Materials Letters 110 (2013) 80–82

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Enlarged polymorphic phase transition boundary

and enhanced piezoelectricity in ternary component
0.8Ba1
xCaxTiO3–0.1BaTi0.8Zr0.2O3–0.1BaTi0.9Sn0.1O3 ceramics
Wei Li a, Zhijun Xu a,n, Ruiqing Chu a, Huarong Zeng b, Kunyu Zhao b
a
College of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, China
b
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

art ic l e i nf o a b s t r a c t

Article history: Enlarged polymorphic phase transition boundary was observed in the ternary component 0.8Ba1
xCax-
Received 2 June 2013 TiO3–0.1BaTi0.8Zr0.2O3–0.1BaTi0.9Sn0.1O3 ceramics. The polymorphic phase transition existed at consider-
Accepted 2 August 2013 able compositions (x ¼ 0.005–0.04) and was bounded by the orthorhombic and tetragonal phases. More
Available online 9 August 2013
importantly, enhanced piezoelectric constant d33 ¼420 pC/N was obtained in the region of polymorphic
Keywords: phase transition. Our work may provide a new guide for designing excellent piezoelectric materials by
Piezoelectric ceramics enlarging polymorphic phase transition boundary.
Sintering & 2013 Elsevier B.V. All rights reserved.
Dielectric
Piezoelectricity
Polymorphic phase transformation

1. Introduction
Lead zirconatetitanate (PZT) ceramics are the most widely used
piezoelectric materials due to their superior piezoelectric proper-
ties close to the morphotropic phase boundary (MPB). Never-
theless, they are not environmentally friendly for the lead oxide
toxicity. Therefore, it is vital to develop lead-free ceramics with
comparable piezoelectric properties to those of PZT [1–5].
Recently, high piezoelectric constants d33 ¼300–600 pC/N were
obtained in the Ba(Zr0.2Ti0.8)O3–(Ba0.7Ca0.3)TiO3 (BCT–BZT) sys-
tems which were close to a triple point of cube–rhombohedral–
tetragonal (C–R–T) [3,6–8]. The strong piezoelectric responses
have been interpreted in terms of isotropic flattening of a free
energy profile associated with the C–R–T triple point which was a
tricritical point [9]. For such instable structure, ferroelectrics often
exhibit large, anisotropic increase in piezoelectric, dielectric, and elastic
responses. Thus, it is not surprising that anomalies in the electro-
mechanical response, including a peak in d33, are observed in BCT–BZT
ceramics near the polymorphic phase transition (PPT) [10]. In these
lead-free ceramics, the enhanced piezoelectric properties are accom-
panied by the occurrence of a PPT around room temperature [11–14].
In this paper, the enlarged PPT and enhanced piezoelectric proper-
ties were studied in the ternary component 0.8Ba1
xCaxTiO3–
0.1BaTi0.8Zr0.2O3–0.1BaTi0.9Sn0.1O3 ceramics. The study may provide
a new guide for developing lead-free ceramics with excellent piezo-
electric properties.
2. Experimental procedure
The 0.8Ba1
xCaxTiO3–0.1BaTi0.8Zr0.2O3–0.1BaTi0.9Sn0.1O3 (BCT–
BZT–BST) ceramics (x ¼0, 0.005, 0.01, 0.02, 0.04, 0.06, 0.10 and
0.20) were prepared by conventional solid-state reaction techni-
que. Raw materials of BaCO3 (99.0%), CaCO3 (99.0%), ZrO2 (99.0%),
TiO2 (99.5%) and SnO2 (99.0%) were mixed according to a pre-
determined ratio with addition of alcohol. The mixed raw materi-
als were dried at 80 1C for 12 h and then calcined at 1250 1C
for 4 h. Thereafter, calcined powders were remixed and pressed
into 12 mm-diameter pellets and sintered at 1450 1C for 4 h in air.
Phase structure was examined using an X-ray diffraction meter
with a Cu Kα radiation (λ¼1.5406 Å) (XRD, D8 Advance, Bruker
Inc., Germany). Dielectric properties were measured using the
precision impedance analyzer (4294A Agilent Inc., USA) at
100 kHz. Ferroelectric domains were studied by piezoresponse
force microscopy (PFM) (SPA 400, SPI3800N, Seiko Inc. Japan).
Piezoelectric coefficient was measured using aquasi-static d33
meter (YE2730 SINOCERA, China).
3. Results and discussion

n
Corresponding author. Tel./fax: +86 6358230923. Fig. 1 shows the XRD patterns of the BCT–BZT–BST ceramics
E-mail addresses: liwei_727@163.com (W. Li), zhjxu@lcu.edu.cn (Z. Xu). with different compositions of x. It can be seen that all the samples

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.08.008
 W. Li et al. / Materials Letters 110 (2013) 80–82 81

5.70

110

200
200
BCT-BZT

002
211
002
111
5.65
100

220

Orthorhombic
210
x=0.20 5.60 Tetragonal
4.04
x=0.10

Lattiace parameter (Å)

Intensity(a.u.)

4.02
x=0.06 PPT-1 a
4.00
b
x=0.04 c
3.98
x=0.02 5.75

5.70
BCT-BZT-BST
x=0.01

Orthorhombic
5.65
x=0 4.04 Tetragonal
20 30 40 50 60 70 44 45 46 47 4.02
2 Theta/(Degrees)
4.00 PPT-2
Fig. 1. X-ray diffraction patterns of the BCT–BZT–BST (x ¼0, 0.01, 0.02, 0.04, 0.06,
0.10 and 0.20) ceramics.
3.98
0.00 0.01 0.02 0.03 0.04 0.05 0.06

12000 0.14
x of Ca content
x=0
x=0.01 Fig. 3. Lattice parameters of the BCT–BZT–BST and BCT–BZT ceramics as function of x.
10000 x=0.02 0.12
x=0.04
x=0.06
8000 x=0.10 TO–T decreases by a factor of 4.8 1C/mol% with the increase of Ca
0.10
x=0.20
Dielectric constant

content. The temperatures of TO–T decrease linearly, while the Curie

Dielectric loss

6000 temperatures of TC do not shift obviously [16,21–23]. This result

4000
2000
0
-20 0 20 40 60
Temperature(°C)
Fig. 2. Temperature dependence of dielectric constant for the BCT–BZT–BST (x ¼ 0,
0.01, 0.02, 0.04, 0.06, 0.10 and 0.20) ceramics measured at 100 kHz.
show pure perovskite structure, suggesting that Ca, Zr and Sn have
diffused into the BaTiO3 lattice to form a solid solution. At room
temperature, the BCT–BZT–BST ceramics at x ¼0 possess orthor-
hombic phase [15,16], which is characterized by a strong peak of
(002) at around 2θ of 451. The BCT–BZT–BST ceramics become
tetragonal phase [17,18], featured with splitting of the (002)/(200)
peaks at around 2θ of 451, with increasing Ca content. The BCT–
BZT–BST ceramics possess pure tetragonal phase at xZ0.06.
Therefore, it can be suggested that the orthorhombic phase and
tetragonal phase coexist in the composition range of 0 ox r0.04
for BCT–BZT–BST ceramics at room temperature [18–20].
The temperature dependences of dielectric constant and dielectric
loss for BCT–BZT–BST ceramics measured at frequency of 100 kHz
between –20 1C to 140 1C are shown in Fig. 2. The BCT–BZT–BST
ceramics at 0rxo0.20 exhibit two obvious polymorphic phase
transitions corresponding to the orthorhombic–tetragonal (TO–T) and
tetragonal–cubic transitions (TC), respectively, and the dielectric losses
are lower than 0.03 [16,17]. The temperatures of TO–T are about 40 1C,
35 1C, 28 1C, 22 1C, 15 1C and
8 1C, corresponding to the BCT–BZT–
BST ceramics at x¼ 0, x¼0.01, x¼ 0.02, x¼0.04, x¼ 0.06 and x¼0.10,
respectively. With further increase of Ca content (x¼0.20), the
orthorhombic to tetragonal phase transition cannot be observed above
–20 1C. The TO–T transition peaks shift towards lower temperature with
increasing Ca content. It can be noted from the inset of Fig. 2 that the
0.08
indicates that the TO–T can be shifted near room temperature while
the TC maintains above 90 1C with doping Ca content in the BCT–BZT–
0.06
BST ceramics.
Fig. 3 shows the lattice parameters of the BCT–BZT–BST and the
0.04
BCT–BZT [24] ceramics, which are calculated by refining X-ray
diffraction data. The varied lattice parameters are considered as
0.02
the further evidence of phase transition from orthorhombic to
tetragonal symmetry. The lattice parameters of orthorhombic
0.00
BCT–BZT ceramics are a¼ 3.987 Å, b¼ 5.657 Å, and c ¼5.663 Å at
80 100 120 140
x¼ 0, while those are a ¼b¼4.002 Å and c ¼4.032Å for the tetra-
gonal BCT–BZT ceramics at x¼0.02. The tetragonal lattice para-
meters do not change obviously with increasing Ca content
(x 40.02). The discontinuous change is observed at x ¼0.005–
0.02, suggesting where the PPT-1 between the orthorhombic and
tetragonal phase should exist [18]. Same phenomena is observed
in the BCT–BZT–BST ceramics, and the PPT-2 is enlarged to the
region of x ¼0.005–0.04, which is twice as large as that of BCT–BZT
ceramics. It can be observed that the piezoelectric constants of
both systems reach high level with increasing Ca content, as
shown in Fig. 4. At compositions of x ¼0.01 and 0.02, d33 of the
BCT–BZT ceramics are 370 pC/N and 320 pC/N, while the d33 of the
BCT–BZT–BST ceramics are 420 pC/N and 400 pC/N, respectively. It
is believed that the observed high piezoelectric properties should
be attributed to the PPT occurring near room temperature
[3,4,25,26]. The PPT causes instability of the polarization state, so
that polarization direction can be easily rotated, resulting in a high
piezoelectricity [9,27].
It is worth noting that there are differences between the two
PPT on enhancing piezoelectricity. The piezoelectric response of
BCT–BZT–BST ceramics is higher than that of the BCT–BZT cera-
mics, and the region of PPT of BCT–BZT–BST ceramics is larger than
that of BCT–BZT ceramics. The reasons why the BCT–BZT–BST
exhibits better piezoelectric properties than that of the BCT–BZT
can be understood through both the intrinsic effect (polarization
rotation and extension) [3,28] and the extrinsic effect (contribu-
tion from domain) [29]. The larger piezoelectric response reveals
that the crystal lattice at the PPT of the BCT–BZT–BST can
respond to the external electric field more easily than that of the
82 W. Li et al. / Materials Letters 110 (2013) 80–82
450
BCT-BZT
BCT-BZT-BST
400
d33(pC/N)
350
300
PPT-1
250
PPT-2
0.00 0.01 0.02 0.03 0.04 0.05 0.06
x of Ca contant
Fig. 4. Piezoelectric constant as function of x for the BCT–BZT–BST and BCT–BZT
ceramics, the inserts are PFM images of ferroelectric domains for (a) BCT–BZT and
(b) BCT–BZT–BST at PPT.
BCT–BZT [24,30]. The symmetry mismatch originated from local
and long-range structures, the random local strain and the
inequality of the octahedral tilting between TiO6, ZrO6 and SnO6
is expected to be enhanced by adding the third component of BST
[3,31]. On the other hand, such high-d33 compositions coincide
with a miniaturized nanodomain structure [14,32]. The insets of
(a) and (b) in Fig. 4 show the domain configurations of BCT–BZT
and BCT–BZT–BST at PPT. Irregular domains are observed in both
samples indicating transient state between orthorhombic and
tetragonal phase. With addition of the third component BST, more
complex domain structure and smaller domain size exist in the
BCT–BZT–BST. The microstructural characterization should be
referred to the transition from normal ferroelectric phase to
relaxor ferroelectric phase, which diffuse the phase transition
and enhance the piezoelectricity [29,31]. Enhanced piezoelectric
property and enlarged PPT boundary are obtained in the ternary
component BCT–BZT–BST ceramics. This special feature encoun-
tered here is important to the design of lead-free piezoelectric
material.
4. Conclusions
The ternary component BCT–BZT–BST ceramics were prepared
using a solid-state reaction technique. Enhanced piezoelectric property
and enlarged PPT were obtained in the BCT–BZT–BST system. The PPT
from orthorhombic to tetragonal phase around room temperature was
identified in the range of 0oxr0.04. High piezoelectric constant of
d33 ¼420 pC/N was obtained for the sample at x¼0.01.
Acknowledgments
This work was supported by the National High Technology
Research and Development Program of China (No. 2013AA030501),
the Natural Science Foundation of Shandong Province of China (Nos.
ZR2011EMQ015 and ZR2012EMM004) and the Research Foundation of
Liaocheng University (No. 318011301).
References
[1] Saito Y, Takao H, Tani T, Nonoyama T, Takatori K, Homma T, et al. Nature
2004;432:84–7.
[2] Zhang S-T, Kounga AB, Aulbach E, Ehrenberg H, Rödel. Journal of Applied
Physics Letters 2007;91:112906.
[3] Liu W, Ren X. Physical Review Letters 2009;103:257602.
[4] Zhang S, Xia R, Shrout TR, Zang G, Wang J. Journal of Applied Physics
2006;100:104108.
[5] Guo Y, Liu Y, Withers RL, Brink F, Chen H. Chemistry of Materials
2011;23:219–28.
[6] Wu J, Xiao D, Wu W, Chen Q, Zhu J, Yang Z, et al. Scripta Materialia
2011;65:771–4.
[7] Li W, Xu Z, Chu R, Fu P, Zang G. Journal of the American Ceramic Society
2010;93:2942–4.
[8] Hao J, Bai W, Li W, Zhai J. Journal of the American Ceramic Society
2012;95:1998–2006.
[9] Damjanovic D. Journal of the American Ceramic Society 2005;88:2663–76.
[10] Xue D, Zhou Y, Bao H, Zhou C, Gao J, Ren X. Journal of Applied Physics
2011;109:054110.
[11] Ehmke MC, Ehrlich SN, Blendell JE, Bowman KJ. Journal of Applied Physics
2012;111:124110.
[12] Zhou J-J, Li J-F, Zhang X-W. Journal of the European Ceramic Society
2012;32:267–70.
[13] Zang G-Z, Wang J-F, Chen H-C, Su W-B, Wang C-M, Qi P, et al. Applied Physics
Letters 2006;88:212908.
[14] Gao J, Xue D, Wang Y, Wang D, Zhang L, Wu H, et al. Applied Physics Letters
2011;99:092901.
[15] Maiti T, Guo R, Bhalla AS. Applied Physics Letters 2006;89:122909–13.
[16] Jaffe B, Cook WR, Jaffe HL. Piezoelectric ceramics.London: Academic Press; 1971.
[17] Zhang P, Shen M, Fang L, Zheng F, Wu X, Shen J, et al. Applied Physics Letters
2008;92:222908.
[18] Zhu LF, Zhang BP, Zhao XK, Zhao L, Zhou PF, Li JF. Journal of the American
Ceramic Society 2013;96:241–5.
[19] Guo Y, Kakimoto K-i, Ohsato H. Applied Physics Letters 2004;85:4121.
[20] Jiang M, Liu X, Chen G. Scripta Materialia 2009;60:909–12.
[21] Lei C, Bokov AA, Ye ZG. Journal of Applied Physics 2007;101:084105.
[22] Zhang L, Wang X, Yang W, Liu H, Yao X. Journal of Applied Physics
2008;104:014104.
[23] Yoon M-S, Ur S-C. Ceramics International 2008;34:1941–8.
[24] Li W, Xu Z, Chu R, Fu P, Zang G. Materials Letters 2010;64:2325–7.
[25] Wang K, Li J-F. Advanced Functional Materials 2010;20:1924–9.
[26] Zhang JL, Zong XJ, Wu L, Gao Y, Zheng P, Shao SF. Applied Physics Letters
2009;95:022909.
[27] Fu H, Cohen RE. Nature 2000;403:281–3.
[28] Damjanovic D. Applied Physics Letters 2010;97:062906.
[29] Shvartsman VV, Kleemann W, Dec J, Xu ZK, Lu SG. Journal of Applied Physics
2006;99:124111.
[30] Wu J, Xiao D, Wu W, Chen Q, Zhu J, Yang Z, et al. Journal of the European
Ceramic Society 2012;32:891–8.
[31] Lu SG, Xu ZK, Chen H. Applied Physics Letters 2004;85:5319.
[32] Ma N, Zhang B-P, Yang W-G, Guo D. Journal of the European Ceramic Society
2012;32:1059–66.