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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.
240
qsample
wa
qxylene
wa wb
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
V m M=qsample
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)
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
241
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
242
Table 3
Elastic, optical and thermal parameters of the samples.
Label
Packing density
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
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.
243
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.
Y 83:6 V t
X
G i xi
K 100 V 2t
X
Gi xi
X
S 300 V 2t =10:2 V t 1 Gi xi
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.
244
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.
Fr a=s 1 r2 =2r
11
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.
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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
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