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Current Applied Physics 14 (2014) 396e402

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Current Applied Physics


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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


and Ren in 2009 using conventional solid state route have attracted
Piezoelectrics are a class of smart materials which can convert great attention due to its excellent piezoelectric properties
mechanical energy into electrical energy and vice versa and they (d33 w 600 pC/N) [4]. A material whose composition lies at the
are being widely used in various electronic and microelectronic morphotropic phase boundary (MPB) shows good piezoelectric
devices [1,2]. Lead zirconate titanate (PZT) based ceramics had been properties. MPB between two ferroelectric phases causes instability
the most widely used among them because of its superior piezo- to the polarization state, which eases the rotation of the ferro-
electric properties (d33 w 300e550 pC/N) [3]. However, such lead electric domains [3,4]. BZTeBCT also shows a phase diagram similar
based materials (which contain atleast 60% lead by weight) are to the Pb-based systems like PZT, PMNePT, and PNNePZT, that is,
facing global concerns due to its high toxicity. Hence, the growing with a morphotropic phase boundary (MPB) consisting of a triple
demand of replacing these lead based piezoelectrics has made re- point of paraelectric cubic phase (C), ferroelectric rhombohedral (R)
searchers to focus more on development of efficient lead free sys- and tetragonal (T) phase [3]. Hence BZTeBCT is presently one of the
tems [2]. important candidates for many piezoelectric applications due to its
BaTiO3(BT) is one of the most researched lead free piezoelectric lead free nature with an MPB similar to lead based systems and
ceramics inspite of its lower Curie temperature (Tc w 120  C) and with superior piezoelectric properties reported in literature [4,5].
inferior piezoelectric properties (d33 w 200 pC/N), but BT ceramics The conventional solid state reaction method used to prepare
exhibits high dielectric and ferroelectric properties [3]. Recently BZTeBCT requires relatively higher calcination temperature
developed lead free xBa(Zr0.2Ti0.8)O3e(1  x)(Ba0.7Ca0.3) (1350  C) [4,5] and solid state sintering results in inhomogeneous
microstructure and impurity phases, which adversely affects the
* Corresponding author. Tel.: þ91 4066794454.
properties of the system. In comparison, chemical solution syn-
E-mail address: ddse@uohyd.ernet.in (D. Das). 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 397

particle sizes and better homogeneity, which cannot be achieved by Polarization versus electric field measurements (P vs E hyster-
solid state route [6]. Very few literature have reported on the esis loops) were conducted using a Piezoelectric Evaluation System,
synthesis of BZTeBCT using wet chemical synthesis techniques [7e TF analyzer 2000 from M/s aixACCT GmbH. Polarization vs Electric
9]. In this study, a wet chemical technique, viz. solegel method was field (P vs E) measurements were carried out using a triangular
used to synthesis the BZTeBCT powders. waveform at 1 Hz. Samples with the highest density measured from
The phase pure material was subjected to optimized processing Archimedes method were subjected to electrical poling at a field of
conditions to achieve better sintered density of the sample with 1 kV mm1 for 30 min at 100  C immersed in a silicone oil (Dow
homogenous and uniform microstructure of these BZTeBCT ce- Corning DC-704Ò) bath and cooled with the field. After aging for
ramics. The dielectric, piezoelectric and the ferroelectric properties 24 h the poled samples were used to determine the piezoelectric
obtained from the solegel synthesized BZTeBCT were measured charge coefficient using a SS01 Piezo-d meter from Sensor Tech-
and have been correlated with its structure in this work. nology Limited; Canada. The dielectric measurements were carried
out on an Agilent E4980A precision LCR meter with a frequency
2. Experimental range of 20 Hze2 MHz. The LCR meter was interfaced with a
computer controlled programmable temperature controller and
The xBa(Zr0.2Ti0.8)O3e(1  x)(Ba0.7Ca0.3)TiO3 (x ¼ 0.5) ceramic the dielectric data was measured for a temperature range of 35  Ce
was synthesized by using analytical reagent (AR) grade chemicals 145  C at a heating rate of 1  C min1.
obtained from SigmaeAldrich chemicals, USA. The starting mate- Piezoelectric strain measurements (strain vs electric field) were
rials used for the solegel synthesis of BZTeBCT were Barium ace- also carried out using the same Piezoelectric Evaluation System.
tate (Ba(CH3COO)2), Zirconium oxychloride (ZrOCl2$8H2O), calcium The maximum applied electric field for bipolar measurements were
nitrate tetrahydrate (Ca(NO3)2$4H2O) and titanium isopropoxide 3 MV/m at 1 Hz. Dynamic piezoelectric charge coefficient was
(C12H28O4Ti) of >99% purity. Required quantity of Barium acetate, measured by taking the ratio of maximum strain to peak electric
according to the stoichiometric ratio, was added to acetic acid and field, Smax/Emax, from the unipolar strain measurements. The
stirred till it got dissolved completely. Stoichiometric ratios of zir- maximum electric field for unipolar measurements was 0.7 MV/m
conium oxychloride and calcium nitrate tetrahydrate were also at a frequency of 0.1 Hz. Resonance data were acquired using an
taken in ethanol and stirred till it got completely dissolved. After Agilent E4980A precision LCR meter in the frequency range from
complete dissolution, the three solutions prepared separately were 100 kHz to 600 kHz on poled samples. The planar electromechan-
mixed together and required quantity of titanium isopropoxide was ical coupling factor kp was calculated following IEEE standards [10]
added to it. The precursor solution so obtained was continuously and using the following expression,
stirred and heated at 100  C for about 4 h, which resulted in pre-
cipitate gel formation. The resultant gel was dried overnight and k2p Df h i
2
¼ ðsp Þ  1 þ h21 (1)
the solidified lumps were ground to fine powders using a mortar 1 k2p f ð1 þ sp Þ
and pestle.
Calcination temperature was optimized by calcining the as- where Df is the difference between the lowest frequency of anti-
synthesized powders at 900e1100  C for 4 h to get phase forma- resonance and resonance, f is frequency, sp is the planar Poisson’s
tion and to remove the unreacted materials from the as-synthe- ratio and h1 is the lowest root derived from the following Eq. (2),
sized powder. The calcined powders were subjected to X-ray
diffraction studies to confirm phase formation. The calcined pow- J1 ðh1 Þ ¼ 1  sp (2)
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 where J1 is the modified quotient of Bessel (cylinder) functions.
calcination. The calcined milled powders was mixed with polyvinyl
alcohol (PVA) and compacted into pellets of 1 cm diameter and 3. Results and discussion
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 as-synthesized powders were calcined at various temper-
The green samples were initially subjected to binder burnout at atures, 900  C, 1000  C and 1100  C for 4 h to determine the
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. 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 The intensity of the tetragonal peaks in both the (200) and (211)
shows the X-ray diffraction spectra of the calcined (calcination of peaks is predominant compared to the rhombohedral peak in-
the as-synthesized powders) BZTeBCT powders calcined at tensity. Similar peak splitting has been observed and analyzed by
different temperatures. XRD peaks obtained from powder calcined Ehmke et al. [14].
at 900  C had few impurity peaks (results from the unreacted ox- Transmission electron microscopy (TEM) studies were carried
ides, which is not clearly visible in Fig. 1, as the high intensity peaks out for calcined and milled BZTeBCT powders. Fig. 3 shows the TEM
have suppressed the visibility of unreacted small peaks) compared image of calcined and milled BZTeBCT particles. The average par-
to those obtained at 1000  C and 1100  C, indicating incomplete ticle size estimated from TEM analysis was measured to be w35e
phase formation at 900  C. Not much difference in the powder 50 nm, which confirms the results obtained from XRD line broad-
diffraction pattern is observed for powders calcined at 1000  C and ening of the calcined and milled powder. The selected area
1100  C. With increase in the calcination temperature the impurity diffraction (SAD) pattern, shown in the inset of Fig. 3, confirms the
phase diffused into BZTeBCT lattices to form a solid solution. Hence crystalline nature of BZTeBCT powder. High resolution TEM image
the calcination temperature of BZTeBCT was fixed at 1000  C for of a selective particle was also taken, where lattice fringes
4 h. (d110 w 0.28 nm) is clearly observed. The measured interplanar
The calcination temperature observed in this study is w300  C spacing value of d110 from TEM micrograph correlates well with the
less than that reported for the conventional solid state reaction corresponding ‘d’ spacing value obtained from the X-ray diffraction
process [4,5,11]. The reduced calcination temperature obtained in data for the (110) plane. The lattice fringes also do indicate the
this study may be due to the small particle size of the precursor formation of well crystallized BZTeBCT synthesized by solegel
powders resulted from solegel synthesis process. Crystallite size of synthesis method.
the calcined milled powders was estimated using Debye Scherrer Fig. 4a shows the SEM micrograph of the polished surface of the
relation as given in Eq. (3) below [12], pellet sintered at 1550  C for 2 h. The SEM micrograph shows a
homogenous distribution of grains with a dense packed micro-
0:9l structure and the grain size was measured to be w10e20 mm.
d ¼ (3)
b cos q Elemental mapping, as shown in Fig. 4b, of the sintered pellet re-
veals the homogenous distribution of the constituent elements
where 0.9 is the shape factor, l is the X-ray wavelength, 15.417 nm, throughout the microstructure. The BZTeBCT sample sintered at
b is the line broadening at half the maximum intensity in radians 1550  C for 2 h has resulted in a density of w95% of the theoretical
and q is the Bragg’s angle. The average crystallite size of BZTeBCT density, which was measured by Archimedes method following the
was estimated to be ‘d’ w 35e40 nm. ASTM standard (C373eC388). Both density and grain size do have
Fig. 2 shows the X-ray diffraction spectra of sintered (at 1550  C an important effect on the piezoelectric properties of the material,
for 2 h) BZTeBCT sample and single-phase perovskite structure is hence selection of appropriate sintering schedule (both peak tem-
evident in the room temperature XRD data. The inset of Fig. 2 shows perature and soaking time) is important in achieving good piezo-
the split (200) and (211) reflections, which indicates the coexis- electric properties. High sintering temperature generally results in
tence of rhombohedral and tetragonal phases in the system. MPB deformation and non-stoichiometry in the BZTeBCT ceramics [5].
for BZTeBCT ceramics, reported by Liu et al. [4] and other re- To avoid compositional changes calcined powders of the same
searchers, too consists of region of coexisting rhombohedral (R3m) composition of the ceramics are generally used as supporting
and tetragonal (P4mm) [13,14] phases. powders during sintering at elevated temperatures. Calcium from
The peak splitting observed for (200) peak can be attributed to BZTeBCT reacts with the alumina crucible resulting in stoichiom-
the split of (002) and (200) contribution from tetragonal reflection etry loss, hence ZrO2 powder bed has been used to support the
and also the contribution from the rhombohedral peak due to pellets during sintering and the temperature was elevated to as
presence of MPB. The low angle of the split peaks corresponds to high as 1550  C in this study.
combination of the (002) peak from tetragonal and rhombohedral Polarization versus electric field measurements (PeE hysteresis
phase and the higher angle corresponds to (200) tetragonal phase. 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
Fig. 2. X-ray diffraction spectra of sintered (1550  C) BZTeBCT with inset showing switching insufficient. Excessive poling field also tends to over-pole
peak splitting of (200) and (211) peaks. 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 strain data. A large strain of 0.15% was obtained under a relatively
BCT ceramics is about three times that of coercive field (Ec). From low electrical field of 3 MV/m for the positive field and a strain of
the hysteresis loop (P vs. E measurement) the required field for w0.13% for the negative field. The bipolar loop shows the changes
poling was estimated depending on the sample thickness. The in strain from the remnant state to the strain at maximum applied
sintered samples were electrically poled at 1 kV/mm at 100  C for electric field.
30 min. A very limited hysteresis has been observed with such a large
Piezoelectric charge coefficient, d33, was measured using SS01 strain as seen in Fig. 6a, such high strain behavior in such soft pi-
Piezo-d meter and the d33 of the samples was found out to be ezoelectrics could be attributed to the easy motion of the ferro-
w530 pC/N, which is the highest value reported so far for BZTeBCT electric domains and limited effect of pinning of these domains due
ceramics synthesized by any wet chemical routes [7e9]. In our to the internal bias field [13]. Poling of piezoelectric ceramics at
earlier study we could achieve d33 w 490 pC/N for solegel derived elevated temperatures could assist the re-orientation of ferroelec-
BZTeBCT ceramics with a sintered density of 93% of the theoretical tric domains. The piezoelectric coefficient increases by 40% when
density [22]. The room temperature d33 obtained in this investi- the field applied during poling is maintained while cooling the
gation is better than those of PZT-5A,4 and is comparable to many samples through the Curie temperature [11,13]. Moreover opti-
Pb free piezoelectric ceramics reported in the open literature [2e mized poling conditions such as proper poling temperature and
4,13]. appropriate poling voltage is required to induce such high strain
Fig. 6a shows the electric field induced strain hysteresis loop for and obtain enhanced piezoelectric properties in BZTeBCT. It is
BZTeBCT ceramics. The samples were poled before acquiring the 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

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
Fig. 5. Polarization and current vs electric field e hysteresis loop. 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-
charge carrier accumulation at the grain boundaries inducing an tivity (dielectric constant) of BZTeBCT ceramics sintered at 1550  C
internal bias field that can enhance the piezoelectric response of at 1 kHz and 100 kHz frequencies. The relative permittivity was
the proper poled samples [11,13,15]. measured for a temperature range of 35  Ce145  C at a heating rate
Fig. 6b shows the unipolar strain loop for BZTeBCT ceramics at of 1  C min1. The relative permittivity, εr of BZTeBCT ceramic is
poled state. The maximum applied field for unipolar measurements seen to increase with increase in temperature and reaches
was 0.7 MV/m at a frequency of 0.1 Hz. The samples were poled maximum at the Curie temperature (Tc). The phase transition
before acquiring the strain data. A maximum strain of w0.066% is temperature is seen to be w95  C (highest value of εr ¼ 20,020),
obtained under a relatively low electrical field of 0.7 MV/m. The which is similar to that obtained by other researchers [14e16]. The

Fig. 6. a. Bipolar strain vs electric field measurement for poled BZTeBCT. b. Unipolar Fig. 7. a. Relative permittivity vs temperature for poled BZTeBCT. b. Inverse dielectric
strain measurements of BZTeBCT poled sample. 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 401

rhombohedral to tetragonal phase transition reported at 34  C by arises mainly from the motion of the domain walls [20]. Grain size
Damjanovic et al. [16] is not observed here since the relative influences the domain structure, the balance of depolarization
permittivity was measured from 35  C. The dielectric constant of energy and the domain wall energy. Moreover the grain size effect
the normal ferroelectrics above the Curie temperature (for T > T0) on piezoelectric properties in perovskite-type ferroelectrics is
can be expressed by CurieeWeiss law described by: known to be strongly influenced by the movement of the 90
domain walls [21]. The correlation between the domain size (d) and
εr ¼ CðT  To Þ1 (4) the grain size (t) can be expressed as,
" ! #1=2
where C is the CurieeWeiss constant and To is the CurieeWeiss s
temperature. The CurieeWeiss constant C reflects the nature of the d ¼ $t (7)
ε* P02
ferroelectric transition. The inverse dielectric constant versus
temperature at 1 kHz was plotted and fitting the curve in the
where, s is the energy density of the domain wall, Po is the spon-
paraelectric regime resulted in determining the onset of Curiee
taneous polarization and ε* effective dielectric constant, respec-
Weiss behavior (DTm) or the degree of diffuseness, which is given
tively. The domain wall motion is a collective behavior and the
by the following equation [18,19],
domain walls with small areas will react more energetically to the
influence of external electrical field or stress. In the present work,
DTm ¼ Tcw  Tm ð CÞ (5)
the samples were prepared using optimized conditions to attain the
grain size of >10 mm. Therefore, contribution from clamping of
where Tcw represents the temperature from which εr starts to
domain walls at grain boundaries due to very small grain sizes is
follow the CurieeWeiss law and Tm denotes the temperature at
eliminated [21]. Due to the absence of grain boundary the domain
which εr reaches the maximum value. The estimated DTm was
wall motion inside a large grain is relatively easier when compared
found to be w36  C.
to a piezoelectric with a smaller size grains. The coexistence of the
To evaluate the phase-transition modes an empirical compre-
mixed phases within the individual grain also enables the domain
hensive power law [18,19] has been used, which is applicable to the
walls to rotate easily within the grain without much resistance
dielectric spectra of an intermediate type (i.e., neither normal nor
from the grain boundaries (which pins the domain wall movement
relaxor ferroelectric), and is given by
and hence are high energy barriers) as observed in the present case
for the samples with homogeneous microstructure and having
1 1 ðT  Tm Þg
 ¼ (6) large grain sizes [14]. In this work, the observed piezoelectric
εr ðεr Þm C
properties (d33, kp, d33*, strain) are comparable to most of the lead
based piezoelectrics and can primarily be attributed to the
where ‘g’ is the diffuseness exponent and ‘C’ is the CurieeWeiss
composition (close to the MPB composition of the system) with the
constant. The estimated g is w1.5, which was extracted from the
coexistence of rhombohedral and tetragonal phases and dense
plot shown in Fig. 7b of log (1/εr  1/(εr)m) vs. log (T  Tm). Values
homogeneous microstructure with large grain sizes.
of g can extend numerically from 1 to 2, depending on the phase-
High density and homogeneous microstructure are among the
transition modes. For Eq. (6) reverts to the CurieeWeiss law for
most desired features for any piezoelectric material in obtaining
g ¼ 1, whereas for g ¼ 2, Eq. (6) is equivalent to the quadratic law.
good piezoelectric and ferroelectric properties [5]. Solegel syn-
The diffuseness exponent g indicate the normal ferroelectric phase
thesis method used here in synthesis of BZTeBCT resulted in dense
transition mode [18].
and uniform microstructure with optimal grain size, which has led
Various electromechanical parameters were calculated from the
to such excellent piezoelectric and ferroelectric properties. Such
resonance measurements obtained from the solegel derived BZTe
lead-free BZTeBCT ceramics with excellent piezoelectric and
BCT ceramics. The resonant and anti-resonant frequencies were
ferroelectric properties could be a candidate material for trans-
obtained from the admittance peaks respectively of the admittance
ducer and actuator applications.
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 4. Summary
solegel derived BZTeBCT samples. The electromechanical coupling
factor of a piezoelectric material is an indicator of the effectiveness Lead free piezoelectric ceramics “barium zirconate titanatee
with which a piezoelectric material can transform its input elec- barium calcium titanate” [xBZTe(1  x)BCT](x ¼ 0.5), were suc-
trical energy into mechanical energy [3]. The planar coupling factor cessfully been prepared by solegel synthesis method. Calcination of
(kp) was calculated using the Eqs. (1) and (2) given above and was the as-synthesized BZTeBCT powders at 1000  C resulted in the
found to be 0.45, which is comparable to the results obtained by formation of complete perovskite phase. X-ray diffraction (XRD)
other researchers for BZTeBCT ceramics synthesized using solid and transmission electron microscopy (TEM) studies confirmed the
state route [5,15]. formation of single phase BZTeBCT ceramics with particle sizes
The piezoelectric properties have a strong dependence on the <50 nm. Sintered samples at 1550  C for 2 h resulted in a sintered
grain size of the ceramics as reported in the literature for BZTeBCT density of w95% of theoretical density. Scanning electron micro-
ceramics also. It has been reported that grain size of w10 mm is scopy of the sintered sample indicate a very uniform and dense
critical in developing high performance BZTeBCT ceramics [5]. In microstructure, with an average grain size of about 10 mm. High
the present work also a grain size of w10 mm is observed in the piezoelectric coefficient of d33 w 530 pC/N, d33* of 942 pm/V (at low
resultant microstructure of the sintered BZTeBCT ceramics. The field of 0.7 MV/m), kp of 0.45, strain of 0.15%, Pr of 11.55 mC/cm2 and
grain size dependence of piezoelectric properties could be attrib- relative permittivity of 20,020 at the Curie temperature of 95  C
uted to the change in domain structure with increase in grain size indicated a homogeneous microstructure of the sample with
[16,20]. The piezoelectric properties in a system could arise from optimal grain sizes obtained via optimum processing of the ce-
two main contributions i.e. intrinsic and extrinsic contributions. ramics. The excellent piezoelectric and ferroelectric properties of
Intrinsic contributions are due to the relative ions shift to maintain this lead-free ceramics can primarily be attributed to the MPB
the ferroelectric crystal structure and the extrinsic contribution 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- [10] IEEE, An American National Standard, IEEE Standard of Piezoelectricity, ANSI/
IEEE, New York, 1988. Std 176-1987.
geneous microstructure.
[11] S. Shi, R. Zuo, S. Lu, Z. Xu, X. Wang, L. Li, Poling dependence and stability of
piezoelectric properties of Ba(Zr0.2Ti0.8)O3e(Ba0.7Ca0.3)TiO3 ceramics with
Acknowledgments huge piezoelectric coefficients, Curr. Appl. Phys. 11 (2011) s120.
[12] B.D. Cullity, Elements of X-ray Diffraction, Addison Wesley, 1979.
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