Current Applied Physics 14 (2014) 396e402

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Current Applied Physics

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

Large piezoelectric strain observed in solegel derived BZTeBCT

ceramics
J. Paul Praveen a, Kranti Kumar a, A.R. James b, T. Karthik c, Saket Asthana c, Dibakar Das a, *
a
School of Engineering Sciences & Technology, University of Hyderabad, Hyderabad 500046, India
b
Ceramics and Composites Group, Defence Metallurgical Research Laboratory, Hyderabad 500058, India
c
Advanced Functional Materials Laboratory, Department of Physics, Indian Institute of Technology, Hyderabad 502205, India

a r t i c l e i n f o a b s t r a c t

Article history: High performance lead (Pb)-free piezoelectric ceramics with excellent piezoelectric properties is in great
Received 21 August 2013 demand for sensor and actuator applications. Barium zirconate titanateebarium calcium titanate [xBZT
Received in revised form e(1
x)BCT] (x ¼ 0.5) is one such lead free system, which exhibits high piezoelectric properties similar
11 December 2013
to lead zirconate titanate (PZT). In this study we report the synthesis and characterization of this lead
Accepted 27 December 2013
Available online 8 January 2014
free [xBZTe(1
x)BCT] (x ¼ 0.5) via wet chemical solegel method. Calcination of the BZTeBCT precursor
only at 1000  C (against 1300  C reported in the literature) for 4 h resulted in formation of single phase
nanoparticles (<50 nm) as confirmed by X-ray diffraction (XRD) and transmission electron microscopy
Keywords:
Piezoelectric
(TEM) studies. Highly dense and homogenous microstructure with 95% of the theoretical density was
Ferroelectric obtained by solid-state sintering of the green pellets at 1550  C. Remanent polarization (Pr) of 11.55 mC/
Lead-free cm2 and relative permittivity of 20,020 at the Curie temperature of 95  C were obtained. Electrically
Dielectric poled BZTeBCT ceramics samples exhibited high piezoelectric charge coefficients, d33 w 530 pC/N,
d33* w 942 pm/V, large electromechanical coupling coefficient kp w 0.45 and a large strain of 0.15%,
which are comparable to those of lead based piezoelectric ceramics. The excellent piezoelectric prop-
erties of this solegel derived BZTeBCT system has been analyzed and correlated to its structure in this
report.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction TiO3 (x ¼ 0.5) ceramics (hereafter abbreviated as BZTeBCT) by Liu

Piezoelectrics are a class of smart materials which can convert
mechanical energy into electrical energy and vice versa and they
are being widely used in various electronic and microelectronic
devices [1,2]. Lead zirconate titanate (PZT) based ceramics had been
the most widely used among them because of its superior piezo-
electric properties (d33 w 300e550 pC/N) [3]. However, such lead
based materials (which contain atleast 60% lead by weight) are
facing global concerns due to its high toxicity. Hence, the growing
demand of replacing these lead based piezoelectrics has made re-
searchers to focus more on development of efficient lead free sys-
tems [2].
BaTiO3(BT) is one of the most researched lead free piezoelectric
ceramics inspite of its lower Curie temperature (Tc w 120  C) and
inferior piezoelectric properties (d33 w 200 pC/N), but BT ceramics
exhibits high dielectric and ferroelectric properties [3]. Recently
developed lead free xBa(Zr0.2Ti0.8)O3e(1
x)(Ba0.7Ca0.3)
* Corresponding author. Tel.: þ91 4066794454.
E-mail address: ddse@uohyd.ernet.in (D. Das).
and Ren in 2009 using conventional solid state route have attracted
great attention due to its excellent piezoelectric properties
(d33 w 600 pC/N) [4]. A material whose composition lies at the
morphotropic phase boundary (MPB) shows good piezoelectric
properties. MPB between two ferroelectric phases causes instability
to the polarization state, which eases the rotation of the ferro-
electric domains [3,4]. BZTeBCT also shows a phase diagram similar
to the Pb-based systems like PZT, PMNePT, and PNNePZT, that is,
with a morphotropic phase boundary (MPB) consisting of a triple
point of paraelectric cubic phase (C), ferroelectric rhombohedral (R)
and tetragonal (T) phase [3]. Hence BZTeBCT is presently one of the
important candidates for many piezoelectric applications due to its
lead free nature with an MPB similar to lead based systems and
with superior piezoelectric properties reported in literature [4,5].
The conventional solid state reaction method used to prepare
BZTeBCT requires relatively higher calcination temperature
(1350  C) [4,5] and solid state sintering results in inhomogeneous
microstructure and impurity phases, which adversely affects the
properties of the system. In comparison, chemical solution syn-
thesis of ceramic do have advantages of chemical purity, very fine

1567-1739/$ e see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cap.2013.12.026
 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402
particle sizes and better homogeneity, which cannot be achieved by
solid state route [6]. Very few literature have reported on the
synthesis of BZTeBCT using wet chemical synthesis techniques [7e
9]. In this study, a wet chemical technique, viz. solegel method was
used to synthesis the BZTeBCT powders.
The phase pure material was subjected to optimized processing
conditions to achieve better sintered density of the sample with
homogenous and uniform microstructure of these BZTeBCT ce-
ramics. The dielectric, piezoelectric and the ferroelectric properties
obtained from the solegel synthesized BZTeBCT were measured
and have been correlated with its structure in this work.
2. Experimental
The xBa(Zr0.2Ti0.8)O3e(1
x)(Ba0.7Ca0.3)TiO3 (x ¼ 0.5) ceramic
was synthesized by using analytical reagent (AR) grade chemicals
obtained from SigmaeAldrich chemicals, USA. The starting mate-
rials used for the solegel synthesis of BZTeBCT were Barium ace-
tate (Ba(CH3COO)2), Zirconium oxychloride (ZrOCl2$8H2O), calcium
nitrate tetrahydrate (Ca(NO3)2$4H2O) and titanium isopropoxide
(C12H28O4Ti) of >99% purity. Required quantity of Barium acetate,
according to the stoichiometric ratio, was added to acetic acid and
stirred till it got dissolved completely. Stoichiometric ratios of zir-
conium oxychloride and calcium nitrate tetrahydrate were also
taken in ethanol and stirred till it got completely dissolved. After
complete dissolution, the three solutions prepared separately were
mixed together and required quantity of titanium isopropoxide was
added to it. The precursor solution so obtained was continuously
stirred and heated at 100  C for about 4 h, which resulted in pre-
cipitate gel formation. The resultant gel was dried overnight and
the solidified lumps were ground to fine powders using a mortar
and pestle.
Calcination temperature was optimized by calcining the as-
synthesized powders at 900e1100  C for 4 h to get phase forma-
tion and to remove the unreacted materials from the as-synthe-
sized powder. The calcined powders were subjected to X-ray
diffraction studies to confirm phase formation. The calcined pow-
ders were subjected to ball milling in a planetary ball mill (Fritsch
Pulverisette 7) for 2 h to reduce the increased particle sizes due to
calcination. The calcined milled powders was mixed with polyvinyl
alcohol (PVA) and compacted into pellets of 1 cm diameter and
0.15 cm thickness in high chromium high carbon hardened steel die
using a uniaxial hydraulic press at an applied pressure of 375 MPa.
The green samples were initially subjected to binder burnout at
500  C for 2 h with a slow heating rate of 1  C/min. After removal of
the binder the samples were subjected to sintering in a high tem-
perature programmable furnace. The sintering of the green pellets
was performed at 1550  C for 2 h at a heating rate of 5  C/min and
also cooled down with the same heating rate. The density of the
sintered pellets was estimated using the Archimedes’ method
following the ASTM standard (C373eC388). The final sample ge-
ometries for the measurements of the properties were similar to
the IEEE standards [10].
A Bruker D8 Advance X-ray diffractometer was used to analyze
the calcined powders and sintered pellets with qe2q geometry
using Cu Ka radiation in the 2q range in between 20 and 80 . The
microstructural analysis of the sample was performed on sintered
pellets using a HITACHI S-3400N SEM. Transmission electron mi-
croscopy studies were conducted using a Tecnai G2 TEM to observe
and determine the particle size of the calcined powders. The sin-
tered circular disc samples were polished and silver paste was
applied on both faces of the disc to make electrical contact for the
dielectric properties measurements. The silver paste coated sam-
ples were fired at 500  C and soaked for 15 min to form proper
electrodes.
397
Polarization versus electric field measurements (P vs E hyster-
esis loops) were conducted using a Piezoelectric Evaluation System,
TF analyzer 2000 from M/s aixACCT GmbH. Polarization vs Electric
field (P vs E) measurements were carried out using a triangular
waveform at 1 Hz. Samples with the highest density measured from
Archimedes method were subjected to electrical poling at a field of
1 kV mm
1 for 30 min at 100  C immersed in a silicone oil (Dow
Corning DC-704Ò) bath and cooled with the field. After aging for
24 h the poled samples were used to determine the piezoelectric
charge coefficient using a SS01 Piezo-d meter from Sensor Tech-
nology Limited; Canada. The dielectric measurements were carried
out on an Agilent E4980A precision LCR meter with a frequency
range of 20 Hze2 MHz. The LCR meter was interfaced with a
computer controlled programmable temperature controller and
the dielectric data was measured for a temperature range of 35  Ce
145  C at a heating rate of 1  C min
1.
Piezoelectric strain measurements (strain vs electric field) were
also carried out using the same Piezoelectric Evaluation System.
The maximum applied electric field for bipolar measurements were
3 MV/m at 1 Hz. Dynamic piezoelectric charge coefficient was
measured by taking the ratio of maximum strain to peak electric
field, Smax/Emax, from the unipolar strain measurements. The
maximum electric field for unipolar measurements was 0.7 MV/m
at a frequency of 0.1 Hz. Resonance data were acquired using an
Agilent E4980A precision LCR meter in the frequency range from
100 kHz to 600 kHz on poled samples. The planar electromechan-
ical coupling factor kp was calculated following IEEE standards [10]
and using the following expression,
k2p Df h i
2
¼ ðsp Þ
1 þ h21 (1)
1
k2p f ð1 þ sp Þ
where Df is the difference between the lowest frequency of anti-
resonance and resonance, f is frequency, sp is the planar Poisson’s
ratio and h1 is the lowest root derived from the following Eq. (2),
J1 ðh1 Þ ¼ 1
sp (2)
where J1 is the modified quotient of Bessel (cylinder) functions.
3. Results and discussion
The as-synthesized powders were calcined at various temper-
atures, 900  C, 1000  C and 1100  C for 4 h to determine the
Fig. 1. X-ray diffraction spectra of BZTeBCT calcined at various temperatures.
398 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402
optimized calcination temperature for phase formation. Fig. 1
shows the X-ray diffraction spectra of the calcined (calcination of
the as-synthesized powders) BZTeBCT powders calcined at
different temperatures. XRD peaks obtained from powder calcined
at 900  C had few impurity peaks (results from the unreacted ox-
ides, which is not clearly visible in Fig. 1, as the high intensity peaks
have suppressed the visibility of unreacted small peaks) compared
to those obtained at 1000  C and 1100  C, indicating incomplete
phase formation at 900  C. Not much difference in the powder
diffraction pattern is observed for powders calcined at 1000  C and
1100  C. With increase in the calcination temperature the impurity
phase diffused into BZTeBCT lattices to form a solid solution. Hence
the calcination temperature of BZTeBCT was fixed at 1000  C for
4 h.
The calcination temperature observed in this study is w300  C
less than that reported for the conventional solid state reaction
process [4,5,11]. The reduced calcination temperature obtained in
this study may be due to the small particle size of the precursor
powders resulted from solegel synthesis process. Crystallite size of
the calcined milled powders was estimated using Debye Scherrer
relation as given in Eq. (3) below [12],
0:9l
d ¼
b cos q
where 0.9 is the shape factor, l is the X-ray wavelength, 15.417 nm,
b is the line broadening at half the maximum intensity in radians
and q is the Bragg’s angle. The average crystallite size of BZTeBCT
was estimated to be ‘d’ w 35e40 nm.
Fig. 2 shows the X-ray diffraction spectra of sintered (at 1550  C
for 2 h) BZTeBCT sample and single-phase perovskite structure is
evident in the room temperature XRD data. The inset of Fig. 2 shows
the split (200) and (211) reflections, which indicates the coexis-
tence of rhombohedral and tetragonal phases in the system. MPB
for BZTeBCT ceramics, reported by Liu et al. [4] and other re-
searchers, too consists of region of coexisting rhombohedral (R3m)
and tetragonal (P4mm) [13,14] phases.
The peak splitting observed for (200) peak can be attributed to
the split of (002) and (200) contribution from tetragonal reflection
and also the contribution from the rhombohedral peak due to
presence of MPB. The low angle of the split peaks corresponds to
combination of the (002) peak from tetragonal and rhombohedral
phase and the higher angle corresponds to (200) tetragonal phase.
Fig. 2. X-ray diffraction spectra of sintered (1550  C) BZTeBCT with inset showing
peak splitting of (200) and (211) peaks.
The intensity of the tetragonal peaks in both the (200) and (211)
peaks is predominant compared to the rhombohedral peak in-
tensity. Similar peak splitting has been observed and analyzed by
Ehmke et al. [14].
Transmission electron microscopy (TEM) studies were carried
out for calcined and milled BZTeBCT powders. Fig. 3 shows the TEM
image of calcined and milled BZTeBCT particles. The average par-
ticle size estimated from TEM analysis was measured to be w35e
50 nm, which confirms the results obtained from XRD line broad-
ening of the calcined and milled powder. The selected area
diffraction (SAD) pattern, shown in the inset of Fig. 3, confirms the
crystalline nature of BZTeBCT powder. High resolution TEM image
of a selective particle was also taken, where lattice fringes
(d110 w 0.28 nm) is clearly observed. The measured interplanar
spacing value of d110 from TEM micrograph correlates well with the
corresponding ‘d’ spacing value obtained from the X-ray diffraction
data for the (110) plane. The lattice fringes also do indicate the
formation of well crystallized BZTeBCT synthesized by solegel
synthesis method.
Fig. 4a shows the SEM micrograph of the polished surface of the
pellet sintered at 1550  C for 2 h. The SEM micrograph shows a
homogenous distribution of grains with a dense packed micro-
structure and the grain size was measured to be w10e20 mm.
(3)
Elemental mapping, as shown in Fig. 4b, of the sintered pellet re-
veals the homogenous distribution of the constituent elements
throughout the microstructure. The BZTeBCT sample sintered at
1550  C for 2 h has resulted in a density of w95% of the theoretical
density, which was measured by Archimedes method following the
ASTM standard (C373eC388). Both density and grain size do have
an important effect on the piezoelectric properties of the material,
hence selection of appropriate sintering schedule (both peak tem-
perature and soaking time) is important in achieving good piezo-
electric properties. High sintering temperature generally results in
deformation and non-stoichiometry in the BZTeBCT ceramics [5].
To avoid compositional changes calcined powders of the same
composition of the ceramics are generally used as supporting
powders during sintering at elevated temperatures. Calcium from
BZTeBCT reacts with the alumina crucible resulting in stoichiom-
etry loss, hence ZrO2 powder bed has been used to support the
pellets during sintering and the temperature was elevated to as
high as 1550  C in this study.
Polarization versus electric field measurements (PeE hysteresis
loops) were carried out using a triangular waveform at a frequency
of 1 Hz and are shown in Fig. 5. BZTeBCT sample showed a remnant
polarization (Pr) of 11.55 mC/cm2 and a coercive field (Ec) of
0.166 kV/mm. The current was also measured for the same electric
field, where the current shows a maximum of 1.7 mA with increase
in electric field and reduces to zero with further increase in the
electric field. The remnant polarization is higher than those re-
ported in literature synthesized by any wet chemical synthesis
routes [7e9] and also comparable to those obtained by Wang et al.
for BZTeBCT ceramics synthesized by conventional solid state re-
action method followed by calcination at 1300  C and sintering at
1540  C. The high value of Pr could possibly be attributed to any of
the following: uniform distribution of grain sizes, absence of
domain-wall pinning centers, low defect density, compositional
homogeneity, etc. [3]. Low coercive field (Ec) shows that the BZTe
BCT ceramic is soft with respect to the electric field because the free
energy profile for polarization rotation is anisotropically flattened
at the MPB [4], hence very low field is required to align the domains
easily. The coercive field has been used in determining the poling
field required to align the ferroelectric domains of BZTeBCT ce-
ramics. Very low poling electric field makes the polarization
switching insufficient. Excessive poling field also tends to over-pole
the samples incorporating physical damages leading to dielectric
 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402 399

Fig. 3. TEM micrograph of calcined and milled BZTeBCT at 1000  C.

breakdown of the samples [11]. The optimum poling field for BZTe
BCT ceramics is about three times that of coercive field (Ec). From
the hysteresis loop (P vs. E measurement) the required field for
poling was estimated depending on the sample thickness. The
sintered samples were electrically poled at 1 kV/mm at 100  C for
30 min.
Piezoelectric charge coefficient, d33, was measured using SS01
Piezo-d meter and the d33 of the samples was found out to be
w530 pC/N, which is the highest value reported so far for BZTeBCT
ceramics synthesized by any wet chemical routes [7e9]. In our
earlier study we could achieve d33 w 490 pC/N for solegel derived
BZTeBCT ceramics with a sintered density of 93% of the theoretical
density [22]. The room temperature d33 obtained in this investi-
gation is better than those of PZT-5A,4 and is comparable to many
Pb free piezoelectric ceramics reported in the open literature [2e
4,13].
Fig. 6a shows the electric field induced strain hysteresis loop for
BZTeBCT ceramics. The samples were poled before acquiring the
strain data. A large strain of 0.15% was obtained under a relatively
low electrical field of 3 MV/m for the positive field and a strain of
w0.13% for the negative field. The bipolar loop shows the changes
in strain from the remnant state to the strain at maximum applied
electric field.
A very limited hysteresis has been observed with such a large
strain as seen in Fig. 6a, such high strain behavior in such soft pi-
ezoelectrics could be attributed to the easy motion of the ferro-
electric domains and limited effect of pinning of these domains due
to the internal bias field [13]. Poling of piezoelectric ceramics at
elevated temperatures could assist the re-orientation of ferroelec-
tric domains. The piezoelectric coefficient increases by 40% when
the field applied during poling is maintained while cooling the
samples through the Curie temperature [11,13]. Moreover opti-
mized poling conditions such as proper poling temperature and
appropriate poling voltage is required to induce such high strain
and obtain enhanced piezoelectric properties in BZTeBCT. It is
assumed that poling at appropriate temperature also assists in

Fig. 4. a. SEM micrograph of sintered BZTeBCT at 1550  C for 2 h b. Elemental mapping of BZTeBCT sintered at 1550  C.
400 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402
Fig. 5. Polarization and current vs electric field e hysteresis loop.
charge carrier accumulation at the grain boundaries inducing an
internal bias field that can enhance the piezoelectric response of
the proper poled samples [11,13,15].
Fig. 6b shows the unipolar strain loop for BZTeBCT ceramics at
poled state. The maximum applied field for unipolar measurements
was 0.7 MV/m at a frequency of 0.1 Hz. The samples were poled
before acquiring the strain data. A maximum strain of w0.066% is
obtained under a relatively low electrical field of 0.7 MV/m. The
Fig. 6. a. Bipolar strain vs electric field measurement for poled BZTeBCT. b. Unipolar
strain measurements of BZTeBCT poled sample.
converse piezoelectric effect is measured from the ratio of the
maximum strain to peak electric field Smax/Emax, which was
calculated to be 942 pm/V. This compares well with the Smax/Emax of
900 pm/V reported for 50BZTe50BCT [14] measured for a
maximum electrical field of 0.5 MV/m. The large strain and high
converse piezoelectric coefficient measured at such low electric
field in this system clearly shows the soft elastic nature of the
crystal lattice of BZTeBCT system. The enhanced piezoelectric
behavior in BZTeBCT could be attributed to the presence of the MPB
reported by Liu and Ren [4], where the flattening of the energy
barrier near the MPB facilitates the easy rotation of the polarization
vector between tetragonal <001> and rhombohedral <111> po-
larization directions. Also the presence of tricritical point, where a
cubic phase can also co-exist along with the rhombohedral and
tetragonal phase, as reported by Damjanovic et al. [16], or the
possibility of existence of an additional orthorhombic phase, as
reported by Keeble et al. [17], could reduce the energy barrier
further allowing easy rotation of the polarization vectors and po-
larization extension leading to high strain in the system.
Fig. 7a shows the temperature dependence of relative permit-
tivity (dielectric constant) of BZTeBCT ceramics sintered at 1550  C
at 1 kHz and 100 kHz frequencies. The relative permittivity was
measured for a temperature range of 35  Ce145  C at a heating rate
of 1  C min
1. The relative permittivity, εr of BZTeBCT ceramic is
seen to increase with increase in temperature and reaches
maximum at the Curie temperature (Tc). The phase transition
temperature is seen to be w95  C (highest value of εr ¼ 20,020),
which is similar to that obtained by other researchers [14e16]. The
Fig. 7. a. Relative permittivity vs temperature for poled BZTeBCT. b. Inverse dielectric
permittivity at 1 kHz as a function of temperature (inset graphs of log (1/ε
1/εm)).
 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402
rhombohedral to tetragonal phase transition reported at 34  C by
Damjanovic et al. [16] is not observed here since the relative
permittivity was measured from 35  C. The dielectric constant of
the normal ferroelectrics above the Curie temperature (for T > T0)
can be expressed by CurieeWeiss law described by:
εr ¼ CðT
To Þ
1
where C is the CurieeWeiss constant and To is the CurieeWeiss
temperature. The CurieeWeiss constant C reflects the nature of the
ferroelectric transition. The inverse dielectric constant versus
temperature at 1 kHz was plotted and fitting the curve in the
paraelectric regime resulted in determining the onset of Curiee
Weiss behavior (DTm) or the degree of diffuseness, which is given
by the following equation [18,19],
DTm ¼ Tcw
Tm ð CÞ
where Tcw represents the temperature from which εr starts to
follow the CurieeWeiss law and Tm denotes the temperature at
which εr reaches the maximum value. The estimated DTm was
found to be w36  C.
To evaluate the phase-transition modes an empirical compre-
hensive power law [18,19] has been used, which is applicable to the
dielectric spectra of an intermediate type (i.e., neither normal nor
relaxor ferroelectric), and is given by
1 1 ðT
Tm Þg

¼
εr ðεr Þm C
where ‘g’ is the diffuseness exponent and ‘C’ is the CurieeWeiss
constant. The estimated g is w1.5, which was extracted from the
plot shown in Fig. 7b of log (1/εr
1/(εr)m) vs. log (T
Tm). Values
of g can extend numerically from 1 to 2, depending on the phase-
transition modes. For Eq. (6) reverts to the CurieeWeiss law for
g ¼ 1, whereas for g ¼ 2, Eq. (6) is equivalent to the quadratic law.
The diffuseness exponent g indicate the normal ferroelectric phase
transition mode [18].
Various electromechanical parameters were calculated from the
resonance measurements obtained from the solegel derived BZTe
BCT ceramics. The resonant and anti-resonant frequencies were
obtained from the admittance peaks respectively of the admittance
against frequency scan. The resonant fr and anti-resonant fre-
quencies fa were used to evaluate the values of electromechanical
coupling coefficient from Eqs. (1) and (2) described before for the
solegel derived BZTeBCT samples. The electromechanical coupling
factor of a piezoelectric material is an indicator of the effectiveness
with which a piezoelectric material can transform its input elec-
trical energy into mechanical energy [3]. The planar coupling factor
(kp) was calculated using the Eqs. (1) and (2) given above and was
found to be 0.45, which is comparable to the results obtained by
other researchers for BZTeBCT ceramics synthesized using solid
state route [5,15].
The piezoelectric properties have a strong dependence on the
grain size of the ceramics as reported in the literature for BZTeBCT
ceramics also. It has been reported that grain size of w10 mm is
critical in developing high performance BZTeBCT ceramics [5]. In
the present work also a grain size of w10 mm is observed in the
resultant microstructure of the sintered BZTeBCT ceramics. The
grain size dependence of piezoelectric properties could be attrib-
uted to the change in domain structure with increase in grain size
[16,20]. The piezoelectric properties in a system could arise from
two main contributions i.e. intrinsic and extrinsic contributions.
Intrinsic contributions are due to the relative ions shift to maintain
the ferroelectric crystal structure and the extrinsic contribution
401
arises mainly from the motion of the domain walls [20]. Grain size
influences the domain structure, the balance of depolarization
energy and the domain wall energy. Moreover the grain size effect
on piezoelectric properties in perovskite-type ferroelectrics is
known to be strongly influenced by the movement of the 90
domain walls [21]. The correlation between the domain size (d) and
(4) the grain size (t) can be expressed as,
" ! #1=2
s
d ¼ $t (7)
ε* P02
where, s is the energy density of the domain wall, Po is the spon-
taneous polarization and ε* effective dielectric constant, respec-
tively. The domain wall motion is a collective behavior and the
domain walls with small areas will react more energetically to the
influence of external electrical field or stress. In the present work,
(5)
the samples were prepared using optimized conditions to attain the
grain size of >10 mm. Therefore, contribution from clamping of
domain walls at grain boundaries due to very small grain sizes is
eliminated [21]. Due to the absence of grain boundary the domain
wall motion inside a large grain is relatively easier when compared
to a piezoelectric with a smaller size grains. The coexistence of the
mixed phases within the individual grain also enables the domain
walls to rotate easily within the grain without much resistance
from the grain boundaries (which pins the domain wall movement
and hence are high energy barriers) as observed in the present case
for the samples with homogeneous microstructure and having
(6) large grain sizes [14]. In this work, the observed piezoelectric
properties (d33, kp, d33*, strain) are comparable to most of the lead
based piezoelectrics and can primarily be attributed to the
composition (close to the MPB composition of the system) with the
coexistence of rhombohedral and tetragonal phases and dense
homogeneous microstructure with large grain sizes.
High density and homogeneous microstructure are among the
most desired features for any piezoelectric material in obtaining
good piezoelectric and ferroelectric properties [5]. Solegel syn-
thesis method used here in synthesis of BZTeBCT resulted in dense
and uniform microstructure with optimal grain size, which has led
to such excellent piezoelectric and ferroelectric properties. Such
lead-free BZTeBCT ceramics with excellent piezoelectric and
ferroelectric properties could be a candidate material for trans-
ducer and actuator applications.
4. Summary
Lead free piezoelectric ceramics “barium zirconate titanatee
barium calcium titanate” [xBZTe(1
x)BCT](x ¼ 0.5), were suc-
cessfully been prepared by solegel synthesis method. Calcination of
the as-synthesized BZTeBCT powders at 1000  C resulted in the
formation of complete perovskite phase. X-ray diffraction (XRD)
and transmission electron microscopy (TEM) studies confirmed the
formation of single phase BZTeBCT ceramics with particle sizes
<50 nm. Sintered samples at 1550  C for 2 h resulted in a sintered
density of w95% of theoretical density. Scanning electron micro-
scopy of the sintered sample indicate a very uniform and dense
microstructure, with an average grain size of about 10 mm. High
piezoelectric coefficient of d33 w 530 pC/N, d33* of 942 pm/V (at low
field of 0.7 MV/m), kp of 0.45, strain of 0.15%, Pr of 11.55 mC/cm2 and
relative permittivity of 20,020 at the Curie temperature of 95  C
indicated a homogeneous microstructure of the sample with
optimal grain sizes obtained via optimum processing of the ce-
ramics. The excellent piezoelectric and ferroelectric properties of
this lead-free ceramics can primarily be attributed to the MPB
composition of this ceramics with simultaneous existence of more
402 J.P. Praveen et al. / Current Applied Physics 14 (2014) 396e402
than one crystallographic phases at room temperature and homo-
geneous microstructure.
Acknowledgments
The authors are grateful to the financial support received from
the University Grants Commission through UPE-Phase-II project
(UH/UGC/UPE Phase-2/Interface studies/Research projects/R-4)
and the School of Engineering Sciences and Technology (SEST) at
the University of Hyderabad. The help extended by Mr. Mahesh, Mr.
Ajeet Kumar, of CCG at DMRL Hyderabad in carrying out the
piezoelectric measurements is greatly appreciated.
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