J. Am. Ceram. Soc.

, 80 [6] 132732 (1997)

Heat Capacity Changes at the Glass Transition in

Mixed-Alkali Tellurite Glasses
Takayuki Komatsu* and Tsutomu Noguchi
Department of Chemistry, Nagaoka University of Technology, Nagaoka 940-21, Japan

Ryuji Sato*
Department of Materials Engineering, Tsuruoka National College of Technology, Tsuruoka 997, Japan

The heat capacity changes (Cp ) at the glass transition

in mixed-alkali tellurite glasses of (20x)Li 2OxNa 2O
80TeO2 that show different fragilities, depending on the
Na2O/Li2O ratio, have been measured to obtain moredetailed information on the structure of tellurite glasses or
supercooled liquids with a fragile character. A large
increase in Cp is clearly observed at the glass transition in
all the samples. The values of the heat capacity of glasses
and supercooled liquids (Cpg and Cpe , respectively) and Cp
(equal to Cpe Cpg ) at the glass transition temperature, Tg ,
are almost the same, irrespective of the Na2O/(Na2O
Li2O) ratio, indicating the absence of a clear, mixed-alkali
effect on Cp at Tg . The values of Cpg at 200C, Cpe at 300C,
and Cp at Tg are }75, 120, and 45 J(molK)1, respectively. The ratio of the heat capacity of the glassy state to the
heat capacity of the supercooled liquid state, i.e., Cpe /Cpg , is
1.6; this large value indicates that the (20x)Li 2OxNa 2O
80TeO2 system should be included in the category of fragile
liquids. It has been suggested that the structural units of
TeO4 trigonal bipyramid and TeO3 trigonal pyramid are
weakly connected to each other and, thus, the intermediate
structure varies largely as the temperature increases, which
leads to a fragile character. The change in the fragility
that is caused by the mixing of dissimilar alkali ions is not
detected through Cp (i.e., there is no mixed-alkali effect on
thermodynamic fragility); however, it is observed from the
viscosity behavior at }Tg (i.e., the presence of the mixedalkali effect on kinetic fragility).

The concept of fragility in supercooled liquids, introduced

by Angell,7,8 gives new insights for glass transition, structural
relaxation phenomena, glass or supercooled liquid structure,
and so on. As defined by Bohmer et al.,9 the degree of fragility,
m, at the glass transition temperature, Tg , can be expressed as
m

d log
d

Tg
T

(1)
T T g

where is the average relaxation time and T is temperature.

Furthermore, using Eq. (1), we can express the degree of fragility approximately as10,11
m

d log

Tg
d
T

E
2.303RTg

(2)

T Tg

where is the shear viscosity, E the activation energy for

viscous flow at Tg , and R the gas constant. From Eq. (2), one
can say that the glasses with high E values at Tg or with low
Tg values in a given glass system have a tendency to be more
fragile than those with low E or high Tg values. As a general
trend, heat capacity changes, Cp , during the glass transition in
the so-called fragile glass-forming liquids with large m values
(estimated using Eq. (1) or (2)) are much larger than those in
strong glass-forming liquids with small m values.7,8 However,
there are some liquids (such as glycerol) that have large Cp
values but relatively strong viscosity behavior, i.e., the presence
of liquids with thermodynamically fragile and kinetically
strong characters.8 In this paper, therefore, we use the terms
kinetic fragility, estimated from Eq. (1) or (2), and thermodynamic fragility, estimated from Cp , to avoid any confusion
with the use of the term fragile.
Recently, Komatsu et al.11 examined the mixed-alkali effect
on the thermal stability, viscosity, and electrical and dielectric
properties in (20x)Li2OxNa 2O80TeO2 glasses and proposed that mixed-alkali tellurite glasses are less fragile (kinetic)
than single-alkali tellurite glasses. The mixed-alkali tellurite
glasses, e.g., 10Li2O10Na 2O80TeO2 , are still largely fragile
in comparison to silica (SiO2 ) glass. The reported data on E
and m, estimated from Eq. (2) for the mixed-alkali tellurite
glasses, are shown in Fig. 1.11 Mixed-alkali tellurite glasses
clearly have small values of m, in comparison to those of singlealkali tellurite glasses. Moynihan et al.12 measured the Cp values
of mixed-alkali silicate glasses with the compositions of
24.4(Na 2O K 2O)75.6SiO2 and reported that the Cp curves
in the glass transition region of all the glasses, for identical
heating rate and thermal histories, could be superimposed on
the same reduced plot, meaning that there was no clear, mixedalkali effect on Cp ; that is, there is no mixed-alkali effect

I. Introduction
ELLURIUM oxide-based (TeO2-based) glasses are of scientific and technical interest, because of their low melting
temperatures, high refractive indices, and good infrared transmissions,1,2 and many studies of such characteristics as the
structural, optical, and electrical properties of TeO2-based
glasses have been reported. For example, transparent glassceramics in the potassium oxideniobium oxidetellurium
oxide (K 2ONb2O5TeO2 ) system that show a second harmonic
generation recently have been discovered.3,4 To the best of our
knowledge, however, there are only a few papers on the relaxation behavior of TeO2-based glasses in the glass transition
region,5,6 although an understanding of structural relaxation is
extremely important for the basic science and the technical
applications of glasses.

M. C. Weinbergcontributing editor

Manuscript No. 191847. Received May 3, 1996; approved December 10, 1996.
Supported by a grant from the Nippon Sheet Glass Foundation and a grant from the
Murata Science Foundation.
*Member, American Ceramic Society.

1327

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Journal of the American Ceramic Society Komatsu et al.

on thermodynamic fragility in silicate glasses with a strong

character. It is of interest to measure Cp at the glass transition
region in mixed-alkali tellurite glasses with a fragile character.
The purpose of the present study is to examine the effect of
the mixing of dissimilar alkali ions (Li and Na) on Cp , i.e.,
thermodynamic fragility, during the glass transition of tellurite
glasses in the (20x)Li 2OxNa 2O80TeO2 series that show
different kinetic fragilities and to obtain more-detailed information on the structure of TeO2-based glasses or supercooled liquids with a fragile character.

Vol. 80, No. 6

paper, the molecular weight of glasses was calculated as a sum

of the molecular weight of each oxide component; e.g., the
molecular weight of 1 mol of 10Li2O10Na 2O80TeO2 glass is
the sum of the molecular weights of 0.1 mol of Li 2O, 0.1 mol of
Na 2O, and 0.8 mol of TeO2 .
Raman scattering spectra at room temperature for the glasses
were measured in the wavenumber range of 1001000 cm1
using an argon-ion laser (with a wavelength of 514.5 nm and a
laser power of 100 mW) and a laser Raman spectrometer
(Model NR-1100, Jasco, Tokyo, Japan). The spectra were
deconvoluted using a symmetrical Gaussian function.

II. Experimental Procedure

The nominal compositions that were examined in the present
study were (20x)Li 2OxNa 2O80TeO2 (x 0, 5, 10, 15,
and 20). Commercial powders of reagent TeO2 (99%), Li 2CO3
(99%), and Na 2CO3 (99%) were mixed and melted in a platinum
crucible at 800C for 20 min in an electric furnace. The batch
weight was 20 g. The quenched glasses were prepared by pouring the melts onto an iron plate and pressing them quickly to a
thickness of 12 mm by using another iron plate. The glass
transition and crystallization onset temperatures (Tg and Tx ,
respectively) were determined using differential scanning calorimetry (DSC) (Model Thermoflex TAS 200, DSC8230D,
Rigaku Co., Tokyo, Japan) at a heating rate of 10 K/min.
The quenched glasses were first heated to 300C (the supercooled liquid state), which is sufficiently higher than Tg (240
265C) but is much lower than Tx (360C), and then cooled to
a temperature of Tg at a cooling rate of 10 K/min. Such
annealed glasses were used for Cp measurements. The value of
Cp at the glass transition region in a heating process was measured using DSC. The heating rate was 10 K/min, which was
the same rate as the cooling for the prior sample preparation.
The Cp values of the quenched glasses also were measured. The
sample weight was 70 mg. Standard specimens of alumina
(sapphire) were used as the reference Cp standard. The experimental errors for Cp were 7 J(molK)1 for the quenched
glasses and 3 J(molK)1 for the annealed glasses. In this

Fig. 1. Values of () fragility, m, and () activation energy for

viscous flow, E , in the glass transition region, as a function of the
Na 2O/(Na 2O Li 2O) ratio for the (20x)Li 2OxNa 2O80TeO2 system. Degree of fragility was estimated from m E /(2.303RTg ), where
Tg is the glass transition temperature and R is the gas constant. These
data were taken from Komatsu et al.11

III. Results
As a typical example, Fig. 2 shows the Cp values in the glass
transition region for 10Li 2O10Na 2O80TeO2 glass that has
been annealed at a heating rate of 10 K/min. An increase in Cp
is clearly observed at the transition from the glassy state to the
supercooled liquid state. The glass (solid) is lacking a typical
liquidlike motion; however, the motion in supercooled liquids
has a large amplitude and can be translational, rotational, and
conformational, depending on the molecular structure. Therefore, an increase or discontinuity in Cp occurs in the glass
transition region. When the motion of an equilibrium cannot be
realized at the temperature at which the system froze when it is
cooled, an overshoot in Cp , i.e., a maximum in Cp , is observed
before a supercooled liquid is attained. Similar patterns in the
Cp-vs-T curve are observed in other (20x)Li 2OxNa 2O
80TeO2 glasses, irrespective of the Na2O/Li 2O ratio. The Cp
value for the glassy 10Li 2O10Na 2O80TeO2 sample at 200C
is 75 J(molK)1, and the supercooled liquid at 300C has a Cp
value of 120 J(molK)1. From the Cp-vs-T curves, we have
determined the heat capacities of the glasses and the supercooled liquids (Cpg and Cpe , respectively), the value of Cp at
the glass transition (equal to Cpe Cpg ), and the Tg values; their
definitions are illustrated in Fig. 3.
The Cp values for quenched and annealed samples of
(20x)Li 2OxNa 2O80TeO2 are shown in Fig. 4 as a function
of the Na 2O/(Na 2O Li 2O) ratio. The value of Cp for the
quenched samples, i.e., 60 J(molK)1, is larger than those
for the annealed samples in all compositions, i.e., 45
J(molK)1. Furthermore, the Cp values notably are almost
the same (within an experimental error), irrespective of the
Na 2O/Li 2O ratio, indicating the absence of a clear, mixed-alkali
effect on Cpg , Cpe , and Cp . The Cp value of 45 J(molK)1 is

Fig. 2. Heat capacity, Cp , in the glass transition region for the

() annealed glass and () crystallized sample of 10Li 2O10Na 2O
80TeO2 . Heating rate was 10 K/min.

June 1997

Heat Capacity Changes at the Glass Transition in Mixed-Alkali Tellurite Glasses

Fig. 3. Heat capacity, Cp , in the glass transition region for the

annealed glass of 20Li 2O80TeO2 (Cpg and Cpe are the heat capacities
of the glasses and supercooled liquids, respectively, and Cp Cpe
Cpg at the glass transition temperature, Tg ). Heating rate was 10 K/min.

very similar to those of TeO2TlO 0.5 glasses (annealed) that

were reported by Zahra and Zahra;6 e.g., Cp 41 J(molK)1
for 0.78TeO20.22TlO 0.5 . Furthermore, the Cp value for
quenched glasses (60 J(molK)1) is almost the same as the
Cp value that was reported by Lee et al.5 for quenched
20Li 2O80TeO2 glass (65 J(molK)1). Notably, these values
of Cp in TeO2-based glasses are larger than the Cp value of
16 J(molK)1 that was reported for an as-quenched sample of
20Na 2O80SiO2 .13
The heat capacity for the crystallized 10Li 2O10Na 2O
80TeO2 sample, Cpc , which is obtained by a heat treatment at
400C for 5 h, is shown in Fig. 2. This heat-treated sample
contains only crystalline phases, which has been confirmed
from the powder X-ray diffractometry (XRD) pattern. In the
temperature region of 200300C, the Cpc value is almost constant; i.e., Cpc 73 J(molK)1. Furthermore, the Cpc value at

Fig. 4. Heat capacity changes, Cp , at the transition region, as a

function of the Na 2O/(Na 2O Li 2O) ratio for the () quenched and
() annealed (20x)Li 2OxNa 2O80TeO2 glasses.

1329

200C is very similar to the Cpg value. The Cp values of a glass

and corresponding crystal are known to be similar; however,
the former is slightly higher than the latter.14,15
The Tg values for (20x)Li 2OxNa 2O80TeO2 glasses are
shown in Fig. 5 as a function of the Na2O/(Na 2O Li 2O) ratio.
A very slight negative deviation in Tg is observed, because of
the mixing of Na 2O and Li 2O. Balaya and Sundandana16 also
observed the mixed-alkali effect on Tg for (30x)Li 2OxNa 2O
70TeO2 glasses.
Figure 6 shows the Raman scattering spectra at room temperature for the quenched glasses. The patterns are almost the
same, irrespective of the Na 2O/Li 2O ratio, implying that the
type and intensity (I ) of basic structural units do not change,
because of the mixing of Li and Na ions. As an example, the
peak deconvolution of the spectrum of 20Na 2O80TeO2 glass is
shown in Fig. 7, where the spectrum is well fitted using six
peaks: 301 (I 7.3%), 469 (I 14.4%), 601 (I 7.6%), 662
(I 27.4%), 726 (I 26.5%), and 788 (I 16.8%) cm1.
The assignment of the Raman scattering peaks in TeO2-based
glasses has been discussed by many authors (e.g., Sekiya
et al.17). It has been recognized that vertex-sharing TeO4 trigonal bipyramids (tbp), TeO31 polyhedra, and TeO3 trigonal pyramids (tp) that have nonbridging oxygen atoms (NBOs) are
present and that these structural units comprise a continuous
network in TeO2-based glasses.17 The structural units of TeO4
tbp and TeO3 tp are shown in Fig. 8. The peak at 469 cm1,
shown in Fig. 7, is assigned to symmetric stretching vibrations
of Te O Te linkages, which are formed by the vertex sharing
of TeO4 , TeO31 , and TeO3 .17 The peak at 662 cm1 is assigned
to antisymmetric vibrations of Te O Te linkages that are
formed by TeO4 and TeO31 .17 The peak at 726 cm1 is assigned
to the stretching vibrations between tellurium and NBOs of
TeO31 and TeO3 .17 In other words, the Raman scattering spectra that are shown in Figs. 6 and 7 indicate that the structure
of (20x)Li 2OxNa 2O80TeO2 mixed-alkali tellurite glasses
consists of a continuous network that is formed by TeO4 ,
TeO31 , and TeO3 , which is similar to other TeO2-based glasses.
IV. Discussion
The values of Cpg , Cpe , and Cp for the annealed
(20x)Li 2OxNa 2O80TeO2 samples are 75, 120, and
45 J(molK)1. The ratio of the heat capacity of the glassy state
to the heat capacity of the supercooled liquid state (Cpe /Cpg ) is
1.6, irrespective of the Na2O/Li 2O ratio. As noted by Angell,7,8

Fig. 5. Values of glass transition temperature, Tg , as a function of the

Na 2O/(Na 2O Li 2O) ratio for the () quenched and () annealed
(20x)Li 2OxNa 2O80TeO2 glasses.

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Journal of the American Ceramic Society Komatsu et al.

Vol. 80, No. 6

Fig. 8. Basic structure units of TeO4 trigonal bipyramid (tbp) and

TeO3 trigonal pyramid (tp) in TeO2-based glasses.

Fig. 6. Raman scattering spectra taken at room temperature for

(20x)Li 2OxNa 2O80TeO2 glasses.

the so-called strong (kinetic) liquids have a tendency to have

small changes in the Cp value at Tg (i.e., Cpe /Cpg 1.1), whereas
the fragile (kinetic) glasses have large increases in the Cp value
at Tg . The Cpe /Cpg value of 1.6 that has been obtained in the
(20x)Li 2OxNa 2O80TeO2 system is included in the category

Fig. 7. Raman scattering spectrum, taken at room temperature, for

20Na 2O80TeO2 glass and deconvolution using a symmetric Gaussian
function.

of fragile liquids; in other words, the (20x)Li 2OxNa 2O

80TeO2 supercooled liquids are thermodynamically fragile.
Zahra and Zahra6 also reported large values of Cpe /Cpg (1.43
1.66) in various TeO2-based glasses that contain TlO0.5 , AgO 0.5 ,
or AgI. Kowada et al.18 and Tatsumisago et al.19 measured the
high-temperature Raman spectra for TeO2-based glasses, such
as 20Li 2O80TeO2 , and reported that TeO4 tbp units that are
present in the glasses at room temperature change to TeO3 tp
units with NBOs as the temperature is increased above the
melting temperature. Such a structural change above the glass
transition would cause a large change in viscous-flow behaviors, i.e., a large kinetic fragility, and also would give a large
Cp value at Tg , i.e., a large thermodynamic fragility. Lee et al.5
measured the viscosities and Cp values of Li 2OTeO2 glasses at
the glass transition region and found that Li 2OTeO2 liquids
were more fragile (both kinetically and thermodynamically)
than Na 2OSiO2 liquids.
It is well recognized that liquids with low Cp values, such
as SiO2 , have generally tetrahedrally coordinated network
structures that are expected to experience relatively little disruption during heating; in contrast, liquids with large Cp values have intermediate-range structures that are expected to
change substantially as the temperature increases. Because the
Cp values for tellurite glasses are large and the values of Tg are
considerably small (250C), the structural units of TeO4 tbp
and TeO3 tp (short-range order) are considered to be weakly
connected to each other and, thus, the intermediate structure
varies easily as the temperature increases. These structural and
bonding features would be an origin for the fragile character of
tellurite glasses.
The mixing of dissimilar alkali ions causes the change in
the kinetic fragility of (20x)Li 2OxNa 2O80TeO2 glasses;
mixed-alkali glasses are less fragile, or stronger, kinetically
than single-alkali glasses, as shown in Fig. 1.11 In the present
study, however, any change in the magnitude of Cp , because
of the mixing of dissimilar alkali ions, is not observed, although
it has been demonstrated that TeO2-based glasses are fragile
thermodynamically. In other words, the kinetic fragility
decreases because of the mixing of dissimilar alkali ions; however, the thermodynamic fragility does not change. We can
conclude that the mixed-alkali effect in TeO2-based glasses is
observed in kinetic fragility but not in thermodynamic fragility.
Angell8 proposed, using the entropy model that was proposed
by Adam and Gibbs,20 that an alternative way in which an
observed low fragility can be interpreted, even when there is
evidence of a large Cp value, is to suppose that there are high
barriers separating the minima and that such high barriers could
be understood if the rearrangement of the molecules in the
stress-relaxation process were to involve the rupture of some
type of specific bond. In the previous paper,11 the thermal stability against crystallization in (20x)Li 2OxNa 2O80TeO2
glasses also was largely enhanced by the mixing of dissimilar
alkali ions. This indicates that the mobility of alkali ions is
decreased by the mixing of dissimilar alkali ions and the

June 1997

Heat Capacity Changes at the Glass Transition in Mixed-Alkali Tellurite Glasses

1331

Fig. 9. Temperature dependence of heat capacity, Cp , for () paratellurite TeO2 crystal (from White et al.23), () annealed glass, and () a
crystallized sample of 10Li 2O10Na 2O80TeO2 .

rearrangement of structural units during heating is depressed.

These features might be why a change in the fragility is
observed from the viscosity behavior at Tg in mixed-alkali tellurite glasses (i.e., kinetic fragility) but is not detected in Cp
(i.e., thermodynamic fragility).
As discussed by Bohmer et al.9 and Greaves and Ngai,21 it is
of particular interest to analyze relaxation behaviors to obtain
more-detailed information on the fragility concept and the
mixed-alkali effect in oxide glasses. To our knowledge, there
has been no report on the kinetics of relaxation at the glass
transition region in tellurite glasses. We intend to compare the
differences in the relaxation kinetics of (20x)Li 2OxNa 2O
80TeO2 glasses. Komatsu et al.11 focused on the correlation
length and homogeneity in the structure of mixed-alkali tellurite
glasses to explain the change in kinetic fragility due to the
mixing of dissimilar alkali ions. The chemical disorder,
together with anisotropic molecular interactions, results in
local, strongly fluctuating energy barriers against reorientational motions, which, in turn, leads to a broad distribution of
relaxation times.21 Therefore, it is expected that the mixedalkali tellurite glasses that have a high thermal stability against
crystallization (i.e., reorientations of TeO4 tbp or TeO3 tp structural units), such as 10Na 2O10Li 2O80TeO2 , will have a broad
distribution of relaxation times, in comparison to single-alkali
tellurite glasses, which is similar to mixed-alkali silicate
glasses.12
The Cpg value of 75 J(molK)1 for the glasses was compared with the classical DulongPetit value of 3Rn, and an n
value of 3.01 is obtained. This value agrees well with the
number of atoms in the constituent oxides of Li 2O, Na 2O, and
TeO2 . Kincs et al.22 also found that the Cpg value of xNa 2S
(1x)B2S3 glassy samples approaches 90%95% of the classical DuLongPetit heat capacity 3Rn; for example, the Cpg value
of 114.6 J(molK)1 for glassy B2S3 corresponds to 92% of the
3Rn value of 124.7 J(molK)1 for n 5. They concluded that
the glass exhibits a glass transition just when all or almost all
the vibrational modes of motion in the glass are fully excited.
White et al.23 measured the Cp value of a paratellurite TeO2
crystal in the temperature range of 2283 K and reported a Cp
value of 60 J(molK)1 at 283 K. In paratellurite, TeO4 groups
share all vertices to form a three-dimensional structure. Their
data are plotted in Fig. 9, together with our data for the 10Li2O
10Na 2O80TeO2 samples. These data lie on one line, even
though the chemical compositions are largely different from

each other. Furthermore, the Cp value becomes constant at

temperatures above 400 K, which would be the reason why
TeO2-based glasses hold a classical DulongPetit heat capacity
at temperatures that are similar to Tg (520 K).
V. Conclusion
The heat capacity changes (Cp ) at the glass transition in
mixed-alkali tellurite glasses of (20x)Li 2OxNa 2O80TeO2
that show different kinetic fragilities have been measured. A
large increase in the Cp value is clearly observed at the glass
transition in all the samples. The values of Cpg , Cpe , and Cp at
Tg demonstrate that the (20x)Li 2OxNa 2O80TeO2 system is
included in the category of fragile liquids. However, the mixedalkali effect on Cp at Tg has not been found; that is, the
thermodynamic fragility that is estimated from the Cp value at
Tg does not change, because of the mixing of dissimilar alkali
ions, although the mixed-alkali effect on the kinetic fragility
that is estimated from the viscosity change at Tg is observed.
It has been suggested that the structural units of TeO4 trigonal
bipyramid and TeO3 trigonal pyramid are weakly connected to
each other and, thus, the intermediate structure varies largely as
the temperature increases, which leads to a fragile character in
tellurite glasses.
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