Radiat. Phys. Chem. Vol. 47, No. 6, pp.

811-814, 1996
Copyright 1996ElsevierScienceLtd
0969-806X(95)00168-9
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Pergamon

ELECTRIC A N D DIELECTRIC PROPERTIES OF SOME

GAMMA-IRRADIATED CABAL GLASSES
H. A. EL-BATAL l, H. F A R O U K 2 and F. M. E Z Z - E L D I N
~Glass Research Department, National Research Center, Dokki, Cairo, Egypt, 2Physics Department,
Faculty of Science, AI-Azhar University, Nasr-City, Cairo, Egypt and 3National Center for Radiation
Research and Technology, Nasr-City, Cairo, Egypt

(Received 11 July 1994; accepted 26 May 1995)

Abstract--Electrical conductivity and dielectric properties have been studied for the glass system
CaO-B203 A1203 in the temperature range 40-200~'C. The substitution of 5% B203 by CaO or replacing
5% CaO by Na20 or MgO cause a decrease in the conductivity, but the decrease obtained by soda is
greater than that of magnesia. The activation energies of the tested glasses were calculated. All the glasses
investigated showed a dielectric constant almost independent of temperature at fixed frequency. The effect
of subjecting the glass to a constant dose of gamma-rays changes both the electrical conductivity and
dielectric constant. The experimental results were discussed in relation to the specific conduction
mechanism in such glasses. Also the effect of varying glass composition or temperature on the mobility
or migration of current carrier was considered. The possible creation of induced defects in glass on
irradiation was evaluated. Copyright 1996 Elsevier Science Ltd.

INTRODUCTION
In many applications glass must serve as an electrical
insulator or conductor and therefore understanding
of the electrical conductivity is important.
In most oxide glasses the electrical conductivity
results mainly from ionic motion of monovalent
cations whereas in commercial glasses the conducting
species are sodium ions. Lithium ions also are quite
mobile in oxide glasses. Potassium and hydrogen ions
sometimes carry current although their mobility is
usually lower than that of sodium and lithium.
Even in glasses with no nominal addition of monovalent ions, the conductivity is believed to result
from transport of monovalent species present only
as impurities. Owen (1961) assumed that in the
nominal pure CaO-B2 O3-A1203 (Cabal) glass system,
the d.c. conduction proceeds by the drift in the
electric field of oxygen ions. Doremus (1972) claimed
that electrolysis experiments on lead-silicate glasses
give indication that electrons carry part or all of the
current in the glasses. Ashour and Nassar (1973)
assumed that the conduction in lead-silicate glasses
occurs mainly by the migration of the oxygen ions.
However, Melling and Duncan (1979) believed that
the conducting species in lead-silicate glasses is ionic
being probably Pb 2+ or O - vacancy with Pb 2+ being
the most likely.
Trap and Stevels (1963) introduced a concept that
has been accepted by which a mechanism of cation
jumping along interstices (or holes) in the glass
network which contribute to the electric conduction
of glass.
The probability of jumps has been assumed to be
controlled by a great number of interdependent fac811

tors, such as the number and charge of the mobile

ions involved, the average distance between the
centres of the interstices, the number of the accessible
surrounding interstices and the frequency of the
vibration of the mobile ions within the interstices.
It is further assumed (Pengnian and Xihuai, 1989)
that the ionic conduction of glasses is always accompanied by dielectric relaxation. Such dielectric
relaxation arising from ionic motion is called conductivity relaxation. In recent years, conductivity relaxation has been widely studied while the fast ionic
conduction of glasses is investigated by Liu et aL
(1986). These studies are not only essential for understanding the mechanism of the ionic conduction but
also beneficial to the application of such glasses as
dielectrics.
Further work is still needed to clarify with some
confidence the conduction mechanism in alkali free
glasses. The objective of this work is to investigate the
electrical conductivity and dielectric property of some
Cabal glasses before and after being subjected to a
nominal dose of gamma-rays. Also the effect of
replacing some of the lime by either soda or magnesia
on such electrical properties was studied.

EXPERIMENTAL DETAILS

Preparation of glasses
Chemically pure raw materials were employed for
preparing the glass batches. B203 was added as
orthoboric-acid H 3BOj and alumina was introduced
in the form of calcined A1203. Soda, lime and magnesium oxide were introduced in the form of their
respective anhydrous carbonates.

H. A. EI-Batal et al.

812

The batches were thoroughly mixed together into

a homogeneous mixture. It was then melted in an
electric furnace at 1300 _+20C for 3 h. After satisfactory homogeneity was achieved, the melts were
poured into moulds on a stainless steel plate preheated to an appropriate temperature in the form of
discs. The samples were then transferred to an electric
furnace for annealing at about 500 + 10C and then
left to cool to room temperature at a rate of 25'~C/h.
The discs were then ground and polished to give the
final dimensions diameter of about 1 mm thickness
with the two faces exactly parallel with a tolerance of
+ 0.004 mm.
The electrical conductivity of these glass samples
was measured in the temperature range 20 200C
using d.c. Microvolt Ameter model (hp 425A), and
the activation energy was then calculated.
The dielectric constant of these glasses was
measured in the temperature range 20~180"C, using
Dekameter DK 300, at 1 kHz.
Irradiation procedure

The annealed glasses were irradiated at room temperature using 6Co Gamma Chamber 4000 A (Indian
type). The dose rate was 1.25 Gy/s. The glass samples
were placed in the gamma-cell in a manner that each
sample was subjected to a dose of 5.5 102 kGy. The
temperature during irradiation was between 30 and
33C. By using a Fricke dosimeter, the absorbed dose
in glass is expressed in terms of absorbed dose in
water, rather than in terms of dose in glass. No cavity
theory correction was made.
RESULTS AND DISCUSSIONS

Figure 1 reveals the electrical conductivity values

for glasses as a function of lIT. It can be seen that
the electrical conductivity of all the glasses studied
increases with the temperature. This fact is understood by considering that the thermal agitation is
believed to weaken the binding force between cations
ions (calcium ions) and the network building ions
(boron or aluminium ions). This in turn directs or
initiates the mobility of such cations. Each cation ion
can easily migrate and mechanism of jumping along
interstices in the network would contribute to the
observed increase in the electrical conduction of glass.
The fact that the resistivity of the glasses decreases
with the increase of the temperature has been previously cited by Bockris et al. (1952) and Peyches
(1966) as evidence for ionic conduction mechanism in
glass.
Because of the disordered structure and from the
point of view that the glasses have a salt constitution
typical for strong electrolytes (Feltz, 1987), it has
been suggested that all of the alkali ions (or current
carrier ions) are mobile because they are able to
escape from their sites into surrounding vacant interstices. As a consequence, the mobility should predominantly be thermally activated.

12

r./
/

/x
[]
0

I1

IE~

Glass
Glass
Glass
Glass

a
b
c
d

t~,{

10

E
o
I~
J

23

27

31

35

39

104/T ( C )

Fig. 1. Relation between volume conductivity ( - log a) and

temperature (104/T~'C), for the unirradiated glasses.
The temperature dependence of the conductivity
yield straight lines which can be interpreted as due to
thermal activation of the mobility based on the
assumption that the total concentration of the current
carrier is involved in the conduction process.
The conductivity of glasses is very markedly dependent on chemical composition. This is expected as the
spatial arrangements of the building network forming
units and the available interstices and cavities are
changed and hence the ease of jumping of the migrating ions between different sites would change.
In Fig. 1, the curve (b) reveals that the substitution
of 5 mol% B~O3 by 5 mol% CaO causes a decrease
in the electrical conductivity than the curve (a) of the
base glass. This can be explained taking in consideration that all A I 2 0 3 c o n t e n t remains constant and
that by this substitution the oxygen ions content
decreases. Some of the boron atoms are assumed
(Stallworth and Bray, 1990; Scholze, 1990) to change
their coordination from four to three due to the
maximum limiting ratio for BO4/BO 3 usually assumed to occur in glasses containing B 2 0 3 . If the
electrical conductivity is assumed to be solely dependent on the movements of the Ca 2 ions, the result
obtained will be higher with the increase of the CaO
content and this is not the case.
It can be proposed in analogy with Owen's (1961)
postulation that the conduction proceeds at least
partly, in such CaO-B203-AI203 (Cabal) system by
the drift, in the electric field of oxygen ions. The most
probable means by which this can occur is by an
interstitial mechanism in which a network-former
takes the place of a network-modifier which at the

Gamma-irradiated Cabal glasses

same time moves to a network-former, i.e. the migrating ions are at network-former and networkmodifier site alternatively. However, this assumption
does not exclude the sharing of the calcium ion, as a
part of current carrier of even slow mobility or
migration, so that the Cabal glasses with known
compact structure possess a relatively low electrical
conductivity value.
Feltz (1987) has assumed that the concentration of
holes and vacancies and their distribution is very
important for the mobility of ions in the glass structure. Indeed, the packing of atoms in the Cabal
glasses is believed to be efficient and resemble the
silicate glasses than borate glasses (Abou-EI-Azm and
Ashour, 1958).
In Fig. 1 curves (c) and (d) reveal that the replacement of 5% CaO by N a 2 0 or MgO causes a decrease
in the electrical conductivity. This decrease can be
realized and interpreted as follows. When on alkali
(or alkaline earth) is progressively substituted for
another in glasses where the total alkali content is
kept constant, the electrical conductivity does not
vary linearly with the fraction substituted, but goes
through a minimum in the composition range in
which the two alkali oxides are present in nearly
equimolar amounts. This deviation from linearity has
been called the mixed alkali or mixed mobile oxide
effect (Sakka et al. 1979; lngram, 1994).
Several theories for the mixed alkali effect were
previously published. Hendrickson and Bray (1972)
proposed a theory in which electrodynamic interaction between different alkali ions increases the
activation energy formation, thus reducing the mobilities of the ions. Doremus (1974) concluded that the
mixed alkali effect in oxide glasses results from
short-range rearrangements as an ion is replaced by
one of a different size. Ionic interactions alone probably cannot account for the mixed alkali effect. The
recent contribution by Ingram (1994) proposes a
dynamic structure model incorporating a pathway
concept and the interconversions and mismatch
between ions and sites.
The electrical conductivity of a glass is largely
dependent on the concentrations of component oxides. Considering that the conductivity is given by the
product of the mobility and the charge carrier concentrations, only two ways are suitable for interpretation: either the mobility sharply increases, or the
mobile ion concentration varies considerably which
in turn implies that only part of the existing cation are
free to move.
A weak electrolyte model for the mixed alkali effect
on electrical conductivity in glass has been developed
by Moynihan and Lesikar (1981) for the dilute
foreign alkali region. It is proposed that adding small
amounts of foreign alkali leads to the formation of
alkali-foreign alkali interstitial pairs which, by mass
action, suppress the mobile species concentration.
The values obtained of the activation energy were
found to depend on the type of modifier oxide. Table

813

Table I. Glass samples composition (mol%)

CaO
B203
AI203
MgO
Na20
30
40
30
35
35
30
25
40
30
5
25
40
30
5

Glass
a
b
c
d

Table 2. Activationenergy values for glass samples before and after

irradiation (eV)
Glass E~ before irradiation
Eg after irradiation
a
0.375
0.4024
b
0.40196
0.4000
c
0.39344
0.4412
d
0.37255
0.4167

2 shows the effect of introducing N a 2 0 or M g O in

replacement of CaO on the activation energy values.
It can be assumed that the magnitude of the
activation energy depends on the type of the ion
involved which must overcome the energy barrier
between occupied and vacant sites. Also it depends
on the availability and freedom of mobile ions to
migrate in the glass network.
Figure 2 shows the effect of temperature, mixed
ions and irradiation on the dielectric constant.
The dependence of the dielectric constant on the
composition of glass is obtained by way of the
polarizability and the potential for movement of the
ions. In glasses, the oxygen ion is the most easily
polarizable ion. The introduction of network
modifiers, through the formation of more easily
polarizable nonbridging oxygens, will raise the dielectric constant with the decreasing field strength of the
network modifiers, the nonbridging oxygens are less
strongly bound.
Na + ions have a greater potential, which raises the
dielectric constant. Also the effect of MgO can be
explained taking into consideration the ability of
Mg 2+ ions to share as network former in the glass
structure.

23
22~ 21-

". .

.:

_~ 2oe~ 19-

O" 0 "

.0

.0

o--o
Glassa
~ Glass b
,x /x Glass c
O--------OGlass d

O-

O" O.

"0

O-

...o
....
~,, ...zx
O....O

O"

O-

Glass a after irradiation

Glass b after irradiation
Glass c after irradiation
Glass d after irradiation

1817
30

I
50

I
70

I
90

I
120

I
130

I
150

I
170

Temperature (C)
Fig. 2. Relation between the dielectric constant and temperature ('C) for investigated glasses before and after
irradiation at 55 x 102 kGy.

814

H . A . E1-Batal et al.
eventually become trapped in what we might imagine
as a blind canyon (Ezz-Eldin et al. 1994).
The cumulative effect of all the previous processes
is assumed to bring the observed decrease in the
electrical conductivity.

12

Acknowledgements--The authors are indebted to Professor

A. A. Bahgat for use of conductivity measurement facilities.

'E
7
E

10
REFERENCES

c
t~

,-~

23

A
n
O

Glass
Glass
Glass
Glass

27

31

35

39

] 04IT

(C)

Fig. 3. Relation between volume conductivity ( - l o g a) and

temperature (104/T:'C), for the irradiated glasses.
Effect o f irradiation

Figure 3 shows the effect of irradiation on the

electrical conductivity of the investigated glasses. It is
observed that gamma-irradiation causes an obvious
decrease in the electrical conductivity than the effect
of varying the glass composition.
The interaction of irradiation with solids (including
glasses) depend on the type of radiation, the composition of solid itself, and the defects within it. It is
generally accepted that ionizing radiation of glass
produces mainly excitation and ionization, and may
also cause a small amount of atomic or lattice
displacement (Friebele, 1991). Also (Ehrt and Vogel,
1991) assumed that gamma-rays may cause partial
rupture of chemical bonds, partial destruction of the
network, introduction of defects and discoloration.
The results obtained may be explained on the following basis. High irradiation doses are believed to cause
the concentration of these defects to fall. Vacancies
and interstitials recombine or vacancies migrate to
the glass surface. Eventually, migration becomes very
slow or ceases and then further irradiation will
produce a corresponding reduction in the concentration of defects.
Both the cation and the anion in the glass lattice
may form interstitials and vacancies, and the negatively charged anions are so much larger than the
cations that the energy required to squeeze the anion
into an interstitial site is prohibitive. In addition, the
decaying of electrical conductivity at high doses are
produced by mobile ions which can move through the
network but have rather long relaxation times and

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