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Ceramics International 40 (2014) 1490714912
www.elsevier.com/locate/ceramint
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
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.
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 14911
When the energy barriers are small, the d33 values of the line B the composition containing more R phases near the MPB
and line C samples are larger than those of the line A samples. region.
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, Acknowledgements
the higher the piezoelectric coefcient [21]. Two paths can lead to
This research was nancially supported by the National
high piezoelectric coefcient of the ferroelectric ceramics in the
Natural Science Foundation of China (no. 11272102).
vicinity of MPB [2224], one is the polarization rotation of low
symmetry phase, and the other is polarization direction change
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