Journal of Non-Crystalline Solids 505 (2019) 354–366

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

Synthesis of Eu2O3 doped BaO-TiO2-GeO2 based glass-ceramics: T

Crystallization kinetics, optical and electrical properties
⁎
Anirban Chakrabarti, Atiar Rahaman Molla
Glass Division, CSIR-Central Glass and Ceramic Research Institute, 196 Raja S.C. Mullick Road, Kolkata 700032, India

A R T I C LE I N FO A B S T R A C T

Keywords: Eu3+ doped transparent glass-ceramics (GCs) containing non-centrosymmetric ferroelastic Ba2TiGe2O8 (BTG)
Glass-ceramics crystals as the major crystalline phase have been synthesized. BTG crystal phase was generated in the glass
Crystallization kinetics matrix with mole percent composition 30BaO-15TiO2-55GeO2 synthesized by melt quenching technique fol-
Refractive index lowed by controlled crystallization through ceramming heat-treatment. A diffusion controlled surface crystal-
Photoluminescence
lization event with zero and constant nucleation rates was determined through a comparative study of some
Dielectric properties
Hysteresis loop
linear and nonlinear solid state reaction models. Nonlinear crystallization kinetics studies facilitated determi-
nation of the experimental ceramization temperature and time for fabrication of transparent glass-ceramics
containing BTG nanocrystals. XRD, FTIR, TEM and FESEM measurements confirmed the dispersion of BTG
nanocrystals of size 20–100 nm in the glass matrix. Local crystal environment around Eu3+ ions facilitated the
enhancement of photoluminescence of glass-ceramics with respect to the precursor glass. High dielectric con-
stant, low loss and dissipation factors were observed for the GCs.

1. Introduction of the crystallites (r) ≤ λ/10 resulting in minimum Rayleigh scat-

tering.
In recent times there is a surge in demand for fabrication of glass- b) Refractive index of the glass matrix is maintained close to the crystal
ceramics having high transparency, chemical durability and improved phase generated even when r > > λ [2].
thermal and electrical characteristics for application in optoelectronics,
telecommunications and photonic devices like optical gratings and However, to obtain a sufficient polarization in case of ferroelectric
waveguides. It is of practical importance and interest to synthesize crystals embedded in the glass matrix, the average crystal size must be
glass-ceramics containing non-centrosymmetric polar crystals like, fer- large enough in order to generate a reasonably good ferroelectric re-
roelectric crystals, for applications in the area of electro-optic switching sponse. These conditions represent a difficult tradeoff and remain a
and second harmonic generation (SHG). The property of second har- challenge for the researchers worldwide [3].
monic generation can also be applied to photonic switching for multi- In ferroelectric materials domain-wall motions of 180°(║) and 90°
plexing, sampling, image processing and other applications. Several (┴) with respect to the polarization axis has been identified as the key
switches that open or close in picoseconds have been demonstrated, like physical phenomenon for application of these materials in microelec-
the Mach-Zhender interferometric switches has a response time of tronics and sensors [4]. The 90° domain-wall motion is identified to be
10−11 s, fabricated from ferroelectric single crystal LiNbO3 [1]. an elastic motion (ferroelastic) which gives rise to the piezoelectric
Compared to ferroelectric materials synthesized using ceramic phenomena. In this work a non-centrosymmetric polar orthorhombic
route, production of ferroelectric glass-ceramics through glass melt- crystal Ba2TiGe2O8(BTG) has been generated as a major crystalline
quenching technique leads to improved properties like, high transpar- phase in the glass matrix of composition BaO-TiO2-GeO2. Halliyal et al.
ency, low porosity, higher mechanical and dielectric breakdown for the first time reported ferroelastic, piezoelectric and pyroelectric
strengths, and high thermal and chemical durability. Sufficient trans- properties of BTG single crystals and studied first order phase transi-
parency in these glass-ceramics can be ensured in two possible ways: tions at −50 °C on cooling and near 0 °C on heating [5]. The authors
opined that BTG is a divertible but irreversible ferroelectric below
a) Controlled homogenous crystallization, restricting to average sizes −50 °C with symmetry in point group 1 or m (mm2 F1 –mm2 Fm).
Crystal structure of BTG consists of flat sheets of corner lined

⁎
Corresponding author.
E-mail address: atiar@cgcri.res.in (A.R. Molla).

https://doi.org/10.1016/j.jnoncrysol.2018.11.002
Received 5 September 2018; Received in revised form 1 November 2018; Accepted 2 November 2018
Available online 25 November 2018
0022-3093/ © 2018 Elsevier B.V. All rights reserved.
A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

TiO5pentahedra and Ge2O7 pyrogermanate groups perpendicular to the 2. Experimental techniques

(001) hkl planes which are interconnected through 10-fold coordinated
Ba2+ ions. Peculiar pentahedral coordination of Ti4+ ions in square A glass with mole percent stoichiometry30BaO–15TiO2–55GeO2
pyramidal TiO5 units generates permanent electric dipoles along the (BT1.67G) doped with 0.5 mol% Eu2O3(in excess) (BT1.67G + 0.5Eu)
(001) direction in this fresnoite BTG crystal [5]. Due to such structural (BTGE) was prepared from high purity raw materials such as germa-
features, BTG crystals are expected to show significant optical non- nium(IV) oxide, GeO2 (crystalline powder: 99.998% trace metals basis;
linearity and a large degree of spontaneous polarization along the (001) Sigma-Aldrich, India), barium(II) carbonate, BaCO3 (99%; Fluka
directions giving rise to predominantly ferroelastic (┴ domain-wall Chemica, Kolkata, India), titanium(IV) oxide, TiO2 (99.80%; Merck
motion) properties at room temperature [6]. India Ltd.), europium (III) oxide, Eu2O3 (99.99%; Sigma Aldrich,
Ogawa et al. studied the crystallization behavior and optical non- Zeppelinstr, Karlsruhe, Germany) using conventional melt-quenching
linearity of BTG crystals in BaO-TiO2-GeO2 glass thin films through technique. About 150 g of glass batch was prepared, thoroughly mixed
atomic force microscopy (AFM), Raman and Maker fringe techniques and melted in a platinum crucible in an electric furnace at 1300 °C for
[7]. Surface crystallization of the glass films and a second-order non- 2 h in air with intermittent stirring using a silica glass rod. The glass
linear optical constant of −0.8 pm/V was reported. Hane et al. studied melt was poured on to an iron mold kept at room temperature for
second harmonic generation (SHG) in the transparent crystallized glass producing glass cullet. The cullet thus formed was re-melted twice at
fibers from molar composition 30BaO–15TiO2–55GeO2 containing BTG 1300 °C following the same procedure to ensure homogenization and
crystals [8]. Linearly polarized micro Raman scattering spectra de- refining of the glass melt. Finally, the glass melt was poured onto the
monstrated that the glass fibers possess surface crystallization with the pre-heated iron mold, followed by annealing at 630 °C for 4 h to remove
growth of BTG crystals from surface to the interior. The nomenclature the internal thermal stresses developed in the glass and then slowly
of the composition with mole percent stoichiometry 30BaO–15- cooled down to room temperature @ 0.5 °C/min. The as-prepared glass
TiO2–55GeO2 has been recently abbreviated as BT1.67G in a review block was cut, grinded into dimensions of 12 × 12 × 1 mm3 and po-
report by Wisniewski et al. [9]. With the same glass composition, Ta- lished to carry out the ceramization process. The precursor glass sam-
kahashi et al. studied the optical nonlinearity and the formation me- ples were subjected to single-stage heat-treatment for crystal growth at
chanism of BTG crystals in transparent crystallized glasses synthesized 750 °C with varying durations of 3, 6, 9,12 and 15 h. Heating and
through melt-quenching technique. The authors for the first time re- cooling rates of 1 °C/min was kept constant throughout the entire heat-
ported fabrication of transparent surface crystallized glass-ceramics treatment experiment.
containing grain oriented BTG crystals by means of heat-treatment at Archimedes principle was applied to measure the density of the base
690 °C–750 °C for 3 h and reported a high second-order optical non- glass and glass-ceramics, using water as the buoyancy liquid. Non-iso-
linearity of 10 pm/V for the GC heat-treated at 720 °C for 3 h [10,11]. thermal differential scanning calorimetry (DSC) analysis of a precursor
An enhancement of second-order optical nonlinearity in a high mag- bulk glass sample was carried out up to 1200 °C from room temperature
netic field (H = 10 T) in crystallized BT1.67G glass was reported by at four different heating rates: 10, 20, 30 and 40 K/min using a
Toyohara et al. [12]. The orientation of BTG crystals along its polar- NETZSCH instrument (Model STA 449 F3; NETZSCH- Gerätebau GmbH,
ization axis and the intensity of SHG were enhanced in the sample Selb, Germany) with an accuracy of ± 0.5 °C.The glass transition tem-
fabricated with magnetic field ┴ to the glass surface during crystal- perature (Tg), onset of crystallization (Tx), the crystallization peak
lization. Zhu et al. reported enhanced red emission of Eu3+ ions in temperature (Tp) and onset of melting temperature (Tm) of the pre-
Eu2O3 doped BaO-TiO2-SiO2 glasses by generating fresnoite Ba2TiSi2O8 cursor glass sample were determined from the DSC analysis. The
(BTS) crystalline lines and dots using femtosecond laser irradiation thermal data obtained from DSC analysis have been used for nonlinear
[13]. Enhanced up conversion luminescence of Eu3+ ions was reported reaction model crystallization kinetic studies using
in Eu2O3 doped SrO-TiO2-SiO2 based heat-treated glass-ceramics con- NetzschThermokinetics 3.1 software (version – 072010). The coeffi-
taining microcrystalline particles of Sr2TiSi2O8 (STS) [14].Also, un- cient of thermal expansion (CTE), glass transition temperature (Tg), and
doped fresnoites like BTS, STS and BTG exhibit blue-green fluorescence dilatometric softening temperature (Td) of the precursor glass sample
if excited with a radiation of 254 nm or cathode rays [9]. Recently, were evaluated using a horizontal push-rod dilatometer (Model DIL 402
Xiang et al. synthesized BTG ceramics through microwave sintering PC; NETZSCH-Gerätebau GmbH, Selb,Germany) having an instru-
route and reported a very low dielectric loss of 1.1 × 10−3 (at 10 GHz) mental error limit of ± 1 K. The XRD patterns were recorded using an
and a coefficient of thermal expansion (CTE) of 11.0 ppm/°C[15]. Cao XPERT-PRO MPD diffractometer (PANalytical, Almelo, the
et al. studied the luminescence properties of BTG:Mn4+ red-emitting Netherlands) with CuKα radiation of 1.5406 Å at 25 °C, having a source
phosphor synthesized through conventional solid state reaction power of 40 kV and 30 mA, for identification of the developed crystal
method. A quantum efficiency of 35.6% was achieved at an optimal phases of the powdered glass-ceramic samples. The 2θ scan was carried
Mn4+ concentration of 0.6 mol% [16]. out in the range of 5°-80°with a step size of 0.02°. A high-resolution FE-
To the best of our knowledge there is no report on crystallization SEM (Gemini Zeiss Suprat 35 VP model of Carl Zeiss Microimaging
kinetics, optical and dielectric properties of Eu2O3 doped GmbH, Berlin, Germany) was employed to investigate the micro-
30BaO–15TiO2–55GeO2 (BT1.67G + 0.5Eu) (BTGE) based glass and structure of the heat-treated glass-ceramics after etching the bulk
glass-ceramic nanocomposites. The purpose of this study is to under- samples in 10 vol% aqueous HF solution for 1–2 min, followed by ul-
stand the mechanism of crystallization in BTGE glass system through a trasonic cleaning in acetone, overnight drying at ~80 °C and then
comparative study of linear, nonlinear and model-free reaction kinetics. coating with a thin carbon film. The TEM images of very fine powdered
A novel heat-treatment protocol has been optimized theoretically from glass-ceramic samples were obtained using an FEI (Model TecnaiG2
the nonlinear kinetic studies and validated experimentally to synthesize 30ST; FEI Company, Hillsboro, OR) instrument. The FTIR reflectance
BTGE glass-ceramics with sufficient transparency. The aim of this study spectra of the precursor glass and glass-ceramic samples were recorded
is to ascertain the type of crystallizationin BTGE glass-ceramics by de- using an FTIR spectrometer (Model, Frontier FT-IR/FIR Spectrometer;
termining the kinetic parameters like activation energy (Ea), Avrami Perkin-Elmer Corporation, Norwalk, CT) in the wave number range
index (n), crystal growth dimensionality (m) through some commonly 1000–400 cm−1 at a resolution of ± 2 cm−1 and at 15° angle of in-
studied solid state reaction models and analyze their microstructure, cidence. The optical absorption and transmission spectra were recorded
thermal, optical, photoluminescent and electrical properties. using a Perkin-Elmer UV–Vis-NIR spectrophotometer (Model Lambda
950; Perkin-Elmer Corporation, Waltham, MA) in the wavelength range
of 400–800 nm. The fluorescence emission and excitation spectra were
recorded using a bench-top modular spectrofluorometer (Quanta

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

Master; Photon Technology International, Birmingham, NJ) attached followed by an onset of crystallization event (Tx) at 818 °C, crystal-
with a Xe arc lamp as the excitation source. The refractive index of the lization peak temperature (Tp) at 855 °C and onset of melting tem-
base glass was measured using laser sources by a Prism Coupler (Model perature (Tm) at 1130 °C, which are within the instrumental error limit
2010/M; Metricon Corporation, New Jersey) with an accuracy of ± 0.5 °C. The Tg and softening temperature (Td) of the BTGE glass
of ± 0.0001 at five different wavelengths of 473, 532, 632.8, 1064 and determined from dilatometry experiment was found to be 680 °C and
1552 nm respectively. The dielectric constant, dielectric loss and dis- 700 °C respectively.The variation of co-efficient of thermal expansion
sipation factors of the base glass and glass-ceramics were measured at (CTE) (α) over the temperature range from 50 °C up to the softening
room temperature from low to high selected frequencies using a Hioki point has been displayed in Fig. 1b, in which the CTE over the tem-
LCR meter (Model 3532–50 Hitester, Hioki, Ueda, Nagano, Japan), perature range of 50–400 °C was found to be 9.8101 × 10−6 ± 1 K−1.
after coating both sides of the samples with conducting silver paint In oxide glasses, ratio of the temperatures of the onset of glass transition
followed by drying at 50 °C for 24 h. Hysteresis loop (P-E loop) mea- and melting (Trg) gives an indication about the nature of nucleation
surements of the coated samples were made at room temperature using (surface/bulk) occurring in the system during ceramization process.
a ceramic multilayer actuator test bench (aixCMA, Germany) at a fre- The calculated value of this reduced glass transition temperature (Trg)
quency of 1 kHz. for BTGE glass has been found to be 0.60. It has been reported that
stoichiometric oxide glasses having a Trg value ≥0.60 exhibit hetero-
genous or surface nucleation, whereas glasses with Trg ≤ 0.60 exhibit
3. Results and discussion
homogenous nucleation [17]. The Trg value obtained for BTGE glass is
in boarder line, thus it can be both heterogeneous or homogenous nu-
3.1. Thermal properties
cleation/crystallization which can only be confirmed from crystal-
lization kinetics studies. The thermal stability of a glass system against
Bulk samples of BTGE base glass were subjected to non-isothermal
nucleation or crystallization is determined by the temperature differ-
heat-treatments using DSC at various heating rates of 10, 20, 30 and
ence between Tx and Tg (ΔTx). Higher value of ΔTx indicates greater
40 K/min. The DSC thermograms obtained at each heating rates have
stability of the glass matrix against crystallization during ceramization.
been presented in Fig. 1a. The thermogram obtained at the heating rate
The value of ΔTx obtained for BTGE glass is 136 °C. The stability of a
of 10 K/min has been considered as a standard to determine the onset of
glass system against crystallization and glass forming ability against
glass transition temperature (Tg), onset of crystallization (Tx) and
vitrification on cooling is determined by a parameter KH (KH = Tx – Tg/
crystallization peak temperature (Tp) and onset of melting temperature
Tm – Tx), known as the Hruby's parameter. According to Hruby's theory
(Tm) of precursor BTGE glass. As shown in Fig. 1a, the onset of en-
[18], the value of KH greater than 0.5 for a specific glass indicates ex-
dothermic signal at 682 °C gives the glass transition temperature (Tg),
cellent glass forming ability and higher stability against crystallization
on heating. The KH parameter for the present glass composition is found
to be 0.43 which indicates a moderate glass forming ability and higher
tendency of crystallization upon heat-treatment.

3.2. Crystallization kinetics

The crystallization event in a solid state material like glass is as-

sumed to be single step chemical transformation as follows:
Asolid → Bsolid + C volatile (1)
Thermal property data obtained from non-isothermal DSC analysis
can be used to determine the kinetic parameters like,activation energy
of crystallization (Ea), A (pre-exponential factor) and temperature de-
pendence of rate constant k(T) through the Arrhenius rate equation. In
such non-isothermal conditions, a rapid scan over the experimental
temperature range is performed and as shown in Fig. 1a the signals for
onset of crystallization (Tx) and the exothermic crystallization peak
temperature (Tp) shift to higher temperatures with increasing heating
rate (β). The process of crystallization kinetics was studied using the
crystallization peak temperatures (Tp) obtained at various heating rates
from 10 to 40 K/min. The activation energy of crystallization was de-
termined and compared by using some of the best studied solid state
reaction linear mathematical models of Kissinger [19], Augis-Bennett
[20], Ozawa [21], Matusita [22] and nonlinear nth-dimension Avrami-
Erofeev[23] reaction model. The activation energy of crystallization
(Ea) obtained from the mathematical models were correlated with iso-
conversional model free Friedman method [24]. The values of Avrami
index (n) derived from the linear models of Augis-Bennett, Matusita and
nonlinear Avrami-Erofeev model gave a conclusive idea regarding the
nature and mechanism of crystallization in BTGE glass system.

3.2.1. Crystallization kinetics using linear reaction models

3.2.1.1. Kissinger-Augis-Bennett-Ozawa-Matusita (K-A-O-M) models. The
reaction models of Kissinger, Augis-Bennett and Ozawa are based on the
Fig. 1. (a)DSC thermograms of precursor bulk BTGE glass samples recorded at following two assumptions:
heating rates of 10,20, 30 and 40 K/min, (b) Dilatometric thermogram of BTGE
bulk cylindrical sample. a) At the exothermic crystallization peak temperature, a fixed fraction

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

Fig. 2. Plots of (a) Kissinger, Augis-Bennett and Ozawa for the exothermic crystallization peak obtained at different heating rates of 10–40 K/min, (b) Plot of
crystallization fraction versus temperature of BTGE glass for crystallization temperature at different heating rates, (c) Plots of ln[−ln(1-x)] versus ln β at selected
temperatures, (d) Plots of ln[−ln(1-x)] versus 1000/T at heating rates of 20, 30 and 40 K/min.

(x) of the total amount of reactant is crystallized and the rate of 2.5RTp2
reaction (dx/dt) is maximum. n=
∆TFWHM Ea (5)
b) Number of nuclei is independent of the heating rate (β) and hence
crystal growth in the base glass occurs at some pre-existing nu- where ΔTFWHM is the full width at half maximum intensity for the
cleation sites. exothermic crystallization peaks obtained by integrating the peaks after
taking into account proper baseline correction. The average value of the
The mathematical equation for Kissinger, Augis-Bennett and Ozawa Avrami exponent is found close to 2.0 indicating a predominant surface
(K-AeO) models are as follows: crystallization event in the BTGE glass matrix [25].
In contrast to the linear K-A-O models, the Matusita reaction model
β E takes into account the type of nucleation and mechanism of growth
(i) Kissinger: ln = − a + const .
T p2 RTp (2) process during the crystallization event. It assumes sigmoidal type ki-
netics, where at some intermediate extent of conversion (dx/dt) the
β E growth rate reaches a maximum value [26].
(ii) Augis − Bennett: ln = − a + ln K 0
Tp RTp (3) The general form of Matusita equation is represented as follows:

mEa
Ea ln[−ln(1 − x )] = −nlnβ − 1.052 ⎛ ⎞ + constant .
(iii) Ozawa: ln β = − + const . ⎝ RT ⎠ (6)
RTp (4)
where ‘m’ is the dimension of crystal growth.
As shown in Fig. 2a, the activation energy of crystallization was
β β As shown in Fig. 2b, typical sigmoidal curves of crystallized fraction
calculated from the slope of the best fit plots of ln T , ln T and lnβ (x) versus temperature (T) were obtained at various heating rates from
p2 p
versus 1000/Tp and was found to be (322 ± 68.9), (331.6 ± 68.9) 10 to 40 K/min. Transformation temperatures of 868,873 and 878 °C
and (341.2 ± 68.8) kJ/mol for Kissinger, Augis-Bennett and Ozawa were selected within the exothermic crystallization peaks from Fig. 2b
models respectively. and best fit plots of ln[− ln (1 − x)] versusln β were obtained for each
The value of the Avrami index (n) was determined for the crystal- selected temperatures as shown in Fig. 2c. From the slope of the plot,
lization event at the exothermic peak temperature (Tp) obtained at the mean value of Avrami exponent (n) is found to be 2.0 for the
various heating rates of 10–40 K/min using the Augis-Bennett reaction crystallization event. The value of ‘n’ obtained in this case is identical as
model. The Avrami exponent was calculated from the Augis-Bennett obtained from Augis-Bennett reaction model which indicates a possi-
model using the following equation: bility of surface crystallization.

357
A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

The Avrami exponent (n) and the crystal growth dimensionality (m)
shares a linear relationship as follows:
n = a + mb (7)
where a = 0 and 1, for a zero and constant nucleation rate; a > 1 for
an increasing nucleation rate and a < 1 for a decreasing nucleation
rate respectively and b is related to the mechanism of growth process,
with a value of 0.5 for diffusion controlled and 1 for an interface con-
trolled process[27]. Four different cases can be considered from Eq. (7)
with the value of ‘n’ = 2.0 and are as follows:

Case 1: zero nucleation rate (a = 0) and interface controlled crystal

growth (b = 1).
Case 2: zero nucleation rate (a = 0) and diffusion controlled growth
(b = 0.5).
Case 3: constant nucleation rate (a = 1) and interface controlled
growth (b = 1).
Case 4: constant nucleation rate (a = 1) and diffusion controlled
growth (b = 0.5)lnβ.

Analysis of all the four cases revealed that mechanism of crystal

growth in BTGE glass proceeds on a fixed number of nucleation sites
(zero nucleation rate) at the onset of crystallization. With the progress
of crystallization, constant nucleation rate is predominant when nu-
cleation and crystal growth tends to occur simultaneously (0 ≤ a ≤ 1).
The crystal growth dimensionality (m) lies between 2 and 4
(2 ≤ m ≤ 4) indicating a fractal dimension of crystal growth. The ac-
tivation energy of crystallization calculated from the slope of the plot of
ln[− ln (1 − x)] versus 1000/T as shown in Fig. 2d, was found to be
(251 ± 31.0) kJ/mol. A diffusion controlled surface crystallization
event with a nonlinear (parabolic) growth of crystals has been predicted
from the case studies.

3.2.2. Crystallization kinetics using nonlinear Avrami-Erofeev reaction

model Fig. 3. (a) Curve fitting for exothermic peaks of BTGE glass using nth dimension
Nucleation and growth mechanisms in composite materials like Avrami-Erofeev equation, (b) Isothermal prediction of crystallized fraction
glasses are best described by nonlinear multivariate regression method upon crystallization with respect to heat treatment time at different tempera-
of Avrami-Erofeev reaction model [28]. The general form of nth di- tures of 900, 850, 800 and 750 °C respectively.
mension Avrami-Erofeev equation, involving crystallized fraction (x)
and Avrami index (n), is as follows:
Table 1
n−1 The values of activation energies (Ea), pre-exponential factor (A), Avrami index
f (x ) = n (1 − x )[−ln(1 − x )] n (8)
(n) and growth dimensionality (m) obtained from various crystallization
The kinetic parameters were optimized to generate the best non- models.
linear curve fittings for the exothermic crystallization peaks obtained at
Kinetic Kinetic parameters
various heating rates of 10–40 K/min using the NetzschThermokinetics models
3.1 software, as shown in Fig. 3a. The values for the activation energy
of crystallization (Ea), Avrami exponent (n) and the Arrhenius para- Activation energy Average Avrami Crystal growth
(Ea) (kJ/mol) log A index (n) dimensionality (m)
meter (A) obtained are (319 ± 1.63) kJ/mol, 2.0 and 3.98 × 1012
respectively. Linear
Commonly, the Jhonson-Mehl-Avrami-Erofeev-Kolmogorov Kissinger 322 ± 68.9
(JMAEK) relation is accepted as the rate equation for most types of Augis-Bennett 331.6 ± 68.9 2.0
Ozawa 341.2 ± 68.8
interface and diffusion controlled crystallization event in composite
Matusita 251 ± 31.0 2.0 2≤m≤4
systems [29]. According to this theory, the value of ‘n’ is close to ‘2’ for
a diffusion controlled surface crystallization with a 3-D and 2-D crystal Non-linear
n-Avrami- 319 ± 1.63 12.6 2.0 ≥2
growth at a zero and constant nucleation rate respectively. Hence the Erofeev
predicted mechanism of crystallization from linear Matusita and non-
linear Avrami-Erofeev reaction models has been found to be similar.The
values of activation energies (Ea), pre-exponential factor (log A), Av- crystallized product (x) versus time (t) at the four selected temperatures
rami index (n) and growth dimensionality (m) obtained from the re- have been shown in Fig. 3b.Rapid rate of crystallization is observed
action models of K-A-O-M and Avrami-Erofeev are tabulated in Table 1. near the crystallization onset temperature (Tz = 818 °C) and around the
exothermic peak temperature (Tp = 855 °C), taking < 10 min to
3.2.2.1. Isothermal prediction: Optimization of heat-treatment complete at 900 and 850 °C respectively. Crystallization is found to
protocol. The optimized kinetic parameters obtained from the Avrami- be > 99% complete near the crystallization onset temperature at
Erofeev reaction model were applied for prediction of isothermal 800 °C. This theoretical prediction supports the experimental
conversion of the glass system at various fixed temperatures of 900, observation, in which a precursor BTGE bulk sample turned
850, 800 and 750 °C respectively. The plots of variation of fraction of

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

opaquewith appearance of well-defined cracks after single-stage heat-

treatment at Tp for 30 mins. XRD analysis of the powdered sample (not
shown here) revealed identical diffraction peak positions at same 2θ
values and d-spacing mainly corresponding to the Ba2TiGe2O8 crystal
phase, confirming its formation at the crystallization peak temperature.
Thus, synthesis of transparent BTGE glass-ceramics appeared to be a
difficult task. Appearance of cracks in the GC sample when heat-treated
at Tpoccurred possibly due to mismatch in coefficient of thermal
expansion (CTE) between the glass matrix and the crystal phase. As
seen in Fig. 3b, the progress of crystallization will slow down at 750 °C
compared to 900, 850, 800 °C. The progress of crystallization becomes
sluggish at 750 °C and is > 99% complete after 200 min. A slow rate of
crystallization at 750 °C opens up the possibility of controlled
crystallization to restrict the crystallite sizes in nanometer scale in
order to prepare transparent glass-ceramics. The optimized
ceramization temperature and time has been determined as 750 °C
and 3 h respectively. Transparency in BTGE glass-ceramic samples
could be retained by heat-treating the glass samples at 750 °C for
varied durations of 6, 9, 12 and 15 h. A reduction in transparency was
observed in the glass samples heat-treated for 12 h and 15 h compared
to the base glass and other glass-ceramic samples. The glass-ceramics
fabricated byheat-treatment upto 9 h appeared fully transparent which
indicates the evolution of nano sized crystals at the glass surface.
Appearance of cracks were observed in the GC samples heat-treated for
15 h and beyond,which could be due to higher crystal volume fraction
and mismatch in CTE between the glass matrix and BTG crystal phase.
Similar studies related to crystallization kinetics and theoretical
optimization of heat-treatment protocol have been recently reported
by us for Eu3+ doped ferroelectric BaBi2Ta2O9 (BBT) and CaBi2Ta2O9
(CBT) glass-ceramic systems [30, 31].

3.2.3. Model free Friedman method: Correlation of activation energy

The isoconversional differential Friedman method is devoid of any
particular assumptions unlike that of the K-A-O-M models and the Fig. 4. (a) Plots of log (dx/dt) versus 1000/T using model free Friedman
nonlinear Avrami-Erofeev model. It evaluates the activation energy of method, (b) Variation of activation energy and pre-exponential factor as a
crystallization (Ea) as a function of conversion (f(x)) without any fixed function of crystallization fraction.
assumptions, due to which reliable and consistent kinetic information
could be obtained from the non-isothermal data [32]. Friedman equa-
Table 2
tion at a specific crystallized fraction ‘x’ for different heating rates (β),
The values of activation energies (Ea) at specific crystallized fraction (x), along
is given as: with the logA values estimated from differential Friedman analysis.
dx Ea Crystallized fraction (x) Activation energy (kJ/mol) log A (s−1)
ln ⎛ ⎞ = ln Ax − + ln f (x )j
⎝ dt ⎠ x , j RTx , j (9)
0.01 363.6 ± 14.6 14.2
where the jth term represents different heating rates. 0.02 369.9 ± 18.5 14.5
0.05 372.1 ± 18.3 14.8
Using NetzschThermokinetics 3.1 software and from Eq. (9), the Ea 0.10 362.7 ± 16.9 14.4
values at various stages of crystallization for different crystallized 0.15 353.8 ± 17.6 14.1
fraction (x) have been evaluated from the slope of the best fit plots of 0.20 347.2 ± 19.0 13.8
log (dx/dt) versus 1000/T as shown in Fig. 4a. The variation of acti- 0.25 341.5 ± 19.8 13.6
0.30 336.7 ± 20.7 13.4
vation energy and the Arrhenius parameters (log A) with each crys-
0.35 332.1 ± 21.1 13.3
tallized fraction has been displayed in Fig. 4b along with error limits. 0.40 327.6 ± 20.7 13.1
The values of activation energies (Ea) and log A at specific crystallized 0.45 322.4 ± 20.4 12.9
fraction (x) along with error limits are summarized in Table 2. From 0.50 317.5 ± 21.0 12.7
Fig. 4b and Table 2 a small increase in Ea is observed during the start of 0.55 312.8 ± 22.6 12.5
0.60 308.3 ± 24.5 12.3
crystallization and decreases steadily with the progress of crystal- 0.65 305.3 ± 26.0 12.2
lization. The values of Ea are found to be consistent with the values 0.70 303.2 ± 24.7 12.2
obtained from the K-A-O-M and the Avrami-Erofeev reaction models 0.75 300.4 ± 23.1 12.1
which justify the predicted mechanism of crystallization occurring in 0.80 296.0 ± 24.0 11.9
0.85 285.3 ± 36.0 11.5
the BTGE glass system.
0.90 266.2 ± 49.3 10.7
0.95 247.4 ± 54.4 9.9
3.3. Phase evolution and microstructure 0.98 250.9 ± 47.3 10.1
0.99 255.3 ± 40.8 10.4

3.3.1. XRD and FTIR analysis

X-ray diffraction experiment was performed on fine powdered
15 h. The XRD patterns for a fully amorphous sample (base glass:
samples of BTGE precursor glass and glass-ceramics formed after single- BTGE0h) and for the samples heat-treated at 750 °C for varying
stage heat-treatment at 750 °C with varying durations of 3, 6, 9, 12 and

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

Fig. 5. (a) XRD patterns of the powder samples of BTGE base glass and GC samples synthesized at 750 °C for varying duration of 3, 6, 9, 12 and 15 h, (b) Variation of
average crystallite size in the glass-ceramic samples with respect to heat-treatment duration.

durations are shown in Fig. 5a. The amorphous nature of the base glass
is indicated by a broad and halo band at around 29° angle of diffraction.
As shown in Fig. 5a, XRD patterns of the heat-treated samples (BTGE3h
- BTGE15h) indicate structuring of this halo band along with the ap-
pearance of several well defined diffraction peaks, which confirms the
precipitation of crystalline phase in the amorphous glass matrix. Most
of the series of sharp diffraction peaks could be attributed to the polar
orthorhombic Ba2TiGe2O8fresnoite crystal (JCPDS Card File No.
77–0428), except for a few diffraction peaks around 2θ (de-
grees) = 24.45, 26.79, 31.10, 42.08, 43.48, which are due to the for-
mation of a secondary trigonalBaGe4O9 (BGO)crystalline phase (JCPDS
Card File No. 43–644). The intensities of the diffraction peaks increase
with the increase in heat-treatment time from BTGE3h to BTGE15h
samples, with the diffraction intensity at 2θ = 28.54° being the highest,
corresponding to the (311) hkl planes of BTG crystal. This indicates the
increase in average crystal sizes with increase in heat-treatment dura-
tion. To confirm this, the average crystallite size for each heat-treated
samples has been calculated from the full width at half maximum in-
tensity (FWHM) of the intense diffraction peak (311) at 2θ = 28.54°
using Scherrer's formula [33] as follows:
0.9λ Fig. 6. FTIR reflectance spectra of BTGE precursor glass and glass-ceramic
d= samples.
βcosφ (10)

where dis diameter of the average crystallite size, λ is the wavelength of

tetrahedral units present in the BaGe4O9 crystals [36]. The bands ap-
CuKα radiation (1.5406 Å), β is the integral FWHM of the peak at 2θin
pearing at 453 and 485 cm−1 could be attributed to the vibrations of Ba
radians and φ = half of Bragg angle (2θ) in radians
(II)-O bonds of ten coordinated Ba2+ ions in crystals of BaGe4O9and
The variation of average crystallite size with heat-treatment time is
Ba2TiGe2O8 respectively. Increase in intensity of the reflectance bands
shown in Fig. 5b. The average crystallite size is found to increase with
with increase in heat-treatment time is found to be very less which
increase in heat-treatment duration and lies in the range of 20–80 nm
indicates that further formation of thenanocrystallitesat the interface is
for the samples heat-treated for 3–15 h.
prevented for longer heat-treatment times to satisfy the chemical
Further studies were carried out on the base glass and glass-ceramic
composition required by the crystallizing phase [37]. Thus X-ray dif-
samples with FTIR reflectance (FTIRR) spectroscopy in order to confirm
fraction and FTIRR spectroscopy analysis confirms the evolution of the
the evolution of crystal phases. The FTIRR spectra of the base glass and
crystalline phases in BTGE glass matrix, with Ba2TiGe2O8(BTG) as the
heat-treated samples in the wave number range of 1000–400 cm−1 are
major crystal phase. Transmission electron microscopy (TEM) analysis
presented in Fig. 6. It is seen that structural modifications are occurring
provided further confirmation regarding evolution of BTG crystal phase
in the glass matrix with heat-treatment as revealed by the variation of
in the glass matrix, discussed in Section 3.3.2.
the FTIRR spectra of BTGE base glass (BTGE0h) compared to the glass-
ceramic samples. The bands observed at 524 and 563 cm−1 correspond
to two different modes of Ge-O-Ge symmetric stretch in Ge2O7 groups, 3.3.2. TEM and FESEM analysis
whereas Ge-O-Geantisymmetric stretching modes of vibration in Ge2O7 Selected area electron diffraction (SAED) and high resolution (HR)
groups are observed in the range of 892–910 cm−1 [34]. The re- TEM analysis was carried out to determine the formation of BTG na-
flectance band appearing at 757 cm−1 corresponds to the vibration of nocrystalline phase in the glass matrix upon heat-treatment. SAED
equatorial TieO bonds in TiO5 square pyramidal units, and the band at pattern and HR image of the glass sample heat-treated for 3 h (BTGE3h)
802 cm−1 corresponds to the vibration of the axial TieO bond of TiO5 has been displayed in Fig. 7a and 7b respectively. The diffused hallow
units in Ba2TiGe2O8 [35]. The overlapped vibration at 740 cm−1could of the SAED pattern indicates the formation of nanocrystals in the BTGE
be attributed to the symmetric GeeO stretching vibration of [GeO4] glass matrix. Indexing of the SAED patterns reveal the hkl planes (311),

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

Fig. 7. (a) SAED TEM image of BTGE3h glass-ceramic sample, (b) HR TEM image of BTGE3h glass-ceramic sample; (c), (d), (e), (f) FESEM images of BTGE glass
samples heat-treated at 750 °C for varying durations of 3,6,9 and 12 h.

(002) of BTG crystals that were identified using XRD analysis. The HR Fig. 7(d)-(f). As shown in inset of Fig. 7f, flower shaped morphology
TEM image shown in Fig. 7b displays two type of patterns which relates with spherical crystal clusters was observed for the BTGE12h sample
to the presence of two different crystal phases in the glass matrix. An and the spherical growth is predominant with increase in isothermal
interplanar spacing of 3.12 Å corresponding to the (311) hkl plane of heat-treatment time. A good degree of crystal volume fraction is ob-
BTG has been obtained as shown in Fig. 7b. Hence, nanocrystalline served for the 12 h heat-treated sample with interlocked orientations of
BTGE glass-ceramics could be fabricated through controlled crystal- crystal cluster particles on the surface.Spherical polycrystalline gran-
lization by heat-treating the precursor glass at 750 °C, as predicted from ules of average size in the range 50–100 nm were observed in the glass-
the crystallization kinetics studies. ceramic samples fabricated for 3–12 h. Recently, Wisniewski et al. re-
Etched surfaces of the BTGE glass-ceramics were studied using a ported polygon and dendritic crystal morphologies in Ba-fresnoite
field emission scanning electron microscope (FESEM), in order to de- (Ba2TiSi2O8) glass-ceramics synthesized at 810 °C for 5 h or more with
termine the morphologies of the crystals developed. A high contrast for varying percentages of SiO2 [39].
the surfaces is required for this study, which was successfully achieved
by etching the glass-ceramics in 10 vol% hydrofluoric acid (HF) that
exposed the crystals embedded in the glass matrix giving an excellent 3.4. Optical properties
contrast. The FESEM micrographs for the 3 h (BTGE3h), 6 h (BTGE6h),
9 h (BTGE9h) and 12 h (BTGE12h) heat-treated samples are shown in 3.4.1. Transmission spectra and optical band gap energy
Fig. 7(c), (d), (e) and (f) respectively. The sample heat-treated for a Fig. 8a shows the transmission spectra of the BTGE glass and glass-
lower time i.e. 3 h (BTGE3h), exhibits spherical and dendritic cluster ceramics in the UV-VIS range of 300–800 nm. The spectra reveal
morphologies (shown as inset in Fig. 7c). Such kind of dendritic characteristic bands of Eu3+ ion due to the 4f-4f transitions from the
morphologies can occur in conditions of high degree of crystalline an- ground state multiplets7 F0, 1 to different excited states of Eu3+ ions in
isotropy. Dendritic morphology indicates a regular fractal like crystal 4f6 configuration. Two well defined peaks at 393 nm and 465 nm are
growth which was earlier predicted from crystallization kinetics studies observed which correspond to 7F0 → 5L6 and 7F0 → 5D2 transitions of
[38]. With increase in heat-treatment time, spherical cluster growth is Eu3+ ions. A small absorption peak at 532 nm is also observed which
predominant which can be seen from the micrographs displayed in occurs due to transition from thermally excited ground state multi-
plet7F1 to the 5D1 excited state (7F1 → 5D1). The transmission

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

Fig. 8. (a) Photograph and transmission spectra of BTGEbase glass and glass-ceramic samples, (b) Optical bandgap energy curves of BTGE base glass and glass-
ceramic samples.

percentage at wavelength 475 nm is diminished due to scattering of observed for the sample heat-treated upto 9 h (BTGE9h; 3.70 eV) and
short wavelength light by the crystals. An upliftment of the baseline is was observed to be highest for the BTGE12h glass-ceramic sample with
observed for the glass sample heat-treated for 12 h (BTGE12h) with a value of 3.88 eV. Such increase in the Eg values of glass-ceramics with
diminishing intensities of the absorption peaks, while no absorption respect to the base glass can be explained in terms of density of loca-
bands were observed for the 15 h heat-treated sample (BTGE15h). Inset lized state model proposed by Mott and Davis [40]. In amorphous
of Fig. 8a is the photograph of precursor glass and the heat-treated states/materials the optical absorption depends on the states' short-
samples. From the figure it is observed that there is no appreciable range order (localized electronic states) and its defects. During glass
decrease in transparency of the base glass and the glass samples heat- formation, chemical recombination of the compounds produces un-
treated upto 9 h, while transparency decreases in 12 h and 15 h heat- saturated and saturated bonding network inside the glass matrix. The
treated samples. With increase in heat-treatment duration, crystal size unsaturated bonds produce some defects in the amorphous matrix
and crystal volume fraction increases which is evident from XRD and which in turn increases the density of the localized sates [41]. However,
FESEM analysis.The average crystal size obtained from XRD and FESEM with increasing duration of isothermal heat-treatment crystallization of
analysis for BTGE12h and BTGE15h samples lies between 80 and the glass samples occurs, which produces a more ordered network to
100 nm. Generally, upliftment of baseline with decrease of transpar- minimize the number of defects and localized states thereby increasing
ency in glass-ceramic samples occurs mainly due to the following two the optical band gap. This is also confirmed from FESEM analysis of the
reasons in accordance with the Rayleigh scattering model: surface morphologies of BTGE glass-ceramics. As shown in the micro-
graphs in Fig. 7 and for the 12 h heat-treated sample, the microstructure
i) average crystallite size is observed to be denser with homogenous distribution of the crystal
ii) refractive index (RI) difference between the crystalline and amor- clusters and higher crystal volume fraction. Also, due to surface crys-
phous phases. tallization in BTGE glass-ceramics, the thickness of the crystalline layer
is expected to increase giving rise to a more homogenous ordered
According to this model, crystallite size needs to be smaller than λ/20 network which minimizes the localized states thereby increasing the
(λ = wavelength of the visible light) for minimum scattering losses. optical band gap energy.
Although the average crystallite size in BTGE12h and BTGE15h lies in
nanometric scale (80–100 nm), it is greater than λ/20 in the visible
wavelength range of 400–800 nm due to which significant scattering 3.4.2. Refractive index
losses occurred resulted in decrease in percentage transmittance with The variation of refractive index (RI) of the precursor glass and
decrease in the absorption intensity. In spite of large transmission glass-ceramics with wavelength is displayed in Fig. 9. The RI of the
losses, moderate to low transparency is observed in BTGE12h and samples wasmeasured at five different wavelengths of 473, 532, 632.8,
BTGE15h glass-ceramic samples. The optical band gap energies were 1064 and 1552 nm. The RI values measured at five different wave-
calculated according to Tauc's model of optical absorption using the lengths of 473, 532, 632.8, 1064, 1552 nm for the base glass (BTGE0h)
following equation [31]: are 1.8572, 1.84262, 1.8286, 1.8063 and 1.7984 ( ± 0.0001) respec-
tively. The RI values of 1.8445, 1.829, 1.8088, 1.8007 ( ± 0.0001) were
αhϑ = B (hϑ − Eb )n (11)
obtained at 532, 632.8, 1064 and 1552 nm wavelengths for the glass
where Eb is the optical band gap energy, B is a constant related to band sample heat-treated for 3 h (BTGE3h). The refractive indices at other
edge parameter, and n = 1/2, 2, 1/3, and 3 corresponding to direct wavelengths, like the Fraunhofer F (nF = 486.1 nm), D
allowed, indirect allowed, direct forbidden and indirect forbidden op- (nD = 589.3 nm) and C (nC = 656.3 nm) spectral wavelengths were
tical transitions. Considering direct allowed transitions in oxide glasses calculated through Cauchy dispersion fitting functions as shown in
(taking n = ½), the plot of (αhυ)2 vs. hυ is represented in Fig. 8b. The Fig. 10. These data were used to calculate other RI related optical
band gap energy values were obtained from the plots by extrapolating parameters which have been tabulated in Table 3. The coupling spots
the linear portions to intersect at zero absorption on the energy axis could not be located in the Prism coupler for the glass samples heat-
(hυ). The Eb values (3.63–3.65 eV) were found to be similar for the base treated at longer durations (6–12 h).
glass (BTGE0h) and the samples heat-treated for 3 h (BTGE3h) and 6 h The refractive indices at 589.3 nm of the base glass and the glass
(BTGE6h) respectively. An increase in the band gap energy values was sample heat-treated for 3 h were estimated to be 1.83413 and 1.836
respectively. A 0.1% increment in the RI values is observed for the

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Table 3
Some calculated physical and optical properties of BTGE precursor glass and
glass-ceramics.
Properties BTGE0h BTGE3h

Average molecular weight (g/mol) 130.48

Density (g/cc) 4.766 4.862
Molar volume (Vm) 24.62 24.13
Refractive indices
nF (486.1 nm) 1.85295 1.85341
nD (589.3 nm) 1.83413 1.836
nC (656.3 nm) 1.82592 1.82857
n (632.8 nm) 1.82763 1.83092
Abbe number (υ) 30.859 33.655
Dispersive power (1/ υ) 0.0324 0.0297
Molar refractivity,(RM) (cm3) 10.787 10.604
Electronic polarizability, (αe) (cm3 × 10−24) 4.277 4.205
Third order susceptibility (χ3) (10−14) 2.112 1.865

crystallized sample (BTGE3h) as compared to the base glass. An in-

crease in the RI value could be attributed to the effect of crystallization
Fig. 9. Cauchy dispersion fittings of variation of refractive indices as a function on the glass surface with the formation of highly polar Ba2TiGe2O8
of wavelength of the base glass and glass sample heat-treated at 750 °C for 3 h. crystals containing asymmetric [TiO5] and [Ge2O7] groups. However,
such a low increase in the RI values at all the wavelengths of nF, nD and
nC could be due to the contribution from the impurity phase BaGe4O9,
whose RI is reported to be 1.79 and is lower than the BTGE glass matrix
[10]. In order to understand the effect of crystallization on RI of the
samples, several other RI-related properties like molar refraction (RM),
electronic polarizability (αe), third order susceptibility (χ3) and Abbe
number (υ) of the precursor glass and glass-ceramics were calculated
which are tabulated in Table 3.
From the table it could be seen that the molar refraction for the
glass-ceramic(10.604) calculated at 632.8 nm is less than the precursor
glass (10.787). The decrease in molar volume of the sample happened
due to densificationof samples upon crystallization.The molar refrac-
tion depends directly on the molar electronic polarizability(αe) and the
value of αeis found to be less for the BTGE3h GC sample (4.205 Å3) as
compared to the base glass (4.277 Å3). Such high values of electronic
polarizabilities in the precursor glass and glass-ceramic could be at-
tributed to the high αe values of the free oxide ions (αO2−) of BaO
(3.652 Å3), TiO2 (2.368 Å3), GeO2 (1.720 Å3), Eu2O3 (2.408 Å3) and
cations such as Ba2+ (1.563 Å3), Ti4+ (0.187 Å3) and GeO2 (0.143 Å3)
[42].The Abbe number (υ) was calculated for BTGE base glass and
glass-ceramic samples. The values obtained for the base glass and the
GC sample heat-treated for 3 h has been found to be 30.855 and 33.655
respectively. Generally, a high value of Abbe number will give low
wavelength dispersions (1/υ) i.e. low chromatic aberration. This
property could be useful for adjustment of focal lengths of achromatic
lenses in which low chromatic aberrations are desired. Second order
nonlinear optical interactions are reported to occur in the non-cen-
trosymmetric BTG crystals. In nonlinear optics, the dependence of in-
duced polarization (P) with the optical susceptibility (χ) and the ap-
plied electric field (E) vector of visible light is described as:

P = ε0 [χ 1 E + χ 2 E + χ 3 E + …] (12)

The second order optical response (described as χ2 susceptibility)

becomes identically zero for a material like glass having short range
order with localized electronic states. However, third-order nonlinear
optical interactions (described by the χ3 susceptibility) could be ob-
served in both centrosymmetric and non-centrosymmetric mediums.
The χ3 susceptibility for the precursor glass (BTGE0h) and glass-
Fig. 10. (a)Photoluminnescence spectra atan excitation wavelength of 465 nm ceramic (BTGE3h) has been calculated to be 2.112 × 10−14 and
of BTGE precursor glass and glass samples heat-treated at 750 °C for 3 h and
1.865 × 10−14respectively. A decrease in the χ3 value is observed for
12 h, (b) Photoluminescence decay curves and variation of average lifetime of
BTGE3h sample with respect to the base glass which could be due to the
Eu3+ ions in the base glass and glass-ceramics.
contribution from the secondary phase BaGe4O9 having a lower re-
fractive index than the glass matrix.

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A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

3.4.3. Emission spectra and fluorescence decay [45]. This kind of microstructural environmentcan help minimizing the
Fig. 10 depicts the photoluminescence spectra and room tempera- nonradiative multiphonon relaxation rate of the Eu3+ions. Such non-
ture fluorescence decay curves of Eu3+ ionsin the base glass and glass- radiative decay process shares an inverse exponential relationship with
ceramic samples obtained after excitation at 465 nm wavelength. Due the energy gap (ΔE) between levels involved in the process as: [46]
to transitions within the energy levels of 4f6 configuration of Eu3+, p
−1
characteristic emission peaks are observed between 581 and 707 nm TNR = A ⎡ ⎧ ⎛ hϑ ⎞ ⎫ + 1⎤
wavelengths.The spectra exhibit five emission peaks at 581, 594, 615, ⎢ ⎨exp ⎝ kT ⎠ − 1⎬ ⎥ exp (−β∆E )TNR
⎣⎩ ⎭ ⎦
658 and 707 nm as shown in Fig. 10a. These six emission peaks can be −1 p

pointed out to the 5D0 → 7F0,1,2,3,4 transitions of Eu3+. The intense = A⎡ ⎧ ⎛ hϑ ⎞ ⎫ + 1⎤

⎢ ⎨exp ⎝ kT ⎠ − 1⎬ ⎥ exp(−β∆E)
emission peak at 615 nm can be designated to the induced electric di- ⎣⎩ ⎭ ⎦ (13)
pole transition 5D0 → 7F2 of Eu3+. As seen from the figure, the intensity
where TNR is the nonradiative decay rate, parameters A and βdepend on
of this electric dipole transition is dominant in all the samples and is
the host matrix, p relates to the number of phonons required to bridge
found to be the highest for the glass sample heat-treated for a longer −1 −1
duration of 12 h. { ( ) − 1} {exp ( ) − 1}
the energy gap and exp
hϑ
kT
hϑ
kT
is the Bose-Einstein
Intra-electronic transitions within the same subshell (like f-f tran- phonon occupation number.
sitions) of a lanthanide ion (Eu3+) are forbidden by Laporte rules of From Eq. (13) it can be ascertained that a decrease in nonradiative
selection (Δl = ± 1), which could be relaxed via the spin-orbit cou- relaxation rate is favourable for the con-
−1 p
pling or crystal field perturbations. Such phenomenon is possible with a
change in environment of the lanthanide ions from centrosymmetric to
{ ( ) }
hϑ
dition A ⎡ exp kT − 1
⎣
+ 1⎤ < < ΔE.
⎦
Thus a low phonon host for a rare earth ion can minimize the
a non-centrosymmetric environment with high degree of metal-ligand
nonradiative decay rates to enhance the photoluminescence intensity
covalency (spin-orbit coupling) or crystal field stabilization energy.
and the average life time. The radiative decay rate will also decrease
Hence, in this case, change in the site symmetry of the Eu3+ ions would
due to alterations in the crystal field symmetry at the rare earth site.
give rise to hypersensitive transitions, like, the induced electric dipole
Hence, in the present case microstructure of the BTGE12h sample help
transition 5D0 → 7F2, obeying selection rules of |ΔJ| ≤ 2, |ΔL| ≤ 2 and
decreasing the nonradiative decay rate of Eu3+ ions which enhances
ΔS = 0.
the intensity of red emission at 615 nm by 2-fold as compared to the
From the spectra given in Fig. 10a, a marginal increase in emission
base glass.
intensityof 5D0 → 7F2is observed for the sample (BTGE6h) heat-treated
for shorter duration (6 h) as compared to the base glass (BTGE0h). This
could be attributed to the fact that during initial stages of heat-treat- 3.5. Electrical properties
ment, formation of small sized non-centrosymmetric BTG crystals with
low volume fraction occurs predominantly at the glass surface during 3.5.1. Dielectric properties
which most of the Eu3+ ions are partitioned into the residual glassy Room temperature dielectric parameters, like, dielectric constant
phase. The room temperature fluorescence decay curves from the 5D0 (εr), dielectric loss (εr’) and dissipation factors (tan δ) were measured
state of Eu3+ ions in all the samples exhibited a single exponential for BTGE glass and glass-ceramic samples at selected frequencies from
decay as shown in Fig. 10b. Inset of Fig. 10b shows the variation of 1 kHz to 5 MHz.The variation of the dielectric parameters has been
average lifetime of Eu3+ in all the samples which steadily increases displayed in Fig. 11a-c. As shown in Fig. 11a, the measured dielectric
with heat-treatment duration. The local field asymmetry defining constantat a frequency of 1 kHz progressively increases from base glass
factor, described by the relative intensity ratio of (5D0 → 7F2): (5D0 → (BTGE0h; εr = 164.63) to the glass-ceramic samples (BTGE12h;
7
F1), has been found to be greater than unity for all the samples. The εr = 187), which confirms the evolution of non-centrosymmetric polar
asymmetry ratio of the glass-ceramic samples has been found to de- BTG crystals in the glass matrix. A high dielectric permittivity
crease with respect to the base glass, indicating a change in the crystal (εr = 187) was obtained at 1 kHz for the glass sample heat treated for
field symmetry around Eu3+ions. The europium ions with a valency of 12 h (BTGE12h) along with high dielectric loss (εr’ = 0.173) and dis-
+3 could be incorporated into the Ba2+ sites in the BTG crystals and sipation factor (tan δ = 9.25 × 10−4). A decrease in dielectric permit-
two incorporated Eu3+ ions will lead to one vacancy at a Ba2+ site for tivity of the glass and glass-ceramic samples is observed with increasing
maintaining charge neutrality[43, 44]]. The asymmetry factor and the frequency upto 100 kHz. This decrease in dielectric constant with in-
average life time of Eu3+obtained for all the samples are tabulated in creasing frequency of the alternating current (AC) for a heterogeneous
Table 4. dielectric material like glass-ceramic is due to the space charge polar-
Microstructural analysis from FESEM discussed in section 3.3.2 can ization effect. Such kind of polarization effect arises due to accumula-
also provide some insight regarding the improvement of photo- tion of charge carriers at the glass-crystal interface in the glass-ceramic
luminescence with increase in isothermal ceramization time. During system containing glass and crystal phases of different conductivities.
crystallization in the BTGE glasses with increase in heat-treatment The polarization effect gets reduced when the charge carriers could not
duration, a homogenous distribution of crystal cluster particles is ob- follow the increasing frequency of AC electric field and lags behind. A
served for the 12 h heat-treated sample with even distribution of crystal fall in this interfacial polarization with increasing frequency thus re-
boundariesand interlocked orientation of the clusters (Fig. 7e). Nano- duces the dielectric constant along with dielectric loss and dissipation
crystals embedded in the glass matrix having such kind of micro- factor for all the samples, as shown in Fig. 11a, b and c respectively. An
structure can create dense local crystal lattice fieldsand strong partition unusual rise in dielectric constant is observed for all the samples at
higher frequencies from 1 MHz to 5 MHz as displayed in Fig. 11a. The
total polarization on application of an electric field in a dielectric ma-
Table 4 terial like glass-ceramics is expressed as the sum of electronic polar-
Asymmetric factors and average lifetime values for BTGE base glass and glass- ization (Pe), ionic polarization (Pi), dipolar polarization (Pe) and space
ceramic samples.
charge polarization (Ps). In the high megahertz frequency region, the
Sample identity Asymmetric factor Average lifetime (μs) effect of space charge polarization becomes negligible due to increasing
lag time of the mobile charge carriers. The BTGE glass-ceramics consist
BTGE0h 5.578 900
of highly polar non-centrosymmetric Ba2TiGe2O8 crystals which possess
BTGE6h 5.345 915
BTGE12h 4.661 940 permanent electric dipole moments. Presence of such permanent elec-
tric dipoles may give rise to the dipole polarization effect at higher

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Fig. 11. Variation of dielectric parameters of BTGE precursor glass and glass-ceramics as a function of frequency: (a) dielectric constant, (b) dielectric loss and (c)
dissipation factors; (d) Polarization-electric field (P-E) hysteresis loops of BTGE glass samples heat-treated at 750 °C for 3 h and 12 h.

frequencies, in which the dipole vectors get aligned with the direction remnant polarization (Pr) of 0.005 μC/cm2. Such kind of ferroelectric
of applied electric field to increase the dielectric permittivity of the hysteresis at high electric fieldcould be due to the rotation of some 90°
medium. At a frequency of 5 MHz, the best dielectric parameters are domain wallsto give riseto ferroelectric domains(180° domain walls)
obtained for the BTGE12h glass-ceramic sample having high dielectric across a small region in the BTG crystals. A small value of spontaneous
constant of 210 with lowest dielectric loss of 0.013 and dissipation polarization arises due to the drop of the applied electric field across
factor of 0.687 × 10−4. low permittivity glass matrix, making switching of polarization in the
domains difficult. The theoretical energy densities in the BTGE12h
glass-ceramic sample has been calculated from the hysteresis cur-
3.5.2. Hysteresis loop veusing the following equations:
The BTG crystals are reported to show piezoelectric and ferroelastic
Pmax
properties at room temperature which arises due to polarization of the Js = ∫0 EdP (14)
material by application of a mechanical stress in addition to an electric
field. The BTG crystals have mutually perpendicular orientation of the Pmax
polarization domains (90° walls) [6] and exhibit spontaneous polar- Jr = ∫P
r
EdP
(15)
ization along the (001) directions. Regions with uniformly oriented
spontaneous polarization within the crystal can give rise to ferroelectric where, Js and Jr are the stored and recoverable energy storage density
domains of oppositely oriented polarization (180° walls) [47].The room respectively.
temperature polarization-electric field (P-E) hysteresis loops of the The calculated values of Js and Jr has been found to be 3.5 × 10−5
BTGE glass-ceramics were measured at a frequency of 1 kHz. Re- and 2.25 × 10−5 J/cm3 respectively.
presentative P-E loop images of BTGE glass sample heat-treated for 3 h
and 12 h are presented in Fig. 11d. As seen from the figure, linear loop 3.6. Conclusions
is observed in the BTGE3h sample having small crystallite size and low
crystal volume fraction. In order to switch the ferroelectric domains Eu2O3 doped BT1.67G (BTGE) glass andtransparent glass-ceramics
with application of an electric field, a sufficiently large domain size is have been synthesized for the first time. Detailed analysis of crystal-
necessary, which calls for crystallites of bigger size [30]. However, lization kinetics through linear and nonlinear solid state reaction
poling of the BTGE12h glass-ceramic sample was possible at a high models revealed a diffusion controlled surface crystallization me-
electric field of 2.5 kV/cm and was found to exhibit hysteresis loop with chanism with zero and constant nucleation rates. Nonlinear crystal-
a maximum spontaneous polarization (Pmax) of 0.014μC/cm2 and lization kinetics studies enabled to determine the experimental

365
A. Chakrabarti, A.R. Molla Journal of Non-Crystalline Solids 505 (2019) 354–366

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