the fracture surface
energy, y, calculated from KIC and the sur-
face energies, which are estimated from the
surface tensions. The former, in Table 13-1
column 3 to 5, are about one order of mag-
nitude larger than the latter, e.g. for silica
glass at 300 K y = 4.37 N/m calculated from
Klc = 0.794 MPa m 1/2 and from surface
tension y = 0.34 N/m (see Scholze, 1988).
13.3.2.2 Fractography and Crack Velocity
The usual brittle fracture of glass is char-
acterized by the fracture or crack velocity

Table 13-1. Fracture mechanics data for some glasses (Wiederhorn, 1969).

Glass Young's Fracture surface energy in Jm 2

KIC-value in MPam 1 / 2 at
modulus at various temperatures (K) various temperatures (K)
in GPa
11 196 300 77 196 300

Silica glass 72.1 4.56 4.83 4.37 0.811 0.839 0.794

96% silica 65.9 4.17 4.60 3.96 0.741 0.779 0.722
Lead-alkali 65.3 4.11 - 3.52 0.734 0.680
Soda-lime 73.4 4.55 4.48 3.87 0.820 0.812 0.754
Aluminosilicate 89.1 5.21 - 4.65 0.963 0.910
Borosilicate 63.7 4.70 _ 4.63 0.774 0.768
684 13 Mechanical Properties of Glasses

V{. Schardin and Struth (1937) found that

after a relatively slow start the crack tip
propagates to a maximum value V[max
which is typical for each glass, e.g. for silica
glass Vu max = 2200 m/s, for sheet glass
Vf, max = 1-500 m/s. They calculated from
the elasticity theory:
= 0.38 (13-23)
Figure 13-16 a. Principle of crack surface modulation
while Kerkhof (1963) calculated from with ultrasonic waves during crack propagation,
molecular considerations: V{ = Vh, under tensile stress, a0 • Vt = velocity of
transversal waves, T = transversal ultrasonic source
(13-24) (Kerkhof, 1980).

where Q is the density, y the surface energy

and f0 the mean distance of the ions. For a
mirror glass with E = 74 GPa, Q == 2.520
g/cm3, y = 0.305 N/m and r 0 = 2.0 • 10" 1 0 m
(Scholze, 1988), the maximum fracture ve-
locity is 2059 with Eq. (13-23) and 1556 m/s
with Eq. (13-24). The latter value agrees
very well with the experimental value of
1520 m/s. The most exact experiments on
crack velocity were performed using the
ultrasonic modulation technique of frac-
ture surfaces developed by Kerkhof (1980).
Fig. 13-16 a shows the principle and the — direction of crack propagation
result from which the crack velocity V{, can Figure 13-16 b. Microscopic interference field of the
be directly determined by V{ = X • v, where crack surface in the starting range of the ultrasoni-
X is the wavelength of the modulated crack cally modulated crack propagation: v = 923 kHz,
height of the photon graph is 0.4 mm, Crack velocity
surface and v the frequency of the ultra-
at the right-hand end about 100 m/s (Kerkhof, 1980).
sonic wave. If X becomes too small at low
V{ or too large at the beginning or end of
the fracture process, v should be chosen
smaller or larger, respectively. In this way men is broken, one can observe (Fig. 13-17)
the increase of V{ with crack propagation fracture mirrors; these are regions with a
can be obtained in an elegant manner (Fig. smooth surface around the fracture origin
13-16 b). For further methods, the reader is (below) which corresponds with the area of
referred to work by Kerkhof (1970, 1980, the starting fracture. At a certain distance
1983), Kerkhof and Richter (1987), and when the crack propagates with high ve-
Scholze (1988) which also contains a great locity, the fracture mirror becomes coarser.
variety of fracture phenomena with glasses. This distance, am9 is proportional to the
Two very frequently observed typical reciprocal of the square stress, a~2, or in
phenomena may be mentioned here, the other words the product am a2 is constant
so-called fracture mirror and the Wallner (Kerkhof, 1970, 1980). This constant is
lines. If a glass rod or a sheet glass speci- called the fracture mirror constant and al-
 13.3 The Phenomenon of Uncontrolled Brittle Fracture 685

lows one to calculate the specific fracture

energy, GSP:
GSJ> = 4(1-^) a2 aJ(nE) (13-25)
The roughness of the fracture surface is a
criterion that in this region the maximum
fracture velocity has been reached.
The Wallner lines can be detected on the
fracture mirror area as many fine crossing
curves (Fig. 13-18 a) from which the crack
velocity can be measured and calculated in
a much more laborious way and with a
Figure 13-18 a. Fracture surface of a broken glass rod
larger error than by using the ultra-sonic
(diameter about 6 mm) with Wallner lines. Crack
modulation technique. Fig. 13-18 b gives from below (Kerkhof, 1980).
the explanation for the evaluation of the
crack velocity and the origin of the Wallner
lines: supposing a constant fracture veloc-
ity, Vf the production of a single Wallner
line (ABCDE) is shown in Fig. 13-18 b
(Schardin, 1950). Around the crack origin
P are drawn 5 concentrical successive frac-
ture fronts with equal time differences At.
They correspond to 5 ultrasonic lines with
the same time difference At as if the moving
crack had been treated with transversal ul-

Figure 13-18 b. Schematic sketch for the construc-

tion of a Wallner line (ABCDE). P: origin of crack
(Schardin, 1950; Kerkhof, 1980).

trasonic waves. The first cycle through

Figure 13-17. Fracture mirror of a glass rod with
9.4 mm diameter (Kerkhof, 1980).
point A is the fracture front after the time
t0 corresponding to the distance V{ t0. Sup-
pose that at point A a small surface crack
exists at which the stored elastic energy
will be set free the moment the fracture
front arrives at A. Suppose further that the
elastic energy expands radial-symmetri-
cally as a transversal wave with a velocity,
Vt9 and that this wave coincides with
the fracture fronts at the points B, C, D
and E always after the time differences
= *2-'o>
686 13 Mechanical Properties of Glasses
etc. In this way a single Wallner line is
formed as a trace by the superposition of
the fracture process with the velocity, V{9
and the elastic ultrasonic wave released at
point A. In order to calculate V{, the pulse
velocity Vt must be known. For that reason
it is necessary to determine the whole frac-
ture process from a field of crossing Wall-
ner lines or to determine the crack velocity
point by point from angle measurements at
one or two crossing Wallner lines (see for
example Kerkhof, 1970, 1980).
13.3.3 The Phenomenon of the High Strength
of Glass Fibers
The famous investigation of Griffith
(1920) and the results on the increasing
strength of glass fibers with decreasing di-
ameter has not only enormously increased
knowledge on the large scale of strength
values, especially for glasses, bulk glass
samples, glass fibers and glass products,
but has also suggested for a long period
that the strength of glass fibers depends
only on the diameter (170 to 3400 MPa for
1 mm to 3 jam diameter). This was at least
partly confirmed by various other authors:
Anderegg (1939), Hasegawa et al. (1972)
and Rexer (1939). In contrast, radius-
independent strength was measured by
Thomas (1960).
During various discussions about these
contradicting results the question arose
about the influence of the size effect on
strength measurements (see Sec. 13.3.1.2).
Anderegg (1939) found that the strength of
fibers of constant diameter decreases with
increasing length, an effect which is also
found for float glass plates (Struck and
Briinner, 1989; Blank et al., 1990) with dif-
ferent extensions (Kerper and Scuderi,
1964 a, b). Thus, the interpretation of
Griffith's results was changed to the argu-
ment that the radius effect is due to de-
creasing probability for the presence of
cracks with decreasing radius or volume.
Of all possible cracks, surface cracks are
most important for the strength values.
Thus, Thomas (1971) found that rods with
1.3 cm diameter showed a mean strength
value which was about 35% lower than
that of fibers with 3 to 50 \xm diameter
made from the same glass. The measured
highest strength values, however, did not
differ. This observation is related to that of
Bartenev (1968) who has found repeatedly
that industrial glass fibers exhibit no sim-
ple distribution of strength values, but a
distribution with three distinct strength
maxima as is shown in curve 1 of Fig.
13-19. Very carefully prepared pristine
glass fibers show a distribution like curve 2
and annealed fibers that like curve 3. The
maximum at 3000 MPa is due to a defect-
free glass fiber while the maximum of curve
2 at 2000 MPa is due to ultrafme defects at
the surface and that at 900 MPa is due to
very fine cracks or surface defects of first
order according to Bartenev. Ritter et al.
(1978) have produced surface defect-free
silica fibers with strength values of up to
6 GPa (see also Kurkjian et al., 1982).
Decreasing strength values from 6 to
2.6 GPa may be explained by corrosion ef-
fects or by the action of very small atmo-
spheric dust particles (Maurer, 1977).
1
ibu fion-
2
3
1
\ 'f\ \
/~ y
1
A
1 \
0 2000 4000
— Strength in MPa*-
Figure 13-19. Relative distribution D of the tensile
strength of alumino-borosilicate glass fibers (diameter
10 um) with different surface defects according to
Bartenev (1968). Curve 1: industrial fibers, curve 2:
pristine glass fibers, curve 3: annealed glass fibers.
 13.3 The Phenomenon of Uncontrolled Brittle Fracture
According to extended investigations by
Pahler and Bruckner (1981, 1985 a, b) and
Stockhorst and Bruckner (1982, 1986), the
properties of pristine glass fibers depend
on two main factors: thermal and mechan-
ical prehistory. Only if the detailed and
complete rheological variables (tempera-
ture, velocity and pressure (or mass flow))
during the drawing process are known and
varied and the drawing force, drawing
stress, fiber diameter and quenching rate
can be estimated, is a separation of thermal
and mechanical prehistory possible.
With respect to the properties of pristine
glass fibers it is necessary to coat the fibers
with a protective layer of polymer or to
catch the fibers by electromagnetically op-
erated clamps during the fiber drawing
process. A typical criterion for a flawless
pristine fiber is that the fiber explodes into
very small pieces at fracture without leav-
ing any pieces between the two clamps. In
this way maximum strength values were
obtained by Pahler and Bruckner (1981)
at low drawing rates or low mass flow
rates, at low relative humidity (< 30% for
£-glass) and at a viscosity of lg rj = 2.8, rj in
dPa s. In such a way tensile strength values
up to 4000 MPa were obtained for E-glass
fibers. The fiber radius itself is not the only
parameter which is responsible for high
strength values - much more important are
the temperature profile, the deformation
rate, cooling rate and drawing stress within
the originating fiber (along the gob), which
are all related to the inverse fiber radius
and the wetting condition of the nozzle
(Fig. 13-20). Thus, Griffith is confirmed,
but only partly and in an indirect manner.
Young's modulus, the shear modulus,
and calculated from these values the ap-
parent Poisson ratio as a function of the
mentioned drawing parameters all give
direct evidence of the anisotropic structure
of the fibers when compared with the
687
Independent parameter
nozzle temperature Tn pressure on drawing speed Vz
the nozzle p
mass flow m-a^p exp (- Z?1 / 7"n) + 6
t
fiber radius /? =
drawing force F - a2 / n 1 / 3 e x p ( 6 2 / r n )
[ffi/[pjrVz)]v2
T T
drawing stress cr=Fz/[jrR2) cooling rate T=a3/R
Figure 13-20. The most important parameters for fi-
ber preparation by the nozzle-drawing method and
their mutual dependence.
isotropic structure of bulk glass (Pahler
and Bruckner, 1985 a). £-glass fibers as
well as metaphosphate glass fibers show
values of the apparent Poisson's ratio
which are very different from those for the
bulk glasses and sometimes exceed the
value ^ = 0.5 (Fig. 13-7 in Sec. 13.2.1.4).
Another interesting point is that the
elastic moduli do not parallel the strength,
as is usual for bulk glass when the compo-
sition is altered, but follow a contrary
course to the strength (Fig. 13-6 in Sec.
13.2.1.4). Thus, something must be changed,
if the Griffith Eq. (13-15) is to remain valid.
This change may be seen in the difference
between bulk and fiber glass structure, as
will be shown later in this section.
Deviations from Hooke's law at high
stress levels (Fig. 13-21) indicate that the
measured tensile strength can reach 50 to
90% of the maximum attainable theoreti-
cal strength (Pahler and Bruckner, 1985 b),
which is determined largely by the ionic
portion of the bonding. Flaws on which
fracture depends lie in the nanometer
range and tend to be sharply angular and
oriented along the length of thefibers.In
such a way only the much smaller cross
section of an elongated microcrack perpen-
dicular to the fiber axis is acting when frac-
688 13 Mechanical Properties of Glasses
• 75-
1 2 3
— Relative fiber strain in % •
Figure 13-21. Stress-strain diagram of E-glass fibers
with 10 \xm radius and the differentiated curve as
strain-dependent Young's modulus.
ture occurs and not the larger cross section
parallel to the fiber axis.
Measurements on other, more structure-
sensitive properties of £-glass fibers (Stock-
horst and Bruckner, 1982), as well as alkali
and alkaline earth metaphosphate glass
fibers (birefringence, density, shrinkage at
Tg and X-ray diffraction, Stockhorst and
Bruckner, 1986), have shown that glass
fibers are more anisotropic the larger the
stress was during the drawing process (me-
chanical prehistory) and the larger the noz-
zle temperature and the cooling rate (ther-
mal prehistory) were. For alkali metaphos-
phate glass fibers, the orientation effect of
the PO 4 chains along the fiber axis can be
shown by wide angle X-ray diffraction pat-
terns (Stockhorst and Bruckner, 1986). A
measure of anisotropy or even of orienta-
tion of structural units is the birefringence,
An, shown for the three glass types men-
tioned versus drawing stress during fiber
fabrication in Figs. 13-22 a to d. In all three
cases An increases with drawing stress and
with nozzle temperature and values are
obtained from An « 40 (£-glass fibers) up
to 10000 nm/mm (alkali metaphosphate
glass fibers). The latter value is comparable
with those found in stretched organic poly-
mers.
From these structure-sensitive measure-
ments it is easy to understand that cracks,
microcracks and flaws within and at the
surface of fibers will be oriented with their
longest axis parallel to the fiber axis; thus,
only the smallest cross-section dimension
of very flat and elongated cracks will be
responsible for fracture.
It may therefore be concluded that the
high strength of pristine glass fibers can be
explained by the anisotropic arrangement
of the structural units (flow units) and their
sharply elongated structural defects and
microcracks. Otherwise it is impossible to
understand that an open network such as
that produced by very high quenching
rates (thermal prehistory of thin fibers) can
produce much higher strength values than
an annealed glass or glass fiber. The drastic
decrease in strength of annealed fibers as
shown in Fig. 13-19, curve 3, can also be
understood with the anisotropic structure
of the fibers: the rearrangement of the fiber
structure and reelongation of microcracks
to an isotropic network results in a drastic
decrease in strength.
13.4 Controlled Fracture
Propagation and Time Dependent
Phenomena
In Sec. 13.3 stresses were applied which
lead immediately to fracture with unstable
crack propagation. If, in contrast, very low
stresses are applied, the glasses will not
 13.4 Controlled Fracture Propagation and T i m e Dependent P h e n o m e n a 689

10000

9000

8000

| 7000

g 6000
c
<
S 5000
CT1

£ 4000

3000
25Na2 O-25Li 2 O-50P 2 0 5
TD = 375°C
2000

1000
20 40 60
0- 50 100 150
(a) — Drawing Stress o z in MPa
(c) Drawing stress o in MPa

10000

9000

8000 m=3,0mg/s J&

/ / m=2,0mg/s

20 40 60 80 100 120
(b) — — Drawing stress in MPa •-

25Na2O-25Li2O-50P2O5
TD=400°C
Figure 13-22. Birefringence of glass fibers versus
drawing stress during fiber spinning; parameter: noz-
zle temperature, a: £-glass fibers; b: calcium-barium
metaphosphate glass fibers; c and d: sodium-lithium
metaphosphate glass fibers with the mass flow, m, as 50 100 150
parameter and TD = drawing temperature. Drawing stress o in MPa •

fracture but will show birefringence, if the
stress optical constant is not zero. At inter-
mediate stresses, however, glass does not
fracture immediately but supports the
stress only for a certain time interval. The
higher the stress, the shorter this time in-
terval will be, and the strength becomes
time dependent. This kind of fracture is
called static fatigue. This is equivalent with
the fact that the Klc value will be reached
only after a certain time during loading.
The origin of this dependence of load on
690 13 Mechanical Properties of Glasses
loading duration is that flaws and cracks
increase slowly under load until they have
reached the critical crack length of Klc at
which rapid crack propagation or failure
occurs. Therefore it is important to know
the dependence of fracture propagation
velocity on various effects such as stress,
temperature and surrounding medium.
On the basis of a detailed analysis of
these effects and from exact measurements
of subcritical crack propagation the proof
test was developed, particularly by Wieder-
horn and Evans (1974). If stresses are ap-
plied to glasses at constant stress rates, the
fracture stress, that is, the strength of a
glass, depends on the stress rate. The
higher the stress, the larger the stress rate.
This phenomenon is called dynamic fa-
tigue.
13.4.1 Subcritical Crack Propagation
In carefully performed measurements it
is possible to apply just those intermediate
stresses to a glass sample provided with a
well-defined crack before experiment so
that the velocity of the crack propagation
can be controlled and varied over many
orders of magnitude. Wiederhorn (1974)
has reported this in a review article. A very
strong dependence on the surrounding at-
mosphere or fluid media and on tempera-
ture has been found. Measurements in vac-
uum at constant temperature indicated
that the logarithm of the subcritical frac-
ture velocity, \gVf, increases proportion-
ally to the stress intensity factor, KY (not to
the stress!), and increases with rising tem-
perature (Wiederhorn et al, 1974), with an
activation energy of about 500 kJ/mole.
The interpretation of this activation value
is not yet quite clear.
It should be emphasized that a subcriti-
cal V{ could not be measured for a few
glasses, such as silica glass and borosilicate
glass, because fracture happened immedi-
ately. This shows a dependence of the elas-
tic constant on temperature and pressure
(see Sec. 13.2.1.3) other than that for usual
silicate glasses. Possibly, the stress at the
crack tip is released first and when the
pressure dependence becomes normal at
higher load, the fracture velocity is turned
immediately into the unstable condition.
The main results obtained from subcriti-
cal crack propagation in glass in various
environments may be summarized by the
following generalization, in addition to
those already mentioned:
- The Vf — Klc curves may be divided into
three different regions (Wiederhorn, 1967),
all of which can occur in a material but do
not necessarily need to occur (Fig. 13-23):
Region I is determined by the velocity
which is needed for the surrounding me-
dium to react with the glass at the crack
tip.
Region II, the horizontal part of the
curves in Fig. 13-23, is determined by the
velocity which is necessary to transport the
surrounding medium to the location of the
crack tip. This velocity limits the influence
of the medium on the crack propagation
velocity.
Region III is independent of a gaseous
medium. This region corresponds to the
behavior in vacuum. Liquid media, how-
ever, can influence the subcritical crack
propagation up to still higher velocities
due to physical processes (Fig. 13-24).
- The Klc value is a point on the
lg V{ — KY curve within region III at about
10 mm/s < Vf < 100 mm/s, and is some-
what arbitrary.
- At extremely low crack velocity values
(Vf < 10 ~6 mm/s), a value Klo can be as-
sumed below which no crack propagation
happens. This is called the static fatigue
limit.
 13.4 Controlled Fracture Propagation and Time Dependent Phenomena
Figure 13-23. Crack velocity, V{, of glass versus stress
intensity factor Kx in air with various relative humid-
ities and under liquid water (Wiederhorn, 1967).
Figure 13-24. Crack velocity, V{, versus Xj for glass
under liquids with various viscosities. The numbers at
the curves indicate the same regions as in Fig. 13-23.
The larger the viscosity, the more the crack propaga-
tion under liquids is reduced. The regions 2, 3 and 4
coincide in the case of water (Richter, 1985).
691
Wiederhorn (1967) suggested, with the
help of the stress-corrosion theory of
Charles (1958) and Hillig and Charles
(1965), that an accelerated chemical reac-
tion takes place under the influence of
the enhanced stress at the crack tip. In
aqueous solutions, however, this interpre-
tation is not satisfying. Therefore Freiman
et al. (1985) and Michalske and Freiman
(1983) assume that the reaction with the
glass network at the crack tip is important
for crack propagation and that those reac-
tions only happen when the absorbing
molecules dissociate at the stressed bond-
ings of the glass network.
More investigations are necessary, par-
ticularly because no one knows the exact
geometry of the crack tips. Doremus (1982)
assumes a crack tip radius of about 10
atomic distances and Lawn et al. (1985) as-
sume about one atomic distance (0.14 nm),
where a radius has no physical sense; at
this point the continuum character of the
theory of fracture mechanics has its limit.
13.4.2 Fatigue and Lifetime
13.4.2.1 Static Fatigue
From the results of fracture velocity ver-
sus KY one may state that fatigue occurs
only in the presence of water, not in vac-
uum, that no fatigue takes place at very
low temperatures because of the very low
reaction rates, and that fatigue increases
with increasing temperature.
The consequence of the existence of sub-
critical crack propagation is that at a cer-
tain stress in or on a glass specimen a crack
elongation can be expected. After a certain
time under this stress a critical crack length
can be reached at which fracture occurs
spontaneously. This time-dependent frac-
ture or strength is called fatigue. It can be
measured with static, dynamic and cyclic
methods and is connected to fracture me-
692 13 Mechanical Properties of Glasses
chanical data. Wiederhorn (1975) has given
detailed descriptions in a review article on
this topic. The interpretation of this phe-
nomenon is usually based on the stress cor-
rosion theory of Charles (1958) and Hillig
and Charles (1965), which was mentioned
in Sec. 13.4.1: the crack elongates by the
reaction of an agent, e.g., water, with the
glass network until the critical length is
reached. With this interpretation a blunt-
ing effect at the crack tip should occur par-
allel to the elongation. Doremus (1973), on
the other hand, thinks that the reaction
with water produces a sharpening of the
crack tip which leads to a decrease of
strength when the tip radius is very small.
Oka et al. (1981) remind one that the sur-
face energy should decrease upon contact
with water.
It should be emphasized that the reac-
tion with water can also lead to the oppo-
site effect, an increase of strength, if a crack
is corroded in such a way that blunting
(increase of the crack tip radius) and short-
ening of the crack occurs. This is called
aging (Fig. 13-25), and happens preferably
when a low stress, or no stress, is applied
during corrosion (Bando et al., 1984; Hi-
rao and Tomozawa, 1987). This explains
the old observation that glass breaks more
easily immediately following scratching
than after a certain time has elapsed.
Going back to the effect of stress corro-
sion and fatigue, the so-called universal
uniform dissolution
Figure 13-25. Schematic sketch of the alteration of a
crack tip in the presence of water (blunting and aging,
Bando et al., 1984).
0.5-
0 4 8
tog (i-/t os )
Figure 13-26. Universal fatigue curve. Curve 1:
ground sodium calcium silicate glass according to
Mould and Southwick (1959-1961); curve 2: E-glass
fiber; curve 3: silica glass fiber; curve 4: acid-etched
sodium calcium silicate glass. Curves 2 to 4 are from
Ritter and Sherburne (1971).
fatigue curve (Fig. 13-26), according to
Mould and Southwick (1959, 1961), may
be mentioned here. Curve 1 was obtained
from many experiments under various
conditions: sodium calcium silicate glass
samples were roughened by defined grind-
ing of the surface. It was found that the
strength, a, relative to the strength at liquid
N 2 temperature (77 K), <rN, and the time,
t, relative to the time t0 5 at which is
a = 0.5 <rN, give a single curve for all mea-
surements, known as the universal fatigue
curve (curve 1 in Fig. 13-26) when plotted
as a/aN versus Ig (t/t05). This indicates that
the strength decreases by about 7% of the
value crN if the loading time is increased by
a factor of 10, and that the mechanism of
fatigue is unique although the rate of
fatigue depends on various experimental
conditions.
Further measurements, made by Ritter
and Sherburne (1971), showed deviations
from curve 1 in Fig. 13-26, particularly
with regard to the slope. The largest devia-
tion is found for the same glass type whose
surface was treated not by grinding but by
acid-etching (curve 4).
The lower slope indicates a lower suscep-
tibility to fatigue, obviously resulting from
a surface relatively free of faults as com-
 13.4 Controlled Fracture Propagation and Time Dependent Phenomena 693

pared to a surface with deep cracks. Vari- 13.4.2.2 Lifetime and Proof Test
ous equations were proposed to describe
One of the main reasons that great ef-
the fatigue curves, e.g., lg t = at + b± lgcr
forts were made with experiments on slow
or Igt = a2 + b2/(T.
crack propagation in glasses was a wish
A special point of interest is the static
to get information about the long-time
fatigue limit. Evidence for the existence of
strength and/or life-time of real structural
such a limit requires measurements at ex-
components of glasses from short-time ex-
tremely low subcritical fracture velocities
periments. Starting from Eq. (13-18) for Kl9
and stresses. Such measurements were per-
it follows by differentiation that
formed by Wiederhorn and Bolz (1970)
who found deviations from the lg V{ — Kx n da
curves within region I (see Fig. 13-23) at Vf with Vf=da/dt
a dt 2KX
1/2
K r values < 0.3 MPam becoming nearly (13-26)
stress-independent (Fig. 13-27). This is if <ja, the applied stress, is assumed to be
equivalent to a limit of fatigue for the in- constant. From the experimental results
vestigated glasses of about 20-25% of the (Figs. 13-23 and 13-24) the empirical Eq.
critical stress intensity factor, Klc. This (13-27) follows for the crack velocity, V{:
limit seems, however, to be variable and
can be changed to 50% of Klc for glasses Vf = AK? = da/dt (13-27)
with low chemical stability (Gehrke et al., where the constant, n, represents the slopes
1986), which is usually combined with low of the curves in Figs. 13-23 and 13-24,
strength. The reason for this may be seen in which are about n = 20 to 30 for the range I
the formation of corrosion layers, as was and n = 80 for range III. A, the crack prop-
described above in connection with aging. agation parameter, is within +0.5 to —0.5
in region I and + 7 in region III for V{ in
m/s and KY in MPam 1 / 2 .
The lifetime, tf, the time at failure, can be
easily obtained from Eq. (13-26) after inte-
gration over KJVf from K Ia , the value at
the beginning of loading with the starting
crack length a, to Klc, where the depen-
dence of KY versus Vf is given by Eq. (13-27)
tf = 2anlc2a;n/[^(n-2)AK^2] (13-28)
where aIC is the strength in an inert envi-
ronment.
An example from Scholze (1988) may be
given here. From Fig. 13-23, it follows that
0.2 0.3 0.4 0.5 0.6
for 10 and 100% relative humidities n = 25
K} in MPam1/2 - — and 22, and A = 2.8 and 4.0, respectively.
For usual sodium calcium silicate glasses
Figure 13-27. Crack velocity, V{, versus J^ of various
XIC = 0.75 MPam 1 / 2 . With a crack depth
glasses under water at 25 °C at very low Vi-values.
Curve 1: sodium calcium silicate glass; curve 2: of 10 nm a critical strength results from Eq.
borosilicate glass; curve 3: alumino-silicate glass; (13-18): <rIC = 4230MPa. The lifetime un-
curve 4: silica glass (Wiederhorn and Bolz, 1970). der a permanent loading of 1/3 of the crit-
694 13 Mechanical Properties of Glasses
ical strength, oa = 1410 MPa, is calculated
from Eq. (13-18) to be t{ = 4 days in 10%
relative humidity and in 100% relative hu-
midity only ti = 75 minutes.
The calculation of reliable lifetimes de-
mands some critical remarks:
- the values for K1C and olc must be deter-
mined exactly because of the high expo-
nents of n,
- for different experimental methods dif-
ferent equations are applied (see Kerkhof
etal., 1981),
- cracks usually have different depths and
the largest one determines the strength.
Statistics have been applied, as described
for instance by Jakus et al. (1978), in an
attempt to overcome these restrictions.
Frequently Weibull statistics are used;
however, Doremus (1983) argued that this
is not always necessary.
A prognosis or a guarantee of the life-
time can be obtained by proof testing (Rit-
ter et al., 1980). This procedure starts with
a pre-loading of the samples by a pre-
stress, crp, which is larger than the working
stress o-w, applied later. All those specimens
for which Klc < op < 'n ap will be fractured.
The rest comprises specimens with cracks
a < ap, which means Klc > <rp^Jna. For
the practical application of the structural
component the specimen should show
oa > <7p, thus, with oa yfna = Kla it follows:
<jp/<ja<Klc/Kla or l/X I a ><rp/(<7aKIC).
With a < olc Eq. (13-28) is altered to:
tf> (13-29)
n(n-2)A ona, i - 2
From plots of lg t versus lg oa one can esti-
mate how large the value for op has to be
in order to achieve a certain desired life-
time (Ritter etal., 1980).
13.4.23 Dynamic Fatigue
The parameters n and A of Eqs. (13-27 to
13-29) can also be obtained from the
dynamic fatigue. If Eq. (13-26) is integrated
not for a = constant but for da/dt = at,
that means for linearly increasing stress as
is the case for usual fracture stress mea-
surements, one obtains for the fracture
stress, af:
(13-30)
with
B = 2/[n(n-2)AK?c2] and:
fna (13-31)
where ain is the strength in an inert envi-
ronment, a condition for which slow crack
propagation is fairly excluded. Eq. (13-30)
means that the fracture stress is lower the
slower the loading rate is. The reason is
that the cracks have more time for elonga-
tion at slow rates compared with larger
rates, and the longer the crack depths, the
lower the stresses needed to reach Klc.
In a plot lg o versus lg(do-/dt), Eq.
(13-30), a straight line results with a slope
l/(rc + l). These dynamic fatigue measure-
ments are the simplest method for the de-
termination of crack propagation parame-
ters.
13.5 Techniques for Increasing
Strength and Toughness of Glasses
Three possibilities for increasing the
strength of glasses are described in this sec-
tion: thermal, chemical and fiber-rein-
forced strengthening. A special problem for
glasses, with exception of metallic glasses
(see Chap. 9 of this volume), is the restric-
tion of their application as structural com-
ponents because of their brittleness or very
low toughness. Typical values for Klc are
 13.5 Techniques for Increasing Strength and Toughness of Glasses
only around 1 MPam 1 / 2 . The only way to
increase the toughness of glasses is to in-
corporate ceramic fibers. In this way not
only is the strength increased by a factor of
up to more than 10, but the toughness also
increases by a factor of up to more than 30
(Sec. 13.5.3).
13.5.1 Strengthening by Thermal Tempering
This kind of strengthening is based on
quenching glass (flat glass) in air (Gardon,
1980) or in liquids (flat glass and glass pip-
ing, Gora et al., 1977). The result is that
compressive stresses are built up in the sur-
face area which contract the surface cracks.
When loading occurs the surface compres-
sive stress must first be turned into tensile
stress before the specimen breaks under a
certain tensile stress value.
In order to build up permanent com-
pressive stresses in the surface, the quench-
ing process has to start from a To above Tg.
If the quenching rate is kept constant, a
parabolic temperature profile in the cross
section of, e.g. a flat glass plate, is built up
and kept constant. No stress will be built
up as long as To > Tg because viscosity is
too low. When To at the surface, Ta, under-
goes Tg, the thermal expansion mismatch
(Hagy and Ritland, 1957; Oel et al., 1979)
between surface layers (Ta<Tg) and the
interior of the glass plate with temperature
T{ still larger than Tg leads to the first step
of the stress profile because the surface lay-
ers are solid and the interior is still liquid.
The second step of a more pronounced
parabolic stress profile is built up at room
temperature during temperature equaliza-
tion and the reduction of the temperature
profile (Fig. 13-28). The first step of stress
distribution can thus simply be calculated
thermoelastically from the temperature
profile at the instant that the surface, and
after that the midplane, reaches Tg. This
695
0 1 2 3 4
Thickness x in m m - * -
Figure 13-28. Parabolic stress distribution of ther-
mally strengthened glass plates. Solid curve: normally
quenched in one way; dashed curve: quenched and
heat-treated in a second step (Dannheim and Oel,
1983).
treatment does not consider the visco-elas-
tic behavior of glasses around Tg, where
solidification and stress-forming processes
are time-dependent and thus dependent on
cooling rate dT/dt, characterized usually
by a distribution function of stress relax-
ation times. Additionally, structure-related
changes in viscosity, density and Young's
modulus have to be considered within the
rg-region during quenching for a more
refined approach to stress profile forma-
tion (Gardon, 1980; Scherer, 1986; Rekh-
son, 1986).
All the above-mentioned effects and
properties depend strongly on glass com-
position and geometry but also on surface-
related properties such as the heat transfer
coefficient, surface tension, contact angle,
thermal conductivity, and specific heat.
Also of importance are the properties of
the quenching medium, its temperature rel-
ative to that of the specimen and its boiling
tendency which influences the heat transfer
coefficient (Singh et al., 1981). Strength can
be increased in these ways by a factor of up
to four (Gardon, 1980).
The stress profile shown in Fig. 13-28,
solid curve, with the maximum compres-
sive stress at the surface is optimal only
696 13 Mechanical Properties of Glasses
with respect to strength experiments. If a
surface crack is produced in practice, it
propagates towards lower stresses and
will grow. On the other hand, if the com-
pressive stress profile has its maximum be-
neath the surface, the crack propagation
will be hampered and suppressed within
the region of increasing compressive stress
(stress barrier effect, see dashed curve in
Fig. 13-28). This can be done by multi-step
methods in two ways: by an inverse ther-
mal quench, e.g., by rapid heating in metal
melts in order to relax the surface compres-
sive stress partly (Schaeffer, 1985), or by a.
subsequent ion exchange below Tg (see Sec.
13.5.2).
13.5.2 Chemical Strengthening
As early as 1892, Schott proposed to
strengthen a glass by coating it with a glass
having a smaller thermal expansion coeffi-
cient. This can be done easily today by the
sol-gel method, described by Fabes et al.
(1986) (see also Chap. 2).
Another way to produce compressive
stress in the surface layers is in principle
the ion-exchange method with its various
combinations. If the sodium ions of a glass
are exchanged with lithium ions from a
LiNO 3 salt melt above Tg, the surface lay-
ers exhibit a smaller thermal expansion co-
efficient than the interior and give rise to
compressive stresses after cooling down to
room temperature. This method (Hood
and Stookey, 1957) has the disadvantage
that the specimens will be more or less eas-
ily deformed. This disadvantage is also
present for some variations of this method
with ion-exchange treatments above Tg, by
which surface layers are produced consist-
ing of transparent glass ceramic based on
lithium alumino silicates with their well-
known extremely low thermal expansion
coefficients. The strength values of normal
glass products with such surface-modified
layers are up to 800 MPa (Stookey et al.,
1962; Schroder and Gliemeroth, 1970).
In contrast to ion exchange treatments
above Tg, there is the mechanism of ion
exchange below Tg. When a Na 2 O-con-
taining glass is treated in a KNO 3 salt
melt, a lattice dilation (ion stuffing) is pro-
duced by the ion exchange Na + ^ K + , and
compressive stresses are built up by the
incorporation of the larger K + ions into
the glass surface layer (stress-induced dif-
fusion). Interdiffusion processes determine
this procedure, which is of great practi-
cal importance. The A12O3 content of the
glasses improves the diffusion rate of the
alkali ions. Too high temperatures close
to Tg enhance the exchange rate, but the
compressive stresses will be destroyed by
the increasing rates of the relaxation pro-
cesses. This phenomenon is noticeably ac-
tive down to Tg - 100 K (Sane and Cooper,
1987). If the glass specimens are quenched
before the ion-exchange process, a larger
ion exchange results because of the larger
free volume as compared with a slowly
cooled glass sample (Zheleztsov and Yan-
beeva, 1983). The ion exchange depths
are usually 100 to 300 jim. Compressive
stresses up to 1000 MPa are reached at the
surfaces, and must be overcome before
fracture occurs in a tensile stress situation.
Fig. 13-29 gives a comparison of the stress
profiles between low temperature (below
Tg) ion exchange and thermal strengthen-
ing (Olcott, 1963).
surface
surface
200 0 200 400 600 800
-«-tensile compressive stress in MPa-*-
Figure 13-29. Stress profile through the cross section
of a flat glass plate after ion exchange (dashed curve)
and after quenching (solid curve) (Olcott, 1963).
 13.5 Techniques for Increasing Strength and Toughness of Glasses
100 200 , 300 400
Layer thickness in u
Figure 13-30. Relaxed stress profiles after ion ex-
change in Na 2 SO 4 + ZnSO 4 (Zijlstra and Burggraaf,
1969). Curve 1: 10 min. at 590°C; curve 2: 15 min. at
580 °C; curve 3: 25 min. at 585 °C.
The above-mentioned effect of a relaxed
stress profile is shown in Fig. 13-30, and is
due to a stress relaxation caused by viscous
flow and seems not to be directly con-
nected to the mixed-alkali effect (Tomandl
and Schaeffer, 1977).
13.5.3 Fiber-Reinforcement of Glasses
As was shown in the previous sections,
glasses usually show low tensile and flex-
ural strength, except for pristine thin glass
fibers, and a pronounced brittle fracture
behavior. This is the main reason for their
limited technical application as construc-
tion elements of engines and other prod-
ucts. Strength-increasing effects as de-
scribed in Sees. 13.5.1 and 13.5.2 by
thermal or chemical means enhance the
strength indeed, but do not influence the
brittle fracture behavior. One possible way
to overcome these disadvantage is the in-
corporation of ceramic fibers (SiC- and C-
fibers) into glass matrices. This principle
was first energetically promoted by Prewo
etal. (1981).
One of the most successful and econom-
ical procedures is the so-called slurry tech-
nique for preparing the "prepregs" (Sambell
et al, 1972; Levitt, 1973), where an organic
binder is used to glue the glass particles to
697
the fibers. If, however, an alkoxide solution
is used as a binder material (Hegeler and
Bruckner, 1989; Hegeler etal, 1989), the
wetting of glass particles and fibers as well
as interfacial properties can be optimized.
The strength of the "prepregs" can then be
increased by sol-gel transition (see Chap. 2)
up to such a hardness that the prepregs can
be well-handled and cut into pieces by a
diamond saw. Any suitable alkoxide solu-
tion may be applied. The finished prepregs
are densified by means of an inductively
heated hydraulic press in a graphite die
and in N 2 or Ar atmosphere.
Optimization procedures with respect to
optimum mechanical and thermal proper-
ties are possible by variation of the follow-
ing parameters (Hegeler and Bruckner,
1989, 1990):
First, thermal and mechanical treatment
- an optimum is at about 1250 °C for
DURAN glass (viscosity around 10 4 dPas),
at a pressure of lOMPa.
Second, the fiber content - for which an
optimum also exists at a volume concen-
tration of about 50%.
Third, the forces acting between fibers
and matrix - chemical and mechanical
forces. Optimum values for flexural strength
and toughness are obtained if these forces
are neither too low nor too high. If on the
one hand the contact between fibers and
matrix is too high, e.g., for a strong chemi-
cal bonding, the strength will be moderate
and the toughness will be low; if on the
other hand the forces are too low, the
strength will be also very low and tough-
ness will be good. The best effect will be
produced in between, for which the ther-
mal expansion mismatch, as well as the
condition of the interfacial layer of fiber
and glass matrix, are important.
The thermal expansion mismatch is re-
sponsible for the stress (with its three com-
ponents - radial, axial and circumferen-
698 13 Mechanical Properties of Glasses

cial), between fibers and glass matrix, and pull out

primarily determines, together with the
hot-pressing pressure, the strength of the
composite. In addition to, the friction coef-
delaminafion
ficients, the adhesive and gliding friction of fibers
coefficient, between the two components
of the composite determine not only the crack
fiber
strength but also the toughness. This influ- fractures
ence is determined largely by the interface
composition and properties (Hegeler and
Bruckner, 1990). It was found that a thin
carbon layer (Brennan, 1988) is very ad- Figure 13-31. Pull-out effect of a fiber-reinforced glass
vantageous for a good (not too low and not composite, schematically.
too high) adhesion to optimize the so-
called pull-out effect (Fig. 13-31), which
1200
should neither be too large nor too small. bulk 45vot.%>
glass
If no pull-out effect is observed after frac- MPa

ture, the composite is usually brittle. Much

more investigation has to be done to opti-
900-
100

mize the interfacial layers (see also Vol. 13,
Chaps. 7 and 11).
Some typical results are presented here.
Fig. 13-32 is an example of the stress-strain
behavior for two composites. The high
strength and the large work of fracture (in-
tegral over the stress-strain curve) are re-
markable compared with those of a usual
bulk glass. The effect is tremendous, an in-
crease in strength by a factor of up to more
than 10, and an increase in Klc values by a
factor up to more than 30 are possible. The
great disadvantage of low strength perpen-
dicular to the fiber orientation may be
overcome by a layered structure, e.g. by
0o/90° cross-ply composites. Figs. 13-33 a
and b show the strength of composites with
unidirectionally and bidirectionally ori-
ented SiC-fibers versus the angle of load-
ing. In Fig. 13-33 a it is noteworthy that no
decrease in strength is reached before 30°,
and in Fig. 13-33b a reduction in strength
of only 30% occurs at 0° and 90°, com-
pared with 0° in Fig. 13-33 a. The aniso-
tropic strength decrease is only 100 MPa
at 45°.
U
0 0.1 %
600-
300-
0.2 0.4 0.6 0.8 1.0 1.2
Strain in %
Supremax glass/SiC fibers
Figure 13-32. Stress-strain diagrams of SUPREMAX
glass/SiC-fiber composites with 40 and 45 vol% fiber
content compared to that of bulk glass (inserted fig-
ure).
13.6 Mechanical Behavior Above
the Glass Transition Temperature
While the tensile and flexural strength of
glasses is primarily a surface property
which depends on the most severe flaws at
the surface and which is valid within the
pure elastic and brittle region of glasses,
the question arises as to what happens with
the characteristic mechanical properties if
viscoelastic and viscous influences become
 13.6 Mechanical Behavior Above the Glass Transition Temperature 699

peratures, the influence of different stress

rates on the strength becomes more and
600-
more pronounced. At temperatures above
Bending strength
r g , a strongly temperature-dependent crit-
ical deformation rate can be identified as a
necessary condition for brittle fracture at
^00-
small bending deflections which are well
within the linear elastic theory (Manns and
Bruckner, 1983). This critical deformation
200-
rate may be taken as a limiting criterion as
between plastic-viscous (or visco-elastic)
and brittle-elastic behavior of the super-
0 30 60 90 cooled glass melt (Fig. 13-34).
(a) Loading angle a indegrees —•»- Strength measurements on glass plates
using the double ring method within the
brittle-elastic region, where the linear elas-
600- tic theory is still valid, are shown in Fig.
13-35 for a commercial borosilicate glass
with original surfaces versus temperature.
400- A steep increase in bending strength occurs
t Bending strength
around Tg and above. In order to be able
to measure bending strength up to the Lit-
200- tleton temperature (where rj = 10 7 6 dPas),
Shear strength
sufficiently large deformation or strain
rates have to be applied, characterized by
I the rate-dependent values of the elastic
0 30 60 90
(b) —Loading angle oc in degrees-—•• modulus E* = 25 or 40 GPa.
A possible interpretation of the results
Figure 13-33. Bending and shear strength of a
DURAN glass/SiC-fiber composite with unidirec-
of Fig. 13-35 is that viscous flow within
tionally oriented fibers (a) and of a composite with surface cracks, and particularly at the
0°/90° crossply oriented fibers (b) versus loading angle crack tips, takes place and leads to a blunt-
a; 40 vol% fiber content each. ing of the crack tip and therefore to an
increase in strength. As will be seen from
Sec. 13.6.3, even non-Newtonian flow (de-
more and more dominant with increasing crease of normal viscosity under high de-
temperature around and above Tg, a ques- formation rates and stresses) has to be con-
tion which is also of great importance for sidered under the applied stresses and
practical forming processes. strain rates.

13.6.1 High-Temperature Strength

13.6.1.1 High-Temperature Strength
as a Surface Property
If the flexural strength of a commercial
silicate glass is measured at elevated tem-
13.6.1.2 High-Temperature Strength
as a Volume Property
A totally different kind of high-tempera-
ture fracture and strength was found re-
cently, which is not a surface property but
700 13 Mechanical Properties of Glasses

Figure 13-34. Curve of minimum

deformation rate for the brittle
bending fracture of float glass
plates (double ring method). As
received surfaces are plotted ver-
sus temperature with the restric-
tion that the bending of the plate
at fracture is smaller than the
plate thickness. The symbols indi-
cate the applied deformation rates
for the strength measurements,
characterized by the observed ap-
parent (that means rate-depen-
600 650 700
dent) elastic moduli £* in GPa.
Temperature in °C

300-
/
I
• o -- 2MPa/s /
250- o E* < 25 / o
a E*^40 a/

200- a/ o -

1 Figure 13-35. Bending strength of

o
1°
a borosilicate flat glass plates with
150- / a
as received surfaces versus temper-
-t T 9 5 % confidence ature at various loading rates,
i limits of mean
100- characterized by £*. (J): strength
of annealed samples.
0 100 200 300 400
Temperature in °C

a volume property. Starting from simple

first crack
experiments in which a glass cylinder is
compressed between the pistons of a uni-
Flow range versal servo-hydraulic test machine at dif-
ferent deformation rates, the response of
the glass sample above Tg is a curve like
that in Fig. 13-36 at a moderate rate. After
the viscoelastic and flow range has been
0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6 passed, the first axial macro-crack appears
Axial compressive deformation in mm — •
at the equator line of the deformed cylin-
Figure 13-36. Typical force-deformation diagram of a der. The tensile strength of the specimen
compressed cylindrical glass sample (DGG standard can be calculated from the values of the
glass I, T = 658 °C, s = 8 mm/s) with viscoelastic
range, viscous flow range and situation of the first
stress strain curve (Hessenkemper and
macrocrack at the equator-line of the deformed cylin- Bruckner, 1989). Results are given in Fig.
der. 13-37, where the tensile strength is plotted
 13.6 Mechanical Behavior A b o v e the Glass Transition Temperature
100 200 300 400
- A x i a l compression stress in MPa — » -
versus the axial compressive stress for var-
ious silicate glasses at constant Newtonian
equilibrium viscosity r\0 = 10 8 Pas, and in
one case also at rj0 = 10 1 2 Pas. There are
differences in the tensile strength values of
up to 300% depending on the composition
of the glasses, which are given in Tables
13-2 and 13-3.
The temperature dependence of the
high-temperature tensile strength is seen
from the glass containing CaO-MgO, with
4 and 8 mol%, respectively, as an example
(Fig. 13-37): the strength decreases by
60 MPa when the temperature is changed
from 557 to 697 °C or the viscosity from
1012 to 10 8 Pas.
The increasing strength with increasing
axial compressive stress in Fig. 13-37 is in-
terpreted as a load-dependent change of
structure of the glass melts and agrees with
both stress-dependent relaxation behavior
(see Sec. 13.6.2) and non-Newtonian flow
behavior (see Sec. 13.6.3).
It is remarkable that high-temperature
tensile strength within the viscous flow
range is a volume property, as was shown
by Hessenkemper and Bruckner (1989).
While surface-dependent strength values
within the brittle and viscoelastic range are
connected to a relatively high variation of
30% and more, which is typical for statisti-
701
Figure 13-37. High-temperature
tensile strength for various glass
melts versus axial compressive
stress at constant Newtonian equi-
librium viscosity rj0 = 10 8 Pas and
in one case also at t]0 = 10 12 Pas.
500
cally acting surface influences, the varia-
tion of the tensile strength values within
the viscous range is only around 5% and
the fracture strength values are strictly in-
dependent of the surface roughness.
13.6.2 Non-Linear Relaxation Behavior
When glass melts are treated in such a
way that the stress limit of fracture is
reached the relaxation behavior will no
longer be linear. This was shown by Hes-
senkemper and Bruckner (1989, 1990 a) in
numerous experiments. The main results
of these investigations are shown in Figs.
13-38 a and b, where the relaxation modu-
lus E(t)max is plotted versus the deforma-
tion rate, h, of a compressed glass cylinder
within the viscoelastic range (Fig. 13-38),
and for various glass melts and at various
equilibrium viscosities, rj0. The large differ-
ences in E (Omax n o t o n ly between different
viscosities, rj0, but also between the vari-
ous compositions of the glass melts (see
Tables 13-2 and 13-3) are evident. The re-
laxation modulus increases with h and with
increasing viscosity.
Of special interest is that the shift factor
of the Wiliams-Landel-Ferry equation is
no longer constant above 20 MPa axial
compressive stress, <7ax, but decreases with
702 13 Mechanical Properties of Glasses

Table 13-2. Compositions and properties of industrial glasses.

Borosilicate glass Optical glass Float glass

in mol% in wt.% in mol% in wt.% in mol% in wt.%

SiO 2 81.8 80 73.0 69 70.1 71.3

B2O3 8.8 10
A12O3 1.8 3 0.35 0.6
Na 2 O 5.0 5 8.2 13.3 14
K2O - 6.1 0.02 0.03
MgO 1.5 1 5.9 4.0
CaO 1.1 1 9.1 10.1 9.6
BaO - 0.8 2
ZnO - 2.7 3.5
Sb 2 O 3 - 0.1 0.5
SO 3 - 0.22 0.31
Sum 100 100 99.84
Tg in °C 550 529 546
a in l O ^ K " 1 3.25 9.35 8.96
E in GPa 59 64.5 73
G in GPa 25 26 32
Density Q in g/cm3 2.226 2.565 2.495

Table 13-3. Compositions and properties of glasses with exchanged CaO/MgO contents.

Glass no. 1 Glass no. 2 Glass no. 3

in mol% in wt.% in mol% in wt.% in mol% in wt.%

SiO 2 74 73.33 74 74.11 74 74.5

A12O3 1.5 2.52 1.5 2.55 1.5 2.58
Na 2 O 12 12.27 12 12.4 12 12.53
K2O 0.5 0.78 0.5 0.78 0.5 0.79
MgO O0 0.00 4 2.68 8 5.42
CaO 12 11.1 8 7.48 4 3.77
Sb 2 O 3 0.5 0.5 0.5
Tg in °C 565 547 548
a in 10" 6 K~ 1 8.7 8.25 7.6
(100 to 200 °C)
E in GPa 75 72 71
G in GPa 31 30.5 30.5
Density Q in g/cm3 2.52 2.479 2.45

increasing aax (Hessenkemper and Bruck- laxation time T at a constant temperature

ner, 1990 a). As a result, above this loading
limit thermorheological simplicity (Ferry,
1970; Kurkjian, 1963; Mills and Sievert,
1973) is not achieved, relaxation behavior
is load- and/or rate-dependent, and the re-
or constant equilibrium viscosity, rj0, is no
longer a constant but depends on the de-
formation rate, h (Fig. 13-39). This means
that relaxation processes are faster under
load than without load.
 13.6 Mechanical Behavior Above the Glass Transition Temperature 703

- 2 - 1 0 1
(a) •Deformation r a t e : log h',K in m r n / s -

a 32- /
Q_
ID
/glass 3
24-
/ no^O12Pas
glass 3 /
Pas /

16-

/
7
glass 1
8
Figure 13-38. Relaxation modulus
versus axial deformation rate of
the samples, lg/i, at various equi-
8- ^^--^glass 1 / vio Pa^
^ ^ no-1O12 Pas librium viscosities, rj0; a) optical
glass, b) glasses no. 1 and 3 (see
Table 13-3).
-3 -2 -1 0 1
(b) Deformation rate : log h, h in mm/s

Another point of interest is that a corre-

h in mm/s
Figure 13-39, Relaxation time, T, of an optical glass
melt versus deformation rate, h, at a Newtonian equi-
librium viscosity rj0 = 10 8 Pas.
lation between the relaxation modulus and
the high-temperature tensile strength ex-
ists: the larger the relaxation modulus the
lower the ht-tensile strength and vice versa
(compare Figs. 13-38 a and b with Fig.
13-37!).
In this way a clear definition for the brit-
tleness of a glass melt is given which has
important consequences for the concept of
workability of a glass melt in glass forming
processes (Hessenkemper and Bruckner,
1990 b).
704 13 Mechanical Properties of Glasses

13,6.3 Non-Newtonian Flow Behavior to 1 0 1 4 > ^ 0 > 2 • 10 5 Pas, where special

In this section the well-known effects of
time-dependent viscosity due to thermal
non-equilibrium processes (see, e.g., Chap.
3 of this volume and Scherer, 1986; Rekh-
son, 1986) are excluded and only load-de-
pendent viscosity effects will be regarded.
The first measurements of non-New-
tonian flow behavior of silicate glasses were
done by Li and Uhlmann (1970) at con-
stant tensile stresses and by Simmons et al.
(1982) at constant tensile strain rates using
the fiber elongation method. These mea-
surements are restricted to the (Newtonian)
viscosity ranges 1 0 1 6 > ^ 0 > 1 0 1 2 5 P a s and
10 13 >77 0 >10 10 Pas.
Studies of glass cylinders under com-
pressive stresses with a parallel plate plas-
tometer have also been made under non-
Newtonian flow conditions, first in the
range of 1011 >rj0 > 1 0 8 3 Pas (Manns and
Bruckner, 1988), which was then extended
care was taken to eliminate the heating ef-
fects of dissipated mechanical energy (Hes-
senkemper and Bruckner, 1988). At high
deformation rates the observed stress-
strain curves (see, e.g. Fig. 13-36) exhibit a
pronounced temporary stress maximum.
The measured data reveal a continuous de-
crease in glass viscosity during pressing at
high pressing rates of more than a factor of
10 compared with the Newtonian values
(Fig. 13-40). These data agree very well
with the above-mentioned data obtained
by the fiber elongation method in com-
parable ranges. The enhanced fluidity of
the glass melt is explained mainly by struc-
ture-viscous flow behavior produced by a
load-dependent alteration of the structure
of the glass melt in connection with orien-
tation, at least with anisotropic effects.
The phenomenon of non-Newtonian
flow behavior increases clearly with in-
creasing temperature at constant axial

o--
~o 0,2-
T581 \ '
\ T* u*
^ 0,4- v 596
<? • O i l
"5, 0.6- .629
o a 634
-1 0,8- • 648 Figure 13-40. Viscosity of a
o657 float glass melt normalized
1.0- by the Newtonian equilib-
rium viscosity, r\0, versus
0i axial compression rate at
b) -*v-*^ various temperatures;
a) normalized initial viscos-
3 in °C:
° OA ity, igrjJrjQ, at the begin-
• 581 \ \ V ning of the compression
v596
A 611 \ \ \ \D^ \
process; b) normalized final
- 0.8 . 629
N
A\ 1 viscosity, lgrjf/fj0, at the
• 634 end of the compression
• 648 process or at the moment
o 657 of the first crack occur-
12- rence.
10" 10' 10" 10" 10
Axial compression rate e in s"

compressive stresses. This effect is similar
to the increasing birefringence and shrink-
age of glass fibers at To with increasing
fiber drawing temperature at constant
drawing stress (see Sec. 13.3.3). It also con-
firms that the isotropic structure of a glass
melt changes to an anisotropic and even to
an oriented structure under high enough
load, which influences not only the flow
behavior but also the relaxation behavior
(see Sec. 13.6.2) and the high-temperature
tensile strength (see Sec. 13.6.1.2) in the
manner described.
Up to what temperature does this in-
creasing effect continue? Is there a limit,
and what kind of limit - a saturation or a
maximum? The answer is given by flow
birefringence measurements of various
melts, e.g. borate, sulphide and metaphos-
phate melts, which indicate maxima of the
specific birefringence (zlft/stress)at viscosi-
ties between about 104 to 102 Pa s, a region
at which the fiber drawing process is possi-
ble (Bruckner, 1987). Thus, at temperatures
below this maximum the anisotropic and
orientation effect increases and above this
maximum it decreases with rising tempera-
ture.
13.7 Further Properties
13.7.1 Microhardness
13.7.1.1 Indentation Process
and Phenomena
The term microhardness is occasionally
called diamond indentation hardness. Two
different diamond tools may be applied:
the Vickers diamond, which is a regular
pyramid with a peak angle of 136°, and the
Knoop diamond, which is an elongated
rhombus pyramid with angles of 172.5°
and 130° at the diamond peak. The two
13.7 Further Properties 705
microhardnesses are given by Eq. (13-32):
MHV= 0.1855 F/d2 and
MHK = 1.4233 F/d2 (13-32)
where F is the load in N, and d the diago-
nal line in mm. In the case of the Knoop
diamond, d is the longer diagonal line of
the indentation. The microhardness is ob-
tained then in 10 7 N/m 2 or lOMPa. The
diamond penetrates into the glass until the
load is compensated by the increasing con-
tact area. This process is a combination of
elastic and plastic deformation of the glass
as long as no cracks at the edges are pro-
duced. If no elastic component is acting,
the microhardness should be independent
of the load, F But this is not the case: it
increases with decreasing load due to elas-
tic springback at the moment when the
sample is unloaded. If, as is usual, the in-
dentation is observed after loading, one
has to regard and evaluate the so-called
springback value, c, in Eq. (13-33)
MHKcorr, = 1.4233 F/(d + c)2 (13-33)
in which c as well as MHKcorr are really
load-independent values as was shown by
Kranich and Scholze (1976), but c depends
on moisture. It decreases with increasing
relative humidity and increasing loading
time. This was also found by Hirao and
Tomozawa (1987).
Water penetratres into the stressed glass
surface during the measurement and in-
creases the plastic component of the defor-
mation process.
In order to avoid the elastic springback
effect, which is about 50% at the peak,
measurements of d have been made under
load by observation through the glass sam-
ple from below (Kranich and Scholze,
1976; Michels and Frischat, 1982) or by
measuring and recording the indentation
depth (Frohlich et al., 1977, 1979; Weiss,
1987). However, the elastic components
706 13 Mechanical Properties of Glasses
are not totally eliminated by this method
because both the glass and the diamond
react elastically under load. In this respect,
the experiments of Bartenev et al. (1969)
are of interest, because the plastic deforma-
tion is also related to a densification of the
glass (Ernsberger, 1968) in a way similar to
permanent densification, as was treated in
Sec. 13.2.2.1. Bartenev et al. annealed the
glass sample after the indentation process
and showed that small indentations are
healed completely, whereas large indenta-
tions lead to smaller ones which show at
the border of the indentation elevations.
This indicates a very complicated flow and
densification process on which more re-
search needs to be done.
13.7.1.2 Influence of Chemical Composition
The indentation process is at least partly
a deformation or flow process which is
comparable as a first approximation with
the Newtonian, or (according to Douglas
1958), with a non-Newtonian viscosity at
low temperatures. Therefore, it is expected
that alkali oxides, as substitutes for SiO 2 ,
decrease (Fig. 13-41) and CaO, MgO, ZnO,
B 2 O 3 and A12O3 increase the microhard-
ness. This was confirmed by Ainsworth
(1954) with MHV and by Kennedy et al.
(1980) with MHK measurements. Besides
10 20 30
R 2 0 in mol. % • shown in Fig. 13-42 for silica glass and for
Figure 13-41. Knoop microhardness of binary alkali
silicate glasses (Kennedy et al., 1980).
the viscosity, a certain connection to the
polarizability of the various components
may be appropriate for interpretation of
these results (Petzold et al., 1961). In this
way there seems to be a parallel also to the
elastic constants (see Sec. 13.2.1.2), particu-
larly the compressibility. It is understand-
able that OH groups in glasses reduce
microhardness as well (Sakka et al., 1981;
Takata et al., 1982).
The mentioned relation to the elastic
constants was treated by Yamane and
Mackenzie (1974), who treated the micro-
hardness (MH) as the resistance against
elastic and plastic deformation and den-
sification, as given by the expression
MH « 19(a GK) 1/2 , where a is the thermal
expansion coefficient, and G and K the
shear and compression moduli, respec-
tively.
Bartenev and Sanditov (1982) deduced
the relation between MH and the elastic
constants Young's modulus £ and Poisson
ratio ix\ MH = (1 - 2 p)E/[G (1 + //)] which
is a rough estimation that the MH is about
6 to 10% of the Young's modulus of a glass.
Last but not least, Kerkhof and Schin-
ker (1972) found the relation between the
MH and the flow stress, which is propor-
tional to the molecular strength expressed
by the equation: H ~ v^gy/f)112 in which
vl is the longitudinal sound velocity, Q
the density, y the surface energy, and f the
mean atomic distance.
13.7.1.3 Temperature Dependence
and Thermal Prehistory
The microhardness of glasses decreases
with increasing temperature in a similar
way as bonding strength and viscosity. The
trend of the temperature dependence is
a sodium calcium silicate glass (West-
brook, 1960). Therefore, if a state of higher

1000
750-
£ and chemical composition see Chap. 12 of
500- \ / S i O 2 -glass
x 250- \ glasses.
Na-Ca-silicate glass
-200 0 400 800
Temperafure in °C
Figure 13-42. Temperature dependence of Vickers mi-
crohardness (Westbrook, 1960).
temperature is frozen-in, as in the case of a
tempered glass, the microhardness will be
lower than that of an annealed glass be-
cause the structure of a tempered glass is
more open (larger specific volume) than
that of an annealed one. Attention should
be paid to the elastic springback effect
which will be much larger if the surface of
the glass sample is under compressive
stress (Kranich and Scholze, 1976). There-
fore such measurements have to be done
under load (see Sec. 13.7.1.1). Hara and
Kerkhof (1962) have shown that the micro-
hardness of tempered glass is about 4%
lower than that of annealed glass.
13.7 Further Properties 707
nary borate and silicate glass is given in
Fig. 13-43. For more details concerning C
this volume. In the present section the
stress-optical coefficient will be regarded as
a tool to measure stress distributions in
The essence of all stress-optical methods
is to conclude from the relative path differ-
ence, 3 = AndjX {X = wavelength of light),
and from the known stress-optical coeffi-
cient, C, the difference between the princi-
pal stresses, which is equal to twice maxi-
mum shear stress. Two cases have to be
distinguished:
a) the stress differences are so large that
they can be made visible by isochromates:
S = N = ±1, ±2, ± 3 , etc., where N is the
interference order, and
b) the stress differences are so small that
the corresponding path differences can be
compensated and measured by compensa-
tors: (5 < + 1.
The situation for silicate glasses is such
that a tensile stress of (T^lOON/mm 2 ^

13.7.2 Stress-Optical Coefficient

13.7.2.1 Stress-Optical Coefficient within
the Elastic Range of Glass
The stress-optical coefficient, C, is de-
fined by the well-known linear connection
between stress difference, Aa, and birefrin-
gence, An: An = 3/d = CAa, where 3 is the
path difference and d the geometric length
of the light beam through the glass. It is
10 20 30 40
also called the photoelastic or the Brewster R 2 0 in mol. % - » -
constant (1 Brewster = 10~ 6 mm 2 /N) and
Figure 13-43. Stress-optical coefficient, C, of binary
is a value which is characteristic for a glass alkali borate and alkali silicate glasses according to
composition. The range of C is from about Matusita et al. (1984 a, b), composed by Scholze
— 3 to -1-5 Brewster. An example for bi- (1988).
708 13 Mechanical Properties of Glasses
1000 kp/cm2 ^100 MPa (a2 = 0) for a sheet
glass of 2 mm thickness has to be applied to
produce a path difference of 5 = 1, i.e., to
produce the first isochromate. This stress is
of the order of magnitude of the strength of
bulk glasses. Therefore it is more suitable
to use model materials such as polymers
(Araldite B) in order to determine stress
distributions in certain constructions, at
cracks, edges or holes, because these mate-
rials have much larger Brewster constants
(25 to 55) than silicate glasses (about 3).
In this way (see case b) it is necessary
to use a polarizer and an analyzer (e.g.
"crossed Nicols") or a polarizing micro-
scope with a Berek compensator, a Babinet
or a Brace-Kohler compensator in order to
determine the path difference, S (Kerkhof,
1980). With the help of a X/A plate it is
possible to distinguish between tensile and
compressive stress by the color change
from the red of first order to blue or yellow.
Besides pure mechanical stresses produced
in glasses by external forces, other stresses,
such as temporary and permanent thermal
stresses, stresses produced by flaws and
crystalline inclusions in glasses with differ-
ent thermal expansion coefficients are also
important.
Q)
£ 3.4-
container glass (Na)
I + 1 MPas"1
& 3.3-
• 10 MPas"1
x 100 MPas"1
I 3.2- o 500 MPas~1
S 31.
"5
£ 3.0-
o of a modified K-Ca-silicate glass
g 2.9
500 Tg 600 500
Temperature in °C
13.7.2.2 Stress-Optical Coefficient within
the Viscoelastic Range
The stress-optical coefficient depends on
temperature because the polarizability is
also temperature dependent. From room
temperature to Tg this dependence is small
(about 7%, van Zee and Noritake, 1958),
but at and above Tg this dependence is very
large and time or rate dependent (Manns
and Bruckner, 1981), thus, there is a certain
influence of thermal prehistory.
Figs. 13-44 a and b show the stress-opti-
cal coefficient as a function of temperature
at various load velocities within the vis-
coelastic range of two glasses, a commer-
cial colorless sodium calcium container
glass and a laboratory glass of the same
composition in which Na 2 O is substituted
by K 2 O. The lower the stress rate, the
larger is C. This particular stress rate de-
pendence is illustrated particularly in Figs.
13-45 a and b for the same two glasses
(Manns and Bruckner, 1981).
The conclusions which may be drawn
from these results are that, first, the K 2 O
containing glass generally shows the larger
C-values due to the larger polarizability.
Second, the large temperature coefficients
Figure 13-44. Temperature depen-
dence of the stress-optical coeffi-
cient of a commercial Na-Ca-
silicate container glass (Na); a), and
(with K 2 O as substitute for Na 2 O),
(K); b), at various stress rates.
600 Tg 700

3.1- N 638,9
© 628.7
• 608.9
• 589,3
3.0
10Z
10- 10° 10 103
• Stress rate o in MPas"-
Figure 13-45. Stress-optical coefficient versus stress
rate for the two glasses (Na) and (K) at various tem-
peratures, a) industrial container glass, (Na), b) modi-
fied container glass (K); see Figs. 13-44 a and b.
C of the glasses above Tg may be inter-
preted to be due to a thermally induced
depolymerization of the glass network (re-
versible network splitting and reconnect-
ing process), the mechanism for which is
the statistical network splitting effect (bond
opening) which increases with rising tem-
perature and vice versa. It is also a mecha-
nism for the statistical network closing ef-
fect (bond connection), which increases
with decreasing temperature; thus, in total
it is a matter of a bond switching process.
Third, under the influence of mechanical
stresses, the network fragments and ions
need a certain time interval in order to
change energetically into other positions
than those of the unstressed state. This is
related to viscous, or better viscoelastic,
13.8 References 709
flow by which an anisotropic effect or even
an orientation effect will be produced. This
mechanism is similar to effects which are
described in Sec. 13.6.2 and is also similar
to flow birefringence (Wasche and Bruck-
ner, 1986a, b, 1987; see also Bruckner,
1987).
13.8 References
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Compte Rendu du Colloque U.S.C.V. sur la Nature
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Adams, R., McMillan, P. W. (1977), /. Mater. ScL 12,
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Ainsworth, L. (1954), /. Soc. Glass Techn. 38, 479-
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Anderegg, F. O. (1939), Ind. Eng. Chem. 31, 290-298.
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Appen, A. A., Kozlovskaya, E.J., Fu-Si, H. (1961),
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Bradt, R.C. (Ed.) (1974-1986), Fracture Mechanics
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Chermant, J. L., Osterstock, R, Vadam, G. (1979),
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Coenen, M. (1983), Glastechn. Ber. 56, 188-195.
Coenen, M., Amrhein, E. M. (1961), Compte Rendu
du Symposium sur la resistance mechanique du
710 13 Mechanical Properties of Glasses
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Dourlet, Charleroi, Belgique.
Cohen, H. M., Roy, R. (1961), /. Am. Ceram. Soc. 44,
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Dannheim, H., Oel, H.J. (1983), in: Festigkeit
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Davidge, R. W. (1979), Mechanical Behaviour of Ce-
ramics. Cambridge, London, New York: Cam-
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Day, D.E., Rindone, G. (1962), J. Am. Ceram. Soc.
45, 496-504.
Deeg, E. (1958), Glastechn. Ber. 31, 1-9, 85-93,
124-132, 229-240.
DeGuire, M.R., Brown, S.D. (1984), J. Am. Ceram.
Soc. 67, 210-213.
Dietzel, A. (1981), Glastechn. Ber. 54, 49-51.
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13.8 References 713
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14 Electrical Properties of Glasses
Malcolm D. Ingram

Department of Chemistry, University of Aberdeen, Aberdeen, Scotland, U.K.

List of Symbols and Abbreviations 716

14.1 Introduction 718
14.2 Phenomenological Aspects of Ion Transport 719
14.2.1 Cationic and Anionic Conductors 719
14.2.2 Impedance Analysis and Conductivity Measurement 720
14.2.3 Typical Vitreous Electrolytes 721
14.2.4 Systematic Variations in Conductivity 722
14.2.5 The Mixed Alkali Effect 723
14.2.6 The Conductivity Spectrum 724
14.2.7 Electrical Relaxations and the Decoupling Index 725
14.3 Mechanisms of Ion Transport 727
14.3.1 Basic Theory 727
14.3.2 The Weak Electrolyte Theory 728
14.3.3 The Anderson Stuart Model 729
14.3.4 Pathway Models 730
14.3.5 Ionic Interaction Theories 732
14.3.6 Ion-Correlation Effects and Defect Models 733
14.4 Transition Metal Oxide Glasses 734
14.4.1 Polaronic Hopping Mechanism 734
14.4.2 High Frequency and High Voltage Effects 736
14.4.3 High Pressure Effects 738
14.4.4 Switching Phenomena 738
14.4.5 Double Injection of Ions and Electrons 739
14.4.6 Electrochromic Devices 740
14.5 Semiconducting Glasses 741
14.5.1 General Principles 741
14.5.2 Amorphous Silicon (a-Si and a-Si:H) 743
14.5.2.1 Electrical Properties 743
14.5.2.2 Chemistry of the Defect States 743
14.5.2.3 Glassy Properties of Hydrogenated Films 744
14.6 Applications of Amorphous Silicon and Related Materials 745
14.6.1 Range of Device Technologies 745
14.6.2 Photovoltaic Devices 746
14.6.3 Spatial Light Modulators 747
14.6.4 Reflective Coatings 747
14.7 Conclusion 747
14.8 References 748

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
716 14 Electrical Properties of Glasses

List of Symbols and Abbreviations

a intersite distance
B lattice parameter
c velocity of light
c fraction in lower oxidation state
D* tracer diffusion coefficient
EA microscopic activation energy
EX measured activation energy
£ gap band gap energy
e electronic charge
e~~ electron
F Faraday's constant
/ frequency
G elastic modulus
H enthalpy
HR Haven ratio
J electronic transfer integral

k Boltzmann's constant
M* complex electric modulus, (e*)" 1
M\ M" real and imaginary electric modulus
JV number per unit volume
n (co) frequency dependent refractivity
R the universal gas constant
Rz decoupling index (ratio)
r cation radius
T absolute temperature
Tg glass transition temperature
Te equilibration temperature
t time
t+ cationic transport number
u electrical mobility
WH polaron hopping energy
WP polaron binding energy
X{ charge fraction
Z* complex electric impedance
Z', Z" real and imaginary impedance
z charge (or valency) of an ion

a optical absorptivity
p parameter in the KWW equation
y co valency parameter
e (relative) permittivity
80 permittivity of free space
 List of Symbols and Abbreviations 717

s* complex permittivity
e\ E" real and imaginary permittivity
A optical basicity parameter
ft chemical potential
v frequency
a electrical conductivity
^a.o Gd.c. electrical conductivity for alternating and stationary currents
T relaxation time
TS , iff structural and conductivity relaxation time
cp decay of the electric field
co angular frequency (2nf)

a-Si amorphous silicon

a-Si:H hydrogenated amorphous silicon
DSC differential scanning calorimetry
EXAFS extended X-ray absorption fine structure
f.w.h.m. full width at half maximum
GD glow discharge
KWW Kohlrausch-Williams-Watts
SAXS small angle X-ray scattering
718 14 Electrical Properties of Glasses
14.1 Introduction
Ionic conductivity in glass has been
studied for over a hundred years and there
are indications that glassy (and amor-
phous) electrolytes are showing promise
for use in all-solid-state batteries and in
electrochromic devices. These develop-
ments are at an early stage, and much ef-
fort is still being directed toward discover-
ing new glassy systems and to optimising
the levels of ionic conductivity in these ma-
terials. Remarkably, the main electrical ap-
plication of ionic conductivity is still in the
use of glass electrodes in analytical chemis-
try where very low levels of conductivity
suffice, and the dominant effect is the sur-
face interaction. By way of contrast, the
existence of semiconducting glasses has
been clearly recognised for only some
twenty years, but already their technologi-
cal applications, as e.g. in xerography and
in solar cells for pocket calculators, are
extensive and are increasingly affecting
everyday life.
This difference in the pace of technolog-
ical development is part of a wider experi-
ence in the field of solid state ionics, and
points up the difficulties in establishing re-
liable electrode-electrolyte interfaces and
in avoiding unwanted chemical and elec-
trochemical side reactions. To complicate
matters further, many of the glasses which
are good ionic conductors are either very
hygroscopic or else sensitive to light. By
contrast, materials widely used in mi-
croelectronics applications such as amor-
phous silicon (a-Si) are remarkably robust,
and can also be used in architectural appli-
cations.
Apart from these technical aspects, con-
siderable progress has been made in recent
years in understanding the mechanisms of
both ion and electron transport in glasses
and amorphous materials. In this context,
"glasses" are taken to mean bulk solids
quenched from the melt, and exhibiting a
glass transition temperature Tg, whereas
"amorphous" materials include thin films
deposited by sputtering or evaporation. It
is a moot point if such a distinction has
physical significance, and certainly for all
these materials there are important conse-
quences arising from the influence of disor-
der and thermal history.
In the case of ionic conductivity, the
focus is naturally on identifying the links
between ion mobility on the one hand and
glass structure and chemical bonding on
the other. Some theoretical approaches,
such as the weak electrolyte and ionic in-
teraction theories, draw attention to more
general parallels with solution electro-
chemistry.
With electronic conductors, controversy
related at first to the existence (on nonexis-
tence) of band gaps. These issues were
largely resolved as a result of the work of
Mott and others (see e.g. Mott and Davis,
1979). It now emerges that the electrical
properties (and especially the key role of
dopants) are also very much influenced
by chemical equilibria involving electron
donors and acceptors, as well as defects in
the glass structure.
In effect, there is a growing tendency for
theoretical discussions in the fields of ionic
and electronic conductivity to converge on
problems in glass chemistry. However, his-
torically there has been some tendency for
ionic and electronic processes to be treated
as distinct phenomena, with chemists con-
centrating largely on ionic, and physicists
on electronic systems.
In the present chapter the main features
of ionic and electronic processes in glass
are reviewed, so as to clarify the remark-
able diversity of phenomena which are ob-
served and to highlight some of the appli-
cations which are currently envisaged.
 14.2 Phenomenological Aspects of Ion Transport 719

Ionic and mixed ionic-electronic conduc-

tors are dealt with first (this is essentially
the field of solid state ionics), and then
there is a discussion of the growing impor-
tance of amorphous silicon and other
"tetrahedral" semiconductors. The impor-
tant properties of chalcogenide glasses and
of metallic glasses will not be discussed
here, since these are described in Chap. 7
and Chap. 9 of in this Volume.

14.2 Phenomenological Aspects

of Ion Transport

14.2.1 Cationic and Anionic Conductors

The electrolytic properties of ordinary
glass were demonstrated over one hundred
years ago by Warburg, who electrolyzed
Na + and other alkali cations through the
walls of thin glass tubes and showed that
Faraday's laws were obeyed. More re-
cently Hughes and Isard (1972) employed
Tubandt's method, with a series of disks of
glass pressed together, to prove unequivo-
cally the cationic nature of the conduction
process in a range of single and mixed al-
kali silicate glasses.
The cation mobility (and the corre-
sponding immobility of the anions) can be
understood intuitively by reference to the
widely cited Warren Biscoe version of the
structure of alkali silicate glasses (reduced
to two dimensions) shown here in Fig. 14-1.
According to this simplified picture,
cations are placed in "holes" in a glass
structure, whose shape is largely predeter-
mined by the partially broken (or modi-
fied) silicate network. Glasses are thus
members of an important class of solid
electrolytes, which includes fast-ion con-
ductors like jS-alumina and oc-Agl, where
the cationic transport number, t+ = \.
Na
Figure 14-1. A schematic 2-dimensional representa-
tion of the "classical" Warren-Biscoe structure of al-
kali silicate glasses, showing the possibilities of local-
ized and extended cationic motion within an anionic
framework.
This form of monopolar conduction is
prevalent in a wide range of borate, phos-
phate and silicate glasses of varying stoi-
chiometries. Nevertheless, O 2 " migration
can also occur in certain special circum-
stances. Layers of PbO have been observed
to form on sodium borate glasses during
electrolysis at Pb anodes. Apparently, O 2 ~
migration occurs in preference to the elec-
trolysis of Pb 2 + ions into the glass. Baucke
and Duffy (1983) attributed this to a struc-
ture-switching mechanism involving the
ability of boron to adopt both 3 and 4 fold
coordinations.
Measurable levels of anionic conductiv-
ity are found only in fluoride glasses (see
720 14 Electrical Properties of Glasses

Chap. 5). A typical conductivity, e.g. for n

glass

62ZrF 4 -30BaF 2 -8LaF 3 glass (Ravaine AVWW 1

etal., 1983) is 3 x l O " 6 S c m ~ 1 at 300°C
This is very similar to the cationic conduc-
tivity found in 20Na 2 O-80SiO 2 glass. As
remarked above, mixed anionic-cationic
\[
conductivity is not common in glass. How-
ever, very recently, Kulkarni and Angell
^glass
(1988) have reported a "mobile-ion cross-
over", from anions to cations, occurring (a)
as LiF is replaced by PbF 2 in the system
LiF-PbF 2 -Al(PO 3 ) 3 .
The glasses discussed in the rest of this
Chapter will mainly be cationic conduc- N

tors. This reflects the greater interest c

shown in these systems, and the evidence a
-a
<D
that electrical properties of anionically- a.
conducting fluoride glasses are otherwise
rather unexceptional.
E t

14.2.2 Impedance Analysis

and Conductivity Measurement
The most common way of measuring the
conductivity of glass (see e.g. Grant et al.,
1978; Tuller et al., 1980) is to affix gold or
aluminum blocking electrodes, and to de-
termine the complex impedance diagram
using a variable frequency admittance
bridge (typically in the frequency range
10°-10 6 Hz) or an equivalent frequency re-
sponse analyzer. The simplest equivalent
circuit for such a conductivity cell is shown
in Fig. 14-2 a. The glass is represented here
by a parallel RC element, and the electrical
double layer (and the resulting space
charge effect) by a series capacitance. The
value of R, the resistance of the glass, will
be found directly from the intercept on the
Z' axis. This "ideal" electrolyte behaviour
is illustrated in Fig. 14-2b. In general, the
"real" behaviour only approximates to this
ideal; the semicircular arc is usually some-
what flattened, and the electrode "spike"
angled somewhat away from the vertical.
Real impedance, Z '
(b)
Figure 14-2. (a) A simple equivalent circuit for a solid
(glassy) electrolyte with blocking electrodes, (b) The
complex impedance plot expected for such "ideal"
behavior.
More will be said later about the causes of
this nonideal or dispersive behaviour.
Conductivities measured in this way are
usually referred to as d.c. quantities, and it
is assumed that identical values would be
obtained at "true" d.c. using electrochemi-
cally reversible (i.e. ionically nonblocking)
electrodes. Support for this assumption
comes in some cases from direct experi-
ment, and from the very general observa-
tion of a frequency-independent admit-
tance region (the conductivity plateau - see
Fig. 14-7 below).
 14.2 Phenomenological Aspects of Ion Transport 721

Although it is certainly more convenient Temperature, T in °C

800 300 100 0 -100
to evaporate Au electrodes onto a glass
than to arrange for the preparation and KN03 melt
handling of liquid sodium electrodes, care 0 -- \< f
needs to be taken if blocking electrodes are
to be used in conjunction with fixed fre- melt \
quency measurements. Depending on the
resistance of the glass and the measure-
ment frequency, the resistance actually
Kg
T
Na 2 0-3Si0 2 \ \
^ \

^
Ag5l4B03
^ \ ^ glass
^ "

recorded could move significantly away -6-

from the intended Z' intercept shown in
Fig. 14-2 b. If the value of R is small (as in
the case of a highly conductive glass) then
the frequency would have to be high (even
as much as 1 MHz) to avoid moving onto
the electrode spike, while if R is large (as in
conventional silicate glasses at ca. 100 °C)
then the frequency would have to be low
(say < 1 kHz) to avoid moving onto the
electrode semicircle. These two circum-
stances will lead to the measurement of
incorrectly low and high conductivities, re-
spectively. Generally, the ionic conductiv-
ity of glass is thermally activated (see next
section) so fixed-frequency measurements
on any given sample are useful only over
limited temperature ranges.
14.2.3 Typical Vitreous Electrolytes
Figure 14-3 taken from Ingram (1987)
shows Arrhenius plots (graphs of log o
versus 1/T) for two rather different cation
conductors. The corresponding behaviour
of a typical molten salt, KNO 3 , is included
for comparison.
The conductivity data of sodium trisili-
cate glass (Na 2 O • 3 SiO2) illustrate a num-
ber of typical features. Above Tg, the
Arrhenius plot is curved (the characteristic
"free volume" behaviour). Below Tg, a
straight line is obtained in accordance with
the Arrhenius equation
-EX/RT) (14-1) potassium nitrate, continuing down to sub-
glass \
•*-— — - ^\
i
1 2
. i \ I
3 4
i
5
i
6
1O3/7" in K"1
Figure 14-3. Arrhenius plots showing temperature-
dependent ionic conductivities in "typical" glass-melt
combinations (Ingram, 1987, reproduced by kind per-
mission of The Society of Glass Technology).
where E£ is the apparent conductivity acti-
vation energy.
For this particular glass, E% = ca.
65kJmol~ 1 . The value of the activation
energy is high enough to ensure that al-
though there is a reasonable conductivity
at Tg (> 10~ 3 S cm" 1 ), cooling to ambient
reduces a to below 10~ 9 Scm~ 1 . Above
300 °C silicate glasses can be regarded as
electrolytes, whereas at 25 °C they behave
much more like insulators (or dielectrics).
The Ag 5 I 4 BO 3 glass is an example of a
recently discovered class of optimized (or
fast ion conducting) glasses, which contain
Agl as a major ingredient. The conductiv-
ity is very high at Tg (ca. 5 x 10" x S cm"%
but this glass also differs from sodium
trisilicate in its low energy of activation (ca.
20kJmol - 1 ). As a consequence, the con-
ductivity falls off very slowly with de-
creasing temperature; values greater than
10~~4 S cm" 1 can be measured right down
to - 1 0 0 ° G
The Arrhenius plot shown here is virtu-
ally a direct extension of the line for molten
722 14 Electrical Properties of Glasses
ambient temperatures. Somehow therefore,
"liquid-like" ion mobilities (reminiscent
also of Ag + ions in crystalline a-Agl) have
become trapped within the rigid glass ma-
trix. How this comes about is obviously a
very important question in the context of
"glassy state ionics". It is considered fur-
ther in Sec. 14.3.
14.2.4 Systematic Variations
in Conductivity
Among the characteristic features of vit-
reous electrolytes are the wide variations of
conductivity to be found within many "bi-
nary" systems. Data in Fig. 14-4 for
sodium borate glasses at 300 °C illustrate
this phenomenon very clearly. The concen-
tration of network modifier (mainly Na 2 O,
but augmented with Na 2 SO 4 , "Na 2 Cl 2 ",
i i r particular composition lies. Hunter and
-3
-5
Z. -6
o Glasses
• Na 2 0-B 2 0 3
o plus "Na2Cl2"
A plus "Na 2 F 2 "
• plus Na2S04
-9 • plus AI2O3
-10
10 20 30 40 50
mol % (Na20 + Na2SO4, etc.)
Figure 14-4. Compositional dependence of ionic con-
ductivities in sodium borate glasses, where the range
of glass-formation has been extended by various sub-
stitutions (Hunter and Ingram, 1984).
etc.) is varied from 10 to 50mol%. Over
this range of composition the conductivity
rises by seven orders of magnitude. This is
clearly out of all proportion to the increase
in the concentration of Na + ions.
Such effects are common to all glass-
forming systems (M 2 O-SiO 2 , P 2 O 5 , etc.),
see e.g. Martin and Angell (1986) and
Pradel et al. (1989). Always there is a
smooth increase in the logarithm of the
conductivity with increasing mole fraction
of the ionogenic component, which is also
the network modifier. Only at very high
modifier concentrations, and in certain sys-
tems, is there any indication that the con-
ductivity reaches a maximum value.
Very generally the rise in isothermal
conductivity parallels a decrease in the ac-
tivation energy. For many practical pur-
poses, it is necessary only to know that E£
varies from 50 to 100 kJ mol" 1 over most
oxide glasses, and where in this range a
Ingram (1984) showed that in Na + -ion
glasses, E£ decreases continuously with in-
crease in the calculated optical basicity pa-
rameter, A (Fig. 14-5). Using the empirical
"master curve" it is possible to forecast E%
values directly from the chemical stoi-
chiometry, since A = X1A1 -\-X2A2 ...
where X±, X 2 , etc. are the charge fractions
of different oxide components (Na 2 O,
SiO2 ...), and A1, A2 are assigned basicity
values. Such a correlation of E£ with A will
account for increases in conductivity with
Na 2 O content and for the higher conduc-
tivities of silicate as compared with phos-
phate glasses.
Reference has already been made in Sec.
14.2.3 to the existence of glasses containing
silver iodide, which are outstandingly good
ionic conductors. In fact there is a whole
family of such glasses (see e.g. Martin and
Schiraldi, 1985) where Agl can be mixed
either with recognized glass-formers like
 14.2 Phenomenological Aspects of Ion Transport 723

120 -
1
similar to silver iodide. Other examples of
Glasses glasses where such effects are found include
• Na2O-SiO2 the Cul-containing glasses (Minami and
•
110 - • i O Na 2 0-B 2 0 3 -Si0 2 Machida, 1989), and the so-called "Bor-
i o Na 2 0-Al 2 0 3 -Si0 2 deaux" glasses which typically are lithium
c borates doped with lithium chloride
100 ~ 1\ • Na 2 0-B 2 0 3

Na 2 0-Al 2 0 3 -B 2 0 3 -
(Levasseur et al., 1979; Button et al., 1981).
In these latter glasses the presence of LiCl
\ u Na 2 0-P 2 0 5 is useful both in extending the range of
Na2O- 0 2 -Si0 2 -P 2o5 glass formation in regard to total lithium
90- content, and also in enhancing the mobility
of Li + ions.
\ D

80- -
C
\ "
14.2.5 The Mixed Alkali Effect
The trends outlined in Sec. 14.2.4 imply
••o
> 70- • \ - a direct link between ionic conductivity
D
e£\ 1
• and glass stoichiometry, and would sug-
o
gest that variations in conductivity are re-
€
60- - lated to the presence of certain chemical
entities in glass (see also Mueller et al.,
•o 1987). It is remarkable therefore that the
50- mixing of different alkalis in glass produces
^ • N\ a pronounced minimum in the conductiv-
o °
1 1 1 1
ity. This effect is illustrated in Fig. 14-6.
0.45 0.55 0.65 Although many physical properties (such
Optical basicity parameter, A as the molar volume, shown here) do show
Figure 14-5. The variation of the apparent activation the expected additivity relationship, the
energy for d.c. conductivity, £*, with the calculated conductivity of a mixed lithium-potassium
(optical) basicity parameter in a range of Na + -ion disilicate glass is some four orders of magni-
conducting glasses (Hunter and Ingram, 1984).
tude lower than either of the corresponding
single alkali disilicates.
This effect appears to be "universal" to
AgBO2 and AgPO 3 or with non-glass- all ion-conducting glasses, even though
formers like Ag 2 MoO 4 and Ag 3 AsO 4 . In there is no obvious analog in electronic
all these systems the conductivity increases conductors. Very probably it is a mismatch
substantially with increasing silver iodide effect arising from the differing sizes and
content. To give an example, in the case of coordination requirements of different
AgI-AgPO 3 glasses, the conductivity cations. EXAFS studies (Greaves, 1989)
increases smoothly from 3xlO~ 7 to clearly indicate that each type of alkali
7xlO~ 3 Scm~ 1 , as the Agl content in- modifies the network structure to suit its
creases from zero to 50 mol%. own requirements. Li + -ions create for
In recent years, effort has been devoted themselves smaller sites than do K + -ions.
to finding other salts which will show a There can therefore be no rapid "exchange
conductance enhancement (dopant) effect of sites" reaction involving Li + and K + (or
724 14 Electrical Properties of Glasses
Mole fraction,
Figure 14-6. The mixed alkali effect in (Li2O/
K 2 O): 2 SiO2 glasses at 150°C Note the linear varia-
tion in molar volume (reproduced by courtesy of D. E.
Day, 1976).
other pairs of dissimilar ions), since such an
exchange entails expanding the network
around the former and contracting it
around the latter.
The mixed alkali effect is undoubtedly of
practical importance, as e.g. in the formu-
lation of glasses with high electrical resis-
tivity and good chemical durability.
Mainly, however, its elucidation is seen as
presenting a severe test of all theories of
ionic conduction in the vitreous state
(Tomandl and Schaeffer, 1985).
14.2.6 The Conductivity Spectrum
Reference has already been made in
Sec. 14.2.2 to the dispersive properties of
ionic conductors which lead to the appear-
ance of flattened semicircles and other
nonideal impedance behaviour. These ef-
fects are widespread and emerge as a natu-
ral consequence of the ionic hopping
process. This conclusion can be reached
from a consideration of Fig. 14-7 (Angell,
1989) showing data for the conductor,
3AgI-2(Ag 2 O-2B 2 O 3 ).
Figure 14-7, often referred to as the
conductivity spectrum, is a log-plot of con-
ductivity versus frequency. It features the
characteristic "d.c." plateaux, which corre-
spond directly to the interceps (R) on the
corresponding complex impedance dia-
grams, illustrated schematically in Fig.
14-2b. Clearly,
a (plateau) = <7dc. = (l/A)/R (14-2)
Another salient feature is the steady rise
in "a.c." conductivity, which follows ap-
proximately a power law dependence when
n is tending towards unity.
<Ja.c. = Bcon (14-3)
especially at higher frequencies. This con-
ductivity increase continues into the far in-
frared region (where the absorption band
arising from cations vibrating in their lat-
tice sites is reached). The inclusion of data
from far infrared spectroscopy is made
possible by converting the spectral absorb-
tivity, a, into conductivity units through
the equation
o = c - n(co) • s0 - a (14-4)
where c and e0 have their usual signifi-
cance, n(co) is the frequency dependent re-
fractive index (ca. 2.0) and a is the mea-
sured absorptivity in Neper cm" 1 .
The d.c. conductivity is thermally acti-
vated, which is shown more explicitly by
transferring the d.c. conductivities from
Fig. 14-7 a onto the Arrhenius plot in Fig.
14-7 b. Comparison of these two graphs
shows the far infrared conductivity emerg-
 14.2 Phenomenological Aspects of Ion Transport 725

Figure 14-7. (a) The con-

ductivity spectrum of a sil-
ver iodoborate glass
(3AgI-2Ag 2 O-2B 2 O 3 )
over a range of tempera-
tures, (b) The correspond-
ing Arrhenius plot showing
the near equivalence of the
limiting high frequency
conductivity obtained from
the far IR absorption with
the limiting high tempera-
ture conductivity in the liq-
uid state (reproduced by
courtesy of C. A. Angell,
1989).
k 6 8 10 12 2 4 6
log10 (f/Hz) 10 3 / T in K"1

ing (Angell, 1989) as the effective maximum glass (Wong and Angell, 1976; Burns et al.,
value for the d.c. conductivity in the glass- 1989) exist for the whole spectral range
melt system. This value, which is approxi- from audio, through radio and microwave
mately lOScm" 1 , corresponds either to frequencies, into the far infrared region.
the vibrations of Ag + ions within their Some of this latter data set is used in the
sites, or to the (fully-activated) diffusion of discussion of conductivity relaxations
Ag + ions at higher temperatures. which follows.
Returning again to the discussion of the
dispersive or power law region, it can make
more sense to think of the conductivity as 14.2.7 Electrical Relaxations
"falling away" from the maximum (infra- and the Decoupling Index
red) value, rather than as "rising above"
Further consideration of the conductiv-
the (much lower) values found on the d.c.
ity spectra in Fig. 14-7 a could suggest that
plateaux. With falling temperature, the ef-
the low-frequency limit of the power law
fect of the activation energy is that the vi-
region (note the arrows on the diagram)
brating Ag + ion must wait for longer peri-
corresponds to some kind of hopping rate
ods before it has enough energy to
(see e.g. Almond, 1989) or to the inverse of
complete a jump. The processes which give
a conductivity relaxation time, xa. This lat-
rise to ion migration are thus moved to
ter viewpoint underlines the use of electric
progressively lower frequencies. The slop-
modulus spectroscopy which was pio-
ing region of the conductivity spectrum is
neered by Macedo and Moynihan in the
thus a direct indication of this waiting pro-
early 1970's. The complex electric modu-
cess. The longer this sloping region, the
lus, M*, was defined (Macedo et al., 1972)
more slowly the ions diffuse, and the lower
as the reciprocal of the complex permittiv-
is the d.c. conductivity.
ity and can be calculated from normal per-
Conductivity spectra similar to that il-
mittivity or impedance data using equa-
lustrated in Fig. 14-7 a are found for all the
tions of the kind
glass systems which have been investigated
so far. Extensive data for sodium trisilicate M* = i = jco (14-5)
726 14 Electrical Properties of Glasses
Typical loss modulus spectra (plots of
M" versus log / ) in this case for a sodium
trisilicate glass (Burns et al., 1989), are
shown in Fig. 14-8. The spectra are broad
peaks (with full widths at half maximum,
f.w.h.m. = ca. 2.3 decades) which are
shifted progressively towards higher fre-
quencies as the temperature increases. In-
deed, the activation energy, d(ln/ max )/
d(l/T) = ca. 65kJmol~ 1 , which is very
close to the measured E% value for d.c.
conduction. This is indicative of a process
involving the migration of ions, and a re-
sulting relaxation of the electric fields
within the glassy material. The conductivity
relaxation time is defined as the inverse of
the (angular) peak frequency, ^ T I / ^ J " 1 .
It can either be measured directly or
else estimated from a knowledge of
the d.c. conductivity using the equation,
TG = £0S(G)-1 (Howell et al., 1974).
0.03-
0.02-
T
O peak in the electric modulus spectrum.
E Moynihan has prepared tables of M' and
0.01 -
Figure 14-8. Electric loss modulus spectra (graphs of
M" versus log/) for Na 2 O • 3 SiO2 glass over a range
of temperatures (reproduced by courtesy of W. M.
Risen, Burns et al., 1989).
Several points emerge from these modu-
lus spectra which are of very general signif-
icance. First, the loss peaks are much
broader than the simple "Debye" peaks
(f.w.h.m. = 1.14 decades) which would be
expected on the basis of the equivalent cir-
cuit shown in Fig. 14-2 above. Such disper-
sive behaviour can formally be attributed
to distributions of conductivity relaxation
times, and could be modelled by including
a series array of parallel RC elements in the
equivalent circuit in Fig. 14-2 a. However,
it is more useful in the context of current
viewpoints to look for an explanation in
terms of the transition from localized to
long range ionic motions (already dis-
cussed in connection with Fig. 14-7 a) and
to regard the width of the electric modulus
spectrum as a measure of the inherent
complexity of the conduction mechanism.
One way of expressing this complexity is
by means of the Kohlrausch-Williams-
Watts (KWW) equation (Moynihan et al.,
1973; Howell et al., 1974). The decay of the
electric field cp within the glass follows the
stretched exponential law
<p(0 = 9 0 exp[(-T/T p y ? ] (14-6)
where TP is characteristic relaxation time,
and 0 < / ? < l . /? would equal unity for
a simple exponential relaxation, which
would correspond to the simple Debye
M" evaluated for a wide range of "normal-
ized" frequencies, which facilitate the fit of
the modulus spectrum to the KWW equa-
tion, and determination of /? from experi-
mental data. In many glasses, /? = ca. 0.5,
even where the chemical compositions and
the actual conductivities are very different.
There is some evidence that (I is higher in
glasses with low concentrations of mobile
ions (e.g. low-alkali silicates) or having
high activation energies, and also, perhaps

surprisingly, that /? increases with increase
in temperature.
Ngai et al. (1984) have shown how the
jS-parameter can be used to calculate a true
microscopic activation energy EA from the
measured activation energy, Ejf, using the
equation
EA=P-EX (14-7)
The energy EA is associated with single-ion
processes, while the measured "d.c." activa-
tion energy includes a variety of additional
interactions and cooperative effects associ-
ated with a net flow of ions in the conduc-
tor. The microscopic relaxation time is in
fact much shorter than the observed relax-
ation time, (27c/max)'"1. Within this con-
cept, it is not necessary to postulate a dis-
tribution of relaxation times in order to
explain the breadth of the modulus spec-
trum. Instead it is simply an indication of
the effect of the interactions between indi-
vidual mobile ions.
Experimentally, these electric modulus
peaks correspond quite closely in fre-
quency to the ^-relaxations (ultrasonic ab-
sorptions or internal friction peaks) seen in
the mechanical loss spectra (Angell, 1989;
see also Sec. 11.3.1.2). They occur therefore
at much higher frequencies (or lower tem-
peratures) than do the primary a-relax-
ations, which are manifested by the glass
transition temperature, Tg. Angell (1983)
has highlighted this distinction by defining
a decoupling index, Rx = Ts/Tff, which is the
ratio of the structural (mechanical) to the
electrical relaxation times at Tg.
For Tg as determined in the normal
differential scanning calorimetry experi-
ment (DSC), TS = ca. 200 s, and the value
of xa can be taken as approximately
10 ~ 12 (a) ~* s. A typical sodium silicate
glass could have a conductivity of
5 x 10~ 3 S cm" 1 at Tg, and so the value of
RT obtained is 200 x 1012 x 5 x 10" 3 = 1012.
14.3 Mechanisms of Ion Transport 727
The motion of cations in glass is thus
strongly decoupled from the normal pro-
cesses of structural relaxation. This is espe-
cially true for the fast-ion conducting
glasses like Ag 5 I 4 BO 3 . Figure 14-3 shows
that the mobile silver ions below Tg seem to
have escaped completely from the struc-
tural "entanglements" which led to vitrifi-
cation.
In this latter respect vitreous conductors
differ quite markedly from the important
class of polymer electrolytes, where ion
mobility is a melt property and ionic mo-
tions are strongly coupled to segmental
motions of the polymer chains (McLin and
Angell, 1988; see Chap. 11). For this reason
polymer electrolytes (unlike the inorganic
glasses) can only be used in electrochemi-
cal applications well above their glass tran-
sition temperatures.
14.3 Mechanisms of Ion Transport
14.3.1 Basic Theory
Appropriate Arrhenius equations (Eq.
14-1 in Sec. 14.2.3), summarize the main
facts concerning the ionic (d.c.) conduc-
tivities of most glasses. The important
parameters would seem to be the pre-expo-
nential factors (a0) and the activation ener-
gies (£*)• A complete theory of ionic con-
ductivity would be expected therefore to
provide these parameters for any given
glass, and plausible interpretations of
trends and changes on a molecular basis.
It is customary to concentrate on the
variations in activation energy. This is
partly because the conductivity nearly al-
ways rises as the activation energy falls and
this largely overshadows any variations in
the pre-exponential factor. Also, melt be-
haviour is generally nonarrhenian above Tg
(see Figs. 14-3 and 14-7 above), so the val-
ues of d0 for the glass and the high-temper-
728 14 Electrical Properties of Glasses
ature limiting conductivity in the glass-
melt system do not coincide. For practical
purposes, it in fact makes more sense to
specify the experimental values of Tg, <r(Tg)
and EX, and to develop the theoretical
treatment accordingly.
The starting point of most of the main
theories of ion transport is that a thermally
activated hopping process is involved.
From this point on, however, a remarkable
diversity of viewpoints has evolved, and
only slowly is a consensus emerging as to
how best to deal with the broad generality
of the observed phenomena. Some theories
emphasise analogies with conventional
electrolyte behaviour, while others focus
on aspects of glass structure.
14.3.2 The Weak Electrolyte Theory
According to Ravaine and Souquet
(1977), there exists in any sodium silicate
glass (or similar material) an ionic dissocia-
tion equilibrium which can be written for-
mally as
Na 2 O ^± Na + + ONa~ (14-8)
+
where Na is a free cation and ONa" rep-
resents a cation firmly bound (at least tem-
porarily) to the anionic framework.
From conventional thermodynamics,
0 = 0Na2o + Krinfl N a 2 o (14-9)
If the dissociation constant is small, so that
the concentration of free ions is also small,
this may be written more informatively as
M = /4, 2 o + R r i n [ N a + ] 2 (14-10)
where activity coefficients have been dis-
carded and charge neutrality has been as-
sumed.
Quite generally
a =N -z-e-u (14-11)
where N9 z and u are respectively the num-
ber, valence and mobility of the charge car-
riers. For a given series of alkali silicate or
similar glasses, experiments have shown
that
a - const • (aNa2O)1/2 (14-12)
By combining Eqs. (14-9) through (14-12),
Ravaine and Souquet concluded that the
variation in conductivity in such a series of
glasses is effectively determined by the
equation
a = const • [Na + ] (14-13)
In other words, the huge variations in
conductivity which are observed both as a
function of temperature and composition,
see e.g. Figs. 14-3 and 14-4, reflect changes
in the number of free Na + ions and not
changes in their mobility. Such an ap-
proach has since been extended to include
Agl-containing and mixed network glasses
(see Ingram, 1987; Pradel et al., 1989 for
further references). The value of this theory
is firstly that it establishes a firm link be-
tween certain kinetic and thermodynamic
quantities, and secondly that it draws an
important distinction between the "mo-
bile" and the "average" cations in glass.
If this distinction can be substantiated,
then it is possible to envisage a more so-
phisticated kind of conduction mechanism.
However, such a development hinges upon
the use of appropriate spectroscopic tech-
niques to identify the mobile ions, and/or
independent electrical methods to deter-
mine their mobility.
At present, the constant mobility hy-
pothesis has not been conclusively verified.
One attempt to measure concentrations of
mobile ions using the mixed-alkali effect
(Moynihan and Lesikar, 1981; Ingram
et al., 1988) indicated apparently that it is
the number of mobile "defects" which are
more nearly constant, rather than the mo-
bility. However, recently Denoyelle et al.
(1990) have measured Hall-effect mobilities
 14.3 Mechanisms of Ion Transport 729

which are, as predicted by the weak elec-

trolyte theory, much larger than values cal-
culated on the assumption that all the ions
are mobile.
One of the attractive features of this ap-
proach is that it enables the observed acti-
vation energy, E%, to be expressed, as the
sum of two terms (Ec = AH/2, and £ M )
which express the contributions from the
dissociation enthalpy and the mobility en-
ergy, respectively. The factor of lA enters
here from the law of mass action since the
ionogen dissociates into two ions (Eq.
(14-8)). Some interesting parallels can be
drawn with the Anderson Stuart model,
described below.

14.3.3 The Anderson Stuart Model Cationic displacements

Given that the variations in thermody-
namic activity in binary or ternary mix-
tures are not usually predictable from first
principles, some other method of calculat-
ing variations in the activation energy is
required. The Anderson Stuart approach
(1954) is the one most commonly em-
ployed.
The basic model is illustrated schemati-
cally for silicate glasses in Fig. 14-9 (see
Martin and Angell, 1986). It is assumed
that when an ion makes a hop into an
adjacent site (which is also vacant), it has to
overcome two energy barriers. First, it
must overcome the electrostatic binding en-
ergy EB pulling it back towards its original
site; then there is an elastic strain energy Es
which is associated with the expansion of
the local structure and the opening up of
suitable "doorways" through which the ion
can move.
By various approximations it can be
shown that for an ion of valency z
(14-14)
"o)
Figure 14-9. A schematic view of the Anderson-Stuart
model for ion hopping processes in glass. The dia-
gram shows a shallow energy well where an ion can
residue after overcoming the electrostatic binding en-
ergy, Eh (reproduced by courtesy of S.W. Martin,
Martin and Angell, 1986).
where z0 and r0 are the valency and ra-
dius of the non-bridging oxygen (or other
anion) respectively, B is a lattice parameter
depending on the distance between neigh-
bouring sites, r is the cation radius, rD is the
radius of normal (unexpanded) doorways
in the glass, G is the elastic modulus, and y
is a "co valency parameter". Values of G can
often be found in the literature, and rD can
be estimated from the diffusion constants
of inert gases.
Generally, the procedure for assigning
numerical values to the B- and y-parame-
ters is somewhat arbitrary, so this is not a
truly quantitative theory. Another draw-
back to this theory is that there are "too
many" parameters. The large increases in
conductivity which accompany composi-
tional change (as for example in the
730 14 Electrical Properties of Glasses
sodium borate or silicate glasses) can
therefore be explained in several ways.
Looking in more detail at Eq. (14-14), a fall
in activation energy could be associated
with a rise in Na 2 O content, either because
of (i) a decrease in the lattice parameter, J3,
consequent upon the cation sites being
moved closer together, (ii) an increase in
the covalency parameter, y, consequent
upon a rise in the basicity (polarizability)
of the oxide ions (see also Fig. 14-5), or
(iii) decreases in G and in r D , consequent
upon a disruption of the network and an
increase in the number of nonbridging oxy-
gens.
Where "anomalies" occur, as in the
rather low activation energies seen in the
sodium aluminosilicate glasses, then these
can be conveniently explained by focusing
on other parameters such as r0, the radius
of the oxide ion or alternative anionic
groupings in these glasses involving tetra-
hedral aluminium. None of these explana-
tions is entirely convincing in the absence
of independent structural information.
However, Eq. (14-14) is a useful guide to
the experimentalist in the choice of glass
compositions which are likely to exhibit
the best ionic conductivities. Since the aim
is to reduce the contributions to E% from
both the electrostatic binding energy and
the electrostatic strain energy, then it is
advantageous if the oxide ion is replaced
by a larger, more polarizable anion. Such a
change will tend to maximize the values of
y and r 0 , and, conversely, minimize the val-
ues of G and (r — rD). Such reasoning is con-
sistent with the fast-ion conductivity found
in Agl-containing glasses, Fig. 14-3. It has
led later to the discovery of LiI-Li 2 S-P 2 S 5
and LiI-Li 2 S-GeS 2 glasses (Malugani
et al., 1983; Pradel and Ribes, 1989). These
are among the best room-temperature
Li + -ion conducting solid electrolytes
known at the present time.
The original Anderson Stuart model has
been modified very slightly in Fig. 14-9 to
include in the energy profile subsidiary
minima corresponding to ions which have
escaped from their sites, but have not yet
progressed to another stable position.
These ions may correspond to the free ions
in the weak electrolyte theory. Martin and
Angell (1986) suggest in fact that EB and Es
of the Anderson Stuart theory correspond
to Ec and EM of the Ravaine Souquet the-
ory. If this is valid, these two theories are
simply different versions of the same un-
derlying physical model.
The main attraction of the Anderson
Stuart theory is the emphasis on calculat-
ing the energy of activation. The seeming
simplicity of the theory means it is easy to
see what other effects have been ignored.
First, there is no discussion of disorder, and
whether or not the microscopic (local) acti-
vation energies are influenced by the exis-
tence of defects or medium range order in
the vitreous state. Secondly, there is no dis-
cussion of long-range ionic interactions,
and whether or not cooperative effects in-
fluence the activation energies. Ways of
considering some of these factors will now
be considered.
14.3.4 Pathway Models
The need for considering the possible ex-
istence of pathways becomes more evident
in systems of chemical complexity, where
an exotic constituent such as silver iodide
imparts a substantial increase in conduc-
tivity. Thus, Minami (1985) postulated the
existence in such glasses of conduction
pathways "tracked by iodide ions". This
basic model has been extended, and further
elaborated, to include the presence of a-
Agl like clusters (Tachez et al., 1986), and
their linking together to form percolation
pathways (Mangion and Johari, 1987).

Another approach (Ingram et al., 1988,
1990; Ingram, 1989) is based on existing
cluster-tissue theories of glass structure
(Hayler and Goldstein, 1977; Phillips,
1979; Rao and Rao, 1982; Goodman, 1985)
where relatively close-packed regions, or
clustered "pseudophases", are surrounded
by a more open and disordered connective
tissue. The solidification of this connective
tissue near to or just below Tg, when the
long-range structure is already determined
by the interlocking clusters, puts the clus-
ters under compression and leaves the tis-
sue in a highly stretched condition.
Some of the principal attributes of this
model are sketched in Fig. 14-10. The main
point is the location of preferred pathways
for ion migration within the connective tis-
sue. The model is relevant to several as-
pects of glass behaviour in that:
(i) The steep falls in conductivity associ-
ated with the mixed alkali effect arise be-
cause the foreign ions block off the best
conduction pathways within the connec-
tive tissue.
(ii) The evidence for medium range order
in silver-iodide containing glasses, which
comes mainly from neutron scattering ex-
periments (Boerjessen et al., 1989; Tachez
et al., 1989) is consistent with a connective
tissue of Agl-rich material surrounding
clusters of borate or phosphate units. The
tendency for Agl to stabilize glass forma-
tion in many such systems (molybdates, ar-
senates, etc.) is also consistent with its ten-
dency to form a stable connective tissue.
(iii) Evidence from vibrational spectros-
copy for the existence of two distinct
cationic environments in alkali borate
glasses (Kamitsos et al., 1987) is also con-
sistent with the presence of the cluster and
tissue phases, and provides information on
their relative amorphicities.
(iv) The existence of a network of pre-
ferred pathways leads directly to the ap-
14.3 Mechanisms of Ion Transport 731
Clusters v N
Connective
tissue
Conduction Blocking by
pathway foreign cations
Figure 14-10. A schematic of the cluster-bypass
model, showing preferred pathways for ion migration
located in a connective tissue surrounding microdo-
mains or "clusters" of more densely packed material.
pearance of topological constraints, which
various authors have linked to the occur-
rence of dispersive behaviour in glass (Ya-
mamoto and Namikawa, 1977; Shlesinger
and Montroll, 1984; Palmer et al., 1984).
Put very simply, the accumulation of
charge carriers at junctions or constric-
tions in the connective tissue could intro-
duce delays, and be responsible for the ap-
pearance of a "distribution of waiting
times" in the ionic hopping process. The
universal character of the relaxation pro-
cesses in glass (as seen in the broad modu-
lus spectra and the near constancy of the
KWW jS-parameters, ca. 0.5, see Sec. 14.2.7
above) could reflect the existence of similar
pathway topologies in different glasses.
(v) Finally, the mechanical loss peaks
which are observed in all conducting
glasses (Sec. 14.2.7 above) could be attrib-
uted to the exchange of mobile ions be-
tween the cluster and tissue phases (where
the greatest differences in compression/
tension occur). It is noteworthy (Angell,
1989) that the strongest mechanical relax-
ations occur either in mixed-cation glasses
where stress can be released because the
732 14 Electrical Properties of Glasses
cations differ in size, or else in the Agl-
containing glasses where the chemical dif-
ferentiation between clusters and tissue is
probably most highly developed (so again
cation exchange will involve significant
volume relaxations).
Clearly, this cluster-tissue model marks
a decisive move away from the random
network theory of Zachariasen (1932) to-
wards the "microcrystallite" or "pseu-
dophase" concepts of Porai-Koshits (1985)
and his school. In that respect it obviously
has implications for development of theory
in other branches of glass science.
It is useful here to see what additional
light it can shed on earlier theories of ionic
conductivity. The presence of the clusters
and tissue phases under different condi-
tions of compression and extension intro-
duces an important element of disorder
not present in the original Anderson Stuart
picture. If the ions in glass are moving in
the tissue phase with a relatively open
structure, then this will minimize the con-
tributions from the elastic strain energy. As
a consequence, the predominant factors in-
fluencing ion mobility will be electrostatic
in origin, see also Martin and Angell
(1986), Mueller et al. (1987). On the other
hand if these compressive stresses force the
chemical potential (or indeed the chemical
composition) of the tissue to differ from the
average value for the glass, then large vari-
ations in the local thermodynamic activity
are possible. This could be another way to
lead into the weak electrolyte theory and
the connection between ion mobility and
to establish thermodynamic data.
14.3.5 Ionic Interaction Theories
Mention has just been made above to
the way in which topological factors asso-
ciated with the pathway model could influ-
ence the distribution of relaxation times.
An alternative and more general mecha-
nism would involve the kinds of long range
ion-ion interactions which form the basis
of the standard Debye Hueckel theory of
dilute electrolyte solutions.
Various authors have in the past at-
tempted to extend this classical theory to
glassy electrolytes (Ingram, 1987; Hyde
et al., 1987). The problem is that the con-
centration of ions is usually too high for
the detailed electrolyte theory to apply.
An alternative mathematical approach is
given by Funke (1988, 1990), which also
has some resemblance to Jonscher's
screened charge model (1975). The essence
of the idea (inherent in the Debye-Hueckel
theory) is that any cation will disturb the
other mobile ions (in this case cations) in
its immediate vicinity. Generally, there will
be less cations around (i.e. they will have
moved further away) than if the initial
cation were absent. According to choice,
this perturbation can be called the "screen-
ing charge" or the "ion atmosphere", and
as the ion moves about in the glass this
perturbation must accompany it also.
However, see Fig. 14-11, the "ion atmo-
sphere" around any cation cannot recon-
stitute itself as soon as an ion has hopped
into its neighboring site. Indeed, immedi-
ately after the hop has occurred, the distur-
bance in the surrounding cations remains
centred on the original site, and so there is
a net force tending to restore the cation to
this initial position.
It is this "backwards correlation" effect,
diminishing with time, which can be
thought responsible for the existence of
high a.c. conductivities and for the ob-
served conductivity dispersions. Only after
the ion atmosphere has reformed around
the new cation site is the electric field re-
laxed and the ion hop completed. For this
reason, the d.c. conductivity is lower than
the a.c. value, and the observed hopping

.Q
O
E
before immediately
hopping after hopping
Figure 14-11. A schematic representation of the "charge screening effect" implicit in both the Jonscher and Funke
theories of power law behavior.
rate is slower than the microscopic hop-
ping rate. The ion atmosphere model is
thus entirely consistent with Ngai's phe-
nomenological approach to relaxation and
dispersive behaviour in glass (Sec. 14.2.7),
and provides additional mechanistic in-
sights into the nonexponential relaxation
process.
Recently, Elliott (1988) has revived inter-
est in the "diffusion-triggered" version of
the ion-hopping process. Essentially, an
ion cannot hop until another ion (in effect
an interstitial defect) has moved towards it.
This is almost like saying that the ion does
not hop until there has been an appropriate
change in its ion atmosphere. In a sense,
this model is very like Funke's (except that
"cause" and "effect" have been reversed) in
that ionic transport is envisioned as a
highly concerted process, involving both
the "moving" ion and its neighbors.
Work presently in progress (Dieterich
et al., 1990; Bunde et al., 1990) makes use
of Monte Carlo simulation methods. It
suggests, however, that a combination of
"pathway constraint" and coulombic inter-
action is needed to obtain good agreement
between theoretical and experimental con-
ductivity dispersions. Discussion of ion at-
mospheres, therefore, does not preclude a
discussion of disorder and pathway effects
in glass.
14.3 Mechanisms of Ion Transport 733
after relaxation
of ion-atmosphere
14.3.6 Ion-Correlation Effects
and Defect Models
Ionic diffusion in glass has been studied
for many years, and provides information
concerning the transport mechanism, and
support for various "defect" hypotheses,
including mobile cation vacancies and
paired interstitialcies. Usually, this ap-
proach involves a comparison of the mea-
sured conductivities and diffusivities.
Quite generally, the Nernst-Einstein
equation can be written as
okT
(14-15)
where D* is a tracer diffusion coefficient,
and HR is the charge correlation factor or
Haven ratio, and cr, k, AT, e and T have their
usual meaning. For dilute aqueous solu-
tions, where the diffusional processes
of ions are completely uncorrelated, the
Haven ratio is exactly unity; i.e. the
Nernst-Einstein equation is obeyed. For
molten salts, the Haven ratio is generally
greater than one, because the strong cou-
pling of cations to anions leads to the ap-
pearance of "nonconductive diffusional
transport" processes.
For typical sodium silicate glasses, how-
ever, values of the Haven ratio lie in the
range 0.44 to 0.55, and HR approaches
734 14 Electrical Properties of Glasses
unity only occasionally as in nearly pure
SiO2 (where the cations are so far apart for
their motions to be uncorrelated). The
lower figures for the alkali silicate glasses
have variously been interpreted as indicat-
ing a mixture of vacancy and interstitial
processes, cation clustering, phase separa-
tion, and preferred conduction pathways
(Beier and Frischat, 1985; Ingram, 1987).
The confusion arises because any con-
straint which encourages the sequential
hopping of the cations, such as e.g. along
the pathways in the connective tissue (see
Sec. 14.3.4), will mean that the amount of
charge transported will be larger than is
calculated from the movement of individu-
ally labeled cations. (Two cations making a
concerted hop carry twice the charge of the
single cation which is radioactively la-
beled.) Such cations moving along path-
ways of low dimensionality will of course
have enhanced opportunity to move back-
wards as well as forwards. This introduces
additional correlation effects in diffusion,
which also lead to a reduction in the Haven
ratio.
To date, it is still not even clear if ionic
diffusion and transport in glass is primarily
a vacancy or an interstitialcy process. The
Anderson Stuart and Funke theories (Sec.
14.3.2 and 14.3.5, respectively) are very
much in the spirit of "vacancy" mecha-
nisms. In both cases, it is assumed that the
primary process is the jumping of a cation
into a nearby (equivalent) site. By contrast,
the Elliott model (Sec. 14.3.5) must be seen
as an "interstitialcy" mechanism, since the
jumping process is itself triggered by the
arrival of an additional cation.
It could be argued perhaps that the in-
terstitial mechanism would be favoured by
a homogeneous glass structure, where the
extra cation is free to trigger ionic motions
in all directions. On the other hand, if
cationic motion is channelled along prede-
termined pathways, then the free flow of
ions will occur only if these passages (and
especially the junctions) are not allowed to
become blocked or overcrowded. This
might suggest a preference for a vacancy
mechanism. This kind of uncertainty con-
cerning the primary transport mechanism
serves to emphasise the conclusion already
drawn in this Section. The mechanism of
ion migration in glass cannot be separated
from a discussion of all aspects of the glass
structure.
14.4 Transition Metal Oxide
Glasses
14.4.1 Polaronic Hopping Mechanism
One class of electronically conducting
glasses shows many similarities to the ionic
conductors. This includes some binary com-
positions like TiO 2 -SiO 2 , V 2 O 5 -P 2 O 5 ,
and FeO-P 2 O 5 , where the oxidation state
of the transition metal ion changes as a
result of reactions in the molten state in-
volving the gain or loss of oxygen. Typi-
cally, glasses in the V 2 O 5 -P 2 O 5 system
prepared by melting in normal ambient at-
mospheres will contain a mixture of V4 +
and V5 + , and the electronic conductivity
will arise from the intervalence transfer of
electrons from V 4 + to V 5 + ions.
This process can also be regarded as the
migration of a polar on. The presence of the
"extra" electron (i.e. the one in the d-shell
of the V 4 + cation) results in a deformation
of the local environment (changes in bond
length, etc.). In effect, the electron and its
induced deformation can be regarded as a
pseudoparticle which can only migrate by a
thermally activated (or phonon assisted)
process. This is the process of polaronic
hopping (Sayer and Mansingh, 1987; Levy
and Souquet, 1989) and it has a number of
characteristic features.
 14.4 Transition Metal Oxide Glasses 735

The somewhat nonlinear Arrhenius be-

haviour is exemplified by the conductivity -3 -
of various glasses in Fig. 14-12. The devia-
-
tions from the Arrhenius equation are seen
more clearly in the more highly conducting -5 -
glasses and always at subambient tempera-
tures. The detailed theory involves a dis- \ . TiO2-SiO2
cussion of both disordering effects and ~ -7 - -

-V
"variable range hopping" and will not be
attempted here. It is fully discussed by
Sayer and Mansingh and in a number of -9 -
standard texts, listed below. ) 3 -P 2 0 5
'-10-
A number of useful points can be made,

\
\
however, concerning the mobility of polar- -11 \
N JiO 2 -P 2 O 5 "
ons in glass. The basic idea is that electrons Mo0 3 -P 2 0 5
-12 X -

are always transferred between levels of \

equal energy, and that the energy required -13- ^ FeO-P2O5

\
\ BaO-B2O3-SiO2 - T i 0 2
WH to permit this is supplied by phonon 1 1

scattering. WH depends both on the po- 2 3 4 5 6 7

laron binding energy WP, and on the elec-
tronic transfer integral J, which can be
considered as an interaction (binding) en-
ergy between two nearby sites. The effec-
tive activation energy is therefore the dif-
ference between two terms
WH = ±WF-J (14-16)
1 0 3 / r in K"1
Figure 14-12. Arrhenius plots showing the variation
of conductivity with temperature in a range of elec-
tron conducting glasses. Note the nonlinearity in the
plots which is found in the more highly conducting
glasses at low temperatures. (Reprinted with permis-
sion from: Noncrystalline Semiconductors, Vol. Ill,
Pollak, M. (Ed.). Copyright CRC Press, Inc., Boca
Raton, FL, Sayer and Mansingh, 1985.)

Two limiting cases are:
(i) When J is almost as big as lA WP. (The
factor of Vi enters through the law of mass
action for similar reasons to those men-
tioned in connection with ionic dissocia-
tion, Sec. 14.3.2 above.) Wu is therefore rel-
atively small, and the electron always
avails itself of an opportunity to move. The
time during which adjacent sites have the
same energy is thus much longer than the
time it takes for the electron transfer to
occur. This is the so-called "adiabatic"
regime.
(ii) When J is small and Wn and WP are
large. The time required for an electron to
jump is then large compared to the time for
lattice motion. An electron will miss many
opportunities to hop from one site to an-
other. This is "non-adiabatic" hopping.
Generally, in glasses the effect of disor-
der is to reduce the extent of overlap be-
tween neighboring sites and thus to reduce
the magnitude of the overlap integral J.
This reduces the likelihood of adiabatic be-
havior. This point is illustrated in Fig.
14-13 by the variation in the effective high-
temperature activation energy (WH) with
transition-metal ion spacing for a series of
glassy systems (Sayer and Mansingh,
1983). Only in the vanadium system is it
possible to introduce sufficient transition
metal ions to enhance the intersite interac-
tion to trigger a changeover to the adia-
batic hopping process.
736 14 Electrical Properties of Glasses
0.6 FeO-P2O5
Mo0 3 -P 2 0 5
0.5
2 <u
o Figure 14-13. Variation
£ 0.3
o
< value of EJ with site
0.2
V205 (gel)
I I
A 5
Spacing between transition metal ion in
The electronic conductivity depends not
only on the proximity of other transition
metal ions, but also on the fraction c which
exists in the lower oxidation or valence
state. Quite generally, for the high temper-
ature region, one expects
ad.c = const • c(l - c) • exp [ - WH/R T]
(14-17)
The prediction is that the maximum con-
ductivity would be obtained with a 50:50
distribution between the two oxidation
states. However, many systems (Sayer and
Mansingh, 1987) deviate from this pre-
dicted behavior. For V 2 O 5 -P 2 O 5 glasses,
for example, the maximum occurs at
c = 0.16, and only for FeO-P 2 O 5 and cer-
tain vanadate-borate glasses is there a
maximum at c = 0.5. Some kind of chemi-
cal ordering effect is clearly apparent in
these systems, which is presently not well
understood.
FeO-CaO-P2O5
W0 3 -Zn0-Ba0
of high-temperature
spacing in transition
metal ion glasses (re-
produced by courtesy
of M. Sayer, Sayer and
I Mansingh, 1983).
6
14.4.2 High Frequency
and High Voltage Effects
The strong parallels between ionic and
electronic conduction processes in glass
are apparent in both the frequency-depen-
dent conductivities (see Sec. 14.2.6 and
14.2.7 above) and the high-voltage effect.
Owen (1977) reports that the dielectric loss
curves (and therefore also the a.c. conduc-
tivities) for BaO-V 2 O 5 -P 2 O 5 glasses effec-
tively replicate the corresponding pattern
of behavior seen in sodium silicate glasses
(Fig. 14-14). The characteristic loss spectra
(actually peaks in [&" — odc Jco] versus log /
where co = 2nf is the angular frequency)
lead at higher frequencies into "low loss"
regions (where aac = Boo1), and are indica-
tive presumably of the same kind of (com-
plex) hopping process.
Even more remarkably, in electronic
conductors the above mentioned dielectric
loss peaks are accompanied by mechanical
losses which can be observed by internal
friction, acoustic attenuation and related

techniques. Chomka et al. (1978) report the
appearance of mechanical loss peaks upon
addition of Fe 2 O 3 to MgO-P 2 O 5 glasses.
The temperature at which these peaks ap-
pear decreases with increasing Fe 2 O 3 con-
tent, and moves to higher temperatures
with increasing frequency of measurement.
The activation energies for mechanical and
dielectric relaxation are in fact very similar.
This is a clear indication that the electron
does possess particle properties and that
electron migration in these glasses is
strongly coupled to local relaxations in the
glass structure.
Another type of dispersive behavior is
observed when large electric fields are ap-
plied. The transition metal oxide glasses
are ohmic up to fields of 105 Vcm~ \ but at
higher fields the conductivity increases. To
a fair approximation, the data, see Fig.
14-15, obey the equation
sinh[eaF/2kT]
(14-18)
eaF/lkT
Here a(F) and a0 are respectively the field-
dependent and zero-field conductivities,
"a" is the intersite distance, and all other
3
Sodium silicate glasses
• V2O5-P2O5 glasses
3 -1
Jii
\ "Debye"
-2 relaxation
_2
J well known in solution electrochemistry.
Figure 14-14. Characteristic "dielectric loss"
(e" — oAcJw versus log / ) curves in BaO -V 2 O 5 -P 2 O 5
glasses which superpose the curves for the corre-
sponding behavior in ionic systems, e.g. sodium sili-
cate glasses (reproduced with permission, Owen,
1977).
14.4 Transition Metal Oxide Glasses 737
1000 2000 3000
Normalized field. FT in
Figure 14-15. High field (non-ohmic) effects in some
ionically and electronically conducting glasses. The
increase in the conductivity of sodium borosilicate
glass is commensurate with the effects seen in two
typical "polaronic" systems (reproduced with permis-
sion, Owen, 1977).
symbols have their usual significance
(Owen, 1977). The values of "a" needed to
fit Eq. (14-18) generally lie within the range
20-40 A, which is about five times the
average separation of the transition metal
ions. Large jump distances are also needed
to fit Eq. (14-8) for the ion-conducting
glasses (Owen, 1977; Ingram et al., 1980).
The origins of the high-field dispersion
are still under investigation (see e.g. Hyde
et al., 1987). It is evident that (with the ex-
ception of the chalcogenide glasses; Owen,
1977) the conductivity remains ohmic until
the "added" electrical energy (eaF) be-
comes comparable with the thermal ener-
gies. The excess electrical energy might be
utilized either (i) to release ions (or polar-
ons) from deeper than average traps, or (ii)
to lift ions (or polarons) over larger than
average energy barriers, or else (iii) to over-
come the "ion atmosphere" effects which
can retard the hopping process (Sec.
14.3.5). This last alternative would be the
direct analog of the Wien effect, which is
Whatever the details of the high field
mechanism, it is noteworthy that these
characteristic distances of 20-40 A seem to
be required to balance the overall energet-
ics of ion migration. Indirectly, this could
738 14 Electrical Properties of Glasses
be yet more evidence which supports the
cluster/tissue model of glass, described in
Sec. 14.3.4 above, where correlations are
implicated well beyond the normal range
of short range order in glass.
14.4.3 High Pressure Effects
Differences between ionic and electroni-
cally conducting glasses are apparent in
the effects of external pressure. Figure 14-16
shows how the conductivities of As 2 Se 3 ,
25Fe 2 O 3 -75P 2 O 5 ,and20Na 2 O-80B 2 O 3
glasses are influenced by moderate in-
creases in pressure (Arai et al., 1973,1974).
These are examples of respectively: (i) semi-
conducting (see Sec. 14.5 below), (ii) polar-
onic, and (hi) ionically conducting glasses.
The behavior of the iron phosphate glass
lies midway between the typical semicon-
ductors (where the conductivity strongly
rises) and typical electrolytes (where it
3.0
As2Se3 (25°C)
20Na20-80B203(61°C)
1.0 2.0
Pressure. P in kbar
Figure 14-16. Pressure effects on electronic and ionic
conductivities in glass. The pressure coefficient
changes from positive to negative as the mechanism
changes from a semiconducting, through polaronic
hopping, to a simple ionic mechanism (reproduced by
courtesy of H. Namikawa, Arai et al., 1973-74).
falls). This could be a "self-cancellation ef-
fect" involving the two contributions to the
hopping energy given in Eq. (14-16). In-
crease in pressure will slow down polaron
migration (because there is a finite activa-
tion volume associated with the displace-
ment of the polaron), but there will also be
a counterbalancing increase in mobility,
associated with increased orbital overlap
between electron orbitals in neighboring
transition metal ions.
14.4.4 Switching Phenomena
Another way in which electronic and
ionic conductors differ is in the contrasting
effects of devitrification. Usually the con-
version of glass into crystals results in a
conductivity decrease in ionic systems,
whereas in electronic conductors the con-
ductivity always increases. This could be
the origin at the switching effect which is
found both in chalcogenide (Ovshinsky,
1968) and transition metal oxide glasses
(Sayer and Mansingh, 1987) (see Sec. 7.6.5).
Many of the switching-effect studies
have been made on V2O5 based glasses and
on V2O5 films (Gattev and Dimitrev, 1981;
Nadkarni and Shivodar, 1983). Above a
certain threshold voltage, the glass sample
enters a low resistance state, which returns
to a higher value (closer to its initial state)
when the current is reduced to zero (Tat-
sumisago et al., 1983). After this forming
process, switching occurs at lower thresh-
old voltages.
The process is not fully understood, but
it may be related to the reversible forma-
tion and decay of crystalline nuclei along
pathways of high conductivity. At present
the applications of these materials in com-
mercial devices seems unlikely, but there
are still important questions which merit
further investigation.

14.4.5 Double Injection of Ions
and Electrons
A major application which is envisaged
for these transition metal oxide glasses is as
solid electrodes in electrochemical devices.
This is because they exhibit mixed ionic
and electronic conductivity, and can ac-
commodate varying amounts of hydrogen
or alkali metal by variations in the oxida-
tion state of the transition metal ion. This
is the process of ionic intercalation or dou-
ble injection of ions and electrons. Using
Li + ions and glassy V2O5 as examples, we
can write
= Li^ ^2-
(14-19)
In this reaction (which is usually re-
versible), Li + ions will arrive from the elec-
trolyte and electrons from the external cir-
cuit.
Crystalline intercalation materials have
been used for many years in electrochemi-
cal cells. The best known is probably
y-MnO 2 which is used to store hydrogen
(H 3 O + + e~) in Lechanche type cells, and
/?-MnO2 which is used to store Li in most
commercially available Li-batteries. Such
a battery can be written schematically as
~Li | Li+-ion electrolyte | mixed conductor+
(14-20)
where the positive plate (or cathode) is the
intercalation electrode. The output voltage
of such a device depends on the difference
in the chemical potentials of lithium in the
pure metal and in the transition metal
oxide phases, respectively.
Many such electrode materials exist; all
are characterized by an open structure, of-
fering many vacant sites for intercalable
cations, and empty electronic orbitals on
the transition metal ions. Examples include
TiS 2 , V 6 O 13 , WO 3 and MoO 3 .
14.4 Transition Metal Oxide Glasses 739
According to Levy and Souquet (1989),
the use of glassy electrodes is especially
advantageous because additional cations
are welcomed into the disordered structure
with a substantial release of free energy.
This of course increases the amount of en-
ergy which can be stored in electrochemi-
cal cells (Eq. (14-20), above).
Another advantage of glassy electrodes
(Levy and Souquet, 1989) is that ionic mo-
bilities are generally higher in glasses than
in the corresponding crystals. This leads to
improved (i.e. lower) response times, which
means that the electrochemical cells can be
discharged and recharged more quickly.
Within the context of solid state ionics,
the development of solid state devices in-
volving both glassy electrolytes and/or
glassy intercalation electrodes has been a
major activity in the last ten years. Some of
this effort has gone into the synthesis of
Li + -ion conducting glasses (and polymer
electrolytes), and otherwise into the con-
struction of multilayer devices, containing
thin layers of electrolyte and electrode ma-
terial. See, for example, Jourdaine etal.
(1988).
A major achievement has been the devel-
opment of Li + -ion conducting vitreous
electrolytes based on the thio-analogs of
the phosphate, borate and silicate glasses
(see Sec. 14.2.4 above). Gabano (1985) in-
corporated the iodothiophosphate glasses
of Malugani et al. (1983) into cells of the
type
-Limetal|47LiI-37Li 2 S-18P 2 S 5 |TiS 2 +
(glassy electrolyte) (14-21)
Such cells usually contained a mixture of
electrolyte and crystalline TiS2 as the cath-
ode material (to improve the interfacial
contact), but also performed better when
the temperature was raised to 110°C.
Subsequently, Akridge and Vourlis
(1988) have incorporated several design
740 14 Electrical Properties of Glasses
improvements, including the use of an iso-
static compression technique to minimize
interfacial impedances. These lithium bat-
teries can operate in the temperature range
— 40 to + 200 °C, and have now been com-
mercialized.
However, at present other ways of utiliz-
ing the special properties of amorphous
materials with mixed ionic/electronic con-
ductivity are now commanding attention.
One of these potential areas of application
is electrochromism.
14.4.6 Electrochromic Devices
Following the classic work of Deb
(1973), there has been continued interest in
the phenomenon of electrochromism in
thin films of both amorphous and poly-
crystalline tungstic oxide. The process in-
volves a simultaneous injection of elec-
trons and cations (as in Eq. (14-19)) but the
interest is less in electrochemical energy
storage than in the production of a colour
change. The electrochemical write-erase
mechanism can be given as
WO 3 + x e + x H + = H,WO 3
(pale yellow) (deep blue)
(14-22)
where the blue colour (and also the elec-
tronic conductivity) in WO 3 arise from a
Viewing face of mirror
(W 5 + /W 6 + ) intervalence transfer reaction.
The maximum of the broad absorption
band appears in the near infrared region
(at about 1.5 eV), so the electrochromic ef-
fect cuts out a fair amount of the energy in
the solar spectrum. The optical properties
are not changed if H + is replaced by Li + ,
etc. Applications of electrochromism in-
clude electroptic displays (Faughnan and
Crandall, 1980), daylight modulation
(Lampert, 1984; Cogan etal., 1987) and
variable intensity sunglasses.
An electrochromic mirror which is being
developed for automotive applications
(Baucke and Duffy, 1985; Baucke, 1990) is
illustrated in Fig. 14-17. The light (from
passing cars) passes through the layer of
WO 3 before being reflected by a rhodium
mirror. The device functions in effect as a
rechargeable battery. The protons are nor-
mally stored in a WO 3 layer behind the
mirror, but are brought forward electro-
chemically when the mirror needs to be
darkened.
The electrical properties of WO 3 films
illustrate several aspects of the polaronic
conduction mechanism, and also some im-
portant effects of structural disorder. In
amorphous WO 3 (normally prepared by
thermal evaporation or electron-beam
sputtering), an electron hopping mecha-
nism predominates until x reaches a value
Transparent
electrode
W03 Layer
Electrolyte
Reflector Figure 14-17. A schematic
design for an electro-
W03 Layer
chromic mirror intended
Electrode for automotive applications
(reproduced by courtesy of
I A. Duffy, Baucke and
Duffy, 1985).

0.2 0.3 (U 0.5
Composition parameter, x
Figure 14-18. Conductivities of amorphous HXWO3
films plotted versus x at 300 and 4.2 K. Note the
sharp rise in o occurring when x = ca. 0.33 at the very
low temperature, indicative of an insulator to metal
transition (after Crandall and Faughnan, 1977).
of about 0.33 (Crandall and Faughnan,
1977). At this point an insulator-to-metal
transition occurs, and the d-electrons on
the tungsten atoms become fully itinerant.
This transition and the associated mini-
mum in the metallic conductivity can be
readily seen in Fig. 14-18. Tungstic oxide
films with x>0.33 are essentially metallic
in nature, and can be used to reflect the
sun's rays. They are especially attractive
therefore for "smart window" applications.
In polycrystalline films (Dautremont-
Smith etal, 1977; Goldner and Rauh,
1983) there is less structural disorder, and
the insulator-to-metal transition occurs at
lower x-values. For this reason the poly-
crystalline films are sometimes preferred
for the window applications, but display
devices containing amorphous films may
benefit from the higher cation diffusivities
within the WO 3 and the shorter response
times.
Referring again the Eq. (14-16) above, it
seems that the overlap parameter J will be
larger in the crystalline as compared to the
14.5 Semiconducting Glasses 741
amorphous films. In the crystalline films,
the polaronic hopping will be more adia-
batic in character so the transition to
metallicity will be favoured. Alternatively
in the language of band theory, there is a
much cleaner "mobility edge" in the crys-
talline systems and so it is easier to popu-
late the extended electronic states. In the
next section, a class of amorphous materi-
als will be discussed where the explicit use
of band theory is essential.
14.5 Semiconducting Glasses
14.5.1 General Principles
Much of the basic understanding of
semiconducting glasses comes from the ex-
tensive work of Mott and his co-workers.
The starting point is the conception that in
optically transparent glasses a "true" gap
exists between the valence and conduction
bands. In effect this can be seen as a
straightforward consequence of chemical
bonding, and of the energy separation ex-
isting between bonding and antibonding
orbitals. In SiO2 glass this gap is as high as
10 eV, which means this material is trans-
parent well into the far ultraviolet region.
Typical semiconducting glasses, such as
amorphous silicon, have much lower
bandgaps and find important applications
which rely on their photovoltaic and pho-
toconductive properties. These materials
have been intensively studied within the
context of solid state physics. They are well
characterized using a variety of techniques,
including thermoelectric power, the Hall
effect, and drift mobility measurements.
A fuller discussion of these methods is
given in standard texts which are listed at
the end of this chapter (see also Chap. 7).
The emphasis now will be on the special
properties of amorphous semiconductors.
742 14 Electrical Properties of Glasses
Amorphicity (or disorder) shows up in
the electrical properties several ways. First,
there is the Anderson localization (see e.g.
Mott, 1972, 1977) which affects electrons
near the bottom of the conduction band
and also, correspondingly, those holes near
the top of the valence band. Such electrons
in the "tail states" diffuse slowly through
the glass, moving from one shallow trap to
another. Only electrons above the mobility
edge are free to occupy extended states
within the conduction band. Figure 14-19
is a schematic representation of the result-
ing "mobility gap".
Figure 14-19 also shows the presence of
"states in the gap". According to Mott
these do not arise as a necessary conse-
quence of amorphicity (as would be the
case in the Cohen-Fritzsche-Ovshinsky
model, 1969) but depend on the presence of
Mobility edge
"Tail states
Fermi level
CD Defect states
c
LU
Density of states —
Figure 14-19. A schematic density-of-states diagram
for an amorphous semiconductor, based largely on
Mott's ideas. The Fermi level is "pinned" between
partially occupied donor and acceptor states deep in
the band gap.
specific defects. These could be non-bridg-
ing oxygens (nBO's) in SiO 2 or "dangling
bands" in amorphous silicon (see below).
These defects on "gap states" provide a
home for the most energetic electrons in
the system, and so they serve to pin the
Fermi level in a restricted range of posi-
tions within the mobility gap. The effect of
this "pinning" is very important in chalco-
genide glasses (see Chapter 7) where there
seems to be little possibility of raising or
lowering the Fermi level even by normal
doping procedures.
There is also another way in which
amorphicity reduces the possibility of con-
trolling the electronic properties of glassy
materials. This is Motfs 8-AT rule, which
states that all atoms in glass are free to
select coordination numbers best suited to
their bonding requirements. Thus, silicon
can complete its "octet" (or valence shell)
when it is 4-coordinate, and similarly for
oxygen the preferred coordination number
is 2. This rule explains, for example, why so
many multicomponent oxide glasses are op-
tically transparent, and are also good elec-
tronic insulators.
It is convenient to classify the different
types of glass reviewed in this Chapter by
reference to the simple band scheme of Fig.
14-19. The ionic conductors described in
Sec. 14.2 and 14.3 are large band-gap mate-
rials, where electronic semiconduction can
be ignored in most circumstances. The
transition metal oxide glasses (Sec. 14.4)
may also possess large band gaps, since
conduction involves d-electrons effectively
localized in gap states.
The semiconducting glasses to be dis-
cussed below have band gaps typically
around 1 to 2 eV, and exhibit a range of
distinctively new electrical phenomena.
However, as these systems are becoming
better understood, it is apparent that their
behavior is susceptible to many of the

structural and chemical influences encoun-
tered in ionically conducting glasses (see
also Chap. 7, which covers the electrical
behavior of chalcogenide glasses).
14.5.2 Amorphous Silicon
(a-Si and a-Si:H)
14.5.2.1 Electrical Properties
The story of amorphous silicon is one
where scientific advance has led fairly
quickly to successful commercial exploita-
tion. The decisive step forward was the dis-
covery by Spear and Le Comber (1976)
that amorphous silicon prepared by the
glow-discharge (GD) decomposition of
silane (SiH4) could be doped with phospho-
rus and boron to produce n- and p-type
semiconductors respectively.
This is clearly shown in Fig. 14-20,
which is taken from Spear and Le Comber
(1976). The "intrinsic" n-type conductivity
is enhanced by the introduction of phos-
Figure 14-20. The doping of amorphous silicon
(a-Si:H) with B and P. The conductivity rises are
indicative of both p- and n-type semiconductivity (re-
produced by courtesy of P. G. Le Comber, Spear and
Le Comber, 1976).
14.5 Semiconducting Glasses 743
phine (PH3) into the silane gas stream. By
contrast, introduction of diborane (B2H6)
causes a reversal to p-time semiconductiv-
ity.
The conductivity is increased by many
orders of magnitude on doping (in p.p.m.
levels) in either direction. The introduction
of electrons into the valence bond or holes
into the valence band must therefore be
linked to significant upwards and down-
wards movements in the Fermi level.
How has this effect come about? Is the
8-iV rule still valid? What has happened to
the gap states which should (as in Fig.
14-19) restrict the movement of the Fermi
level? The answer to all these questions lies
in the special role of hydrogen, and in a
complex interplay of defect/dopant con-
trolled equilibria.
14.5.2.2 Chemistry of the Defect States
Amorphous silicon prepared by the GD
process is strongly hydrogenated. Typi-
cally, it contains 5 to 10at.% H and is
properly written a-Si: H. Most of this hy-
drogen will be present (see e.g. Street et al.,
1987 b) as a result of a chemical reaction
involving a breakup of the tetrahedral net-
work of the silicon
= Si — Si = + 2H = 2( = Si:H) (14-23)
(silicon network) (hydrogenated silicon)
where ":" represents here an electron pair
bond formed between Si and H, and the
other three Si-Si bonds are undisturbed.
By the same reaction the hydrogen will
remove any "dangling bonds", i.e. single or
paired electrons on three-coordinate Si
atoms. It is this absence of "states in the
gap", which can act either as electron
donors or acceptors, which opens up the
possibilities for doping with boron and
phosphorus.
744 14 Electrical Properties of Glasses
Moreover, the doping of a-Si:H does
seem to be strongly influenced by the 8-JV
rule (Street, 1982; Street etal., 1985), and
only some 1% of added phosphorus, for
example, enters dopant positions. Much of
the dissolved phosphorus is 3-coordinate,
as would be expected from 8 — 5 = 3.
Street argues that the formation of 4-co-
ordinate phosphorus involves chemical re-
actions like
Si3" + P4 (14-24)
where the superscripts refer to formal
charges and the subscripts to the coordina-
tion numbers. The appearance of phospho-
rus in a doping position (P4) is compen-
sated by the appearance of a charged
silicon atom (Si 3"). Both charged species
satisfy the 8-N rule and have a completed
octet of outer electrons. Equation (14-24)
does not in itself result in n-type conduc-
tion since the "liberated" electron has been
trapped within a dangling bond (or lone
pair) on the Si 3" entity.
Alternatively (Street etal., 1985), reac-
tion (14-24) might be written in two steps,
involving electrons from tail states near the
bottom of the conduction band
(14-25)
Si3 (14-26)
Applying the law of mass action to Eqs.
(14-25) and (14-26), it can be shown that
both the concentration of electrons in tail
states and in dangling bonds should vary
as the square root of the total con-centra-
tion of phosphorus (strictly with [P^]172).
Actually, this square root dependence is
observed experimentally, but the correla-
tion is better when the activity of phospho-
rus (as expressed by the concentration of
PH 3 in the gas phase) is used rather than
the actual (or stoichiometric) concentra-
tion of phosphorus in the solid phase. This
is a highly suggestive result. It parallels to
a remarkable degree the correlations be-
tween the thermodynamic activity of ionic
dopants and ionic conductivity (see Eq.
(14-12), Sec. 14.3.2), which formed the basis
of Ravaine and Souquet's weak electrolyte
theory of glass.
Le Comber (1989) has remarked on the
significant effect which doping has on the
position of the Fermi level, which would be
surprising if the nature of donor (e.g. Si3")
and acceptor levels (e.g. P4) were to re-
main fixed with changing dopant concen-
tration. Very likely the situation is more
complicated and more chemical species are
involved. Very recently, Boscherini et al.
(1989) have determined the local bonding
configurations of phosphorus using the
EXAFS method. They report the existence
of 5-fold as well as 3-fold coordinated
phosphorus, which clearly requires a mod-
ification to existing models of the doping
process. For a further discussion of (hydro-
genated) a-Si, see Vol. 4, Chap. 10. For a
discussion of the relaxation and crystal-
lization of a-Si, see Chap. 9, Sec. 9.3.4 of
this volume.
14.5.2.3 Glassy Properties
of Hydrogenated Films
Reference has already been made to the
role of hydrogen and the large concentra-
tions which have been incorporated within
a-Si:H films. It is thought (see e.g. Street
et al., 1987 b) that much of this hydrogen
accumulates along internal surfaces (com-
pare the "connective tissue", Sec. 14.3.4) or
inside internal microbubbles and voids.
Recently, Williamson etal. (1989) have
used small angle X-ray scattering (SAXS)
to prove the existence of such microvoids
containing 5-9 atoms of hydrogen even in
device quality a-Si: H.
 14.6 Applications of Amorphous Silicon and Related Materials 745

(Eq. (14-6)), which has already been used to

describe electrical relaxations in ionic
n-type a-Si: H glasses. There seems indeed to be no sharp
distinction between the properties of amor-
phous semiconductors and conventional
glassy materials.

-2 -2
Cooling rate K s'
A 5-10 14.6 Applications of Amorphous
• 1-2
• 0.03-0.05 Silicon and Related Materials
• "rested"
-3
2.0 3.0 14.6.1 Range of Device Technologies
1O3/7" in
Figure 14-21. Arrhenius plots of conductivity in
a-Si: H showing the influence of thermal history (cool- The present scope for the industrial and
ing rate). Te is an effective "equilibration temperature" commercial exploitation of amorphous sil-
above which annealing effects are absent (reproduced icon devices (Le Comber, 1989) is summa-
by courtesy of R. A. Street, Street et al., 1987 a). rized in Table 14-1. It is apparent that all
these devices in one way or another relate
to topical issues such as energy conserva-
This hydrogen retains some mobility in tion or information storage and retrieval.
a-Si: H at higher temperatures, but it seems For a fuller discussion of the technical
to "freeze" on cooling. This argument has and scientific details, the reader is referred
been used by Street et al. (1987 a) to explain to the original literature (see e.g. Le
the unusual shapes of the Arrhenius plots Comber, 1989) and to the standard texts
shown in Fig. 14-21. Below an equilibra- on the physics of amorphous materials,
tion temperature, Te = 130°C, we see some of which are listed below. Three ex-
"glass like" behavior where the conductiv- amples are supplied here to give a general
ity depends not only on the actual temper- idea of the advantages stemming from the
ature, but also on the cooling rate. One use of amorphous materials.
could postulate that the clusters of Si:H
bonds act as "percolation impedances"
(McLeod and Cord, 1988), whose presence
tends to divert electrons away from more Table 14-1. Applications of amorphous silicon.
favorable pathways through the material.
Device Commercial product
If the process of hydrogen clustering is ar-
rested at Te, then the d.c. conductivities Photovoltaic cell Calculators, watches,
will be higher than expected on the basis of battery chargers, etc.
continuing structural change. Photoconducting layers Spatial light modulators,
Further evidence for this "glass-like" be- xerography, etc.
havior comes from monitoring the decreas- Reflective coatings Heat reflecting float glass
ing concentration of electrons in tail states, (architectural applica-
tions)
when rapidly quenched a-Si: H is annealed
Thin film field-effect Displays, televisions,
below Te (Kakalios et al., 1987). This decay transistors (FETS) logic circuits, etc.
process obeys the same KWW equation
746 14 Electrical Properties of Glasses

14.6.2 Photovoltaic Devices Electrons

The basic principle of photovoltaism is

illustrated schematically in Fig. 14-22. This
shows the band bending which occurs at a
p - n junction (formed e.g. from B and P-
doped a-Si:H). At equilibrium the Fermi
levels are equalized, so as to keep the
chemical potential of the electrons con-
stant across the interface. When the junc- n-type conductor p-type conductor
tion is illuminated with light of sufficient Figure 14-22. The basic principle of the photovoltaic
energy (£ gap < h v), electrons are promoted effect showing band bending and equalization of the
into the conduction band, and flow across Fermi level (schematic).
in the direction indicated by the arrows.
The output voltage will be determined by scale a-Si:H devices, conversion efficiencies
the amount of band bending which has are typically 8-9% (Hamakawa, 1987).
occurred. Such solar cells are routinely installed in
One application to be envisaged for wrist watches and pocket calculators. One
these devices is in the area of solar energy can easily envisage the electrical energy
conversion. Optical absorption data (Gib- which is generated during periods of strong
son et al., 1978) for amorphous and crys- illumination being stored in Li batteries of
talline silicon are compared with the en- the kind described in Sec. 14.4.5. Such hy-
ergy profile of the solar spectrum in Fig. brid photovoltaic/electrochemical systems
14-23. The shift of absorption edge to could indeed be "all-vitreous-state" in con-
longer wavelengths in the amorphous ma- cept.
terial means that more of the solar energy
106
can be utilized. Very thin films (a few jim
thick) of the amorphous material will ab- a-Si:H
E
sorb most of the useful sunlight. 0.20
Another advantage of a-Si: H is that it o
can be alloyed with other elements such as 10' 0.16
C or Ge by mixing in either methane (CH4)
or germane (GeH4) into the gas feed for the 0.12
GD process. These substitutions have the CL

effect of increasing the bandgap with C I 10* 0.08

(useful in light emitting diodes) or decreas-
ing the bandgap with Ge, which means
that longer wavelength light can be used
for solar energy conversion. According to
Le Comber (1989) energy conversion effi-
ciencies of 13-15% have been reported for
small area devices using combinations of
a-Si:H and a-SiGe:H cells. The advan-
tages of such composite devices are dis-
cussed by Catalano et al. (1989). For larger
0.04
0.8 0.6 0.4
A in (jm
Figure 14-23. Optical absorption spectra for c-Si and
a-Si: H compared with the solar energy spectrum. The
shift to longer wavelengths favors the use of amor-
phous silicon for solar energy conversion (reproduced
by courtesy of R. A. Gibson, Gibson et al., 1978).

14.6.3 Spatial Light Modulators
The structure of an a-Si: H spatial light
modulator is illustrated in Fig. 14-24 (Le
Comber, 1989). This device depends on the
photoconductive properties of a-Si: H,
which allows an activating voltage to reach
the liquid crystal display only in those re-
gions where the write beam has impinged
upon the a-Si:H coating. Writing times as
short as 0.4 ms have been reported for such
devices.
There is no special reason for restricting
use to a-Si:H in combination with liquid
crystal displays. One might also envisage a
combined photoconductive/electrochrom-
ic device (see Sec. 14.4.6) which would
again depend entirely on the electrical and
electrochemical properties of amorphous
materials for its operation.
14.6.4 Reflective Coatings
One product based on amorphous sili-
con, which does not stem directly from its
electrical properties, is the "Reflectafloat"
glass which is now marketed for its archi-
Transparent electrodes
Write beam Read beam
> certainty about the structure". This state-
Glass -Glass
a-Si;H Liquid
crystal
Figure 14-24. A spatial light modulator based on the
photoconductive properties of a-Si:H (reproduced
with permission, Le Comber, 1989).
14.7 Conclusion 747
tectural applications. According to Le
Comber (1989), a very thin (only 35 nm)
and uniform layer of a-Si is deposited in-
dustrially onto float glass in a 3.5 m wide
reactor. This a-Si layer has a large reflectiv-
ity in the visible and infrared regions, and
thereby reduces the amount of light energy
entering or leaving a building through its
glass windows.
A remarkable property of this film is its
chemical and mechanical durability. It is
hard enough to be used on glass without
additional protection. This is indicative of
possibilities for other applications, where
the electrical properties could be of more
direct interest and a durable coating is re-
quired.
14.7 Conclusion
A broad review of electrical phenomena
in glass has been presented in this Chapter.
The aim has been to focus attention on the
growing importance of amorphous materi-
als in both electrochemistry and solid state
electronics. Already in the latter field, new
knowledge has led directly to important
technological advances.
Attention has also been focussed on the
problems relating to the underlying theory.
This problem, as stated by Mott as long
ago as 1972, is that "in amorphous materi-
als we are faced with two difficulties: the
lack of a rigorous theory, and a great un-
ment was clearly intended for electronic
properties, but it relates also to ionic be-
havior.
To some extent electrons are easier to
study than ions because at least they obey
the Pauli Exclusion Principle. It is known
that they must occupy available atomic or
molecular orbitals, whose presence and na-
ture can be inferred from various spectro-
748 14 Electrical Properties of Glasses
scopic techniques and with the help of
chemical intuition and molecular orbital
theory. Also the electron energy levels are
predetermined by short-range-order effects,
which even in glass are quite well under-
stood.
In the case of ionic transport no such
quantum effects exist, and it may not be
possible even to distinguish the "mobile"
from "immobile" ions, without some
knowledge of medium-range-order in glass.
To date, no general consensus exists on
how best to approach this topic but this
situation should improve as the structure
of glass becomes better understood.
14.8 References
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264.
Button, D. P., Tandon, R. P., Tuller, H. L., Uhlmann,
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Catalano, A., Arya, R, R., Fieselmann, B., Goldstein,
B., Newton, X, Wiedeman, S., Bennett, M., Carl-
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Chomka, W., Gzowski, O., Murawski, L., Samato-
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Cogan, S.F., Plante, T.D., McFadden, R. S., Rauh,
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Phys. Rev. Lett. 22, 1065.
Crandall, R.S., Faughnan, B.W. (1977), Phys. Rev.
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Dautremont-Smith, W. C , Green, M., Kan, K. S.
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Day, D. E. (1976), J. Non-Cryst. Solids 21, 343.
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Dieterich, W., Peterson, X, Bunde, A., Roman, H.E.
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14.8 References 749
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General Reading
Cox, P. A. (1987), The Electronic Structure and Chem-
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ground to Electronic Properties of Solids).
Duffy, X A. (1990), Bonding, Energy Levels and Bands
in Inorganic Solids. Harlow, Essex: Longman (A
750 14 Electrical Properties of Glasses
Chemist's Approach to Semiconduction and Glass
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Solids 21, 373. (Review of the Optical Basicity Con-
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2nd ed. Harlow, Essex: Longman (Glass Structure,
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(Ionic Interactions and Solution Electrochem-
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Mott, N. (1987), Conduction in Non-Crystalline Mate-
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Zallen, R. (1983), The Physics of Amorphous Solids.
New York: Wiley Interscience (General Properties
of Glass and Selected Applications).
15 Materials Technology of Optical Fibers
John B. MacChesney and David J. DiGiovanni

AT&T Bell Laboratories, Murray Hill, NJ, U.S.A.

List of Symbols and Abbreviations 753

15.1 Introduction 754
15.1.1 Digital Transmission 754
15.2 Signal Propagation 756
15.2.1 Total Internal Reflection 756
15.2.2 Numerical Aperture 756
15.2.3 Attenuation 757
15.2.3.1 Intrinsic Mechanisms 757
15.2.3.2 Loss Induced During Processing 757
15.2.4 Dispersion 758
15.2.4.1 Intermodal Dispersion 758
15.2.4.2 Chromatic Dispersion 758
15.2.4.3 Dispersion-Shifted Fiber 759
15.3 Fiber Fabrication Technologies 760
15.3.1 Double-Crucible Technique 760
15.3.2 Vapor-Deposition Techniques 761
15.3.3 Outside Processes: Outside Vapor Deposition 761
15.3.4 Vertical Axial Deposition 761
15.3.5 Inside Processes: Modified Chemical Vapor Deposition 764
15.3.5.1 Chemical Equilibria: Dopant Incorporation 764
15.3.5.2 Reduction of Hydroxyl Contamination 766
15.3.5.3 Thermophoresis 766
15.3.6 Plasma Chemical Vapor Deposition 767
15.4 Fiber Draw 768
15.4.1 Dimensional Control 769
15.4.2 Strength 769
15.4.3 Polymer Coating 769
15.4.4 Loss 770
15.5 Overcladding 770
15.5.1 Sol-Gel Processes 770
15.5.1.1 Alkoxide Sol-Gel Processing 771
15.5.1.2 Colloidal Sol-Gel Processing 771
15.6 Minimizing Defects 773
15.7 Active and Passive Fiber Devices 774
15.7.1 Optical Fiber Sensors 774

Materials Science and Technology

Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
752 15 Materials Technology of Optical Fibers

15.7.2 Optical Fiber Lasers and Amplifiers 775

15.7.2.1 Fabrication of Rare-Earth Doped Optical Fiber 776
15.8 Fluoride Glasses for Fibers 777
15.9 Summary 778
15.10 References 778
 List of Symbols and Abbreviations 753

List of Symbols and Abbreviations

a core radius
at chemical activities of solid species i
Ci concentration of species i
I intensity measured after distance /
/0 input light intensity
Kt equilibrium constant of species i
L optical loss
/ distance
n± refractive index of the cladding
n2 refractive index of the core
Pt partial pressure of gaseous species
r radius
T temperature
7^ temperature at which the gas and the tube wall equilibrate
Trxn gas reaction temperature
V normalized frequency
xt mole fraction of species i in solid
a refractive index profile parameter
yt activity coefficient
A =(n1 — n2)/n2; relative refractive index difference
0O critical angle
X wavelength of light in vacuum
AC alternating current
CVD chemical vapor deposition
DC direct current
IR infrared
MCVD modified chemical vapor deposition
NA numerical aperture
OVD outside vapor deposition
PCM pulse code modulation
PCVD plasma chemical vapor deposition
UV ultraviolet
VAD vertical axial deposition
754 15 Materials Technology of Optical Fibers
15.1 Introduction
Communication by means of light pulses
transmitted through glass fiber is rapidly
replacing that of electronic messages trans-
mitted over wire. Optical communication
is superior because the frequency of visible
or infrared radiation used as the signal car-
rier is vastly higher than the frequency of
the electronic carrier used in wire transmis-
sion. Since the information carrying capac-
ity increases directly with the carrier fre-
quency, the potential afforded by optical
communication is enormous.
The message capacity of communica-
tions systems has increased progressively
over the last century, as illustrated in Fig.
15-1, culminating in the development of
optical communication. In the original
telephone, two wires were required to
transmit a single conversation using a DC
carrier. With an AC carrier, greater than
10000 voice circuits per channel can be
accommodated at frequencies up to one
gigahertz (109Hz). However, since the re-
sistance of copper wires increases with fre-
quency, greater message capacity requires
the use of other transmission media. Single
sideband microwave radio transmission al-
lows frequencies up to 10 GHz but is lim-
Terrestrial system (1.7 Gb/s)
107
CD Undersea cable (274Mb/s)
c 106
o Coaxial system
x:
o 105 ~ Communication satelites-
CD
O 10*
O
1000 Microwave links,
1800 channels
100 v sage capacity showing exponential
CD
Coaxial cable. 600 channels
10
-12 Voice channels
1 First telephone lines
j | I I | I
1890 1910 1930 1950 1970 1990 2010 2030 2050
Year
ited by the availability of frequency bands.
Further improvements are realized with
coaxial cable, but since losses are high, am-
plification is required every mile or two.
Both microwave and coaxial transmission
are currently being supplanted by trans-
mission through hair-thin glass fibers
made of exquisitely pure fused silica. Such
fibers provide both enormous bandwidth
and low loss.
Glass as a transmission medium
(Kompfner, 1965) was first explored in the
1960's, but at the time, the quality of com-
mercially available glass was totally in-
adequate for optical transmission. Optical
loss due to impurities was 104 —105 times
higher than it is routinely today. This
chapter will first outline the architecture
and requirements of optical communica-
tions systems and then describe the devel-
opment of materials processing of glass
having unprecedented transparency into
waveguide structures of precisely con-
trolled dimensions and composition.
15.1.1 Digital Transmission
To better understand the issues faced in
the development of optical fiber, it will be
helpful to understand the architecture of
Figure 15-1. Chronology of mes-
increase with time. Number of
voice circuits transmitted per fiber
pair increases rapidly with signal
i__ frequency.

Electronic
processing
Encoder Driver Laser
3 1 2
Input signal
JM/L
11 01 10
Encoded signal
Figure 15-2. Diagram illustrating digital transmission. Analogue waveform is sampled periodically and con-
verted to digital code which is transmitted through fiber and reconstructed after detection.
current communication systems. As dia-
grammed in Fig. 15-2, an electronic circuit
is used to modulate the output of a laser
whose light is coupled into the fiber and
carried to an electronic detector such as a
photodiode. After detection, the informa-
tion is reconstructed electronically. Instead
of transmitting the analogue electronic sig-
nal directly, better light propagation is
achieved by transforming the analogue
waveform into a digital signal and trans-
mitting a sequence of light pulses in a
scheme called pulse code modulation,
PCM. This is accomplished by sampling
the analogue waveform periodically and
assigning each sample a value between 0
and 256. Since a voice circuit has a maxi-
mum frequency of 4000 Hz, the waveform
must be sampled 8000 times per second.
This forms a string of numbers which is
converted to binary code. That is, each
number is represented by a string of 0's and
l's. This string is used to turn the laser on
and off at a frequency of 64000 times per
second, generating a sequence of discrete
light pulses, each of the same amplitude,
which is transmitted through the fiber. As
the light propagates, it is attenuated so that
15.1 Introduction 755
Optical Electronic
transmission processing
•-1 Amplifier Decoder
Fiber Detector 3 1 2
Output signal
JIM/L
11 01 10
Reconstructed
signal
the signal which reaches the photodetector
after traveling tens of kilometers is much
diminished in amplitude. However, for ac-
curate reconstruction, it is necessary only
to determine whether the laser was on or
off; the light intensity is not important. Ex-
amination of the pulses as they arrive at
the detector shows that the pulses may be
considerably broadened in time, as illus-
trated by the pulse shapes shown in Fig.
15-2. This is the result of dispersion and
eventually limits both the transmission dis-
tance and signal frequency since it causes
initially discrete pulses to run into one an-
other. Thus, for accurate reconstruction of
the original waveform, the digital pulses
must only be intense enough to register
over background noise as long as they are
not so broadened as to merge into one
another.
The challenge to materials science has
been to fabricate a glass structure which
can minimize both loss and dispersion and
allow transmission of pulses at high fre-
quency over long distances. While the
drive of the past two decades has greatly
increased the message capacity of commu-
nications systems, this increase is expected
756 15 Materials Technology of Optical Fibers
to continue into the future as higher fre-
quency systems use an ever greater fraction
of the available optical bandwidth.
15.2 Signal Propagation
Before describing the evolution of fiber
processing, it will be useful to describe
some of the concepts used in the technol-
ogy and some of the terms which define the
waveguiding structure (cf. Chap. 12).
15.2.1 Total Internal Reflection
The refractive index of a material is a
measure of the ratio of the speed of light in
a perfect vacuum to its speed through the
material. The higher the refractive index,
the more the light is retarded or the slower
it travels. When light travels from one
medium to another, it is refracted or "bent"
by an angle whose sine is proportional to
the relative indices of the two media. This
is known as "SnelFs Law". Light which
travels in a higher refractive index medium
and impinges on the interface with a lower
refractive index medium at an angle
greater than a critical angle, 0O measured
Cross Index Input Light path
section profile pulse
Multimode
stepped index
Multimode
graded index
Single mode
stepped index
from the normal to the interface, is totally
reflected. The upper diagram of Fig. 15-3
illustrates propagation through a step-in-
dex multimode fiber. The fiber is called
multimode since there are many paths the
light may follow. Those rays following
paths which "graze" the interface are to-
tally reflected. Such "total internal reflec-
tion" provides the means by which light
can be transmitted for long distance with-
out radiative losses.
15.2.2 Numerical Aperture
A basic parameter of lightguides is
known as the numerical aperture (NA).
The NA is a measure of the light collecting
capability of the fiber and defines the min-
imum angle, @0, of incident light that can
be totally internally reflected:
NA = i (15-1)
when the relative index difference A
and where
A =• (15-2)
n1 is the refractive index of the cladding
and n2 is the index of the core.
Output
pulse
Figure 15-3. Structure of
a optical fiber showing light
trajectories for different re-
fractive index profiles.

The number of modes that can propa-
gate in a fiber is governed by Maxwell's
electromagnetic field equations and is re-
lated to a dimensionless quantity V called
the normalized frequency:
(15-3)
where X is the wavelength of light in vac-
uum and a is the core radius. For example,
as the core radius becomes smaller, there
are fewer paths which the light may follow
and still undergo total internal reflection.
When V is less than 2.405 for a step index
core profile, only a single mode of light, the
fundamental mode, can propagate; all
other modes are cut-off. This governs the
design of single mode fibers shown in the
lower of the diagrams of Fig. 15-3.
15.23 Attenuation
15.2.3.1 Intrinsic Mechanisms
Probably the mose important character-
istic of an optical material for communica-
tion is the amount of absorption of the
light as it propagates through the material
(see Chap. 12 of this volume). Optical loss,
L, is measured in terms of dB/km where
L = 10 - log —, where J o is the input inten-
sity, / is the intensity measured after a dis-
tance /. The first challenge to be faced in
developing optical communications was
finding a glass which is transparent at a
desirable wavelength. In general, the in-
trinsic transmission window of glass is
bounded at short wavelengths by ultravio-
let absorption due to electronic transitions
of the glass cations, and at longer wave-
lengths by molecular vibration. Between
these limits, transparency is determined by
Rayleigh scattering. These mechanisms
and their wavelength dependence are
15.2 Signal Propagation 757
10-1
r
§2
0.1 1.0
Wavelength ((jm)
Figure 15-4. Optical loss window is limited by elec-
tronic transitions, molecular vibrations and Rayleigh
scattering. Also shown are losses due to 1 ppm of
impurities.
shown in Fig. 15-4. Ultraviolet absorption
is determined by the electronic band-gap of
the materials. It decays exponentially with
increasing wavelength and becomes negli-
gible in the near IR. Rayleigh scattering
results from glass composition and density
fluctuations with size scale less than the
wavelength of light. Losses from this
source decrease as the fourth power of
wavelength but tend to increase as dopants
are added to the glass. The steeply rising
absorption curve at longer wavelengths
(> 1.55 jim) is due to cation-oxygen
(molecular) vibrational modes in the glass
lattice, such as Si-O.
15.2.3.2 Loss Induced During Processing
Superimposed on these intrinsic loss
mechanisms are losses arising from imper-
fections created during fabrication of the
glass fiber. Scattering can be increased by
perturbations to the waveguide structure
such as imperfections at the core-clad in-
terface or bubbles or cracks. Perturbations
larger than the wavelength of light, such as
diameter fluctuations, cause Mie scatter-
ing. Even in perfect fibers, impurities incor-
porated in the glass from the starting mate-
758 15 Materials Technology of Optical Fibers
rials or introduced during processing cause
specific absorption bands. In glass, such
absorption bands can be quite broad and
dominate the loss spectrum. Transition
metal ions and hydroxyl (OH~) impurities
are the most common and the most both-
ersome. Representative impurity bands
(Schultz, 1974), are shown in Fig. 15-4 in
which the loss levels are those expected
from about 1 ppm of individual impurities.
In addition, defects in the glass network
such as suboxide species of silicon and ger-
manium can be formed during high tem-
perature processing or from exposure to
radiation. These defects also have charac-
teristic absorption bands.
In practice, a typical fiber loss curve is
dominated by the intersection of the UV
absorption edge and the X~A dependence
of Rayleigh scattering. Thus, lowest loss
exists in the range 1.3 jim to 1.55 jim,
though the Si-OH overtone at 1.38 jum
splits this zone into two separate telecom-
munications windows. Until recently, com-
munications systems could not exploit the
lowest loss at 1.55 (im due to problems
with signal dispersion, as described below.
15.2.4 Dispersion
While the importance of lower attenua-
tion is obvious, the effects of dispersion are
subtle but equally important. As described
above, current communications systems
use digital transmission in which discrete
light pulses propagate through the fiber.
After traveling many kilometers they are
diminished by absorption and broadened
by dispersion. Eventually these pulses be-
come so broadened as to be indistinguish-
able from each other. The distance the sig-
nal can travel before this happens depends
upon how well dispersion is controlled.
In multimode fibers there are two
sources of dispersion, intermodal disper-
sion resulting from the different paths indi-
vidual modes travel and chromatic disper-
sion which is quantitatively much smaller.
[For a detailed discussion of propagation
characteristics see Midwinter (1979) and
Miller and Chynoweth (1979).]
15.2.4.1 Intermodal Dispersion
Intermodal dispersion arises since differ-
ent modes may travel zig-zag or helical
courses within the fiber's core while the
fundamental mode travels a shorter
straight line. Each mode thus arrives at a
different time. To diminish delay, fibers are
designed so that modes which travel the
furthest propagate through lower refrac-
tive index glass within which their speed is
faster. This is accomplished by grading the
index profile of the core as shown at the
center of Fig. 15-3. Minimum intermodal
dispersion is achieved with an index distri-
bution which varies as n2[\— A (r/a)*],
where n2 is the index of the core, A is the
relative index difference, a is the core ra-
dius and the profile parameter, a, has a
value of approximately 2, though the opti-
mum value is wavelength dependent.
15.2.4.2 Chromatic Dispersion
In singlemode fibers where intermodal
dispersion is not a factor, the main source
of pulse broadening is chromatic disper-
sion. Optical sources have finite spectral
width, that is, they emit light over a small
range of wavelengths, and the slightly dif-
ferent wavelengths travel at different veloc-
ities owing to two effects, material and
waveguide dispersion. The total chromatic
dispersion which exists in a singlemode
fiber is the sum of these two components,
illustrated in Fig. 15-5. In this figure, dis-
persion is presented as picoseconds of
pulse spreading per kilometer of fiber tra-
 15.2 Signal Propagation 759
20.0
Material
proper design of the fiber core diameter
and refractive index profile. The conven-
tional step index profile produces a shal-
-p 10.0 low wavelength dependence, while a trian-
Total
chromatic gular shaped fiber core having higher index
dispersion
and smaller core radius results in a steeper
in
3r 0 wavelength dependence. It is thus possible
c
o
U)
to balance waveguide dispersion against
Waveguide
0) material dispersion and shift the point
1-10.0 where they cancel. As illustrated in Fig.
15-6, step index profiles show zero disper-
sion at 1.3 jim, but this point may be
-20.0 shifted to 1.55 jLim by using a small core
1.1 1.2 1.3 U 1.5 1.6
and high refractive index. Such a disper-
Wavelength (jjm)
sion-shifted design is important for more
Figure 15-5. Total chromatic dispersion is the sum of advanced systems, just now being planned,
material dispersion and waveguide dispersion.
since the lower intrinsic absorption at
1.55 |im can now be exploited.
More complex index profiles can yield
versed per nanometer of spectral width of
low dispersion over a broad wavelength
the optical source, ps/km-nm, and is plot-
region (Cohen, 1983), as indicated by the
ted against signal wavelength for a typical
dispersion-flattened profile in Fig. 15-6.
fiber.
Total chromatic dispersion crosses zero at
Material dispersion is the intrinsic re-
two wavelengths and has a broad spectral
fractive index variation of the bulk mate-
region of low dispersion between. Such
rial, with wavelength. For glasses of high
fibers are important for systems where
silica composition it increases with wave-
length, passing through zero close to
1.3 jam. Since current waveguides are com-
1.3 pm
posed principally of SiO2 lightly doped 20.0 Operation
with other ions, material dispersion is es- Smaller core
sentially independent of the fiber design. higher index

Waveguide dispersion, on the other hand, 10.0 JLVJL

More complex
depends upon the spread of optical power structure

beyond the fiber core into the surrounding

cladding, which has a different wavelength/ 1.6 1.7
Wavelength (|jm)
velocity relationship since it is a different Q.
in
material. Light propagating in different Q
-10.0
physical regions of the fiber travels at Dispersion
slightly different speeds and arrives at dif- shifted

ferent times. -20.0 L.

Figure 15-6. Waveguide dispersion depends on the

15.2.4.3 Dispersion-Shifted Fiber index profile and can be balanced against material
dispersion to shift the zero-dispersion wavelength to
Since waveguide dispersion is a function 1.55 jim. More complex profiles can yield dispersion-
of the fiber design, it may be controlled by flattened fibers.
760 15 Materials Technology of Optical Fibers
many channels operating at wavelengths
around 1.3 or 1.55 }im are multiplexed on
a single fiber.
15.3 Fiber Fabrication Technologies
The foregoing has attempted to put into
perspective the challenge presented by op-
tical communications to materials science:
fabrication of a fiber having the highest
purity to achieve low losses and with a
precise index profile to achieve low disper-
sion at the particular wavelength of opera-
tion.
Pioneering work on fibers began in the
1960's with the intention of producing mul-
timode fibers with acceptably low loss. At
that time, optical quality glass exhibited
losses on the order of 1000 dB/km, but
losses of less than 20 dB/km were required
if this new transmission mode was to com-
pete with existing copper wire systems. It
was quickly realized that reduction of tran-
sition metal impurities was the major ob-
stacle.
15.3.1 Double-Crucible Technique
The first attempt at producing high pu-
rity glass, the so-called double-crucible
technique, proceeded along the lines of
conventional glass melting but used spe-
cially prepared constituents (Pearson and
French, 1972; Beals and Day, 1980).
Soda-lime-silicate and sodium-borosilicate
glasses were made from materials purified
to parts per billion levels of transition
metal impurities by ion exchange, electrol-
ysis, recrystallization or solvent extraction.
These starting glasses were melted, fined,
drawn to cane and fed into an ingenious
continuous casting system composed of
concentric platinum crucibles, shown in
Fig. 15-7. A thin stream of core glass
Core glass Inner crucible
Cladding glass Outer crucible
Furnace
Fiber
Figure 15-7. Double crucible process for making
multicomponent glass fibers.
flowed from the upper crucible, passed
through the reservoir of cladding glass and
was concentrically surrounded by the clad-
ding as it flowed through the orifice of the
lower thimble. The time and temperature
of core-cladding contact in the cladding
reservoir were controlled enabling diffu-
sion to produce the index gradient needed
to minimize intermodal dispersion.
Despite its elegance, overwhelming
problems beset this method from the start.
First, contamination during processing
raised the impurity level from the ppb level
in the constituents to ppm levels in the
fiber. Many attempts were made to elimi-
nate this contamination and improvement
was achieved by using the oxygen partial
pressure of the atmosphere during process-
ing to control the redox conditions within
the molten glass. Absorption by iron and
copper, the two principal contaminants,
could thus be minimized by altering their
valence state. Iron could be oxidized pri-
marily to the Fe 3 + state and copper re-
tained in the monovalent state by process-
ing in a controlled oxygen atmosphere.
Thus, strong absorptions by Fe 2 + and
Cu 2 + at near infrared wavelengths were
diminished.

Fibers adequate for commercial systems
of the time were made this way. Losses as
low as 5 dB/km were achieved at 0.9 jam
but the lower losses offered by the 1.3-
1.5 jam window were unattainable using
this technique. Fundamental electronic vi-
brations as well as severe OH ~ contamina-
tion were intrinsic to the starting materials
as well as the glass composition and could
not be appreciably lowered by improved
processing. The method was still-born as it
was introduced to the market owing to the
advent of a superior technology.
15.3.2 Vapor-Deposition Techniques
The double crucible technique was short
lived because vapor deposition techniques
soon appeared which were capable of
lower losses from the visible into the infra-
red (see Chap. 2 of this volume). These
techniques appeared in the early 1970's
and may be categorized as either inside or
outside processes. Both use oxidation of
silicon tetrachloride vapor to produce sub-
micron amorphous silica particles. Other
chloride vapors such as germanium tetra-
chloride and phosphorus oxychloride are
used as sources of dopants in the silica.
Outside deposition utilizes flames hydroly-
sis whereby chloride vapors pass through a
methane-oxygen or hydrogen-oxygen flame
to produce a "soot" of SiO2 particles. The
particles partially sinter as they collect on
a mandrel. The inside process uses these
same reactants together with oxygen, but
the reaction occurs inside a silica tube in
the absence of hydrogen. The high temper-
ature needed to react halide vapors with
oxygen are provided by an oxygen-hydro-
gen burner which traverses along the tube
as it rotates on a glass working lathe. The
reactions produce particles by oxidation
rather than hydrolysis. These particles are
deposited on the inside wall of the tube
15.3 Fiber Fabrication Technologies 761
downstream of the torch and are sintered
to form a vitreous layer as the torch moves
past the deposit.
15.3.3 Outside Processes:
Outside Vapor Deposition
Two versions of outside processes have
been developed. These are the Outside Va-
por Deposition (OVD) (Keck et al., 1973)
process developed by Corning Glass
Works, and the Vertical Axial Deposition
(VAD) (Izawa and Inagaki, 1980) version
developed by a consortium of Japanese
cable makers and Nippon Telephone and
Telegraph Corporation. In the former,
shown in Fig. 15-8, soot is deposited layer
by layer on a horizontal, rotating mandrel
at sufficiently high temperatures to par-
tially sinter the particles to form a porous
silica cylinder. A core of GeO 2 -SiO 2 com-
position is deposited first, followed by an
SiO2 cladding. At the conclusion of deposi-
tion, the mandrel is removed and the tube
is sintered at 1500-1600 °C to vitreous sil-
ica in a furnace having an atmosphere of
He, O 2 and Cl 2 . The central hole is col-
lapsed either during the sintering or subse-
quently as the preform is drawn to fiber.
15.3.4 Vertical Axial Deposition
The VAD process also forms a cylindri-
cal body using soot, but deposition occurs
end-on as shown in Fig. 15-9. Here a po-
rous soot cylinder is formed without a hole
by depositing the core and cladding simul-
taneously using two torches. When com-
plete, the body is sintered under conditions
similar to those used for OVD. A funda-
mental difference between the two pro-
cesses is that while the composition profile
of the OVD preform is determined by
changing the composition of each layer,
the VAD profile depends upon subtle con-
trol of the gaseous constituents in the flame
762 15 Materials Technology of Optical Fibers

0 2 + Metal halide vapors

a) Burner

.Soot boule

Mandrel

Soot preform cross section Preform sintering Fiber drawing

-Soot

Furnace Furnace

A I A IAI Glass
Air gap * I *• Clad
Core

b) C) d)

Figure 15-8. Outside Vapor Deposition (OVD) process. Diagram shows four steps: (a) deposition on a mandrel;
(b) profile of soot preform after removal of mandrel; (c) preform sintering; (d) fiber drawing.

and the shape and temperature distribu-
tion across the face of the growing soot
boule.
Critical to the development of VAD was
the design of torches composed of up to ten
concentric silica tubes. Typically, reactant
vapors pass through one or more of the
central passages where they are protected
from premature reaction by a ring of inert
shield gas. The outer series of tubes alter-
nate between hydrogen and oxygen to
compose the flame. By manipulation of gas
flows, the temperature and particle distri-
bution in the flame can be controlled to
determine the surface temperature distri-
bution and the shape of the boule.
In spite of this rather fragile control of
composition, VAD had one significant ad-
vantage over first generation OVD. Recall
that at this time, transmission systems were
using graded index, multimode fiber. The
high refractive index differences between
core and cladding required by such fiber
was obtained with heavy core doping. This
produced a large mismatch in thermal ex-
pansion between core and cladding and

a)
in9
Cladd
torch
Core torch
Soot preform cross section
Figure 15-9. Vertical Axial Deposition (VAD) process, (a) End-on growth of boule; (b), (c), (d) see Fig. 15-8.
caused cracking of consolidated OVD pre-
forms at the inner surface as the preform
cooled below the glass transition tempera-
ture. Since VAD preforms do not have a
central hole, they can better withstand
thermal stress.
The major challenge to VAD was how to
create an optimized index profile to mini-
mize mode-dispersion. Initially it was
thought that control of the GeO 2 distribu-
tion across the boule required several
GeCl4 sources, each of different composi-
tion. However, it was found that such grad-
15.3 Fiber Fabrication Technologies 763
I To elevator drive
-fB
Preform sintering Fiber drawing
Soot
Furnace Furnace
Glass
c) d)
ing could be accomplished by control of
the boule surface temperature distribution.
Eventually, process development focused
critically upon the shape of the growth face
and the temperature profile across it. Fig.
15-10 (Edahiro et al., 1980) shows GeO 2
incorporation into silica as a function of
the temperature of the boule endface. Be-
low 400 °C, GeO 2 is lost by vaporization of
discrete crystalline particles when the
boule is sintered at high temperature.
764 15 Materials Technology of Optical Fibers
Non-crystalline
o form j tures are injected into a rotating tube
o
t_
"c
Q>
O
c
o Hexagonal
o crystalline form
a* N f
O \ / to produce amorphous particles which de-
\
\ /
I i
0 200 400 600 800
Substrate temperature (°C)
Figure 15-10. Relation between substrate tempera-
ture and GeO 2 concentration in VAD process.
15.3.5 Inside Processes:
Modified Chemical Vapor Deposition
Inside processes such as Modified
Chemical Vapor Deposition (MCVD) had
a different origin. Following the tradition
of the electronics industry, chemical vapor
deposition (CVD) techniques were used to
produce doped silica layers inside silica
substrate tubes (MacChesney et al, 1973).
The concentration of reactants was very
low to inhibit gas phase reaction in favor of
a heterogeneous wall-reaction which pro-
duced a vitreous, particle free deposit on
the tube wall. The tube was collapsed to a
rod and relatively low loss fiber obtained.
However, deposition rates were impracti-
cally low and attempts to increase them
always produced silica particles which de-
posited on the tube wall and resulted in
excess loss. The solution was to exactly re-
verse CVD practice: intentionally produce
a gas phase reaction by increasing the reac-
tant flows by more than ten times. Submi-
cron particles were thus produced which
deposited on the tube wall and were fused
into clear, pore-free glass as the torch tra-
versed along the tube.
MCVD was thus developed (Mac-
Chesney et al., 1974) to the process dia-
gramed in Fig. 15-11. High purity gas mix-
which is mounted in a glass working lathe
I
/
and heated by a traversing oxy-hydrogen
/ torch. Homogeneous gas phase reaction
occurs in the hot zone created by the torch
posit downstream of the hot zone. The heat
from the moving torch sinters this deposit
i
to form a pure glass layer. Torch tempera-
tures are sufficiently high to sinter the de-
posited material, but not so high as to de-
form the substrate tube. The torch is
traversed repeatedly to build up, layer by
layer, the core or cladding. Composition of
the individual layers is varied between
traversals to build the desired fiber index
structure. Typically 30-100 layers are de-
posited to make either singlemode or
graded index multimode fiber.
15.3.5.1 Chemical Equilibria:
Dopant Incorporation
After the initial demonstration of feasi-
bility, fundamental investigations estab-
lished the knowledge required to create a
commercial process. For instance, it was
necessary to better understand the chemis-
try of the MCVD process in order to con-
trol the incorporation of GeO 2 and limit
hydroxyl impurities. In addition, to in-
crease fabrication efficiency, it was neces-
sary to understand the mechanism by
which particles deposit on the substrate
tube as well as the manner in which the
silica particles are sintered into pore-free
glass. Although process development pre-
ceded quantitative understanding, opti-
mization of the commercial process re-
quired this knowledge.
The chemistry of SiCl4 and GeCl 4 oxi-
dation was investigated by infrared spec-
 15.3 Fiber Fabrication Technologies 765

I. Tube setup
V> / N »
>-»v Heat source

II. Deposition 7^ i ( J
^ ^ <d?*5^
V> S N »
Heat source Figure 15-11. MCVD pro-
cess consists of deposition
III. Collapse of glass layers inside silica
^3^^^/ \ ^ tube, collapse of tube to
Heat source solid rod and drawing of
IV. Fiber drawing ^_ preform into fiber.
Fiber
Heat source

troscopy (Wood et al., 1987). Samples of concentrations at high temperatures are

effluent gases from typical MCVD reac- strongly influenced by the equilibria:
tions demonstrated that as the maximum
SiCl4(g) + O2(g)
hot zone temperature reaches 1300 K,
SiCl4 begins to oxidize to Si 2 OCl 6 . This is -> SiO2(s) + 2Cl2(g) (15-4)
shown in Fig. 15-12. Up to 1450 K, the
and
amount of oxychloride increases to a max-
imum, while at higher temperatures the GeCl4(g) + O2(g)
SiCl4, Si 2 OCl 6 , and POC13 content de- - GeO2(s) + 2Cl 2 (g). (15-5)
crease until their concentration in the efflu-
ent is insignificant above about 1750 K.
Above this temperature, all reactants are
converted to oxides.
The behavior of GeCl 4 is different. Its
concentration in the effluent gas stream de-
creases between 1500 K and 1700 K, but
above 1700 K remains approximately 50
percent of its original value. It is clear that
the major part of the initial germanium is
unreacted and escapes in the effluent.
These results indicate that at low tem-
peratures (T<1600K) the extent of the
reaction for SiCl4, GeCl 4 , and POC1 3 is
controlled by reaction kinetics, while at
1000 U00 1800 2200
higher temperatures thermodynamic equi- T(K)
libria become dominant. It is clear from
Figure 15-12. MCVD effluent composition as a func-
rate studies that the residence times in the tion of hot zone temperature. Starting reactants:
hot zone are sufficient to produce equilib- 0.5g/min SiCl4, 0.05 g/min GeCl 4 , 0.016 g/min
rium above 1700 K. The SiCl4 and GeCl 4 POC1 3 , 1540cm 3 /niinO 2 .
766 15 Materials Technology of Optical Fibers
Equilibrium constants for these reactions
may be written
(15-6)
K GeO 2 (15-7)
where Pt are the partial pressures of gas-
eous species and a{ represent the chemical
activities of the solid species. The activities
can be approximated by ytxi9 where xt is
the mole fraction of the particular species
in the solid and yt is the activity coefficient.
An activity coefficient of unity implies an
ideal solution obeying Raoult's law. The
equilibrium constants for these reactions
have been determined as a function of
temperature and indicate that Eq. (15-4)
strongly favors the formation of SiO2 at
high temperature, as verified by the experi-
ments described above. Oxidation of
GeCl4 by Eq. (15-5), on the other hand, is
incomplete since the equilibrium constant,
i£ GeO2 , is less than unity at temperatures
above 1400 K. This means that only a frac-
tion of the germanium starting concentra-
tion will be present as GeO 2 . The presence
of significant Cl2 concentration resulting
from the complete oxidation of SiCl4 shifts
the equilibrium further toward GeCl 4 by
the law of mass action. Low oxygen partial
pressure has the same effect.
15.3.5.2 Reduction of Hydroxyl
Contamination
A second important aspect of MCVD
chemistry is the incorporation of the impu-
rity OH" (Walker et al., 1981). Reduction
of OH" in optical fibers to ppb levels is
essential for realization of low attenuation
in the 1.3-1.55 jum region. Hydrogen spe-
cies originate from three sources: diffusion
of OH~ from the substrate tube during
processing, impurities in the starting
reagents and carrier oxygen gas, and con-
tamination from leaks in the chemical de-
livery system.
The OH ~ level in the fiber is controlled
by the reaction
H 2 O + Cl2 (15-8)
with equilibrium constant
(15-9)
The concentration of OH incorporated
into the glass, CSiOH, is described by
<r> \2(P \i/2
(15-10)
(Po2)1/4
During deposition in MCVD, Cl2 is typi-
cally present in the range 3-10% due to
oxidation of the chloride reactants. This is
sufficient to reduce OH~ by a factor of
about 4000. However, chlorine is typically
not present during collapse and significant
amounts of OH ~ can be incorporated by
diffusion of torch byproducts through the
silica tube. Fig. 15-13 shows the depen-
dence of the SiOH concentration in the
resultant glass as a function of typical POl
and P cl2 concentrations used during
MCVD deposition and collapse with
10 ppm H 2 O in the starting gas. The figure
also shows typical contamination of the
VAD and OVD soot processes.
15.3.5.3 Thermophoresis
Turning now from the reaction equi-
libria, we consider the mechanism of depo-
sition of particles on the tube walls. The
SiO2 particles produced by vapor phase
reaction have diameters in the range
0.02-0.1 |im and are thus entrained in the
gas flow. Without the imposition of a tem-
perature gradient they would remain in the
gas stream and exit from the tube end.
However, temperature gradients in the gas

MCVD collapse conditions
10-9
10"
108 106 10* 102
D 1/2
stream produced by the traveling torch
give rise to the phenomenon of ther-
mophoresis (Simpkins et al, 1979). Here,
particles residing in a thermal gradient are
bombarded by energetic gas molecules
from the hot region and less energetic
molecules from the cool region. A net mo-
mentum transfer forces the particle toward
the cooler region. Within an MCVD sub-
strate tube, since the wall is cooler than the
center of the gas downstream of the torch,
particles are driven toward the wall where
they deposit. The MCVD process is shown
schematically in Fig. 15-14 in terms of:
1) heat transfer in the hot zone, 2) reaction,
3) particle formation, 4) particle deposition
beyond the hot zone where the tube wall
Reaction zone Quartz substrate
Thermophoretic deposit
POCl3
GeCL ^ He
Consolidated f\
deposit
Torch
Traverse
Figure 15-14. Particle formation and thermophoretic
deposition in MCVD.
15.3 Fiber Fabrication Technologies 767
"|.MCVD deposition
& consolidation
Figure 15-13. Typical incorpora-
tion of OH ~ during processing
stages of MCVD, for 10 ppm H 2 O
in chemical precursors.
10° 10" 10"
becomes cool relative to the gas stream
and 5) consolidation of previously depos-
ited particles in the hot zones as the torch
traverses to the right.
A mathematical model for thermo-
phoretic deposition (Walker et al., 1980 a),
experimentally verified, concluded that de-
position efficiency (ratio of SiO 2 equivalent
entering tube to that contained in exhaust)
may be expressed as e = 0.8 [1 — Te/TTxn]
where Trxn is the gas reaction temperature
and Te is the temperature downstream of
the torch at which the gas and the tube wall
equilibrate. Typically, Te is about 400 °C
and Trxn about 2000°C, giving an efficiency
on the order of 60%. Note that the effi-
ciency is not a function of the maximum
tube temperature.
Examination of the process of consoli-
dation of the soot layer on the inner surface
of the silica tube revealed the mechanism
to be viscous sintering (Walker et al.,
1980 b). By this mechanism the rate of con-
solidation is proportional to the sintering
time and surface tension and inversely pro-
portional to the void size, initial soot den-
sity and glass viscosity.
15.3.6 Plasma Chemical Vapor Deposition
A second inside process, Plasma Chemi-
cal Vapor Deposition PCVD (Kuppers
768 15 Materials Technology of Optical Fibers
2.45 GHz
Mirrnwnvp 1200°C
cavity Furnace
I I
Reactants •
c ~ ~ ^ — I — Plasma
I I
Substrate
Traverse
Figure 15-15. Schematic representation of PCVD
process.
and Lydtin, 1980) is similar to MCVD in
that it uses the same reactants inside a sil-
ica substrate tube which is collapsed after
deposition and drawn to fiber. However,
the oxidation of reactants in the tube is
initiated by a non-isothermal microwave
plasma inside the tube rather than by heat-
ing the exterior of the tube, as shown in
Fig. 15-15. In addition, the generation of
the plasma requires a reactant vapor pres-
sure of only a few torr. A microwave cavity,
operating at 2.45 GHz, traverses along the
substrate tube and promotes chemical re-
action. However, a particulate soot is not
produced but instead, deposition occurs
directly on the tube wall to form a thin
glass layer. Furthermore, the reaction and
deposition of both GeO 2 and SiO 2 is much
more efficient than in MCVD, approach-
ing 100%. Another advantage, especially
for multimode preforms, is that since the
plasma involves no latent heat, it can be
traversed very rapidly to produce hun-
dreds of layers. The resulting deposit thus
has a very smooth and precise index profile
essential for minimizing intermodal disper-
sion.
15.4 Fiber Draw
Typical preforms produced by the above
methods are about a meter in length and
between 2 and 7.5 cm in diameter. These
are drawn into 125 jim diameter fiber by
holding the preform vertically and heating
the end of the preform above the glass soft-
- Pump
(10"3bar)
ening temperature until a gob of glass falls
from the end. This forms a neck-down re-
gion which provides transition to a small
tube
diameter filament. Uniform traction on
this filament results in a continuous length
of fiber. Before this fiber contacts a solid
surface, a polymer coating is applied to
protect the fiber from abrasion and pre-
serve the intrinsic strength of the pristine
silica. The fiber is then wound on a drum.
While the basic principles of fiber draw-
ing were established prior to the advent of
optical fiber technology, stringent fiber re-
quirements necessitated improvements in
process control and understanding of the
effects of draw conditions on optical per-
formance. Fiber is now drawn without in-
ducing excess loss while maintaining high
strength, dimensional precision and uni-
formity.
Feed mechanism
Preform
Furnace
\ Fiber diameter
monitor
Fiber cooling
distance
Coating applicator
"I Coating concentricity
monitor
Curing furnace or lamps
Coating diameter
monitor
Capstan
Figure 15-16. Schematic of draw process.

The essential components of a draw
tower, shown schematically in Fig. 15-16,
are a preform feed mechanism, a furnace
capable of 1950-2200 °C? a diameter mon-
itor, a polymer coating applicator, a coat-
ing curing unit, a traction capstan and a
take-up unit. The furnace is typically either
a graphite resistance type or an inductive-
ly-coupled radio frequency zirconia fur-
nace. The former requires an inert atmo-
sphere to prevent oxidation of the graphite
element. The zirconia furnace may be oper-
ated in air but must be held above 1600°C,
even when not in use, since the volume
change associated with the crystallo-
graphic transition of zirconia at this tem-
perature can cause stress-induced fracture.
Its advantage is that the heater element
emits fewer contaminating particles.
15.4.1 Dimensional Control
The uniformity of the fiber diameter de-
pends on control of the preform feed rate,
the preform temperature and the pulling
tension. Over long lengths of fiber
(>100cm) diameter variations can result
from changes in preform diameter and
drifts in furnace temperature and the
speeds of the feed and capstan motors. Di-
ameter variations with shorter length pe-
riod arise from perturbations in the tem-
perature of the neck-down region caused
by thermal fluctuations. These may be
minimized by control of convective cur-
rents and nonuniform gas flows inside the
furnace as well as acoustical and mechani-
cal vibrations. The diameter monitor posi-
tioned below the furnace provides feed-
back to the capstan, adjusting the draw
tension to maintain constant fiber diame-
ter.
15.4 Fiber Draw 769
15.4.2 Strength
Although the intrinsic strength of silica
is extremely high, about 14 GPa, in prac-
tice, long lengths of fiber are considerably
weaker due to mechanical flaws which act
as stress concentrators (see Chap. 13 of this
volume). The strength of a given length of
fiber is thus a reflection of the most serious
flaw. Flaws are due to either chemical at-
tack or mechanical abrasion from contact
of the preform or fiber with a solid mate-
rial. Strength degradation due to mechani-
cal abrasion of the preform may be elimi-
nated by fire-polishing the preform before
draw, but dust evolved from the furnace
element may degrade strength. A clean at-
mosphere in the path from the furnace to
the coating applicator afforded by filtered
air can greatly reduce damage.
Flaws which are present after draw gen-
erally do not cause immediate failure but
require a period of growth, introducing the
concept of fatigue. Although the exact
mechanisms have not yet been established,
it is currently believed (DiMarcello et al,
1985) that corrosion by OH~ causes
growth of subcritical flaws to the point
where fracture occurs. Fatigue may be
minimized by preventing OH ~ from reach-
ing the silica surface, for example by draw-
ing in a dry environment and simulta-
neously applying hermetic coatings to the
fiber surface. Hermetic coatings are cur-
rently being developed since the suscepti-
bility of the fiber to fatigue is a major con-
cern for longterm reliability.
15.4.3 Polymer Coating
As the optical fiber exits the furnace, ide-
ally it has a flaw-free, pristine surface. Ex-
posure to the atmosphere and physical
contact would rapidly degrade this surface
if it were not immediately protected. Once
the fiber has been given sufficient time to
770 15 Materials Technology of Optical Fibers
cool, it enters the coating cup, a vessel filled
with a liquid polymer. As the fiber emerges
from the bottom of the die, a uniform coat-
ing is formed and is subsequently cured.
The best coatings are those which may be
induced to cross-link rapidly, such as ther-
mally-cured silicone rubbers and UV-
cured urethane acrylates. The primary
function of the coating is to protect the
fiber from abrasion, but the coating may
degrade the optical properties of the fiber if
not free of particles, applied concentrically
and without defects. Otherwise, the coat-
ing causes nonuniform stress upon solidifi-
cation and increases the fiber loss. Low
modulus coatings can actually improve the
optical properties of the fiber by reducing
microbending losses since they tend to
cushion the fiber from stress induced dur-
ing cabling or deployment.
15.4.4 Loss
As mentioned above, optical loss may be
increased in the draw process by nonuni-
formities in fiber diameter and coating
thickness. These are waveguide losses, but
additional loss mechanisms are also pres-
ent. For example, increased losses can oc-
cur for high draw tension in pure silica core
fiber as a result of ruptured Si-O bonds.
High draw temperature can cause defects,
such as a germanium suboxide species,
which have well-defined absorption bands.
Similar GeO 2 defects may be induced by
the UV lamps used to cure the coatings.
These latter defects may be controlled by
filtering out the short UV light and using
UV-absorbing coatings on the fiber.
15.5 Overcladding
Drawing technology and each of the
processes OVD, VAD, MCVD, and PCVD
have been developed to the point where
they yield both multimode and single
mode fiber whose loss is limited only by the
intrinsic properties of fused silica, their
principal constituent. In their initial form,
each produced a preform yielding only
about 10 km of fiber. However, as single-
mode replaced multimode fiber, a third
generation of fiber processing evolved. In
multimode fiber, the ratio of core diameter
to fiber diameter is typically about 0.5
while this ratio is less than 0.1 for single-
mode fiber. Thus, the processing time of
singlemode preforms is shortened consid-
erably due to the smaller core region.
However, since the glass from the substrate
tube comprises the bulk of the fiber, the
yield from each preform is limited by the
size of this tube. The yield of each preform
may be increased by using an "overclad-
ding" technique, as follows. After a pre-
form core rod with an oversized core re-
gion is fabricated by conventional means,
the outer diameter is built up to attain the
proper proportions. The outer diameter is
increased either by jacketing the preform
with a second silica tube or by using it as
a bait rod for subsequent OVD or VAD
soot deposition. This procedure increases
the length of fiber produced from a vapor
deposited preform, yielding up to a hun-
dred kilometers of fiber.
15.5.1 Sol-Gel Processes
Given a singlemode fiber technology
based on overcladding core rods with silica
tubes or soot, it is natural to consider other
means of preparing overcladding material.
Alternate overcladding processes become
particularly appealing since fibers can be
designed so that negligible optical power
penetrates beyond a radius of 30 to 40 jim
(MacChesney et al, 1985). Thus, the vapor
derived core and cladding need comprise

only about 5% of the fiber mass while the
remaining 95% may be derived from lower
quality, less expensive materials.
15.5.1.1 Alkoxide Sol-Gel Processing
Suitable overcladding material may be
prepared by sol-gel and powder forming
techniques (see Chap. 2 of this volume). In
one instance, a chemical precursor, typi-
cally a silicon alkoxide such as Si(OC 2 H 5 ) 4 ,
is reacted with water in the presence of
ethanol and an acid catalyst. The sol is cast
into cylindrical molds and polycondensa-
tion of the resulting silanol groups pro-
duces a filamentary siloxane gel network.
The gel body is dried and consolidated to
form silica glass as films or bulk bodies.
Alternatively, commercial colloidal pow-
ders obtained from flame hydrolysis, com-
monly known as "fumed silica", are formed
into bodies by mechanical compaction
(Dorn et al, 1987), centrifugation (Buch-
mann et al., 1988), or casting/gelation (Shi-
bata et al., 1986). In this last approach, the
silica particles (generally 0.05-0.5 jim) are
dispersed in water to form a sol. Control of
pH or addition of surface active agents is
used to promote electrostatic or steric sta-
bilization to inhibit interparticle attractive
forces which cause agglomeration. The dis-
persed colloid containing up to 60wt.%
silica is cast after the stabilizing forces are
dissipated. Gelation by van der Waals at-
tractive forces soon follows to produce a
semirigid body. After drying, the porous
silica body can be sintered to glass much
like the soot boules formed in the OVD
and VAD processes.
Drying of the gel body is accompanied
by large stresses due to shrinkage and cap-
illary forces which generally cause the
body to fracture. To date, alkoxide derived
bodies as large as overcladding tubes have
not been successfully fabricated using this
15.5 Overcladding 771
approach. However, there has been much
effort to fabricate all-gel preforms since
the chemical precursors are available in
high purity and the refractive index of
the glass may be altered by adding dop-
ant alkoxides. Fibers with a raised-index
cores, doped with alkoxides such as
Ge(OC 2 H 5 ) 4 , have not yielded fiber with
losses comparable to that produced by va-
por technique since the germanium dioxide
either dissolves in the liquor or precipitates
in some crystallized form. The usual prod-
uct after consolidation contains pores and
its index is raised only marginally, suggest-
ing that any germanium present in the gel
is lost in firing.
The alkoxide route has achieved its best
success in fabricating fibers with a silica
core and lowered index cladding (Shibata
et al., 1987). Hydrolysis and polycondensa-
tion of Si(OC 2 H 5 ) 3 F lowers the index by
incorporating fluorine. The sol is cast,
gelled and dried to yield a porous silica
body with surface area of 200-650 m2/g-
Such high surface area allows consolida-
tion at low temperatures in a fluorine con-
taining atmosphere. The result is a down-
doped tube (A = - 0.62%) which is col-
lapsed with a stream of oxygen flowing
down the center. This removes the fluorine
from the inner tube wall and produces a
core region with higher refractive index
than the fluorine doped cladding. Losses as
low as 0.4 dB/km have been reported for
such fiber.
15.5.1.2 Colloidal Sol-Gel Processing
The colloidal approach has achieved
more success in producing large bodies for
overcladding. The starting material is com-
mercial fumed silica such as Aerosil OX-50
(Degussa A.G., Frankfurt, FRG). This is
distinguished from other colloidal silicas
by its comparatively large size (mean parti-
772 15 Materials Technology of Optical Fibers
TEOS
"Fumed" silica (C2H5O)4Si
Gel tube
1Dry
1 iI
Preform
assembly
Core
rod
Dehydrate/, Draw
consolidate
Fiber
Figure 15-17. A hybrid sol gel strategy in which gel is cast into tubes and used to overclad a core rod.
Alternatively gel is granulated then fusion-sprayed on a preform to accomplish overcladding.
cle size 40 nm). It is produced by flame
hydrolysis and is similar to "soot" pro-
duced by OVD and VAD.
The larger particles result in gel bodies
of lower density and larger pore size. Thus,
drying stress is reduced since the capillary
forces are decreased. Furthermore, lower
density enhances permeation of the porous
silica body by reactive gasses such as Cl 2 .
Consolidation in a chlorine containing at-
mosphere inside a non-contaminating sil-
ica muffle allows removal of impurities
such as OH~, transition metal and alkali
ions introduced during processing as well
as those initially present. Recall that this
situation is just the reverse of that encoun-
tered in the earlier Double Crucible pro-
cess, which failed because very pure start-
ing materials were contaminated during
processing.
SiCl,
Gel granulate/consolidate
Synthetic sand
Particle feed to
1 Plasma torch
Preform c: - •• •* -
overclad
MCVD core rod
Draw
Fiber
Purification from transition metals may
be enhanced by use of a low oxygen partial
pressure atmosphere, as indicated by the
reaction
Fe 2 O 3 + 2Cl 2 -> 2FeCl 2 + 3/2O 2 (15-11)
By firing in an atmosphere protected from
air intrusion, oxygen partial pressures can
be in the range of 10 ~6 atm. Thus, at tem-
peratures between 600 and 1000°C, iron
and other impurities are effectively removed
(MacChesney et al, 1987 b; Clasen, 1988).
This was demonstrated by intentionally
contaminating a gel body with 1 wt.% he-
matite. After a two step dehydration/con-
solidation treatment, the residual iron con-
tent was only 40 ppb.
The process of overcladding with gel-
derived material may be accomplished us-
ing two strategies, as diagrammed in Fig.

15-17. On the left, in the "rod-in-tube" pro-
cess, an overcladding tube is formed from
gel and then consolidated directly onto a
core rod (MacChesney et al, 1987 a). Tubes
for the rod-in-tube process are formed by
dispersion, milling, casting and gelation of
colloidal silica. After removal from the
mold and air drying, they are placed over
a core rod and the assembly is dehydrated,
consolidated and drawn into fiber. A satis-
factory interface, free of bubbles and other
defects, must be obtained between the core
rod and the gel-derived overcladding tube.
By proper cleaning of the core rod and
under appropriate consolidation condi-
tions, the loss of the eventual fiber can be
as low as that of the original core rod. On
the right, instead of casting a tube, the wet
gel is granulated into particles which are
fed through an oxygen plasma torch to de-
posit glass droplets onto the core rod
(Fleming, 1987). Since these particles are
100 jim in diameter, they deposit on the
rod by impaction, rather than by weak
thermophoretic forces. Deposition effi-
ciency is thus quite high.
Although, commercial development of
sol-gel or powder methods for making
fiber has not yet appeared, the necessary
conditions for the technology have been
demonstrated.
GeO 2 -P 2 O 5
100
10
\
1.0 Initial
• - - - ^-Radiation
—— H2 diffusion
200°C Heating
0.1 I I I _|
0.8 1.0 1.2 U 1.6
Wavelength (|jm)
15.6 Minimizing Defects 773
15.6 Minimizing Defects
It might appear at this point that the
fabrication of telecommunication fibers is
well controlled and understood and that
the only remaining goal is to make optical
fiber cheaper. This is not so. As processing
technology has improved, more stringent
reliability and performance requirements
demand further improvements in process-
ing. To wring out the last few hundredths
of a dB/km of loss, to minimize disper-
sion in the 1.3 and 1.55 jim communica-
tions windows, to achieve theoretical fiber
strength and to protect the fiber from envi-
ronmental effects such as radiation and ex-
posure to hydrogen and moisture, the
nature of silica and the effects of processing
parameters must be understood.
Both moisture and molecular hydrogen
diffuse rapidly through the polymer coat-
ing which protects the fiber from abrasion.
Moisture attacks the fiber surface and low-
ers the strength by static fatigue (Kurkjian
etal, 1989) while hydrogen and ionizing
radiation produce defect centers which in-
crease the optical loss. Fig. 15-18 (Itoh
etal., 1986) shows the effect of hydrogen
and radiation on GeO 2 -P2O 5 -SiO 2 core
and GeO 2 -SiO 2 core fiber. Gamma radia-
tion causes an increase in loss across the
Ge0 2 -Si0 2
V
Figure 15-18. Effect of hy-
Initial "*^-~ / drogen and radiation on
• - - - ^-Radiation (a) GeO 2 -P 2 O 5 -SiO 2 and
— H2 diffusion
200°C Heating (b) GeO 2 -SiO 2 core fiber,
I I | from Itoh et al, (1986).
0.8 1.0 1.2 U 1.6
Wavelength (JJP
774 15 Materials Technology of Optical Fibers
spectrum by introducing defects in the sil-
ica network. H 2 incorporated interstitially
introduces several distinct peaks between
1.0-1.2 jim while defects caused by the re-
action of hydrogen with GeO 2 species re-
sults in broadband loss. At temperatures
above 200 °C, H 2 reacts with the silica net-
work to form OH ~~ groups which increase
loss at 1.38 jim.
Removal of P 2 O 5 , once commonly used
as a processing aid, alleviates some of the
degradation caused by radiation and H 2 ,
but the presence of GeO 2 , the principal
core dopant, still contributes to fiber loss.
It is thus essential that H 2 be prevented
from penetrating the fiber. Since the poly-
mer coating is not an effective diffusion
barrier, additional hermetic coatings have
been developed. These are applied by
chemical vapor deposition to the virgin
fiber surface during draw and before appli-
cation of the polymer coating. Thin films
(50-100 nm) of aluminum, SiC, SiO2 and
TiO 2 have been used but amorphous car-
bon coatings (Huff et al., 1988) appear the
most satisfactory. These compact and pin-
hole free films result in negligible rates of
H 2 permeation and dramatic reduction in
strength degradation by both static and
dynamic fatigue (Kranz et al., 1988).
15,7 Active and Passive Fiber
Devices
In the development of optical fiber for
communications described above, success
was measured by how well the glass
medium did not interact with the transmit-
ted light or the surroundings. However, it
is possible to intentionally induce interac-
tions for specific purposes. Passive fiber
devices such as modulators, polarizers, iso-
lators and couplers may be made from ei-
ther standard or specially prepared optical
fiber (Miller and Chynoweth, 1979). In ad-
dition, sensors (Giallorenzi et al., 1982);
Culshaw, 1984; Arditty et al., 1989; Scheggi,
1987), may be fabricated by using optical
fibers to carry light signals to and from an
active "optrode". In such an extrinsic sen-
sor, the fiber merely transmits the signal to
and from the sensing device. Active fiber
devices may be fashioned into intrinsic sen-
sors which exploit the active properties of
either the glass or special dopants added to
the fiber. Intrinsic sensors use the optical
fiber itself to interact with the environment
and modulate an optical signal. Fiber
lasers and amplifiers (Urquhart, 1988),
may also be fabricated if rare earth ions are
added to the fiber core. Such active fiber
devices take advantage of several proper-
ties unique to optical fibers such as long
interaction length, small size, high light in-
tensity and an optical as opposed to elec-
tronic carrier.
15.7.1 Optical Fiber Sensors
Fiber sensors carry an optical signal
which is constant in some property such as
intensity, polarization or phase. Perturba-
tion of the fiber environment is detected as
a variation in this property. Light intensity
is the simplest property to modulate and
detect. Extrinsic sensors can measure
acoustical fields using a Fabry-Perot cav-
ity at the fiber tip, strain using microbend-
ing induced by placing the fiber between
corrugated plates, environment by incor-
porating fiber in a structural unit, or chem-
istry using chemically active materials
placed at the fiber end or as a coating.
Intrinsic sensors have been fabricated by
measuring optical absorption of fibers
doped with neodymium or erbium. These
ions have a number of absorption bands
and since the thermal population of the
ground state of these ions changes with

temperature, changes in the absorption
spectra can be used to accurately monitor
temperature (Snitzer et al., 1983) over hun-
dreds of degrees.
Phase modulation may be detected with
the greatest sensitivity by means of a fiber
interferometer (Dandrige and Kersey,
1987). Fiber gyroscopes, for example, make
use of this detection scheme since interfer-
ence between counter-propagating beams
within a loop of fiber allows detection of
less than 10 ~ 4 rad. due to the different dis-
tances that light propagates in the two
arms.
Intrinsic sensors which exploit various
physical phenomena such as the Faraday,
electro-optic and photo-elastic effects may
be used to measure stress and acoustic,
magnetic or electric fields. These phenom-
ena may also be used to induce changes in
polarization for use as photonic devices.
Interaction of the fiber with the field to be
measured may be enhanced further by ap-
plying special active coatings to the fiber.
For example, an acoustic sensor may use
a piezoelectric coating to alter the phase
of the propagating light. These examples
illustrate the vast number of schemes
which may be used to form fiber optic sen-
sors and the field remains fertile for materi-
als solutions.
The field of optical fiber sensors has vast
potential but is beset by practical prob-
lems. Owing to the long interaction length
and high light intensity, optical fibers are
extremely sensitive, not only to the prop-
erty to be measured but to environmental
influences as well. These limitations must
be overcome by advances in materials and
clever detection schemes. Currently, opti-
cal fiber sensors have only been used in
areas which exploit their small size, immu-
nity to electromagnetic interference and
potentially remote nature. Thus, they have
been used for high electric fields, corrosive
15.7 Active and Passive Fiber Devices 775
environments and in biomedical applica-
tions. Although there have been many lab-
oratory demonstrations, widespread appli-
cation has been inhibited mainly by
thermal stability problems and cost.
15.7.2 Optical Fiber Lasers and Amplifiers
Optical lasers and amplifiers (Urquhart,
1988), may be created by using a more so-
phisticated perturbation of the light car-
ried in an optical fiber (see Chap. 12 of this
volume). If the core of a fiber is doped with
optically active elements such as rare earth
ions, it may act as a lasing medium in addi-
tion to guiding light. Pump light coupled
into the fiber core excites the active ions in
the glass and causes a population inversion
between their ground state and some upper
electronic energy level as shown in Fig.
15-19. The radiative transition back to the
ground state emits a photon and may be
either spontaneous or stimulated. Stimu-
lated emission occurs when a signal pho-
ton at the lasing wavelength interacts with
an ion in an excited state and promotes
'VPump
Transmission Er-doped Transmission
fiber fiber amplifier fiber
vv w
X Signal = 1.53-1.55 Mm Splice X Splice
jm =1.48 |jm
Figure 15-19. Energy level schematic of Er3 + ion and
configuration of optical amplifier in which pump-
light is coupled to Er3 + containing fiber.
776 15 Materials Technology of Optical Fibers
de-excitation. This creates a second pho-
ton in phase with the first.
A laser may be made by placing semi-
transparent mirrors at the fiber ends. This
forms a Fabry-Perot cavity and causes res-
onance at a wavelength which is an inte-
gral fraction of the cavity length. The ad-
vantages of using a rare earth glass laser in
fiber form are the long interaction length
between pump and active species, high
light intensity, the availability of diode
laser pumps, and, for lightwave communi-
cations applications, the compatibility
with standard optical fiber.
An optical amplifier may be made using
the device shown in the lower half of Fig.
15-19. If the optical signal (1.53 jam) is in an
emission band of the active ions, the signal
will stimulate depopulation of the excited
states, creating photons in phase with the
incident signal, thus amplifying the optical
signal. Pump light is introduced through a
directional coupler, so it is advantageous if
the geometry of the active fiber matches
that of the transmitting fiber. Fiber ampli-
fiers promise superior performance over
semiconductor amplifiers because of low
noise, high bandwidth, high gain and fiber
compatibility.
15.7.2.1 Fabrication of Rare-Earth Doped
Optical Fiber
Rare earth doped fibers can be fabri-
cated by several techniques. In the MCVD
case (Poole et al., 1985), a volatile chloride
vapor of the desired ion (generally Er 3 + or
Nd 3 + ) is generated by heating a chamber
contained within the substrate tube. The
vapor is carried into the reaction zone
along with SiCl4, GeCl 4 , A12C16 and O 2
used to produce the core deposit. Rare
earth ion concentrations on the order of
100's to 1000's ppm can be achieved in this
manner. However, since phase separation
occurs with even small additions of rare
earths to silica, it is beneficial to have a
homogenizor ion such as Al 3+ present.
A second technique uses solution-dop-
ing (Townsend et al., 1987) of a partially
sintered soot layer deposited in the MCVD
substrate tube. The tube is soaked in a so-
lution containing the desired ions, dried
and dehydrated in an atmosphere contain-
ing O 2 , He and perhaps Cl 2 . After sinter-
ing, the tube is collapsed and drawn into
fiber. Alternatively, the solution technique
can be used to treat a soot-form produced
by VAD (Gozen et al, 1988). Here also, a
soot cylinder is soaked in an aqueous solu-
tion of rare earth ion, dried and dehy-
drated in an atmospheric containing
SOC12 or Cl 2 . After sintering at about
1500 °C, the preform is overclad and drawn
to fiber. In place of a solution, the soot-
form can be "soaked" in an atmosphere
containing rare earth chloride species
volatilized by a furnace temperature in the
vicinity of 1000 °C.
Efforts to optimize the amplifiers con-
centrate on fiber structure and the core
composition. Amplifier efficiency seem-
ingly would be improved by concentrating
the rare earth dopants in the core center
where the optical intensity is highest. Vari-
ations in the host glass can alter the popu-
lation of various energy levels, in particular
to diminish excited state absorption. This
occurs if photons produced as stimulated
emission from excited rare earth ions are
subsequently reabsorbed by an excited ion,
populating energy levels above the upper
lasing level. This effect decreases the
efficiency of 1.53 |im Er 3 + amplification
and destroys 1.3 jim Nd 3 + amplification.
Among the alternate hosts being investi-
gated are those of fluorozirconate glasses.

15.8 Fluoride Glasses for Fibers
Interest in fluoride glass fibers began
over a decade ago because they are pre-
dicted to have extremely low loss (see
Chap. 8 of this volume). Since the loss of
silica fibers is ultimately limited by
Rayleigh scattering which decreases as
A~4, improvement can be achieved by us-
ing a material transparent further into the
infrared. In addition, it has been shown
that the scattering coefficient of a number
of fluoride glasses should be lower than
that of silica. Lines (1988), describes the
theoretical basis which allows prediction of
the wavelength of minimum loss as well as
estimation of its lower limit. Predictions of
minimum loss versus wavelength for a
number of fluoride glasses as contrasted to
silica is shown by Fig. 15-20.
Initial work concentrated on BeF2
glasses, but more recent effort has centered
on ZrF4-based glasses (Poulain et al.,
1977). The most common of these are so-
called ZBLAN glasses, which have typical
composition: 50(mol%) ZrF 4 , 20BaF 2 ,
4 LaF 3 , 3 A1F3 and 23 NaF. Zirconium
concentration can vary between 50-58%,
the alkali can be eliminated, other rare
earth may be substituted for lanthanum,
and constituents such as InF 3 and PbF 2
can be added.
Although estimates of lower loss limits
range from 10 " 2 to 10" 3 dB/km, the low-
est loss achieved to date is just below 1 dB/
km, but only on a length of several tens of
meters. Significant progress toward lower
loss has not been achieved during the past
five years. The problem is mainly one of
purification and the tendency for crystal-
lites to form during processing. Crystalliza-
tion occurs because fluoride glasses, with
the exception of BeF2, are not very stable
and thus require rapid cooling rates to in-
hibit formation of crystallites. In addition,
15.8 Fluoride Glasses for Fibers 777
10
1.0 10
Wavelength (|jm)
Figure 15-20. Predicted minimum loss vs. wave-
length for halide fibers compared to silica.
the task in removing impurities, especially
oxygen, is momentous. Sublimation tech-
niques and reactive gas processing are of
some use, but Zr oxides are persistent and
result in high scattering losses relative to
the potentially low values predicted.
In addition to the difficulties of fabricat-
ing the glass, preparation of a long length
of fiber is beset by durability problems. The
material must be protected from the atmo-
sphere during melting, casting and draw-
ing. Various innovative means have been
devised to do this. By the standard method,
the cladding melt is poured into a cylindri-
cal mold and the periphery allowed to so-
lidify. The center is drained and the core
melt is poured to replace it. Crystallization
caused by moisture at the core/clad inter-
face is suppressed since the material re-
mains above the crystallization tempera-
ture.
A reactive atmosphere is frequently used
to suppress crystallization and prevent
contamination. One technique (Nakai
et al., 1986) uses a carbon double crucible
in an NF 3 atmosphere. The NF 3 is bubbled
through core and cladding melts in the
crucible at 725 °C for purification. The
temperature is lowered to 375 °C and fiber
778 15 Materials Technology of Optical Fibers
is drawn from concentric orifices at 1 0 -
30 mm/min to obtain long length.
In spite of these and other innovative
processing procedures, the comparative
failure of fluoride glasses to achieve perfor-
mance equivalent to that of silica has led to
renewed interest in other low intrinsic scat-
tering oxide glasses. Sodium alumino-sili-
cate has long been known (Van Uitert
et al., 1973) to have substantially lower
scattering losses than silica, but its prepa-
ration as low loss fiber has not been suc-
cessful. In this instance, the stability of
NaCl relative to Na 2 O prevents use of
chlorine to purify and dehydrate the glass.
Recently (Lines et al., 1989), calcium alu-
minate glasses have been shown to have
low scattering loss (0.04 dB/km compared
to 0.16 dB/km for SiO2). Since the mini-
mum loss is near 1.55 j^m rather than fur-
ther in the infrared, this material is thus
compatible with existing communications
systems. Processing of these oxide glasses
appears much easier than it is for the fluo-
rides. However, to date there has been little
serious work to develop fibers exhibiting
these desirable properties.
15.9 Summary
This article has sought to describe the
materials base upon which optical commu-
nication has been built. After an initial
brief attempt at adapting traditional glass
making processes to fiber fabrication, va-
por deposition of vitreous silica was
rapidly developed to become the transmis-
sion medium for optical communications.
Work continued toward the ultimate engi-
neering of silica fiber, to attain minimum
loss and dispersion as well as insuring opti-
mum mechanical reliability. Degradation
by moisture and hydrogen was greatly di-
minished by protecting the fibers with her-
metic coatings. Meanwhile, investigations
were undertaken to produce less expensive
fiber using sol-gel techniques and new
glasses were explored to yield enhanced
performance. Currently, there are major ef-
forts directed at both active and passive
fiber devices.
One fact emerges from this work: vit-
reous silica has exceptional suitability for
optical waveguides. Its thermal expansion,
high intrinsic strength, low absorption and
scattering losses in the visible and infrared
make silica a material as ideally suited to
photonics as its parent, silicon, is to elec-
tronics. By making use of SiCl4 developed
by the electronics industry, vapor phase
processing has yielded ultimately pure ma-
terials with impurity levels in the range of
parts per billion compared to the parts per
million achieved for electronic applica-
tions. Simple and efficient vapor deposi-
tion techniques yield not only the requisite
purity and optical quality but also the
means for making precisely controlled
waveguide structures.
15.10 References
Arditty, H.J., Dakin, J.P., Kersten, R.T. (Eds.)
(1989), Proc. 6th International Conf. on Optical
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Shintani, T. (1988), Development of High Nd 3 +
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780 15 Materials Technology of Optical Fibers
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General Reading
Chai Yeh (1990), Handbook on Fiber Optics: Theory
and Applications. New York: Academic Press.
Fleming, J. W, Sigel, G. H., Takahashi Jr., S., France,
P. W (1989), Optical Fiber Materials and Process-
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Society.
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Vol. I. Orlando, FL: Academic Press.
Miller, S. E., Chynoweth, A. G. (Eds.) (1979), Optical
Fiber Telecommunications. New York: Academic
Press.
Miller, S. E., Kaminow (Eds.) (1988), Optical Fiber
Telecommunications II. Boston: Academic Press.
Nagel, S. R., Fleming, J. W, Sigel, G. H., Thompson,
D. A. (Eds.), Optical Fiber Materials and Proper-
ties, Vol. 88. Pittsburgh, PA: Materials Research
Society.
Suematsue, Y. (Ed.) (1982), Optical Devices and
Fibers. Amsterdam: North Holland.