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Ceramic Materials
Chapter 5: Glass
SS 2007
Dr. F. Filser,
HCI G 529, phone 26435, frank.filser@mat.ethz.ch
Dipl.-Ing. J. Kbler
EMPA Dbendorf, phone 044 823 4223, jakob.kuebler@empa.ch
Learning Targets
Fabrication of glass
t
el
M
Volume
supercooled
liquid
frozen V solidification
liquid
Glass Volmelt - Volcryst
fast
slow
Crystal
Tg Tf
Temperature
Tg
n
d=
2 sin
n = 2d sin
Film
Tube
Powder
(Points)
film
aperture
single
crystal
Zachariasens Network-Hypothesis
2-dimensionel visualization of a
- regular SiO4 - network (SiO2 - quartz, left) and of a
- irregular network (glass, right)
[SiO4] - Network
Glass
Si4+
O2-
O2-
[SiO4]4-
Tetrahedron
Si4+
z.B.
O2- Si4+ Na+,
Ceramics: Glass, Chap 5 K+ slide 14
Material Science II
Network Former
thermocycling
SiO2 Tg
mech. strength
thermocycling
Tg
B2O3
acid resistance
mech. strength
UV transparency
P2O5 IR transparency
chem. resistance
Network Modifier
Li2O
Na2O
Zwischenoxide
MgO Glass becomes longer
Glass becomes longer
Al2O3 mech. strength
chem. resistance
Tg
n
PbO
electrical resistance
Absorption of x-rays (40-80 weight-%)
n
TiO2
resistance against acids
chem. resistance
ZrO2
tarnish for enamels
ZnO hardness
CdO absorption of thermal neutrons (30-60 weight-%)
SiO2 28,
optical glass
PbO 70,
(heavy flint glass)
Na2O 1, K2O 1 (weight-%)
SiO2 29,
glass for X-ray protection PbO 62,
BaO 9 (weight%)
B2O3 83,
X-ray transparent glass BeO 2,
Li2O 15 (weight%)
P2O5 72,
hydrofluoric acid resisting
Al2O3 18,
glass
ZnO 10 (weight%)
B
log = A +
T T0
= 1013 dPas
Vogel-Fulcher-Tamman
Equation
long glass
in log dPas
short glass
T in C
Elongation of Glass I
l
th = 1/ lo i
T
Cooling Rate
Influence of the cooling rate on the formation of glass.
volume
melt
fast
normal cooling
glass
slow
Elongation of Glass II
theoretic
strength
Flaws in
strength of glass structure
glass fibers
strength of normal
glass ware
Macro flaws in
strength of damaged the surface
glass ware
tension compression
surface
a) b)
surface
Stress profiles for the a) thermal and the b) chemical method of pre-stressing.
base attack
Leaching time
Bases attack directly in a detrimental way the network of the glass in contrast to
acids. Bases destroy the network.
The SiO2 molecules are dissolved and remain in the solution as poly-silicates.
The hydroxyl ion start to solubilise the glass network and /or
the gel layer.
Type I:
A surface layer is formed which acts as a protection layer
(adsorption protection layer).
Type II:
A protection layer is formed by leaching out of alkalines. The glass network
remains stable.
Type III:
Leaching and reaction at the surface form two protection layers of different
composition.
Type IV:
Leaching and wear (material removal) take place at the same time.
A new leached out layer is formed at the surface which will be continously
shifted more and more inside the bulk glass by the wear of the glass network
(i.e. material removal).
Type V:
Constant wear of the glass network and material removal.
Hydofluoric acid and strong base attack at silicate glasses account for this type.
Case 4: progressive corrosion takes place when we have the solution deficiency on the glass surface.
Then, the corrosion reaction changes the pH-value of the solution which leads to a stronger corrosion at a
higher rate. The wear or corrosion rate increases with reaction time:
dc
= at
dt
progressive (Case 4)
limited (Case 2)
passivated (Case 1)
constant (Fall 3)
time t
reflected
light
reflected
light
transmitted
light
incident
light beam
glass
air air
Fraunhofer Lines
h g F F e d C C r
Hg Hg Cd H Hg He Cd H He
purple blue blue blue green yellow red red red
What is Dispersion?
The dependence of the refractive index from the light-wavelength.
h g F F e d C C r
Hg Hg Cd H Hg He Cd H He
purple blue blue blue green yellow red red red
404.6 435.8 479.9 486.1 546.0 643. 656.2 706.5
587.56
6 4 9 3 7 85 7 2
prism
screen
white light
What is Dispersion?
The dependence of the refractive index from the light-wavelength.
h g F F e d C C r
Hg Hg Cd H Hg He Cd H He
purple blue blue blue green yellow red red red
435. 479.9 486.1 546.0 643. 656.2 706.5 n F nC
404.66
84 9 3 7
587.56
85 7 2 re l = -----------------
nD 1
nd 1
= -----------------
n F nC
Flint
glasses
Crown
glasses
nd 1
= -----------------
nD--Diagram of optical glasses n F nC
nd 1
= -----------------
n F nC
nD--Diagramm optischer Glser
Chromatic Aberration
Achromatic Lens
Transmission
Wave Length
UV-Rim in Glasses
Transmission
Wave Length
Spectral Transmission ()
http://www.glasswebsite.com
Ceramics: Glass, Chap 5 slide 54
Material Science II
The Float Glass Process
Raw Materials Tin Bath (Float Furnace) Annealing Lehr Cutting System
Glass
Material Reason for Adding
Composition
http://www.pilkington.com
Ceramics: Glass, Chap 5 slide 59
Material Science II
Chemistry of Glass
Glass-Ceramics
Structure
Fabrication
Examples
Glass-Ceramics
Glass-ceramic refers to materials which are fabricated from glass
melts by a process of controlled crystalisation.
Glass-Ceramics
Short-range order
Glass
O2-
SiO4
tetrahedron
Si4+
4 3
G = r G + 4 r 2
3
-> 1. Derivative must be zero for r*
16 3
4 2
G = = r
3 ( G ) 2
3
1
r (T )
(TS T )
1
G (T )
(TS T )2
(E + G )
KB = N exp
kT
[G + E ]
N '' = N exp
kT
E
N ' = N exp
kT
Crystal Growth Rate
(N ' N '') E G
KG = a0 = a0 exp 1 exp kT
N kT
TS
KB, Nucleation
TE
Checking, Shaping
Checking, Shaping
Crystallisation
Nucleation
Cooling
Forming
Melt
Time
Properties of Glass-Ceramics
2nd step
Advantages: Disadvantages:
transparent pre-forms
free of pores
mono-size crystals
Ersatz
Kalk-Natron-glass
72 2 14 - - 10 - - - -
(ordinary glass)
float glass 72 1,5 13,5 - 3,5 8,5 - - - -
enamel 40 1,5 9 6 1 - 10 4 15 13
chalcogenide
12 55 33
glass 1
chalcogenide
13 32 30 25
glass 2
All amounts in weight -%.
Ceramics: Glass, Chap 5 http://de.wikipedia.org/wiki/Glas#Einstellung_der_Glaseigenschaften slide 76
Material Science II
Molten glass poured onto a bath of clean molten tin, will spread out in the same way
that oil will spread out if poured onto a bath of water.
Gravity and surface tension will result in the top and bottom surfaces of the glass
becoming approximately flat and parallel.
2 t
T = ( S g + S gt + St )i
2
g g ( t g )
where Sg, Sgt, and St are the values of surface tension at the three interfaces.