Materials Chemistry and Physics 89 (2005) 428–437

Structure and ionic transport studies of sodium borophosphate

glassy system
P.S. Anantha, K. Hariharan∗
Department of Physics, Solid State Ionics Laboratory, Indian Institute of Technology Madras, Chennai 600036, India

Received 12 July 2004; received in revised form 15 September 2004; accepted 30 September 2004

Abstract

Sodium borophosphate glasses of composition (mol%) 50Na2 O–50[xB2 O3 –(1−x)P2 O5 ], 0 ≤ x ≤ 0.8 have been prepared by melt quenching
method and characterized through XRD, DSC, FTIR and impedance spectroscopy techniques. The glass transition temperature increases with
the substitution of B2 O3 due to the cross-linking of the network and the FTIR study shows the presence of different structural units in the
network. The ionic conductivity study as a function of composition of B2 O3 shows increment in conductivity with two conductivity maxima at
10 and 30 mol% of B2 O3 and conductivity variations with temperature follow an Arrhenius type behaviour. Transport numbers evaluated for
ions and electrons show that Na+ ions are the mobile species in the investigated systems. The frequency dependence of the electric conductivity
follows a simple power law feature. The analysis of various electrical parameters as a function of temperature in different complex planes
shows that the charge transport occurs by the hopping mechanism.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Glasses; Glass transitions; Electrical conductivity

1. Introduction addition of another glass former oxide such as B2 O3 [3–6].

Fast ion conducting glasses have been extensively studied
due to their potential applications in solid-state ionic devices.
For practical use, these glasses must have high ionic conduc-
tivity as well as thermal and electrochemical stability. Sodium
ion conducting borate glasses [1] have been investigated as
they were considered as potential candidates for solid-state
batteries. Sodium phosphate glasses [2] are reported to have
high thermal expansion coefficient and electrical conductivity
with low glass transition temperature as compared to sodium
borate glass. However, their poor chemical durability to wa-
ter limits their practical use. Sodium metaphosphate glass
is composed of phosphate chains and cross-linking these
chains, either by decreasing the modifier to phosphorus ratio
or by adding another glass former oxide significantly changes
the glass properties. Earlier studies indicate that the chemi-
cal durability of phosphate glasses can be improved by the
∗ Corresponding author. Tel.: +91 44 22578667; fax: +91 44 22578651.
E-mail address: haran@iitm.ac.in (K. Hariharan).
In general, the competitive network formation by two net-
work formers is expected to enhance the cationic diffusion
that shows promising characteristics such as high ionic con-
ductivity along with good thermal stability [7–8]. In this con-
text, the present work is directed towards the preparation and
electrical characterization of sodium borophosphate glasses
of the composition (mol%) 50Na2 O–50[xB2 O3 –(1−x)P2 O5 ]
in which P2 O5 of sodium phosphate system is progressively
replaced by B2 O3 .
2. Experimental
Sodium borophosphate glasses of composition (mol%)
50Na2 O–50[xB2 O3 –(1−x)P2 O5 ], 0 ≤ x ≤ 0.8, were prepared
using analytical grade Na2 CO3 , (NH4 )H2 PO4 and B2 O3
reagents as starting materials. The raw materials were
weighed to the desired composition and the mixture was
heated in a platinum crucible first at 600 ◦ C for 1 h to re-
move the volatile products and then melted at 900–1050 ◦ C

0254-0584/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2004.09.029
 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437 429

depending upon the composition for about 2 h with frequent Table 1

stirring to ensure the homogeneity. The melt was then rapidly Glass transition temperature, density and molar volume of (mol%)
50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ] glasses
quenched on to a polished copper mould in air at 120 ◦ C to
avoid shattering of the quenched samples due to thermal stress Composition Tg (◦ C) Density (g/cc) Molar volume (cc)
x (±1.0) (±0.003)
and the samples were annealed well below the glass transi-
tion temperature for about 6 h. Weight loss measurements on 0 284 2.505 40.70 ± 0.05
0.2 332 2.516 37.65 ± 0.05
melting show that the loss was found to be less than 2% for 0.34 359 2.539 35.40 ± 0.04
all compositions. The sodium content was checked through 0.5 412 2.550 32.89 ± 0.04
flame photometry and the error was found to be around 2%. 0.6 422 2.548 31.50 ± 0.04
All the samples were analysed by X-ray diffraction with Cu 0.8 444 2.524 28.94 ± 0.03
K␣ radiation. The glass transition temperature, Tg , was de-
termined using Differential Scanning Calorimetry from room initially up to x = 0.5 after which it decreases; whereas, the
temperature to 500 ◦ C with a heating rate of 10 ◦ C per minute. molar volume decreases almost linearly with composition.
Density measurements were carried out by the fluid displace- The increase in density indicates that the macromolecular
ment method in xylene at room temperature using a balance of structure becomes increasingly more rigid with the substi-
10−4 g sensitivity. Infrared absorption spectra were recorded tution of B2 O3 . DSC curves of selected compositions are
on a FT-IR spectrometer in the 1500–400 cm−1 range using shown in Fig. 1. The glass transition temperature, Tg , in-
pellets made with KBr and finely ground glass powder in a creases non-linearly with the substitution of B2 O3 (Table 1).
20:1 ratio by weight. In an oxide network, Tg is known to depend upon the packing
For electrical conductivity measurements, 1–2 mm thick in the network and hence the rapid increase of glass transi-
bulk glass samples were polished and the flat surfaces were tion temperature in the borophosphate glasses can be related
coated with silver paint to form the electrodes. The sam- to the cross-linking of the network thus providing better ther-
ples were then placed under vacuum in a conductivity cell mal stability for the mixed former glass. Thus, the variation
between two silver discs and the temperature of the sample in Tg with composition can be attributed to the tightness of
was monitored using a chromel–alumel thermocouple posi- packing in the network.
tioned very close to the sample with an accuracy of ±1 ◦ C.
The conductivity of the sample was measured at various 3.2. FTIR studies
temperatures by impedance spectroscopy using a HP 4192A
impedance analyser in the frequency range 5 Hz–13 MHz. The FTIR spectra of the glass samples corresponding to
The electronic contribution to the measured total conductiv- the different compositions are shown in Fig. 2. The posi-
ity has been carried out by dc polarization technique using a
cell of the configuration Ag|glass electrolyte|Ag. A constant
voltage was applied to polarize the cell using millivolt source
and an electrometer was employed to measure the resulting
current as a function of time. A galvanic cell of configuration
Na|glass electrolyte|NaCoO2 was constructed to study the
nature of ion transport. The cathode material, NaCoO2 was
prepared by solid-state reaction route from stoichiometric
amount of Na2 CO3 and Co3 O4 [9]. The material was charac-
terized through XRD and the resulting open circuit voltage of
the galvanic cell was measured using a high input impedance
electrometer.

3. Results and discussion

3.1. XRD, DSC and density studies

All glasses of the composition (mol%) 50Na2 O–

50[xB2 O3 –(1−x)P2 O5 ] were transparent and colourless. The
amorphous nature of the prepared glasses was confirmed us-
ing XRD and the glass-forming region (0 ≤ x ≤ 0.8) has been
identified. Also, the hygroscopic nature of the sodium phos-
phate glass has been considerably reduced on the addition of
B2 O3 in the network. The density and molar volume values Fig. 1. DSC spectra of glasses in the system of composition (mol%)
of the glasses are tabulated in Table 1. The density increases 50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ].
430 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437

524 cm−1 [12]. As phosphate is replaced by glass-forming

Fig. 2. Infrared spectra of (mol%) 50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ]
glasses.
tions and assignments of the absorption bands of glasses
are summarised in Table 2. Assignments of various peaks
in the spectra have been made on the basis of literature
reports [10–16]. The sodium metaphosphate (x = 0) glass
is characterized by a strong broad absorption band around
1277 cm−1 which is attributed to P O asymmetric stretching
vibrational mode. The weak band at 1155 cm−1 has been as-
signed to the symmetric stretching modes (PO2 ) of metaphos-
phate chains [11]. The strong band at 1094 cm−1 is attributed
to asymmetric stretching of PO3 − groups in PO4 3− units.
The weak band at 1019 cm−1 is assigned to the symmetric
stretching mode of (PO3 ) units. The band at 883 cm−1 is at-
tributed to the asymmetric stretching of P–O–P groups which
confirms the chain structure of metaphosphate glasses. The
broad band at 769 cm−1 may be attributed to the symmet-
ric stretching vibration of P–O–P rings. The bending vibra-
tion (δ) of P–O bands are characterized by a broad band at
B2 O3 , new structural groups will result, in which the coor-
dination number of boron is 4. When P2 O5 is replaced with
B2 O3 (for x = 0.2), some new bands are observed around 700
and 776 cm−1 . The bands in the region of 700 cm−1 can be
assigned to the bond-bending vibration of B–O–B linkages
in the borate network. [13]. The small sharp band appear-
ing at 776 cm−1 is characteristic of the borate glass matrix
and can be attributed to different four-fold coordinated bo-
rate groups such as triborate, ditriborate and diborate groups
[14]. The bands appearing in the region 860–1100 cm−1 are
due to B–O bond stretching of tetrahedral BO4 units which
are overlapped with phosphate bands. These bands are as-
signed to the vibration of tetraborate (triborate and pentab-
orate) groups of BO4 units [14,15]. The bands appearing in
the region 1150–1450 cm−1 are attributed to the B–O bond
stretching of trigonal BO3 units [14,16]. The fact that the band
at 1250 cm−1 is still observed at high alkali oxide, where no
boroxol rings are present, indicates that tetraborate groups
should also contribute to the absorption. This group proba-
bly consists of PO4 and BO4 units to form BPO4 by sharing
the negative charge supplied by the oxygen of the modifier
[17]. The phosphate units, which progressively disappear as
B2 O3 content increases, bridge the borate groups. At high
B2 O3 content (x > 0.5), the bonds in the 800–1100 cm−1 re-
gion gets merged into a single band and finally for x = 0.8, a
broad band appears in the region 900–1100 cm−1 . This fea-
ture indicates that the glasses with x > 0.5 are borate rich
glasses. A detailed characterization could not be done be-
cause it is expected that the presence of more than one glass
former greatly increases the number of structural units of
a glass. However, the infrared studies of the investigated
systems suggest that the appearance of new (partially re-
solved) bands are consistent with the presence of new borate
or borophosphate units and the phosphate units bridging the
borate groups.
3.3. Conductivity studies
3.3.1. Conductivity as a function of concentration
To investigate the conduction characteristics, the
impedance and phase angle of the samples of different com-
positions have been measured as a function of frequency.

Table 2
Assignments of Infrared spectra peaks of (mol%) 50 Na2 O–50[xB2 O3 –(1 − x)P2 O5 ] glasses
Attribution x=0 x = 0.2 x = 0.34 x = 0.5 x = 0.6 x = 0.8 Reference
Bending vibration (δ) of P–O–P bands 524 524 540 545 541 520 12
νs of P–O–P bands 769 776 758 777 769 775 10–12
νa of P–O–P bands 883 904 914 852 835 852 10–12
νs of PO4 groups 1019 1015 1020 10–12
νa of PO4 groups 1094 1092 1097 10–12
νa of PO2 groups 1277 10–12
B–O–B bending vibration bands 720 702 688 702 13
B–O stretching bands of BO4 units 860–1100 860–1100 850–1100 860–1100 880–1100 14, 15
B–O stretching bands of BO3 units 1248–1391 1173–1384 1240–1385 1357–1380 1183–1385 14, 16
 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437
Fig. 3. Variation of conductivity of (mol%) 50Na2 O–50[xB2 O3 –(1 −
x)P2 O5 ] glasses as a function of B2 O3 /B2 O3 + P2 O5 . Inset: complex
impedance plots in the system 50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ] at 200
◦ C.
These values were used to obtain the real (Z ) and imagi-
nary (Z ) parts of the complex impedance and were plot-
ted on a complex plane. The above plots were analysed
using ‘EQUIVCRT’ non-linear least squares fitting pro-
gram [18] to obtain the bulk resistance. Knowing the bulk
resistance and cell constant, conductivity has been calcu-
lated for various compositions. Fig. 3 shows the composi-
tional dependence of electrical conductivity at 473 K for the
glassy system. The inset of the figure shows the complex
impedance plots from which the conductivity has been eval-
uated. As P2 O5 is progressively replaced by B2 O3 , conduc-
tivity in general increases showing two maxima at 10 and
30 mol% of B2 O3 (B2 O3 /B2 O3 + P2 O5 ratio = 0.2 and 0.6,
respectively). Similar conductivity variation has been ob-
served in other mixed former glasses [4–7]. The two con-
ductivity maxima have been qualitatively explained through
the thermodynamic activity enhancement of the dissociat-
ing salt [19,20]. As per weak electrolyte model [21], the
enhancement of conductivity is due to Na2 O activity vari-
ations. The observed conductivity variation can be related
to the formation of different structural units of investigated
system. The structure of pure vitreous B2 O3 consists of a
random network of boroxol rings and BO3 triangles con-
nected by B–O–B linkages through bridging oxygen atoms
[13]. When this type of vitreous B2 O3 is added to metaphos-
phate glass, B2 O3 is expected to induce the shortening of
the metaphosphate chain length. The borate groups mainly
in the BO4 tetrahedra form, in which B is coordinated to
431
four oxygens in a covalently bonded network used as branch-
ing units between metaphosphate chains, with the forma-
tion of more cross-linked networks such as borophosphate
groups. The borophosphate ‘BPO4 ’ unit is made by corner-
sharing PO4 and BO4 tetrahedra [17], which increases the
reticulation of the network. The formation of BPO4 net-
works in the present system makes the glass heterogeneous
and could produce a weak binding area around the struc-
ture of BPO4 favouring the easy migration of Na+ ions [5].
Thus, the first conductivity maxima (x = 0.2) may be due to
the formation of BPO4 groups. At high borate concentra-
tion, the mixed former glass can be considered as borate
like glass and the observed second conductivity maximum
around x = 0.6 has been attributed to the strong interaction
of Na+ ions with BO4 groups. The observed non-linear con-
ductivity behaviour in the present system as a function of
B2 O3 /B2 O3 + P2 O5 ratio depends on the bonding between
Na+ ions and PO4 groups, Na+ ions and some type of BPO4
groups and Na+ ions and BO4 groups. Also an analysis of the
literature [4] indicates that mixtures of trivalent and pentava-
lent glass formers may give glass networks, which enhance
the conductivity. If more than one glass former is present,
the weak electrolyte model [21] predicts that the conduc-
tivity goes through a maximum when another progressively
substitutes an anion of the one former. Similar observations
have been reported by other workers in several mixed for-
mer systems such as (P2 O5 + V2 O5 ) [7] and (P2 O5 + TeO2 )
[22].
3.3.2. Conductivity as a function of temperature
In general the cationic conductivity is given by
σ = neµ (1)
where n is the number of mobile ions per unit volume and µ
is the mobility. Both are temperature dependent. Hence, the
temperature dependence of number of mobile ions per unit
volume in a mixed former sodium borophosphate glass can
be explained through thermodynamical activity of sodium
oxide as follows. In sodium borophosphate glass, the net-
work modifier Na2 O, in the presence of network former mix-
ture (P2 O5 + B2 O3 ), dissociates according to the dissociation
equilibrium,
Na2 O ⇔ Na+ + (ONa)− (2)
In this glass, sodium cationic concentration (N) is high
and it has been evaluated using density values. It is
found to vary between 1.48 × 1022 atoms cm−3 (x = 0) and
2.08 × 1022 atoms cm−3 (x = 0.8). The sodium ions can be
considered to be close enough for a cation to leave its normal
site to occupy an already occupied neighbouring site to form
an interstitial pair. This facilitates a resident sodium cation
(dissociated as per Eq. (2)) to leave its normal position in
order to accommodate the incoming cation. Hence, the coop-
erative motion of this pair of ions in the glass network [21]
and thereby contributing to the cationic conductivity as given
432 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437

by [8]



Ne2 l2 ν0 GF Gm
σ= exp − exp − (3)
6kT 2kT kT
where l is the jump distance between two adjacent sites,
ν0 the attempt frequency, GF = Hf − TSf the free en-
thalpy associated with the formation of an interstitial pair,
Gm = Hm − TSm the free enthalpy associated with the
migration of cations, Hm is the height of the potential barrier
between two sites and other terms have their usual meaning.
The above equation (Eq. (3)) can be simplified as


Ea
σT = σ0 exp − (4)
kT
with


Ne2 l2 ν0 1/2Sf + Sm
σ0 = exp (5)
6k 2
and
Hf
Ea = + Hm
2
In the present work, the conductivity of the glassy system
has been found to obey the Arrhenius relation below the glass
transition temperature as given by Eq. (4). Fig. 4 shows the
variation of log σT versus 103 /T for these glasses and all the
curves has been fitted linearly with a correlation coefficient of
r = 0.993 ± 0.004. The evaluated conduction parameters are
summarised in Table 3. The values of the pre-exponential fac-
tor are almost constant with a mean value of log σ 0 = 5.6 ± 0.3
and hence the observed conductivity variations are closely re-
lated to the activation energy Ea .
In our case, assuming a homogenous distribution of
sodium cations in the glass, the mean jump distance of two
adjacent alkali ion sites is related to alkali ion concentration
as l = (1/N)1/3 . The ionic jump frequency υ0 , estimated from
the far-infrared absorption [23] varies between 0.3 × 1013
and 1.5 × 1013 Hz in different oxide glasses. Taking the mean
value of 1013 Hz for the jump frequency and neglecting the
entropy term, the value of σ 0 has been estimated for each
composition, which is in reasonable agreement with the ex-
perimental data as summarised in Table 3. The calculated
value is slightly lower than the experimental one and the dif-
ferences can be attributed to the entropy contribution, which
has not been taken into account in the calculation of σ 0 . The
(6)
Fig. 4. Arrhenius plots for the glasses in the system (mol%)
50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ].
above results justify the interstitial pair migration mecha-
nism of alkali ions and the migration processes are purely
enthalpic.
3.4. Transport number
The contribution from the electrons to the total measured
conductivity of the samples was investigated using dc polar-
ization method. For this method, two of the best conducting
systems were polarized using two non-reversible [24] sil-
ver electrodes. An electric potential of 200 mV was applied
at 240 ◦ C on a cell arrangement (+) Ag|glass electrolyte|Ag
(−) and the resulting currents were measured as a function
of time. On application of a dc potential across the sample,
an initial current value of 80.4 ␮A, appeared which was pro-
portional to the applied field. It is known that with silver
reversible electrodes, there is a possibility of Ag+ ion migrat-
ing in the glass [25]. However, after three days, the migration
of ions due to the applied electric field is balanced by diffu-

Table 3
Conductivity data of (mol%) 50Na2 O–50[xB2 O3 –(1 − x)P2 O5 ] glasses
B2 O3 x Conductivity σ 200 ◦ C Activation energy Experimental σ 0 Calculated σ 0
(mol%) (S cm−1 ) (±0.5%) Ea (eV) (±0.01) (S cm−1 K) (±0.01) (S cm−1 K)
0 2.38 × 10−6 0.79 5.76 4.88
0.2 1.11 × 10−5 0.72 5.48 4.89
0.34 6.17 × 10−6 0.76 5.6 4.90
0.5 9.46 × 10−6 0.73 5.87 4.91
0.6 1.63 × 10−5 0.68 5.27 4.92
0.8 8.54 × 10−6 0.76 5.77 4.94
 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437
Fig. 5. Complex impedance plots for (mol%) 50Na2 O–10B2 O3 –40P2 O5
glass at various temperatures.
sion due to the concentration gradient and hence the cell gets
completely polarized with a steady-state current of 0.3 ␮A,
which is nearly three orders lower than the initial value. The
ratio of final steady-state current to the initial value gives the
electronic transference number and in the present case, it was
found to be negligible.
In order to study the mobile species responsible for the
conduction features, a galvanic cell of configuration Na|glass
electrolyte|NaCoO2 was constructed and the open circuit
voltage was measured using an electrometer. Sodium is dis-
solved at the anode as Na+ ions, which are transported through
glassy electrolyte to the cathode where they are inserted into
the cathode material. The electrochemical reaction of the gal-
vanic cell as a whole is as follows:
charge
NaCoO2
Na1−x CoO2 + xNa+
discharge
An open circuit voltage of 2.7 V at 300 K was obtained for
the above fabricated cell. The above value is comparable to
the theoretical voltage 2.8 V reported for the Na|NaCoO2
couple [26]. This shows that the charge transport in the
sodium borophosphate glasses is mainly due to Na+ ions.
3.5. AC conductivity studies
Electrical impedance or admittance measurements are
used to study ionic conduction in solids because they enable
the assessment of ionic conductivity and its dependence on
a variety of materials characteristics. Fig. 5 shows the com-
plex impedance plot of a typical composition of the glass
50Na2 O–10B2 O3 –40P2 O5 at various temperatures. As the
temperature increases, the radius of the semi-circular arc cor-
responding to the bulk resistance of the sample decreases
433
Fig. 6. Plots of ac conductivity σ(ω) as a function of frequency for (mol%)
50Na2 O–10B2 O3 –40P2 O5 .
indicating an activated conduction mechanism and the bulk
relaxation shifts to higher frequencies. The inclined small
vertical spikes at the low frequency region of the impedance
plots can be attributed to the electrode polarization [27]. All
the semi-circles are found to be depressed with their cen-
ters below the real axis and the amount of inclination in the
straight line is related to the width of the distribution of re-
laxation time. These results indicate the characteristics of
parallel combination of bulk resistance, capacitance and a
constant phase element (CPE) of the sample to model the
bulk response [28].
The frequency dependent conductivity (σ(ω)) data ob-
tained at various temperatures are shown in Fig. 6. The con-
(7)
ductivity is found to be almost frequency independent in
low frequency region. The dc conductivity has been obtained
from the extrapolation of the frequency independent plateau
region. In the high frequency region, conductivity disper-
sion has been observed. According to the jump relaxation
model [29], the high frequency dispersion arises due to the
high probability for the correlated forward–backward hop-
ping along with the relaxation of the dynamic cage potential.
The high frequency dispersion is predominant at lower tem-
peratures and the dispersion shifts to higher frequency region
with the increase of temperature. The phenomena of the con-
ductivity dispersion in the high frequency region has been
analysed using the Jonscher’s power law [30] feature
σ(ω) = σ(0) + Aωn (8)
where σ(0) is the frequency independent dc conductivity of
the sample, A the weakly temperature dependent quantity
434 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437

Table 4
Fitting parameters of ac conductivity data to Eq. (8)
Temperature (K) n A (S cm−1 rad−n )
483 0.51 7.79 × 10−10
473 0.52 7.0 × 10−10
463 0.53 5.11 × 10−10
453 0.55 3.9 × 10−10
443 0.56 3.41 × 10−10
433 0.59 2.32 × 10−10
423 0.63 1.26 × 10−10

and n is the power law exponent which lies in the range

0 < n < 1.
In the present work, dc conductivity σ(0) has been ex-
tracted from the frequency independent plateau of log σ(ω)
versus log f plot. The values A and n have been varied simul-
taneously to get the best fits of the measured data to Eq. (8).
The parameters obtained by fitting are tabulated in Table 4.
The fitted curves represented by the solid lines in the figure
show reasonably good agreement between experimental and
calculated values.
Fig. 8. Plot of log ε vs. log f at different temperatures for the glass compo-
3.6. Dielectric analysis sition (mol%) 50Na2 O–10B2 O3 –40P2 O5 .

In order to understand the relevance of dielectric spectra
in the present work, the impedance data were converted into
permittivity using the relationship
1
ε∗ = = ε − jε (9)
jωC0 Z∗
where C0 = Aε0 /d, ε0 is the permittivity of free space and ω
is the angular frequency of measurement. Typical plots ex-
hibiting the variation of log(ε ) and log(ε ) as a function of
frequency are shown in Figs. 7 and 8 at different tempera-
tures. The observed variation in ε at lower frequencies could
be attributed to the formation of a space charge region at the
electrode and electrolyte interface. In log ε plot, at higher
Fig. 7. Plot of log ε vs. log f at different temperatures for the glass compo-
sition (mol%) 50Na2 O–10B2 O3 –40P2 O5 .
frequencies, due to rapid reversal of field at the interface,
the contribution of charge carriers towards the dielectric con-
stant decreases with increasing frequency. Finally, ε gets sat-
urated with a constant value of ε∞ (∼10). In ionic conducting
materials, the conduction losses depend on dc conductivity
according to the relation
σ(0)
εσ(0) = (10)
ωε0
In the present case, the conduction losses predominate
at lower frequencies and hence the imaginary part of
permittivity ε shows 1/ω dependence on frequency at all
temperatures. Also ε is found to increase with increase in
temperature. However, the plot of log ε versus frequency
does not exhibit any peak and hence it is difficult to draw any
information regarding the dielectric loss peak frequency. But
for high conducting materials it is difficult to subtract the
dc conductivity effect from the total dielectric loss data with
sufficient accuracy. Therefore, the data were converted into
modulus formalism. It has an advantage that it suppresses
the information about electrode effects [27] and can be used
to study conductivity relaxation [31].
In the present work, the impedance data were converted
into electrical modulus using the relationship
1
M∗ = = jωC0 Z∗ = M  + jM  (11)
ε∗
Figs. 9 and 10 show the frequency dependence of real and
imaginary parts of the modulus spectra, respectively, at dif-
ferent temperatures. The real part of the electric modulus
M exhibits very small values at lower frequencies indicating
that electrode polarization makes negligible contribution to
M* [27]. The observed dispersion in M at lower frequen-
 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437
Fig. 9. Variation of real part of modulus M with frequency for (mol%)
50Na2 O–10B2 O3 –40P2 O5 at various temperatures.
cies can be associated with the ease of migration of the con-
ducting ions or in other words the dispersion is mainly due
to conductivity relaxation. As the frequency of the applied
field is increased, M reaches a constant value M∞ (=1/ε∞ ) at
higher frequencies. The imaginary part of the electric mod-
Fig. 10. Variation of imaginary part of modulus M with frequency for
(mol%) 50Na2 O–10B2 O3 –40P2 O5 at various temperatures. Inset: Arrhenius
plot of the peak frequencies fM .
435
Fig. 11. Plots of normalised (M /M max ) vs. log(f/fM ) for (mol%)
50Na2 O–10B2 O3 –40P2 O5 .
ulus, M , exhibits a low value at lower frequencies which
might be due to the large value of capacitance associated
with the electrodes. The M plot shows a slightly asymmet-
ric peak at each temperature. As the temperature increases,
the peak position shifts to higher frequencies and the fre-
quency corresponding to maximum M is known as relax-
ation frequency fM . The peaks are asymmetric on both sides
of the maxima and the peak height decreases with temper-
ature. The frequency range on the lower side of the peak
frequency fM determines the range in which charge carriers
are mobile over long distances. At the frequency range above
fM , the carriers are spatially confined to their potential wells
[32]. Thus, the peak frequency fM is indicative of transition
from long range to short range mobility and is defined by
the condition 2πfM τ M = 1 [33], where τ M is the conductivity
relaxation time. The inset of Fig. 10 shows the temperature
dependence of relaxation frequency following an Arrhenius
relation fM = f0 exp(−EM /kT) where EM is the activation en-
ergy for the electrical relaxation. In the present work, an ac-
tivation energy of 0.73 ± 0.01 eV has been obtained. This
value is close to the value of activation energy from dc con-
ductivity indicating that the ionic migration is responsible
for the observed dc conductivity and modulus spectrum. The
similarity of dc activation energy and conductivity relaxation
activation energy is the evidence of ionic-hopping mecha-
nism for transport. Fig. 11 shows the normalised plots of
(M /M max ) versus log(f/fM ) at different temperatures which
are found to overlap on a single master curve indicating
that the distribution of relaxation time is independent of
temperature.
436 P.S. Anantha, K. Hariharan / Materials Chemistry and Physics 89 (2005) 428–437

electrical conductivity shows two maxima with the substitu-

tion of B2 O3 . The observed variation in conductivity has been
explained through available structural reports and interstitial
pair migration mechanism. Transport number measurements
show that Na+ ions are the mobile species in the investigated
systems. The Jonscher’s universal power law is used to anal-
yse the ac conductivity data. The correlation between the
activation energies calculated through the analysis of dc con-
ductivity data and different complex plane data shows that
the transport in the investigated systems is through hopping
mechanism.

Acknowledgements

The financial support received from the Department of

Science and Technology (DST), India, in the form of a spon-
sored project is gratefully acknowledged.

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