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DOI 10.1007/s10853-009-4015-5
M. El-Hawary • N. El-Khoshkhany
Received: 13 May 2009 / Accepted: 31 October 2009 / Published online: 24 November 2009
Springer Science+Business Media, LLC 2009
Abstract Binary tellurite glass systems of the forms hosts. The physical properties and structure of crystalline
TeO2(100 - x) - xAnOm where AnOm = La2O3 or V2O5 solids are understood now, but this is not the case for
and x = 5, 7.5, 10, 12.5, 15, 17.5, and 20 mol% for La2O3 amorphous materials. The considerable theoretical diffi-
and 10, 20, 25, 30, 35, 40, 45, and 50 mol% for V2O5 were culties experienced for amorphous solids are amplified by
prepared. Density and molar volume of each glass were the lack of precise experimental information. This study is
measured and calculated. The compressibility model has carried out to fill this gap. The mutual benefits of the
been used to find the difference volume Vd due to the proposed cooperative research effort are seen as providing
exchange of one formula unit between Te and both of La the fundamental base for finding new optical glasses with
and V in the binary glass system and the mean volume VA new applications especially (tellurite-based glass optical
per formula unit in the present binary glass in order to fiber) which are of interest of all countries all over the
check whether or not it is independent of the percentage of world. The physical properties of tellurite glasses have
the modifier for a glass series and also different from series been collected in and also an introduction to ‘‘Telluirte
to another. Differential scanning calorimetric at different Glasses’’ lecture has been provided as resource for the
heating rates was used to gain some insight into the thermal entire international glass community available in video
stability and calorimetric behavior of the present binary streaming format on the IMI website [1].
transition metal and rare-earth tellurite glasses. The glass Previously, the thermal behavior of tellurite glass sys-
transformation temperature Tg and glass crystallization tems has been studied by using the differential thermal
temperature Tc were recorded at different heating rates to analysis (DTA) to measure the glass transformation tem-
calculate both of the glass transition activation and the perature Tg, or specific heat capacity Cp in the temperature
glass crystallization activation energies by using different range starting from room temperature to above the Tg.
methods. Structural, vibrational investigations on thermal properties,
devitrification, vitrification, calorimetric study, and glass
stability of tellurite glasses have been measured [2–9]. The
Introduction present objective is to measure glass transition tempera-
ture Tg, crystallization temperature Tc, and onset of crys-
Tellurite glasses exhibit a range of unique properties of tallization temperature Tx, and also to calculate glass
potential applications as pressure sensors or as new laser stability against crystallization S and glass-forming ten-
dency Kg. The above experimental parameters will be
interpreted quantitatively according to the structure
A. Abdel-Kader—deceased. parameters like average cross-link density n0 c, number of
bonds per unit volume nb and average stretching force
R. El-Mallawany (&) A. Abdel-Kader M. El-Hawary constant F for every glass composition. Also the calculate
N. El-Khoshkhany
glass transition activation energy and the glass crystalli-
Physics Department, Faculty of Science, Menoufia University,
Shebin El-Koom, Egypt zation activation energy have been calculated using dif-
e-mail: relmallawany@hotmail.com ferent methods like Chen’s, Monihan’s, Kissinger’s, and
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872 J Mater Sci (2010) 45:871–887
Ozawa’s models for the very important tellurite glass from mild steel. The sample was transferred after that to
systems, e.g., semiconducting tellurite vanadate glass [10, the annealing furnace. After 1 h at 300 C, the annealing
11] and high non-linear optical properties lanthanide tel- furnace was then switched off and the glass rod was
lurite glasses [12]. allowed to cool inside it for 24 h. The two glass opposite
faces were ground roughly approximated parallel on a
lapping machine with 600 grade SiC powder. Opposite
Experimental work faces were finished optically flat and parallel with a high
Density (gm/cm 3 )
15, 17.5, and 20 mol% and vanadium oxide (V2O5, 99.99% 5
purity, BDH) where x = 10, 20, 25, 30, 35, 40, 45, and 4.75
50 mol%. The diffusion process took place through an
agate mortar and the mixture was thoroughly ground for 4.5
20 min. The powdered mixture was then put into an alu-
4.25
mina crucible and heated in a melting furnace. In order to
reduce any tendency of volatilization, the mixture was kept 4
at 300 C for 15 min. The crucible was then kept in the
same furnace above 300 C, the value of these temperature 3.75
depend upon the composition of each sample and its
3.5
melting temperature. After reaching the required tempera- 0 10 20 30 40 50
ture (850–900 C), the mixture was left for 20 min. To mol%
improve the homogeneity, the melt was stirred from time- Fig. 1 Variation of density with La2O3 content (mol%) for
to-time with an alumina rod. The melt which had a high (TeO2)(100-x) - (La2O3)x glasses and with V2O5 content (mol%)
viscosity was cast at room temperature in a split mold made for (TeO2)(100-x) - (V2O5)x glasses
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J Mater Sci (2010) 45:871–887 873
44 280
38 220
36
200
34
180
32
160
0 5 10 15 20 25 30 35 40 45 50
0 10 20 30 40 50 mol %
mol %
Fig. 4 Variation of Nb (the number of bond per unit volume) with
Fig. 2 Variation of molar volume with La2O3 content (mol%) for La2O3 content (mol%) for (TeO2)(100-x) - (La2O3)x glasses and with
(TeO2)(100-x) - (La2O3)x glasses and with V2O5 content (mol%) For V2O5 content (mol%) for (TeO2)(100-x) - (V2O5)x glasses
(TeO2)(100-x) - (V2O5)x glasses
44 280
43
42 260
41
Average force constant F(N/m)
40 240
Molar volume (cm3)
39
36 200
35
34 180
33 (TeO2)(100-x)-(La 2O3)x
(TeO2)(100-x)-(V2O5)x 160
32
31 0 5 10 15 20 25 30 35 40 45 50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
mol %
Ratio between number of formula units (nB /nA)
Fig. 5 Variation of the average force constant F with La2O3 content
Fig. 3 Variation of the molar volume with the ratio between the (mol%) for (TeO2)(100-x) - (La2O3)x glasses and with V2O5 content
number of network formula units (nB/nA) for (TeO2)(100-x) - (mol%) for (TeO2)(100–x) - (V2O5)x glasses
(La2O3)x glasses and for (TeO2)(100-x) - (V2O5)x glasses
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874 J Mater Sci (2010) 45:871–887
density of each composition was then obtained by using the molecule of the glass) was calculated by the following
following relation expression:
Wa qL ðxMA þ yMB Þ
qg ¼ ð1Þ V¼ ð2Þ
ðW a W L Þ qg
where qL is the relative density of the liquid toluene where the glass composition is represented by x and y
(0.864 g/cm3 at 25 C), Wa and WL are the weights of the and x ? y = 100% and MA, MB are the molecular
glass sample in air and in the liquid, respectively. The weights of materials A and B forming the glassy
molar volume V (i.e., the volume occupied by one gram network.
(a)
(TeO2 )100-x - (La2O3)x
(a)
(TeO2 )100-x (V2O5)x
Exo
X= 17.5
Exo
X= 15 50
T
45
X= 12.5 40
T
35
Endo
25
X= 10
Endo
20
10
X= 7.5
= 20 K/min
Exo
15
T
10
T
= 20 K/min
15
5 10
Endo
Endo
Fig. 6 a Typical DSC traces of the prepared binary lanthanum Fig. 7 a Typical DSC traces of the prepared binary vanadium
tellurite glasses for different compositions at heating rate 10 K/min. tellurite glasses for different compositions at heating rate 10 K/min.
b Typical DSC traces of the prepared binary (TeO2)90 - (La2O3)10 b Typical DSC traces of the prepared binary (TeO2)65 - (V2O5)35
glasses for different heating rates glasses for different heating rate
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J Mater Sci (2010) 45:871–887 875
TeO2 glass [13] 598 673 713 933 75 0.6 115 0.41
TeO2–La2O3
92.5–7.5 624 661 676 923 37 0.68 52 0.21
90–10 666 687 726 928 21 0.72 60 0.3
87.5–12.5 675 707 735 921 32 0.73 60 0.32
85–15 684 708 747 944 24 0.72 63 0.32
82.5–17.5 705 730 755 953 25 0.74 50 0.25
TeO2–V2O5
90–10 563 646 664 993 83 0.57 101 0.31
80–20 550 664 721 1160 114 0.47 171 0.39
75–25 538 676 732 1166 138 0.46 194 0.45
65–35 525 652 705 1170 127 0.45 180 0.39
60–40 519 677 714 1173 158 0.44 195 0.42
55–45 512 685 724 1178 173 0.43 212 0.47
50–50 511 686 714 1180 175 0.43 203 0.44
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876 J Mater Sci (2010) 45:871–887
and decreasing with increasing La2O3 or V2O5 content. The 34.21 cm3. Also for the second series TeO2–V2O5 glass,
molar volume V was calculated from Eq. 2. The change of the molar volume increased from 32.11 to 42.58 cm3 as
molar volume versus mol% concentration of La2O3 and shown in Fig. 2. The molar volume of binary vanadium
V2O5 is shown in Fig. 2. The calculated molar volume of tellurite glasses or binary lanthanum tellurite glasses would
the pure TeO2 crystal and TeO2 glass was 26.6 and be higher than pure TeO2 glass, as shown in Table 1.
31.29 cm3, respectively [13]. This means that the ratio The structural interpretation will be based on the simple
Vglass/Vcrystal is 1.18, i.e., the change is only 18% from model of compressibility by Mukherjee et al. [15] of binary
crystalline solid to be non-crystalline solid. Hence, the fact glass AxB1-y containing nA formula units of type A and nB
that molar volume of the glass is greater than that of the formula units of type B with the percentage x = nA/
crystal which correlates extremely well with longer number (nB ? nA) has stated a relation to find the volume. The
of TeO2 units that can be accommodated in the more open volume of the binary glass containing nA (Avogadro’s
structure of the vitreous state. For the first series of binary number) formula units of type A and nB formula unit of
TeO2–La2O3, the molar volume increased from 32.42 to type B can be easily determined from the density mea-
surements using the following relation
(a)
x=7.5
x=10
700
x=12.5
(a) -9.6
x=7.5
x=15
x=10
x=17.5
x=12.5
-10.0
x=15
x=17.5
Tg (K)
650 -10.4
ln ( /Tg 2)
-10.8
-11.2
600
1.5 2.0 2.5 3.0 3.5
ln (α)
-11.6
1.4 1.5 1.6 1.7
(b) 580
1000/Tg (K-1)
x=10
x=20
x=25 (b) -9.2
x=10
560 x=35 x=20
x=40 x=25
x=45 -9.6 x=35
x=40
x=50
x=45
Tg (K)
-10.4
520
-10.8
500 -11.2
1.5 2.0 2.5 3.0 3.5 1.8 1.9 2.0
ln (α) 1000/Tg (K-1)
Fig. 8 Variation of Tg versus ln(a) for a (TeO2)(100-x) - (La2O3)x Fig. 9 Variation of ln(a/T2g) versus (1000/Tg) for a (TeO2)(100-x) -
glasses and b (TeO2)(100-x) - (V2O5)x glasses (La2O3)x glasses and b (TeO2)(100-x) - (V2O5)x glasses
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J Mater Sci (2010) 45:871–887 877
½MA þ ðnB =nA ÞMB modifier for a glass series and different from series to
V¼ ð3Þ another. Also, the model restricted that the binary glass
q
series has the same structure and no phase changes. This
where q is the density of the binary glass AXB1-X, and MA implies that the volume V of the binary system AXB1-X
and MB are the molecular weights of the formula units A containing nA (Avogadro’s number) formula units of A and
and B, respectively, and x is the percentage. The model nB formula units of B has been written as:
supposed that the composition of binary glass AB changes
V ¼ nA VA þ nB ðVd þ VA Þ ¼ V0 þ ðnB =nA ÞðnA Vd þ V0 Þ
from nA and nB formula units of types A and B,
respectively, to nA - 1 and nB ? 1 corresponding ð4Þ
formula units. While the total number of formula units of where V0 = nAVA represents the molar volume of the vit-
A and B taken together remains unchanged, the volume of reous system consisting of nA formula units of type A only
the vitreous system changes by an amount which called the with the mean volume equal to VA per formula unit and
difference volume Vd due to the exchange of one formula (nB/nA) is the composition ratio. Although we do envisage
unit between A and B in the binary glass system. The the molecular units in the glass network, where A stands for
compressibility model assumed that the difference volume the glass former TeO2 and B stands for the modifier, i.e., any
Vd and the mean volume VA per formula unit of A in the one of La2O3 or V2O5. Equation 4 clearly indicates that the
binary glass AXB1-X independent of the percentage of the plot of V against the composition ratio (nB/nA) follows a
straight line from which the intersect with Y-axis gives V0
(a) 3.2 and the slope gives (nAVd ? V0). From Fig. 3, it was found
x=7.5 that, for the two binary tellurite glasses studied in this study,
x=10
x=12.5
the value of V0 is 32.1717 cm3 for the line of TeO2–La2O3
2.8 x=15 and 31.3645 cm3 for the line TeO2–V2O5, respectively. The
x=17.5 calculated values of the volume obtained from the sample
model agreed with the experimental values of the pure TeO2
ln ( )
2.4 [13]. From the slope of both lines in Fig. 3 and by using
Eq. 4, the values of the quantity (nAVd) are -24.373 and
-19.396 cm3 for the two binary glass series, respectively.
2.0 These values are negative while binary V2O5–P2O3 glasses
have the value of ?9.538 cm3 as stated by Mukherjee et al.
[15]. This change in molar volume was due to the change in
1.6 the structure caused by the change on interatomic spacing,
which could be attributed to the change in the number of
1.4 1.5 1.6 1.7
bonds per unit volume of the glassy network and change of
(1000/Tg ) (K-1)
the stretching force constant of the bonds inside the glassy
(b) 3.2 network. El-Mallawany [7] has used the Mukherjee model
x=10 and calculated V0 of pure TeO2 and also for the binary
x=20
x=25
TeO2–MoO3 glasses. The calculated value of VA for pure
x=35 TeO2 is 10.41 cm3, and for 20 mol% TeO2–MoO3,
2.8
x=40 VA = 9.76 and 9.4 cm3, 50 mol%, whereas for 20 mol%
x=45
TeO2–V2O5, VA = 9.3 and 8.54 cm3, 50 mol%.
x=50
Now for more quantitative analysis, we calculate Nb, the
ln ( )
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878 J Mater Sci (2010) 45:871–887
0.0
Ln[-Ln(1- )]
0.4
-0.5
0.0
-1.0
-0.4 -1.5
1.6 2.0 2.4 2.8 3.2 1.6 2.0 2.4 2.8 3.2
Ln ( ) Ln ( )
0.8
1.2
T = 743 k
T = 721 k
X = 15
0.8 X = 12.5 Ln[-Ln(1- )] 0.4
Ln[-Ln(1- )]
0.4
0.0
0.0
-0.4
-0.4
-0.8 -0.8
1.6 2.0 2.4 2.8 3.2 1.6 2.0 2.4 2.8 3.2
Ln ( ) Ln ( )
1.5
1.0 T = 763 K
X = 17.5
0.5
Ln[-Ln(1- )]
0.0
-0.5
-1.0
1.6 2.0 2.4 2.8 3.2
Ln ( )
Fig. 11 Variation of ln(-ln(1 - v)) versus ln(a) for a (TeO2)(100-x) - (La2O3)x glasses and b (TeO2)(100-x) - (V2O5)x glasses
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J Mater Sci (2010) 45:871–887 879
(b) 2 2
T= 665 k
X = 10 T = 758
X = 20
Ln[- Ln(1-χ)] 1 1
Ln[- Ln(1-χ)]
0 0
-1 -1
-2 -2
1.6 2.0 2.4 2.8 3.2 1.6 2.0 2.4 2.8 3.2
Ln (α) Ln (α)
2 2
T = 735 k
X = 25 T = 708 k
1 1 X = 35
Ln[- Ln(1-χ)]
Ln[- Ln(1-χ)]
0 0
-1 -1
-2 -2
1.6 2.0 2.4 2.8 3.2 1.6 2.0 2.4 2.8 3.2
Ln (α) Ln (α)
2 1
T = 721 k
T = 711 k X = 45
1 X = 40
Ln[- Ln(1-χ)]
0
Ln[- Ln(1-χ)]
-1
-1
-2 -2
1.6 2.0 2.4 2.8 3.2 1.6 2.0 2.4 2.8 3.2
Ln (α) Ln (α)
2
T = 727 k
X = 50
1
Ln[- Ln(1-χ)]
-1
-2
-3
1.6 2.0 2.4 2.8 3.2
Ln (α)
Fig. 11 continued
calculating this parameter, we conclude that the number of number of network bonds per unit volume increased from
network bonds per unit volume, Nb, equals 7.74.1028 m-3 8.07 9 1028 to 9.58 9 1028 m-3 with increasing La2O3
for pure TeO2 glass. For binary TeO2–La2O3 glass, the content from 5 to 20 mol%, and for TeO2–V2O5, the
123
880 J Mater Sci (2010) 45:871–887
number of network bonds per unit volume decreased from Thermal results
7.69 9 1028 to 6.36 9 1028 m-3 with increasing V2O5
content from 10 to 50 mol%. The average force constant of The DSC curves for the glasses are shown in Fig. 6a, b for
the glass F was given by the following relation: TeO2–La2O3, and in Fig. 7a, b for TeO2–V2O5. The curves
show a very broad endothermic peak corresponding to the
f1 ðn1 ÞðNC Þ1 þf2 ðn2 ÞðNc Þ2
F ¼ ð6Þ glass transition which is characterized by the temperature,
ðn1 ÞðNc Þ1 þf ðn2 ÞðNc Þ2
Tg. As shown in Fig. 7a, this transition is followed by more
where f is the stretching force constant of every cation– than one exothermic peak corresponding to several crys-
anion bond (calculated according to the empirical relation tallization temperatures, Tc. The two main successive
f = 17/r3 from Ref. [16], where r is the ionic bond length), crystallization peaks observed by increasing V2O5 mol%.
(Nc)1 is the number of cations per glass formula unit This shows different stages of crystallization, in coinci-
P
i ðNc Þi ¼ xn1 þ ð1 xÞn2 ; for the multicomponent tel-
dence with previous study [17], and that some tellurite
lurite glasses in the form xAn1 Om1 ð1 xÞGn2 Om2 (where glasses are characterized by more than one crystallization
x is the mole fraction). Figure 5 shows a plot of average mechanism. The first exothermic peak may be attributed to
force constant versus mol% concentration of La2O3 and nucleation processes followed by the formation of a crys-
V2O5, respectively. The average force constant of TeO2– talline phase having a low internal free energy. The second
La2O3 was decreased from 196.7 to 160.5 N/m with peak at a higher temperature is attributed to the formation
increasing La2O3 content from 5 to 20 mol%, and was of a more relaxed crystalline phase. The approximate
increased from 234.8 to 264.8 N/m with increasing V2O5 crystallization kinetics can be considered as follows. TeO2
content from 10 to 50 mol%. The quantitative analysis can crystallizes in two main modifications [18]: orthorhombic
be summarized as follows: for lanthanum tellurite glasses, b-TeO2 tellurite and tetragonal a-TeO2 paratellurite [19].
the structure of the glass is weaker and more linked; the In both forms, the basic coordination polyhedron is a
density data and molar volumes show that rare-earth oxides slightly distorted trigonal bipyramid with one equatorial
act as a network former rather than a network modifier in position occupied by a one electron pair. The dependence
tellurite glass by increasing the crosslink density of TeO2. of Tg on the type of modifier is given in Table 2. The
For vanadium tellurite glasses, the density was decreased increases in Tg induced by addition of the modifier could be
while the molar volume would be higher than pure TeO2 explained by the increased degree of polymerization. Tx the
glass, as shown in Table 1. From the change in the molar temperature at which the crystallization process started was
volume, it was clear that the corresponding structural units determined for the present glasses as shown in Table 2.
with its surrounding space increased by introducing vana- The values of the difference between Tg and Tx were
dium oxides into the tellurite network, i.e., the basic calculated to illustrate the size of the working range
structural units are linked more randomly. between Tg and Tx. For pure TeO2 glass, Tx - Tg = 75 K
Table 4 The order of the crystallization reaction at constant temperature, n, and the crystallization activation energy Ec (kJ/mol) in the binary
tellurite glasses
Glass composition n1 n2 Ec (kJ/mol) by the Ec (kJ/mol) Ec (kJ/mol)
Coats–Redfern–Sestak by Kissinger’s by Ozawa–Chen’s
model model model
TeO2–La2O3
92.5–7.5 1.3888 366.6 347.77 363.35
90–10 1.15 373.5 376.74 372.18
87.5–12.5 1.18 371.6 370.79 359.88
85–15 1.05 483.66 461.43 474.39
82.5–17.5 1.14 557.04 531.75 546.17
TeO2–V2O5
90–10 2.17 486.37 458.93 486.37
80–20 2.11 471.40 453.94 468.7
75–25 2.12 371.64 357.50 376.73
65–35 2.01 333.39 320.92 346.27
60–40 1.91 300.14 274.36 266.04
55–45 1.90 2.33 207.85 191.22 204.44
50–50 2.17 3.31 177.09 174.59 198.2
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J Mater Sci (2010) 45:871–887 881
(a) 2 1
X = 7.5
= 20 k/min
X = 10
= 15 k/min = 20 k/min
= 10 k/min = 15 k/min
1 0
= 5 k/min =10 k/min
=5 k/mi
Ln[-Ln(1- )]
Ln[-Ln(1- )]
-1
0
-2
-1
-3
-2
1.42 1.44 1.46 1.48 1.50 1.52 1.40 1.44 1.48
1000/T (k ) 1000/T (k )
2
X = 15
2 X = 12.5 = 20 k/min
= 20 k/min = 15 k/min
= 15 k/min = 10 k/min
= 10 k/min 0 = 5 k/min
= 5 k/min
Ln[-Ln(1- )]
Ln[-Ln(1- )]
-2
-2
-4
-4
1.32 1.36 1.40 1.44 1.24 1.28 1.32 1.36 1.40
1000/T (k ) 1000/T (k )
x = 17.5
0 α = 20 k/ mi n
α = 15 k/ mi n
α = 10 k/ mi n
α= 5 k/ mi n
Ln[-Ln(1- )]
-2
-4
-6
1.28 1.30 1.32 1.34 1.36 1.38
1000/T (k )
Fig. 12 The relation between ln(-ln(1 - v)) versus 1000/T (K) at different heating rates for a (TeO2)(100-x) - (La2O3)x glasses and
b (TeO2)(100-x) - (V2O5)x glasses
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882 J Mater Sci (2010) 45:871–887
(b) 2 3
X = 10
= 5 k/min X = 20
=10 k/min 2 = 5 k/min
1 =10 k/min
=15 k/min
=20 k/min =15 k/min
1 =20 k/min
Ln[- Ln(1- )]
Ln[- Ln(1- )]
0
0
-1
-1
-2
-2
-3 -3
1.40 1.45 1.50 1.55 1.60 1.28 1.30 1.32 1.34 1.36 1.38
1000/T (k ) 1000/T (k )
2 2
X = 25 X = 35
= 5 k/min = 5 k/min
1 =10 k/min 1 =10 k/min
=15 k/min =15 k/min
=20 k/min =20 k/min
Ln[- Ln(1- )]
Ln[- Ln(1- )]
0 0
-1 -1
-2 -2
-3 -3
1.32 1.36 1.40 1.44 1.30 1.35 1.40 1.45 1.50 1.55
1000/T (k ) 1000/T (k )
2
2 X = 40
X = 35 = 5 k/ min
= 5 k/ min 1 =10 k/min
=10 k/min =15 k/min
1 =20 k/min
=15 k/min
Ln[- Ln(1- )]
Ln[- Ln(1- )]
=20 k/min
0
0
-1
-1
-2
-2
-3 -3
1.30 1.35 1.40 1.45 1.50 1.55 1.32 1.36 1.40 1.44 1.48 1.52
1000/T (k ) 1000/T (k )
X = 45
= 5 k/min
=10 k/ min
1 =15 k/ min
=20 k/ min
Ln[- Ln(1- )]
-1
-2
-3
1.28 1.32 1.36 1.40 1.44 1.48
1000/T (k )
Fig. 12 continued
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J Mater Sci (2010) 45:871–887 883
[4] and in this study changed from 37 to 22 K and from 83 indicates a relationship for the prepared glasses. The
to 175 K for binary tellurite-La2O3 and -V2O5, respec- second and third approaches are the use of Kissinger’s
tively. The values of Tm for all glasses obtained from the [20–23] and Moynihan’s [24] formula, which is originally
DTA curves were in the range 921–1180 K as shown in applied to crystallization studies as stated by Eqs. 10 and
Table 2. The values of Tg/Tm were in the range 0.43–0.74. 11 where Et is the glass transition activation energy. The
The glass-forming tendency, Kg, which was a useful dependencies of Tg on the heating rate a of the binary
parameter in comparing the devitrification tendency of the glasses were found to follow Eq. 10 and 11 which stated by
glass, is given by Chen [22] and has often been used to calculate glass
Tc Tg transition activation energy (Et). Plots of ln(a/T2g) versus
Kg ¼ ð7Þ 1/Tg for the prepared tellurite glasses indicate linearity as
Tm Tc
shown in Fig. 9a, b, the obtained values of Et are shown in
and had the values of 0.47–0.21. As can be seen from Table 3. Et has also been calculated using the expressions
Table 3, low values of Kg suggested high tendencies to as in Eqs. 10 and 11
devitrify. Previously, El-Mallawany [4] has calculated Kg .
for other binary tellurite vanadium tellurite glasses of the ln a Tg2 ¼ Et RTg þ const: ð10Þ
form TeO2–MoO3, TeO2–Co3O4, and TeO2–MnO2 and
found that the values of Kg were from 0.46 to 0.41, 0.33 to lnðaÞ ¼ Et RTg þ const: ð11Þ
0.31, and 0.45 to 0.4, respectively. The glass-forming Figure 10a, b shows the relation between ln(a) and 1/Tg for
tendency Kg of the present binary tellurite glasses decrea- the prepared glasses. The values of Et deduced from this
ses from 0.32 to 0.21 for lanthanum tellurite glasses sys- relation are obtained in Table 3. It is clear from the
tem. The behavior is absolutely opposite in the second obtained data for the glass transition transformed temper-
binary glass series become Kg increases from 0.31 to 0.47. ature Tg at heating rate 10 K/min that the Tg depends upon:
Also the glass transition temperature, the activation energy
of the glass transition Et, and the crystallization activation • Tellurite glasses with higher percentage of La2O3 have
energy Ec will be evaluated according to different models the higher values of Tg, and with higher percentage of
as stated in the following section. V2O5 has the lower values of Tg, i.e., La2O3 creates a
Also, it is very important to analyze the variation of Tg more strengthen tellurite glass.
in both tellurite glasses series as a function of both Nb and • The glass transition activation energy Et of La2O3
i.e.,
F; tellurite glass has been increased from 296 to 403.9
kJ/mol by increasing La2O3 from 7.5 to 17.5 mol% (by
Tg ¼ f ðNb ; FÞ ð8Þ using Moynihan’s model) while it has been increased
From Tables 1 and 2, it is clear that for binary glass TeO2– from 285.71 to 392.32 kJ/mol for the same amount of
La2O3 the glass transition temperature Tg increased from La2O3 (by using Chen’s model), so both models
624 to 705 K, the number of network bonds per unit volume confirm each other.
Nb increased from 8.069 9 1028 to 9.584 9 1028 m-3 and
the average force constant F decreased from 196.7 to
160.5 N/m with increasing La2O3 content. While for TeO2–
V2O5, the glass transition temperature Tg decreased from
(a)
563 to 511 K, the number of network bonds per unit volume -10.0
x= 7.5
x= 10
Nb decreased from 7.69 9 1028 to 6.36 9 1028 m-3 and the x= 12.5
average force constant F increased from 234.8 to 264.8 x= 15
x= 17.5
N/m with increasing V2O5 content. -10.5
ln ( /Tp 2)
123
884 J Mater Sci (2010) 45:871–887
x = 35
x = 10
x = 20
-10.4 x = 25 -10.4
Ln( /Tp )
Ln( /Tp )
-10.8 -10.8
-11.2 -11.2
-11.6 -11.6
1.30 1.40 1.50 1.60 1.36 1.38 1.40 1.42 1.44 1.46
1000/Tp (k ) 1000/Tp (k )
-10.0 -9.6
x = 45
x = 40 Tp
-10.0 Tp
-10.4
-10.4
Ln( /Tp )
Ln( /Tp )
-10.8
-10.8
-11.2
-11.2
-11.6 -11.6
1.39 1.40 1.41 1.42 1.30 1.40 1.50 1.60 1.70
1000/Tp (k ) 1000/Tp (k )
-9.6
x = 50
Tp
-10.0 Tp
Ln( /Tp )
-10.4
-10.8
-11.2
-11.6
1.3 1.4 1.5 1.6 1.7
1000/Tp (k )
Fig. 13 continued
Also the glass transition activation energy Et of V2O5 using Moynihan’s model), while it has been decreased from
tellurite glasses has been decreased from 594.96 to 585.58 to 281.25 kJ/mol for the same amount of V2O5 (by
289.79 kJ/mol by increasing V2O5 from 10 to 50 mol% (by using Chen’s model), so both models confirm each other.
123
J Mater Sci (2010) 45:871–887 885
Crystallization temperature and crystallization activation behavior by Ozawa–Chen model and Coast–Redfern–Se-
energy stak are found. According to the cluster model of glasses
[28], the vitreous state (TeO2)100-x - (V2O5)x may in
Kissinger [21] developed a method which is commonly some way consist of a mixture of extremely small crys-
used in analyzing crystallization data in DSC and DTA tallites of size less than 10 nm of the two polymorphic
experiments. While the method proposed by Ozawa [25] is phases of TeO2, which forms the essential framework of
used to deduce the order of the crystallization reaction (n) the glass matrix together with small regions proportional to
at constant temperature the concentration of the added modifier. As the temperature
dfln½ lnð1 vÞg=dflnðaÞg ¼ n ð12Þ is raised to the point at which significant solid-state dif-
fusion of atoms or groups of atoms can occur, that is above
where a is heating rate of binary glass and v is the volume Tg, the diffusion of clusters of size \3 nm, together with
fraction crystallized in time t. statistical collisions between them, results in these clusters
On this basis, plotting ln[-ln(1 - v)] versus ln(a), coalescing. Clusters which differ very little in free energy
which is obtained at the same temperature from a number and orientation collide in such a way that interfaces with
of crystallization exotherms taken at different heating rates, minimum strain are established between them. Such an
should yield the value of the order of the crystallization assemblage of clusters results in partial crystallization, as
reaction (n) at constant temperature n. Now to deduce the the a-TeO2 phase is formed. Above the first crystallization
order of crystallization, the value of (n) is evaluated by peak, there is still some persisting amorphous phase, rep-
plotting ln[-ln(1 - v)] versus ln(a), where v is obtained resenting the remaining clusters of the other polymorphic
from the crystallization exothermic peaks at the same phase of TeO2 with more highly strained interfaces. On a
temperature taken at deferent heating rates. Figure 11a, b further increase in temperature, these highly strained
shows the plots of ln[-ln(1 - v)] versus ln(a) at different interfaces have the opportunity to relax. Such relaxation
constant values of temperature. From the slopes of this occurs by acquiring atoms with the appropriate orientation
relation, the value of n is equal to 1.38, 1.15, 1.18, 1.05, and releasing the strain in the interfaces the neighboring
and 1.14, respectively, by increasing La2O3 from 7.5 to clusters and to the liquid phase. In this way, through sta-
17.5 mol%, whereas n is equal to 2.17, 2.11, 2.12, 2.01, tistical collisions clusters of the remaining polymorphic
1.91, 1.90, and 2.17, respectively, at the first crystallization phase could assemble with minimum or zero strained
peaks by increasing V2O5 from 10 to 50 mol% and at the interfaces and crystallize to form b-TeO2. This second
second crystallization peaks n is equal to 2.33 and 3.31 for stage of crystallization is observed as the second weak
45 and 50 mol% of V2O5 as tabulated in Table 4. The exothermic peak, in the glasses containing Vanadium
values of the crystallization activation energy (Ec) calcu- oxide. The above experimental results will complete the
lated by using the methods of Coast–Redfern–Sestak [26], previous research on binary tellurite glasses either in the
Kissinger [27], and modified Ozawa and Chen [22, 25]. thermal, structural, vibrational, elastic, electrical, or optical
The values of crystallization activation energy Ec calcu- research directions [2–9, 29–40].
lated for all the heating rates by using method of Coast–
Redfern–Sestak [26]. Figure 12a, b shows the plots of
(a) 3.2
ln[-ln(1 - v)] versus 1/T at different heating rates, from x = 7.5
the slopes the average values of the crystallization activa- x = 10
tion energy of the prepared glasses for the first crystalli- x = 12.5
2.8 x = 15
zation peak are calculated and obtained in Table 4. The x = 17.5
values of the crystallization activation energy (Ec) calcu-
lated using Kissinger’s method and modified Ozawa–Chen
2.4
ln ( )
123
886 J Mater Sci (2010) 45:871–887
3.2
(b)
x = 10 x = 35
x = 20
3.0 x = 25
2.8
2.5
Ln ( )
Ln ( )
2.4
2.0 2.0
1.6
1.5
1.35 1.40 1.45 1.50 1.55 1.36 1.38 1.40 1.42 1.44 1.46
1000/Tp (k ) 1000/Tp (k )
3.2
x = 45
x = 40
Tp
3.0
Tp
2.8
2.5
Ln ( )
2.4
Ln ( )
2.0 2.0
1.6
1.5
1.39 1.40 1.41 1.42 1.30 1.40 1.50 1.60 1.70
1000/Tp (k ) 1000/Tp (k )
3.2
x = 50
Tp
Tp
2.8
Ln ( )
2.4
2.0
1.6
Fig. 14 continued
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J Mater Sci (2010) 45:871–887 887
123