Materials Science and Engineering B90 (2002) 224– 233

www.elsevier.com/locate/mseb

Structural, dielectric and electrical conducting properties of

CsB%B%%O6 (B%= Nb, Ta; B%% =W, Mo) ceramics
Tanika Kar *, R.N.P. Choudhary
Department of Physics and Meteorology, Indian Institute of Technology, Kharagpur 721 302, India

Received 29 January 2001; accepted 9 August 2001

Abstract

Polycrystalline samples of the defect pyrochlore-type CsB%B%%O6 (B%= Nb, Ta; B%%=W, Mo) compounds were prepared by
solid-state reaction technique. The formation of the compounds was checked by X-ray diffraction (XRD) method. All the
compounds were found to have a cubic crystal structure at room temperature. Dielectric studies of the tungstate compounds,
CsNbWO6 and CsTaWO6 indicated a small dielectric anomaly at (183 9 2) and (328 92) K, respectively, whereas the molybdate
compounds, CsNbMoO6 and CsTaMoO6 did not exhibit such anomaly. The conductivity measurements indicated ionic transports
(tion ]0.80) in the high temperature region ( ]573 K). © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Ceramics; Inorganic compounds; Permittivity; Electrical measurements; Ionic conduction

1. Introduction have a B2X6 network similar to regular pyrochlores but

Proton conducting ceramics have great technological
AB2X6
or
importance, especially for their applications as sensors,
2B2X6A (
: vacancy) depending on the size of A
steam electrolysis cells and fuel cells. There are different
types of skeleton structures, which facilitate fast ion
conduction [1]. Among all the three-dimensional skele-
ton structures, pyrochlores offer interesting possibilities
to act as fast-ion conductors. The cubic pyrochlores
have a general formula A2B2X6Y where A is a large
cation, B is a small cation octahedrally co-ordinated by
six X anions and Y is O, OH, F, H2O. The B2X6
sub-array forms a rigid skeleton of corner-shared octa-
hedra [1,2]. These octahedra are arranged in a tetrahe-
dral array according to a diamond-type net and a
system of open channel is observed parallel to the [110]
direction and to that equivalent to cubic symmetry. In
a normal pyrochlore, the channel contains an array of
stoichiometry (A2Y)n units. Depending on the chemical
composition, the chemical bond between the rigid
framework (BX3)n and the loose array (A2Y)n may be
weak. Because of the weak interaction, the A and Y
atoms may be partly or completely missing which gives
rise to ‘defect’ pyrochlores [3]. ‘Defect’ pyrochlores
* Corresponding author.
E-mail address: kar-tanilca@lycos.com (T. Kar).
with vacancies introduced in the A2Y array. Thus these
compounds are generally formulated as
cation. Presence of the vacancies makes fast-ion con-
duction possible. These types of compounds have a
tendency of getting contaminated by absorbing mois-
ture from surroundings. Compounds with larger lattice
parameter become hydrated on exposure to air. Defect
pyrochlores with small A+ ion (i.e. Li+, Na+, etc.) are
all hydrated at room temperature [1]. Therefore, at
room temperature, the defect pyrochlores can be repre-
sented by a general formula AB2O6·xH2O (x=ab-
sorbed water content, X= oxygen ion). The maximum
value of ‘x’ is 1. Reasonably dense specimens (having
99% of theoretical density) also absorb water from
atmosphere [4]. This absorbed water can be removed by
heating the compounds. The ionic properties of these
compounds are very much influenced by absorbed wa-
ter. Though studies of structural, thermal and ionic
properties of some members of defect pyrochlore-type
AB/WO6 (where A= alkali ions, B% =Nb, Ta) family
have already been reported [2–10], no information is
available on the dielectric and related properties of
these compounds. Moreover, the molybdate counter-
part of AB%WO6 compounds (i.e. AB%MoO6 com-
pounds) still remain unattended, though W6 + and

0921-5107/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 1 0 7 ( 0 1 ) 0 0 7 4 5 - 0
 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233 225

Mo6 + have comparable ionic radius (i.e. 0.62 A, ). In Table 2

Comparison of cell parameter [a (with standard deviation)], observed
view of the importance of the materials and un-
[o] and calculated [c] d-values of (in A, ) of CsB%MoO6 (B%= Nb, Ta)
availability of dielectric data, we have carried out sys- compounds at room temperature with observed relative intensity in
tematic and extensive studies on structural, dielectric parenthesis
and electrical conducting properties of all the members
of the AB%B%%O6 family (where A= alkali ions, B% = Nb, hkl B%= Nb B%=Ta
Ta; B%% =W, Mo) [11 – 17]. In order to get reproducible
a = 10.4968 (35) a = 10.4631 (39)
and reliable dielectric and conductivity data, all the
measurements are carried out on anhydrous specimens 211 [o] 4.2806 (14), [c] [o] 4.2705 (7), [c] 4.2715
in dry atmosphere. In this paper, we report our studies 4.2853
on preliminary structural and detailed dielectric and 220 [o] 3.7155 (33), [c] [o] 3.6927 (27), [c] 3.6993
3.7112
electrical conducting properties of the polycrystalline
311 [o] 3.1644 (100), [c] [o] 3.1589 (100), [c] 3.1547
CsB%B%%O6 (B% = Nb, Ta; B%% =W, Mo) compounds. 3.1649
222 [o] 3.0329 (49), [c] [o] 3.0279 (47), [c] 3.0204
3.0302
2. Experimental procedures 422 [o] 2.1414 (9), [c] 2.1427 [o] 2.1318 (7), [c] 2.1358
511,333 [o] 2.0229 (35), [c] [o] 2.0145 (30), [c] 2.0136
2.0201
Polycrystalline samples of CsNbWO6 (CNW), 440 [o] 1.8519 (26), [c] [o] 1.8501 (29), [c] 1.8496
CsTaWO6 (CTW), CsNbMoO6 (CNM) and CsTaMoO6 1.8556
(CTM) were prepared by solid-state reaction technique 531 [o] 1.7745 (7), [c] 1.7743 [o] 1.7681 (5), [c] 1.7686
using high purity carbonate and oxides: Cs2CO3 (99%, 620 [o] 1.6543 (11), [c] [o] 1.6516 (8), [c] 1.6544
1.6597
M/s. Lancaster Synthesis, UK), Nb2O5 (99%, M/s.
533 [o] 1.6015 (14), [c] [o] 1.5926 (12), [c] 1.5956
BARC, India), Ta2O5 (99%, M/s. E. Merck, Germany), 1.6007
WO3 (99%, M/s. John Baker Inc., USA) and MoO3 622 [o] 1.5802 (11), [c] [o] 1.5740 (13), [c] 1.5774
(99%, M/s. Loba Chemie Pvt. Ltd., India) in required 1.5825
642 [o] 1.4032 (9), [c] 1.4027 [o] 1.3939 (5), [c] 1.3982
553,731 [o] 1.3602 (13), [c] [o] 1.3610 (12), [c] 1.3622
Table 1 1.3666
Comparison of cell parameter [a (with standard deviation)], observed
[o] and calculated [c] d-values (in A, ) of CsB%WO6 (B%=Nb, Ta)
compounds at room temperature with observed relative intensity in stoichiometry. The ingredients of the desired com-
parenthesis
pounds were thoroughly mixed in agate mortar for 2 h
hkl B%= Nb B%=Ta and calcined in alumina crucibles at 773 K for 10 h in
air atmosphere. The process of grinding and calcination
a = 10.4700 (33) a=10.4600 (39) was repeated several times till the formation of the
compounds. The final calcination was done at 1300 and
220 [o] 3.7078 (32), [c] [o] 3.6927 (27), [c] 3.6982
3.7017
873 K for tungstate and molybdate compounds respec-
311 [o] 3.1589 (100), [c] [o] 3.1589 (100), [c] 3.1538 tively. The formation of the compounds was checked
3.1568 by X-ray diffraction (XRD) method. The XRD pattern
222 [o] 3.0279 (59), [c] [o] 3.0179 (86), [c] 3.0195 of calcined powder was obtained by using X-ray pow-
3.0224
400 [o] 2.6143 (6), [c] 2.6175 [o] 2.6180 (12), [c] 2.6150
der diffractometer (Rigaku Miniflex, Japan) with Cu–
422 [o] 2.1366 (9), [c] 2.1372 [o] 2.1342 (7), [c] 2.1351 Ka radiation (u= 1.5418 A, ) in a wide range of Bragg
511,333 [o] 2.0145 (41), [c] [o] 2.0145 (51), [c] 2.0130 angle (205 2q 5 70°) at a scanning rate of 2° min − 1.
2.0150 The fine and homogeneous powders of the compounds
440 [o] 1.8501 (41), [c] [o] 1.8449 (56), [c] 1.8491
were used to make cylindrical pellets of diameter 5–
1.8509
531 [o] 1.7681 (8), [c] 1.7698 [o] 1.7649 (12), [c] 1.7681 10 mm and thickness 1–2 mm by applying a pressure
620 [o] 1.6529 (11), [c] [o] 1.6516 (10), [c] 1.6539  5 ×106 Pa using a hydraulic press. Polyvinyl alcohol
1.6555 (PVA) was used as binder to reduce the brittleness of
533 [o] 1.5939 (20), [c] [o] 1.5901 (23), [c] 1.5951 the pellets. The binder was burnt out during the sinter-
1.5967
622 [o] 1.5728 (21), [c] [o] 1.5716 (33), [c] 1.5769 ing of pellets in air at temperatures 1373 and 930 K for
1.5784 tungstate and molybdate compounds respectively for 6
444 [o] 1.5122 (5), [c] 1.5112 [o] 1.5044 (8), [c] 1.5098 h in alumina crucibles. The sintered pellets were pol-
551,711 [o] 1.4629 (6), [c] 1.4661 [o] 1.4619 (8), [c] 1.4647 ished with fine emery papers in order to make both
642 [o] 1.3967 (7), [c] 1.3991 [o] 1.3921 (7), [c] 1.3978
553,731 [o] 1.3610 (23), [c] [o] 1.3610 (30), [c] 1.3618
their faces flat and parallel. The pellets were electroded
1.3631 with high purity air drying silver paste and used for all
electrical measurements. Some researchers [6,10] had
226 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233
reported that the electrode material did not affect the
dielectric and electrical conducting properties of the
compounds. The dielectric parameters (m, tan l) were
calculated as function of frequency (103 – 106 Hz) and
temperature using GR1620 AP capacitance measuring
assembly and HP 4342 A Q-meter along with labora-
tory-made three-terminal sample holder and heating
arrangements. The ac conductivity was measured as
function of frequency (22k-1 MHz) and temperature by
HP 4342 A Q-meter. The dc conductivity was measured
as function of applied electric field (10– 110 V/cm) and
temperature using Keithley 617 programmable elec-
trometer. As most of the members of the defect py-
rochlore family with the general formula AB%B%%O6 have
a tendency to get contaminated by moisture [1], special
care was taken to avoid the problem. All the samples
were kept at 400 K for 12 h before each experiment. In
order to prevent rehydration of the samples during
experiments, silica gel was kept inside the sample holder.
The structural data presented here are of hydrated (i.e.
room temperature) phase of the compounds whereas the
electrical data are of their anhydrous phase.
3. Results and discussion
3.1. Structural study
The sharp and single diffraction peaks in the XRD
Fig. 1. Frequency dependence of dielectric parameters of the CsB%B%%O6 (B%=Nb, Ta; B%%=W, Mo) compounds at room temperature.
patterns of all the compounds, which were quite differ-
ent from those of the ingredient carbonate and
oxides, confirmed the formation of the new compounds.
All the XRD peaks were indexed and the cell
parameters were determined in different crystal systems
and unit cell configurations using a standard computer
program ‘PowdMult’ using the observed interplaner
spacings (d-values) of strong, medium and low
intensity peaks spread over wide 2q range. Finally, a
unit cell of cubic crystal system was selected for which
SDd = S(dobs − dcal) was found to be minimum. The
good agreement between the observed and calculated
d-values (Tables 1 and 2) shows the correctness
of the selection of crystal system and unit cell parame-
ter. The tungstate compounds have comparable cell
parameters and the peak positions are not varied
much by the incorporation of Ta5 + ion in place of
Nb5 + ion in the structure. Similar trend is also observed
in the case of molybdate compounds. However, cell
parameter decreases as Ta5 + replaces Nb5 + in both the
tungstate and molybdate compounds. The cell parame-
ter of tungstate compounds obtained by us is slightly
( 0.8%) larger than the reported ones [18], indicating
that the compounds are slightly hydrated at room
temperature [1]. No such comparison is possible for
molybdate compounds because of nonavailability of
data.
 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233 227

Fig. 2. (a) Temperature dependence of dielectric constant (m) of the CsB%WO6 (B%=Nb, Ta) compounds at different frequencies. (b) Temperature
dependence of dielectric constant (m) of the CsB%MoO6 (B%=Nb, Ta) compounds at different frequencies.

3.2. Dielectric study quency indicating a normal behaviour of compounds

having mobile carriers [19]. The variation of dielectric
Fig. 1 shows the frequency dependence of dielectric constant, o of CNW and CTW is very small compared
parameters (i.e. m and tan l) at room temperature (300 to that of CNM and CTM. In the case of CNM and
K). Both the parameters decrease with increasing fre- CTM, m decreases rapidly up to 22 kHz, after that it
228 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233

varies slowly. The variation of loss tangent, tanl is
almost similar to that of m. In the case of tungstate
compounds, tanl remains almost constant, whereas it
decreases rapidly up to 105 Hz in the molybdate com-
pounds, and becomes almost constant afterwards. The
other members of this family behave in a similar man-
ner [11– 17].
Fig. 2(a) shows the variation of m of CNW and CTW
with temperature (100–600 K) at different frequencies
and have very small dielectric anomaly at (18392) and

Fig. 3. (a) Temperature dependence of tangent loss (tan l) of the CsB%WO6 (B%=Nb, Ta) compounds at different frequencies. (b) Temperature
dependence of tangent loss (tan l) of the CsB%MoO6 (B%=Nb, Ta) compounds at different frequencies.
 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233 229

Table 3
Comparison of some dielectric data of CsB%B%%O6 ceramics

B% B%% Frequency (Hz) m300 K tan l300 K Dielectric anomaly at T (K) m]500 K tan l]500
K

104 126 0.008 183 290 1.2

Nb W 105 120 0.005 185 117 0.014
106 118 0.005 185 113 0.0064
104 154 0.17 – 39000 4.9
Nb Mo 105 130 0.0074 – 350 0.15
106 118 0.0069 – 200 0.045
104 91 0.008 328 110 0.60
Ta W 105 90 0.006 330 82 0.015
106 89 0.005 330 80 0.009
104 114 0.21 – 28000 6.6
Ta Mo 105 94 0.014 – 400 0.20
106 82 0.0088 – 220 0.091

Fig. 4. Frequency dependence of specific impedance of the CsB%B%%O6 (B%=Nb, Ta; B%%=W, Mo) compounds at room temperature.

(32892) K, respectively. The value of dielectric con-
stant of CNW is higher than that of its Ta counterpart
(i.e. CTW). In case of CTW, m remains almost invariant
with respect to temperature. However, at 104 Hz, an
increasing trend is observed after 500 K in both the
compounds.
Fig. 2(b) shows the variation of m of CNM and CTM
with temperature (300– 600 K) at different frequencies.
Unlike their isomorphous compounds, CNM and CTM
do not have any dielectric anomaly in the studied
frequency and temperature range. The value of m starts
increasing with temperature and the rate of increase is
much faster at 104 Hz than that of at 105 and 106 Hz in
both the compounds. Similar increasing trend at high-
temperatures (\400 K) is observed in the other mem-
bers of the family already reported by us [11–17].
This type of behaviour may be due to the disordering
of the cation sublattices, which consists of shift of
cation from site to one of the interstices. Although the
disordering of the lattice does not lead by itself to the
appearance of carriers, it does facilitate substantially
their formation. The reason is that the disorder is
accompanied by an increase of m and this weakens the
coulomb interaction between the cation that departed
230 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233

to another unit cell and the vacancy left behind. As a
result, with increasing temperature, a transition from a
state of low m (ordered cation sublattice) into a state of
high m (disordered cation sublattice) can occur [20].
Fig. 3(a) and (b) show the temperature dependence of
loss tangent (tan l) of tungstate and molybdate com-
pounds, respectively. The molybdate compounds are
highly lossy compared to their tungstate counterparts.
This trend in high temperature and low frequency
region can be explained from the increasing movement

Fig. 5. (a) Temperature dependence of measured ac conductivity [|m(…)] of the CsB%WO6 (B%=Nb, Ta) compounds at different frequencies. (b).
Temperature dependence of measured ac conductivity [|m(…)] of the CsB%MoO6 (B%=Nb, Ta) compounds at different frequencies.
 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233 231

Table 4
Comparison of some conductivity data [in (ohm cm)−1] of CsB%B%%O6 ceramics

B% B%% |m(…)300 K [|dc]TOTAL,300 K tion

105 Hz 106 Hz 300 K 400 K 473 K 573 K 673 K

Nb W 4.58×10−8 7.52×10−7 1.42×10−12 0.06 0.11 0.23 0.86 0.87

Nb Mo 3.38×10−7 4.12×10−6 1.25×10−10 0.01 0.08 0.18 0.81 0.82
Ta W 2.78×10−8 5.04×10−7 5.73×10−14 0.03 0.10 0.22 0.89 0.89
Ta Mo 1.12×10−6 6.14×10−6 2.07×10−11 0.03 0.18 0.38 0.85 0.86

Fig. 6. Applied electric field dependence of dc resistivity (zdc) of the CsB%B%%O6 (B%=Nb, Ta; B%%=W, Mo) compounds at room temperature.

of Cs1 + ions in the main skeleton of the structure of
the compound at high temperature [21]. In Table 3,
some dielectric data of all the four compounds at
different frequencies and temperatures have been
compared.
3.3. Ac and dc conducti6ity study
The variation of specific impedance of all the four
compounds with frequency (22k-1 MHz) at 300 K is
shown in Fig. 4. The value of specific impedance con-
tains the contributions from both grains and grain
boundaries, which have entirely different dielectric and
resistive properties. It was observed that the value of
specific impedance varies slowly up to 105 Hz, then
converges and approaches to a plateau. According to
Powers et al., this high frequency plateau is associated
with the resistivity of the grain interior [22]. As the
samples are not available in single crystal form, we
cannot separate the contributions of grain and grain
boundary in the obtained value of specific impedance.
The variation of measured ac conductivity, |m(…), of
the tungstate and molybdate compounds at 105 and 106
Hz with inverse of absolute temperature (1/T) is shown
in Fig. 5(a) and (b), respectively. As expected, the value
of |m(…) is greater than its dc counterpart (Table 4)
because it has contribution from both the ac and dc
conductivity.
Fig. 6 shows the variation of dc resistivity (zdc) of all
the compounds with applied electric field (10–110 V
cm − 1) at 300 K. The resistivity decreases very slowly
with applied electric field that may be due to: (i)
formation of space charge, (ii) change in shape of
moisture in the pores of the compounds under the
influence of applied electric field, (iii) contacts with
electrodes, etc. [23].
232 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233
Fig. 7. Temperature dependence of dc conductivity [(|dc)TOTAL] of the CsB%B%%O6 (B%=Nb, Ta; B%%=W, Mo) compounds at constant electric field.
Fig. 7 gives the variation of total dc conductivity,
(|dc)TOTAL, with inverse of absolute temperature (1/T)
at a constant electric field. The conductivity increases
with temperature and varies as shown in Fig. 7. The dc
activation energy, Ea, was calculated from the slope of
the graph (Fig. 7) using the Arrhenius formula: |=
|o exp(−Ea/KBT), where KB =Boltzmann constant.
The values of activation energy in the high-temperature
( \500 K) region are found to be 1.22, 1.23, 0.71 and
0.79 eV for CNW, CTW, CNM and CTM, respectively.
The nature of octahedral framework (e.g. size of the
bottlenecks) plays an important role in determining the
activation energy of a compound. The value of activa-
tion energy generally depends on the width of the
channel through which conduction takes place, polaris-
ability of the ion taking part in conduction, etc. [18].
The total dc conductivity, (|dc)TOTAL, of a compound
is given by (|dc)TOTAL =|ion +|e, where |ion and |e are
the conductivities due to ion and electron/hole trans-
port respectively. The ionic and electronic transference
number (i.e. tion and te) are a measure of the extent of
ionic and electronic contribution in total conduction
mechanism. Now, tion and te are defined as: tion = |ion/
(|dc)TOTAL = Iion/IT and te =|e/(|dc)TOTAL =Ie/IT, where
Iion, Ie, IT are the ionic, electronic and total current
respectively. At a fixed temperature, the instantaneous
value of current gives (|dc)TOTAL and final stabilised
value of it gives |e [24]. The variation of current
through the samples with time was measured at differ-
ent constant temperatures, viz., 300, 400, 473, 573 and
673 K, respectively. The source voltage was kept con-
stant at 10 V. In all the four compounds, it is found
that ‘tion’ increases very slowly up to 473 K, beyond
that a rapid increasing trend is observed up to 573 K,
which remains almost constant up to 673 K (Table 4).
Therefore, up to 473 K, the conduction mechanism is
mainly dominated by electrons/holes in all the com-
pounds. Above 473 K, ionic contribution in the con-
duction process increases. High values of tion (]0.80)
of all the compounds in the high-temperature region
suggests that they are good ionic conductors in this
region. Large ionic conductivity of Cs1 + ion containing
compounds in spite of large ionic radius of Cs1 + ion
may be due to high polarisability of the said ion [25].
4. Conclusions
It can be concluded that the CsB%B%%O6 (B% =Nb, Ta;
B%% =W, Mo) compounds, members of defect py-
rochlore-type AB%B%%O6 family, have cubic crystal struc-
ture at room temperature. Detailed studies of dielectric
properties reveal that CsNbWO6 and CsTaWO6 have
very small dielectric anomaly at (1839 2) and (32892)
K, respectively, whereas their molybdate counterparts
do not have any such anomaly in the studied frequency
and temperature range. All the compounds behave as
ionic solids (tion ] 0.80) in high-temperature (]573 K)
region.
 T. Kar, R.N.P. Choudhary / Materials Science and Engineering B90 (2002) 224–233
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