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CERAMICS
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Ceramics International 40 (2014) 1490714912
www.elsevier.com/locate/ceramint

Piezoelectric properties of BaTiO3CaTiO3BaZrO3 ceramics with

compositions near the morphotropic phase boundary
W. Wanga, L.D. Wanga, W.L. Lia,b, D. Xua, Y.F. Houa, W.P. Caoa, Y. Fenga, W.D. Feia,n
a
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, PR China
b
National Key Laboratory of Science and Technology on Precision Heat Processing of Metals, Harbin Institute of Technology, Harbin 150001, PR China
Received 24 March 2014; received in revised form 26 May 2014; accepted 16 June 2014
Available online 21 June 2014

Abstract

The phase diagram of BaTiO3CaTiO3BaZrO3 (BTBZCT) ternary system with compositions near the morphotropic phase boundary
(MPB) has been studied. Based on the phase diagram, the relationship between piezoelectric properties and energy barriers of BTBZCT
ceramics with compositions near the MPB has been studied. Experimental result indicates that the piezoelectric response is proportional to the
energy barrier between tetragonal (T) and cubic (C) phases for the samples with the same phase composition. Furthermore, when the energy
barrier is small enough, polarization intensity change of the phase transitions is the decisive factor for the huge piezoelectric response.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Piezoelectric properties; Energy barriers; BZTxBCT ceramics; BTBZCT ternary system

1. Introduction Liu and Ren presented a phase diagram in which pure

As environmentally friendly materials, lead-free piezoelec-
tric ceramics are of potential interest as alternatives to lead-
based piezoelectric ceramics [13]. Recently, pseudo-binary
lead-free (1
x)BaZr0.2Ti0.8O3xBa0.7Ca0.3TiO3 (xBC0.3T)
ceramic have attracted much attention for their huge piezo-
electric response, the piezoelectric coefcients (d33) of
xBC0.3T ceramics with the compositions near x=0.5 are around
560620 pm/V, higher than that of soft PZT [49]. In fact, the
pseudo-binary xBC0.3T system is a section of the ternary
system based on BaTiO3, BaZrO3 and CaTiO3 (BTBZCT),
the thick dash line in Fig. 1a shows the compositions of
pseudo-binary xBC0.3T system given by Liu and Ren [4]. Most
studies are focused on the ceramics with composition at this
thick dash line [5,7,917]; however, the ceramics with
composition around this line in the BTBZCT ternary
diagram have been rarely studied.
n
Corresponding author. Tel.: 86 451 86413908.
E-mail address: wdfei@hit.edu.cn (W.D. Fei).
rhombohedral (R) and tetragonal (T) phase regions are
separated by a morphotropic phase boundary (MPB), and they
pointed out that the huge piezoelectric response of xBC0.3T
resulted from the lowenergy barriers of the phase transitions
near the tricritical point [4,5]. Further studies on xBC0.3T
system indicated that there was a transitional region between R
and T phases in the phase diagram, and the phase composition
of this region was the mixture phase of R and T phases
[9,11,18]. Ehmke et al. reported the phase coexistence of R, T,
and cubic (C) phases and the domain reorientation behavior of
T phase under stress [12,13]. And both polarization rotation
(the domain reorientation of T phase) and extension (the R-T
phase transition) make contributions to the large piezoelectric
response as Damjanovic et al. suggested [1].
Therefore, the low energy barriers of these phases which
lead to easy phase transitions are important to the huge
piezoelectric response. However, the relationship between
energy barrier and d33 has not been well studied yet. In
addition, the phase composition and piezoelectric properties
of the BTBZCT ternary system have not been well

http://dx.doi.org/10.1016/j.ceramint.2014.06.086
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
14908 W. Wang et al. / Ceramics International 40 (2014) 1490714912

Fig. 1. (a) BTBZCT ternary diagram, the thick dash line shows the compositions of Liu and Ren [4], the dot lines (line A, B and C) show the compositions
studied in this paper; (b) the phase diagram of xBC0.3T reported by Liu and Ren [4].

Fig. 2. (a) Typical versus temperature (the composition is (1
1.24y)BT0.52yBZ0.72yCT, y 0.21), (b)(d) phase diagram of the line A, line B and line C
samples, the dark dash lines show the temperature of the piezoelectric test.

investigated, although the pseudo-binary xBC0.3T system has 2. Experimental procedure

been extensively investigated.
In this paper, the phase transitions and piezoelectric properties
of the BTBZCT ceramics with the compositions near the MPB
of the pseudo-binary xBC0.3T system have been studied. And the
results show that the d33 value is inuenced by both the energy
barriers and the type of the phase transitions.
2.1. Composition design
The BTBZCT ternary diagram is shown in Fig. 1. The
compositions of the samples studied in this paper lay on
line A, line B and line C (the dot lines in Fig. 1), respectively.
 W. Wang et al. / Ceramics International 40 (2014) 1490714912 14909

The compositions of the line A samples (from bottom to top) are

(1
1.24y)BT0.52yBZ0.72yCT, of the line B samples are
(1
1.25y)BT0.50yBZ0.75yCT and of the line C samples
are (1
1.26y)BT0.48yBZ0.78yCT (y 0.22, 0.21, 0.2, 0.19),
respectively.

2.2. Experiment method

Polycrystalline BTBZCT samples (with compositions shown

in Fig. 1) were synthesized by conventional solid state reaction
technique. Stoichioimetric quantities of BaCO3 (99%), TiO2
(98%), CaCO3 (99%) and BaZrO3 (99%) were mixed and ground
by ball milling for 10 h with the addition of ethanol. After being
dried, the powder mixtures were calcined at 1250 1C for 3 h in
air. Then the mixture was ground again for 10 h with the addition
of ethanol. After being dried, the powder mixtures were mixed
with PVA binder (3 wt%) and pressed into pellets (10 mm
diameter and 1 mm thick) under uniaxial stress.
Silver electrodes were deposited on both sides of the pellet
samples by magnetron sputtering. The dielectric properties were
measured at 1 kHz as a function of temperature (
50160 1C) on
a Novocontrol CONCEPT40 Broadband Dielectric Spectrometer.
The samples were poled in a silicon oil bath at room temperature
under an electric eld of 3 kV/mm for the measurement of
piezoelectric properties. Then the samples were placed at room
temperature for 24 h, to remove any residual electric charge and
make the samples more stable. Piezoelectric constant d33 was
measured on a quasi-static d33 meter (Model ZJ-4AN; Institute of
Acoustics, Beijing, China); the measurement temperature is 300 K.

3. Results and discussion

3.1. Dielectric properties

The typical dielectric permittivity () versus temperature is

shown in Fig. 2a. In the gure, it can be found that there are
three peaks. According to literature [4,5,9,11], R phase exists
in the temperature region below the peak at the lowest
temperature, T phase exists in the temperature region between
the peaks at the middle temperature and the highest tempera-
ture. The phase diagrams of line A, line B and line C are
established on the bases of dielectric measurement, as shown
in Fig. 2b to d. The phase diagrams of line A, line B and line C
all have pure T phase and R phase regions, and an R plus T
mixture phase region between the two pure phase regions.
In our study, the piezoelectric coefcients were measured at
300 K. According to the phase diagrams, it can be found that the
phase structures of line A and line B samples are R and T mixture
phases, while those of line C samples are pure T phases at 300 K. Fig. 3. (a)(c) piezoelectric properties of the line A, line B and line C samples
at 300 K, respectively.
3.2. Piezoelectric properties
3.3. The energy barriers and piezoelectric responses
The d33 values of the line A, line B and line C samples at 300 K
are shown in Fig. 3, it can be seen that the d33 values decrease with According to LandauDevonshire theory [19,20], the free
the decrease of y; the d33 values of the line A samples decrease energy of the system is given by:
slower than those of the line B and line C samples. Discussions of
these phenomena are presented hereinafter. G G0 AP2 BP4 DP6 1
14910 W. Wang et al. / Ceramics International 40 (2014) 1490714912

Fig. 4. (a) Free energy of the system, (b) d33 versus T C
T, (T 300 K) and (c) the polarization intensity change of the R-T phase transition and the Tin-plane-
Tout-plane domain reorientation.

where A 20 T
T 0 , T0 is the CurieWeiss temperature. As values of the BTBZCT ceramics near the MPB are strongly
shown in Fig. 4a, the energy barrier between T and C phases is inuenced by the energy barriers.
E B GP0
GP, where GP0 and GP are the maximum For further discussion, linear regression is done by using the
and minimum values in GP curve. p0 and p can be resolved d33 values of the line A, line B and line C samples versus T C
T,
using the following equation respectively. As shown in Fig. 4b, the d33 values versus T C
T
G of the line A samples can be well tted by one straight line, while
0 2 that of the line B and line C samples can be well tted by the
P
other straight line. The tted results possibly imply that the huge
Then we can obtain the following relation piezoelectric response mechanism of the line B samples is similar
 2 3=2 to that of the line C samples, but it is different from the line A
4 B
E B GP0
GP p
3A 3 samples. According to the phase diagram given in Fig. 2b to d,
27 D D the phase compositions of the line A samples are the mixture of R
2 and T phases at 300 K. The content of R phase in the line B
where BD 0 T C
T 0 and 0 1=0 C, C is the CurieWeiss
samples may be much lower than that of the line A samples.
constant, 0 is the Vacuum permittivity. Then we get that
Since the phase compositions of the line B samples locate at the
 3=2
40 3=2 1 3 MPB, the phase compositions of the samples are mainly T
E B p T C T 0
T 4 phases. And the phase compositions of the line C samples are
27 D 2 2
pure T phases. For this system, the energy barriers of the phases
The phase transition between T and C phases of this system are small, therefore, the RT phase transition [4] and the domain
is closed to a second order phase transition [4], so we get that reorientation of T phase [13] between the in-plane domain T
T C  T 0 , then we get that phase (Tin-plane) and out-plane T phase (Tout-plane)- may exist in all
 3 1=2 samples. Considering the phase compositions, the phase transi-
20
Eb T C
T 3=2 5 tions of the line A samples are mainly the phase transitions
27D between R and T phases, while those of the line B and line C
 3 1=2 samples are mainly the domain reorientations of T phases.
2
The difference of 27D0 among the samples could be
From Fig. 4b, it can be seen that the d33 values decrease with
ignored, if the CurieWeiss constant C and D are not sensitive the increase of Eb (the energy barrier between T and C phases)
to the composition. The energy barriers of the samples are mainly for the samples with similar phase compositions. The phenom-
inuenced by T C
T3=2 (T is the measurement temperature). enon that the d33 value is strongly inuenced by the energy
Therefore, the energy barriers (Eb) of the samples are proportional barrier between T and C phases indicates that the piezoelectric
to T C
T at temperature T. response is closely related to the TC phase transition. And
The variation of d33 values with T C T (T 300 K in the this result implies that the R-T phase transition and Tin-plane-
present study) is shown in Fig. 4b. It can be found that the d33 Tout-plane domain reorientation may take place through R-C-T
values of the line A, line B and line C samples decrease with the phase transition and Tin-plane-C-Tout-plane phase transition,
increase of T C
T, respectively. This result suggests that the d33 respectively.
 W. Wang et al. / Ceramics International 40 (2014) 1490714912
When the energy barriers are small, the d33 values of the line B
and line C samples are larger than those of the line A samples.
This result could be explained as follows:
The piezoelectric effect of ferroelectrics is the response property
under stress, and the larger the polarization change under stress,
the higher the piezoelectric coefcient [21]. Two paths can lead to
high piezoelectric coefcient of the ferroelectric ceramics in the
vicinity of MPB [2224], one is the polarization rotation of low
symmetry phase, and the other is polarization direction change
caused by phase transition. The polarization direction changes
under stress in the present system include two ways. On one
hand, the polarization change is from PR (with the polarization
direction of the pseudo-cubic (1 1 1) direction) to PT (with the
polarization direction of the pseudo-cubic (0 0 1) direction) when
the R-T phase transition happens. On the other hand, the
polarization change is from PTx to PTz when the Tin-plane-Tout-
plane domain reorientation happens. The two type changes in
polarization above lead to the large piezoelectric response in this
system [2224].
As shown in Fig. 4c, the P of the Tin-plane-Tout-plane domain
reorientation is larger than that of the R-T phase transition.
Therefore, the domain reorientation of T phases contributes more to
the piezoelectric response than the R-T phase transition. When Eb
is small enough the two phase transformations are easy, P is the
main determinant factor for the d33 value rather than Eb. But the
two phase transformations become more difcult to take place
when the energy barrier becomes larger; then the d33 value
decrease. And as shown in Fig. 4b, the d33 values of the line B
and line C samples decrease dramatically with the increase of Eb,
while those of the line A samples decrease slowly. This phenom-
enon indicates that when the energy barrier is large, the R-T
phase transition is much easier to take place than the Tin-plane-Tout-
plane domain reorientation and the Eb value is the main determinant
factor of the d33 value rather than P.
In summary, the d33 values are decided by both the energy
barrier between T and C phases and the polarization intensity
changes of the phase transitions for the BTBZCT system. When
Eb is small enough and both of the two phase transitions are easy
to take place, P is the main determinant factor of the d33 value.
4. Conclusions
The phase diagram of the BTBZCT ternary system with
compositions near the MPB has been given in this paper. The
relationship between the piezoelectric response and energy
barrier (between T and C phases) has been studied. The
experimental results indicate that the piezoelectric response is
proportional to energy barriers between T and C phases for the
samples with the same phase composition. When Eb is small
enough, all phase transitions of this system are easy, P is the
main determinant factor of the huge d33 value, but when it
becomes larger, Eb is the main determinant factor of the huge
d33 value rather than P. Furthermore, according to the phase
diagram, the TC of the composition containing more T phase is
higher than the TC of the composition containing more R
phase. And these results suggest that the composition contain-
ing more T phase may have a larger d33 and a higher TC than
14911
the composition containing more R phases near the MPB
region.
Acknowledgements
This research was nancially supported by the National
Natural Science Foundation of China (no. 11272102).
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