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J Materiomics 2 (2016) 75e86
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Enhanced thermal energy conversion and dynamic hysteresis behavior of

Sr-added Ba0.85Ca0.15Ti0.9Zr0.1O3 ferroelectric ceramics
Satyanarayan Patel a,1, Deepakshi Sharma b,1, Anupinder Singh b, Rahul Vaish a,*
a
School of Engineering, Indian Institute of Technology Mandi, 175001, Himachal Pradesh, India
b
Department of Physics, Guru Nanak Dev University, Amritsar, 143005, Punjab, India
Received 7 December 2015; accepted 26 January 2016
Available online 13 February 2016

Abstract

This paper deals with a study of Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 (BCT-BZT-Sr) (x ¼ 0%, 5%, 10% and 15%) polycrystalline ceramics for
thermal energy conversion applications using the Olsen cycle. A maximum energy conversion density of 108 kJ/m3 was observed in pristine
BCT-BZT for cycle operating at 30e90  C and 0e20 kV/cm. Moreover, the samples with Sr contents (x) of 5%, 10% and 15% display an energy
conversion density of 179 kJ/m3, 149 kJ/m3 and 200 kJ/m3, respectively. The Sr addition almost double the energy conversion over the pristine
sample under the similar conditions. Also, the temperature (T )-dependent dynamic hysteresis scaling relations for coercive field (EC) and
remnant polarization (Pr) were systematically investigated. The power-law scaling exponents are obtained for EC versus T as EC f T
0.65,
EC f T
0.61, EC f T
0.56 and EC f T
0.63 for the samples with Sr contents of 0%, 5%, 10% and 15%, respectively. Similarly, the scaling
relations for Pr are Pr f T
1.59, Pr f T
1.59, Pr f T
1.36 and Pr f T
1.32 for the samples with Sr contents of 0%, 5%, 10% and 15%,
respectively.
© 2016 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
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Keywords: Energy harvesting; Olsen cycle; Dynamic hysteresis scaling; Ferroelectric

1. Introduction design of morphotropic phase boundary (MPB)-based new

In last few decades, ferroelectric materials have been used
in a wide range of scientific and technological applications.
All of these applications can be credited to their versatile
properties, i.e., piezoelectric/pyroelectric/ferroelectric effects
[1e5]. These are used in a variety of smart applications such
as sensors, actuators and transducers. They also possess a high
energy conversion potential, which can be used to power
micro-electromechanical systems (MEMS) and other nano/
micro devices [1e3,5e8]. Technologically and commercially
important ferroelectric materials include Pb(ZrxTi1
x)O3
(PZT) and Pb(Mg1/3Nb2/3)O3 (PMN) ceramics [5,9,10]. In
recent years, significant efforts have been directed towards the
* Corresponding author. Tel.: þ91 1905 237921; fax: þ91 1905 237945.
E-mail address: rahul@iitmandi.ac.in (R. Vaish).
Peer review under responsibility of The Chinese Ceramic Society.
1
These authors contributed equally to this work.
solid solutions such as xPb(Mg1/3Nb2/3)O3-(1
x)PbTiO3,
yPb(Mg1/3Nb2/3)O3-(1
y)PbxZn1
xTiO3, 8/65/35 PLZT and
yPb(ZrxTi1
x)O3-(1
y)PbZn1/3Nb2/3O3 [11e15]. Ferroelec-
tric materials fabricated near their MPB are capable of dis-
playing remarkably enhanced piezo/pyro/ferroelectric
properties. However, as serious environmental and health
problems of Pb toxicity, researchers have focused on devel-
opment of competing lead-free ferroelectric/piezoelectric
materials. Hence recent studies are focused on compositions
based on BaTiO3, Bi0.5Na0.5TiO3, K0.5Na0.5NbO3 and their
MPB compositions for ferroelectric applications [9,16e18].
In this case, lead-free Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCT-BZT)
ceramics have been recently studied due to its promising
piezoelectric and pyroelectric properties as compared to other
lead-free and lead-based materials [19e24]. A colossal
piezoelectric coefficient (d33) of 630 pC/N and high coupling
coefficient (kp) of 0.56 were reported which are comparable
with Pb-based existing materials [19]. It possesses a rather

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76 S. Patel et al. / J Materiomics 2 (2016) 75e86
high pyroelectric coefficient of 5.84e17.14  10
4  C/m2$K
at 300 K [20]. Also, BCT-BZT exhibits electric field-
dependent tunable dielectric properties, which can be tuned
up to 82% at an applied DC field of 40 kV/cm [21]. Also, it
exhibits a low dielectric loss of 0.01. These potential proper-
ties were credited to the coexistence of two phases (i.e.,
rhombohedral-tetragonal) with an intermediate (unstable)
orthorhombic phase, which minimizes the switching energy
barrier. The effects of composition and MPB on the ferro-
electric properties of BCT-BZT were studied extensively
[23,25e29]. It was indicated that BCT-BZT could be a po-
tential material for substitution of current lead-based materials
for many technologically important applications.
Some studies were also carried out on the caloric applica-
tion of BCT-BZT ceramics [30,31]. Gurvinderjit Singh et al.
reported a high electrocaloric coefficient of ~0.38 K mm/kV in
single crystal of 0.45BaZr0.2Ti0.8O3-0.55Ba0.7Ca0.3TiO3 near
the tetragonal-to-cubic phase transition [32]. A peak electro-
caloric effect of 0.45 K (347 K) was predicted for 0e3 kV/mm
electric field in Fe-doped bulk (Ba0.865Ca0.135Zr0.1089-
Ti0.8811Fe0.01)O3 [30]. However, BCT-BZT shows a large
electric and stress induced strain. Hence, a recent work
showed a rather high elastocaloric effect of 1.55 K at an initial
material temperature of 340 K and applied compressive stress
of 0e250 MPa (under a constant electric field of 2 MV/m) in
this compound [33]. Moreover, the most befitting application
of BCT-BZT could be that of high-field thermal energy har-
vesting. In this case, Vats et al. reported the Olsen cycle based
energy conversion in BCT-BZT [34]. They found the
maximum harness-able energy density of ~87 kJ/m3, when
cycle was operated at 20e120  C and 1e10 kV/cm. This work
will deal with Sr added Ba0.85Ca0.15
xTi0.9SrxZr0.1O3 (BCT-
BZT-Sr) (x ¼ 0%, 5%, 10% and 15%) for thermal energy
conversion using the Olsen cycle. In addition, the dynamic
hysteresis scaling was also performed to investigate the effect
of Sr addition on the BCT-BZT ferroelectric properties.
Furthermore, the domain dynamic behavior was analyzed
using the activation energy variation.
2. Experimental
Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 (BCT-BZT-Sr) poly-
crystalline ceramics were prepared via a solid state reaction
route. Four different samples were made by differing the
composition of strontium (x ¼ 0%, 5%, 10%, 15%). For this
purpose, reagent grade powders of barium carbonate (BaCO3),
calcium oxide (CaO), titanium oxide (TiO2), zirconium oxide
(ZrO2) and strontium carbonate (SrCO3) were mixed in a
stoichiometric ratio. This mixture was ground in acetone to
obtain the physical homogeneity using mortar and pestle.
Afterward, the mixture was calcined twice at 1350  C and
1400  C for 6 h with intermediate grinding to ensure physical
and chemical homogeneity. PVA was added in calcined pow-
der and the powder was cold-pressed to form green pellets
with the size of 12 mm  1 mm (diameter  thickness).
Finally, sintering was carried out at 1450  C for 4 h with a
heating and cooling rate of 6  C/min. The phase formation of
the calcined and sintered samples was determined by powder
X-ray diffraction (XRD). The density of sintered pellets was
determined according to the Archimedes principle. The sur-
face profile and morphology of the sintered pellets were
analyzed by scanning electron microscopy (SEM). Silver paste
was coated on the flat surfaces to make electrical contacts for
polarization versus electric field (PeE ) hysteresis measure-
ment. The PeE hysteresis loops were measured at different
temperatures using PeE loop tracer (Marine India).
3. Results and discussion
Fig. 1 shows the XRD patterns of the BCT-BZT-Sr ceramics
at room temperature. The absence of extra peaks indicates the
formation of desired phase. All the major peaks can be indexed
based on the standard XRD pattern of polycrystalline tetrag-
onal BaTiO3/CaTiO3. Fig. 2(a)(b), (c) and (d) show the SEM
micrographs of sintered samples with Sr contents of 0%, 5%,
10% and 15%, respectively. Clearly, all the samples appear to
be dense and relatively free of defects. This notion is also
confirmed by the density measurement, revealing that all the
sintered samples possess ~94% of the theoretical density.
Fig. 3(a), (b), (c) and (d) show the P-E loops for the samples
with Sr contents of 0%, 5%, 10% and 15%, respectively at
various electric fields and a constant temperature (30  C). All
the PeE loops are recorded at constant a/c frequency of 50 Hz.
The results indicate that as the electric field increases, minor
unsaturated P-E loops start moving towards saturation and
finally form saturated loops. This can be attributed to an in-
crease in coercive field (EC), saturation polarization (PS) and
remnant polarization (Pr). The hysteresis parameters variations
appear due to the domain growth and domain rotation/align-
ment, which take place in the direction of applied electric field.
In addition, it shows that the saturation polarization increases
with the increase of Sr content. This is due to a fact that BCT-
BZT-Sr ceramics coexist the rhombohedral and tetragonal
phases whereas Sr doping can induces the lattice distortion and
changes the phase composition. It is since the ionic radius of
Sr2þ is greater than that of Ca2þ.
Fig. 4(a), (b), (c) and (d) show the P-E loops for the BCT-
BZT samples doped with Sr contents of 0%, 5%, 10% and
15%, respectively, as a function of applied temperature and
constant electric field. At a given electric field, the corre-
sponding coercive field (EC), saturation polarization (PS) and
remnant polarization (Pr) decrease as the temperature in-
creases. Therefore, it opposes the electric-field induced
ferroelectric switching of dipoles as the temperature increases,
hence decreasing the polarization. As a result, the EC, PS and
Pr decrease with the increase of temperature.
High-field thermal energy conversion can be attempted
using ferroelectric loops using the Olsen cycle. The Olsen
cycle, proposed by Olsen et al. is an analogy of the Ericson
cycle, which can be utilized to produce electricity using a
high-field pyroelectric effect [7,35e38]. Olsen proposed that
since a traditional PeE loop operates in an anti-clockwise
manner to turn electricity into heat; it would be possible to
produce electricity using waste heat if the cycle can be
 S. Patel et al. / J Materiomics 2 (2016) 75e86 77

Fig. 1. X-Ray diffraction patterns of Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 (BCT-BZT-Sr) when x ¼ 0%, 5%, 10% and 15%.

Fig. 2. Scanning electron micrographs (SEM) of sintered pellets for the samples with Sr contents of (a) 0%, (b) 5%, (c) 10% and (d) 15%.
78 S. Patel et al. / J Materiomics 2 (2016) 75e86
Fig. 3. Polarization versus electric field (PeE) hysteresis loops as a function of applied electric field at a constant temperature of 30  C for Ba0.85Ca0.15
xSrx-
Ti0.9Zr0.1O3 samples when x ¼ 0%, (b) x ¼ 5%, (c) x ¼ 10% and (d) x ¼ 15%.
operated in a clockwise manner. The Olsen cycle allows for
rather high conversion efficiencies up to 37.5% of the Carnot
cycle (measured experimentally) [7,35e38], and consists of
two isothermal and two isoelectric field processes (see
Fig. 4(c)). The area under the cycle shows the energy con-
version density of the material. The Olsen cycle is completed
in four processes [7,35e38], i.e., process 1e2 is performed at
a constant lower temperature of TL as electric field increases
form lower limit (EL) to higher limit (EH), correspondingly,
polarization of the material increases; In process 2e3, heat
(QS) is supplied to the material, which increases the temper-
ature and produces lattice vibration. Thus material depolarizes
at a constant electrical field. This generates a large depolari-
zation current, which can be stored or used for powering
electronic equipment using suitable circuit. Temperature of the
material increases from a lower temperature (TL) to a higher
temperature (TH); In process 3e4, lowering of the electric field
from EH to EL is done at a constant temperature, TH. The
polarization also decreases due to the absence of electric field,
which generates a weak depolarization current. Finally, in
process 4-1, the extraction of heat from the system at a con-
stant electric field (EL) is done so that the material reaches to
its initial state and completes the cycle. A detailed discussion
on the Olsen cycle is available in a number of articles
[7,37,38]. The energy conversion density can be estimated by
Refs. [7,37,38]:
ZPmax
W¼ EdP ð1Þ
Pr
where W represents the energy conversion density in the ma-
terial, E is the applied external field and Pr and Pmax are the
remnant and maximum polarization, respectively. This cycle
was employed on the BCT-BZT-Sr compositions. Fig. 5(a),
(b), (c) and (d) show the results of the samples with Sr con-
tents of 0%, 5%, 10% and 15%, respectively. For the energy
conversion, EL and TL are kept constant at 0 kV/cm and 30  C,
respectively. However, Fig. 5 shows the effect of TH as a
function of EH. It is indicated that the energy density increases
with the increase of the temperature and electric field span.
This is due to a fact that the polarization increases as the
electric field increases. Hence, the amount of energy conver-
sion scales up. Similarly, the energy density also increases as
the TH increases due to the decrease of maximum polarization.
It is also interesting to note that the slope of energy conversion
differs from each other in the compositions. This effect can be
a result of shift in the Curie temperature of the materials due to
 S. Patel et al. / J Materiomics 2 (2016) 75e86
Fig. 4. Plot of (PeE) hysteresis loops under different temperature at a constant electric field the samples with Sr contents of (a) 0%, (b) 5%, (c) 10% and (d) 15%.
the addition of Sr. Fig. 6 shows the energy density for all the
compositions when EL ¼ 0 kV/cm, TH ¼ 90  C and
TL ¼ 30  C. The maximum energy conversion of 108 kJ/m3
appears in pristine BCT-BZT ceramics. However, for the
samples with Sr contents of 5%, 10% and 15%, the energy
density of 179 kJ/m3, 149 kJ/m3 and 200 kJ/m3 could be ob-
tained, respectively. The cycle parameters are 30e90  C and
0e20 kV/cm. Therefore, the addition of Sr improves the en-
ergy storage density by ~200% as compare to the parent
compound (BCT-BZT). Moreover, a maximum energy con-
version of 300 kJ/m3 is obtained for 15% Sr BCT-BZT (see
Table 1).
Table 1 shows a comparison of the Olsen cycle-based en-
ergy conversion density in bulk ferroelectric materials. Some
researchers applied the Olsen cycle on thin film ferroelectrics
and reported a great amount of energy conversion potential
[37e40]. However, thin films possess a small volume, hence it
cannot fulfill the energy requirements for practical application.
In Table 1, there are only bulk ferroelectric materials for the
comparison. However, most of the materials exhibit a great
converted energy density in a large temperature range, above
room temperature and under a high electric field. In order to
compare the performance of the composition, we selected
some materials, which have TL of <100  C or DE (EL
EH)
79
of <100 kV/cm (see Table 1). It is due to a fact that materials
having TL of >100  C or DE (EL
EH) of >100 kV/cm may
not be used in the practical applications. Clearly, the present
composition has a relatively large energy conversion potential
in small temperature and electric field ranges. Vats et al. [34]
reported the waste energy conversion using BCT-BZT, which
was found to be 87 kJ/m3 (see Table 1). However, compared to
the previously reported energy conversion, the energy con-
version obtained in this study can be increased by 200% due to
the addition of 15% Sr content. It can be concluded that for
small electric field and temperature change BCT-BZT-Sr is a
fairly promising material for thermal energy harvesting.
The temperature-dependent dynamic hysteresis behavior
was analyzed for all the understudy compositions. Figs. 7 and
8 show the coercive field (EC) and remnant polarization (Pr) as
functions of temperature at various electric fields. In Fig. 7(a),
there are the coercive field (EC) versus temperature (T ) log-
arithmic plots, shows a similar decay pattern of EC with T at all
the applied electric field. The dependence of ln EC on ln T was
determined by the linear least square-fitting method (with
R2 ~ 0.96e0.98). The scaling relation between EC and T can
be determined from the slope of ln EC versus ln T. An inset of
Fig. 7(a) shows an electric field dependence slope (a). Hence,
the dependence of EC and T can be written as
80 S. Patel et al. / J Materiomics 2 (2016) 75e86

Fig. 5. Energy conversion density as a function of applied higher electric field (EH) at different temperatures for Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 when (a) x ¼ 0%, (b)
x ¼ 5%, (c) x ¼ 10% and (d) x ¼ 15% when lower electric field (EL) and temperature (TL) are 0 kV/cm and 30  C, respectively.

ln EC ¼ a ln T þ YEC ð2Þ ln EC ¼ a1 ln T þ YEC ¼ ð0:0013E
0:65Þln T þ YEC ð3Þ

where a1 ¼ (0.0013E-0.65) and E is the applied electric field.

where a and YEC are slope and Y-intercept. For BCT-BZT, it
can be written as
Fig. 6. A comparison plot of energy conversion density versus higher electric
field (EH) for all the compositions when cycle is operated between 30 and
90  C at a lower electric field (EL) of 0 kV/cm.
In Eq. (3), YEC can be only calculated when T approaches to
zero. The ferroelectric dipoles freeze at absolute zero tem-
perature, and this behavior is totally different from the dipoles
at high temperature. The dipole wall motion is entirely
different at T ¼ 0. Therefore, we can neglect the effect of
Y-intercept because we do not deal with the effect on EC when
T ¼ 0. Moreover, YEc is only used to fulfill the validity of
linear fit. Eq. (3) can be rewritten as
ln EC ¼ ð0:0013E
0:65Þln T ð4Þ
For a constant electric field, contribution of E is negligible
as compared to the other factors. Hence, we can safely neglect
this factor and these assumptions are used in this work.
Therefore, for a constant electric field, Eq. (4) can be
expressed as
ln EC ¼
0:65 ln T ð5Þ
The scaling relation between Ec and T can be written as
EC f Ta1 or EC f T
0.65, where a1 is the dimensionless con-
stant. Similarly, the scaling relation between EC and T can be
written as EC f Ta2, EC f Ta3 and EC f Ta4 for the samples with
 S. Patel et al. / J Materiomics 2 (2016) 75e86 81

Table 1
Comparison of energy conversion potentials in bulk ferroelectric materials.
Materials Energy conversion (kJ/m3) TL ( C) TH ( C) DT ( C) EL (kV/cm) EH (kV/cm) DE (kV/cm) Reference
PZST 100 146 159 13 0 29 29 [35]
PZST 131 157 177 20 4 32 28 [41]
PMN-10PT 186 30 80 50 0 35 35 [3]
PMN-32PT 100 80 170 90 2 9 7 [42]
PZT (hard) 189 25 160 135 1 20 19 [8]
PZN-4.5 PT 217 100 160 60 0 20 20 [6]
8/65/35 PLZT (thick films) 888 25 160 135 2 75 73 [38]
PZT (soft) 92 25 160 135 1 20 19 [8]
PZN-5.5 PT 150 100 190 90 0 12 12 [7]
60/40 P(VDFeTrFE) 521 25 110 85 200 500 300 [37]
61.3/29.7/9 P(VDFeTrFEeCFE) 900 25 120 95 200 600 400 [36]
K[(Nb0.90Ta0.10)0.99Mn0.01]O3 629 120 160 40 1 50 49 [34]
Ba0.85Sr0.15Ti0.9Zr0.1O3 300 30 90 60 0 30 30 Present work
Bi0.5Na0.38 K0.12TiO3 1986 25 110 85 1 52 51 [43]
Bi0.5Na0.35 L0.15TiO3 1146 25 120 95 1 112 111 [43]
0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 87 20 120 100 1 10 9 [34]
0.88Bi0.5Na0.5TiO3-0.02SrTiO3-0.1Bi0.5Li0.5TiO3 2130 20 140 120 1 60 59 [40]
(Bi0.5Na0.5)0.915(Bi0.5K0.5)0.05 Ba0.02Sr0.015TiO3 1523 20 160 140 1 40 39 [39]

Fig. 7. Logarithmic plots of coercive field (EC) versus temperature (T ) under different electric fields for Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 when (a) x ¼ 0%, (b)
x ¼ 5%, (c) x ¼ 10% and (d) x ¼ 15%. The inset indicates the corresponding plots for slope versus electric field.

Sr contents of 5%, 10% and 15%, which are shown in Fig. 7(b), scaling relations for the samples with Sr contents of 5%, 10%
(c) and (d), respectively. The corresponding inset of Figures and 15% are EC f T
0.61, EC f T
0.56 and EC f T
0.63,
shows the variation of slopes with applied electric field. The respectively.
82 S. Patel et al. / J Materiomics 2 (2016) 75e86

It is assumed that a slight difference in the scaling exponent ln Pr ¼ b1 ln T þ YPr ð6Þ

should appear, which could be the effect of difference in
switching behavior due to applied electric field. Hence, the
estimated scaling relation can be explained based on the domain
switching as functions of E and T. The phenomenon in which the
ferroelectric material changes from one spontaneously polarized
state to another is due to electrical or mechanical loads known as
domain switching. The reversal of the spontaneous polarization
in a ferroelectric crystal is governed by two mechanisms, i.e., the
nucleation of new domains and the growth of these domains by
domain wall motion [31,44]. At low electrical fields, nucleation
is the slower mechanism and hence dominates the switching
process. At high electrical fields, domain wall motion de-
termines the rate of switching [31,44]. During this process, a
hysteresis loop increases. Above a particular electrical field,
further polarization stops, which may lead to its dielectric
breakdown [45]. Therefore, we only considered the saturated P-
E loops to avoid the effect of electric field.
The similar calculations were performed to obtain a
temperature-dependent relation for Pr. Fig. 8 shows ln Pr
versus ln T at different electric fields. Pr versus T plots for
BCT-BZT are shown in Fig. 8(a) and can be written as
where b1 represents the slope and YPr represents the Y-inter-
cept. It can be thus expressed as
ln Pr ¼ b1 ln T þ YPr ¼ ð0:0052E
1:59Þln T þ YPr ð7Þ
Taking the similar assumption, we can write the above
equation as
Pr fT b1 or Pr fT
1:59 ð8Þ
The similar scaling relation was established for BCT-BZT-Sr
having Sr contents of 5%, 10% and 15%, as shown in Fig. 8(b),
(c) and (d), respectively. The insets of the corresponding figures
show the electric field dependent slope. The scaling relation for
Pr versus T can be written as Pr f Tb2 or Pr f T
1.59, Pr f Tb3 or
Pr f T
1.36 and Pr f Tb4 or Pr f T
1.32 for the samples with Sr
contents of 5%, 10% and 15%, respectively.
Also, this polarization domain wall motion depends upon T.
Temperature is inversely proportional to the parameters EC, Pr
and PS. This is because the lattice vibration increases with the
increase in temperature, enhancing the rotation of domains and
decreasing the stability of the polarization. This behavior can
be explained by back-switching dependency of polarization on
the temperature [44,46]. In general, domain polarization

Fig. 8. Logarithmic plots of remnant polarization (Pr) versus temperature (T ) at different electric fields for Ba0.85Ca0.15
xTi0.9SrxZr0.1O3 when (a) x ¼ 0%, (b)
x ¼ 5%, (c) x ¼ 10% and (d) x ¼ 15%. The inset indicates the corresponding plots for slope versus electric field.
 S. Patel et al. / J Materiomics 2 (2016) 75e86
movement takes place in two steps, firstly, switchable polari-
zation in domain, which is known as PS and another is back-
switched polarization, which is known as Pr. Polarization
reaches to PS when the external electrical field is applied and,
it again comes to stable polarization Pr in the absence of
electrical field. Such a phenomenon is known as back-
switching polarization. Back-switching polarization (Pbc) can
be expressed by Ref. [46].
Pbc ¼ PS
Pr
Fig. 9(a), (b), (c) and (d) show the Pbc versus T plots at
various electric fields for the samples with Sr contents of 0%,
5%, 10% and 15%, respectively. In Fig. 9(a), back switching
polarization firstly increases with increase in temperature up to
315 K, and then decreases with temperature. The similar be-
haviors are also shown in Fig. 9(b), (c) and (d). It is indicated
that at 315 K, there should exist a phase transition. However, it
possesses a diffuse phase transition in this region. In the high-
field ranges, the relationship between PS-Pr and T obeys the
Arrhenius law [44,46].
PS
Pr ¼ P0 expð
EA Þ=ðkB TÞ
Fig. 9. Plots for back switching polarization (PS-Pr) versus temperature (T ) under different magnitude of electric field for Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 (a) x ¼ 0%,
(b) x ¼ 5%, (c) x ¼ 10% and (d) x ¼ 15% Sr content.
83
where EA is the average activation energy of trapped charge
defect such as oxygen vacancy, and P0 is a constant. The acti-
vation energy of the domain switching can be estimated by the
slope of ln (PS
Pr) versus 1/T. Therefore, Fig. 10(a), (b), (c)
and (d) show ln (PS
Pr) versus 1000/T plots for the samples
with Sr contents of 0%, 5%, 10% and 15%, respectively. A slope
of applied electric field dependence of the activation energy can
be fitted well to a simple exponential decay function. Fig. 11
shows the activation energy (EA) dependence on the electric
ð9Þ field. It decreases with increase in electric field. This can be an
effect of a large number of space charge carriers in oxida-
tionereduction processes due to the lower activation energy.
4. Conclusions
High-field thermal energy conversion was explored using
the Olsen cycle for Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 (BCT-BZT-
Sr) compositions. The maximum energy conversion density of
108 kJ/m3 was observed in the sample without Sr content
when the cycle was operated at 30e90  C and 0e20 kV/cm.
However, the energy conversion densities of 179, 149 and
ð10Þ
200 kJ/m3 were obtained for the samples with Sr contents of
5%, 10% and 15%, respectively, showing almost 200% im-
provements in the energy conversion density due to the
84 S. Patel et al. / J Materiomics 2 (2016) 75e86
Fig. 10. Plots of ln (PS-Pr) versus 1000/T under different magnitude of electric field for Ba0.85Ca0.15
xSrxTi0.9Zr0.1O3 samples when (a) x ¼ 0%, (b) x ¼ 5%,
(c) x ¼ 10% and (d) x ¼ 15%.
addition of Sr. Also, the maximum energy conversion potential
was 300 kJ/m3 for the sample with Sr content of 15% at
30e90  C and 0e30 kV/cm. The temperature-dependent
hysteresis characteristics of BCT-BZT-Sr (when x ¼ 0%,
5%, 10% and 15%) were studied. Ferroelectric scaling
Fig. 11. Activation energy versus electric field for all the Sr added composi-
tions of BCT-BZT.
relations for coercive field (EC) and remnant polarization (Pr)
as functions of temperature (T ) were estimated. The scaling
relations for EC versus T were EC f T
0.65, EC f T
0.61,
EC f T
0.56 and EC f T
0.63 for the samples with Sr contents
of 0%, 5%, 10% and 15%, respectively. The scaling relations
for Pr versus T were Pr f T
1.59, Pr f T
1.59, Pr f T
1.36 and
Pr f T
1.32 for the samples with Sr contents of 0%, 5%, 10%
and 15%, respectively. The temperature-dependent back-
switching kinetics of ferroelectric domain was clarified by the
Arrhenius law to analysis the hysteresis characteristics with
respect to the effect of temperature in an external electric field.
Acknowledgments
One of the authors (Rahul Vaish) acknowledges the support
from the Indian National Science Academy (INSA), New
Delhi, India, through a grant by the Department of Science and
Technology (DST), New Delhi, under INSPIRE faculty award-
2011 (ENG-01) and INSA Young Scientists Medal-2013.
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Satyanarayan Patel, PhD Scholar, Indian Institute in international peered reviewed SCI Journals. His present research interests
of Technology Mandi, India, Email: satyanarayan_ include ferroelectric materials for energy storage and solid state refrigeration.
patel@students.iitmandi.ac.in. Satyanarayan Patel Satyanarayan is also interested in FEM modeling, energy harvesting from
received a Bachelor degree in Mechanical Engi- mechanical vibration and heat, ferroelectric scaling laws and piezoelectric
neering with honors from Rajasthan Technical Uni- devices.
versity Kota, India in 2010 and Master degree in
Energy Engineering from Malaviya National Insti-
tute of Technology Jaipur, India in 2012. From 2012
onwards he has been enrolled as a PhD. research
scholar at Indian Institute of Technology Mandi,
India. He has published more than 40 research papers