Journal of Molecular Structure 1086 (2015) 239245

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Effect of intermediate oxide (Y2O3) on thermal, structural and optical

properties of lithium borosilicate glasses
Satwinder Singh, Gaurav Kalia, K. Singh
School of Physics & Materials Science, Thapar University, Patiala 147004, India

h i g h l i g h t s
 Phase separation observed in glasses with modier and intermediate oxides.
 Higher concentration of Y2O3 prevents the glass formation.
 Glass transition temperature and Urbach energy exhibited non-linear variation.

a r t i c l e

i n f o

Article history:
Received 1 December 2014
Received in revised form 15 January 2015
Accepted 17 January 2015
Available online 24 January 2015
Keywords:
Lithium borosillicates
Glass-ceramics
Phase separation
Optical properties

a b s t r a c t
Glass and glass ceramic samples with composition 55SiO230B2O3(x)Li2O(15  x)Y2O3, where x = 0, 5,
10, 15 are prepared by conventional melt-quench technique. The structural, physical, thermal, optical,
mechanical and conducting properties of these glasses are studied using X-ray diffraction (XRD), Differential Thermal Analyzer (DTA), Fourier Transform Infrared spectroscopy (FTIR), UVvisible spectroscopy
and Impedance spectroscopy. Theoretical elastic moduli are calculated for the better understanding of
the glass network strength. All samples, except with x = 0 glass, are amorphous in nature. Two broad
halos are observed in x = 5 and x = 10 glasses, indicating phase separation in these glasses. Optical band
gap of the samples decreases with increasing Y2O3 content. The lowest band gap is observed 3.60 eV for
x = 15 glass. Urbach energy increased with an increase in Y2O3 concentration. Y2O3 played different roles
at different concentrations and enhanced the phase separation tendency in glass. The typical conductivity
was observed 106 S/cm at 620 C for x = 10 glass.
2015 Elsevier B.V. All rights reserved.

Introduction
Glasses containing two alkali metal oxides exhibit unusual nonlinear variation in properties such as density, molar volume, viscosity etc. Similarly, the presence of B2O3 glass former along with
SiO2, in the glass composition, decreases the characteristic temperatures of the glass with systematic replacement of SiO2 by B2O3.
Glasses containing both the formers have been widely used for
optical lenses with high refractive indices and low dispersion. Hexagonal structured oxides such as Y2O3 and La2O3 mixed with alkali
oxides in the glass composition, improve their mechanical, thermophysical and chemical properties [13]. Such glasses have been
proven to be highly efcient luminescence materials and have
applications in photonic, optic and biomedical elds. Glasses based
on heavy metal oxides like Y2O3, have been an area of special interest. This is because of their characteristic structural and physical
Corresponding author.
E-mail address: kusingh@thapar.edu (K. Singh).
http://dx.doi.org/10.1016/j.molstruc.2015.01.031
0022-2860/ 2015 Elsevier B.V. All rights reserved.

properties, such as high refractive index, high thermal expansion,

high density, low transformation temperature and excellent infrared transmission. Moreover, they can be used as shielding materials for nuclear waste. In our earlier research work, it was found
that Y2O3 usually increases the thermal stability of the glasses
[4]. On the other hand, Li2O acts as a strong glass modier. Hence,
it reduces the glass transition temperature and affects other properties of glasses [5,6]. However, the actual role played by any
constituent oxide depends on its amount and distribution in the
network and also on the residual composition of the glass [7].
The glass and glass ceramics has complex structure, which depends
on a number of factors including processing technique, initial composition, role played by the constituents, etc. The addition of Li2O
at the cost of glass formers leads to the creation of non-bridging
oxygens (NBOs). Creation of NBOs causes the formation of different
structural units in the parent glass network and results in change
in the structural and optical properties. In addition, glass network
modication leads to the change in the rigidity of the glass and
glass ceramics. Rigidity of the network is actually dependent on

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S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

the average bond dissociation energies of the constituent bonds.

More energy is required to dissociate a bond, more rigid will be
the structure. The rigidity or strength of the network affects optical, thermal and structural properties. Generally, glasses with more
NBOs have a weak glass structure and exhibit low glass transition
temperatures (Tg) and low optical band gap [8]. Moreover, the
replacement of Li2O with Y2O3 is expected to modify the B2O3 glass
network than SiO2 due to its proximity with B2O3 structurally. In
addition to this, the replacement of Li2O by Y2O3 increases the
thermal stability and prevents the devitrication of glass due to
formation of strong bonds with oxygen. Therefore, it is worthwhile
to investigate various properties of glass by systematic replacement of Li2O (modier) with intermediate oxides (Y2O3), which
can act as modier and glass former depending on glass
compositions.
In the present investigation, the effect of Y2O3 on structural,
thermal, optical and conducting properties of lithium borosilicate
glass are studied. The elastic moduli for all the glasses were calculated theoretically using the bond dissociation energies of the various constituents. The changes in the above-mentioned properties
are explained in terms of modier to intermediate oxide replacement in relation to changes in the glass network rigidity, cross
linking and creation of NBOs in glass network.
Materials and methods
The initial chemical compositions of the samples are given in
Table 1. The required chemicals in oxides and carbonates form
(Loba Chemie Purity >99.5%) were thoroughly ground and mixed
in an agate mortar pestle for 1 hour (h) in an acetone medium.
The homogeneous powder, thus obtained, was melted at 1550 C
in a recrystallized alumina crucible using a programmable electric
furnace. After holding the melt at the melting temperature for 1 h,
it was quenched in air between two thick copper plates. The density of the glasses was calculated at room temperature by Archimedes principle, with xylene as the immersion medium and using the
following equation:

qsample

wa
 qxylene
wa  wb

where qsample is the density of the sample, qxylene is the density of

xylene at room temperature, wa is the weight of the sample in air
and wb is the weight of the sample in the xylene. Density of xylene
at room temperature is 0.863 g/cm3. Sample weights were measured on Mettler Toledo (NewClassic ML) measuring balance having
least count 0.1 mg. Structural characterization of the samples was

Table 1
Chemical composition (mol%) of the samples along with label.
Label

SiO2

B2O3

Y2O3

Li2O

Y15L0
Y10L5
Y5L10
Y0L15

55
55
55
55

30
30
30
30

15
10
5
0

0
5
10
15

carried out using X-ray diffraction and Fourier Transform Infrared

Spectroscopy (FTIR). X-ray diffraction patterns of these samples in
the 2h range 2080 were obtained using PANalytical XPert PRO
diffractometer with Cu Ka (wavelength = 1.54 ) radiation. During
the experiment the scan speed was 3 min1 and step size was
0.0130. The differential thermal analysis (DTA) was performed in
the temperature range of 301000 C by Diamond Pyris (Perkin
Elmer) TG/DTA setup in the air with alumina as reference material
using 40 C/min heating rate. The detection limit of the balance and
temperature controller were 0.1 mg and 0.1 C, respectively. Perkin Elmer- Spectrum-RX-I FT-IR spectrometer was used to obtain
the FTIR spectra of the samples in the range 4001600 cm1. Glass
powder was mixed with KBr and was pelletized. Total spectrum
was normalized to the blank spectrum of KBr, in order to get samples rectied spectra. UVvisible spectra of the powder samples in
the diffused reectance mode were recorded on HITACHI U-3900 H
double beam spectrophotometer within the spectral range 200
800 nm. Scanning speed was 120 nm/min and resolution of the
instrument was 0.20 nm. Before taking measurements, the instrument was calibrated using standard sample (Barium sulphate) for
100% reection and empty sample holder for 0% reection.
AC conductivity measurement was done on a selected sample
within the temperature range 30500 C. It was measured using
two probe method over the frequency range of 202  106 Hz.
Conductivity measurements were carried out on gold sputtered
pellets in air atmosphere using multifrequency Solatron LCR meter
(Model S1260). Heating rate was kept at 5 C min1 and before taking conductivity measurements, the sample was held at programmed temperature for 2 min to ensure the temperature
stability of 1 C.
Results and discussion
Physical parameters
The density of the glass samples increased with Y2O3 concentration as given in Table 2. Y2O3 has much higher molar mass than
Li2O, which leads to the increase in the density of the samples with
respective replacement of Li2O in the glass composition. In general,
the density follows the additive rule of mixture. The density of
present glasses exhibited more or less linear behavior and followed
the additive mixture rule with slight deviation as shown in Fig. 1.
Based on the measured density, molar volume of all the samples
was calculated using the following equation:

V m M=qsample

where M denotes the molecular weight of the sample. The molar

volume also increases with Y2O3 as shown in Fig. 1. Usually, the
molar volume decreases with an increase in density in case of single
alkali oxide contained glasses [9,10]. However, in the present case,
both the quantities increased with the increase in Y2O3 content in
the glass. Similar behavior of molar volume and density was also
observed in other reports [11,12]. The deviation from the linearity
in the molar volume is associated with the mixed effect of modier
and intermediate oxides in the present glasses. The presence of both

Table 2
Physical parameters of the samples.
Sample id

Molecular weight
(g/mol)

Measured density
(g/cm3)

Molar volume
(cm3/mol)

Excess volume
(cm3/mol)

Oxygen molar volume

(cm3/mol)

Oxygen packing density

(mol/L)

Y15L0
Y10L5
Y5L10
Y0L15

87.80
78.01
68.21
58.41

3.22
2.99
2.58
2.30

27.27
26.09
26.44
25.40

0.45
0.12
1.74
2.21

11.13
11.10
11.75
11.81

89.84
90.18
85.10
84.65

S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

241

Fig. 1. Variation in density and molar volume with Y2O3.

Fig. 2. XRD patterns of the samples (+ ? SiO2). XRD of Y10L5 glass to show the two
halos (inset).

(Li2O + Y2O3) the constituents leads to the phase separation (as

discussed in X-ray diffraction and DTA analysis) and disturbs the
uniform cross-linking in glass matrix. It is a possible reason for
deviation of linearity in molar volume (Fig. 1). In general, the presence of modier and intermediate oxides may have complex effects
on the structural behavior of the glasses due to different eld
strengths, electronegativity, etc. [13]. The excess volume was calculated to compare the compactness of the samples. Excess volume
(Ve) and oxygen molar volume (Vo) values were calculated using
the following relations, respectively:

Ve Vm 

X
xi V m i

Vo

X xi M i

qsample

!

1
xi ni


4

where Vm(i) and Mi are the molar volume and molecular weight of
ith oxide, respectively, xi is the fraction of the oxide present in the
composition and ni is the number of oxygen atoms in ith oxide.
Excess volume indicates the deviation from the ideal mixing volume. Network modications by the modiers in the glass network
cause the deviation from ideal mixing volume. Higher Y2O3 containing glass exhibited lesser excess volume and hence has the more
compact structure with lower cross-linking. The higher eld
strength of Y3+ than Li+ is reasonable to increase the compactness
of the glass matrix. In fact, higher concentration of Y2O3 i.e. 10
and 15 mol% led to the negative excess volume. It clearly indicates
the presence of lower cross-linking and better compactness of these
glasses. Negative excess volume has also been observed for borosilicate glasses in our reports, where different intermediate oxides
have been used in glass [14]. Using the density data, the oxygen
packing density (OPD) was also calculated according to the following relation:

OPD

qsample
M

X-ray diffraction
Fig. 2 shows the XRD patterns of the quenched glass samples.
Absence of crystalline peaks in the patterns conrms the amorphous state of the samples in Y0L15, Y5L10 and Y10L5 glasses. Only
Y15L0 sample exhibits a crystalline peak at 26.63 indicating the
presence of small crystalline phases embedded in the glass matrix.
The single crystalline peak in Y15L0 is assigned to Quartz (SiO2)
(ICDD No. 01-081-0065). Basically, other XRD peaks of quartz are
small and weak as compared to the most intense XRD peak
26.58. So, these peaks are not visible in XRD pattern of Y15L0
glass. The crystallite size of quartz phase was also calculated using
Scherer formula and found to be 46 nm. It is well reported in literature that higher content of Y2O3 prevents the glass formation.
Higher amount (P10 mol%) of Y2O3 usually promotes the nucleation of crystalline phases in the glass matrix [15,16]. In the present
case, it was observed that a broad halo centered at 30 shifted
towards lower angle, particularly 22 for Y0L15 sample. On the
other hand, another small halo at 41 is also present, particularly
in Y5L10 and Y10L5 glasses. Interestingly, this particular halo is
absent in Y0L15 and Y15L0 glasses having either modier or intermediate oxides. It indicates that the presence of both intermediate
and modifying oxides leads to the phase separation in the present
glasses. It might be occur two ways, either different glassy phase
with different composition is present or different glassy phase with
the same composition but with different density exists in the glass
matrix. Yttrium in Y3+ state has high ionic eld and may have
enhanced the phase separation. The phase separation is a common
phenomenon, particularly, where two glass former or modiers are
present in the glass composition [17,18]. For the conrmation of
phase separation, the DTA experiment was performed on all the
glass samples and results are discussed in following section.
DTA analysis

 Number of oxygen atoms per unit formula unit

5

The oxygen packing density is showing an increasing trend with

Y2O3 addition except Y10L5 glass. Number of oxygen atoms in a
formula unit and the molecular weight of the compositions
increase linearly, but as it is clear from Fig. 1, the variation in the
density with compositions is not perfectly linear. The slight deviation of the density from the linear behavior results in the observed
trend in the oxygen packing density of the present glasses and
glass ceramics.

The glass transition temperature (Tg) is the temperature at

which the glass material starts behaving as a viscoelastic material.
However, it is a heating rate dependent phenomenon, but Tg for
different samples obtained at same heating rate can give useful
information about the local structure of the glass. Generally, modier oxides added to the glass network, break glass the network
and weaken the overall local structure with the creation of NBOs.
Consequently, the Tg shifts towards the lower temperatures. In
the present case, Y0L15 glass has lowest glass transition temperature 535 C. When lithium oxide is replaced by Yttrium oxide by

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S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

Table 3
Elastic, optical and thermal parameters of the samples.
Label

Packing density

Youngs modulus (GPa)

Bulk modulus (GPa)

Shear modulus (GPa)

Optical band gap (eV)

Urbach energy (eV)

Tg1 (C)

Tg2 (C)

Y15L0
Y10L5
Y5L10
Y0L15

0.65
0.64
0.60
0.60

90.4
90.4
85.2
84.4

70.1
69.7
61.6
60.2

37.5
37.5
35.8
35.5

3.64
3.71
3.80
3.90

0.51
0.54
0.33
0.31

550
585
610
535

720
785

Fig. 3. Proposed structure of the local network of present glasses.

Fig. 5. FTIR spectra of the as quenched glasses.

Fig. 4. Variation in Tg1 with concentration of Y2O3.

5 mol%, the Tg increases i.e. 610 C. This can be related to the fact
that Y2O3, when added in small amount, might act as a glass former. It is well reported that small quantity usually 65 mol% intermediate oxide acts as glass former [7]. Further replacement of Li2O
with Y2O3 causes the decrease in Tg, Y15L0 has Tg 550 C. It
clearly indicates that higher amount of Y2O3 i.e. >5 mol% acts as
network modier and decreases the glass transition temperature.
The lowest Tg is observe for Y0L15 glass. It indicates that Li2O is
a strong modier than Y2O3. Additionally, the Y5L10 and Y10L5
glasses exhibit second Tg2 (as given in Table 3), which indicates
the phase separation occurred in these glasses due to the formation
of glass matrix within the glass matrix. Proposed structure of the
local network of the glass is represented in the Fig. 3. The variation

in Tg with the Y2O3 content is shown in the Fig. 4. The dotted line at
5 mol% separates the regions, where Y2O3 changes its role from
glass former to network modier.
FTIR analysis
Fig. 5. shows the FTIR spectra of all the samples. These spectra
consist of major transmission bands at 680 cm1, 1000 cm1,
1090 cm1 and 1375 cm1. However, there are some minor
changes in band intensities and peak positions for these samples
with respect to each other. Shifting of the bands towards lower
or higher wavenumbers is due to the relative change in the
strength of the chemical bonds by the change in glass composition.

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S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

The bands in the spectra are broad and diffused due to the possible
tendency of the structure to have randomness and defects. This
fact is also supported by the large values of Urbach Energy of these
samples (explained later). The most intense and broad IR band at
1090 cm1 and extending beyond 1000 cm1 can be attributed to
the combined stretching vibrations of BOB and SiOSi network
of tetrahedral structural units [1921]. The overlapping of bands
due to the vibrations of different bonds, makes the transmittance
band broader. Secondly, changes in the bond angles or bond
lengths of the building units due to network modications also
make the bands broader [22,23]. It can be observed that transmission band at this position shows maximum sharpness for Y15L0
sample. It supports the XRD results, where Y15L0 exhibited nanocrystalline phase of SiO2. In the crystalline phase of a material, the
bond lengths and bond angles are well dened and lead to sharp IR
bands [24]. The bands at 1375 cm1 in all the samples are due to
vibrations of BO3 units [25]. The FTIR band at 680 cm1 may be
due to bending vibrations of BOB bonds [20,26]. Y15L0 sample
exhibits a medium IR band at 805 cm1. Also, in the spectra of
Y0L15 sample, there is a low intensity band at this position. It
may be attributed to the formation of boroxol rings in these samples. Absence of any band in mixed samples (Y5L10 and Y10L5)
samples at this position indicates that their glass structures contain only BO3 and BO4 units. It is also supported by DTA results,
the highest Tg was observed in the case of Y5L10 sample. It can
be associated with the higher BO4 units than BO3 units. Further
increase in Y2O3 (10 mol%) enhances the formation of BO3 units
and Y2O3 overall acts as glass modier. It can be seen in both
Y0L15 and Y15L0 samples that a band 1598 cm1 is present
and is absent from other samples. IR band near this position is generally due to BO bond stretching vibrations of trigonal BO3 groups
[27]. Also, Y15L0 and Y0L15 show a band and a shoulder edge,
respectively, at 920 cm1 in their spectra, it indicates the presence of [BO6] octahedral units in the glass network. These observations indicate that higher content of Li2O (15 mol%) or Y2O3
(15 mol%) in glass acts as modiers. However, in the mixed glasses,
Y2O3 acts as former up to 5 mol%, and after that it acts as the modier. These results are in good agreement with the DTA results of
these glasses. Shifting of the IR bands with respect to Y2O3 concentration is also observed. However, it did not follow any trend. This
can be explained considering the fact that alkali oxides and intermediate oxides behave differently when added to silicate and
borate glass network. Alkali oxide added to the silica network creates NBOs and leads to weakening the network, which further
decreases the Tg of the glass. On the other hand, alkali oxide in
the borate network upto a certain amount rst helps to change
BO3 units to BO4 units, while further addition causes the NBOs creation [28]. Secondly, the alkali ions (Li+ in the present case) are
shared by both silica and borate network in the borosilicate
glasses. Hence, dual role played by lithium ions in the both types
of networks results in complex variation in the network modication and leads to observed trends in the present glasses.

where q is the density of the sample, M is the molar weight, Vi is the

packing density parameter and xi is the mole fraction of the component. Packing density parameter for an oxide of the form of MxOy
can be calculated as:

V i 4=3  bpNA xr 3m yr3o c

NA is the Avogadros number, rm and ro are the ionic radius of the

metal and oxygen respectively.
Using above equations the Young modulus can theoretically be
given as:

Y 83:6  V t

X
G i xi

Bulk and Shear modulus of the samples were calculated using

the equations:

K 100  V 2t

X
Gi xi

X
S 300  V 2t =10:2  V t  1 Gi xi

Bond dissociation energies for the oxide constituent oxides, i.e.

SiO2, B2O3, Y2O3 and Li2O were taken as 15.4, 18.6, 17.7, 19.2 kcal/
cm3, as given in Ref. [29]. Shannon radii were used in the present
case for ionic radii of the metal and oxide ions. The calculated values are summarized in Table 3. Elastic modulus of inorganic
glasses ranged over 10200 GPa [28,30]. The observed values in
the present case are lying in the above-mentioned range. It can
be seen that the theoretical values of moduli are decreasing with
increasing Li2O content. This indicates that the strength of the glass
network decreases with the increase in the Li2O amount. This can
be explained by the fact that Li2O is a stronger network modier
than the Y2O3 and hence leads to the weaker network. In other
words, the eld strength of Y2O3 is higher than Li2O, so the bond
strength is higher in case of Y2O3 contained glasses. So, mechanical
properties increases with increasing content of Y2O3 in glasses.
UV/vis analysis
Diffused reectance spectra of the samples are shown in Fig. 6.
The signature of phase separation phenomena in the glasses could
be established by the UVvis spectra. A hump at 262 nm is clearly
seen in Y2O3 containing glasses and is absent in the Y0L15 glass.
This hump might be originated due to the presence of glass matrix
within the glass network. From diffused reectance spectra, the
optical band gaps of the as-quenched samples were calculated

The mechanical properties such as Youngs modulus, Bulk modulus and Shear modulus have been calculated theoretically. Studies
of these properties be used to access considerable information
regarding the structure of the glasses. Makishima and Mackenzie
have derived equations to predict the mechanical parameters of
the glass systems using the bond dissociation energies of the constituent oxides [29]. Ionic packing density can be calculated as
follows:

X
V i  xi
i

10

Mechanical parameters

V t q=M 

6
Fig. 6. Diffused reectance spectra of the glasses.

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S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

10

Y15L0

Y10L5

(F(R) h )2

(F(R) h )2

8
4
3
2

4
2

(a)

(b)

0
2.0

2.4

2.8

3.2

3.6

2.5

4.0

3.0

Y0L15

1.6

(F(R) h )2

(F(R) h )2

4.0

Y5L10

2.0

3.5

Energy (eV)

Energy (eV)

1.2
0.8

2
0.4

(d)

(c)
0

0.0
2.4

2.7

3.0

3.3

3.6

3.9

4.2

Energy (eV)

2.0

2.5

3.0

3.5

4.0

4.5

Energy (eV)

Fig. 7. Optical band gap of the samples (a) Y15L0, (b) Y10L5, (c) Y5L10 and (d) Y0L15.

using KubelkaMunk function. For innite length of the sample,

the absorption coefcient (a) can be related to the reectance (r)
by the following relation:

Fr a=s 1  r2 =2r

11

where F(r) is the KubelkaMunk function. r is the reectance and

s is the scattering coefcient. (F(r) hm)2 vs. hm plots were extrapolated to meet the energy axis (x-axis) corresponding to (F(r)
hm)2 = 0 (Fig. 7). The intercept gives the value of optical band gap
of the sample [31].
Optical band gaps of the as quenched samples fall in the insulator region. Y0L15 sample exhibits maximum optical band gap
(3.90 eV). As Li2O is replaced by Y2O3, the optical band gap of
the samples decreased and attains a minimum value 3.66 eV
for Y15L0 sample. However, as discussed in the previous section,
the NBOs ratio should be higher in the Y0L15 glass than other
glasses. Usually, the optical band gap decreases with the increase
in NBOs. The opposite trend is observed in the present glasses, it
might be associated with the higher optical band gap of Li2O than
Y2O3. Urbach energy (EU) of the samples was calculated using the
equation av b exphm=EU . Urbach energy can be obtained from
ln F(R) vs. photon energy plot, by taking the reciprocal of the slope
of the linear portion [32]. Optical band gap and Urbach energy values are given in Table 3. The Urbach energy increased with the
increase in the Y2O3 content. Actually, Y2O3 is an intermediate
oxide, and hence can act as modier as well as network former.
But in the present case, it seems to be acting as a network modier,
particularly in Y10L5 and Y15L0 samples. Conclusively, the optical
band gap and Urbach energy also depends on the other factors than
NBOs. The addition of Y2O3 leads to the phase separation, which
modies the glass network. The X-ray diffraction spectra clearly

indicated the phase separation, where Y2O3 is present in glasses.

Y15L0 sample, interestingly, have slightly lower EU than Y10L5
glass. This might be due to the crystalline phase formed in this particular glass, which enhances the degree of order in the network
and leads to the lower value of Urbach energy as compared to
Y5L10 glass.
AC conductivity analysis
Based on the DTA, FTIR and UVvis results, the most phase separated glass (Y10L5) was selected for the study of its conductivity
behavior. Usually, phase separation in glasses leads to more frustration and enhances the ionic conductivity. The AC conductivity
of the glass was accessed by the means of impedance spectroscopy.
The conductivity of the sample increased with an increase in the
temperature. That is due to the increased mobility of the Li+/Y3+
ions with temperature. Ionic conductivity in oxide glasses is interrelated to the structure of glass. In the glass systems, conduction is
mainly due to the motion of the ions through the glass network.
NBOs provide hopping sites for Li+/Y3+ ions in the network. Glass
with more NBOs has an open structure and offers large free volume
for the ions to drift [33].
Colecole plots for the glass were obtained at various temperatures. Upto 600 C the colecole plots consisted of single semicircle. At 620 C, colecole exhibit a line along with the semicircle.
This straight line occurs due to the polarization of the electrode.
Colecole plot for the sample at 620 C is shown in Fig. 8. Generally, the impedance data is interpreted in terms of the equivalent
circuits comprised of the components such as resistance (R), capacitance (C), constant phase element (CPE) etc. In such cases, R represent the bulk conductivity of the material. CPE is associated with
space charge polarization regions and specic processes on the

S. Singh et al. / Journal of Molecular Structure 1086 (2015) 239245

245

the glass formation. Y2O3 changes its role from glass former to network modier as its concentration exceeds 5 mol% in the present
glasses. FTIR bands become sharp with Y2O3 concentration. Elastic
moduli decreased with increase in Li2O concentration. The optical
band gap is observed to be in the insulating range for all the present glasses. The optical band gap increases with increasing Li2O.
However, Urbach energy could not follow any trend due to glass
phase separation effect. The conductivity is of the order of
106 S/cm at 620 C, with activation energy 1.20 eV, indicating
that the present glasses are predominantly ionic conductors.
Acknowledgements
Authors are thankful to UGC for nancial support under the
scheme MANF for minority students under the award letter number
F1-17.1/2012-13/MANF-2012-13-SIK-PUN-11203/(SA-III/
Website). We are thankful to Ms. Samita Thakur and Ms. Sakshi
Gupta for their valuable suggestions and discussions.

Fig. 8. Colecole plot for Y10L5 glass at 620 C.

References

Fig. 9. Arrhenius plot for Y10L5 glass.

electrodes. In the present case, the semicircle was tted with the
combination of a resistance (R1) and constant phase element
(CPE-1) joined in parallel and another constant phase element
CPE-2 in series with the former combination [34]. The equivalent
circuit is also shown in the inset in Fig. 8. The activation energy
was obtained from the Arrhenius plots of conductivity (Fig. 9).
The activation energy was calculated by following equation:

rT A exp



Ea
kT

12

where r is conductivity of the glass, Ea is activation energy, A is a

constant, T is absolute temperature and k is Boltzmann constant
(8.617  105 eV K1). The Arrhenius plot was tted linearly with
the experimental data with R2 > 0.997. The activation energy is
found to be equal to 1.20 eV, which indicates that it is predominantly an ionic conductor. The conductivity of the sample at
500 C is found to be equal to 5.57  107 S/m, which implies that
this glass is a poor electrical conductor. The optical band gaps of
the present glasses also support their insulating behavior.
Conclusions
Y2O3 plays important role in the present compositions and
inuences the structure of the glass accordingly. The addition of
Y2O3 at the cost of Li2O leads to the phase separation in glasses
with increasing density. Higher content of Y2O3 (15 mol%) prevents

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