3. 2
Advances in Condensed Matter Physics
Table 1: The density, transition temperature, thermal expansion, acoustic Debye temperature, and softening temperature of zinc tellurite
glasses.
ZT0
ZT1
ZT2
ZT3
ZT4
ZT5
ZT6
ZT7
ZnO-TeO2 (mol%)
Density
(g/cm3 ) (± 0.01)
0–100
10–90
15–85
20–80
25–75
30–70
35–65
40–60
Thermal expansion coefficient
(× 10−6 K−1 ) (± 0.01)
4.80
5.09
5.10
5.14
5.19
5.21
5.28
5.29
ZnO) on the TeO2 -rich side of the phase diagram [10]. These
types of glasses are characterized by a high refractive index
which increases with TeO2 content [11–13].
Apart from their applications, there is a lack of data on
structural investigations as well as the thermal properties of
these ZnO-TeO2 glass systems in the literature. Therefore, the
aim of this research is to study the effect of zinc on the thermal
properties of tellurite glass system in order to understand the
fundamental origin of such properties.
Temperature (K)
Transition
Debye
Softening
658
654
653
646
647
638
637
633
12.40
12.14
12.36
12.51
12.66
12.90
12.54
12.78
263
259
259
257
257
252
253
251
857
852
833
802
783
736
722
694
Intensity (a.u.)
Glass
sample
ZT7
ZT6
ZT5
ZT4
ZT3
ZT2
ZT1
ZT0
2. Experimental and Materials
Systematic series of binary zinc tellurite glasses in the form
(ZnO) 𝑥 (TeO2 )1−𝑥 (where 𝑥 = 0 to 0.4 with internal of
0.05 mole fraction) have been successfully prepared via
melt quenching technique. The density of the glasses was
determined by Archimedes method with acetone as buoyant
liquid. The preparation of the tellurite-based glass systems
and related experimental method has been discussed elsewhere [14–16].
To check the amorphous state, the X-ray diffraction was
carried out for each glass sample by using a computercontrolled X’pert Pro Panalytical set. Both longitudinal
and shear ultrasonic velocities were measured in different
compositions of the glass system by using the MBS8000
Ultrasonic Data Acquisition System at 10 MHz frequency
and at room temperature. The thermal expansion coefficient
was measured using L75D1250 dilatometer with the rectangular parallelepiped 3 × 3 × 6 mm3 of each glass samples.
The thermal expansion was obtained over a range of 30∘
to 210∘ C, while the glass transition temperature (𝑇 𝑔 ) was
determined by the differential thermogravimetric analysis
(Setaram instrumentation Labsys DTA/6) at heating rate of
20 K min−1 . The accuracy in the measurement of 𝑇 𝑔 is ±2∘ C.
3. Results and Discussion
Table 1 presents the density, transition temperature, thermal
expansion, acoustic Debye temperature, and softening temperature of (ZnO) 𝑥 (TeO2 )1−𝑥 zinc tellurite glasses.
10
20
30
2𝜃
40
50
Figure 1: The XRD patterns of zinc tellurite and pure tellurite glass.
3.1. XRD Analysis. The XRD patterns of the present glass
samples depicted in Figure 1 were found to show no discrete
or continuous sharp peaks but broad halo at around 26∘ –
30∘ , which reflected the characteristic of amorphous glass
structure. This indicates the absence of long-range atomic
arrangement and the periodicity of the three-dimensional
network in the glassy materials.
3.2. Density. The density of a glass is an important property capable of evaluating the compactness. The density is
affected by the structural softening/compactness, change in
coordination number, and dimension of interstitial spaces
of the glass. The increase in the density (as depicted in
Table 1) can be related to two reasons: The first reason is
the replacement of TeO2 by ZnO which has high relative
molecular weight where the molecular weight of TeO2 and
ZnO is 159.6 and 81.38, respectively. The second reason may
be due to the transformation of TeO3 to TeO4 where the
formation of TeO3+1 polyhedron has one nonbridging oxygen
atom. This increase can be attributed to the zinc ions that
occupy the interstitial position, and therefore the threedimensional structure of tellurite glass is not destroyed. These
behaviors of the studied glasses are agreed with reported data
elsewhere [4, 7].
4. Advances in Condensed Matter Physics
3
𝛼𝐿 =
Δ𝐿
,
𝐿𝑥Δ𝑇
(1)
where 𝐿 is the original length of the sample, Δ𝐿 is the increase
in length, and Δ𝑇 is the increase in temperature. Since glasses
are usually isotropic materials with relatively small thermal
expansion coefficients, 𝛼V = 3𝛼 𝐿 can be used to approximate
𝛼V with very little error in calculation.
All reported thermal expansion coefficients for glasses
are actually average linear thermal expansion coefficients
over some specified temperature ranges. The particular temperature ranges from 0 to 300∘ C, 20 to 300∘ C, or 25 to
300∘ C. The data for experimental studies may be reported
for almost any temperature range. Since most linear thermal
expansion coefficients lie between 1 and 50 × 10−6 K−1 ,
metallurgists, ceramists, and other material scientists usually
report values with units of ppm K−1 . Traditionally, however,
glass technologists used 10−7 K−1 as the basis for reporting
thermal expansion coefficients.
An understanding of how the thermal expansion coefficient varies as a function of the glass composition is needed.
The linear 𝛼th of any solid material depends strongly on the
anharmonic nature of interatomic forces.
Figure 2 shows the plot of thermal expansion coefficient
versus chemical composition of binary zinc tellurite glasses at
various temperatures and summarized in Table 1.
The thermal expansion coefficient indicates the relation
between the volume of a glass and its temperature. This
property is a strong function of glass composition. In the
range between room temperature and 𝑇 𝑔 , the expansion
coefficient of the glass was often assumed to be independent
of temperature and was defined as 𝛼 = (Δ𝐿/𝐿 0 )Δ𝑇. From
Figure 2 it can be seen that the thermal expansion coefficient
increases as the ZnO content added from 0.10 mole fraction
to 0.40 mole fraction.
The substitution of ZnO might be due to the change of
the coordination number of TeO2 from 4 to 3. This change is
associated with the creation of non-bridging oxygens (NBOs)
that caused the decrease in rigidity. Further substitution
of ZnO, that is, 0.35 mole fraction, decreases the thermal
expansion coefficient which can be supported by the earlier
work [18]. Further increasing the modifier content stabilizes
TeO4 units with NBO. The decrease of thermal expansion
14
14
𝑦 = 0.0001𝑥 2 + 0.0078𝑥 + 12.278
𝑅2 = 0.5521
10
12
11
8
10
2
𝑦 = −0.0003𝑥 + 0.0221𝑥 + 4.8296
6
𝑅2 = 0.9541
4
2
9
8
Thermal expansion (×10−6 K−1 )
13
12
Density (g cm−3 )
3.3. Thermal Expansion. Thermal expansion is one of the
very important properties of materials for many technological and practical applications. The aim of the present work
is to characterize glass thermal expansion coefficient, and
their transition temperatures. There is a strong dependence
between the glass transition temperature, 𝑇 𝑔 , thermal expansion coefficient and the kind of the modifier [17].
The thermal expansion coefficient of a material is a
measure of the rate of change in volume and therefore
density with temperature. Although the thermal expansion
coefficient is actually defined in terms of the volume of the
substance, this value is somewhat difficult to measure. As a
result, the expansion coefficient for glasses is usually only
determined in one direction; that is, the measured value is
the linear thermal expansion coefficient, 𝛼 𝐿 :
7
0
10
20
30
ZnO content (mol%)
6
40
Figure 2: The density and linear expansion coefficient of TeO2 -ZnO
glasses.
coefficient increased the tightness of the structure. Above 0.35
mole fraction, the conversion of TeO4 to TeO3 occurs again
which causes the decrease in rigidity.
3.4. Thermal Stability. Thermal stability is defined as the
resistance to permanent change in properties caused solely
by heat. Glass stability is defined in terms of resistance to
crystallization of a glass during heating. Glass stability is
most important during processes involving re-forming of an
existing glass. The glass forming ability automatically leads
to glass stability [19]. Thermal stability is frequently characterized by the difference in temperature between the onset
of the glass transformation range (𝑇 𝑔 ) and the occurrence
of crystallization (𝑇 𝑥 ) for a sample heated at a specified
linear rate. These measurements are routinely carried out
using a differential scanning calorimeter (DSC) or differential
thermal analyzer (DTA).
The exact definitions of 𝑇 𝑔 and 𝑇 𝑥 are subjected to
the preference of the experimenter, as is the choice of the
appropriate heating rate used in the study. Typical thermal
spectra may contain one or more exothermic peaks due to
crystallization of different phases, but the lowest temperature
peak is considered in discussing glass stability. Once a
significant number of crystals are formed, subsequent events
at higher temperatures are not considered important in glass
stability.
It is known that the glass transition temperature (𝑇 𝑔 )
is affected by the alteration of the glass structure, and the
structure of the thermally stable glasses is close-packed
structure. The glass transition temperature 𝑇 𝑔 helps to reveal
the close or loosely packed structure of the glass [20], where
the higher single-bond energy in glass network, the more
stable the glass-forming system.
3.5. Glass Transition Temperature. Glass transition temperature, 𝑇 𝑔 , plays a vital role in understanding the physical
properties of glass [21]. DTA curves for the studied glass
5. 4
Advances in Condensed Matter Physics
900
900
700
Debye temperature (K)
800
𝑦 = −0.0758𝑥2 − 1.4117𝑥 + 863.81
700
𝑅2 = 0.9787
2
600
600
𝑦 = −0.0068𝑥 − 0.3747𝑥 + 658.59
𝑅2 = 0.9614
500
400
500
400
𝑦 = −0.0003𝑥2 − 0.2841𝑥 + 262.79
300
300
𝑅2 = 0.9348
200
200
100
Transition/softening temperature (K)
800
of the glass is associated with an increase in the lattice vibrations. The observed acoustic Debye temperature, obtained
from the ultrasonic velocity data, [13, 24, 25] is
100
0
10
30
20
ZnO content (mol%)
40
Figure 3: The acoustic Debye, transition and softening temperatures
of ZnO-TeO2 glasses.
samples with different ZnO contents have been obtained to
determine the glass transition temperature (𝑇 𝑔 ) values. Generally, glasses with close-packed structure will have thermal
stability, while those with loose-packed structure will have
unstability [17]. In the present investigation, all of the glasses
have an endothermic change between 385.21 and 360.52∘ C,
which attributes to the glass transition temperature, 𝑇 𝑔 .
The Zn2+ is incorporated into the glass structure as a
network modifier, resulting in loose packing of the glass
structure. As a result, a continuous decrease in 𝑇 𝑔 with the
increase in network modifier content has been observed
(Figure 3). In the present glasses, the decrease in 𝑇 𝑔 values
with increase in Zn2+ content contributes to a decrease
in thermal stability of the glasses leading to loose-packed
structure as discussed elsewhere [21].
The glass transition reflects a change in the coordination
number of the network forming atoms and destruction of
the network structure brought about by the formation of
some non-bridging atoms [22]. The decrease in the glass
transition temperature values implies that the number of
bridging oxygen groups decreases. This is mainly due to the
addition of ZnO which weakens the bond between each atom
sample (increases the number of NBOs atom). The bond is
easier to break and hence the 𝑇 𝑔 of the sample decreased.
Furthermore, it also implies a decrease in rigidity of the glass
network.
3.6. Acoustic Debye Temperature. Acoustic Debye temperature (𝜃 𝐷) is a characteristic property of a solid lattice related
to its acoustic phonon spectrum [23] where it represents
the temperature at which nearly all modes of vibration in a
solid are excited [24]. Debye temperature is a characteristic
temperature of glass; any modifier added to the host network
affects this temperature [25]. Also the increase in the rigidity
9𝑍𝑁 𝐴 1/3
ℎ
) ,
Θ 𝐷 = ( ) 𝑀 𝑆(
𝑘
4𝜋𝑉 𝑚
(2)
where 𝑀 𝑆 , the mean velocity, is given by
𝑀 𝑆 = [(
1
2
) + ( 3 )]
𝑉 𝐿3
𝑉𝑠
−1/3
(3)
ℎ the Planck’s constant, 𝑘 the Boltzmann’s constant, 𝑁 𝐴 the
Avogadro’s number, and 𝑍 the number of atoms given by
𝑍 = ∑ 𝑥 𝑖 𝐿 𝑖,
(4)
where 𝑥 and 𝐿 are the mole fraction and number of atoms in
the 𝑖th oxide.
Regarding the compositional dependence of the Debye
temperature, it can be seen that Debye temperature decreases
from 263 K to 251 K as ZnO content increases (Figure 3).
It decreases when the ultrasonic velocity decreases. The
observed decrease in 𝜃 𝐷 indicates a monotonic decrease in
the total vibrational energy of the system. This is because
any of the conceivable vibrational units resulting from the
substitution will be of lower energy. Also, the observed
decrease in Debye temperature is mainly attributed to change
in the number of atoms per unit volume and also the existence
of non-bridging oxygen. It also indicates the loosing packing
structure of the glasses with creation of NBOs as discussed
above. In general the acoustic Debye temperature of the
present glasses is particularly sensitive with the addition of
ZnO content.
3.7. Softening Temperature. Softening temperature (𝑇 𝑠 ) is
another important parameter defined as the temperature
point at which viscous flow changes to plastic flow. In actual
practice, it plays a crucial role in determining the temperature
stability of the glass. Softening temperature (𝑇 𝑠 ) is related to
the ultrasonic velocity of shear waves (𝑉𝑠 ) by the equation
𝑇𝑠 =
𝑉𝑠 2 𝑀
,
𝐶2 𝑍
(5)
where 𝑀 is the effective molecular weight, 𝑍 is the number
of atoms in the chemical formula, and 𝐶 is the constant
of proportionality and has the value 507.4 (ms−1 K1/2 ) for
alumina-silicate glasses and is assumed to be the same for the
glasses under investigation.
The higher the value of softening temperature of a glass,
the greater the stability of its elastic properties [24, 25].
Values of softening temperature for ZnO-TeO2 glasses were
calculated and presented in Table 1. Figure 3 shows that
on addition of ZnO to TeO2 , the softening temperature
decreases from 857 K to 694 K with increasing ZnO content.
This shows that the stability of the glasses decreases as the
network modifier content increases. This change is what may
be expected from the decrease of elastic moduli.
6. Advances in Condensed Matter Physics
5
Table 2: Nonlinear regression analysis of the variables ( ̂ = 𝛿̂ 2 + 𝛽̂ + 𝛼) for various properties of ZnO–TeO2 glass.
𝑌
𝑥
𝑥
Variables ( ̂
𝑌)
Density
Thermal expansion coefficient
Transition temperature
Acoustic Debye temperature
Softening temperature
𝛿
−0.0003
0.0001
−0.0068
−0.0006
−0.1037
𝛽
0.033
0.008
−0.375
−0.275
−0.609
3.8. Regression Analysis. All the current experimental data
were analyzed using Microsoft Excel, by fitting regression
curves, and the results of the regression coefficients are
presented in Table 2. The regression coefficients obtained
from each curves are shown in Figures 2 and 3. In Table 2,
̂ stands for the variables shown in the first column and ̂ is
𝑌
𝑥
the ZnO concentration. As can be seen in previous figures,
for most of the variables a nonlinear polynomial ( ̂ = 𝛿̂ 2 +
𝑌
𝑥
𝛽̂ + 𝛼) gives the best fit.
𝑥
Except for the softening temperature, the overall results
from Table 2 show that the addition of ZnO with less than
40 mol% into the tellurite glass system causes small effect (less
than 10%) on their thermal properties.
4. Conclusion
A number of experimental techniques have been employed
to determine a number of important thermal properties of
zinc tellurite glass system. The thermal properties of tellurite
glasses such as the linear thermal expansion coefficient, the
acoustic Debye temperature, glass transformation temperature, 𝑇 𝑔 , and softening temperature were studied with respect
to ZnO content. The addition of ZnO content increases the
densities of ZnO-TeO2 glasses due to a change in crosslink
between TeO2 chains and coordination number of Te2+
ions. The addition of ZnO on TeO2 network also causes
the decreasing values of the acoustic Debye, transition, and
softening temperatures of ZnO-TeO2 glasses probably due
to the change in Te2+ coordination number. The increase of
ZnO in the tellurite glass system results in lower network
rigidity, which in turns results in decrease of most of their
thermal properties. Experimental data shows that the density
and thermal properties are greatly a strong function of
glasses composition. The changes in microstructure glassy
network can have an effect on the physical as well as thermal
characteristics of zinc tellurite glass.
Acknowledgment
The authors like to thanks the Universiti Putra Malaysia
(UPM) who funded this research project under the Research
University Grant Scheme (RUGS 2-2012) Project no. 05-0212-1838RU.
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Article
The Effect of Remelting on the Physical Properties of
Borotellurite Glass Doped with Manganese
Syed Putra Hashim Syed Hashim, Haji Abdul Aziz Sidek *, Mohamed Kamari Halimah,
Khamirul Amin Matori, Wan Mohamad Daud Wan Yusof and Mohd Hafiz Mohd Zaid
Glass and Ultrasonics Studies Centre (GUSC), Department of Physics, Faculty of Science, Universiti Putra
Malaysia, 43400 UPM Serdang, Selangor, Malaysia; E-Mails: hyzzam2003@yahoo.com (S.P.H.S.H.);
halimah@science.upm.edu.my (M.K.H.); khamirul@science.upm.edu.my (K.A.M.);
wmdaud@science.upm.edu.my (W.M.D.W.Y.); mhmzaid@gmail.com (M.H.M.Z.)
* Author to whom correspondence should be addressed; E-Mail: sidek@science.upm.edu.my;
Tel.: +603-8946-6682; Fax: +603-8943-2508.
Received: 7 October 2012; in revised form: 26 December 2012 / Accepted: 29 December 2012 /
Published: 7 January 2013
Abstract: A systematic set of borotellurite glasses doped with manganese (1–x)
[(B2O3)0.3(TeO2)0.7]-xMnO, with x = 0.1, 0.2, 0.3 and 0.4 mol%, were successfully
synthesized by using a conventional melt and quench-casting technique. In this study, the
remelting effect of the glass samples on their microstructure was investigated through
density measurement and FT-IR spectra and evaluated by XRD techniques. Initial
experimental results from XRD evaluation show that there are two distinct phases of glassy
and crystallite microstructure due to the existence of peaks in the sample. The different
physical behaviors of the studied glasses were closely related to the concentration of
manganese in each phase. FTIR spectra revealed that the addition of manganese oxide
contributes the transformation of TeO4 trigonal bipyramids with bridging oxygen (BO) to
TeO3 trigonal pyramids with non-bridging oxygen (NBO).
Keywords: borotellurite glass; density; bridging oxygen; FTIR spectra
1. Introduction
Tellurite glass is an extremely promising material for laser and nonlinear applications in optics due
to some of its essential characteristic features, such as high density, high refractive index, low phonon
10. Int. J. Mol. Sci. 2013, 14
1023
maxima, low melting temperature and excellent transparency in the far infrared region [1,2].
Furthermore, tellurite glass has a low melting point and is nonhygroscopic, which is an advantage
when compared to borate and phosphate glasses. These types of glasses are extremely stable against
devitrification, nontoxic and resistant to moisture for long periods of time [2]. It is widely recognized
that the refractive index, n, and density, ρ, of many common glasses can be varied by changing the
base glass composition [3]. In binary tellurite glasses, the basic structural unit of TeO4 is trigonal
bipyramid (tbp) with a lone pair of electrons, and the structural units permit Te–O–Te bonding for
glass formation [4].
The addition of tellurite to any other glass former or network modifier, such as B2O3, is of scientific
and practical interest and may lead to the formation of interesting structural units that affect the
physical properties of the glass network [5]. As reported earlier, the boron coordination number in the
borate glass changed from three to four as more alkaline content was added into the system where the
network linkage was increased. In contrast, the Te coordination number changed from four to three by
the cleavage of the tellurite glassy matrix [6,7]. In fact, the presence of TeO2 in the matrix of alkali
borate glasses decreases its hygroscopic nature; however, it improves the quality and enhances the IR
transmission [8,9]. The role of alkali, alkaline earth, and transition metal oxides (TMO) in the
borotellurite network is to modify the host structure through the conversion of the structural units
of the borate system from [BO3] to [BO4] and the tellurite network from trigonal bipyramid [TeO4]
to trigonal pyramid [TeO3] [10–13]. The elastic moduli of borotellurite glasses (TeO2–B2O3) have
been reported and discussed based on the bond compression model [10,12].
In this work, borotellurite glasses doped with manganese oxide (MnO) in the form of (1–x)
[(B2O3)0.3(TeO2)0.7]-xMnO, with x = 0.001, 0.002, 0.003 and 0.004, were prepared by using a
conventional melt and quench-casting technique. The main objective of this work is to determine the
optimum concentration of manganese needed to prepare the glass by examining amorphous
characteristics using X-ray diffraction. The effect of remelting each glass sample is also studied.
2. Results and Discussion
The XRD patterns for the various compositions of (1–x)[(B2O3)0.3(TeO2)0.7]-xMnO glasses are
shown in Figure 1, and the existence of a peak for MnO concentrations of 0.1 mol% and 0.2 mol%,
which is related to the existence of a crystalline phase in the samples, is shown in Figure 1a. The
addition of the MnO has disturbed the borotellurite glass system. In general, crystal growth can occur
at any temperature if a seed crystal is available. It may establish and enhance crystal growth inside a
system where a detectable growth rate can occur at any temperature below the Tm. These crystalline
peaks correspond to cubic manganese telluride borate, Mn3B7O12.65Te0.85, with the reference number
00-026-1255 [11–13]. At 0.3 mol% and 0.4 mol% MnO, the glass systems are in the amorphous state
due to the optimum concentration of MnO, where it acts as a stabilizer for the glass system. Figure 1a
also shows that no sharp peaks exist at 0.3 mol% and 0.4 mol% of MnO [10–15].
Manganese ions seem to exist in the Mn2+ and Mn3+ states in the glass network. However, at lower
concentration of MnO, a majority of the manganese ions are in the Mn2+ state. The linkage of the Mn2+
and Te4+ ions is expected to be extremely weak because the difference in ionic radii of the Mn2+ (0.8 Å)
and Te4+ (0.84 Å) is high when compared to that of Mn3+ (0.58 Å) and Te3+ (0.52 Å) ions [15].
11. Int. J. Mol. Sci. 2013, 14
1024
To study the remelting effect on the glass structure, all of the glass samples were then remelted. In
general, the features of the XRD patterns confirm that all of the remelted glasses are in the amorphous
state (Figure 1b), as indicated by the broad hump that occurs at approximately 2θ = 20°–30° for all of
the remelted glass samples.
All of the prepared glasses are free of bubbles, purple in color and of good quality. The density (ρ)
and molar volume (Vm) of the glass samples are shown in Figure 2 and Table 1. The density of the pure
borotellurite increased steadily with the addition of TeO2 into the glass structure, as depicted in Figure 2a.
It can be observed that the density decreases gradually with the compositions for both glasses before
and after remelt with an addition of MnO (see Figure 2b,c).
Figure 1. The XRD pattern of (a) the original sample and (b) the remelted MnO–B2O3–TeO2
glass samples.
0.1%
0.1%
0.2%
0.2%
0.3%
0.3%
0.4%
(a)
0.4%
(b)
The density results as depicted in Table 1 show that as the manganese cation concentration
increases, the glass structure becomes more open, allowing for the likely creation of more nonbridging
oxygen (NBO) [15,16]. Additionally, Figure 2 shows that the molar volume increases with the
introduction of manganese content. In the present samples, the glass densities vary from 4.57 to
5.56 gcm−3 and 3.23 to 4.38 gcm−3 after remelt, revealing a rather linear relationship with the
manganese content. However, there are slight differences in the density between the before and after
remelt (Figure 2c) samples due to the existence of a crystalline phase inside the glass system. The
occurrence of crystal growth causes a decrease of NBO. The remelting effect of this glass network is
the reconstruction of the structure of the glass system and an increase of NBO, causing a decrease in
the density.
The composition dependence of the molar volume gives information about the coordination state of
the manganese cations. The density and molar volume for these glasses are compatible with the ionic
size, atomic weight, and amount of different elements in the glasses.
12. Int. J. Mol. Sci. 2013, 14
1025
Table 1. The glass composition (mol%), density and molar volume of (100–x)
[(B2O3)30(TeO2)70]-xMnO.
MnO
0.1
0.2
0.3
0.4
B2O3
29.97
29.94
29.91
29.88
TeO2
69.93
69.86
69.79
69.72
ρ (g/cm3)
5.555
5.370
4.764
4.569
ρremelt (g/cm3)
4.3773
3.885
3.5798
3.2253
Vm (cm3)
22.734
23.507
26.483
27.604
Vm,remelt (cm3)
27.597
29.668
30.649
32.300
Figure 2. The density and molar volume of (a) borotellurite glasses; (b) the original
(100–x) [(B2O3)30(TeO2)70]-xMnO glass samples and (c) the remelted samples.
13. Int. J. Mol. Sci. 2013, 14
1026
Figure 2. Cont.
The experimental FTIR spectra for the borotellurite glasses doped with manganese (100–x)
[(B2O3)30(TeO2)70]-xMnO, with x = 0.1, 0.2, 0.3 and 0.4 mol%, are presented in Figure 3a,b. The FTIR
spectral bands of the glasses and their assignments are summarized in Table 2. The data were analyzed
following the method proposed by Condrate [17], comparing the experimental data of the glasses with
those of their corresponding crystalline compounds.
The present study shows that the quantitative evolution of these glass structures are greatly
influenced by the MnO concentration. The addition of MnO to the glass matrix leads to a drastic
reduction in intensity between the ~520 and ~650 cm−1 absorption bands due to the Te–O bond
between the trigonal bypiramidal unit [TeO4] and bridging oxygen and also contributes to the specific
vibration of the Mn–O bond [18–20]. If we take into account the Mn–O bond vibrations’ contribution
to the ~520 cm−1 absorption band, it seems that the controlled addition of manganese ions constricts, to
a large degree, the bending motion of different boron-oxygen bonds and gradually increases the
number of Mn–O linkages.
The vibration of the B-O arrangement in the infrared region of 400–1400 cm−1 is more
profound [20,21]. The medium absorption observed at ~1200 cm−1 is attributed to the B–O asymmetric
stretching of the tetrahedral BO4 [18] and orthoborate group [21,22]. The intensity of this band
decreases for the original samples from x = 0.1% to x = 0.4%. As for the remelted sample, the
intensities of these bands remain the same as the concentration of manganese ions is increased.
The band intensity at ~1400 cm−1 is due to the asymmetric stretching of the B–O bond from the [BO3]
trigonal unit in varied borate rings [18,22,23]. The band intensity decreases with the increase in
concentration of manganese ions for the original samples.
The band intensities between ~1600 cm−1 and ~3200 cm−1 are assigned to the bending of O–H and
the asymmetric stretching of O–H, respectively [24,25]. The occurrence of the O–H bond inside the
glass for the x = 0.1% to x = 0.3% original samples corresponds to the existence of a crystal structure
of manganese telluride borate, which is highly soluble and simply reacts with H2O. As the band
14. Int. J. Mol. Sci. 2013, 14
1027
intensity at ~1200 cm−1 and ~1400 cm−1 decreases, the band intensity at ~1600 cm−1 and ~3200 cm−1
also decreases and eventually disappears for the x = 0.4% original sample. There is no bending of O–H
or stretching of O–H for the remelted sample because no crystal structure exists in the glass matrix, as
affirmed by Figure 1b.
Table 2. Frequencies and their assignments for the FT-IR spectra of (100–x)
[(B2O3)30(TeO2)70]-xMnO.
Peak positions (cm−1)
~520
~650
~1200
~1400
~1600
~3200
Assignments
Corresponds to the Mn–O bond
The Te–O bond of the trigonal bypiramidal unit [TeO4] with NBO and the
contribution of the specific vibration of the Mn–O bond
The asymmetric stretching vibration of the B–O bond for the tetrahedral and
orthoborate group
The asymmetric stretching of the B–O bond from the [BO3] trigonal unit in
diverse borate rings
The bending of O–H
The asymmetric stretching of O–H
Figure 3. Selected FT-IR spectra of (a) the original sample; (b) the remelted sample.
%T
3. Experimental Section
A 13 g batch of the (1–x) [(B2O3)0.3(TeO2)0.7]-xMnO glass system, with x = 0.1, 0.2, 0.3 and 0.4 mol%,
was prepared by mixing all of the components together. The mixture was mechanically ground and
homogenized using an agate mortar for 15 min. The mixture was then preheated inside an alumina
crucible in an electrical furnace for half an hour at a temperature of 400 °C. The preheated mixture was
then transferred to the second furnace for one hour at a temperature of 950 °C. To improve
homogeneity, the crucible was constantly shaken inside the furnace. The melt was then poured into a
stainless steel cylindrically shaped split mold, which was preheated at 350 °C before being transferred
15. Int. J. Mol. Sci. 2013, 14
1028
to an annealing furnace for two hours at 350 °C. After two hours, the furnace was allowed to cool to
room temperature.
The cylindrically shaped samples obtained were then cut using low speed diamond blade to make
parallel fine surfaces of 6 mm thickness. The unused part of the glass was taken and ground in to a fine
powder. The fine powders were then remelted, and the entire procedure above was then repeated to
examine the remelting effect. The entire procedure for the remelted sample preparation was the same,
including the preheating, melting and annealing temperature, so that the conditions of the samples
could be maintained as the conditions of the original samples.
The amorphous nature of the glasses was ascertained from XRD analysis using an X-ray
Diffractometer (PAnalytical (Philips) X’Pert Pro PW 3040/60).
The density of each glass was measured using the Archimedes method with distilled water as the
immersion liquid. A bulk glass was weighed in air (Wair), immersed in distilled water and then
reweighed (Wdw), where the density of the distilled water was 1.00 g cm−3. The relative density is given
as ρs = ρdw (Wair/Wdw) [26].
4. Conclusions
Borotellurite glass doped with manganese oxide was prepared by the melt-quenching technique.
The XRD, density and molar volume of the glasses were discussed. The overall features of the XRD
curves showed that the occurrence of peaks for the 0.1 mol% and 0.2 mol% samples are due to the
existence of crystal seeds inside this glass structure. However, for the 0.3 mol% sample, the XRD
pattern confirms the amorphous nature of the glass. The remelting effect, on the other hand,
reconstructs the glass structure and avoids the nucleation of crystal growth. This result was confirmed
by the XRD patterns showing the amorphous nature of all of the remelted glasses. Density was
observed to decrease with the increase of MnO in the glass and the remelting effect. However, a
slightly different density was shown for both glass systems due to the existence of crystallites inside
the remelted glass network. This effect reconstructed the structure of the glass system and increased
the amount of nonbridging oxygen inside the system, causing the density to decrease after it was
remelted, which was proven by the FT-IR spectral analysis.
Acknowledgments
The researchers gratefully acknowledge the financial support from Universiti Putra Malaysia for
this study through the Research University Grant Scheme (RUGS) no. 91748.
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79
5200
and ZnO by Higazy [30] to phosphate glass, which increases the density. In the present work, PbO has been added to the phosphate glass
network to improve its chemical durability as a glass modifier. The
elastic properties of (PbO)x(P2O5)1−x glasses have been discussed by
looking at the structural modifications that take place in the glass
network.
5000
4800
4600
4400
2. Experimental
4200
A series of (PbO)x(P2O5)1−x lead phosphate binary glasses (where
x = 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 mol%) were prepared by the conventional melt quenching method. The starting materials, phosphorus
pentoxide (P2O5) with a purity of 97% and lead oxide (PbO) with a
purity of 98% were weighed in appropriate quantities according to
the mol% of the samples. The powdered mixture was placed in a crucible and melted in an electrical furnace to obtain a homogenous melt
at 1100 °C for 1 h. A special mold was made to obtain samples with a
cylindrical shape and dimensions of 10 mm × 20 mm. The glass melt
was poured into the stainless steel mold. All of these glass samples
were annealed at 400 °C (below Tg) for 1 h to remove the thermal
strain.
The glass samples were later cut and polished to obtain flat, parallel end faces that were suitable for ultrasonic measurements. The density measurement was performed using the Archimedes method with
acetone as the buoyant liquid. The room-temperature ultrasonic measurements were carried out at 10 MHz using x-cut and y-cut quartz
transducers. A pulse superposition technique was employed using an
Ultrasonic Data Acquisition System (Matec 8020, Matec Instruments,
USA). Burnt honey was used as a bonding material between the glass
samples and the transducers. By measuring the thickness of the sample
(d), longitudinal (Vl) and transverse (Vt) wave velocities were calculated using the relation V = 2d/t. The absolute accuracy in the measurement of the velocity is ±5 m s−1, and the relative error is ±0.1%.
In an amorphous solid, the elastic strain produced by a small stress
can be described by two independent elastic constants, C11 and C44.
Elastic moduli were calculated using the following standard relations.
2
Longitudinal modulus C11 ¼ L ¼ ρV l ;
ð1Þ
2
Shear modulus C44 ¼ G ¼ ρV t ;
ð2Þ
Bulk modulus K ¼ L–ð4=3ÞG;
ð3Þ
Young’s modulus E ¼ ð1 þ σ Þ2 G;
ð4Þ
Poisson’s ratio σ ¼ ðL–2GÞ=2ðL–GÞ;
ð5Þ
3. Results and discussion
The density of the binary lead phosphate glasses (PbO)x(P2O5)1−x
together with the molar volume, sound velocities (both longitudinal
and transverse), the calculated elastic constants (C11 and C44), the
bulk modulus (K), Young's modulus (E), Poisson's ratio (σ) and the
4000
3800
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
PbO mol%
Fig. 1. Variation of density versus PbO mol%.
Debye temperature obtained from the experimental results are given
in Table 1.
Lead phosphate glasses are interesting systems to study because
the glass phase can be formed over a wide concentration. Moreover,
PbO can enter the glass network both as a network modifier and also
as a network former [23]. It was suggested that the addition of PbO
to phosphate networks results in the formation of POPb bonds,
leading to a dramatic improvement in the chemical durability of the
phosphate glasses [31].
The variation of density versus mol% of PbO as shown in Fig. 1,
suggests that the addition of PbO to phosphate glass networks causes
a nonlinear increase in density. As shown in Fig. 1 the densities of
(PbO)x(P2O5)1−x glasses increase with an increase of the PbO content.
This change in density by the addition of PbO is related to the change
in the atomic mass and the atomic volume of the constituent elements. The atomic masses of the Pb and P atoms are 207.20 and
30.87, and their atomic radii are 1.75, and 1.28 Å, respectively. This
explains the increase in density with the increase in the PbO content.
There is a nonlinear increase in density up to 40 mol%. For higher
amounts of PbO, the increase in the density is highly pronounced.
The addition of PbO and the decrease in the P2O5 concentration in
the glass network caused the densities to increase, which indicates
that the Pb 2+ acts as a network modifier, altering the structure of
the glass by reducing nonbridging oxygens (NBOs) in the network,
so that the structure turns out to be more compact. The possible reactions in the glass network can be represented as follows:
h
i
h
i
P2 O5 ≡2 POO3=2 and PbO≡ PbO2=2
h
i
h
i h
i2−
h
iþ
PbO2=2 þ 2 POO3=2 ↔ PbO4=2
þ 2 PO4=2
The additional oxygen sharing and charge-balance requirements
are met by the conversion of P_O in [POO3/2] units to form PO in
[PO4/2] + units. It is therefore suggested that the P_O bonds are titrated continuously to incorporate Pb into the network [32]. This process
gives rise to the formation of POPb linkages.
Fig. 2 shows that the molar volume of the glasses increases with increases in the PbO content. Both the density and the molar volume of
Table 1
The values of density, molar volume, sound velocities, elastic moduli, Poisson's ratio and Debye temperature of (PbO)x(P2O5)1−x glasses.
Glass sample
(x)
ρ
(kg/m3)
Vm
(cm3/mol)
Vl
(m/s)
Vt
(m/s)
C11
(GPa)
C44
(GPa)
K
(GPa)
E
(GPa)
σ
ƟD
(K)
0.1
0.2
0.3
0.4
0.5
0.6
4136
4275
4470
4521
4706
4856
36.3
37.0
37.1
38.6
38.8
39.3
2706
2857
2912
3011
3141
3237
1576
1664
1702
1765
1788
1844
30.3
34.9
38.0
41.0
46.4
50.9
10.3
11.8
12.9
14.1
15.0
16.5
16.6
19.1
20.6
22.2
26.4
28.9
25.5
29.4
32.1
34.9
37.9
41.6
0.238
0.242
0.243
0.244
0.256
0.261
256
253
251
249
244
240
20. 80
K.A. Matori et al. / Journal of Non-Crystalline Solids 361 (2013) 78–81
60
C11
50
39
Elastic modulus (GPa)
Molar Volume (cm3/mol)
40
38
37
36
E
40
30
K
20
C44
10
35
0
0.1
0.2
0.3
0.4
0.5
0.6
0
0.7
0
PbO mol%
0.1
0.2
0.3
0.4
0.5
0.6
0.7
PbO mol%
Fig. 2. Variation of molar volume versus PbO mol%.
Fig. 4. Variation of elastic moduli versus PbO mol%.
the glasses increase with an increase in PbO. The density and molar volume increase by replacing P2O5 by PbO. As shown in Fig. 1 and Fig. 2 the
density of (PbO)x(P2O5)1−x glasses varies from 4136 to 4856 kg m −3
and that the molar volume varies from 36.3 to 39.3 cm3 mol−1. Generally, the density and the molar volume show opposite behaviors, but in
this study, different results were obtained. In this glass, the substitution
of phosphorus by lead causes an expansion of the network. Similar
trends for densities and molar volumes have already been reported
elsewhere for other glass systems [16,24,33,34].
It is clear that by increasing PbO, the molar volume increases,
which is similar to the variation density that occurs with increasing
PbO content. The Pb ions may enter the glass network interstitially;
hence, some network POP bonds are broken and replaced by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore, if one assumed that the only effect of adding Pb cations was to
break down the network POP bonds, then an increase in the
molar volume with PbO content would be expected for the entire
vitreous range of the studied glass system. Experimentally, this effect
increases the molar volume, and as a consequence, the values of the
density are increased. The addition of PbO increased the values of
the density, which is most likely attributable to simultaneous filling
up of the vacancies in the network by the interstitial Pb ions with
an atomic mass of 207.20. This increase in density indicates a structural change in the glass network, which is accompanied by an increase in the molar volume [35].
The addition of PbO in glass interstices causes more ions to fill up
the network, thus compacting the glass structure and increasing the
rigidity of the network. As a consequence, both velocities Vl and Vt
increase with the addition of PbO, as shown in Fig. 3. An increase of
the ultrasonic velocities with an increase in the PbO concentration
has been observed, which indicates that PbO plays a dominant role
in the velocities. In this (PbO)x(P2O5)1−x glass system, PbO plays
the role of a network modifier. It will modify the glass structure,
thus causing the glass to become harder. Although the glass is harder,
this does not mean that the glass is dense.
The independent elastic constants for isotropic solids and glasses
are the longitudinal modulus (C11) and the shear modulus (C44). The
calculation of other elastic constants and Poisson's ratio depends on
the values of the density and on both of the velocities. The sound velocities also determine Young's modulus, which is defined as a ratio
of the linear stress over the linear strain and is related to the bond
strength. Additionally, the bulk modulus is defined as the change in
volume when a force is acting upon it in all directions.
Fig. 4 shows the variation of the elastic moduli; C11, C44, K and E
versus mol% of PbO. It can be observed that for every type of glass,
there is a similar pattern in the elastic moduli with increases of the
PbO content in the composition. The values of the elastic moduli increase linearly with increases in the PbO content. In general, the addition of PbO to a phosphate glass network increases the rigidity, the
velocity and hence the elasticity of the glass. The increase in the rigidity of the glass contributes to the increase in the velocity and elastic
moduli.
Poisson's ratio obtained from elastic moduli remains almost constant and linearly increases from 40 mol% PbO and above, while the
Debye temperature obtained from ultrasonic velocities shows a continuous decrease with the addition of PbO, as shown in Figs. 5 and 6.
Although the modulus is sensitive to structural changes in glasses
because it depends on the change in the cross-link density, the observation made about Poisson's ratio supports the finding that there is no
appreciable change in cross-link densities with the addition of PbO.
The change in the cross-link density of the glass network is well
understood from the variation in Poisson's ratio. In general, a high
cross-link density has a Poisson's ratio on the order of 0.1 to 0.2 [29],
while a low cross-link density has a Poisson's ratio between 0.3 and
0.5. In the present system, Poisson's ratio (Fig. 5) is almost constant
3400
0.27
Longitudinal velocity
Poisson's ratio
Velocity (m/s)
2900
2400
Transverse velocity
1900
0.26
0.25
0.24
1400
0.23
0
0.1
0.2
0.3
0.4
0.5
PbO mol%
Fig. 3. Variation of sound velocities versus PbO mol%.
0.6
0.7
0
0.1
0.2
0.3
0.4
0.5
Pbo mol%
Fig. 5. Variation of Poisson's ratio versus PbO mol%.
0.6
0.7
21. K.A. Matori et al. / Journal of Non-Crystalline Solids 361 (2013) 78–81
81
Debye temperature (K)
260
Acknowledgments
255
The researchers gratefully acknowledge the financial support for
this study from the Malaysian Ministry of Higher Education (MOHE)
through the Fundamental Research Grant Scheme (5523753).
250
245
References
240
235
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
PbO mol%
Fig. 6. Variation of Debye temperature versus PbO mol%.
(changes from 0.238 to 0.261) when the PbO content is increased. The
observed Debye temperature, obtained from the ultrasonic velocity
data, is particularly sensitive to the PbO content (Fig. 6). The observed
decrease in the Debye temperature with the addition of PbO supports
the finding that the addition of PbO content indicates the compact
packing structure of the glass structure and a reduction in the creation
of NBOs, as discussed above.
4. Conclusions
The elastic properties of binary (PbO)x(P2O5)1−x lead phosphate
glass systems have been studied to ascertain the role of Pb 2+ ions in
these glasses. Based on the results obtained, the density and molar
volume increase with the addition of PbO in the (PbO)x(P2O5)1−x
glass system. The velocities (Vl and Vt) and elastic moduli (C11, C44,
K, and E) show gradually increasing trends as PbO is being added
into the lead phosphate glass network. Poisson's ratio remains almost
constant in the early stage and then increases, while the Debye temperature obtained from ultrasonic velocities shows a continuous decrease with the addition of PbO content. The addition of PbO in the
glass network caused the densities to increase according to the atomic
mass and atomic radii of the Pb atoms. In addition, the addition of PbO
and the decrease of the P2O5 concentration in the glass network
caused the densities to increase, which indicates that the Pb 2+ acts
as a network modifier, altering the structure of the glass by reducing
the non-bridging oxygens (NBOs) in the network and causing the
structure to be more compact.
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22. Int. J. Mol. Sci. 2013, 14, 3201-3214; doi:10.3390/ijms14023201
OPEN ACCESS
International Journal of
Molecular Sciences
ISSN 1422-0067
www.mdpi.com/journal/ijms
Article
Structural and Optical Properties of Lead-Boro-Tellurrite
Glasses Induced by Gamma-Ray
Iskandar Shahrim Mustafa 1, Halimah Mohamed Kamari 2,*, Wan Mohd Daud Wan Yusoff 2,
Sidek Abdul Aziz 2 and Azhar Abdul Rahman 1
1
2
School of Physics, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang, Malaysia;
E-Mails: iskandarshah@usm.my (I.S.M.); arazhar@usm.my (A.A.R.)
Physics Department, Faculty of Science, Universiti Putra Malaysia, 43400 UPM, Serdang,
Selangor, Malaysia; E-Mails: wmdaud@science.upm.edu.my (W.M.D.W.Y.);
sidek@science.upm.edu.my (S.A.A.)
* Author to whom correspondence should be addressed; E-Mail: halimah@science.upm.edu.my;
Tel.: +603-89466657; Fax: +603-89454454.
Received: 25 October 2012; in revised form: 9 January 2013 / Accepted: 12 January 2013 /
Published: 4 February 2013
Abstract: Spectrophotometric studies of lead borotellurite glasses were carried out before
and after gamma irradiation exposure. The increasing peak on the TeO4 bi-pyramidal
arrangement and TeO3+1 (or distorted TeO4) is due to augmentation of irradiation dose
which is attributed to an increase in degree of disorder of the amorphous phase. The
structures of lead tellurate contain Pb3TeO6 consisting of TeO3 trigonal pyramid connected
by PbO4 tetragonal forming a three-dimensional network. The decrease of glass rigidity is
due to irradiation process which is supported by the XRD diffractograms results. The
decreasing values of absorption edge indicate that red shift effect occur after irradiation
processes. A shift in the optical absorption edge attributed to an increase of the conjugation
length. The values of optical band gap, Eopt were calculated and found to be dependent on
the glass composition and radiation exposure. Generally, an increase and decrease in
Urbach’s energy can be considered as being due to an increase in defects within
glass network.
Keywords: tellurite glass; optical band gap; Urbach’s energy; irradiation
23. Int. J. Mol. Sci. 2013, 14
3202
1. Introduction
Glass in an amorphous (non-crystalline) solid material. Glasses are typically brittle and optically
transparent. The most familiar type of glass, used for centuries in windows and drinking vessels, is
soda-lime glass, composed of about 75% silica (SiO2) plus sodium oxide (Na2O) from soda ash, CaO,
and several minor additives. Some glasses that do not include silica as a major constituent may have
physico-chemical properties useful for their application in fibre optics and other specialized technical
applications. These include fluoride glasses, tellurite glasses, aluminosilicates, phosphate glasses,
borate glasses and chalcogenide glasses. Tellurite glasses contain tellurium oxide (TeO2) as the main
component. Tellurium dioxide is known as a conditional glass former, which it is, needs a modifier in
order to easily form the glassy state. The formation of glass on two glass formers interest both
scientific and practical locale. The structural network will be perturbed and may lead to the formation
of new structural units [1,2]. Glass forming substances are fall into two categories of inorganic
compounds containing bonds which are partially ionic and partially covalent, and, inorganic or organic
compounds which form chain structures with covalent bonds within the chains and van der Waals’
bonds between the chains. Glasses containing heavy metal oxide (HMO) have recently attracted the
attention of several researchers for the excellent infrared transmission compared with conventional
glasses. The γ-irradiation on glasses is found to affect the optical and physical properties [3,4]. Hence,
radiation damage caused by electrons, alpha particles and gamma rays has been thoroughly
investigated [5]. The structural and physical properties of PbO glasses are well described by Worrel
and Henshell [6]. In previous work, Atul et al. [7] have studied borate glasses containing heavy-metal
oxides and shown that it has potential applications in radiation shielding. The objective of the present
work is to study the effect of radiation on the structural and optical properties of lead borotellurite
glass system. To achieve this, a systematic study on optical properties has been performed to
understand the variation of irradiation dose as a function of PbO composition in borotellurite glasses.
In addition, X-ray diffraction patterns and Raman spectra measurements were also performed in order
to support the available data.
2. Results and Discussion
2.1. Raman Spectra
Marker labeling of Raman peak is shown in Table 1. Raman spectrum in Figures 1 and 2 were
corrected for baseline and normalized which allows for an effective comparison across a
heterogeneous set of samples. Eventually, the baseline correction utilized the multiple point level
method (Savitzgy-Golay) in which the baseline is leveled at a value that is the average of the baseline
points. Normalization of Raman spectral was performed based on the common normalization method
referring to min/max technique. The min/max (normalization) method is expressed by:
(1)
where I is the intensity after baseline correction was performed, Imin is the minimum intensity and Imax
is the maximum intensity on single spectral measured. Raman spectrum in Figure 1 shows significant
24. Int. J. Mol. Sci. 2013, 14
3203
peak at <100 cm−1 which indicate the strong presence of Pb and Te in the chemical bonding through
vibrational mode due to addition of PbO and glass network. PbO stands out as unique because of its
dual role [8], one as modifier, if Pb–O bond is ionic and the other as glass former with PbO4 structural
units, if Pb–O bond is covalent. Occasionally, PbO concentration deteriorates glass forming ability [9]
of (TeO2)y[(PbO)x(B2O3)1−x]1−y system. The addition of heavy metal oxide modifiers to pure TeO2
leads to the progressive formation of distorted TeO3+1 polyhedron followed by the creation of regular
trigonal TeO3 pyramids that contain non-bridging oxygen. In all compositions, the appearance of the
low-frequency Boson peak (<200 cm−1) affirms the presence of the glass structure. The increase broad
shoulders at 410 cm−1 indicate that new features to vibrations of one of the partially crystalline phase
of Pb3TeO6. The existence of Pb3TeO6 is confirmed by X-ray analysis. Clearly, the shoulders at
410 cm−1 were getting broader as the content of PbO increased, possibly due to the PbO unique ability.
At low portions of PbO (up to 0.2% mol), it enters the glass network by breaking up the Te–O–Te and
B–O–B bonds and introduces coordinate defects known as dangling bonds along with non-bridging
oxygen ions (Te–O−…Pb2+…−O–Te) which in turn neutralizes the negative charge of non-bridging
oxygens (NBO) by forming TeO3 and BO4 units. Normally, the oxygen of PbO breaks the local
symmetry while Pb2+ ions occupy interstitial positions. As PbO increases (from 0.3% to 0.5% mol),
a considerable portion may be acts as a double bridges between adjacent TeO4 such as
=Te–O–Pb–O–Te= which can formed besides the formation of PbO4 and TeO3 units. Therefore, for
PbO ≥ 0.3% mol, Pb2+ acts as glass forming agent and is incorporated in the glass network in the form
of PbO4 units. Decreasing on (ss) Te–O–Te and B–O–B bending shoulder at approximately 490 cm−1
and 450 cm−1 ascribe that the splitting of Te–O–Te and B–O–B bonds and hence, the bridging
oxygen’s (BOs) are converted into NBOs. The pure B2O3 was known to consist of the boroxol rings by
linking among trigonal-plane BO3 units, but the network structure was altered through the addition of
PbO. Some parts of the boroxol ring of BO3 units were changed into BO4 tetrahedral units [10].
TeO4 trigonal bipyramids is known to be the main structural unit of the network of all tellurite
glasses [11], as well as of the lattices of crystalline TeO2 polymorphs. All stable tellurite glasses are
multi-component and, what is important, cations on non-tellurite components have a coordination
number other than four. The tellurite structural units of two types are always present in
multi-component tellurite glass network, namely, fourfold coordinated Te atoms (TeO4 trigonal
bipyramids, where all O atoms from bridging bonds with the environment) and threefold coordinated
Te atoms (O=TeO2 trigonal pyramids, where one of O atoms is non-bridging, one forms O=Te double
bond and one O atoms form bridging bonds with the environment). The spectral features from
710 cm−1 to 730 cm−1 and 790 cm−1 in Figure 1 correspond to the TeO4 bi-pyramidal arrangement and
the TeO3+1 (or distorted TeO4) and TeO3 trigonal pyramids structures respectively. It can be clearly
observed that the evolution of TeO4 to TeO3+1 and TeO3 units which one of the Te sp3 hybrid orbital is
occupied by a lone pair of electron. This transformation causes increases in the number of
non-bridging oxygen (NBO) atoms. Legitimately, the increasing peak on the TeO3 trigonal pyramids
shows that modification of lattice and interstitial occurs in the system due to addition of PbO
and B2O3.
25. Int. J. Mol. Sci. 2013, 14
3204
Table 1. Marker labeling Raman peak according to chemical bonding and stretching [12].
Raman Shift (cm−1)
Bonding
S—Strong
W—Weak
B—Bending
G—Group
as—Asymmetry stretching
ss—Symmetry stretching
(S) <100cm−1;
(S) 450 cm−1;
410 cm−1;
(W) 490 cm−1;
(S) 710 cm−1 ;
(S) 730 cm−1;
(S) 790 cm−1–860 cm−1;
Pb, Te
B–O–B (b)
Te–O–Te (ss)
TeO4 bi-pyramidal arrangement
TeO3+1 (distorted TeO4)
Te–O bending vibrations in TeO3
trigonal pyramids and TeO6
Figure 1. Raman spectra (at ambient temperature) of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses
with different compositions before irradiation.
1.0
Normalized Raman Intensity (a.u.)
0.9
0.8
0 Pb
0.7
0.1 Pb
0.2 Pb
0.6
0.3 Pb
0.5
0.4 Pb
0.5 Pb
0.4
Boson frequency
peak region
0.3
0.2
0.1
0.0
0
200
400
600
Raman Shift (cm-1)
800
1000
Figure 2. Raman spectra (at ambient temperature) of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses
with different irradiation doses at x = 0.5% mol, y = 0.7% mol.
1.0
Normalized Raman Intensity (a.u.)
0.9
0 kGy
5 kGy
10 kGy
20 kGy
25 kGy
0.8
0.7
0.6
0.5
0.4
Boson frequency
peak region
0.3
0.2
0.1
0.0
0
200
400
600
Raman Shift (cm-1)
800
1000
26. Int. J. Mol. Sci. 2013, 14
3205
The presence peaks at <100 cm−1 in Figure 2 do not indicate any strong changes of intensity due to
variation of gamma irradiation exposure. Eventually, the decrease in broad shoulders at 410 cm−1 also
indicates the existence of new features in the vibrations of the partially crystalline phase of Pb3TeO6.
The existence of Pb3TeO6 is confirmed by X-ray analysis. Clearly, the shoulders at 410 cm−1 were
getting lower as the irradiation dose increased, possibly due to the network compaction. The spectral
features from 710 cm−1 to 730 cm−1 and 790 cm−1 correspond to the TeO4 bi-pyramidal arrangement
and the TeO3+1 (or distorted TeO4) and TeO3 trigonal pyramids structures respectively. It can be
clearly observed that the evolution of TeO3+1 and TeO3 units occurs as the TeO2 concentration
decreases. Legitimately, the decreasing peak on the TeO4 bi-pyramidal arrangement and TeO3+1
(or distorted TeO4) is due to augmentation of irradiation dose which is attributed to an increase in
degree of disorder of the amorphous phase. According to El-Alaily and Mohamed [3], irradiation with
gamma rays are assumed to create displacements, electronic defects and/or breaks in the network bonds,
which allow the structure to relax and fill the relatively large interstices that exist in the interconnected
network of boron and oxygen atoms causing expansion followed by compaction of the volume.
Shelby [13] also suggested that the boron-oxygen bond is more likely to be affected by irradiation.
2.2. XRD
The XRD diffractograms result in Figure 3 shows the partially crystalline precipitation before and
after irradiation exposure for x = 0.5% mol; y = 0.7% mol. All the glass that was prepared proved to fit
the amorphous state. In addition to the enhanced amount of PbO, the glass had been acclimatized to the
partially crystalline phase from the full amorphous phase. It also shows the presence of a hunch for 2θ
around 20°–35°. All these XRD reflections were assigned to the two polymorphic phases; hexagonal
of tellurium (Te, PDF2 No. 00-036-1402) and monoclinic of lead tellurate (Pb3TeO6, PDF2
No. 00-033-0770). The intensity of the XRD reflections indicate that more monoclinic crystals are
reduced in quenched samples as the modifier content increases. The structures of lead tellurate contain
Pb3TeO6 probably consisting of TeO3 trigonal pyramid connected by PbO4 tetragonal, forming a
three-dimensional network. The decrease of glass rigidity is due to irradiation processes which are
supported by the XRD diffractogram results in Figure 3. The XRD result shows the presence of
crystalline precipitation before irradiation process. However, the partially crystalline peaks vanished
due to 5 kGy of gamma irradiation exposure. Eventually, modification of lattice and structural
arrangement along with network compaction occurs in the system due to irradiation exposure of more
than 5 kGy which comprises the presence of crystalline peaks. As the irradiation dose increases (above
20 kGy), the crystalline peaks once again begin to diminish. Obviously, the partially crystalline glass
still proved to fit the amorphous state as the irradiation dose increased.
27. Int. J. Mol. Sci. 2013, 14
3206
Figure
3. X-ray diffractogram patterns (at ambient temperature) of
(TeO2)y[(PbO)x(B2O3)1−x]1-y glasses (x = 0.5% mol; y = 0.7% mol) with varied gamma
irradiation dose.
25 kGy
Tellurium, syn, Te
(110)
Lead Tellurate, Pb3TeO6
Relative Counts (a.u.)
20 kGy
(440)
Tellurium, syn, Te
(114)
Tellurium, syn, Te
(114)
Lead Tellurate, Pb3TeO6
10 kGy
(440)
Lead Tellurate, Pb3TeO6
(422)
(440)
Tellurium, syn, Te
(114)
0 kGy
10
5 kGy
Lead Tellurate, Pb3TeO6
(422)
(440)
Tellurium, syn, Te
(114)
20
30
40
50
60
70
80
2θ
2.3. Optical Absorption Spectra
The optical absorption spectra were taken in the ranges of 340 to 550 nm. The optical absorption is
one of the most productive tools to understand the band gap of optical materials. The optical properties
of a solid are governed by the interaction between the solid and the electric field of the electromagnetic
wave. The optical absorption measurements coefficient α() near the fundamental is calculated from
absorbance A, using the following Equation [14]:
2.303 ⁄
(2)
where d is the thickness of the samples. The rapid change in α(ω) against ω is called “the fundamental
absorption edge” and the corresponding energy is defined as “the optical energy gap (Eopt). In the
compound, a typical absorption edge can be broadly ascribed to any of the three processes: (i) residual
below-gap absorption; (ii) Urbach tails; and (iii) interband absorption. In the second process, the
absorption edge depends exponentially on the photon energy according to the Urbach relation. In
crystalline materials the fundamental edge is directly related to the conduction band and valence band,
i.e., direct and indirect band gaps, while in the case of amorphous materials a different type of optical
absorption edge is observed. Figure 4 illustrates the variation of absorption coefficient, α with incident
photon energy at different doses.
Urbach edge analysis is a useful way to parametrically characterize glass optical absorption edge
and potentially distinguished intrinsic contributions to absorbance. Urbach’s absorption edge is formed
in the region of photon energies below the forbidden gap. The interaction between lattice vibrations
and localized states in tail of band gap from the glass samples has a significant effect on the optical
properties. The plot of ln (α) against photon energy, ħω is linear for the absorption region near the
fundamental absorption edge. Thus, it is evaluated that the absorption coefficient near the fundamental
absorption edge is exponentially dependent on the photon energy and obeys the Ubach’s rule. Figure 5
illustrates the dependence of Urbach’s absorption edge with different irradiation of prepared glasses.
28. Int. J. Mol. Sci. 2013, 14
3207
The absorption edge decreases with the increase of dose. Significantly, the decreasing values of
absorption edge indicate that after irradiation processes, there is red shift effect on the
(TeO2)y[(PbO)x(B2O3)1−x]1−y glasses. The red shift effect is a process when the absorbance band shifts
to longer wavelength and widens due to irradiation. A shift in the absorption edge can be attributed to
an increase of the conjugation length. The number of Te atoms and Pb atoms per conjugation length is
found to increase with increasing dose which create structure defect within the prepared
(TeO2)y[(PbO)x(B2O3)1−x]1−y glass.
Figure 4. Optical absorption edge, α of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with
y = x = 0.5% mol; 0.7% mol at various irradiation exposure. The lines represent
the expolation.
8
0 kGy
7
5 kGy
6
10 kGy
20 kGy
(cm‐1)
5
25 kGy
4
3
2
1
0
1.5
2.0
2.5
ħω (eV)
3.0
3.5
Figure 5. The dependence of Urbach’s absorption edge on different irradiation dose for
(TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with y = x = 0.5% mol; 0.7% mol.
3.10
Absorpotion edge, ħω (eV)
2.90
2.70
2.50
0 % mol Pb
0.1 % mol Pb
0.2 % mol Pb
0.3 % mol Pb
0.4 % mol Pb
0.5 % mol Pb
2.30
2.10
1.90
1.70
1.50
0
5
10
15
Dose (kGy)
20
25
30
The optical band gap energy is determined by using the following Equation [15]
(3)
29. Int. J. Mol. Sci. 2013, 14
3208
where α is the absorption coefficient, ħω is the incident photon energy, A is a constant and Eopt is the
optical band gap. Values of n are 2 and 1/2 for direct and indirect transitions, respectively. Figure 6
shows the information of indirect band gap (αħω)1/2 against photon energy ħω of
(TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with x = 0.5 mol %; y = 0.7 mol % at various irradiation exposure,
plotted in the absorption region. Indirect energy gap is determined from the linear regions of the plots
as shown in the figures and corresponding values presented in Table 2. The Eopt has been calculated
approximately from the linear region of the arc extrapolating to meet the ħω axis at (αħω)1/2=0.
Figure 6. Plot of (αħω)1/2 against photon energy for indirect band gap of
(TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with y = x = 0.5% mol; 0.7% mol at various irradiation
exposure. The lines represent the pattern.
6
(αħω)1/2 (cm‐1 eV)1/2
5
4
3
0 kGy
5 kGy
10 kGy
20 kGy
25 kGy
2
1
0
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5
ħω (eV)
The variation of indirect optical band gap with mole fraction of PbO content before and after
irradiation is shown in Figure 7. The connected lines do not resemble any significant explanations
rather than to show the decreasing and increasing pattern of the graph. The optical band gap values of
the indirect process before irradiation decreases through the augment of PbO from 0% mol to
0.15% mol. This is due to the increase of the network disorder and consequently the extension of the
localized states within the gap. More likely, PbO enters the glass network by breaking up the Te–O–Te
and B–O–B bonds and introduces coordinate defects known as dangling bonds along with
non-bridging oxygen. Normally, the oxygen of PbO breaks the local symmetry while Pb2+ ions occupy
interstitial positions. PbO content >0.2% mol shows a slight increase before tends to decline slowly
for 0 kGy and increase for irradiated samples with 5 kGy up to 25 kGy (towards 0.5% mol).
Consequently, as PbO increases (from 0.2% to 0.5% mol), modification of lattice and interstitial
occurs in the system with the nearest neighboring atoms and arrangements, such as PbO4 and/or BO4.
A considerable portion may act as double bridges between adjacent TeO4 which can form in addition
to the formation of PbO4 and TeO3 units. Therefore, for PbO ≥ 0.2% mol, Pb2+ acts as glass forming
agent and is incorporated in the glass network in the form of PbO4 units. The optical band gap, Eopt
values for indirect transition decrease with increasing of irradiation dosage as the content of
PbO ≤ 0.2% mol due to increase in degree of disorder of the amorphous phase. Obviously, the Eopt
values for indirect transition increase with increasing of irradiation dosage as the content of
30. Int. J. Mol. Sci. 2013, 14
3209
PbO > 0.2% mol. It is believed that the increasing of irradiation create displacements, electronic
defects and/or breaks in the network bonds, which allow the structure to relax and fill the relative large
interstices that exist in the interconnected network of boron and oxygen atoms causing expansion
followed by compaction of the volume.
Figure 7. Variation optical band gap, Eopt of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses for
indirect transition with x = 0%–0.5% mol; y = 0.7% mol at various irradiation exposure.
The lines represent the extrapolation.
3.00
Eopt (eV)
2.50
2.00
0 kGy
1.50
5 kGy
10 kGy
1.00
20 kGy
25 kGy
0.50
0
0.1
0.2
0.3
0.4
0.5
0.6
PbO, x (mol %)
In many crystalline and non-crystalline semiconductors, the α(ω) depends exponentially on the ħω.
This exponential dependence, known as the Urbach rule, can be written in the form [16]:
∆
(4)
where B is a constant and ΔE is the width of the band tails of the localized states which also known as
Urbach energy. The value of Urbach energy (ΔE) is calculated by taking the reciprocals of the slopes
of the linear portion of the ln α() against ħω curves in the lower photon energy regions. Figure 8
shows the reciprocal of the slopes of the linear portion from the ln α() against ħω curves in the lower
photon energy regions for (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with x = 0.5% mol; y = 0.7% mol at
various irradiation exposure. The reciprocal values will be used to calculate the value of Urbach
energy (ΔE) using the Equation 3. The values of (ΔE) of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses’ various
irradiation exposure with x = 0.0%–0.5% mol; y = 0.7% mol are visualized in Figure 9 and tabulated in
Table 2. Generally, an increase and decrease in Urbach energy can be considered as being due to
defects within the glass network.
31. Int. J. Mol. Sci. 2013, 14
3210
Figure 8. Optical absorption coefficient of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with
y = x = 0.5% mol; 0.7% mol at various irradiation exposure. The line represents the pattern.
2.5
2.0
ln α (cm‐1)
1.5
1.0
0.5
0 kGy
5 kGy
10 kGy
20 kGy
25 kGy
0.0
‐0.5
‐1.0
‐1.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
3.3
3.4
ħω (eV)
Figure 9. Variation Urbach energy, ΔE of (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses for indirect
transition with x = 0%–0.5% mol; y = 0.7% mol at various irradiation exposure. The lines
represent the pattern.
2.0
0 kGy
5 kGy
10 kGy
20 kGy
25 kGy
ΔE (eV)
1.5
1.0
0.5
0.0
0
0.1
0.2
0.3
0.4
0.5
0.6
PbO, x (mol %)
Urbach’s energy is a characteristic energy which determines how rapidly the absorption coefficient
decreases for below band gap energy. Urbach measured the absorption tail for different temperatures
and showed that the Urbach’s energy is approximately kT, the thermal energy. The temperature
dependence of the urbach tail led to the conclusion that the below-bandgap transitions are assisted
transition. The Urbach tail can be caused by mechanisms other than phonon-assisted absorption.
Considering Figure 9, before irradiation took place, the Ubach energy having a non-prominent increase
pattern when the content PbO in the network increase which illustrating the saturation of defects at
high content of PbO. Other than that, it is more likely due to the increase of the disorder and
consequently the more extension of the localized states. For every irradiation dose of between 5 kGy
and 25 kGy, Ubach energy increases as the content of PbO ≤ 0.2% mol suggesting the increasing of
disorder and consequently the further extension of the localized states. Nevertheless, Ubach energy for
every irradiation dose from 5 kGy up to 25 kGy decreases as the content of PbO > 0.2% mol
advocating the possibility of long range order locally arising from the minimum in the number
of defects.
32. Int. J. Mol. Sci. 2013, 14
3211
Table 2. Optical characteristic for (TeO2)y[(PbO)x(B2O3)1−x]1−y glasses, y = 0.7% mol.
PbO, x
(mol %)
0.00
0.10
0.20
0.30
0.40
0.50
Dose
(kGy)
0
5
10
20
25
0
5
10
20
25
0
5
10
20
25
0
5
10
20
25
0
5
10
20
25
0
5
10
20
25
Direct transition
Eopt (eV)
3.22
3.13
2.82
2.76
2.74
3.22
2.97
2.82
2.72
2.62
3.18
2.98
2.54
2.62
2.66
3.16
2.94
2.66
2.68
2.76
3.16
3.04
2.74
2.78
2.80
3.10
3.00
2.80
2.82
2.92
Indirect transition
Eopt (eV)
2.78
2.48
2.10
1.84
1.80
2.78
2.28
1.96
1.70
1.60
2.72
2.38
1.16
1.36
1.60
2.73
2.30
1.64
1.68
1.80
2.66
2.40
1.59
1.62
1.80
2.58
2.38
1.82
1.92
1.90
Urbach energy
ΔE (eV)
0.27
0.36
0.65
0.68
0.73
0.27
0.43
0.81
1.06
1.09
0.28
0.38
1.58
1.17
0.94
0.25
0.41
1.23
1.00
0.79
0.30
0.35
1.17
1.00
0.87
0.28
0.34
0.87
0.70
0.70
With the increasing of irradiation dosage, the content of PbO ≤ 0.2% mol, the Ubach energy
increases significantly, this suggests the increase in degree of disorder of the amorphous phase. As the
content of PbO increases to be greater than 0.2% mol, the Ubach energy increases with 5 kGy and
10 kGy of irradiation dose and begins to decrease with irradiation dosage of 20 kGy and 25 kGy. It is
believed that the increasing of irradiation creates displacements, electronic defects and/or breaks in the
network bonds, which allow the structure to relax and fill the relative large interstices that exist in the
interconnected network, causing expansion followed by compaction of the volume.
33. Int. J. Mol. Sci. 2013, 14
3212
3. Experimental Section
The ternary (TeO2)y[(PbO)x(B2O3)1−x]1−y glass system (x = 0.0%–0.50% mol and y = 0.7% mol)
were prepared using a conventional melt-quenching method [17]. All the glass samples arranged were
homogenous, transparent and bubble free. The glasses were prepared by mixing together specific
weights of Tellurium dioxide—TeO2 (Alfa Aesar 99.99%), Lead oxide, Litharge—PbO (99%) and
Boron oxide—B2O3 (Alfa Aesar, 97.5%). Appropriate amounts of TeO2, PbO and B2O3 were weighed
by using an electronic balance having an accuracy of 0.0001 g. The chemicals were then thoroughly
mixed in an Agate pestle mortar for half an hour and poured into an Alumina crucible. The crucible
was transferred to a furnace and heated at 950 °C for 2 h to aid the melting process. When the melting
process was complete, the molten liquid was cast into a stainless steel cylindrical shape mold which
had been preheated at 340 °C for 30 min. The produced glass samples were annealed at the
temperature range 340 °C for 2 h, and then the furnace was turned off for cooling process reaching the
atmospheric temperature. The glass samples were cut using Buhler ISOMET diamond cutter at a
thickness of approximately 2 mm for the required measurements.
The irradiation process had been conducted using 6°Co gamma rays (J.L. Sherperd & Associates,
model 109-68# 3044) with the dose rate of 5.52 kGyh−1 on March 2004. The 6°Co radioisotope
produced two gamma rays of energy 1.17 MeV and 1.33 MeV, often indicated in the machine as the
average energy of 1.25 MeV, is the most widely used gamma source not only for research, but also for
the food preservation, sterilization of medical equipment and pharmaceutical raw materials. The dose
, where λ is the decay
rate at the day of irradiation was calculated using decay equation
constant, Dt is the dose rate at time t and D0 is the dose rate calibrated using Fricke dosimeter (Ferrous
Sulphate). The half-life of 6°Co is 5.3 years. The irradiation has been conducted at the building 41,
SINAGAMA at Malaysia Nuclear Agency. Raman spectra were measured using a Raman spectrometer
(RSI 2001 B, Raman system, INC) equipped with a 532 nm solid-state diode green laser. Grams/32,
version 6 software was used to analyze the spectra. All spectra were corrected for baseline; smoothed
and Fourier Transformed (FT). The baseline correction utilized the multiple point level method in
which the baseline is leveled at a value that is the average of the baseline points. A constant correction
factor of 80% of the degree of smoothing parameter was used throughout the data collection. The
Fourier smoothing was accomplished by the peak data, applying a triangular filter function at the
specified cut-off point of 40% and then reverse Fourier transforming the data. Optical absorption
measurements in the wavelength range of 190 to 800 nm with 0.1 nm internal spacing at slow scan
speed were performed at room temperature using SHIMADZU spectrophotometer model UV-1650PC
(absorption within ± 0.1 a.u. and wavelength within ± 2 cm−1). Phase identification of the samples will
be determined by X-ray Powder Diffractometer, Philip X’Pert Pro Holland, using Cu-Kα
monochromatized radiation (λ = 1.5418 mm). The operating generator tension is 40 kV while
generator current is 30 mA. X-Ray diffraction patterns of powders were recorded at room temperature
with a diffraction angle from 2θ = 5°–90° and at a rate of 0.01°/min. The XRD measurements were
held using bulk dimension since the results gained did not shows any significant difference between
bulk dimension and powder dimension.