Accepted Manuscript

Physical characteristics of PbO−ZrO2−SiO2:TiO2 glass ceramics embedded with

Pb2Ti2O6 cubic pyrochlore crystal phase: Part-I electrical properties

A. Subba Rao, J. Ashok, B. Suresh, G. Naga Raju, N. Venkatramaiah, V. Ravi Kumar,

I.V. Kityk, N. Veeraiah
PII: S0925-8388(17)31300-2
DOI: 10.1016/j.jallcom.2017.04.100
Reference: JALCOM 41504

To appear in: Journal of Alloys and Compounds

Received Date: 16 February 2017

Revised Date: 5 April 2017
Accepted Date: 11 April 2017

Please cite this article as: A. Subba Rao, J. Ashok, B. Suresh, G. Naga Raju, N. Venkatramaiah, V.
Ravi Kumar, I.V. Kityk, N. Veeraiah, Physical characteristics of PbO−ZrO2−SiO2:TiO2 glass ceramics
embedded with Pb2Ti2O6 cubic pyrochlore crystal phase: Part-I electrical properties, Journal of Alloys
and Compounds (2017), doi: 10.1016/j.jallcom.2017.04.100.

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 ACCEPTED MANUSCRIPT

30 oC
0.06

0.04
M'

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0.02
o
350 C

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0 350 oC T8
0.021

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T8

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M"

0.011

o
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Fig. 7. (b) Dispersion of electric moduli M'(ω) with the frequency evaluated in the temperature range
30 C 330-440 K for the glass T8
M
0.001 Frequency (Hz)
100 1000 10000 100000 1000000
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Frequency (Hz)
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Dispersion of electric moduli M' and M"(ω) with frequency in the temperature range 30‒350 oC
for the PbO-ZrO2-SiO2 glass crystallized with 0.8 mol% of TiO2
C EP
AC
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Physical characteristics of PbO−ZrO2−SiO2:TiO2 glass ceramics embedded with

Pb2Ti2O6 cubic pyrochlore crystal phase: Part-I Electrical properties

A. Subba Rao1, J. Ashok1, B. Suresh1, G. Naga Raju1, N. Venkatramaiah2, V. Ravi

Kumar1*, I.V. Kityk3, N. Veeraiah1*
1
Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar- 522 510, A.P., India

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2
Solid state and Structural Chemistry Unit (SSCU), Indian Institute of Science (IISc), Bangalore-560012.
3
Faculty of Electrical Engineering, Czestochowa University of Technology, Armii Krajowej 17, PL-42-
217 Czestochowa, Poland
Abstract

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This study is mainly focused on electrical characteristics of PbO−ZrO2−SiO2: TiO2 glass ceramics

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embedded with Pb2Ti2O6 cubic pyrochlore crystal phases. The samples were synthesized by usual melt
quenching technique and subsequent heat treating at crystallization temperature for prolonged times. The
samples were characterized by XRD, SEM and DSC, IR, EPR and optical absorption spectroscopy techniques.

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Later, dielectric properties viz., dielectric constant, loss tangent, electric modulii, electrical impedance and a.c.

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conductivity over wide ranges of frequency and temperature, have been measured as a function of TiO2
content. The results of characterization techniques viz., XRD, SEM and DSC, indicated that the samples are
embedded with multiple crystal grains (with sizes varying from 0.1 to 1 µm) cemented with residual glass
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phase. The volume fraction of the crystal grains is found to increase with increase of TiO2 content. The XRD
studies on PbO−ZrO2−SiO2:TiO2 glass ceramics revealed that Pb2Ti2O6 cubic pyrochlore crystal phase is the
principal phase present in the bulk samples. The studies have also confirmed that a small part of Pb(Zr
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0.5Ti0.5)O3 and Ti2O3 crystal grains are also present in the titled glass ceramics. The results of IR spectral
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studies have indicated that there is an increasing degree of polymerization of glass network with increasing
TiO2 content up to 0.6 mol%. This is attributed to the presence of Ti ions predominantly in Ti4+ state (in this
concentration range of TiO2) that take part in the network forming positions with TiO4 and also substitutionally
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positioned octahedral sites. The results of optical absorption and EPR spectral studies have pointed out that a
part of the Ti ions were reduced to Ti3+ state and such ions were predicted to act as modifiers. These studies
have also indicated that the concentration of Ti3+ ions is higher in the samples crystallized with 0.8 and 1.0
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mol%. The values of dielectric parameters are decreased with increasing of crystallizing agent. The decrease
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is attributed to the participation of Ti ions in the formation of Pb2Ti2O6 cubic pyrochlore crystalline phases
with TiO4 structural units. Quantitative analysis of the dielectric properties of PbO−ZrO2−SiO2:TiO2 glass
ceramics together with the results of spectroscopic studies indicated that the electrical insulating strength is the
highest for the glass crystallized with 0.6 mol% of TiO2.

Keywords: PbO−ZrO2−SiO2 glass ceramics; Pb2Ti2O6 pyrochlore crystal phases; Dielectric relaxation effects;
a.c. conductivity
*Corresponding Authors:vrksurya@rediffmail.com nvr8@rediffmail.com
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1. Introduction

ZrO2-mixed silicate glasses are well known due to their extraordinary high mechanical

strength and high fracture toughness [1–4] and are also more electrical, chemical and thermal

resistant. The silicate glasses/ glass ceramics with appropriate amounts of ZrO2 are highly useful

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in waste loading of high–level radioactive nuclear waste [5, 6]. Such glasses are also being

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extensively used as bioactive glasses for dental restorations and these materials offer great

possibilities to mimic the properties of natural teeth. Polini et al (2013) and Jones (2013) have

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done commendable work along these lines on these glasses [7-9]. Further, the presence of ZrO2

in silicate glass matrices is reported to have extended the transparency spectral range (0.3 µm ‒

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8 µm) and hence are highly useful as optical filters, laser mirrors and alternative gate dielectrics

in microelectronics and NLO devices [10,11].

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The physical properties of the glasses can be further improved if they are crystallized with

appropriate nucleating agent with optimal concentration and annealing conditions. Glass ceramic
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materials possess outstanding electrical, mechanical, optical and thermal characteristics (since
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they are strain free and contain inter-twinned crystals that hinder the crack growth inside the

materials) with respect to analogous amorphous materials. Moreover, it is also possible to retain
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the transparency of glass even after the crystallization depending upon the crystallization

conditions and the nucleating agent used. Several transition metal oxides (depending upon
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desirable characteristics and the applications) are being used for producing huge concentration of
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nucleation centres in bulk glasses [12-14].

Among various crystallizing agents, TiO2 is anticipated to be more effective mineralizer in

the proposed glass system; this oxide was already used as nucleating agent successfully in

several other glass systems [15, 16] and found to improve the physical properties. The titanium
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ions, predominantly, exist in Ti4+ state and reported to occupy tetrahedral and octahedral

positions in the glass network. Since the empty or unfilled 3d-shells of Ti ions contribute

significantly to the non-linear optical second-order polarizabilities described by the third rank

polar tensors, the TiO2 containing glasses/ glass ceramics find potential applications in non-linear

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optical devices. To elaborate more, in this glass system the lead as well as Ti ions play crucial

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role in the applications of these materials for NLO devices and for other optoelectronic devices.

The highly polarizable Pb ions and the effective charge transfer of Ti-O complexes are the

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important factors that make this material to exhibit NLO properties. By varying the cationic

subsystem one can operate by the energy gaps and effective local polarizabilities which define

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the effective light operation by their properties [17]. In addition it was also reported earlier that
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by proper monitoring the concentration of Ti4+ ions one can achieve the intense

photoluminescence at about 500 nm attributed to the substitutional titanium (Ti4+) ions with
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(TiO6)8_ structural units in the glass network [18]. Hence, such glasses are also useful for
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photonic devices.
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Further, there is a possibility for Ti4+ ions to get reduced to Ti3+ valence state and such ions

were reported to act as modifiers in the glass network [19, 20]. The concentrations of Ti4+ and
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Ti3+ ions present in the glass network is highly sensitive to the concentration of TiO2 and

annealing conditions of the glass. If PbO−ZrO2−SiO2 glass material is crystallized with TiO2
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there is a possibility for the formation of PbTiO3 ferroelectric, Pb(ZrTi)O3 and intermediate
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crystal phase like Pb2Ti2O6. The presence of such crystal phases are expected to influence the

electrical properties of the glass ceramic to a large extent. The glass ceramics containing such

crystal phases are useful for electronic devices as multilayer capacitors, nonvolatile memories,

ultrasonic transducers and pyroelectric detectors [21]. Several other systems that containing
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metastable lead pyrochlores eg., Pb2Ru2O6, Pb2Ir2O6 were investigated extensively. Although,

several studies are available on PZT ceramics [22, 23], those studies are mainly confined to

sintered ceramic materials and as such the electrical properties transparent PbO−ZrO2−SiO2:

TiO2 glass ceramics embedded with above crystal phases are very rare.

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Following the reasons presented above the present investigation is devoted to report the

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results of dielectric properties viz., dielectric constant, ε', loss tan δ , ac conductivity, σ

ac(ω), electric moduli, M, and electrical impedance, z over wide ranges of frequency and

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temperature of PbO−ZrO2−SiO2 glasses crystallized with different concentrations of TiO2. These

studies not only help in assessing the influence of TiO2 on insulating strength of the titled glass

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ceramic but are also useful in obtaining structural modifications taking place inside the material.
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For having some pre-structural understanding which may facilitate the understanding of
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variations in the electrical properties, the auxiliary studies viz., optical absorption, EPR and IR

spectroscopic studies have also been carried out.

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2. Experimental
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The chemical compositions of the glasses chosen for the present study are 36 PbO‒4

ZrO2‒ (60 ‒ x) SiO2: x TiO2 (where x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0 mol % and the samples are
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labeled as T0, T2, T4, T6, T8 and T10, respectively). The samples were prepared by conventional

melt quenching technique. The starting materials used for the preparation of the samples were
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Analytical grade reagents (99.9 % pure) of PbO, ZrO2, SiO2 and TiO2 (Sigma Aldrich) powders.
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The appropriate proportions of the compounds were taken and thoroughly mixed in an agate

mortar and melted in silica crucible in the temperature range 1350‒1400 oC in a PID

temperature-controlled furnace for about 30 min. The resultant melt was then poured in a brass

mold and subsequently annealed at 450 oC. For crystallization, the glass samples were slowly
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heated initially (at the rate of 5 oC/min) up to crystallization temperature ∼850 oC (determined

from DSC traces) and then were held at this temperature for 96 h. After that samples were

gradually cooled to the off-set temperature of the crystallization peak and then chilled in air to

room temperature. The final weight of the bulk samples is well within the values of original glass

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batches with an error of ± 2.0%. Density d of these samples was determined with an accuracy of

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0.001 by standard principle of Archimedes using o- xylene (99.99% pure) as the buoyant liquid

with an Ohaus balance (Model AR 2140).

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The samples were ground and polished to optical quality. The final dimensions of the

samples used for dielectric measurements were about 1 cm×1 cm ×0.2cm. The glass transition

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temperature and the glass forming ability of the glasses were determined by differential scanning
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calorimetric (DSC) study using Shimadzu Thermal Analyzer Model DTG-60H instrument with a

programmed heating rate 10 oC/min to an accuracy of ±1 oC. Scanning electron microscopy

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(SEM) studies were carried out on these samples to observe the crystallinity using Tescan
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(Model VEGA3 LMU) scanning electron microscope. The crystalline phases in the heat-treated
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samples were identified using Rigaku D/Max ULTIMA III X–ray diffractometer with CuKα

radiation. Silver electrodes with thickness of about 100 nm were deposited onto both sides of the
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samples using a sputter coater. The dielectric measurements were carried out in the frequency

range 100 Hz – 1 MHz and in the temperature range 30‒350 oC. The other details of dielectric
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measurements were reported in our earlier papers [24, 25]. Optical absorption spectra of the
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samples were recorded on a JASCO V‒670UV‒vis‒NIRspectrophotometer with spectral

resolution 1 nm. Infrared transmission spectra were recorded on a JASCO‒FT/IR‒5300

spectrophotometer up to a resolution of 0.1 cm−1 using KBr pellets containing pulverized sample
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(1.5 mg). ESR spectra were recorded at room temperature using JEOL Model JES FA200

instrument operated at X-band frequency with field modulation of 100 kHz.

3. Results

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Using the values of the density d and average molecular weight M of PbO‒ZrO2‒SiO2: TiO2

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glass ceramics, several physical parameters such as Ti ion concentration Ni and mean Ti ion

separation ri , polaron radius rp are evaluated using the standard equations mentioned in our

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earlier papers [26] and presented in Table 1.

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In Figs. 1 (a) and 1 (b) the SEM photograph and X-ray diffractogram of one of the pre- heat

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treated samples, respectively, are presented. The figures clearly confirm the amorphous nature

of the samples before heat treatment. Fig. 2 represents the X –ray diffraction patterns of the post
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heated samples. The diffractograms exhibited strong and sharp reflection peaks suggesting that

the post heat treated products are well crystallized.

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The patterns exhibited several diffraction peaks most of them due to Pb2Ti2O6 cubic

pyrochlore phase with the lattice parameter, a = 10.38 Å,, (JCPDS 52-1764 Card number) [27] .
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The diffraction patterns of T8 and T10 samples exhibited an additional peak predicted to be due to

the reflections from (110) planes of Pb(Zr 0.5Ti0.5)O3 crystal phase [28]. A peak identified as
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being due to Ti2O3 crystal phase is also detected in the difractrograms at about 2θ = 58o [29].
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This peak is found to be more visible in the diffractograms of the samples T8 and T10 . The Ti

ions acted as nucleating agent and precipitated as high density crystal phases with Ti3+ and Ti4+

ions. The intensity of the diffraction peak due to Ti4+ crystal phases increases gradually with

increasing TiO2 content.

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The surface morphology of the samples crystallized with different concentrations of TiO2

obtained from SEM photographs is depicted in Fig. 3(a).The pictures exhibited well defined

randomly distributed crystallites with different sizes (varying within 0.1 …1.0 µm) embedded in

residual amorphous phase. The concentration of crystal grains is found to increase (with the

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enhanced aggregates) with the gradual increase of TiO2 content. In Fig. 3 (b) the EDS spectrum

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for one of the crystallized samples T6 is presented. The spectrum clearly indicated all the

elements are quite intact in the bulk samples.

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DSC scans of the PbO‒ZrO2‒SiO2: TiO2 glass ceramics (along with that of one of the

pre-crystallized samples) are presented in the Fig. 4. The thermograms of the heat treated

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samples exhibit weak endothermic effect due to glass transition in the vicinity 550‒630 oC
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followed by multiple exothermic effects due to crystallization in the temperature region 850‒930
o
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C. The thermogram of pre-heat treated samples exhibited single exothermic peak indicating that

these samples are potentially free from crystallinity.

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The FT-IR spectra are recorded in the spectral range 400‒2000 cm-1 of PbO−ZrO2−SiO2
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glasses crystallized with different TiO2 contents and are presented in Fig. 5. The spectrum of

glass ceramic T2 exhibited broad intense band within the 900‒1100 cm-1 spectral range with
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meta-centreat about 1030 cm-1.This band is identified as caused by asymmetric stretching

vibrations of the O–Si–O bonds for SiO4 tetrahedral units. The other bands located at about 780
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cm-1 are assigned to symmetric stretching vibrations of Si–O bonds of SiO4 units [30]. The
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vibrational band due to the vibrations of TiO4 structural units and also the vibrational band due to

Zr-O-Zr linkages are expected to be in this region [31, 32]. A band due to rocking vibrations of

Si–O– Si linkages in SiO4 units is detected at about 420 cm-1[30] in this spectrum. The spectrum

also exhibited another band due to the vibrations of ZrO4 structural units at about 535 cm-1. The
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vibrational band due to vibrations of TiO6 (distorted octahedral) structural units is also detected

at about 645 cm-1 [31].

With the increasing TiO2 content up to 0.6 mol%, the intensity of the vibrational bands

due to asymmetrical structural units of silicate groups and also that of TiO6 structural units is

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decreased while the bands due to symmetrical structural units of silicate, TiO4 and ZrO4 are

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observed to grow at the expense of these bands. However, when the concentration of TiO2 is

increased beyond 0.6 mol%, a reversal trend in the intensity of these bands is observed.

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In Fig. 6(a) the optical absorption spectra for PbO–ZrO2–SiO2 glasses crystallized with

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different concentrations of TiO2 recorded at ambient temperature in the spectral range 300–850
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nm are presented. The pre-crystallized TiO2 free glass exhibited absorption edge at about 415

nm. Afterwards the crystallization with 0.2 mol% of TiO2 caused the edge to shift to 412 nm. As
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the concentration of TiO2 is increased up to 0.6 mol%, the absorption edge is shifted spectrally to
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blue region. To be more specific for the glass ceramic T6 cut off wavelength is observed at 401
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nm. For further increase of TiO2 content a slight red shift of the edge (with respect that of T6

sample) is observed. The absorption spectra of all the crystallized samples exhibited two bands
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spread over the spectral region 500-700 nm. These bands are identified as caused due to 2
B2g →
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B1g, 2A1g octahedral transitions of Ti3+ ions [33]. The intensity of these bands is observed to
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decay gradually with the increase of TiO2 content up to 0.6 mol% and exhibited an increasing
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trend beyond this concentration. To evaluate optical band gaps (Eo) for the titled glass ceramics

we have drawn the Tauc plots between (α hω) ½ and hω are presented in Fig. 6(b). By

extrapolating of the linear parts of these curves we have evaluated the optical band gaps and

presented them in in Table 2. The value of Eo exhibited the maximal effect at 0.6 mol% of TiO2.
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EPR spectra of PbO-ZrO2-SiO2:TiO2 glass-ceramics are recorded at ambient temperature and

have exhibited an intense spectral line centered at about g = 1.941. The intensity of this signal

exhibited the minimal effect at 0.6 mol% of TiO2 (Fig. 7 and its inset). This resonance signal is

attributed to tetragonally compressed octahedral sites of Ti3+ ions [34, 35].

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The variations of dielectric constant ε′(ω) of PbO-ZrO2-SiO2 glass crystallized with 0.2

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mol% of TiO2 with frequency (measured at different temperatures) and with temperature

(measured at different frequencies) are presented in Figs. 8(a) and 8(b), respectively. The

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dispersion of ε′(ω) exhibited larger values at lower frequency and at higher temperatures and

with increase of frequency, it is decreased and reached ε′∞(ω) at higher frequency and it is

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observed to be nearly temperature independent in the high frequency spectral region. The

variations of ε′(ω) with frequency and with temperature for all the other samples, are found to be
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similar. In inset of Fig. 7(a) we have presented the variation of ε′(ω) with the concentration of

crystallizing agent TiO2; the variation exhibited minimal magnitude at 0.6 mol% of TiO2.
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Variation of tan δ either with frequency or with temperature of these glass ceramics
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exhibited a similar trend. In the Fig. 9, the dispersion of dielectric loss and temperature for one

of the glass ceramics viz., T4 is presented. The dielectric dispersion curves exhibited some
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relaxation effects. With increasing temperature, the frequency maxima are shifted towards the
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higher frequencies and with increasing frequency, the temperature maxima are shifted towards
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the higher temperatures. From the plots of ln f vs 1/T as per the relation, f = fo exp(-Wd/kBT) (f0

is a constant, kB is the Boltzmann constant, T is the absolute temperature and f is the relaxation

frequency), we have estimated the effective activation energy, Wd, for the particular dipoles.

The activation energy is found to be maximal for the glass ceramic T6 (inset of Fig. 9).
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It is quite likely that sometimes the dipolar effects are strongly influenced (or may be

completely masked) by electrode polarization. To avoid such contributions, the electric moduli

formalism is much helpful. The real and imaginary components of electric moduli, M′(ω) and

M″(ω) using real and imaginary parts of dielectric constant at different temperatures for all the

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glass ceramics is shown here. We have evaluated real and imaginary electric moduli, M′(ω) and

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M″(ω) dispersion from real and imaginary parts of complex dielectric constant, ε*, using the

following expressions:

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ଵ ఌ ᇲ ሺఠሻ ௜ఌ ᇲᇲ ሺఠሻ
‫ = ∗ ܯ‬ఌ∗ ሺఠሻ = మ మ + మ మ = ‫ܯ‬ᇱ ሺ߱ሻ + ݅‫ܯ‬ᇱᇱ ሺ߱ሻ (1)
൫ఌ ᇲ ሺఠሻ൯ ା൫ఌ ᇲᇲ ሺఠሻ൯ ൫ఌ ᇲ ሺఠሻ൯ ା൫ఌᇲᇲ ሺఠሻ൯

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ఌ ᇲ ሺఠሻ ఌ ᇲᇲ ሺఠሻ
⇒ ‫ܯ‬ᇱ ሺ߱ሻ = మ
൫ఌ ᇲ ሺఠሻ൯ ା൫ఌ ᇲᇲ ሺఠሻ൯
మ and AN
‫ܯ‬ᇱᇱ ሺ߱ሻ= మ
൫ఌ ᇲ ሺఠሻ൯ ା൫ఌᇲᇲ ሺఠሻ൯
మ (2)
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The variations of these moduli versus frequency at different temperatures for the glass

ceramic T8 and a comparison plot for all the glass ceramics drawn at 350 oC are presented in
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Figs. 10(a) and 10 (b). The variations demonstrated well defined dipolar relaxation effects. From
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the intersection points of M'(ω) and M″(ω) we have evaluated the dielectric relaxation time ΤM

for all the samples at 350 oC and they are presented in the Table 3.The value of ΤM is found to
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increase gradually with the increasing TiO2 content up to 0.6 mol% in the glass ceramic.
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Fig. 11(a) represents the impedance spectra of the glass ceramic sample T2 evaluated at
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different temperatures, whereas Fig. 11(b) represents the comparision spectra of all the glass

ceramics drawn at 350 oC. As the temperature increases the diagrams seemed to be the closed

semicircles and at higher temperatures the semicircles have exhibited inclined spur at lower

frequency side. Further, with the increase of temperature of measurement the area under the

semicircle is gradually decreased and with the increase of of TiO2 content upto 0.6 mol%, the
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curves become more open and the area under the arcs is increased. The magnitude of the straight

spur is also found to decrease with the increase of TiO2 content.

Variation of a.c. conductivity, σac, with frequency (at different temperatures) and with

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temperature (at different frequencies) for one of the glass ceramics viz., T6 is presented in the

Figs. 12(a) and 12(b), respectively. In the low frequency region (ω →0) and at higher

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temperatures, the conductivity is found to be linearly independent of frequency and it

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corresponds to the d.c. conductivity, whereas at higher frequencies it exhibited dispersion in

power law fashion. In Fig. 12 (c), the comparison plots of σac with 1/T for the glasses crystallized

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with different concentrations of TiO2 measured at a frequency of 10 kHz are presented. For better

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understanding the influence of TiO2 content on the conductivity, we have plotted the variation of

a.c. conductivity with the concentration of TiO2, (measured at a temperature of 350 oC and at a
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frequency of 10 kHz) and presented as the inset of Fig. 12(c). The variation exhibited minimal

effect at 0.6 mol% of TiO2. In the high temperature region at where log σac vs 1/T found to be
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near linear we have evaluated the activation energy, Wac, for the conduction for all the samples
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and presented in Table 4. The activation energy with the concentration of TiO2 exhibited the

maximal effect at 0.6 mol% TiO2 (in set of Fig.12(c)).

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4. Discussion
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In PbO–ZrO2–SiO2:TiO2 glass ceramics, SiO2 is well known to participate in the glass

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network with tetrahedral [SiO4/2]0 units. Zirconium ions take part in the glass network forming

mainly with ZrO4 structural units and form the linkages of the type Si–O–Zr with SiO4 structural

units. PbO acts as a modifier and also participates in the network forming with PbO4 structural

units. Since the starting chemical compound of titanium oxide used in the glasses is TiO2, the Ti

ions are expected to exist mainly in Ti4+ state. Nevertheless, the reduction and oxidation of
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titanium ions viz., Ti4+ ↔ Ti3+ is quite possible (since the reduction potential Eo ∼ 0.2 V) during

melting, annealing and crystallization processes of the glasses. The results of optical absorption

and EPR spectral studies (Fig. 6 (a) and Fig. 7) clearly demonstrated that a part of Ti ions do

exist in Ti3+ state in addition to Ti4+ state. The tetravalent ions occupy mainly tetrahedral and

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substitutional octahedral (as corner-sharing [TiO6]2- units) and also distorted octahedral sites,

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whereas Ti3+ ions occupy only modifying positions and induce structural defects in the glass

network. To be more specific, the Ti3+ ions depolymerize silicate glass network and convert Q4

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units of silicate into Q3, Q2, Q1 and Q0 units. The presence of Ti3+ ions in the glass matrix is

confirmed from optical absorption and EPR spectra. These studies have, however, indicated that

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the proportion of such Ti3+ ions is gradually decreased with increase in the concentration of TiO2
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upto 0.6 mol%. The increase in the intensity of the peaks due to predominant Pb2Ti2O6

crystalline phase in the XRD pattern suggests that there is a gradual increase in the concentration
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of substitutionally positioned octahedral Ti4+ ions with increase of TiO2 concentration upto 0.6
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mol%. Though Pb2Ti2O6 (with Fd3m space group) is a meta stable stoichiometric phase, in
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several reports it was confirmed that this phase is kinetically stable and exists in bulk samples

even upto 500 oC [36] and would be converted to PbTiO3, P4/mmm perovskite phase only at
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higher temperatures. The structure of this crystal phase consists of intertwined corner-connected

TiO6 octahedra and and TiO4 tetrahedral units [23].

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The predicted structural fragment of this crystal phase is presented in the Fig. 13. XRD

studies have also shown the presence of another significant crystal phase viz., Pb(Zr0.5Ti0.5) O3 in

the glass ceramic samples T8 and T10. Earlier studies using XANES spectra on lead zirconium

titanate ceramics [37] it was reported that in this crystal phase the Ti ions are penta-coordinated
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while the sixth oxygen of the octahedra is situated far from the Ti ions. In general in this crystal

phase the Ti ions are assumed to be in highly distorted octahedral positions.

DSC patterns of the heat treated samples exhibited multiple exothermic (crystallization)

peaks; such observation suggests that the samples comtain different crystal phases. We have

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observed the gradual increase of the total area under the exothermic peaks (connected with

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enthalpy) with increasing TiO2 content. This result suggests that the crystallization is initiated

from inner part of the samples and is expanded gradually to the surface. It is also obvious from

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DSC plots that the crystallization occurs also for the materials without TiO2. Moreover, the first

exothermic peak is seen also in the thermogram of T0 sample. However the area under the peaks

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in the same temperature region is increased with the increase of TiO2 content in the material.
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This may be considered as a manifestation of the increasing fraction of the crystal phase in the

sample and, probably due to the formation of the new crystal phase in which a part of lead ions
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are replaced by Ti ions. Similarly the next two exotherms look as if connected with the process
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controlled by Ti ions contributing to the crystallization area. The feeble peak, observed at
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elevated temperature reveals that crystallization is due to the presence of TiO2.

IR spectral studies indicated that with increasing concentration of nucleating agent up to

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0.6 mol%, lead to gradual increase in the intensity of l due to symmetrical vibrations of SiO4,

ZrO4 and TiO4 structural units, whereas that of asymmetrical bands of silicate units and TiO6
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structural units is gradually decreased. This observation indicates that there is a decreasing
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concentration of induced defects with increasing TiO2 content up to 0.6 mol% or indirectly

supports the view point that there is an increasing degree of polymerization of the glass network

with increase in the concentration of nucleating agent TiO2 up to 0.6 mol%. Such increase in the
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14

degree of polymerization (connectivity between various structural units) leads to an increase in

the electrical resistivity of the glass ceramic samples.

The variation of dielectric constant ε′(ω) for studied glass ceramic samples exhibited an

increasing trend with increasing temperature particularly at lower frequencies. Such increase is

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normally attributed to space charge polarization due to the accumulation of charge carriers at the

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metallic electrodes [38-40]. The lower values of dielectric permittivity, ε′(ω) at higher

frequencies is due to lacking of sufficient rapidity in the rotation of charge carriers in the

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direction of the electric field.

We have observed the decrease of permittivity, ε′(ω), at any frequency and temperature

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with the gradual increase of TiO2 content up to 0.6 mol% in the glass matrix. As discussed above

there is an increasing degree of polymerization of the glass network due to the increasing
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presence of tetrahedral titanium ions. As a result easy path ways available for the migration of

charge carriers are blocked. Hence contribution of the charge carriers to the space charge
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polarization decreases. In consequence, there is a decrease of ε′(ω) with the increase of TiO2
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content up to 0.6 mol% [41-43].

The variation of dielectric loss either with frequency and temperature (and more clearly the
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electric moduli) exhibited the dipolar relaxation effects. The relaxation intensity, however, is
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decreased with the increasing TiO2 content up to 0.6 mol%. In this type of glass ceramics the

complexes of trivalent Ti ions (3d1) with the oxygens do posses net dipole moment and act as
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dipoles. The observed relaxation effects can safely be assigned to Ti3+ ions [44]. The observed

gradual increase of activation energy for the dipoles in the network of glass ceramics from T2 to

T6 confirms the decrease of freedom for dipoles to orient in the field direction. This result is
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15

well in agreement with the earlier argument that there is an increasing degree of rigidity in the

glass ceramic network with increase of TiO2 content upto 0.6 mol%.

For further understanding of dipolar relaxation effects we have scaled values of real and

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imaginary electric moduli M' and M" with M'∞ and M"max, respectively at different

temperatures (in the high temperature region viz., 300, 330 and 350 oC) are plotted with the

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frequency ω / ωmax . Such plots for one of the glass ceramics viz., T8 is presented in the Fig. 14.

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The curves exhibited virtually no dispersion and are observed to be fitted into single master

curve. This behavior indicates that the relaxation dynamics is temperature independent in the

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high temperature region.

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The area under the semicircular arc in the impedance spectra represents bulk impedance of

the sample, whereas the linear spur appeared in the low frequency side represents electrode
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polarization due to the accumulation of thermally stimulated charge carriers. The area under the

curve gradually increased with increasing TiO2 up to 0.6 mol% indicating an increase of
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electrical rigidity of the glass ceramic sample. Beyond 0.6 mol%, a considerable decrease in the
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area under the semicircular arc and also increase in the magnitude of linear spur are observed.

These observations suggest that the mobility of conducting species is relatively higher in the
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glass ceramic samples T8 and T10.

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The ac. conductivity is observed to decrease, whereas activation energy exhibited an

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increasing trend with the increase in the concentration of crystallizing agent TiO2 upto 0.6 mol%

(zone I, inset of Fig. 12(c)). As mentioned earlier that the spectroscopic studies have revealed

that the proportion of Ti4+ ions that are occupying either tetrahedral or substitutional octahedral

positions increase with increase of TiO2 content upto 0.6 mol% . Such structural units of Ti4+

ions cross link with ZrO4 and SiO4 units and increase the polymerization of the glass network.
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16

Such linkages obstruct the migration of charge carriers in the bulk material and are responsible

for decrease of the conductivity or increase of activation energy. Even though small component

of ionic contribution to the conductivity is possible in zone I (inset of Fig. 12(c)), the transport of

the charge carriers in the bulk material is inhibited due to the high polymerization degree of the

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glass network in these samples. As per Anderson and Stuart model, (i) the electrostatic binding

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energy that arises from Columbic force acting on the ions and (ii) the migration of charge

carriers against the mechanical forces acting on the ion between equilibrium sites in the glass

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network play crucial role in deciding the magnitude of ionic component of the conductivity [45].

The possibility for such contribution to the conductivity decreases with increasing TiO2 from 0.2

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to 0.6 mol% for the reasons that have already been discussed above. The increase of
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conductivity with increase of TiO2 from 0.8 to 1.0 (zone II inset of Fig. 12) is mainly due to

electronic contribution due to the electron transfer between two valance states of Ti ions.
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However, the ionic contribution to conductivity cannot be completely ruled out in these samples.
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As discussed in detail, the trivalent Ti ions that present in larger proportions in the glass ceramic
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samples T8 and T10 act as modifiers and induce structural defects like dangling bonds. As a result

there is a decrease in the electrostatic binding energy and the strain energy for the easy passage
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of conducting ions. Overall, there is a high fragmentation of the lead zirconium silicate glasses

containing higher concentrations of TiO2 which promotes this mechanism with local distortion of
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the network. This type of mechanism is not as favorable in the more rigid matrix containing low
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content of TiO2. Further, there is higher concentration of Ti3+−Ti4+ pairs in these samples which

contribute to the conductivity through mutual transfer of polarons between these two ions in the

samples T8 and T10. This may explain the reason for increase of conductivity with increase of

TiO2 concentrations in zone II.

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17

In the low temperature region a.c. conductivity exhibited nearly temperature

independence. This type of behavior can be explained using quantum mechanical tunneling

(QMT) model.

According to this model a.c. conductivity is described by [46]:

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 ν 
4
π
σ (ω) = e kBT [N (EF )] α ω ln ph  , (3)
2 2 −5

 ω

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3

With the symbols having usual meaning as reported in our earlier papers [24, 47].

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The value of N(EF) , the concentration of defect energy states near the Fermi leval evaluated at

100 kHz, and T = 350 oC, exhibited minimal value at 0.6 mol% of TiO2 (Table 4). This result

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is also well in confirmation with the view point that the network of the glass ceramic sample T6

is more polymerized when compared with that of other samples.

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5. Conclusions
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PbO−ZrO2−SiO2 glasses doped with different concentrations of TiO2 were synthesized

and later they were crystallized. The thermal analysis studies suggested that the samples
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composed of poly crystalline phases, while SEM studies indicated the glass ceramic samples that
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are composed of well defined crystal grains (with the sizes varying within 0.1 – 1.0 µm) that are

distributed randomly in space of the bulk material. The XRD studies have indicated that samples
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are embedded with Pb2Ti2O6 cubic pyrochlore crystal phases in which the Ti ions are present in
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tetrahedral positions. The volume fraction of these crystal grains is found to increase gradually

with increasing TiO2 content.

The IR spectral results suggested that with the increasing TiO2 concentration, there is an

increase in the degree of connectivity between various structural groups in the glass network.

The optical absorption and EPR spectral results have pointed that a small fraction of Ti ions does
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18

exist in Ti3+ state in addition to Ti4+ state especially in the samples crystallized with 0.8 and 1.0

mol%.

The variation of dielectric parameters of the titled glass ceramics indicated an increasing

electrical rigidity of the samples with increasing TiO2 content up to 0.6 mol%. This is attributed

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to decreasing concentration of free charge carriers as well as the progressive blocking of the

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pathways for the transport of the conducting ions. This is due to the predominant participation of

Ti ions in tetrahedral and substitutional octahedral positions. Such glasses may also useful for

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visible lasers, in the optical data storage systems, sensors, medical diagnostics since the glasses

with such coordination numbers of Ti ions are predicted to exhibit intense luminescence

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emission in the region 500-550 nm [18]. Overall, a significant increase in the electrical resistance
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of PbO−ZrO2−SiO2: TiO2 glasses are observed due to the crystallization with growing

concentration of TiO2 up to 0.6 mol%. Hence, such glass ceramics may be useful for considering
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the studied glass ceramics as insulating layers in the display panels. The presence of PbO is
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always very interesting for studies of their nonlinear otpcial features [48-50]. Hence, the studies
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on non-linear optical studies and elastic properties of these glass ceramics are in progress and it

is planned to communicate such results as part-II of this study.

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Acknowledgements

A. Subba Rao wishes to thank University Grants Commission (UGC), New Delhi for granting
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study leave under Faculty Development Programme (FDP). J. Ashok and B. Suresh wish to
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thank University Grants Commission (UGC), New Delhi for sanctioning Rajiv Gandhi National

(RGNF) Fellowship to carry out this work. G. Naga Raju , V. Ravi Kumar and N. Veeraiah

thank the University Grants Commission (UGC), New Delhi and Department of Science and

Technology (DST New Delhi) for the financial assistance to the Physics Department, ANU. To
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19

carry out this work under UGC-DSA1(F.530/11/DSA-I/2015(SAP-I)) and FIST (F. No.

SR/FST/PSI-163/2011(C)) programmes, respectively.

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Caption for Tables

Table1: Summary of the data on physical parameters of the PbO−ZrO2−SiO2:TiO2

glass ceramics.

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Table2: Summary of the data related to optical absorption spectra of the PbO−ZrO2−SiO2:TiO2
glass ceramics

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Table:3 Summary of the data related to dielectric relaxation effects of the PbO−ZrO2−SiO2:TiO2
glass ceramics

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Table:4 Summary of the data related to a.c conductivity of the PbO−ZrO2−SiO2:TiO2 glass
Ceramics
Caption for figures

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Fig.1 (a) SEM photograph of pre-crystallized glass T6.
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Fig.1 (b) XRD diffractogram of pre-crystallized glass T6.

Fig. 2 XRD patterns of the PbO-ZrO2-SiO2: TiO2 glass ceramics.

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Fig. 3(a) SEM pictures for glass ceramic samples T4, T6, and T8.
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Fig. 3(b) Energy dispersive spectra (EDS) of the glass ceramic T8.
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Fig. 4 DSC patterns of PbO-ZrO2-SiO2: TiO2 glass ceramics.

Fig. 5 IR spectra of PbO−ZrO2−SiO2:TiO2 glass ceramics.

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Fig. 6 (a) Optical absorption spectra of PbO−ZrO2−SiO2:TiO2 glass ceramics recorded at room
temperature.
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Fig. 6 (b) Tauc plots for PbO−ZrO2−SiO2:TiO2 glass ceramic samples. Inset represents the
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variation of optical band gap with the concentration of TiO2.

Fig. 7 EPR spectra of the PbO-ZrO2-SiO2:TiO2 glass ceramic recorded at ambient temperature.
Inset represents variation of intensity of the signal with the concentration of TiO2.

Fig. 8 (a) Variation of dielectric constant ε′ for the glass ceramic sample T2 with
frequency at different temperatures from 30 oC to 350 oC. Inset represents the variation of
dielectric constant with concentration of TiO2 (measured at 50 kHz, 350 oC )
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Fig. 8 (b) Variation of dielectric constant dispersion ε′ for the glass ceramic sample T2 with
temperature at different frequencies.

Fig. 9 Variation of dielectric loss dispersion tan δ for the glass ceramic sample T4 with
frequency at different temperatures. Inset represents the variation of activation energy for

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dipoles with the concentration of TiO2.

Fig. 10 (a) Dispersion of electric moduli M' and M"(ω) with the frequency in the

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temperature range 30‒350 oC for the glass ceramic T8.

Fig. 10 (b) The comparison plots of the dispersion of electric moduli (at 350 oC) with frequency

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for all the glass ceramic samples.

Fig. 11 (a) Impedance spectra of glass ceramic T2 drawn at three different temperatures. Inset

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represents the magnified view of impedance diagram drawn at 350 oC
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Fig. 11(b) Impedance spectra of PbO−ZrO2−SiO2:TiO2 glass ceramic samples drawn at 350 oC.

Fig. 12 (a) Isotherms of ac conductivity σac for the glass ceramic T6.
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Fig. 12 (b) The variation of ac conductivity of the glass ceramic T6 with 1/T at
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different frequencies.
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Fig. 12 (c) Variation of ac conductivity with 1/T of PbO−ZrO2−SiO2:TiO2 glass ceramic

measured at 10 kHz. Inset represents the variation of σac and the activation energy for
conduction with the concentration of TiO2.
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Fig. 13 The predicted structural fragment of Pb2Ti2O6 pyrochlore crystal phase.

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Fig. 14 Scaling behavior of the electric modulus spectra for the glass ceramic T8 evaluated at
three different temperatures (300, 330 and 350 oC)
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Table1 Summary of the data on physical parameters of the PbO−ZrO2−SiO2:TiO2

glass ceramics
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Sample Density Ti Ion concentration Inter ionic Polaron radius rp

(g/cm3) (Ni) (x1021ions/cm3) distance ri (A0)
(A0)
T0 4.603 -- -- --

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T2 4.610 4.57 6.02 2.48

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T4 4.623 9.17 4.77 1.92

T6 4.688 13.95 4.15 1.67

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T8 4.720 18.72 3.76 1.51

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T10 4.766 23.62 3.48 1.40

AN
M
D
TE
C EP
AC
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27

Table 2 Summary of the data related to optical absorption spectra of the PbO−ZrO2−SiO2:TiO2
glass ceramics

PT
Sample Cut-of Optical Band Band position Band position
wavelength (nm) gap Eo (eV) (nm) (nm)
2
B2g → 2B1g 2
B2g → 2A1g

RI
T0 415 3.31 - -

SC
T2 412 3.45 670 735

T4 409 3.60 673 739

U
T6 401 4.01 676 743

T8 404
AN
3.81 679 748

T10 407 3.70 682 751

M
D
TE
C EP
AC
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28

Table 3 Summary of the data related to dielectric relaxation effects for the
PbO−ZrO2−SiO2:TiO2 glass ceramics

Glass A.E for dipoles(e.V) Relaxation time for

PT
dipoles τd (ms)

RI
T2 4.553 0.04

T4 4.795 0.14

SC
T6 5.006 1.78

T8 4.293 0.89

U
T10 4.004 0.56
AN
Table 4 Summary of the data related to a.c conductivity for the PbO−ZrO2−SiO2:TiO2 glass
ceramics
M
D

Glass N(EF) (x 1021, eV-1/cm3) A.E for conduction Wac (eV)

(± 0.01) (±0.01)
TE

T2 25.3 0.612
EP

T4 17.4 0.978

T6 1.024 1.630
C
AC

T8 1.85 1.05

T10 10.00 0.892

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29

In te n s ity (a rb .u n its )

PT
RI
10 20 30 40 50 60 70 80
2θ (degree)

SC
Fig.1 (b) X-ray diffractogram of pre-crystallized glass T6
Fig.1 (a) SEM picture of pre-crystallized glass T6

U
AN
M
D
TE
C EP
AC
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30

● (1 1 0)
(2 2 2)

(1 1 6)
■ ▼ ■ Pb2Ti2O6/ Pb5Si3O11
(1 1 1)

(4 0 0)
▼ Ti2O3

(4 4 0)
● Pb (Zr0.52 Ti 0.48) O3
(314)

■ ■
■

PT
T10

RI
Intensity (arb.units)

T8

SC
T6

T4

U
T2
AN
T0
M
10 20 30 40 50 60 70
D

2θ (degrees)
Fig. 2 XRD patterns of the PbO-ZrO2-SiO2: TiO2 glass ceramics.
TE
C EP
AC
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31 T8
T4

PT
RI
U SC
T6
AN
M
D
TE
C EP

Fig. 3(b) Energy dispersive spectra (EDS) of the

AC

glass ceramic T6.

Fig. 3(a) SEM pictures of glass ceramic samples T4, T6, and T8.
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32

-1
Exo

-2

PT
-3 T10
Heatflow ( W/g )

T8

RI
T6
T4
-4

SC
T2
T0

U
-5

AN
Endo

-6
0 100 200 300 400 500 600 700 800 900 1000
M
Temperature ( oC )

Fig. 4 DSC patterns of PbO-ZrO2-SiO2: TiO2 glass ceramics.

D
TE
C EP
AC
 Transmittance, % (arb.units)

1400
T6

T10
T8
T4
T2
T0
AC
C

1200
Si-O-Si/ Si-O-Zr
EP
TE asymmetric streching

1000
D
33

M
AN

800
TiO4 units/
ACCEPTED MANUSCRIPT

Fig. 5 IR spectra of PbO−ZrO2−SiO2:TiO2 glass ceramics.

Wavenumber (cm-1)
Zr-O-Zr units
U
TiO6 units
SC

600
RI
ZrO4 units
PT
PbO4 units
Si-O-Si asymmetric
bending vibrations

400
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34

PT
Intensity (arb.units)

2
B2g → 2B1g 2
B2g → 2A1g

RI
SC
T2

U
T0
T4
AN T10
T8
T6
M
400 500 600 700 800 900 1000
Wavelength λ (nm)
D

Fig. 6 (a) Optical absorption spectra of PbO−ZrO2−SiO2:TiO2 glass ceramics recorded at room
temperature
TE
C EP
AC
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35

11.0 T2 T4 T1 T
T0 T6
4.0

PT
Eo (eV)

9.0 3.6

RI
3.2
7.0 0.0 0.2 0.4 0.6 0.8 1.0

SC
Conc of TiO2 (mol%)
-1 1/2
(eV-cm )

U
5.0
1/2

AN
(αhν)

M
3.0
D
TE

1.0
2.0 2.5 3.0 3.5 4.0
hv (eV)
EP

Fig.6 (b) Tauc plots for PbO−ZrO2−SiO2:TiO2 glass ceramic samples. Inset represents the
variation of optical band gap with the concentration of TiO2.
C
AC
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36

T10

PT
RI
Intensity (arb.units)

T8

T6

SC
T4
Intensity (arb.units)

U
T2
AN
0 0.5 1
M
Conc of TiO2 (mol%)
D

300 325 350 375 400

Magnetic field (mT)

TE

Fig. 7 EPR spectra of the PbO-ZrO2-SiO2:TiO2 glass ceramic recorded at room temperature.
Inset represents variation of intensity of the signal with the concentration of TiO2.
C EP
AC
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37

40
14

35 o
350 C

10

PT
ε'
30

RI
25 6
ε'

0.0 0.2 0.4 0.6 0.8 1.0

Conc TiO2 (mol%)

SC
20

T2

U
15

10
o
30 C AN
100 1000 10000 100000 1000000
M
Frequency (Hz)

Fig.8 (a) Variation of dielectric constant dispersion ε′ for the glass ceramic sample T2 with
D

frequency at different temperatures from 30 oC to 350 oC. Inset represents the variation of
dielectric constant with concentration of TiO2 (measured at 50 kHz,350oC )
TE
C EP
AC
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38

16
0.1 k Hz
T2
ε'

14
1 k Hz

PT
10 k Hz

RI
100 k Hz
12
1 M Hz

SC
10
30 90 150 210 270 330

U
o
Temperature ( C)

AN
Fig. 8 (b) Variation of dielectric constant ε′ for the glass ceramic sample T2 with
temperature at different frequencies.
M
D
TE
C EP
AC
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39

8
o
350 C
5.2

4.9
6

PT
Wd (eV)
4.6

4.3
Tan δ

RI
4 4.0
0.0 0.2 0.4 0.6 0.8 1.0

SC
Conc. TiO2 (mol%)

U
0
o
30 C
AN
100 1000 10000 100000 1000000
M
Frequency (Hz)

Fig. 9 Variation of dielectric loss dispersion tan δ for the glass ceramic sample T4 at
D

different temperatures. Inset represents the variation of activation energy for

TE

dipoles with the concentration of TiO2

C EP
AC
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40

30 oC
0.06

0.04
M'

PT
0.02
350oC

RI
0
0.021 350 oC T8

SC
T8

U
M"

0.011

AN
Fig. 7. (b) Dispersion of electric moduli M'(ω) with the frequency evaluated in the temperature range
30 C 330-440 K for the glass T8
o
M
0.001 Frequency (Hz)
100 1000 10000 100000 1000000
D

Frequency (Hz)
Fig. 10 (a) Dispersion of electric moduli M' and M"(ω) with frequency in the
TE

temperature range 30‒350 oC for the glass ceramic T8.

C EP
AC
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41

0.08 0.08

0.06 0.06

PT
RI
M "
M'

0.04 0.04

SC
T6 T8 T10 T4 T2

U
0.02 0.02

AN
M
0.00 0.00
100 1000 10000 100000 1000000
D

Frequency (Hz)

Fig. 10 (b) The comparison plots of the dispersion of electric moduli (at 350 oC) with frequency
TE

for PbO−ZrO2−SiO2:TiO2 glass ceramic samples. .

C EP
AC
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42

3.0

PT
0.3
2.0
Z" (x106,Ω)

RI
0.2

Z' (x106,Ω)
350 oC
30 oC

SC
0.1

T2
1.0 200oC 0.0

U
0.0 0.1 0.2 0.3
Z'' (x106,Ω)
AN
M
350 oC
0.0
0.0 1.0 2.0 3.0
D

Z' (x106, Ω)
TE

Fig. 11(a) Impedance spectra of glass ceramic T2 drawn at three different temperatures. Inset
represents the magnified view of impedance diagram drawn at 350 oC.
C EP
AC
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43

T6

3.0

PT
Z"(x10 ,Ω)

2.0
6

RI
SC
1.0
T8

U
T10
T4
0.0
0.0
T2
1.0
AN 2.0 3.0 4.0
Z' (x10 , Ω)
6
M
Fig. 11 (b) Impedance spectra of PbO−ZrO2−SiO2:TiO2 glass ceramic samples drawn at
350 oC.
D
TE
C EP
AC
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44

350 oC

10-5

PT
RI
-1
σac (Ω-cm)

SC
10-7

U
AN
30 oC
M
10-9
100 1000 10000 100000 1000000
D

Frequency (Hz)
TE

Fig. 12 (a) Isotherms of ac conductivity σac for the glass ceramic T6.
C EP
AC
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45

10-4

PT
10-5

1 MHz

RI
SC
-6
10
100 kHz

U
-1

AN
σ ac (Ω-cm)

10-7 10 kHz
M
D

1 kHz
TE

-8
10
EP

0.1 kHz
C

-9
10
AC

1.6 2.0 2.4 2.8 3.2

1000/T (K-1)

Fig. 12 (b) Variation of ac conductivity of the glass ceramic T6 with 1/T at

different frequencies.
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10-2 Zone I
10-3
1.6 σac

-1
Zone II

σac (Ω-cm)
1.2

Wac (eV)
10-4
-3

PT
10
0.8

-5

RI
0.4 10
0.0 0.2 0.4 0.6 0.8 1.0
10-4 Conc. TiO2 (mol%)

SC
T0

U
-1

-5
10
AN
σ ac (Ω-cm)

T2

T4
M

10-6 T10
D
TE

T8

-7
10
EP

T6
C

-8
10
AC

1.6 2.1 2.6 3.1

-1
1000/T (K )

Fig. 12 (c) Variation of ac conductivity with 1/T of PbO−ZrO2−SiO2:TiO2 measured at 10

kHz. Inset represents the variation of σac and the activation energy for conduction with
the concentration of TiO2.
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PT
RI
U SC
AN
M
D
TE

Fig. 13 The predicted structural fragment of Pb2Ti2O6 pyrochlore crystal phase.

C EP
AC
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48

1.2
M"/M"max max

T8
M'/M'max

PT
0.8
Electricmoduli

RI
SC
0.4

U
AN
0.0
-2 0 2 4
M
log10 (ω/ωmax)
D

Fig. 14 Scaling behavior of the electric modulus spectra for the glass ceramic T8 evaluated at
three different temperatures (300, 330 and 350 oC)
TE
C EP
AC
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Research Highlights

Study deals with electrical characteristics of PbO−ZrO2−SiO2:TiO2 glass ceramics.

XRD, SEM studies indicated glass ceramics contain Pb2Ti2O6 pyrochlore crystal phases.
3+ 4+

Spectroscopic studies indicated Ti ions exist in Ti ,Ti states in glass ceramics

PT

Dielectric parameters are decreased with increase of crystallizing agent TiO2.

Decrease is attributed to participation of Ti ions in pyrochlore crystalline phases.

RI
U SC
AN
M
D
TE
C EP
AC