Materials Research Innovations

ISSN: 1432-8917 (Print) 1433-075X (Online) Journal homepage: http://www.tandfonline.com/loi/ymri20

Electrostrictive effect and dielectric properties

of lead-free 0·5Ba(ZrxTi1–x)O3–0·5(Ba0·75Ca0·25)TiO3
ceramics near morphotropic phase boundary
(MPB) compositions

Q. Li, W. B. Ma, C. C. Tang, X. Y. Meng, J. Q. Ma & B .B. Niu

To cite this article: Q. Li, W. B. Ma, C. C. Tang, X. Y. Meng, J. Q. Ma & B .B.

Niu (2015) Electrostrictive effect and dielectric properties of lead-free
0·5Ba(ZrxTi1–x)O3–0·5(Ba0·75Ca0·25)TiO3 ceramics near morphotropic phase boundary
(MPB) compositions, Materials Research Innovations, 19:sup4, S45-S49, DOI:
10.1179/1432891715Z.0000000001514

To link to this article: http://dx.doi.org/10.1179/1432891715Z.0000000001514

Published online: 25 May 2015.

Submit your article to this journal

Article views: 36

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ymri20

Download by: [Orta Dogu Teknik Universitesi] Date: 05 April 2016, At: 19:32
 Electrostrictive effect and dielectric properties of
lead-free 0·5Ba(ZrxTi1 – x)O3 –0·5(Ba0·75Ca0·25)-
TiO3 ceramics near morphotropic phase
boundary (MPB) compositions
Q. Li, W. B. Ma*, C. C. Tang, X. Y. Meng, J. Q. Ma and B .B. Niu
The ceramics of 0?5Ba(ZrxTi1–x)O3–0?5(Ba0?75Ca0?25)TiO3(x50?15, 0?20, 0?25 and 0?30) (BZT–
BCT) were synthesized by the conventional solid-state reaction method. And then, the dielectric,
ferroelectric and electrostrictive properties of the ceramics were investigated near morphotropic
phase boundary (MPB). Meanwhile, its crystallographic structure had been found to change from
Downloaded by [Orta Dogu Teknik Universitesi] at 19:32 05 April 2016

tetragonal phase to pseudocubic phase by the raising Zr4+ content from 0?15 to 0?30. And the
grains morphology was observed from SEM. Finally, when the ceramics sintered at 14008C for 2h
with x50?15, The excellent properties were obtained: The electrostrictive strain reaches 0?16%
under 40 kV cm21, and Tm=1028C, which demonstrated that the BZT-BCT has superior strain
capacity as a lead-free system.
Keywords: BZT –BCT, Dielectric, Ferroelectrics, Electrostriction

Introduction (BaTiO3) have excellent electromechanical properties

Electrostriction is a kind of electromechanical coupling
effect, which implies a quadric effect to polarization.
Electrostriction in centrosymmetric materials are free of
some drawbacks such as hysteresis showing in inverse
piezoelectric effect. Electrostriction of the high dielectric
relaxor ferroelectrics usually plays an important role in
pushing the limits of design for modern devices, such as
actuators, force amplifiers, micromechanical controls
and protective devices.
Lead-based piezoelectric ceramics were dominant in
the piezoelectric actuators field because of the strain is
much higher than lead-free piezoelectric ceramics.
However, in lead-based piezoelectric ceramic materials,
toxic lead and its compounds restricted their appli-
cation. Therefore, the development of environment
friendly lead-free piezoelectric ceramics has drawn con-
siderable attentions. Hussaina et al.1 reported that a
large field-induced strain of 0?43% could be obtained in
0?99Bi0?5(Na0?82K0?18)0?5TiO3–0?01LiSbO3. In addition,
solid solutions of perovskite structure between Bi1/2Na1/
2TiO3 (BNT) and Bi1/2K1/2TiO3 (BKT) are considered as
potential candidates because of their excellent properties
near the orthogonal–tetragonal phase boundary.2
However, an extremely high field (w8 kV mm21) is
necessary to obtain *0?1% strain level, which is an
important problem related with these BNT-based elec-
trostrictive materials. At the same time, the authors
found that compositions based on barium titanate
Key Laboratory for Advanced Ceramics and Machining Technology of
Ministry of Education, Tianjin University, Tianjin 300072, China
*Corresponding author, email tju11305@gmail.com
near the morphotropic phase boundary (MPB), because
of the advantage of phase transition taken by MPB to
produce large actuation strains. In the last few years,
dielectric and piezoelectric properties of BZT–BCT lead-
free system have been studied more and more
thoroughly. It was reported that the BaTiO3s structure
and Curie temperature were changed with the doping of
Zr4+. When Zr4+ concentration was *15 at-%, the
system (BaZrxTi1–xO3) exhibited a pinched phase tran-
sition. When Zr4+ concentration was beyond 15 at-%, a
diffuse dielectric anomaly was observed, coupling with
the decrease of the transition temperature. When Zr4+
concentration was w25 at-%, the system (BaZrxTi1–xO3)
showed a typical relaxant behaviour.3 In the previous
work, the authors have confirmed that the
concentration of Ca2+ almost have no significant effects
on the structure and Curie temperature of BZT–BCT
system.
The BZT–BCT-based ceramics have a low Curie
temperature, which limits their application in the high
temperature. However, the ceramic exhibits an intimate
mixture of paraelectric and ferroelectric regions when
the Curie temperature is about room temperature. The
permittivity becomes very high and the polarization can
be induced by even a small field. This indicates that the
dielectric non-linearity of the BZT–BCT ceramics at
room temperature is expected to be very strong in
theory. In terms of temperature stability, this system
may have its unique advantage in practical applications.
The 0?5Ba(Zr0?20Ti0?8)O3–0?5(Ba0?7Ca0?3)TiO3 system
shows comparable piezoelectric properties to PZT-re-
lated systems.4 It exhibited a highly temperature
dependent between the tetragonal and rhombohedral
phases.

Ñ W. S. Maney & Son Ltd 2015

Received 27 October 2014; accepted 27 November 2014
DOI 10.1179/1432891715Z.0000000001514 Materials Research Innovations 2015 VOL 19 NO S4 S45

The large electrostrictive strain is believed to originate
from the non-180u domain rotation. The authors can
deduce that a large strain can be obtained owing to the
large amount of domains reorientation if an imposed
electric field loaded on the BZT–BCT systems. In this
paper, the authors designed the 0?5Ba(ZrxTi1–x)O3–
0?5(Ba0?75Ca0?25)TiO3 (x50?15, 0?20, 0?25 and 0?30)
system as study object. The influence of crystal structure
on the electrostrictive strain and ferroelectric properties
of BZT–BCT were researched. Besides, the possible
mechanisms of electrical and electrostrictive properties
was investigated and discussed.
Experimental procedures
The 0?5Ba(ZrxTi1–x)O3–0?5(Ba0?75Ca0?25)TiO3 (x50?15,
0?20, 0?25 and 0?30) ceramic specimens were prepared by
a conventional solid-state reaction method. The starting
materials were BaCO3 (>99%), CaCO3 (>99%), TiO2
(>99%) and ZrO2 (>99%). These reagents were mixed
for 4 h in a polyurethane jar using agate balls media. The
Downloaded by [Orta Dogu Teknik Universitesi] at 19:32 05 April 2016
slurries were dried and calcined at 1200uC for 4 h in
Al2O3-based crucibles, and then the powders were milled
for 6 h at the same conditions as the above mentioned.
After drying, these powders pressed into green discs with
a diameter of 15 mm under 400 MPa. All the green
bodies were sintered at 1400uC for 2 h in air. Silver
electrodes were screen-printed on both surfaces of the
polished pellets and fired at 735uC for 15 min before
testing
The phase information of the sintered samples were
obtained by X-ray diffraction (XRD, Rigaku, Tokyo,
Japan) with Cu Ka radiation (40 kV/200 mA) and field-
emission scanning electron microscope (FE-SEM,
JOEL6700F, Hitachi Limited, Osaka, Japan). The relative
dielectric constant (er) and dielectric loss were measured at
room temperature on an Inductance, Capacitance,
Resistance (LCR) automatic meter (XC2810A, Tianjin
Xince Electronics Apparatus Technology Co. Ltd.,
Tianjin, China). Curie temperatures were measured by the
relative permittivity–temperature (er2T) curve. The
ferroelectric hysteresis loops and field-induced strain S–E
loops were determined using a standard ferroelectric
tester (WS-2000, Tsinghua University, Beijing, China) at a
frequency of 1 kHz at room temperature.
Results and discussion
Crystal structure analysis
Figure. 1 shows the XRD patterns of all BZT–BCT
ceramics sintered at 1400uC in the 2h range of 10u–80u.
The XRD patterns revealed a pure perovskite phase for
all samples and no secondary phases can be identified,
indicating that the Zr4+ and Ca2+ have completely dif-
fused into the BT lattice to form a stable solid solution.
Meanwhile, from the enlarged patterns of angles ranged
from 44u to 46?5u, an apparent peak-splitting has been
observed at x50?15. When x50?30 the two peaks
gradually merged into one. Therefore, it can be deter-
mined that the structures of BZT–BCT ceramics is a
pure tetragonal phase for x50?15. In addition, a mixed
phase of rhombohedral and tetragonal is formed when
x50?20–0?25.5 At last, the pseudo-cubic phase is
observed when x50?30. Owing to different radius of
Zr =rTi ¼ 115), the interplanar spacing
Zr4+ and Ti4+ (?r4þ 4þ
Li et al. Electrostrictive effect and dielectric properties of lead-free ceramics
1 X-ray diffraction (XRD) patterns of 0?5Ba(ZrxTi1–x)O3–
0?5(Ba0?75Ca0?25)TiO3 lead-free ceramics with x50?15,
0?20, 0?25 and 0?30
increases when Zr4+ replaces Ti4+ in the B-sublattice of
perovskite structure. According to Bragg equation:
2dsinh5nl, the wavelength l is a fixed number. The
diffraction angle (h) is decreasing with the increasing
interplanar spacing value. Therefore, the diffraction
peaks shift slightly towards low diffraction angle with
the increase of Zr4+ content.
SEM analysis of 0·5Ba(ZrxTi1 – x)O3 –
0·5(Ba0·75Ca0·25)TiO3 ceramics
Figure 2 illustrates the SEM micrographs of the
0?5Ba(ZrxTi1–x)O3 0?5(Ba0?75Ca0?25)TiO3 ceramics with
x50?15, 0?20, 0?25 and 0?30. The observations of SEM
confirmed that all samples were dense and well devel-
oped microstructure. Meanwhile, the microstructures at
x50?15 present a bump which means that a complex
internal domain structure is formed inside as the figure
revealed. The grain size shows a dependence on the Zr4+
concentration obviously. The grain morphology is uni-
formly distributed with the increasing of Zr4+.
At x50?15, the samples are at an average grain size of
40 mm and then decrease to 20 mm when x50?30. With
the increasing of Zr4+concentration, the density of
samples increase slightly, which measured by Archi-
medes drainage method.
Dielectric properties
Figure 3 shows the temperature dependence (30–110uC)
of dielectric constant (er) for the BZT–BCT ceramics
measured at 1 kHz. The peak dielectric constant is found
to be broadened and the sample with x50?25 shows the
highest value. The temperature (Tm) is shifted from
102uC (x50?15) to 47uC (x50?30). At x50?25, the
relaxation phenomenon begin to appear and at x50?30 a
pronounced ferroelectric relaxation behaviour occurs,
which is caused not only by inhomogeneous distribution
of A sites (Ca2+ and Ba2+) and B sites (Zr4+ and Ti4+),
but also by the mechanical stress in the grains.6,7
Substituting Zr4+ for Ti4+ will lead to the rhombohedral–
tetragonal phase transition temperature increase and the
tetragonal–cubic phase transition temperature decrease.
Therefore, when Zr4+ reaches a certain content, the
rhombohedral–tetragonal phase transition temperature
and the tetragonal–cubic phase transition temperature will
Materials Research Innovations 2015 VOL 19 NO S4 S46
 Li et al. Electrostrictive effect and dielectric properties of lead-free ceramics
Downloaded by [Orta Dogu Teknik Universitesi] at 19:32 05 April 2016

a x50?15, b x50?20, c x50?25, d x50?30

2 SEM micrographs of BZT–BCT ceramics sintered at 14008C for 2 h

electron displacement polarization. Affected by the above

factors, the c/a ratio and the stability of tetragonal structure
are reduced, which results in the decrease of the Tm.
Figure 4 shows the frequency and temperature
dependence of the relative dielectric permittivity for the
samples x50?15, the frequency range of 100 Hz–
10 MHz. The dielectric permittivity decreases slightly
with the increasing frequency. However, the temperature
(Tm) of the maximum permittivity (er) is not shifted as

3 Temperature dependence of dielectric permittivity (er) for

BZT–BCT pellets sintered at 14008C for 2 h with different
Zr4+ concentrations in 1 kHz

merge into one temperature. The temperature dependence

of dielectric constant only has one phase transition tem-
perature. Larger ionic radius of Zr4+ in the B-lattice will
reduce the displacement of thermal vibration in the oxygen
octahedron. The offset distance between the positive
charge centre and the negative charge centre decreases,
which leads to the decrease of the spontaneous polarization
degree. Besides, the large distance between Zr4+ ionic and 4 Temperature dependence of dielectric permittivity (er) for
near oxygen ionic reduces the degree of oxygen ions’ BZT–BCT (x50?15) ceramics at various frequencies

Materials Research Innovations 2015 VOL 19 NO S4 S47


the frequency increases from 100 Hz to 1 MHz. This
behaviour is a typical example of relaxor ferroelectrics.
It is observed in Fig. 5 that the dielectric constant has
a slight increase when Zr4+ content is v0?25. Then the
dielectric constant increases sharply in the range from
0?25 to 0?30. As the authors are aware, when the phase
transition is close to the room temperature, the high
dielectric constant can be obtained at room temperature.
The increasing dielectric constant values present in
Fig. 5 caused by the phase transition is closed to the
room temperature with x50?3. Besides, the dielectric
constant in BaTiO3 system also depends on ionic
polarizability.8,9 The ionic polarizability of Zr4+ and Ti4+
were 0?345 and 0?180, respectively. Dielectric constant
had a relationship with ionic polarizability as described
in the following equation
3Vm þ 8pa
er ¼ ð1Þ
3Vm 4pa
where Vm and a are the molar volume and the sum of
Downloaded by [Orta Dogu Teknik Universitesi] at 19:32 05 April 2016
ionic polarizabilities, respectively. Ignoring the influence
of the ionic radius difference, raising Zr4+ would lead to
the increase of the sum of ionic polarizability, and as a
result, the dielectric constant would be enhanced.
Ferroelectric and electrostrictive properties
At room temperature, the authors obtained well satu-
rated hysteresis loops with regular shape at 1 kHz, and
typical non-polar materials were evident for all investi-
gated systems as shown in Fig. 6. Non-polar P–E loops
indicated that FE order was disrupted by the modifier of
Zr4+. No evidence of ‘imprint’ phenomenon indicating
that the ceramics present low defects of oxygen
vacancies. The oxygen vacancies will pin the domain
walls so that the hysteresis loops are difficult to reach
saturation.10 Both remnant polarization Pr and coercive
field EC are decreased as the functions of Zr4+. The
decreasing c/a caused by Zr4+doping can lead to the
decline of remnant polarization in single domain as well
as anisotropy, which is the main reason for the decrease
of Pr. The coercive field EC decreased from
4?10 kV cm21 at x50?15 to 1?07 kV cm21 at x50?30,
which means that the domain mobility became easier for
the sample with higher level Zr4+.11 It is because that the
5 Dielectric permittivity versus Zr4+ content at 1 kHz for
BZT–BCT ceramics sintered at 1300–14508C in the air
Li et al. Electrostrictive effect and dielectric properties of lead-free ceramics
6 The P–E hysteresis loops of BZT–BCT ceramics sintered
at 14008C for 2 h in different concentrations with x50?15,
0?20, 0?25 and 0?30
structure of ceramic is pseudo-cubic phase as showed in
XRD when Zr4+ content is equal to 0?30, and the fer-
roelectricity reduces significantly.
Figure 7 shows the room temperature bipolar field-
induced strain curves of BZT–BCT ceramics without a
preceding poling step for Zr4+ contents x50?15, 0?20,
0?25 and 0?30 measured at 1 kHz under a applied electric
field of 40 kV cm21. From the strain results, all samples
have not shown negative strain. The maximum strains of
these four are 0?162, 0?124, 0?126 and 0?101%, respect-
ively. Structure–property correlation studies show the
strain of relaxor BZT have an improvement owing to the
difference in size of Zr4+ and Ti4+cations
Zr =rTi ¼ 115).
12
(?r4þ 4þ
Nevertheless, in this work the
strain level greatly reduces with increasing Zr4+ content,
which can account for the following reasons. First,
tetragonal phase is dominant at x50?15, and in this
tetragonal state, the unit cell can take any one of the six
crystallographically equivalent combinations of strain
and polarization.13 Second, larger ionic radius
Zr4+(0?72 nm) which replaces Ti4+(r50?604 nm) will
prevent the establishment of long-range polar order;
therefore, the microdomain is more disordered.
In addition as a result the microdomain rotation is more
difficult. Third, when x50?15, Tm5102uC, at room
7 Room temperature bipolar field-induced strain (S–E)
loops of BZT–BCT ceramics with different Zr4+ contents
Materials Research Innovations 2015 VOL 19 NO S4 S48

temperature the structure of the ceramic is pure ferro-
electric, and there are more ferroelectric domains par-
ticipate in rotating. In addition, electrostrictive
coefficient (Q11) increases with cation order degree from
disordered to partially ordered, simple and ordered.6
Furthermore, the polarization shows a downward trend
with the increase of Zr4+ in the hysteresis
loop. Therefore, based on
S ¼ Q11 P 2
where S, Q11 and P are the electrostrictive strain, elec-
trostrictive coefficient, polarization, respectively, it is no
wonder that ceramics with x50?15 have a relatively high
electrostrictive strain.
It has been suggested that 0?5Ba(ZrxTi1–x)O3–
0?5(Ba0?75Ca0?25)TiO3 (x50?20, 0?25) ceramics with two-
phase coexistence are prone to have a phase trans-
formation induced by an external electric field, which
leads to the increase of ferroelectric domains and the
orientation becomes easier, and as a consequence, a
larger strain value Smax50?16% when x50?25 under
Downloaded by [Orta Dogu Teknik Universitesi] at 19:32 05 April 2016
50 kV cm21 was obtained.14–16 However, the present
experimental result find that the maximum strain is
obtained at x50?15, and the interpretations are given in
previous sections In a word, the mechanism of enhanced
electromechanical properties in ferroelectrics poly-
crystals is very complex because of the presence of re-
sidual stresses and grain boundary mismatch as well as
the internal domain structure.17–19
Conclusion
The 0?5Ba(ZrxTi1–x)O3–0?5(Ba0?75Ca0?25)TiO3 (x50?15,
0?20, 0?25 and 0?30) lead-free ceramics were synthesized
through a conventional solid-state reaction method
and investigated at room temperature. Specimens
sintered at 1400uC showed different properties with the
change of Zr4+ content. The XRD patterns exhibited the
crystallographic structure changed from tetragonal
phase to pseudo-cubic phase with raising Zr4+ content
Li et al. Electrostrictive effect and dielectric properties of lead-free ceramics
from 0?15 to 0?30, and the SEM graphs revealed that all
samples had homogeneous and dense microstructure
with relatively large grain size. The Tm was decreased
from 102uC to 47uC with the raising of Zr4+ content,
which was caused by inhomogeneous distribution of
Ca2+ and Zr4+ ions. The largest electrostrictive strain
was found in BZT–BCT ceramic with x50?15 and the
value was 0?16%, which the composition was out of the
MPB structure.
ð2Þ
References
1. A. Hussaina, A. Zamanb, Y. Y. Iqbal and H. Kima: J. Alloys
Compd., 2013, 574, 320–324.
2. S. T. Zhang, A. B. Kounga, E. Aulbach and T. Granzow: J. Appl.
Phys., 2008, 103, (034107), 1–8.
3. T. Maiti, R. Guo and A. S. Bhalla: J. Am. Ceram. Soc., 2008, 91,
1769–1780.
4. W. F. Liu and X. B. Ren: Phys. Rev. Lett., 2009, 103, (257602), 1–9.
5. M. C. Ehmke, S. N. Ehrlich, J. E. Blendell and K. J. Bowman:
J. Appl. Phys., 2012, 111, (124110), 1–7.
6. S. Nomura and K. Uchino: Ferroelectrics, 1982, 41, 117–132, .
7. X. G. Tang, K. H. Chew and H. L. W. Chan: Acta Mater., 2004,
52, 5177–5183.
8. D. Hennings: Int. J. High Tech. Ceram., 1987, 3, 91–111.
9. Y. D. Hou, L. M. Chang, M. K. Zhu and X. M. Song: J. Appl.
Phys., 2007, 102, (084507), 1–8.
10. F. Moura, A. Z. Simões, B. D. Stojanovic and M. A. Zaghete:
J. Alloys Compd., 2008, 12, 129–134.
11. J. Y. Wang, X. Y. Zhang and J. J. Zhang: J. Phys. Chem. Solids,
2012, 7, 957–960.
12. T. Maiti, R. Guo and A. S. Bhalla: Ferroeletrics, 2011, 1, 4–26.
13. E. Burcsu, G. Ravichandran and K. Bhattacharya: J. Mech. Phys.
Solids, 2004, 4, 823–846.
14. F. Xiao, W. B. Ma, Q. C. Sun and Z. L. Huan: J. Mater. Sci., 2013,
8, 2653–2658.
15. X. Wang, H. Yamada and C. N. Xu: Appl. Phys. Lett., 2005, 86,
22905–22905-3.
16. B. Z. Li, J. E. Blendell and K. J. Bowman: J. Am. Ceram. Soc.,
2011, 94, 3192–3194.
17. E. Burcsu, G. Ravichandran and K. Bhattacharya: Appl. Phys.
Lett., 2000, 11, 1698–1700.
18. A. B. Haugen, J. S. Forrester, D. Damjanovic, B. Z. Li, K. J. Bowman
and J. L. Jones: J. Appl. Phys., 2013, 113, (014103), 1–5.
19. M. C. Ehmke, J. Daniels, J. Glaum, M. Hoffman, J. E. Blendell
and K. J. Bowman: J. Appl. Phys., 2012, 112, 114108.
Materials Research Innovations 2015 VOL 19 NO S4 S49