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Conductivity studies on microwave synthesized glasses

Article in Bulletin of Materials Science · August 2015

DOI: 10.1007/s12034-015-0958-0

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Bull. Mater. Sci., Vol. 38, No. 4, August 2015, pp. 985–993. 
c Indian Academy of Sciences.

Conductivity studies on microwave synthesized glasses

ASHA RAJIV1 , M SUDHAKARA REDDY1 , R VISWANATHA2 , JAYAGOPAL UCHIL1 and

C NARAYANA REDDY3,∗
1 Department of Physics, School of Graduate Studies, Jain University, Bangalore 560027, India
2 SolidState and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India
3 Department of Physics, Sree Siddaganga College of Arts, Science and Commerce, Tumkur University,

Tumkur 572103, India

MS received 27 March 2015; accepted 6 April 2015

Abstract. Conductivity measurements have been made on xV 2 O5 − (100 − x) [0.5 Na2 O + 0.5 B2 O3 ] (where
10 ≤ x ≤ 50) glasses prepared by using microwave method. DC conductivity (σ ) measurements exhibit temperature-
and compositional-dependent trends. It has been found that conductivity in these glasses changes from the predom-
inantly ‘ionic’ to predominantly ‘electronic’ depending upon the chemical composition. The dc conductivity passes
through a deep minimum, which is attributed to network disruption. Also, this nonlinear variation in σdc and acti-
vation energy can be interpreted using ion–polaron correlation effect. Electron paramagnetic resonance (EPR) and
impedance spectroscopic techniques have been used to elucidate the nature of conduction mechanism. The EPR
spectra reveals, in least modified (25 Na2 O mol%) glasses, conduction is due to the transfer of electrons via aliovalent
vanadium sites, while in highly modified (45 Na2 O mol%) glasses Na+ ion transport dominates the electrical con-
duction. For highly modified glasses, frequency-dependent conductivity has been analysed using electrical modulus
formalism and the observations have been discussed.

Keywords. Conductivity; electrical modulus; impedance; microwave; power law; stretched exponent.

1. Introduction with high Li+ , Na+ , Ag+ , Cu+ and with very high values of
conductivity are called fast ion conductors (FICs) and they
Microwave processing of materials is a relatively new tech- are promising glassy electrolytes for the solid state batte-
nology undergoing rapid developments due to potential ries.5–7 On the other hand, in glasses containing transition
advantages and it offers such as reduced processing time, metal oxide (TMO) such as V2 O5 , Fe2 O3 , CuO, MoO3 , WO3 ,
energy efficiency and products with enhanced properties. The CoO etc, conduction arises from electrons known to be elec-
only requirement of this method is that at least one of the tronic semiconductors. The existence of both low and high
components used for making glass is microwave active. In valence states of transition metal ions (TMIs) is responsible
recent years many glassy materials have been synthesized for the electronic conduction in these glasses.8–10 Further,
as binary or ternary systems using network-forming oxides increase in the concentration of the modifier oxide has been
such as B2 O3 , P2 O5 , TeO2 etc and alkali or silver oxides as found to have profound effect on transport, physical, chemi-
modifiers.1,2 Thangadurai and Weppner3 stressed the impor- cal and optical properties of glasses.11–15 It is expected that
tance of ionic conduction in cathode materials and have dis- transition metal oxide doped with alkali-modified glasses
cussed the structural aspects of ionic conductors suitable for exhibit both ionic and electronic (polaronic) conduction.10,16
application in rechargeable batteries. Generally, alkali-rich glasses exhibit dominant ion conduc-
Alkali oxides added to network-forming glasses expand tivity, while TMI-rich glasses exhibit dominant electronic
the region of glass formation and also modify the networks conductivity.17,18
by creating non-bridging oxygens (NBOs) in the structure. Conductivities in glasses containing vanadium oxide arise
These NBO’s constitutes anionic sites with different binding from the presence of V4+ and V5+ . EPR spectra of V2 O5
energies to the alkali ions. These energies are indeed different containing glasses also originates from V4+ paramagnetic
and stronger than the bond energies of oxygens in the boron centres, whose outer electronic structure 3p6 , 3d1 enables
tetrahedra. Horopanitis et al4 pointed out that, the Li+ trans- unpaired magnetic moments of 3d1 electrons to interact with
port in lithiated boron oxide glasses increases with Li2 O the electromagnetic field in the microwave range, whereas
concentration not only due to Li+ ion concentration but the electronic structure of V5+ is 3p6 , which has total elec-
also due to structural modification. Ion conducting glasses tron spin zero. Since the V4+ ion has electronic spin s = 1/2
and nuclear spin of 51 V is I = 7/2, one should expect interac-
∗ Author for correspondence ([email protected]) tions between corresponding magnetic moments resulting in

985
986 Asha Rajiv et al

the hyperfine structure. Gupta et al19 pointed out that, long 3. Results and discussion
range electron spin–spin interactions between V4+ ions and
the spin orbit coupling cause an anisotropy of the g-factor The X-ray diffraction spectra did not show any sharp peaks
and the broadening of the individual lines.19,20 In glasses (figure 1) indicating that the samples were amorphous. The
only orientation-averaged spectra can be observed, which DSC thermograms from three different stoichiometries are
can lead to additional reduction of hyperfine structure lines. indicated in figure 2. Glass transition temperatures (Tg ) were
It was seen in V2 O5 –TeO2 glasses that, the disappearance of extracted using the intersection of extended linear regions as
hyperfine structure lines at higher contents of V2 O5 is due shown in figure 2 and these values lie in the range 517–640
to superexchange interaction of V4+ –O–V5+ chains.21 Phys- K. The Tg values are comparable with a similar composition
ical property measurements like density and molar volume, prepared by conventional melt quench method.21 The glass
thermal properties like Tg , T , EPR studies of V4+ in the transition temperature reflects the variation of liquidus tem-
glasses and conductivities (both dc and ac) have been per- perature, Tl of the glass forming melt, which implied the
formed and the conductivity behaviour have been examined empirical relation Tl ≈ (3/2) Tg .21 In the present system, Tg
using the measured properties. value increases with increasing Na2 O mol%. This increase
in Tg can be attributed to the replacement of weaker V–
O–V linkages by strong B–O–V and B–O–B linkages. The
2. Experimental dc conductivity of the same composition from different

Glasses were prepared by microwave heating technique

5000
using the general formula: xV2 O5 ·(100 − x) [0.5Na2 O:
0.5B2 O3 ] (where 10 ≤ x ≤ 50) using analar grade sodium
carbonate (Na2 CO3 ), orthoboric acid (H3 BO3 ) and vanadium 4000
pentoxide (V2 O5 ) as starting materials. An appropriate quan-
tity of weighed chemicals were mixed and thoroughly ground
to homogenize the mixture and kept in a silica crucible inside 3000
Intensity

a domestic microwave oven operating at 2.45 GHz and at a

tunable power level up to a maximum of 850 W. Within 6–8
min of microwave exposure a good homogeneous melt was 2000

obtained, which was immediately quenched between copper

blocks. The silica crucible was found to remain clean and
1000
unaffected during the short duration of melting. The glass
was annealed in a muffle furnace for 1 h at 200◦ C to remove
thermal strains that could have developed during quenching. 0
The samples were preserved in a sealed desiccator contain- 20 40 60 80
ing CaCl2 . Glass transition temperature (Tg ) of the samples 2
was recorded using differential scanning colorimeter (Perkin
Elmer DSC-2). For the electrical measurements, the annealed Figure 1. XRD spectrum of NBV9 glass.
samples were thoroughly polished and coated with silver
paste on both sides, which serve as electrodes having a thick-
0.2
ness of about 0.1 cm and diameter of about 1 cm were used.
The resistivity of the sample was calculated by applying a Tg
dc field of 2 V and measuring the current through it using a
digital electrometer (ECIL EA-5600). The temperature was
measured using a chromel-alumel thermocouple placed very
Heat flow (mW)

0.0
close to the sample. The measurements were repeated with
changed polarity of the applied voltages. Capacitance (Cp )
and conductance (G) measurements were carried out on a
Hewlett-Packard HP 4192A impedance-gain phase analyzer
from 100 Hz to 10 MHz in the temperature range 323–405 –0.2 50 V2O5
K. A home-built cell assembly (having two terminal capac-
itor configuration and spring-loaded silver electrodes) was 30 V 2O5
used for the measurements. The temperature was controlled 10 V 2O5
using Heatcon (Bangalore 560090, India) temperature con-
troller with an accuracy of ±1 K achieved in the entire range 400 450 500 550 600 650 700 750 800
of measurements. The temperature of the sample was mea- Temperature (K)
sured using Pt-Rh thermocouple positioned very close to the
sample. Figure 2. DSC thermogram of NBV glasses.
 Conductivity in microwave synthesized glasses 987

batches prepared under identical conditions showed agree- 1.5

ment within 5% error and dc conductivity on the same -4
323
343
373

samples in different runs within 2% error. Figure 3 shows -5 423

the variation of log(σ ) as a function of inverse tempera- 1.2

-6

log ( )
ture for highly modified r = 0.111 to 0.428, where r = -7

V2 O5 /Na2 O + B2 O3 and inset of figure 3 for least modi- -8

fied r = 0.538 to 1. The compositions of the glasses investi- 0.9

0.0 0.2 0.4 0.6 0.8 1.0

E dc (eV)
r

gated and their codes are presented in table 1. It is seen from

figure 3 that, the conductivity values lie in the range 1.02 ×
10−7 to 1 × 10−5 S cm−1 for r = 0.111. Also, it is seen 0.6
from figure 3 that all the investigated samples follow Arrhe-
nius law and the solid line represent the linear least square
fits used to obtain the activation energy (Edc ). The values of 0.3
Edc lie in the range of 0.6 to 0.71 eV and figure 4 represents
the variation of Edc with r, its inset represents the variation 0.2 0.4 0.6 0.8 1.0
of log(σ ) with r. Glasses with r = 0.111 to 0.428 show a r
monotonic increase in Edc , then there is a gradual decrease
from r = 0.528 to 1. Activation energies for r = 0.111 Figure 4. Variation of activation energy with mole fraction of
to 0.428 are comparable with alkali borate glasses with low V2 O5 in NBV glass system. Inset: Variation of log(σ ) with mole
fraction of V2 O5 in NBV glass system.
−5
concentrations of TMO.22 It can be seen from figure 4 inset
r = 0.111 that the conductivity shows a deep minimum at r = 0.538.
r = 0.176 This may be due to the crossover from one conduction mech-
−6 r = 0.25
anism to another. The variations seen in dc conductivity are
r = 0.333
r = 0.428 analysed using impedance spectroscopy and EPR studies.
log( ) (S cm )
−1

−7 3.1 Impedance spectroscopy

−5

−6
The impedance spectra of all the investigated glasses depend
−8 −7 considerably on their chemical composition. The character-
log ( ) (S cm )
−1

−8
istic features of these spectra follow the nature of conduction
r = 0.538

−9
r = 0.667
r = 0.819
mechanism. The experimental spectra (complex impedance
r = 1.0
representation) can be classified into three types (i) single
−9 2.4 2.6 2.8 3.0 3.2
−1
1000/T (K )
semicircle with a low frequency spur, (ii) spectra consisting
2.4 2.6 2.8 3.0 3.2 of two depressed semicircles and (iii) single semicircle with-
−1 out spur. The inclined straight line (spur) at the low frequency
1000/T (K )
region could be the effect of mixed electrode and electrolyte
interface. The magnitude of inclination in the straight line is
Figure 3. Variation of log(σ ) with 1000/T for r = 0.111 to 0.428
in NBV glass system. Inset: Variation of log(σ ) with 1000/T for
related to the width of the relaxation time distribution.23
r = 0.538 to 1.0 in NBV glass system. Conductance (G) and capacitance (Cp ) directly measured
from the impedance bridge were used to compute the real and
imaginary parts of impedance. The real and imaginary parts
Table 1. Code, composition and mole fraction of vanadium in
of impedance Z  and Z  were computed using the relations
sodium-boro-vanadate glass system.
given by Ross Macdonald.24 Typical impedance plots (Cole–
Composition (mol%) Mole fraction of Cole plots) are shown in figure 5, which were used for dc
Code Na2 O:B2 O3 :V2 O5 vanadium, r conductivity determination. Values of Z  (bulk resistance)
corresponding to the intersection of low frequency side of the
NBV1 25:25: 50 1.000 high frequency in the formula
NBV2 27.5:27.5:45 0.818
NBV3 30:30:40 0.666 d
σdc = (1)
NBV4 32.5:32.5:35 0.538 RA
NBV5 35:35:30 0.428 where ‘d’ is the thickness of the sample, ‘R’ is the bulk resis-
NBV6 37.5:37.5:25 0.333
tance of the samples and ‘A’ the conducting area of cross-
NBV7 40:40:20 0.250
NBV8 42.5:42.5:15 0.176
section of sample. σdc values lie in the range 1.3 × 10−7 to
NBV9 45:45:10 0.111 1.1 × 10−5 S cm−1 (for r = 0.111). These values are com-
parable with those presented in figure 3. Plots of log(σ )
988 Asha Rajiv et al

electronic component of conductivity due to the disruption

400000
r = 0.176
323 K
of the glass network and increased population of Na+ ions.
331 K
339 K Also a decrease in electronic conductivity is observed when
347 K r decreases from 1 to 0.538, which can be attributed to the
300000 355 K reduction of V5+ to V4+ caused by the increase in Na2 O con-
363 K
371 K tent. The nonlinear variations can be interpreted using ion–
379 K polaron correlation effect. The hopping electron (polaron
−Z"

200000 387 K formed by its capture by a V5+ ) is attracted towards an

oppositely charged Na+ ion. The tendency for such cation–
polaron pairs are to move together as a neutral entity. The
100000 migration of such an entity does not involve any net displace-
ment of electric charge and does not contribute to conductiv-
ity. Eventually, there is an enhanced population of Na+ ions
0 in the network structure compared with trapped polarons.
0 100000 200000 300000 400000 Thus, the cationic conductivity begins to increase. At r =
Z' 0.538, the interaction between electron–cation is maximum,
suggesting a kind of transition from predominantly ‘elec-
Figure 5. Typical Cole–Cole plot for NBV8 glass at different tronic’ to ‘ionic’ conductivity. Hence, r = 0.538 is consid-
temperatures. ered to be the crossover composition. In the present study,
we identified two regimes viz. highly modified ‘ion’ conduct-
ing and less modified ‘electronically’ conducting regimes. As
55000
discussed in the literature, alkali ion transport is character-
ized by high activation barrier.26,27 Further, electronic con-
44000 tribution to conductivity is significant as ionic contribution2
because

33000 σtotal = σionic + σelectronic

−Z''

log σtotal = log (σionic + σelectronic )

  
σelctronic
22000 = log σionic 1 +
σionic
Eionic σelectronic
11000 ≈ log σ0 − +
kT σionic
the ratio σelectronic /σionic varies from glass to glass, since
0 15000 30000 45000 60000 75000 Na+ /[V4+ ] + [V5+ ] = Na+ /Vtotal = rc varies. This ratio
Z' plays a pivotal role in nonlinear variation of conductiv-
ity. A similar trend is also seen in glasses containing both
Figure 6. Typical impedance plot for NBV4 glass at 323 K alkali oxide and TMO’s.28–31 The conductivity reaches min-
temperature. ima when the concentration of TMO is nearly equal to the
concentration of Na2 O. The other possible explanation for
vs. 1000/T for all the investigated glasses follow Arrhenius the observed conductivity is that polaron percolation paths
law, and activation energies (Edc ) for various compositions are blocked by alkali ions in alkali-rich glasses.28,31 More
are calculated using regression analysis. Edc values lie in the importantly, modifier to network former ratio can be effec-
range 0.57 to 0.715 eV and are comparable with the acti- tive if it is a measure of disruption of the glass network. If
vation energies shown in figure 4. Figure 6 shows impedance the ratio is higher, the glass network becomes more poly-
spectra of glass with r = 0.538 showing two de- merized. In such a case the electron conduction paths are
pressed semicircles, characteristic of mixed conduction. For discontinuous.32 In V2 O5 -rich glasses (r > 0.538) con-
r > 0.538 single semicircles without any spur are seen. ductivity increases, while the activation energy decreases
Garbarczyk et al17 reported that the simulated impedance (see figure 4) due to the abundance of vanadium in V4+
spectra characteristic for ion conduction, mixed conduction valance state. This results in higher value of redox ratio
and electronic conduction with the equivalent electrical C = [V4+ ]/[V4+ ] + [V5+ ], which is clearly reflected in EPR
circuits used to generate the spectra. spectra.
As can be seen from figure 4 inset, isothermal conductiv-
ity pass through a minimum at r = 0.538. The presence of 3.2 EPR spectroscopy
characteristic conductivity minimum and Edc maximum is
attributed to the enhanced interactions between polarons and EPR spectra of the investigated glasses are shown in figure 7.
mobile ions.25 At lower r values, there is a reduction in the As can be seen from figure 7, a strong absorption line arises
 Conductivity in microwave synthesized glasses 989

Figure 8. Illustration of transfer of electron from V4+ site to

neighbouring V5+ site.

along the network-former chains, thereby allowing intersti-

tial diffusion of ions. The network-modifying role of Na2 O
Figure 7. EPR spectra obtained at room temperature for NBV
is explained using a simple structural model. B2 O3 –V2 O5
glass system with V2 O5 mol%.
glass is a continuous random network formed by [BO3/2 ]0
and [VOO3/2 ]0 structural units. Boron is three connected and
from the fact that at high V2 O5 content, most of the vana- three coordinated, while vanadium is three connected but
dium ions are in the V4+ state. The absence of hyperfine four coordinated. Structural entities like boroxols that may
structure (hfs) points to interaction between vanadium cen- be present in the structure are not significant for this model.
tres via V4+ –O–V5+ super exchange mechanism. Generally, Therefore, the network consists of B–O–B, B–O–V, V–O–B
such glasses exhibit electronic conductivity.17 However, the and V–O–V linkages depending upon the composition. All
mechanism of conduction in glasses with high concentration oxygen’s, except the oxygen’s in V=O in the glass network,
of V2 O5 has been suggested as the transfer of an electron are bridging oxygens prior to modification. Addition of Na2 O
from V4+ site to a V5+ site. to a borovanadate network breaks the covalent bonds and
Structural groups formed in V2 O5 -rich glasses provide the converts bridging oxygen’s (BO’s) into NBO’s, which of the
path for conduction of electrons.33 The increase of the elec- bridges is broken by the reaction of O2− is dictated by the
tronic conduction with the increase of V2 O5 can be explained local electron affinity for O2− ions. Chemical affinity is con-
considering the decrease in the average distance between the trolled by the electronegativity of the network formers. The
TMI sites. According to Mott’s polaron theory, the dc con- network-modifying action of Na2 O can be explained as:
ductivity rapidly varies with site spacing and redox ratio.
The observed correlation between the mole fraction of alkali
Na2O O 2− + 2Na+
oxide and the appearance of hfs can be justified, taking into
account that two nearest aliovalent vanadium centres can
B2 O3 ≡ 2[BO3/2 ]0 , V2 O5 ≡ 2[VOO3/2 ]0
exchange an electron via bridging oxygen. The least modi-
fied network is characterized by a strongly crosslinked net-
work. In such a network, the conditions for electron hopping 2[BO3/2]0 + O2− 2[BO2/2O] − (2 BO’s and 1 NBO)
via V4+ –O–V5+ bonds are more favourable than highly dis-
rupted network. An illustration of transfer of electron from Similarly,
V4+ site to neighbouring V5+ site is shown in figure 8. At
r = 0.538, the EPR spectra consists of V4+ line with a weak 2[VOO3/2]0 + O2− 2[VOO2/2O] − (3 BO’s and 1 NBO)
but visible superimposed hfs, which indicate the crossover
An illustration of interstitial diffusion of Na+ in the modified
from non-hfs regime to hfs regime. A similar crossover point
glass network is shown in figure 9.
is seen at this composition in the dc conductivity studies.
Further, in highly modified glasses (r = 0.538) low content
of V2 O5 and high content of Na2 O cause the disruption of the 3.3 AC conductivity studies
glass network. As a result cation (Na+ ) transport dominates
the polaronic conduction. In such glass composition, ionic AC conductivities have been measured in the frequency
conduction paths consists of a regular disposition of NBO’s range of 100 Hz to 10 MHz. A typical plot of log(σ ) vs. log(f )
990 Asha Rajiv et al

− −

+ 2Na2O −
−

4[BO3/2]0 4[BO2/2O] –

+ 2Na2O − −

4[VOO3/2]0 4[VOO2/2O] –

−
Boron, Vanadium, Bridging oxygen, Non-bridging oxygen, Sodium ion

Figure 9. Illustration of interstitial diffusion of Na+ in the modified glass network.

−4.5 Where σ (0) is the frequency independent component of

10V2O5 − 90(0.5Na 2O + 0.5B2O3) conductivity, Aωs represent the dissipative contribution to
−4.8
the total conductivity depending on frequency (ω = 2πf ),
−5.1 A is the temperature dependant constant and s the power law
−5.4
exponent. Nonlinear fit, which obeys Almond–West power
law is shown in figure 11a. It has been reported in the liter-
)
−1

−5.7 ature that, better power law fits were obtained using expres-
log( ) (S cm

−6.0
323 K
sion of the type σ (ω) = σ (0) + Aωs1 + Bωs2 , where B is
331 K
339 K a constant, s1 is the freely floated value (= s) and s2 =
−6.3 347 K 1.0.34,35 The double power law fit is shown in figure 11b.
355 K Further, s values have been obtained for all the glass samples
−6.6
363 K
371 K at different temperatures using both two-term power law and
−6.9
379 K three-term power law. The s values lie in the range 0.4 to 0.7
−7.2 387 K and decreases with temperature. The important features of
2 3 4 5 6 7 8 the power law analysis are (i) the two-term power law seems
log(f ) (Hz) to be adequate in fitting the ac conductivity data and (ii) the
values of s are temperature dependent and less than unity.
Figure 10. Variation of log(σ ) with log(f ) for NBV9 glass Although analysis of the power law exponent is limited by an
system. inherent ‘window effect’, the observed power law exponent
remains within the error ±5% and render the window effect
less important than it appears.36
is shown in figure 10 at various temperatures. All the However, in the essentially flat region dominated by ion
samples performed high frequency dispersion and nearly transport appears to still consist of a non-negligible small
flat frequency insensitive conductivities at low frequencies. temperature-dependant contribution from electron transport.
The switchover from the frequency independent region to This may be of the form σe = σe (0) exp (−Ee/kT),
frequency dependent region signs the onset of conductiv- where σe (0) and Ee are the corresponding pre-exponential
ity relaxation, which shifts towards higher frequencies as and activation energy parameters. We have not attempted to
the temperature increases. However, from figure 10, it is analyse this feature any further.
observed that the temperature dependence of the ac conduc-
tivity is much less than that of the dc conductivity. These con-
ductivities have been fitted to the Almond–West type power 3.4 Electrical modulus formalism
law expression34,35
Electrical modulus is an alternative approach to investi-
σ (ω) = σ (0) + Aωs , (2) gate the complex electrical response of materials, which
 Conductivity in microwave synthesized glasses 991

−5.4 0.18
323 K 10V2O5 − 90(0.5Na2O + 0.5B2O3)
339 K 331 K
−5.6 0.15 339 K
347 K
355 K
−5.8 0.12 363 K
log( ) (S cm )
−1

371 K
379 K
−6.0 0.09
387 K

M'
−6.2 0.06

−6.4 0.03

2 3 4 5 6 7 0.00
(a) log(f ) (Hz) 3 4 5 6 7
(a) log(f ) (Hz)
−5.4
10V2O5 − 45Na2O − 45B2O3 343 K
0.030
−5.6 323 K 10V2O5 − 90(0.5Na2O+0.5B2O3)
331 K
0.025 339 K
−5.8 347 K
355 K
0.020 363 K
log

−6.0 371 K
379 K
M''

0.015
387 K
−6.2

0.010
−6.4

0.005
2 3 4 5 6 7
(b)
log f
0.000
Figure 11. (a) Single power law fit (σ (ω) = σ (0) + Aωs ) for 2 3 4 5 6
NBV9 glass system. (b) Double power law fit (σ (ω) = σ (0) + (b) log(f ) (Hz)
Aωs1 + Bωs2 ) for NBV9 glass system.

nullify the electrode polarization effect. The complex elec- Figure 12. (a) Variation of real M  of the electric modulus with
trical modulus M ∗ = M  + J M  where M  and M  are the log(f ). (b) Variation of imaginary M  of the electric modulus with
real and imaginary parts of electrical modulus, respectively.2 log(f ).
The M  and M  are calculated using the relations given by
Koushik Majhi et al.37 Figure 12a represents the variation analysed by using Kohlrausch–William–Watts (KWW)
of M  vs. log(f ). The electrical modulus spectra represent a stretched exponential function.39,40 The approaches of Rao
measure of the distribution of ion energies in the network et al41 and Elliott et al42 were to establish the basis for
stretched exponent (β) in the relation R(t) = R0 e−((t)/τ ) ,
β
structure.2 As seen from figure 12a, at higher frequencies,
M  reaches a maximum constant value and at low frequen- where R(t) and R0 are the magnitudes of an appropriate
cies M  approaches to zero, which indicates that the electrical parameter at times t = t and t = 0, respectively, τ is the
polarization makes a negligible contribution.38 Further, dis- fundamental relaxation time, β is the stretched exponent and
persion between these frequencies is due to the conductivity then to relate β to s through an assumed relation s + β =
relaxation. As seen from figure 12a the spectrum has a sim- 1. In diffusion-controlled relaxation process,40 microscopic
ilar shape at all temperatures with a long tail. This may be relaxation time is modified as a result of interruption by
attributed to the large capacitance associated with the elec- random event which brings about instantaneous relaxation.
trodes. Figure 12b shows the variation of M  vs. log(f ) for Relaxation is assumed to take place in the neighbourhood of
r = 0.176. It is seen from figure 12b that M  peak shifts to a vacancy in a model proposed by Rao et al43 and is inter-
higher frequencies with increase temperature, suggesting the rupted by a sudden arrival of an ion at the vacancy. Both
involvement of temperature-dependent relaxation process in the models lead to the same formal expression and provide
the glasses under the present study. The M  curves retain the a basis for β. The values of β were determined by inter-
same shapes but differ only in peak position and full-width polating the FWHM values of M  peaks into an expanded
at half maximum (FWHM) value. M  vs. log(f ) is generally FWHM vs. β maps generated from the literature.44 β-Values
992 Asha Rajiv et al

lie in the range 0.5 to 0.6 and are almost temperature and r = 0.111 to 0.428 for a given range of temperatures.49,50
composition insensitive, indicating that ion–ion interactions The reduced plots of conductivity (log(σ/σ (0))) vs. fre-
are independent of temperature and composition.45,46 The quency (log(f/f0 )) are shown in figure 14 and the data
relaxation time characterizing the motion of an ion between points were scaled on to one master curve. It is seen from
equivalent positions is τ = τ0 eEac /kT , where τ0 is the pre- figures 13 and 14 that, the conductivity and dielectric
experimental time, Eac the ac activation energy and, k the relaxation data collapse excellently for the given range of
Boltzmann constant. The relaxation time values, τ , symmet- temperatures. This suggests that the dynamical processes are
rically shift to higher values as the temperature increases temperature independent and good time–temperature super-
(see figure 12b). The conductivity relaxation frequency ωc position, indicating common ion transport mechanism in the

corresponding to the peak (Mmax ) gives the characteristic highly modified glasses.51
relaxation time by the condition ωc τc = 1.47,48 The activa-
tion energy (Eac ) involved in the relaxation process of ions
was calculated using temperature-dependent relaxation fre-
quency. The values of Eac lie in the range 0.61 to 0.705 eV 4. Conclusion
and found to be comparable with Edc . Figure 13 shows the
variation of M  /Mmax

vs. log(f/f0 ) at different tempera- The investigated glasses showed a nonlinear variation of
tures. It is seen from figure 13, the superimposibility of the electrical conductivity when ‘electronically active’ oxide
above variation at different temperatures are very good, sug- (V2 O5 ) was substituted by the ‘ionically active’ network
gesting a common relaxation mechanism in the glasses with modifier (Na2 O). Isothermal variation of dc conductivity as
a function of V2 O5 mole fraction (r = v2 Os /Na2 O + B2 Os )
passes through a minimum conductivity, wherein the con-
duction mechanism follows a crossover from ‘ionic’ to ‘elec-
tronic’. Conductivity is predominantly ionic when r lies
between 0.111 and 0.428, at r = 0.538 shows a minimum
conductivity, where the transition from ionic to electronic
occurs and for r >0.538 electron transfer via aliovalent V4+
–O –V5+ is more favourable. AC conductivity and electri-
cal modulus formalism studies have been carried out for
highly modified glasses (r = 0.111 to 0.428). Further, the
ionic conductivity is analysed using Almond–West power
law and KWW–stretched exponential function. The electrical
modulus approach has been used to investigate the com-
plex electrical response. Electrical modulus spectra reveals:
(1) dispersion of M  over a range of frequencies is due to
the conductivity relaxation, (2) M  peak shifts for higher
frequencies with increase in temperature, suggesting the
involvement of temperature-dependent relaxation process
and (3) values of activation energies involved in the relax-
  ation process lie in the range 0.61 to 0.705 eV and are
Figure 13. Variation of M  /Mmax
 with log(f/f0 ).
comparable to activation energy Edc .
10V2O5 − 90(0.5Na 2O + 0.5B 2O 3)
−0.08

323 K Acknowledgements
−0.06 331 K
339 K
347 K We are grateful to Professor KJ Rao, Solid State and Struc-
−0.04 355 K tural Chemistry Unit, Indian Institute of Science, Bangalore,
363 K
371 K for his encouragement and many helpful discussions. We
−0.02 379 K also thank Jain University, Bangalore, for providing financial
387 K
assistance to carry out this work.
0.00

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