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DIELECTRIC DISPERSION AND SPECTROSCOPIC
INVESTIGATIONS ON NA2SO4–B2O3–P2O5 GLASSES MIXED WITH LOW
CONCENTRATIONS OF TIO2
CHAPTER 3
In CHAPTER–III, a series of Na2SO4–B2O3–P2O5 glasses doped with different
concentrations of TiO2 (0 to 1.0 mol%) have been synthesized. Dielectric properties (over a
range of frequency and temperature) and a variety of spectroscopic (optical absorption,
IR, Raman and ESR) properties of these glasses have been investigated. The values of
dielectric parameters viz., dielectric constant, loss and ac conductivity at any frequency
and temperature are observed to increase with the concentration of TiO2. The optical
absorption and ESR spectral studies have pointed out that a part of titanium ions do exist
in Ti3+ state in addition to Ti4+ state especially in the samples containing higher
concentration of TiO2 The increase of dielectric constant with the concentration of TiO2 is
explained on the basis of space charge polarization due to increasing concentration of
various bonding defects in the glass network. The dielectric relaxation effects exhibited by
these glasses are quantitatively analyzed by pseudo Cole-Cole method and the spreading
of relaxation times is established. The ac conductivity is observed to increase with
increasing content of TiO2 , the mechanism responsible for such increase is well explained
based on the modifying action of Ti3+ ions.
Dielectric dispersion and spectroscopic investigations on Na2SO4–B2O3–P2O5 glasses mixed with low concentrations of TiO2
3.1 Introduction
Alkali sulphate mixed phosphate glasses are being used to immobilize
radioactive waste for long time safe storage [1]. These glasses are also proved
to be suitable for their application in micro batteries, smart card, medical
appliance [2, 3]. These materials exhibit high electrical conductivity (purely
ionic), compatible with the electrode materials and are thermally and
chemically stable. The SO42- ions largely dissolve in the phosphate glass matrix
and mostly remain as isolated units [4]. However, there are also reports
suggesting that sulphate ions and metaphosphate ions interact weakly and form
a small dynamic concentration of dithiophosphate (DTP) units in the glass
matrices [5]. Such weak and variable interaction between these two ions is
expected to influence the electrical properties to a large extent. A considerable
number of previous studies on a variety of physical properties of different
alkali sulfophosphate glasses are available in the literature [6-9]. The
introduction of B2O3 to alkali sulfophosphate glasses is expected to increase
the thermal stability of the glass network (since borate groups form M+[BO4]-
pairs) and also reported to increase the electrical conductivity [10-13].
The chemical inertness, thermal stability and also electrical properties of
alkali borosulfophosphate glasses can further be improved by mixing a small
quantity of TiO2 to the glass matrix. The addition of TiO2 further makes
75
borosulfophosphate glasses suitable for applications in non-linear optical
devices, integrated circuits and low loss optical waveguides [14]. Kityk and his
co-workers have reported extensive studies on non-linear optical (NLO)
properties of similar type of glass systems. Their studies have yielded valuable
information which will be useful for considering these types of glasses for
optically operated NLO devices [15, 16].
Normally, the ions of titanium exist in the glass in Ti4+ state and
participate in the glass network forming with TiO4, TiO6 and some times with
TiO5 (comprising of trigonal bipyramids) structural units [14, 17] . However,
there are also reports suggesting that these ions may also exist in Ti3+ valence
state in some of the glass matrices and acts as modifiers [17, 18]; such
variation in the coordination and valence of titanium ions are expected to cause
the structural modifications and local field variations in the glass network and
expected to influence the electrical properties to a large extent.
This part of the thesis is devoted to the studies on the influence of
titanium ions on dielectric and ac conductivity properties of Na2SO4–B2O3–
P2O5 glasses. To have some pre-assessment over the structural aspects of the
glasses which may help for clear understanding of the dielectric properties, we
have also undertaken the studies on optical absorption, ESR and IR studies.
The detailed compositions of the glasses used in the present study are as
follows:
76
T0: 40.0Na2SO4–30B2O3–30P2O5
T2: 39.8Na2SO4–30B2O3–30P2O5: 0.2TiO2
T4: 39.6Na2SO4–30B2O3–30P2O5: 0.4TiO2
T6: 39.4Na2SO4–30B2O3–30P2O5: 0.6TiO2
T8: 39.2Na2SO4–30B2O3–30P2O5: 0.8TiO2
T10: 39.0Na2SO4–30B2O3–30P2O5: 1.0TiO2
3.2 Brief Review of the previous work on TiO2 glass systems
Titanium is a common constituent of glasses and glass ceramics, and
silica with a few percent of TiO2 [19] is used for length standards and
astronomical mirror blanks because of its low–even negative–coefficient of
thermal expansion [20]. Recently, titania-doped silica played a crucial role in
the development of optical fibres [21]. At low concentrations, titanium
introduces new absorptions at the low-energy side of the principal silica
absorptions in both the IR and ultraviolet (UV). Smith et al have been reported
that, these are due to perturbed vibrational modes involving Ti–O–Si bonds
and to perturbed excitons arising from substitution of Ti4+ for Si4+[22].
TiO2–SiO2 mixed oxide glasses have received considerable attention
because of their interesting properties such as good chemical stability, low
thermal expansion coefficient, and high refractive index that lead to their
potential application in optoelectronic devices. [23-25]
Schultz reported that the SiO2–TiO2 glasses possess interesting
properties, i.e., up to about 10 mol% TiO2, titanium ions exists in fourfold
77
coordination and up to 16 mol% in a metastable state with titanium separated
in a second phase and octahedrally coordinated [26].
Conventional glass ionomer cements (GICs) was originally investigated
by Wilson & Kent [27] nearly 42 years ago. These materials are made of a
powder and liquid, which are mixed to generate a plastic mass, and afterward
changes to a rigid solid. A GI liquid is derived from an aqueous polyalkenoic
acid, for instance polyacrylic acid and the GI-powder is principally made of
fluoroaluminosilicate glass. When the powder and liquid are combined
together, an acid-base reaction happens [28]. GICs are beeing widely used as
an alternative of amalgam for restorative materials owing to their excellent
biocompatibility [29, 30]. These cements are translucent and adhesive to tooth
structure because of the similar coefficient of thermal expansion of glass
ionomer to tooth structure [31]. In previous study by Monmaturapoj, et al [32],
it was found that the glass contained ZrO2 had improved the strength of cement.
TiO2 is well known as the strong and tough material, and has similar structure
to ZrO2. Then, it was selected in this study to be doped in glass structure to
induce the strength. Therefore Not only TiO2 affected on the strength but also
shape of glass particles, powder to liquid ratios and concentration of acidic
copolymer. All these factors were studied for the purpose in improving the
compressive strength of GICs.
78
Chengbin Jing [33] has investigated on the SiO2–TiO2–GeO2 sol–gel
glass system and it was firstly ascertained to be the material to use in the
fabrication of a hollow waveguide for application in CO2 laser delivery.
Lee et al [34] reported that the TiO2 has been confirmed the
improvement in the mechanical properties of MgO–CaO–SiO2–P2O5 glass
systems and solved the problems of formation of cracks and showed that the
growth of crystalline layer is slowed down initial stage. These materials are
found to be very important in the biological and industrial field to elaborate
artificial bones and teeth.
Watanabe et al [35] studied and reported that the TiO2–BaO–ZnO–B2O3
glasses containing transition d-block metal oxides, such as TiO2, and proved
that these materials have potential application for nonlinear optics[36,37] and
as precursors for porous glass-ceramics[38-40]. In these systems, several
studies devoted to establish the role of TiO2 as a network-former and/or
network modifier as well as to determine if Ti4+ ions are fourfold or sixfold
coordinated [41, 42] These last aspects, and the high polarizability of titanium
ions, have been used to explain the increase of linear index and the nonlinear
characteristics for the high content titanium oxide glasses [36, 43, 44].
Inoue et al [45] reported that the TiO2-containiing glasses are expected
as alternatives of Pb-containing glasses and optical materials, and they have
been extensively studied in recent years. In oxide glasses, Ti4+ ions take
various coordinate structures as TiO4, TiO5 and TiO6, resulting in the specific
79
characteristics. Ti ions in tetrahedral TiO4 units are regarded as network former
(NWF), and those in octahedral TiO6 units are as network modifier (NWM). Ti
ions in TiO5 units play an intermediate role between NWF and NWM. TiO5
units are in a tetragonal pyramid structure with an extremely short Ti–O bond
in the axial direction. The oxygen atom in the axial Ti–O bond is regarded as
non-bridging oxygen (NBO), and the rest are attributed to bridging oxygen
(BO). A number of reports have been published concerning the coordination
structures of Ti ions in glass. Sakka et al. [46, 47] reported that Ti ions mostly
existed in TiO4 units in K2O–TiO2 and Cs2O–TiO2 glass systems. Kusabiraki et
al. [48] reported that coordination number of Ti ions in Na2O–TiO2–SiO2
glasses changed from 4 to 6 with increasing Na2O content.
Gulati et al [49] reported that the glass can be used in the ground and
space-based telescope industry for many years. More recently, Ti-doped silica
glass was chosen as a material for reflective mirrors in an extreme ultraviolet
lithography (EUVL) system [50]. In addition to its thermal expansion
properties, Ti-doped silica glass possess optical absorption characteristics that
are useful in making mirrors and other optical components, such as the high
index core of low loss fiber optical waveguides [51]
Hashimoto et al [52] have reported that TiO2–B2O3–P2O5 (TBP) based
glasses are promising materials as molding glasses with high transparency, low
Tg, and high nd. Ma et al [53] have studied the effect of TiO2 on phase
separation and crystallization of glass ceramics in CaO–MgO–Al2O3–SiO2–
80
Na2O system. From FESEM observation and EDS analysis, they concluded
that the more TiO2 content of glass, the more droplet separated phase and
crystal seeds are found after nucleation heat treatment. Tiefeng et al [54] have
studied the third-order optical nonlinear properties of Bi2O3–B2O3–TiO2
glasses using femto-second Z-scan method at 800 nm. The results have showed
that third-order optical nonlinearities are influenced by TiO2 concentration; the
largest value of nonlinear refraction γ obtained for these glasses is ~
8.85×10−14 cm2/W. Gorokhovsky et al [55] have investigated the vitrification
and crystallization behavior of melts produced at 1400 °C in the K2O–B2O3–
TiO2 ternary system. They have discussed that the obtained glass ceramic
materials as a source of fibrous TiO2, for composite reinforcement and as solid
lubricants. Hamzawy et al [56] have studied the effect of different
concentrations of titanium oxide (TiO2) on the crystallization behavior of
Li2O–Al2O3–SiO2 glasses prepared from local raw materials. Duhan et al [57]
have reported the frequency and temperature dependent conductivity
measurements on heat treated titanium bismuth silicate glasses by using
impedance spectroscopy in the frequency range from 20 Hz to 1 MHz. They
have observed an enhancement in conductivity of about 101-102 order is in heat
treated sample as compared to parent glass.
Chen et al [58] have investigated the third order optical nonlinear
properties in Bi2O3–B2O3–TiO2 transparent glass ceramics and they found that
large values of nonlinear refractive indices n2 in both as-quenched (1.983×10-13
81
cm2/W) and heat treated (2.645×10-13 cm2/W) transparent samples. The
influence of titanium ions on various physical properties including colour,
thermal expansion, compressibilities, elastic constants, sound velocities,
densities, viscosities, nucleation rates etc on a variety of inorganic glasses has
been reported by a number of researchers [59-68]. Kishioka et al [69] have
reported that the addition of TiO2 to phosphate glasses stabilizes the glass
structure. Lange and Navrotsky [70] have measured anomalously high
variations in heat capacities in some titanosilicate melts at temperatures just
above the glass transition temperatures. Information on the local structure
environment of Ti4+ ions in oxide glasses under ambient conditions has been
provided by a number of investigators by a variety of techniques like, Raman
spectroscopy [71-76], neutron scattering experiments [77], X-ray photo
electron spectroscopy [78], X-ray scattering experiment [79], X-ray absorption
fine spectroscopy [80-82] etc. Wu et al [83] have reported the dissolution of
TiO2 in calcium zirconoboro silicate glasses.
Lacerda et al [84] have investigated TiO2 - induced phase separation
and crystallization in SiO2–CaO–P2O5–MgO glasses. Laudisio et al [85] have
studied the devetrification behaviour of titanium in lithium germanate glasses.
Barbieri et al [86] have reported the effect of TiO2 on properties of alumino
silicate glasses and glass ceramics by thermal, microscopic and diffractometric
techniques. Fei Duan et al [87] have prepared BaO–SrO–TiO2–SiO2 glass
system and reported the piezoelectric properties of these glasses. Duan et al
82
[88] have studied the effect of changing TiO2 content on structure and
crystallization of CaO–Al2O3–SiO2 glass system. Abrahams and Hadzifejzovic
[89] have measured conductivity due to lithium ions in lithium alumino
phosphate glasses crystallized with TiO2. Grussaute et al [90] have reported
phosphate speciation in sodium phosphate silicate glasses containing TiO2.
Their studies revealed the formation of Ti–O–P covalent bonds, which they
have attributed to the electrostatic field strength of Ti4+ ions. Chowdari et al
[91] have recently reported XPS and ionic conductivity studies on lithium
alumino phosphate glass ceramics containing TiO2. Jivov et al [92] have
studied the crystalline nature of P2O5–CaO–ZnO glass system containing
titanium ions. Shaim et al [93] have reported the role of titanium in Na2O–
Bi2O3–P2O5 glasses on the structural properties. Aboukais et al [94] have
reported the EPR spectra of silica and fluoride glasses implanted with titanium.
Though, a considerable number of studies on some TiO2 glasses and glass
ceramics are available, still there is a lot of scope to investigate the role of
titanium ions on the structural aspects of Na2SO4–B2O3–P2O5 glasses and their
influence on physical properties.
3. 3. Results
3. 3.1. Physical parameters
The physical parameters such as titanium ion concentration Ni, mean titanium
ion separation Ri and polaron radius Rp were evaluated from the measured
83
values of density d and calculated average molecular weight M using the
conventional formulae [95] and were furnished in Table 3.1.
Table 3.1 Physical parameters of Na2SO4–B2O3–P2O5: TiO2 glasses
3. 3.2. DTA studies
In the Fig. 3.1, DTA scan for Na2SO4–B2O3–P2O5 glasses doped with
0.6 mol% of TiO2 is presented; the thermogram exhibited a typical glass
transition with the inflection point at about 415 oC following by an exothermic
peak due to crystallization at about 810 oC. With the increasing content of TiO2
in the glass matrix, the glass transition temperature is observed to decrease
(inset of Fig. 3.1). The value of (Tc–Tg), a parameter that represents thermal
stability of glass against devitrification, is found to decrease with the content
of TiO2 (inset of Fig. 3.1).
Glass → Physical parameter↓
T0 T2 T4 T6 T8 T10
Density d (g/cm3) 2.5556 2.5609 2.5678 2.5776 2.5844 2.5876
Dopant ion conc. Ni (x1020 ions/cm3)
--- 0.25 0.51 0.77 1.03 1.29
Interionic distance Ri (A
o) --- 33.98 26.94 23.49 21.32 19.77
Polaron radius Rp (Ao)
--- 13.69 10.89 9.47 8.59 7.97
Field Strength Fi (1015, cm-2)
--- 0.16 0.25 0.33 0.41 0.47
84
3.3.3 Optical absorption spectra
Fig. 3.2(a) presents optical absorption spectra of Na2SO4–B2O3–P2O5:
TiO2 glass samples recorded at room temperature in the wavelength region
300-1000 nm. The absorption edge for TiO2 free glass is identified at 288 nm,
whereas for the glass T2, it is observed at 312 nm. As the concentration of TiO2
is increased the edge exhibited red shift. Additionally, the spectrum of glass T2
exhibited two clearly resolved absorption bands at 516 and 691 nm.
Table 3.2 Data on optical absorption spectra Na2SO4–B2O3–P2O5: TiO2 glasses
As the concentration of TiO2 is continued to increase, the half width and
intensity of these two bands are observed to increase with the shifting of the
peak positions towards slightly longer wavelength (Table 3.2).
Band positions (nm) Glass
Cut-off wavelength (nm) 2B2g→ 2B1g
2B2g → 2A1g
Optical band gap (eV)
T0 292 - - 4.25
T2 318 509 678 3.90
T4 325 516 691 3.82
T6 329 524 698 3.77
T8 331 527 700 3.75
T10 354 532 706 3.50
85
Fig. 3.1 DTA trace of T6 glass. Inset shows the variation of Tg and Tc-Tg with the concentration of TiO2.
300 400 500 600 700 800 900 1000
Tg
Tc
390
430
0.2 0.4 0.6 0.8 1.0
380
420
Tc -T
g (o C
)
Tg (o C
)
Conc. TiO2 (mol%)
Temperature (oC)
End
oE
xo
86
Fig. 3.2(a) Optical absorption spectra of Na2O4–B2O3–P2O5: TiO2 glasses
2
6
10
14
18
22
26
30
250 350 450 550 650 750 850
2B2g → 2B1g
2B2g → 2A1g
Wavelength (nm)
Opt
ical
den
sity
(cm
-1)
T10
T2
T0
T4
T6
T8
87
Fig. 3.2(b) Tauc plots of Na2O4–B2O3–P2O5: TiO2 glasses. Inset shows the variation of optical band gap with the concentration of TiO2
88
From the observed absorption edges, we have evaluated the optical band
gaps (Eo) of these samples by drawing Tauc plots (Fig. 3.2 (b)) between
(α ωh )1/2 and ωh as per the equation [96]:
( ) ( )2oEc −= ωωωα hh (3.1)
A considerable part of each of these curves is observed to be linear indicating
that Eq. (3.1) is valid. The validity of this quadratic equation points out that the
optical band gap is caused by amorphous optical absorption edge. Some
deviations observed from this dependence may be due to trapping by
disordered states within the energy gap.
From the extrapolation of the linear portion of the curves of Fig. 3.2 (b),
the value of optical band gap (Eo) is determined and its variation with the
concentration of TiO2 is shown as the inset of the Fig. 3.2(b); the variation of
Eo with the content of TiO2 exhibited a decreasing trend
3.3.4 ESR spectra
ESR spectra of Na2SO4–B2O3–P2O5 glasses doped with different
concentrations of TiO2 recorded at room temperature are presented in Fig. 3.3.
The spectrum of glass T2 consists of an intense asymmetric spectral line
centered at about g = 1.970. The half width and the intensity of this signal
exhibited a gradual increase with the concentration of TiO2. The intensity (ℑ )
of the ESR signal, assumed to be proportional to the product of the peak-to-
peak height (I) and the square of its width (∆B)
89
ℑ ≈ I (∆B)2 (3.2)
is evaluated and its dependence with the concentration of TiO2 is shown as an
inset of Fig. 3.3. The figure shows that the intensity of the resonance signal
increases with increase in the concentration of TiO2.
3.3.5 IR spectra
The IR spectra (Fig. 3.4) of Na2SO4–B2O3–P2O5: TiO2 glasses exhibited
conventional vibrational bands due to phosphate groups in the regions 1277-
1295 cm−1 (anti−symmetrical vibrations of −2PO groups / P=O stretching
vibrations), 1085-1106 cm−1 (a normal vibrational mode of −34PO group arising
out of ν3 − symmetric stretching), 927-944 cm−1 (P−O−P asymmetric bending
vibrations/ this region may also consist of bands due to pyrophosphate groups
P2O74−) and another band in the region of 760 - 790 cm-1 due to P–O–P
symmetric stretching vibrations [97]. The spectra have also exhibited three
usual bands originated from borate groups in the regions 1381-1414 cm−1 due
to BO3 units, 944 - 964 cm−1 due to BO4 units and 709-724 cm−1 due to
bending vibrations of B–O–B linkages [98]. In the spectral regions 658-678
cm−1 and 1124-1148 cm−1 vibrational bands corresponding to bending and
asymmetric modes of SO42− groups, respectively are also observed [99, 100];
90
Fig. 3.3 ESR spectra of Na2O4–B2O3–P2O5: TiO2 glasses recorded at room temperature. Inset shows the variation of intensity of the signal with concentration of TiO2
200 250 300 350 400 450 500
T2
T4
T6
T8
T10
Fir
st d
eriv
ativ
e of
abs
orp
tion
(arb
. uni
ts)
Magnetic field (mT)
0.2 0.6 1.0Conc. TiO2 (mol%)
91
With the gradual introduction of TiO2 in the glass network, all the
asymmetrical bands are observed to grow at the expense of symmetrical bands.
The band due to Ti–O–Ti symmetric stretching vibrations of TiO4 units is also
expected in the region of P–O–P symmetric stretching vibrations (at about 760
cm-1). The pertinent data related to IR spectra are presented in Table 3.3.
Table 3.3 Data on infrared spectra Na2SO4–B2O3–P2O5: TiO2 glasses recorded at room temperature (Assignment of band positions in cm-1).
3.3.6 Dielectric Properties
The dielectric constant ε' and loss tan δ at room temperature ( ≈ 30 °C)
of TiO2 free Na2SO4–B2O3–P2O5 glasses at 1 kHz are measured to be 10.8 and
0.004, respectively. With increase in the concentration of TiO2 in the glass
matrix, these values are observed to increase considerably.
SO42- units Glass
sample BO3
units PO2- asym.
ν1 ν2
P-O-P asym. stretching
PO43-
groups/ BO4 units
P-O-P sym. stretch. &TiO 4 units
B-O-B linkages
TiO6 units
T2 1414 1295 1148 658 1085 944 762 709 620
T4 1405 1291 1146 664 1092 953 772 713 612
T6 1398 1286 1141 669 1094 958 779 717 601
T8 1390 1282 1135 671 1101 962 783 719 592
T10 1381 1277 1124 678 1106 964 797 724 581
92
Fig. 3.4 IR spectra of Na2O4–B2O3–P2O5: TiO2 glasses
400500600700800900100011001200130014001500Wave number (cm-1)
Tra
nsm
ittan
ce %
(1)
(1) BO3 units
(2) PO2- asymmetric
(3a) assymetric SO42- units
(3b) bending SO42- units
(4) P-O-P asymmetric
(5) PO43- groups/BO4 units
(6) P-O-P symmetric stretching and TiO4 units
(7) B-O-B linkages(8) TiO6 units
(6)
(5)(4)(3a)
(2)
(3b)(7)(8)
93
Fig. 3.5 represents the temperature dependence of ε' at 1 kHz of
Na2SO4–B2O3–P2O5 glasses doped with different concentrations of TiO2 and
the dependence of ε' with temperature at different frequencies for the glass T2 is
shown an inset of the same figure. The value of ε' exhibited a considerable
increase at higher temperatures especially at lower frequencies; the rate of
increase of ε' with temperature at any frequency is found to increase with
increase in the concentration of TiO2.
Fig. 3.6(a) represents a comparison plot of variation of tanδ with temperature,
measured at a frequency of 10 kHz for Na2SO4–B2O3–P2O5 glasses doped with
different concentrations of TiO2. Fig. 3.6(b) represents the temperature dependence of
tan δ of glass T6 at different frequencies. Variation of tanδ with temperature has
exhibited distinct maxima; with increase in frequency, the temperature maximum of
tanδ shifts towards higher temperatures and with increase in temperature, the
frequency maximum shifted towards higher frequencies, such variation indicates the
relaxation character of dielectric losses in these glasses [104]. The full width at half
maximum (FWHM) and the peak value (tan δ)max of the relaxation curve (that
represent the strength of the relaxation character) are observed to increase gradually
with the content of TiO2. Using the relation:
f = fo exp (_Wd/kBT), (3.3)
94
Fig. 3.5 A comparision plot of variation of dielectric constant with temperature at 1 kHz for Na2O4–B2O3–P2O5: TiO2 glasses. Inset gives the variation of dielectric constant with temperature at different frequencies of glass T2.
0
50
100
150
200
250
300
25 50 75 100 125 150 175 200 225 250Temperataure (oC)
εεεε'
T2
T8
T6
T4
T10
0
50
100
150
25 75 125 175 225Temperataure (oC)
εεεε'
0.1 kHz
100 kHz
10 kHz
1 kHz
95
Fig. 3.6 (a) A comparision plot of variation of Tan δ with temperature at
10 kHz for Na2O4–B2O3–P2O5: TiO2 glasses. (b) Variation of Tan δ with
temperature at different frequencies of glass T6
0.00
0.10
0.20
0.30
25 50 75 100 125 150 175 200 225 250Temperataure (oC)
Tan
δ
T2
T8
T6
T4
T10
0.00
0.10
0.20
25 50 75 100 125 150 175 200 225 250
0.1 kHz
100 kHz
10 kHz
1 kHz
Temperataure (oC)
Ta
n δ
(b)
(a)
96
Fig. 3.7 Variation of sac with 1/T at 100 kHz of Na2O4–B2O3–P2O5: TiO2 glasses. Inset (a) represents the variation of ac conductivity with activation energy, (b) variation of ac conductivity with different frequencies for the sample T6 and (c) Variation of exponent with the concentration of TiO2
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
σ ac
( Ω-
cm)-1
1/T (10-3, K-1)
T2
T8
T6
T4
T10
0.65 0.85A.E. (eV)
σ ac
( Ω-
cm)-1
10-6
10-5
(a)
Frequency (Hz)
σ ac
( Ω-
cm)-
1
10-7
10-5
102104103
105
(b)
0.6
0.9
0.2 0.4 0.6 0.8 1.0
Conc. TiO2 (mol%)
Exp
on
en
t (s) (c)
10-4
10-5
10-6
10-7
97
Fig.3. 8 Variation of ε' and ε'' with 1/T at a frequency 10 kHz for the sample T10
10
30
50
70
90
110
3.3 2.9 2.6 2.4 2.2 2.0
0
1
2
3
4
1/T, 10-3 K-1
εεεε' εεεε''
ε ε
98
0.0
2.0
4.0
15 20 25 30εεεε'
εεεε''
πβ/2πβ/4
ωτo = 1
T
Fig. 3.9 A pseudo Cole–Cole plot at 10 kHz for the glass sample T8
the effective activation energy, Wd, for the dipoles is evaluated for the glasses doped
with different concentrations of TiO2. In Eq. (3.3), f is the relaxation frequency, kB is
the Boltzmann constant, T is absolute temperature and fo is a constant. The
activation energy Wd is found to decrease with increase in the concentration of TiO2
(Table 3.4).
99
Table 3.4 Summary of data on dielectric loss of Na2SO4–B2O3–P2O5: TiO2 glasses:
The a.c. conductivity σac is calculated at different temperatures using the
equation:
σac = ω ε'εo tan δ , (3.4)
(where εo is the vacuum dielectric constant and ω is the angular frequency) for
different frequencies and the plot of log σac against 1/T for all the glasses at
100 kHz is shown in Fig. 3.7; the conductivity is found to increase
considerably with increase in the concentration of TiO2 at any given frequency
and temperature. From these plots, the activation energy for the conduction in
Glass (tanδ)max.avg.
Temp. region of relaxation (oC)
AA. E. for dipoles (eV) (± 0. 01)
Spreading factor β
A. E. for conduction (eV) (± 0. 01)
Exponent s
T2 0.050 113-158 0.65 0.46 0.81 0.65
T4 0.061 97-147 0.62 0.48 0.79 0.70
T6 0.078 90-140 0.59 0.50 0.76 0.73
T8 0.126 79-128 0.56 0.53 0.70 0.77
T10 0.161 68-118 0.53 0.55 0.67 0.81
100
the high temperature region is evaluated and presented in Table 3.4 along with
other pertinent data.
3. 4. Discussion
The composition of Na2SO4–B2O3–P2O5: TiO2 glass system is an
admixture of glass formers, modifiers and intermediates. P2O5 is a strong glass
forming oxide, participates in the glass network with PO4 structural clusters.
The PO4 tetrahedra are linked together with covalent bonding in chains or rings
by bridging oxygens. Neighboring phosphate chains are linked together by
cross-bonding between the metal cation and two non-bridging oxygen atoms of
each PO4 tetrahedron [105]. The presence of such PO4 units in the titled glass
samples is evident from the IR spectral studies. B2O3 is also a strong glass
former, when it is mixed in the phosphate glasses, the tetrahedral boron entities
dominate in the phosphate-rich domain where as trigonal boron entities prevail
in the borate-rich side and form easily B–O–P bridges. The highest stability
occurs for fully polymerized glasses and can be related to the energetics of the
reaction B–O–B + P–O– P = 2(B–O–P); this relation also suggests that the B–
O–P linkage is more stable relatively than the mixture of B–O–B and P–O–P
linkages [106-109].
With the addition of Na2SO4 a gradual depolymerization of the
phosphate chains and formation of short phosphate units take place. During
this process the sulphate units remain as terminal groups without any chemical
101
interaction with the phosphate units [4]. As a consequence, variation in the
density is hardly expected with the variation in the content of Na2SO4; however,
due to the formation of dithiophosphate (DTP) units (due to the weak
interaction between pyrophosphates), a slight increase in the density is possible
(Table 3. 1). Normally the phosphate network contains [POO2/2O]- (phosphate
tetrahedra with one bridging oxygen) and [POO1/2O2]2- (phosphate tetrahedra
with two bridging oxygens) structural groups [110] as shown below:
O
P O P
O
O
OO
O + O2- → O P2
o
O-
o
+ O2- →
O
P O P
O
O-
OO
-O O P2O-
O
O-
Out of these two ions, it is the [POO2/2O]- ion that interacts with sulphate ion
and form SPO73- (dithiophosphate) species [98]. However there are some
affirmative reports (based on Raman and NMR investigations) on
sulfophosphate glasses suggesting that SO42- species do not contribute to
network formation and instead these groups participate in the
depolymerization of the phosphate network similar to Ti3+ and Na+ ions [111].
Titanium ions exist mainly in Ti4+ state in Na2SO4–B2O3–P2O5 glass
network. Nevertheless, the reduction of Ti4+ to Ti3+ is unavoidable during
melting at high temperatures and annealing processes of the glasses. Ti4+ ions
102
occupy both tetrahedral and substitutional octahedral sites as corner-sharing
[TiO6]2- units where as Ti3+ ions occupy only modifying positions and
depolymerize the glass network. TiO4 and TiO6 units of Ti4+ ions enter the
glass network and form linkages of the type P–O–Ti and B–O–Ti.
In detail the interaction of TiO2 with phosphate, borate and borophosphate
networks may be represented as follows:
(i) P2O5 ≡ 2 [POO3/2]; TiO2 ≡ [TiO4/2]; TiO2 + 2 [POO3/2] ⇒ [TiO6/2]2- + 2
[PO4/2]+
and diagrammatically as
O- O- O O O P O Ti O P O [TiO6/2]
2- + 2[PO4/2]
+ O O O- O-
(ii) B2O3 + 2TiO2 + 2O2 → 2[BO6/2]3 + [TiO4/2] + [TiO6/2]
(iii) B 2O3 + 3TiO2 + 2P2O5 + O2 → 2[BO6/2]3 + 4[PO4/2]
+ + 2[TiO4/2] + [TiO6/2]
These equations clearly suggest that incorporation of the Ti ions into the glass
network leads to some d-p charge transfer between the 3d Ti ions and the
surrounding ligands.
103
3. 4. 1 DTA
Tg and Tc–Tg values evaluated from DTA traces show a decreasing trend
with increase in the concentration of TiO2. Such trend indicates the decrease of
augmented cross–link density of various structural groups and closeness of
packing. This is possible only if there is a gradual increasing proportion of
Ti3+ ions that act as modifiers in the glass network.
3. 4. 2 Optical absorption Spectra
The electronic configuration of Ti3+ ion is 3d1. In octahedral field or
tetrahedral field, the ground state 2D of the 3d1 ion splits into 2E and 2T2 states.
In the tetragonally distorted octahedral field, the 2T2 state further splits into
three 2B2g (viz. xy , yz and zx ) states, whereas, the 2E excited state splits
into A1g223 rz − and B1g 22 yx − states. For d1 ions in tetragonally
compressed octahedron, the ground state is B2g xy . Hence, the bands
observed in the optical absorption spectra at about 540 nm and 690 nm of the
studied glass are assigned to 2B2g→2B1g and 2B2g→
2A1g transitions of the Ti3+
ions, respectively [112, 113]. With increase in concentration of TiO2, a gradual
growth of these two bands could clearly be seen; this observation indicates that
there is an increasing fraction of Ti3+ ions in the glass network.
The octahedrally coordinated Ti3+ ions, similar to Na+ ions, act as
modifiers and are expected to induce non-bridging oxygens (NBO’s) in the
glass network. The analysis of IR spectral results have also indicated that, in
104
the samples containing higher concentration of TiO2, the asymmetric
vibrational bands of phosphate groups dominate over symmetric bands. These
factors indicate an increase in the concentration of NBO’s in the glass network
with increase in the concentration of TiO2. Because of these reasons an
increase in the degree of localization of electrons there by an increase in the
donor centers in the glass network is possible. The presence of higher
concentration of these donor centers decreases the optical band gap and shifts
the absorption edge gradually towards higher wavelength side. The gradual
decrease in the proportion of network forming Ti4+ ions in the glass network
leads to an increase in the generation of donor centers; as a consequence, there
will be an increasing overlap between empty 3d states of Ti4+ sites and the
neighboring excited states of localized electrons originally trapped on Ti3+ ions.
Such overlap facilitates for the shrinkage of optical band gap and hence there is
a decrease of optical band gap with increase in the content of TiO2, as observed
(Table 3.3). In other words, the 3d levels of Ti ion within the effective energy
gap will be influenced by bonding-anti-bonding of 2p–O–2p B and s Na levels
to a large extent and contribute for the observed decrease of optical band gap.
The optical activation energy associated with the octahedral band of Ti3+
ions viz., 2B2g→2B1g is decreased from 2.44 eV to 2.32 eV with the increase
in the concentration of TiO2 from 0.2 to 1.0 mol% (Table 3.2); this is clearly a
characteristic signal of inter valence transfer or a polaronic type of absorption.
To be more specific, the associated electrons are trapped at shallow sites within
105
the main band gap. In terms of polaronic perception, this kind of situation is
only possible if the local potential fluctuation is small as compared to the
transfer integral, j. A small overlap between electronic wave-functions
(corresponding to adjacent sites) due to strong disorder is contributive to
polaron formation. So in terms of the polaron exchange the variation of optical
band gap can be explained as fallows: the electron delivered by the impurity
atom at the Ti4+ site converts this into a lower valence state Ti3+ and at the next
stage, the trapped electron at this Ti3+ site is transferred to the neighboring new
Ti4+ site by absorbing a photon energy. Thus the optical absorption in the glass
samples is dominated by polaronic transfer between the Ti3+ and Ti4+ species
[114, 115].
3. 4. 3 ESR Spectra
In the ESR spectra, the central line observed at g =1.987 is due to
tetragonally compressed octahedral excitations of Ti3+ ions from the ground
state xy [116, 117]. The observed increase of intensity and half-width of the
signal with the increase in the content of TiO2 suggests a gradual increase in
the concentration of Ti3+ ions in the glass network.
The other factors e.g., the jumping frequency of the charge carriers (from Ti3+
to Ti4+) which is proportional to exp (–W/kT) also accounts for such variations.
Here W=1/2 WD (mean energy difference between adjacent titanium ion sites)
+ WH (the activation energy for the hopping process of the polarons between
two identical sites). As the concentration of TiO2 is increased gradually, the
106
jumping rate of the polaron increases. This fact, together with the increasing
concentration of the Ti3+ accounts for the increasing intensity of the ESR signal.
3. 4. 4 IR Spectra
The IR spectral studies have revealed the intensity of the bands due to
asymmetric vibrations of phosphate groups and also BO3 groups grow at the
expense of symmetrical bands of phosphate and BO4 groups with increase in
the content of TiO2. Such variations suggest increasing modifying action of
titanium ions by creating larger number NBO’s in the glass network. As a
result, the phosphate coordination reduces from four fold to three fold, two fold
and even to one dimensional and the depolymerization of P–O–P, B–O–B, P–
O–B and also P–O–Ti chains takes place and the strength of the glass network
decreases. Thus the results of IR spectral studies point out that, there is
growing degree of disorder in the glass network with the increase in the
concentration of TiO2.
3. 4. 5 Dielectric properties
The dielectric parameters viz., ε', tan δ and σac are found to increase with
increase in temperature for all the studied glasses. Further, at any frequency
and temperature these parameters are found to increase with increase in the
content of TiO2 in the glass matrix. In general electronic, ionic, dipolar and
space charge polarizations contribute to the dielectric constant. Among these, it
is the space charge polarization (which depends up on concentration defects in
the glass network) that influences strongly the dielectric constant at lower
107
frequencies. As mentioned earlier, the Ti3+ ions similar to Na+ ions act as
modifiers and create dangling bonds and non bridging oxygen ions by
disrupting P−O−P, B−O−B, P−O−B, P−O−Ti and B−O−Ti linkages. In view
of this, the glass network consists of [SO4]2-, [POO1/2O2]
2–, [POO0/2O3]3–, Na+
and (NaSO4)- free ions (formed by the reaction, Na2SO4 ⇔ Na+ + (NaSO4)
− );
the defects thus produced create easy path ways for the migration of charges
that would build up space charge polarization and facilitate to an increase in
the dielectric parameters as observed [118-120]. Thus these results also support
the view point that there is an increasing degree of disorder in the glass
network due to the increasing fraction of Ti3+ ions that act as modifiers.
Conventionally, the dielectric relaxation effects are described with the
variable frequency at a fixed temperature. However, similar information can
also be obtained by analyzing these results at a fixed frequency at variable
temperature as suggested by Bottcher and Bordewijk [121].
Substituting Eq. (3.3) in standard Debye relations for dielectric relaxation, one
can obtain
[ ])ln(1)(),( 21' AkTWtghT ds ωεεεωε +−−+= ∞∞ (3.4)
)lncosh(
)(),( 2
1''
AkTWT
d
s
ωεεωε+
−= ∞ (3.5)
In Eqs. (3.4) and (3.5), ε∞ is temperature independent whereas, εs is largely
dependent on temperature. Keeping the fact in mind that the variation of
108
hyperbolic trigonometric functions in Eqs. (3.4) and (3.5) with temperature is
very minimal, these equations can be rewritten as
[ ]/))(11(1)(),( 21' kTTWtghT mds ωεεεωε −−−+= ∞∞ (3.6)
and [ ]kTTWT
md
s
/))(11(cosh
)(),( 2
1''
ωεεωε
−−= ∞ (3.7)
In Eqs. (3.6) and (3.7), Tm(ωωωω) is the temperature at where εεεε' exhibits
maximum value. Thus, as per the Eqs. (3.6) and (3.7), the plots of εεεε'(ωωωω, T) and εεεε''
(ωωωω, T) against 1/T should be centro symmetric and symmetric curves,
respectively in the dielectric relaxation region. As an example for one of the glass
samples (viz., T10) under investigation, the variations of εεεε'( ωωωω, T) and εεεε'' ( ωωωω, T)
with 1/T are shown in Fig.3. 8. The shape of these curves is well in accordance
with the Eqs. (3.6) and (3.7) and clearly confirms the relaxation character of
dielectric properties of these glasses.
With increase in the concentration of TiO2 an increase in the value of
(Tan δ)max and a shift region of dielectric relaxation towards lower temperature
have been noticed. Such variations indicate an increase in the concentration of
dipoles that contribute to the relaxation effects. The value of the effective
activation energy associated with the dipoles is observed to decrease with
increase in the content of TiO2 in the glass network (Table 3.4). This
observation points out that an increasing freedom for dipoles to orient in the
field direction. Earlier studies on the glasses containing variety of d1 ions (like
V4+, Mo5+, W5+, Cr5+, etc.,) indicated that the geometrical arrangement of these
109
ions with oxygens form complexes in such a way that they contribute to the
dielectric relaxation effects [122-125]; following these arguments , relaxation
effects exhibited by the present studied glasses can be attributed to Ti3+ (d1) ion
complexes.
Further, to know whether there is single relaxation time or spreading of
relaxation times for the dipoles, we have adopted a pseudo Cole-Cole plot
method (instead of conventional Cole-Cole plot between ε'(ω) and ε"(ω) at a
fixed temperature) suggested by Sixou [126] in which ε'(T) vs ε"(T) can be
plotted at a fixed frequency. The nature of variation of ε'(T) and tan δ with
temperature for these glasses indicates that the Cole-Davidson equation:
( )βωτ
εεεωεi
s
+−
+= ∞∞
1)(* . (3.8)
can safely be applied to these glasses. Separating real and imaginary terms of
Eq. (3.8), and rewriting with explicit temperature dependence of terms, one can
get
)(cos)]()[cos(),( TTT s βϕϕεεεωε β∞∞ −+=′ (3.9)
and )(sin)]()[cos(),( TTT s βϕϕεεωε β∞−=′′ . (3.10)
In Eqs. (3.9) and (3.10)
)(tan)(tan)( /11 KTWo
deAT ωωτϕ −− == . (3.11)
110
In Eq. (3.11) oA is a constant and Wd is the activation energy for dipoles.
The plot between ε'(T) and ε"(T) represented by the Eqs. (3.9) and (3.10) at a
fixed frequency is often called pseudo Cole-Cole plot, which cuts ε' axis at εs
and ε∞. Here, εs is known as high temperature dielectric constant (in contrast to
the low frequency dielectric constant in the conventional Cole-Cole plot) and
similarly ε∞ is the low temperature dielectric constant. The plot cuts ε' axis at
an angle of (π /2) β at low temperature side (as per Sixou [126]), here β is the
spreading factor for relaxation times. For Na2SO4–B2O3–P2O5 glass containing
0.8% of TiO2 (glass T8), a pseudo Cole–Cole plot at 10 kHz is shown in Fig.
3.9. The spreading factor β estimated from this plot is 0.61; such plots have
also been drawn for all the glasses and the value of β is estimated in a similar
way; the value of β is found to increase gradually with the increase in the
concentration of TiO2 (Table 3.3). The spreading of relaxation times in these
glasses may be understood as due to the experience of an approximately
random potential energy by the dipoles on diffusing through the distorted
structure of the glass [127, 128].
The activation energy associated with ac conductivity is found to
decrease with increasing TiO2 concentration. When log σac is plotted against
activation energy, Wac, a near linear relationship is found (inset (a) of Fig. 3.7).
This means that the conductivity enhancement is directly related to the
thermally stimulated mobility of the charge carriers in the high temperature
111
region. As mentioned earlier, the glasses under study exhibit mixed, ionic and
polaronic conductivity. Generally, electronic conduction is due to the polaron
hopping between Ti3+ and Ti4+ ions whereas, ionic conduction is due to
migration of Na+ ions. For these glasses, the ac conductivity increases with
increasing content of TiO2 (Fig. 3.7). One of the possible explanations for such
a behavior is that, the entry of Ti3+ ions into the glass network causes to
increase the concentration of dangling bonds in the glass network. This in turn
leads to decrease in the electrostatic binding energy and the strain energy for
the easy passage of conducting ions. Due to these reasons there will be a
substantial decrement in the jump distance of Na+ ions. Such behavior is in
good accordance with the observed decrease in activation energy for
conduction.
The frequency response of real part of ac conductivity is normally
described by power law dependence with ‘s’ as exponent:
10],)/(1[)( <≤+= sscdc ωωσωσ (3.12)
Indicating, σ (ω) is the sum of the dc conductivity and a fractional
power law dependent dispersive conductivity with exponent s. Here ωc is a
characteristic crossover frequency from dc to dispersive conductivity.
Within the framework of the linear–response theory, the frequency–dependent
conductivity can be related to
dtetrkTH
nq ti
R
c ωωωσ −∞
∫−=0
222
)(6
)( (3.13)
112
where q is the charge, nc is the mobile ion density, )(2 tr is the mean
square displacement of the mobile ions and HR is the Haven ratio (lies in
between 0.2 and 1.0) [129] which represents the degree of correlation between
successive hops.
More precisely, in Eq. (3.13) <r2> represents the mean squared
displacement particles performing random walks on a regular lattice. For
excursions shorter than the correlation length the mean squared displacement
r2 varies as a power law
t1-s . Under these conditions Eq. (3.12) modifies to
σ (ω) ∝ ωs (3.14)
with exponent s < 1. For the glass T2 , the value of ‘s’ (obtained by
plotting log σ (ω) vs ω, (inset (b) of Fig. 3.7)), is found to be 0.73. With
increase in the concentration of TiO2 the exponent is found to be increasing
gradually. In general‘s’ is a measure of the degree of interaction with the
environment. In fact this parameter depends on the glass composition and the
limit of measurement temperature. The low values of exponent ‘s’ (< 1) arises
from the distribution of the cluster sizes (determined by mutual correlations
between dipoles formed in the system) and the distribution of their relaxation
rates. Sidebottom while explaining the conduction mechanism in alkali
phosphate glasses, concluded that exponent‘s’ depends upon the
dimensionality of the local conduction space and it increases with increasing
113
dimensionality [130, 131]. Based on these studies the observed increase of ‘s’
( inset (c) of Fig. 3.7 ) with the concentration of TiO2. may be attributed to a
enhancement in the dimensionality of conducting space with increase in the
content of TiO2 [132].
The low temperature part of the conductivity (a near temperature
independent part as in the case of present glasses) up to nearly 70 oC can be
explained on the basis of quantum mechanical tunneling model [133] similar to
many other glass systems reported recently [134-136].
3.5 Conclusions
The glasses of the composition viz., (40-x)Na2SO4–30B2O3–30P2O5:
xTiO2 with 0 ≤ x ≤ 1.0 mol% in the steps of 0.2 were synthesized. Dielectric
and spectroscopic properties were investigated. The optical absorption and
ESR spectral studies revealed the existence of titanium ions in Ti3+ state in
addition to Ti4+ state in the glass network. The IR spectral results indicated the
degree of disorder in the glass network increases with the increase in the
concentration of TiO2. The values of dielectric parameters viz., dielectric
constant, loss and ac conductivity at any frequency and temperature are
observed to increase with the concentration of TiO2; the increasing space
charge polarization is found to be responsible for such an increase. The
dielectric relaxation effects exhibited by these glasses are quantitatively
analyzed by pseudo Cole-Cole method and the spreading of relaxation times is
established. The ac conductivity is observed to increases with increasing
114
content of TiO2; the mechanism responsible for such increase is well explained
based on the modifying action of Ti3+ ions.
115
References
[1] D. A. McKeown, I.S. Muller, H. Gan, I.L. Pegg, C.A. Kendziora, J. Non-Cryst. Solids 288 (2001) 191.
[2] X. Yu, J.B. Bates,G.E. Jellison Jr., F.X.Hart, J. Electrochem. Soc. 144
(1997) 524.
[3] F. Scholz, J. Solid State Electrochem. 15 (2011) 14.
[4] N. Da, O. Grassmé, K. H. Nielsen, G. Peters, L. Wondraczek, J. Non-Cryst. Solids 357 (2011) 2202.
[5] M. Ganguli, M.H. Bhat, K.J. Rao, Solid State Ionics 122 (1999) 23.
[6] I.A. Sokolov, I.V. Murin, V.E. Kriyt, A.A. Pronkin, Glass Phys. Chem. 37 (2011) 351.
[7] V. G. Vyatchina, L. A. Perelyaeva, M. G. Zuev and V. .L Mamoshin, Glass Phys. Chem. 29 (2003) 522.
[8] A.M. Pletnev, R.N. Lapina, O.B. Kozlova, S.G. Bamburov, Glass Phys. Chem. 28 (2002) 1.
[9] B.V.R. Chowdari, K.F. Mok, J.M. Xie, R. Gopalakrishnan, J. Non-Cryst. Solids 160 (1993) 73.
[10] G. Chiodelli, A. Magistris, Solid State Ionics 18 (1986) 356.
[11] R.V. Salokdar, V.K. Deshpande, K. Singh, J. Power Sources 25 (1989) 257.
[12] N.K. Karan, B. Natesa, R.S. Katiyar, Solids State Ionics 177 (2006) 1429.
[13] F. Muñoz, L. Montagne, L. Pascual, A. Durán, J. Non-Cryst. Solids 355 (2009) 2571.
[14] N. Shimoji, T. Hashimoto, H. Nasu, K. Kamiya, J. Non-Cryst. Solids 324 (2003)
50. [15] E. Golis, I.V.Kityk, J.Wasylak & J.Kasperczyk, Mater. Res. Bull. 31
(1996) 1057.
[16] I. V. Kityk and A. Majchrowski, Opt. Mater. 26 (2004) 33.
116
[17] A. Shaim, M. Et-tabirou, Mater. Chem. Phys. 80 (2003) 63.
[18] P. Nageswara Rao, C. Laxmi Kanth, D. Krishna Rao, N. Veeraiah, J.
Quant. Spectrom. Rad. Transfer 95 (2005) 37.
[19] M. E. Nordberg, U.S. Patent 2,326, 059 (3 Aug 1943); J. E. Nitsche, U.S. Patent 3,303,115 (5 Feb. 1967).
[20] P. C. Schultz and H. T. Smyth, in: Amorphous Materials, edited by R. W. Douglas and B. Ellis (Wiley-Interscience, London, 1972) 453
[21] J. Hecht, City of Light (Oxford University Press, London, 1999) 134.
[22] D. Y. Smith, C. E. Black, C. C. Homes, E. Shiles, Phys. Stat. Solidi. (c) 4 (2007) 838.
[23] D. Pickup, G. Mountjoy, G.W. Wallidge, R. Anderson, J.M. Cole, R.J. Newport, M.E. Smith, J. Mater. Chem. 9 (1999) 1299.
[24] C.F. Song, N.K. Li, P. Yang, D. Xu, D.R. Yuan, Thin Solid Films 413 (2002) 155.
[25] Hongpeng You and Masayuki Nogami, J. Phys. Chem. B 108 (2004) 12003.
[26] P. C. Schultz, J. Am. Ceram. Soc, 59 (1976) 214.
[27] A.D. Wilson, B.E. Kent, (1973). Surgical Cement. British Patent No.1316129.
[28] Nicholson, J.W. Chemistry of glass ionomer cements: A review of Biomaterials 19 (1998) 485.
[29] S Hübel, I. Mejàre, Int. J. Paediatr. Dent. 13 (2003) 2.
[30] J.Nourmohammadi, R. Salarian, M.Solati-Hashjin, F. Moztarzadeh Ceram. Int. 33 (2007) 557.
[31] A. Moshaverinia, S. Ansari, M.Moshaverinia, N.Roohpour, J.A. Darr, Rehman, Acta Biomater. 4 (2008) 432. [32] N. Monmaturapoj, S. Tanodekaew, W. Soodsawang, Ch.
Songklanakarin. J. Sci. Tech. 31 (2009) 337.
117
[33] C. Jing, X. Zhao, H. Tao, X.Wang and A. Liu, J. Mater. Chem. 13 (2003) 3066.
[34] Lee, J. shing, Hsu and C. King, Thermochim. Acta 333 (1999) 115.
[35] N. Watanabe , A.Y. Ramos, M.C.M. Alves ,H. Tolentino, L.C. Barbosa O.L. Alves, J. Mater. Res.15 (2000) 793.
[36] E.M. Vogel, J. Am. Ceram. Soc. 72 (1989) 719.
[37] E.M. Vogel, S.G. Kosinski, D.M. Krol, J.L. Jackel, S.R. Frieberg, M.K. Oliver, J.D. Powers, J. Non-Cryst. Solids 107 (1989) 244.
[38] H. Hosono, Z. Zhang, and Y. Abe, J. Am. Ceram. Soc. 72 (1989)1587.
[39] H. Hosono and Y. Abe, J. Non-Cryst. Solids 139 (1992) 86.
[40] H. Hosono, K. Imai, Y. Abe, J. Electrochem. Soc. 140 (1993) L7.
[41] S. Sakka, F. Miyaji, K. Fukumi, J. Non-Cryst. Solids 112 (1989) 64.
[42] J. Zarzycki, J. Mater. Sci. 6 (1971) 130.
[43] E.M. Vogel, M.J. Weber, and D.M. Krol, Phys. Chem. Glasses 32 (1991) 232.
[44] L. Canioni, L. Sarger, P. Segonds, A. Ducasse, C. Duchesne,E. Fargin, R. Olazcuaga, and G. le Flem, Solid State Commun. 84 (1992) 1065.
[45] K. Inoue1, S. Sakida2, T. Nanba1, Y. Miura1 Glass and Optical Materials Organized by S.W. Martin, A. Jha, and N.M. Ravindra Materials Science and Technology (MS&T) 2006: MATERIALS AND SYSTEMS – Vol.1
[46] S. Sakka, F. Miyaji, K. Fukumi, J. Non-Cryst. Solids, 112 (1989) 64.
[47] S. Sakka, F. Miyaji, K. Fukumi, J. Non-Cryst. Solids 107 (1989) 171
[48] K. Kusabiraki, J. Non-Cryst. Solids 95&96 (1987) 411.
[49] S.T. Gulati, M.J. Edwards, Proc. Adv. Mater. Opt. Precis. Struct. CR67 (1997) 107.
[50] K. Hrdina, SPIE 4889 (2002) 113.
[51] H. George, J.R. Sigel, in: M. Tomozawa, R. Doremus (Eds.), Treatise on Mater. Sci. Tech. 12 (1977) 5.
118
[52] T. Hashimoto, M. Murakami, H. Nasu, A. Ishihara, K. Kunii, J. Am. Ceram. Soc. 92 (2009) 1250.
[53] M. Ma, W. Ni, Y. Wang, Z. Wang, F. Liu, J. Non-Cryst. Solids 354 (2008) 5395.
[54] X. Tiefeng, C. Feifei, D. Shixun, N. Qiuhua, S. Xiang and W. Xunsi Physica B, 404 (2009) 2012.
[55] Gonzáles-Lozano, M.A., Gorokhovsky, A., Escalante-García, J. Ivan, J.
Non-Cryst. Solids 355 (2009) 114.
[56] O.A. Al-Harbi, E.M.A. Hamzawy, M. Mujtaba Khan, J. Appl. Sci. 9 (2009) 2981.
[57] S. Duhan, S. Sanghi, A. Agarwal, A. Sheoran, S. Rani, Physica B 404 (2009)1648.
[58] F.F. Chen, S.X. Dai, T.F. Xu, Q.H. Nie, X. Shen, X.S. Wang, Guangzi Xuebao/Acta Photonica Sinica 37 (2008) 215.
[59] F. Farges, J.R. Brown, J. John, Geochimica et Cosmochim. Acta 60 (1996) 3023.
[60] R.B. Greegor, F.W. Lyue, D.R.Sandstrom, P. Schultz, J. Non-Cryst. Solids 55 (1983) 27.
[61] A. Ramos, J. Petiau, J. Phys. C 846 (1985) 491.
[62] T. Dumas, J. Petiau, J. Non-Cryst. Solids 81 (1986) 201.
[63] A.A. Higazy, A.M. Hussein, M.I. Elhofy, Phys. Chem. Glasses 28 (1987) 164.
[64] A.R. Lange, I.S.E. Carmichael, Geochimica Cosmochimica Acta 57 (1987) 3001 .
[65] P.C. Hess, Physical Chem. of Magmas (1991) 152.
[66] D.B. Dingwell , Geochimica Cosmochimica Acta 56 (1992) 3404; Amer. Mineral. 77 (1992) 270.
[67] D.B. Dingwell, E. Paris, C. Romano, Phys. Chem. Mineral. 21 (1994) 501.
119
[68] H. Gan, “The speciation of solution properties of high field strength cations P5+, Ti4+, B3+ in aluminosilicate melts” Ph.D Dissertation, (Brown University, 1994).
[69] A. Kishioka, M. Haba, Bull. Chem. Soc. Jpn. 51 (1978) 2559.
[70] A.R. Langa, A. Navrotsky, Geochimica Cosmochimica Acta 51 (1993) 2931.
[71] T. Huebert, P. Reach, Phys. Chem. Glasses 32 (1991) 58.
[72] L.A. Farrow, E.M.Vogl, J. Non-Cryst. Solids 143 (1992) 59.
[73] S.A. Markgraf, A.S. Bhalla, J. Amer.Ceram Soc.75 (1992) 2630.
[74] H.V. Alberto, B.O. Mysen, Phys. Chem. Glasses 36 (1995) 114.
[75] G.S. Henderson, M.E. Fleet, Canadian Mineral. 33 (1995) 399.
[76] B. Mysen, D. Neuville, Geochimica Cosmochimica Acta 59 (1995) 325.
[77] A.A. Loshmanov, V.M. Sigaev and I.I. Yamzin, Fizika I Khimija Stekla 1 (1975) 35.
[78] T. Hanada, N. Soga, J. Non-Cryst. Solids 38 (1980) 105.
[79] F. Marumo, Y. Yabira and H. Morikawa, In Dynamic Process of Material Transport and Transformation in the Earth’s Interior, Terra Sci. Publ.Co; (1990) 53.
[80] F. Farges, A. Navrotsky and P. Richet, Abstr. Prog. IMA Meeting (Pisa), (1994) 114.
[81] E. Fargin, J. Non-Cryst. Solids 168 (1994) 132.
[82] E. Paris, D.B. Dingwell and C. Romano, Phys. Chem. Mineral. 21 (1994) 510.
[83] H.F. Wu, C.C. Lin, P. Shen, J. Non-Cryst. Solids 209 (1997) 76.
[84] S.R. Lacerda, R.N. Correia, M.H.V. Fernandes, J. Non-Cryst. Solids 221 (1997) 255.
[85] G. Laudisio, A. Aronne, P. Pernice, Thermochimica Acta 294 (1997) 173.
120
[86] L. Barbieri, L. Cristina, B. Anna, P. Gian Carlo, Mater. Res. Bull. 32 (1997) 637.
[87] F. Duan, C. Fang, H. Zhu, Mater. Lett. 34 (1998) 184.
[88] R.G. Duan, K.M. Liang, S.R. Gu, J. Eur. Cerm. Soc. 18 (1998) 1729.
[89] Abrahams, E. Hadzifejzovic, Solid State Ionics 134 (2000) 249.
[90] H. Grussaute, G. Palavit, J.L. Bernard, J. Non-Cryst. Solids 263 (2000) 312.
[91] B.V.R. Chowdari, G.V. Subba Rao, G.Y.H. Lee, Solid State Ionics 136 (2000) 1067.
[92] B. Jivov, Y. Dimitriev, E. Kashchieva, Int. J. Inorg. Mater. 3 (2001) 521.
[93] A. Shaim, L. Montagne, G. Palavit, Mater. Res. Bull. 37 (2002) 2459.
[94] A. Aboukais, V.A. Jachkin, O.A. Trul, E.A. Zhilinskaya, Opt. Mater. 19 (2002) 295.
[95] M. J. Weber, R. A. Saroyan and R. C. Ropp, J. Non-Cryst. Solids 44 (1981) 137.
[96] K. Morigaki, Physics of Amorphous Semiconductors, World Scientific, Singapore, 1999.
[97] G. Murali Krishna, Y. Gandhi, and N. Veeraiah, Phys. Stat. Solidi (a) 205 (2008) 177.
[98] K.J. Rao, Structural Chemistry of Glasses, Elsevier, Amsterdam, 2002..
[99] K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds,
John Wiely & Sons, New York, 1962.
[100] A. Bhide, K. Hariharan, Mater.Chem.Phys.105 (2007) 213.
[101] Y. Dimitriev, V. Mihailova, V. Dimitrov and Y. Ivanova, J. Mater. Sci. Lett. 10 (1991) 1249.
[102] A. Shaim and M. Et-Tabirou, Mater. Res. Bull. 37 (2002) 2459.
121
[103] R. Balaji Rao, D. Krishna Rao and N. Veeraiah, Mater. Chem. Phys. 87 (2004) 357.
[104] B. Tareev, Physics of Dielectric Materials, Mir, Moscow, 1979.
[105] G. Little Flower, M. Srinivasa Reddy, M. V. Ramana Reddy, and N. Veeraiah, Z. Naturforsch 62 (2007) 315.
[106] R.K. Brow, D.R. Tallant, J. Non-Cryst. Solids 222 (1997) 396.
[107] E.T.Y. Lee, E.R.M. Taylor, J. Phys. Chem. Solids 66 (2005) 47.
[108] R.K. Brow, J. Non-Cryst. Solids 194 (1996) 267.
[109] J.J. Videau, J.F. Ducel, K. S Suh, J. Senegas, J. Alloys Compd. 188 (1992) 157.
[110] M. Ganguli, M.H. Bhat, K.J. Rao, Solid State Ionics 122 (1999) 23.
[111] N. Da, A.A. Enany, N. Granzow, M.A. Schmidt, P. St, J. Russell, L. Wondraczek, J. Non-Cryst. Solids 357 (2011) 1558.
[112] X A. Aboukais, L.D. Bogomolova, A.A. Deshkovskaya, V.A. Jachkin Krasil, N.A. Nikova, S.A. Prushinsky, O.A. Trul, S.V. Stefanovsky and E.A. Zhilinskaya, Opt. Mater. 19 (2002) 295.
[113] M.V. Ramachandra Rao, Y. Gandhi, L. Srinivasa Rao, G. Sahayabaskaran and N. Veeraiah, Mater. Chem. Phys. 126 (2011) 58.
[114] O. Cozar, D.A. Magdas, I. Ardelean, J. Non-Cryst. Solids 354 (2008) 1032.
[115] B.V.R. Chowdari, K. Radha Krishnan. J. Non-Cryst. Solids 224 (1998) 151.
[116] Isaac Abrahams and Emina Hadzifejzovic, Solid State Ionics 134 (2000) 249.
[117] B.V. Raghavaiah, C. Laxmikanth and N. Veeraiah, Optics Commun. 235 (2004) 341.
[118] N. Krishna Mohan, G. Sahaya Baskaran, N. Veeraiah, Phys. Stat. Sol. (a) 203 (2006) 2083.
[119] G. Naga Raju, N. Veeraiah, Physica B 373 (2006) 297.
122
[120] G. Murali Krishna, M. Srinivasa Reddy, N. Veeraiah, J. Solid State Chem. 180 (2007) 2747.
[121] C.J.F. Bottcher, P. Bordewijk, Thoery of Electric Polarization, Elsevier,
Oxford, 1978.
[122] L. Bih, El Omari, M. Haddad, J.M. Reau, D. Boudlich, A. Yacoubi, A. Nadiri, Solid State Ionics 132 (2000) 71.
[123] R.M. Abdelouhab, R. Braunstein and K. Baerner, J. Non-Cryst. Solids 108 (1989) 109.
[124] G. Srinivasarao and N. Veeraiah, J. Solid State Chem. 166 (2002) 104.
[125] Y. Gandhi, K.S.V. Sudhakar, M. Nagarjuna and N. Veeraiah, J. Alloys Compd. 485 (2009) 876.
[126] P. Sixou, P. Dansas, D. Gillot, J. Chem. Phys. 64 (1967) 834.
[127] C. Dyre, J. Non-Cryst.Solids 88 (1986) 271.
[128] S.R. Elliott, Physics of Amorphous Materials (Longman Science and Technology, Essex, 1990).
[129] H. Kahnt, J. Non-Cryst. Solids 203 (1996) 225.
[130] S. Lanfredi, P. S. Saia, R. Lebullenger, A.C. Hernandes, Solid State Ionics 146 (2002) 329.
[131] D. L. Sidebottom, Phys. Rev. Lett. 83 (1999) 983.
[132] S. Bhattacharya, A. Ghosh, Phys. Rev. B 70 (2004) 172203.
[133] I. G. Austin, N.F Mott, Adv. Phys.18 (1969) 657.
[134] G. Murali Krishna, N. Veeraiah, N. Venkatramaiah, R. Venkatesan, J. Alloys Compd. 450 (2008) 486.
[135] Ch. Srinivasa Rao, V. Ravi Kumar, T. Srikumar, Y. Gandhi, N. Veeraiah, J. Non-Cryst.Solids 357 (2011) 3094.
[136] K. Srilatha, L. Pavić, A. Moguš-Milanković, Ch. Srinivasa Rao, G.
Little Flower, V. Ravi Kumar, N. Veeraiah, J. Non-Cryst. Solids 357 (2011) 3538.