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CERAMICS
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Ceramics International 41 (2015) 1980–1985
www.elsevier.com/locate/ceramint

Ferroelectric, piezoelectric and mechanical properties in lead free (0.5)Ba

(Zr0.2Ti0.8)O3–(0.5)(Ba0.7Ca0.3)TiO3 electroceramics
A Srinivasa,n, R.V. Krishnaiaha, V.L. Niranjania, S.V. Kamata, T. Karthikb, Saket Asthanab
a
Advanced Magnetics Group, Defence Metallurgical Research Laboratory, Hyderabad 500058, India
b
Advanced Materials Research Laboratory, Department of Physics, Indian Institute of Technology, Yeddumailaram, Medak 502205, India
Received 30 June 2014; received in revised form 9 August 2014; accepted 28 August 2014
Available online 26 September 2014

Abstract

Barium zirconate titanate–barium calcium titanate [(0.5)BZT–(0.5)BCT], a solid solution ceramic, was synthesized by solid state route and its
structure, microstructure, dielectric, ferroelectric, piezoelectric and mechanical properties were investigated. Unipolar and bipolar strain loops
with minimal hysteresis were observed from strain measurements. The d*33 values increased with increase in electric field, reached a maximum of
1257 pm/V at a field of 0.6 kV/mm, subsequently decreased to 530 pm/V at a field of 4.1 kV/mm and showed slim hysteresis. A high value of
dielectric constant (εr
9700) was recorded with the variation of frequency at a temperature around 85 1C (Tc) indicating frequency independent
transition. P vs. E and I vs. E hysteresis measurements confirmed the intrinsic ferroelectric character with Pr of
9.1 mC/cm2 and EC of

0.3 kV/mm. Polarization vs. electric field measurements at different electric fields showed slim and saturated hysteresis behaviour indicating
a coarse grain structure. In the synthesized (0.5)BZT–(0.5)BCT, Vickers hardness, Young's modulus and fracture toughness were evaluated, and
compared with those of lead based compounds and were found to be on par with them.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Powders: solid state reaction; C. Dielectric properties; C. Ferroelectric properties; E. Actuators

1. Introduction
Piezoelectric materials are an important class of functional
materials which convert mechanical energy to electrical energy
and vice-versa. During the past 50 years lead based piezoelectric
ceramics, especially lead zirconate titanate (PZT), have been the
material of choice in various sensors and actuators. However, the
use of lead containing materials causes serious environmental and
health related hazards due to its high toxicity. Therefore, in recent
years, there has been a great impetus to develop environment
friendly piezoelectric ceramics to replace the currently existing
lead based ceramics [1,2].
Barium titanate (BaTiO3) and isovalent element substituted
BaTiO3 are amongst the most promising lead free piezoelectric
materials for use in capacitors, tunable microwaves, optoelectronic
and memory devices [3]. Zr doped BaTiO3 (BaZrxTi1 xO3) and
n
Corresponding author. Tel.: þ91 4024586835; fax: þ 91 4024340884.
E-mail address: adirajs@dmrl.drdo.in (A. Srinivas).
Ca doped BaTiO3 (Ba1 xCaxTiO3) are the two most important
derivatives of BaTiO3 and have attracted the maximum attention
[4]. The material of our interest, (0.5)Ba(Zr0.2Ti0.8)O3–(0.5)
(Ba0.7Ca0.3)TiO3 (abbreviated as BCZT), is a solid solution of
two terminal compounds, i.e., rhombohedral Ba(Zr0.2Ti0.8)O3
(BZT) and tetragonal (Ba0.7Ca0.3)TiO3 (BCT). In this solid
solution, Ba and Ca ions occupy the A sites of the ABO3
perovskite structure with the ionic radius of Ca2 þ (0.99 Å) being
smaller than that of Ba2 þ (1.35 Å) and Zr and Ti ions occupy the
B-sites with the ionic radius of Zr4 þ (0.98 Å) being larger than that
of Ti4 þ (0.72 Å) [1,2]. It has been shown that the addition of Zr4 þ
and Ca2 þ to BaTiO3 has the effect of imparting new functionalities
[5]. Moreover, Zr4 þ ion is chemically more stable than Ti4 þ and
has a larger ionic size which expands the perovskite lattice.
Therefore, the substitution of Ti by Zr depresses the conduction
caused by hopping between Ti4 þ and Ti3 þ and thus also decreases
the leakage current of the BaTiO3 system [3,4]. The temperature
dependence and reliability of dielectric property of barium titanate
are also significantly improved by Ca2 þ ions addition to BaTiO3

http://dx.doi.org/10.1016/j.ceramint.2014.08.127
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 A Srinivas et al. / Ceramics International 41 (2015) 1980–1985
lattice [5,6]. It leads to significant suppression of the dielectric loss
and the temperature coefficient of dielectric constant but only a
slight change in the Curie temperature [7]. Apart from this, the
main reason for choosing this composition i.e., (0.5)Ba(Zr0.2Ti0.8)
O3–(0.5)(Ba0.7Ca0.3)TiO3 is the presence of a morphotropic phase
boundary (MPB) in its phase diagram at this composition which
favors strong ferroelectric and piezoelectric effects [8]. A converse
piezoelectric coefficient of 0.057% at 500 kV/mm was reported for
this particular composition. However, no systematic study has been
carried out on the structure, microstructure, dielectric, ferroelectric
and piezoelectric properties.
Electromechanical actuators directly transform input elec-
trical energy into mechanical energy. Of the many types of
actuator materials, piezoelectric and electrostrictive ceramics
are widely used in applications requiring high generative force,
high frequency operation, accurate displacement, quick
response or small device size. The piezoelectric coefficient
(dij), which determines the level of induced strain at a given
electric field, is the most important parameter which controls
the actuator performance [9]. However, it is also necessary to
study the mechanical properties such as Young's modulus
which is necessary to convert the strain to force delivered by
Fig. 1. (a)X-ray diffraction patterns of (0.5)BCT–(0.5)BZT samples sintered at various temperatures along with the (b and c) de-convoluted XRD pattern in the
selected 2θ-range sintered at 1500 1C.
1981
the actuator as well as hardness and fracture toughness which
determine the reliability during actuator operation. For this
ceramic, no reports are available in literature on its mechanical
properties. In the light of the above, the present study focuses
on the preparation of lead free 0.5(BZT)–0.5(BCT) by solid
state sintering route and its subsequent structural, microstruc-
tural, dielectric, ferroelectric, piezoelectric and mechanical
properties characterization.
2. Experimental procedure
Polycrystalline samples of (0.5)Ba(Zr0.2Ti0.8)O3–(0.5)
(Ba0.7Ca0.3)TiO3 solid solution system were prepared by the
solid state sintering technique. Barium carbonate (BaCO3),
titanium dioxide (TiO2), calcium carbonate (CaCO3) and
zirconium oxide (ZrO2) from Sigma Aldrich, USA, having
99.99% purity were used as precursors. The weighed powders
(as per stoichiometric calculations) were pre-sintered at
1200 1C for 5 h, re-ground, mixed with an organic binder
(0.1% polyvinyl alcohol) and compacted using a pressure of
2  106 kg/m2 to get discs of 15 mm diameter and 1.5 mm
thickness. The discs were heated at 500 1C for 30 min for
1982 A Srinivas et al. / Ceramics International 41 (2015) 1980–1985

removing the binder and then finally sintered at 1500 1C for sample measured by the Archimedes method is about 92% of
5 h in air atmosphere. X-ray diffraction (XRD, PAN analytical the theoretical density.
X'PERT PRO) studies were carried out using Cu Kα (Δ ¼ 1.54 Fig. 3 shows the temperature dependent dielectric constant
Ǻ) radiation. To carry out electrical measurements, the sintered for (0.5)BCT–(0.5)BZT sample measured at various frequen-
discs were electroded with silver on both surfaces and dried at cies ranging from 1 kHz to 1 MHz. The dielectric constant
500 1C for 30 min. The samples were poled electrically at measured at room temperature is about
3000, which is
1.5 kV/mm field for 30 min by using a variable power supply similar to that reported earlier [11–13]. It can also be seen from
(0–5000 V). Ferroelectric and piezoelectric measurements Fig. 3 that (0.5)BCT–(0.5)BZT shows a frequency independent
were carried out using a TF analyzer 2000, aixACCT Systems, behaviour with a strong ferroelectric to paraelectric transition
Germany. The microstructure was observed by using field around 80–85 1C which is also in good agreement with earlier
emission scanning electron microscopy (ZEISS make). The reports [11–13]. The value of dielectric constant (εr) around the
high temperature dielectric measurements were carried out Curie temperature (Tc) is about 9700. However, the phase
using an Agilent 4294A Impedance Analyzer. The d33-values transition near Tc is not very sharp as observed in ideal
were measured using a Piezo-D meter with model number ferroelectrics such as BaTiO3. Rather, it exhibits slightly broad
SS01 of Sensor Technologies Ltd, Canada. Young's modulus and diffused phase transition (DPT) behaviour which could be
and hardness were measured using a CSM Instruments attributed to cation disorder which causes microscopic hetero-
(UNHT, Switzerland) based Nanoindenter with a Berkovich geneity in this compound. A similar kind of observation was
indenter and the fracture toughness was determined using a reported when Sn was doped at Ti site in BaTi1  xSnxO3 (with
microhardness tester with a Vickers indenter. xo 0.15) [14,15]. The Curie temperature of (0.5)BCT–(0.5)
BZT is also reduced to 80–85 1C from 120 1C for the parent
3. Results and discussion compound BaTiO3. The reduction of the Tc may be caused
by the incorporation of stable Zr4 þ into the Ti site [15–17].
Fig. 1(a) depicts the X-ray diffraction patterns for (0.5)
BCT–(0.5) BZT sintered at different temperatures. The XRD
patterns reveal that (0.5) BCT–(0.5) BZT samples sintered at
temperatures below 1500 1C show some secondary phase
formation (as indicated by arrows in Fig. 1(a)) whereas the
samples sintered at 1500 1C for 5 h duration exhibit pure
perovskite phase which is in agreement with respective JCPDS
card no 05-0626 and 85-0368. The observation of single phase
perovskite for the sample sintered at 1500 1C can be attributed
to the solid solubility of both Ca2 þ at Ba-site and Zr4 þ at Ti-
site [10]. The (0.5)BCT–(0.5)BZT sample sintered at 1500 1C
stabilizes in a polycrystalline perovskite structure along with
tetragonal and rhombohedral phases (i.e. MPB formation),
which is clear from the splitting of (002)/(200) peaks at around
2θ
451 as well as the splitting of the (202)/(22 0) peaks
around 2θ
661 as shown in Fig. 1(b) and (c).
Field emission scanning electron micrograph of the (0.5)
BCT–(0.5)BZT sample sintered at 1500 1C (displayed in
Fig. 2) clearly shows a dense microstructure with a grain size Fig. 3. Temperature and frequency dependent dielectric constant for (0.5)
in the range between 8–10 μm. The bulk density of the sintered BCT–(0.5)BZT sample.

Fig. 2. FESEM micrograph of (0.5)BCT–(0.5)BZT sample sintered at 1500 1C.

 A Srinivas et al. / Ceramics International 41 (2015) 1980–1985
Fig. 4. Polarization (P) vs. electric field (E) hysteresis loop and their
corresponding current (I) vs. E switching curves for sintered BCZT ceramics
measured untill their dielectric break-down at 300 K and 1 Hz.
In addition, this kind of behaviour may also occur due to the
compositional fluctuations or structural disordering in the
arrangement of cations in one or more crystallographic sites
causing a microscopic heterogeneity in (0.5)BCT–(0.5)BZT
solid solution. The observation of high dielectric constant
values in the present study can be attributed to the enhanced
grain growth and increase in domain size caused by the higher
sintering temperature
1500 1C used for the densification.
Fig. 4(a) shows the polarization (P) vs. electric field (E)
hysteresis loops for (0.5)BCT–(0.5)BZT. The P vs. E loop shows
a saturated ferroelectric hysteresis with a saturation polarization (Ps)
of 17 mC/cm2, remanent polarization (Pr ¼ 7Pr/2)
9.1 mC/cm2
and a coercive field (Ec ¼ 7Ec/2) of 0.3 kV/mm. These values are
comparable with the values reported by Liu and Ren. [8]. These
values indicate that the prepared (0.5)BCT–(0.5)BZT ceramic is
soft ferroelectric in nature. In addition, the sharp I vs. E switching
curves strongly indicate the intrinsic ferroelectric characteristic of
the sample. The observed values for the (0.5)BCT–(0.5)BZT may
be attributed to the reduction in the electron transport because of
the hopping between Ti4 þ and Ti3 þ which is one of the major
paths of leakage current in barium titanate based ceramics. In
addition, the valence state of Zr4 þ is chemically more stable
because of larger ionic size when compared to that of Ti4 þ which
results in an increase in the perovskite lattice [18].
Fig. 5(a) and (b) shows the dependence of the strain and
derivative of strain with respect to electric field (E) measured at
room temperature with the electric field (E) applied in the same
direction as that of the poling direction. A slim butterfly kind of
hysteresis behaviour was recorded from electric field vs. strain
measurement in the range of  4 kV/mm to 4 kV/mm and the
dynamic piezoelectric coefficient (d*33) as a function of an applied
electric field was evaluated. It can be observed that d*33 increases
initially with increase in the electric field, reaches a maximum of
1257 pm/V at an electric field of 0.6 kV/mm and subsequently
decreases to 552 pm/V at a field of 4.1 kV/mm. On reversing the
field from 4.1 kV/mm, the d*33 retraces the same path initially but
subsequently deviates. A maximum dynamic piezoelectric coeffi-
cient (dS/dE) with a very high value of 1613 pm/V at a field of
1983
Fig. 5. (a) Bi-polar strain (S) vs. electric field (E) measurements for poled (0.5)
BCT–(0.5)BZT sample along with the (b) strain derivative plots.
0.35 kV/mm is observed in the present study exceeding that of all
PZT ceramics (which show dS/dE in the range of 360–900 pm/
V). The property anomaly at MPB of the BZT–BCT system is
analogous to a similar phenomenon found in PZT and PMN–PT
systems. The obtained d*33 values are very high when compared
with the values reported by Liu and Ren [8] in the same system.
Further work is in progress to improve the density of the system
to enhance the piezoelectric properties. The static d33 value
recorded for the present system was around 400 pC/N at room
temperature. The large strain and d33 value make (0.5)BZT–(0.5)
BCT a promising candidate for high performance solid state
actuators and ultrasonic generators. In addition, one can observe
that the maximum value of d*33 is obtained in the electric field
range of 0.35–0.9 kV/mm. Thus, one can conclude that the poling
field of 0.35–0.9 kV/mm should give the best piezoelectric
properties for the present system (0.5)BCT–(0.5)BZT.
Representative load versus indentation-penetration depth
curve from nanoindentation tests done at 10 mN load is shown
in Fig. 6(a). Young's modulus and hardness are calculated
from the unloading curve using Oliver and Pharr analysis [19]
which uses two basic premises:
(i) the deformation upon unloading is purely elastic;
(ii) the compliance of the sample and the indenter tip can be
combined as a system of springs in series, with the effective
1984 A Srinivas et al. / Ceramics International 41 (2015) 1980–1985

Table 1
Comparative mechanical properties of (0.5)BCT–(0.5)BZT and lead based
samples.

Mechanical property (0.5)BCT–(0.5) PLZT PZT Hipped

BZT PZT

Hardness (GPa) 11.671.7 5.0 75 3.857 0.28 4.937 0.19

Modulus (GPa) 1287 7 134 7 5 93 104
Fracture toughness 1.37 0.3 1.3 70.3 1.29 1.15
(MPa m1/2)
Reference Present work 21 22 22

shape function at the contact depth. Finally, the nano-

indentation hardness HO–P and effective elastic modulus Eeff
are calculated by
Pmax
H O–P ¼ ð5Þ
Ac
pffiffiffi
π S
Eeff ¼ pffiffiffiffiffi ð6Þ
2 Ac
The elastic modulus of the sample can then be calculated
from Eeff using Eq. (3), wherein the diamond indenter has a
Poisson's ratio of 0.07 and E of 1141 GPa. The values of
hardness and elastic modulus are tabulated in Table 1 and an
average of 30 indentations are done. The values of Young's
modulus and hardness for the sample obtained are 128 7
7 GPa and 11.67 1.7 GPa, respectively.
Indentation fracture toughness measurements were carried
Fig. 6. (a) Load–penetration depth curves for (0.5)BCT–(0.5)BZT ceramic,
out using a microhardness tester with a Vickers indenter using
and (b) optical image of the residual indentation.
a 25 g load. The load was selected after making several indents
at various loads from 10 g to 1 kg on the specimen. At higher
load the cracks were too long and multiples cracks were
(or reduced) modulus Eeff being
observed whereas at lower loads the cracks were not well
1 1 ν2i 1 ν2s formed. The indents at 25 g load are well defined and the crack
¼ þ ð1Þ pattern is symmetric as can be seen from Fig. 6(b). The
E eff Ei Es
fracture toughness was estimated using the equation given
where E and v represent Young's modulus and Poisson's ratio below [21]:
of the indenter i and sample, s, respectively. sffiffiffiffiffiffiffiffiffiffiffi
 
The method starts with the fit of the unloading curve to the E P
power-law relation K IC ¼ α : ð7Þ
H C 3=2
P ¼ Cðh  hf Þm ; ð2Þ
Here α is the geometry factor (0.016), P is the load, E is the
where C and m are fitting parameters and h and hf are, Young's modulus, H is the hardness and C is length of the
respectively the instantaneous and residual displacements of crack measured from the centre of the indent. Minimum of
the indenter. The unloading stiffness S is then obtained by eight indents were used to calculate the fracture toughness. The
finding the slope at hmax by differentiating Eq. (2) i.e. fracture toughness of the (0.5)BCT–(0.5)BZT specimen was
1.37 0.3 MPa m1/2 which is comparable to that reported for
S ¼ mCðh hf Þm  1 : ð3Þ lead based electroceramics processed by the mechanochemical
The contact depth hc between the indenter and the specimen processing route [20]. As the mechanical properties are also
can be estimated using dependent on the density of the ceramics and the density of the
(0.5) BCT–(0.5) BZT achieved in this study is about 92%,
Pmax
hc ¼ hmax  ε ð4Þ better mechanical properties can be obtained in the sample if
S the density can be improved further. Thus, 0.5(BCT)–0.5
Here, Pmax is the peak load and ε is a constant related to the (BZT) not only has attractive ferroelectric and piezoelectric
indenter geometry. Thus, the projected contact area Ac is properties but also comparable (see Table 1) mechanical
established by evaluating an empirically determined indenter properties to those of PZT and thus has potential to be used
 A Srinivas et al. / Ceramics International 41 (2015) 1980–1985
in ultrasonic and electro-mechanical devices. Studies are in
progress to enhance the piezoelectric and mechanical proper-
ties by using different processing techniques such as CIPing
and HIPing.
4. Conclusions
Lead-free (0.5) BZT–(0.5) BCT electroceramics were
synthesized in single phase perovskite structure when sintered
at 1500 1C. A high value of dielectric constant (εr)
9700 at
85 1C (ferroelectric transition temperature Tc) was obtained at
this sintering temperature with moderate dielectric breakdown
fields. The ferroelectric (P–E) and piezoelectric (S–E) loops of
the (0.5)BZT–(0.5)BCT ceramic show excellent piezoelectric
properties comparable to those exhibited by PZT. The mechan-
ical properties i.e, Young's modulus, hardness and fracture
toughness which are also important in actuator applications are
also comparable to those of PZT. These results confirm the
potential of (0.5)BZT–(0.5)BCT bulk ceramics processed by
solid state sintering route for use in actuator applications.
Acknowledgements
The authors thank Defence Research and Development
Organization (DRDO), India, for providing support and
Director, DMRL, for his encouragement.
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