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Solid State Ionics 113115 (1998) 665675

Studies on Ag 2 O.M x O y .TeO 2 (M x O y 5 WO 3 , MoO 3 , P2 O 5 and


B 2 O 3 ) ionic conducting glasses
B.V.R. Chowdari*, P. Pramoda Kumari
Department of Physics, National University of Singapore, Singapore 119260, Singapore
Received 4 September 1998; accepted 12 September 1998

Abstract
Similarities and differences between the electrical, thermal and spectroscopic characterization results obtained by partial
replacement of TeO 2 by WO 3 , MoO 3 , P2 O 5 and B 2 O 3 in the form of yAg 2 O.(1 2 y)[xM x O y .(1 2 x)TeO 2 ] system are
reported. It has been observed that the compositional variation of glass transition temperature is linear for WO 3 and is
non-linear for MoO 3 , P2 O 5 and B 2 O 3 substitutions. Constituent dependency of conductivity at ambient temperature shows
two maxima for tungstotellurite, molybdotellurite and phosphotellurite glass systems while only a single maximum is
observed for borotellurite glasses. From the individual X-ray photoelectron spectral analysis, it is found that tungsten
exhibits two oxidation states whereas molybdenum, phosphate and borate are not reduced. The non-bridging oxygen atoms
are distinguished from that of the bridging oxygen atoms by deconvoluting the O 1s XPS spectra. Raman spectroscopy
shows that besides the expected TeO 4 trigonal bipyramid, the TeO 3 trigonal pyramid, the tungsten and molybdenum
tetrahedra, the tungstate and molybdate octahedra, phosphate tetrahedra and borate triangles and tetrahedra are also present in
tungstotellurite, molybdotellurite, phosphotellurite and borotellurite glasses, respectively. The intensity ratios of the
Raman peaks (I780 /I660 ) may represent the ratio of the fractions of TeO 3 tp and TeO 4 tbp: (TeO 3 / TeO 4 ). A good agreement
is found for the fraction of TeO 3 / TeO 4 obtained from both Raman and XPS studies. These results are correlated with those
from conductivity and T g studies. The unique crystallization behavior of these tellurite glasses were observed by the high
temperature Raman spectral studies. 1998 Published by Elsevier Science B.V. All rights reserved.
Keywords: Tellurite glasses; Raman spectroscopy; Ionic conductivity; XPS

1. Introduction
Glasses with heavy metal oxides such as TeO 2 as
network former are very attractive for the structural
study from both the academic and the technological
points of view. Therefore, the structure of tellurite
glasses has been investigated for several decades
*Corresponding author.
phychowd@nus.edu.sg

Tel.:

165-7-7226-0314;

e-mail:

based on the IR and Raman spectroscopy and X-ray


and neutron diffraction studies [16]. The main
focus of these studies were on the structural units in
the glass network. Very special kinds of TeO n
polyhedra are found in crystalline forms of TeO 2 ,
binary and ternary tellurite glass systems.
The structure and the properties of the oxide
glasses are dependent strongly on the nature and the
concentration of the constituent oxides. In normal
glass system, the modifier atoms cause the network

0167-2738 / 98 / $ see front matter 1998 Published by Elsevier Science B.V. All rights reserved.
PII: S0167-2738( 98 )00393-2

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B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

to break. In tellurite glasses, however, the modifier


atoms cause the modification of the basic structural
units such as TeO 4 trigonal bipyramid (tbp) and
TeO 3 trigonal pyramid (tp) with one of the equatorial position occupied by a lonepair of electrons. In
order to understand more about this aspect, we have
carried out the studies on Ag 2 O.M x O y .TeO 2 glasses
with various network former oxides (M x O y 5 WO 3 ,
MoO 3 , P2 O 5 and B 2 O 3 ) for different compositions.
The similarities and differences amongst the different
former oxides are discussed and the correlation
between structure and property is also presented.

copy (XPS) studies were done with a VG scientific


ESCALAB MKII spectrometer using Mg Ka X-ray
source. Raman spectra were obtained by the Renishaw micro Raman spectrometer with a laser diode
( l 5 780 nm). Further details of the procedures
adopted in the present study for glass preparation and
characterization by XRD, DSC, XPS and Raman
spectroscopic measurements are described elsewhere
[4,79].

3. Results and discussion

3.1. Glass density and glass transition temperature


2. Experimental procedure
The structureless X-ray diffraction (XRD) spectra
obtained from a Philips PW1710 diffractometer
suggest that the samples are indeed amorphous in
nature. Differential scanning calorimetry (DSC)
studies of these samples using Shimadzu DSC-50
give the glass transition temperature. The density of
the samples were determined by Archimedes method
using iso-propyl alcohol as displacing media. The
conductivity measurements were carried out by using
complex impedance method in the frequency and
temperature ranges 10 Hz to 1 MHz and 25 to
1308C, respectively. X-ray photoelectron spectros-

The glass density is found to decrease as a


function of M x O y 5 MoO 3 , P2 O 5 and B 2 O 3 , whereas
it increases with Mx O y 5 WO 3 ; as shown in Fig.
1(a). As expected, when a lower molecular weight
substance is substituted by a higher molecular weight
substance, the net molecular weight will decrease
resulting in a weak connectivity in the glass network
and hence to the decrease in density. The molecular
weight of different oxides are given in Table 1 [10].
The molecular weight of WO 3 is higher than that of
TeO 2 and therefore it leads to a significant increase
of density with an increase in WO 3 content. However, the molar volume, Vm , is found to increase with

Fig. 1. Compositional dependence of (a) density and (b) molar volume in the 0.30Ag 2 O.0.70[xM x O y .(12x)TeO 2 ] system.

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

667

Table 1
Physical parameters of network former oxides

TeO 2
WO 3
MoO 3
P2 O 5
B2O3

Mol. wt.
(g / mol)

Melting
pt. (8C)

Bond energy
(kcal / mol)

Cross-link
density

Ionic radius

(A)

Electronegativity

159.60
231.85
142.94
141.94
69.62

733
1473
795
585
460

93.4
156
145
142.6
192.7

2
3
3
1
1

0.70
0.62
0.62
0.35
0.23

2.10
2.36
2.16
2.19
2.04

M x O y (as shown in Fig. 1(b)). The molar volume is


inversely proportional to the glass density and directly proportional to the molecular weight of the glass.
Calculating the molar volume in this way enables the
packing density of the glass to be examined independent of the effects of ion mass. Thus, increase
in Vm suggests the increased free space within the
glass structure.
The compositional variation in glass transition
temperature of the 0.30Ag 2 O.0.70[xM x O y .(1 2
x)TeO 2 ] glasses are shown in Fig. 2(a). It is found
that the variation is linear for M x O y 5 WO 3 and is
non-linear when M x O y 5 MoO 3 , P2 O 5 and B 2 O 3 . It
can be seen that the T g passes through a maximum
value only for P2 O 5 and MoO 3 based glasses, similar
to Li 2 O.P2 O 5 .TeO 2 glasses [11]. The variation of T g

in Ag 2 O.P2 O 5 .TeO 2 glasses is similar to that of


Li 2 O.P2 O 5 .TeO 2 glasses, except that the thermal
stability is lower in the case of silver phospho
tellurite glasses. However, the partial replacement of
B 2 O 3 for TeO 2 gave a small variation in the initial
stage up to x 5 0.3 beyond which T g increased
steeply with an increase in B 2 O 3 content, just as in
the case of Li 2 O.B 2 O 3 .TeO 2 glasses [12]. Of the
three groups of cations of the glasses, the
Ag 2 O.WO 3 .TeO 2 glasses have the highest T g values,
followed by Ag 2 O.P2 O 5 .TeO 2 , Ag 2 O.B 2 O 3 .TeO 2
and Ag 2 O.MoO 3 .TeO 2 glasses.
The oxygen packing density (OPD) calculated
from the glass density and composition is found to
increase with M x Oy as shown in Fig. 2(b). It is seen
that the variation of OPD is linear for M x O y 5 WO 3

Fig. 2. Compositional variation of (a) glass transition temperature, T g and (b) oxygen packing density, OPD in the
0.30Ag 2 O.0.70[xM x O y .(12x)TeO 2 ] system.

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B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

and is non-linear when M x O y 5 MoO 3 , P2 O 5 and


B 2 O 3 . Comparison of the Fig. 2(a) and (b) gives us a
oneone correlation between the observed T g values
and the calculated OPD. Thus, the variation in T g
observed in the presently investigated systems may
be attributed to the changes in the glass structure
caused by the partial replacement of TeO 4 by WO 3 ,
MoO 3 , P2 O 5 and B 2 O 3 . Moreover, in the boro
tellurite glasses, the TeO 4 units and BO 4 units have a
strong tendency to link with each other to form
BTeO 3.5 units (just like BPO 4 units in borophosphate glasses), which results in a higher connectivity
in the glass network and thus leads to a higher glass
transition temperature.
Thus, based on these results, the observed increase
in T g and OPD in the presently investigated system
can be interpreted in terms of the formation of a
more rigid and highly cross-linked network resulting
in a tightly packed glass network with increased
thermal stability compared to the corresponding
binary glasses.

3.2. Glass structure


For the past few years, ion conducting glasses
with B 2 O 3 , P2 O 5 , WO 3 and MoO 3 as glass former
oxides are well studied from the viewpoint of their
structure and properties [1315]. Addition of modifier oxide to a glass former involves the incorporation of oxygen atoms into the covalent network, thus
becoming a macroanion. The mechanism of this
incorporation chiefly depends upon the valency and
the characteristic coordination chemistry of the glass
former element. Thus, the oxygen atoms added to the
B 2 O 3 network promote the conversion of three
coordinated BO 3 units into bridging BO 42 units and
then into BO 32n units, with n-NBO atoms. In the case
of TeO 2 , the addition of modifier oxide will lead to a
change in the coordination of Te atoms from 4 to 3
through 3 1 1 along with the creation of NBO atoms.
Unlike B and Te in B 2 O 3 and TeO 2 based glasses
respectively, P in P2 O 5 based glasses retains its four
coordination together with the formation of NBOs.
Studies on the MoO 3 glasses suggests the octahedral
environment for the Mo atoms. However, the continuous structural transition from tbp to tp with NBO
is quite unique to the tellurite glasses due to the
structural units and its connecting style which differs

considerably from the other conventional glass formers such as borate, silicate, phosphate etc.
The purpose of the present study is to compare the
structural roles of immobile cations. Thus, the
spectroscopic investigation of mixed former glassy
systems is studied. The change of the glass structure
depending on the kind of cations is observed from
the Raman intensity of the pertinent Raman scattering bands.

3.3. X-ray photoelectron spectroscopy


The binding energies of the Ag 3d, Te 3d, P 2p, B
1s, W 4f, Mo 3d and O 1s core-level electrons are
determined from the respective XPS spectra. The
binding energy of Ag 3d and B 1s remains fairly
constant with an increase in the M x O y and B 2 O 3
content, respectively. The variations in the binding
energies of Te 3d, P 2p, W 4f and Mo 3d have been
attributed to changes in the next nearest neighbors of
the cations. The W 4f and Mo 3d spectra consist of
two peaks due to spin-orbit interaction in tungsto
tellurite and molybdotellurite glasses, respectively.
However, the W 4f on deconvolution shows the
presence of two oxidation states for tungsten as
shown in Fig. 3(a).

3.3.1. O 1 s spectra
It is considered that these glasses consist of TeO 4
polyhedra and MO n (where M 5 W, Mo, P, B)
polyhedra sharing corners according to the
Zachariasen rules. The MO n and TeO 4 are therefore
connected by Te eq O ax M linkages. The Te eq O ax
M linkages are expected to form from the Te eq O ax
Te and MOM species, because that they have
comparable electronegativity values [10] (given in
Table 1) and can therefore substitute for each other
in bonding with O atoms. These linkages are modified by Ag 2 O in the following reactions:

or
Ag 2 O 1 Te 2 eq O ax 2 Te 2Te 2 eq O 2 Ag 1
or 2Te 2 ax O 2 Ag 1

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

669

and
Ag 2 O 1 Te 2 eq O ax 2 M Te 2 eq O 2 Ag 1
or Te 2 ax O 2 Ag 1 1 M 2 O 2 Ag 1
As a result, tellurium tetrahedra with one, two or
three NBOs are formed. Hence, the oxygen species
such as Te eq O ax Te, Te=O, Te eq O 2 Ag 1 , Te
2
1
ax O Ag , Te eq O ax M, P=O, MOM, MoO ,
Mo
2
1
and MO Ag
are present in the
Mo
Ag 2 O.M x O y .TeO 2 glasses.
On deconvolution, O 1s spectra of the
Ag 2 O.WO 3 .TeO 2 ,
Ag 2 O.MoO 3 .TeO 2 ,
Ag 2 O.P2 O 5 .TeO 2 and Ag 2 O.B 2 O 3 .TeO 2 glasses
have been found to consist of two peaks each [4,7
9]. The deconvoluted O 1s spectrum of the
0.30Ag 2 O.0.28WO 3 .0.42TeO 2 glass is presented as
an example in Fig. 3(b). Based on the considerations
of charge distribution and electron densities of
oxygen atoms, the lower binding energy peak referred as O 1s(1), has been attributed to non-bridging
oxygen (NBO) atoms and the higher binding energy
peak assigned to bridging oxygen (BO) atoms denoted as O 1s(2). The variation of the fractional peak
area of O 1s(1), [as shown in Fig. 4(a)],denoted as
F(A 1 ) suggests that there is a formation of NBO
atoms at the expense of BO atoms. Thus, the
following oxygen species are considered to be
contributing to the O 1s(1) peak: Te eq OAg 1 ,
Te ax OAg 1 , MOAg 1 , P=O, Te=O, WOW,
MoO, MoOMo and MoO , Mo
Mo , and that for O
1s(2) are Te eq O ax Te, Te eq O ax M (where M5P,
B, W and Mo), POP and BOB.

3.3.2. P 2 p spectra
The binding energies of P 2p core level electrons
gradually changed from 132 to 133.9 eV as the x
value increases, since some of the ruptured P=O
linkages are changed into POP and POTe
bonds. As the charge distribution in the P=O bond is
displaced towards the oxygen atom, there is a
deficiency in electron density around the P atom,
causing an increase in binding energy of the P 2p
core level electrons.
Fig. 3. A typical experimental and deconvoluted Gaussian peaks
of (a) W 4f, (b) O 1s and (c) Te 3d XPS spectra in the
Ag 2 O.WO 3 .TeO 2 system.

3.3.3. Te 3 d spectra
The Te 3d spectra observed in these ternary
systems have been deconvoluted into maximum four

670

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

Fig. 4. Compositional variation of F(A 1 ) and F(A 2 ) in the 0.30Ag 2 O.0.70[xM x O y .(12x)TeO 2 ] system. F(A 1 ) is defined as the area ratio of
O 1s(1) and the sum of the O 1s(1) and O 1s(2) peaks and F(A 2 ) is defined as the peak area ratio of Te 3d(1) and the sum of the Te 3d(1),
Te 3d(2), Te 3d(3) and Te 3d(4).

Gaussian peaks. As a typical example, Fig. 3(c)


shows these four peaks and they are labeled as Te
3d(1), Te 3d(2), Te 3d(3) and Te 3d(4). These peaks
are attributed to the different bonding states of
tellurium atoms, namely TeO 4 , TeO 32 , TeO 322 units
and AgTe bond [4,79]. These complex units of
tellurium oxide could be expected, since the effect of
the lone pair electrons is limited by the introduction
of new structural units. These units being BO 3 / BO 4 ,
PO 4 , MoO 4 / MoO 6 , WO 4 / WO 6 etc., which are
compatible with the TeO 4 polyhedra by the transformation of TeO 4 into TeO 3 along with the formation of NBO atoms.
The peak intensity of Te 3d(1) decreases as the
M x O y content increases with the corresponding
increase in the intensities of the other tellurium
peaks. The observed over all decrease in the fractional peak area of Te 3d(1), [as shown in Fig. 4(b)],
denoted as F(A 2 ) suggests that the conversion of
TeO 4 to TeO 3 increases as the M x O y content increases as shown in Fig. 4. This conversion is rapid
when a network former [TeO 2 ] substitutes partially
by another network former [i.e. M x O y 5P2 O 5 and
B 2 O 3 ]. However, it is observed that for M x O y 5WO 3
and MoO 3 , the initial substitution up to x50.3
results in the formation of some oxide linkages rather
than the transformation of TeO 4 to TeO 3 . The

observed considerable change in the F(A 2 ) beyond


x50.3 suggests the conversion of TeO 4 to TeO 3 .
Thus, from Fig. 4(b) it is clear that the modification
of TeO 2 units are higher with P2 O 5 and B 2 O 3
substitution compared to that of the WO 3 and MoO 3
substitutions.

3.4. Raman spectroscopy


The observed Raman bands for the presently
investigated ternary silver tellurite glasses are assigned to the TeO linkage vibrations in TeO 4 and
TeO 3 units [9]. The denconvoluted Raman spectra
for the 0.30Ag 2 O.0.14WO 3 .0.56TeO 2 glass is shown
in Fig. 5(a) and the peak assignments are given in
Table 2. The Raman intensity ratio of 780 and 660
cm 21 bands hereafter referred as I780 /I660 represent
the ratio of TeO 3 and TeO 4 structural units [16]. The
variation of Raman intensity ratio with M x O y is
illustrated in Fig. 5. I780 /I660 increases with increase
in M x O y content indicating the transformation of
TeO 4 to TeO 3 units but, the extent of increase is
found to be different for different kinds of cation
substitutions. In Fig. 6 the ratio of TeO 3 and TeO 4
obtained from the Raman and XPS studies as a
function of composition is represented. In general,
the ratio is found to increase with increase in the

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

671

contributing to the Raman intensity, thereby contributing to the higher TeO 3 / TeO 4 .
In some tellurite systems, crystallization occurs
easily by the heating of glasses but it hardly occurs
when the corresponding melts are cooled [5]. This
behavior may relate to the structural change of the
glasses with crystallization and melting. Hence, the
comparison of the structural units that are present in
glasses, precipitated crystals, and melts should lead
us to a clear understanding of the crystallization
behavior observed in tellurite system. In order to
observe this unique behavior of tellurite glasses, we
have undertaken the high temperature Raman spectral study. This investigation on the tungstotellurite
glasses reveal the presence of the crystallization
species of WO 3 and a-TeO 2 , as shown in Fig. 7.
While no changes are observed in Fig. 7(b) with the
cooling of the melt to solid state, significant changes
can be seen in Fig. 7(a) indicating the crystallization
aspect of WO 3 and a-TeO 2 .

4. Ion conduction

Fig. 5. (a) The experimental and deconvoluted Raman spectra for


the 0.30Ag 2 O.0.14WO 3 .0.56TeO 2 system. (b) Compositional
variation of Raman intensity ratio of 780 and 660 cm 21 bands in
the 0.30Ag 2 O.0.70[xM x O y .(12x)TeO 2 ] system.

M x O y content, although the slopes of the variations


are different. This could be visualized as follows. As
we know, with the partial replacement of one
network former by the other, there is a transformation of TeO 4 to TeO 3 . In addition to this conversion,
there is a formation of TeOM (where M5W, Mo,
P and B) linkages in the glass network. The vibrations of the TeOM linkages may also be

Conductivity is a structure sensitive property,


because the structure decides both the potential
barriers for the transport of mobile ions as well as
the mobile ion concentration. The structure can be
changed by increasing temperature and / or by the
composition of constituents. In the TeO 2 based
glasses, from the ionic conductivity point of view the
transformation from TeO 4 (tbp) to TeO 3 (tp) is
important because this transition involves a continuous formation of NBOs which are responsible for the
changes in the conductivity.
In the present case, the conductivity has been
studied extensively over a wide range of temperature, composition and frequency. As described elsewhere [4,79], conductivity of the Ag 2 O.WO 3 .TeO 2 ,
Ag 2 O.MoO 3 .TeO 2 ,
Ag 2 O.P2 O 5 .TeO 2
and
Ag 2 O.B 2 O 3 .TeO 2 glasses have been found to follow
the Arrhenius equation

Eact
s 5 so exp 2 ]
kT

indicating that the mobility of Ag-ion is the underlying cause.


The isothermal conductivity variations with glass

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B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

Table 2
Raman band assignments for the Ag 2 O.WO 3 .TeO 2 glasses
Peak

Wavenumber (cm 21 )

Vibrational mode

A
B
C
D
E
X
Y
Z

770780
720760
650665
600612
460500
830835
890900
340350

Stretching vibrations of TeO 3 tp


Stretching vibrations of TeO 3 tp
Stretching vibrations of TeO 4 tbp
Stretching vibrations of TeO 4 tbp
Bending vibrations of TeOTe or OTeO linkages
Stretching vibrations of WOW in the WO 4 or WO 6 units
Stretching vibrations of WO 2 and W5O in the WO 4 tetrahedra
Bending vibrations of WOW in the WO 6 units

Fig. 6. Compositional dependence of the ratio of TeO 3 and TeO 4 obtained from the Raman and XPS studies in the
0.30Ag 2 O.0.70[xM x O y .(12x)TeO 2 ] system.

composition given in Fig. 8 shows two conductivity


maxima
at
258C
for
Ag 2 O.WO 3 .TeO 2 ,
Ag 2 O.MoO 3 .TeO 2 and Ag 2 O.P2 O 5 .TeO 2 system,
while there is only one maxima for the

Ag 2 O.B 2 O 3 .TeO 2 glasses. As the temperature increases, the two maxima vanish leaving behind a
single maximum for MoO 3 substitution whereas two
maxima are present for both Mx Oy 5WO 3 and P2 O 5

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

673

Fig. 7. Raman spectra of 0.30Ag 2 O.0.14WO 3 .0.56TeO 2 glass at different temperature (a) when heated from room temperature to molten
state, (b) when cooled from molten state to the solid state.

Fig. 8. Compositional variation of conductivity for the yAg 2 O.(12y)[xM x O y .(12x)TeO 2 ] system.

674

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675

substitutions. The enhancement in the conductivity


observed with the partial substitution of one network
former by another while the modifier oxide content is
kept constant is about an order in magnitude. It is
seen that the conductivity enhancement is the highest
for WO 3 substitution compared to that for the other
M x O y substitutions.
According to the AndersonStuart model [17], the
observed decrease in the activation energy is associated with a decrease in the radius of normal doorways in the glass as a consequence of the disruption
of the network and increase in the number of NBOs.
Since the radii of the substituents were smaller
compared to Te as given in Table 1 [10], the network
of the glass should become increasingly more compact and denser resulting in a decrease in radius of
the normal doorway. Hence the two maxima observed in the conductivity vs. composition curve is
attributed to the mixed former effect and may arise
due to the effect of the glass structure on conductivity. At these two compositions the glassy
matrix may be such that it creates open channels for
the mobile species to migrate, which causes enhancement in ionic mobility and in turn the conductivity.
Moreover, a linear relation between the pre-exponential factor, log so and the activation energy, Eact is
observed in these systems similar to many other
systems [18,19].
The ac conductivity analysis gives the characteristic properties such as relaxation time, tp and carrier
hopping rate, vp . Conductivity relaxation time, [ts 5
(1 /fp )] can be calculated from the peak frequency, fp ,
which is obtained by plotting the normalized complex modulus spectra vs. log f, the frequency. For a
given composition the value of fp is found to increase
with the temperature. Hence, the more compact or
rigid the structure the lower is the characteristic
frequency at a given temperature. Therefore the
effect of glass structure on the relaxation spectra is
manifested most sensitively through the temperature
dependence of their characteristic frequencies [20].
To determine the vp , the experimental data points of
s (v ) vs. frequency, f are fitted to the power law of
the form s (v )5 s (o)1 Av n (where s (o) is a frequency independent term corresponds to the dc
conductivity, A is a temperature dependant parameter
and n is found to vary between 0 and 1) and by
inspecting the frequency at which s (v )52s (o). We

observed that, both the relaxation time, tp and carrier


hopping rate, vp are thermally activated parameters.

5. Summary
The incorporation of B 2 O 3 , P2 O 5 , WO 3 and MoO 3
into the Ag 2 O.TeO 2 glass lead to the structural
modification of the glass network resulting in glasses
with higher thermal stability compared to the corresponding binary glasses. The enhancement in T g and
conductivity with composition is attributed to the
structural modifications and the mixed former effect
in the glass network. The ac conductivity analysis
reveal that both the relaxation time, tp and carrier
hopping rate, vp are thermally activated quantities.
The non-bridging and bridging oxygen atoms were
distinguished from the deconvoluted O 1s XPS
spectra. Raman spectroscopy shows that besides the
expected TeO 4 trigonal bipyramid, the TeO 3 trigonal
pyramid, the WO 4 / WO 6 , MoO 4 / MoO 6 , PO 4 and
BO 3 / BO 4 polyhedra are also present in tungsto
tellurite, molybdotellurite, phosphotellurite and
borotellurite glasses, respectively. The intensity
ratios of the Raman peaks 780 and 660 cm 21 may
represent the ratio of the fractions of TeO 3 tp and
TeO 4 tbp. The high temperature Raman spectral
study reveal the unique behavior of crystallization in
these tellurite glass systems.

Acknowledgements
The authors wish to thank Prof. K.L. Tan for his
interest in this work and Mr. H.K. Wong for his help
in taking XPS spectra. Thanks are also due to Dr.
Shen Zhixian for his support in Raman study.

References
[1] M. Arnandov, V. Dimitrov, Y. Dimitriev, L. Markova, Mater.
Res. Bull. 17 (1982) 1121.
[2] P. Balaya, C.S. Sunandana, J. Non-Cryst. Solids 175 (1995)
51.
[3] G.D.L.K. Jayasinghe, D. Coppo, P.W.S.K. Bandaranayake,
J.L. Souquet, Solid State Ionics 76 (1995) 297.
[4] B.V.R. Chowdari, P. Pramoda Kumari, J. Non-Cryst. Solids
197 (1996) 31.

B.V.R. Chowdari, P. Pramoda Kumari / Solid State Ionics 113 115 (1998) 665 675
[5] M. Tatsumisago, T. Minami, Y. Kowada, H. Adachi, Phy.
Chem. Glasses 35 (1994) 89.
[6] T. Sekiya, N. Mochida, A. Ohtsuka, M. Tonokowa, J. NonCryst. Solids 144 (1992) 128.
[7] B.V.R. Chowdari, P. Pramoda Kumari, Solid State Ionics
8688 (1996) 521.
[8] B.V.R. Chowdari, P. Pramoda Kumari, J. Phys. Chem. Solids
58 (1997) 515.
[9] B.V.R. Chowdari, P. Pramoda Kumari, J. Mater. Sci. 33
(1998) 3591.
[10] R.C. West, M.J. Astle, W.H. Beyer (Eds.), Handbook of
Chemistry and Physics CRC, Boca Raton, FL, 1987.
[11] G.D.L.K. Jayasinghe, P.W.S.K. Bandaranayake, M.A.K.L.
Dissanayake, R.P. Gunavardane, Solid State Ionics 78 (1995)
199.
[12] A.C. Martin Rodrigues, M.J. Duclot, Solid State Ionics
2830 (1988) 729.

675

[13] A. Magistris, G. Chiodelli, M. Villa, J. Power Sources 14


(1985) 215.
[14] M. Villa, G. Chiodelli, M. Scagliotti, Solid State Ionics
1819 (1986) 382.
[15] B.V.R. Chowdari, K.L. Tan, W.T. Chia, R. Gopalakrishnan, J.
Non-Cryst. Solids 119 (1990) 95.
[16] Y. Hemei, A. Osaka, T. Nanba, Y. Miura, J. Non-Cryst.
Solids 177 (1994) 164.
[17] O.L. Anderson, D.A. Stuart, J. Am. Ceram. Soc. 37 (1954)
573.
[18] R.A. Huggins, in: A.S. Mowick, J.J. Burton (Eds.), Diffusion
in Solids, Recent Developments, Academic Press, New York,
1975.
[19] D.P. Almond, A.R. West, Solid State Ionics 23 (1987) 27.
[20] J. Wong, C.A. Angell, Glass Structure by Spectroscopy, New
York, 1976.