Materials Research Bulletin 48 (2013) 2006–2009

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Materials Research Bulletin

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Short communication

Temperature dependences of the ferroelectric and dielectric properties of high

curie temperature PbTiO3–BiScO3–Bi(Zn1/2Zr1/2)O3
Huajun Kang a, Jun Chen a, Laijun Liu b, Liang Fang b, Xianran Xing a,c,*
a
Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China
b
Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Ministry of Education, Guilin University of Technology, Guilin 541004, China
c
State Key of Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China

A R T I C L E I N F O A B S T R A C T

Article history: The piezoelectric ceramics (1  x  y)PbTiO3–xBiScO3–yBi(Zn1/2Zr1/2)O3 exhibit greatly enhanced

Received 31 October 2012 ferroelectric properties above room temperature, between 100 and 200 8C. A strong second harmonic
Received in revised form 22 January 2013 generation (SHG) effect was observed below 200 8C. The highest remanent polarization (40 mC/cm2)
Accepted 2 February 2013
and lowest coercive field (10 kV/cm) were obtained at 200 8C. X-ray diffraction (XRD) analysis was used
Available online 11 February 2013
to investigate the morphotropic phase boundary (MPB) structure of (1  x  y)PbTiO3–xBiScO3–yBi(Zn1/
2Zr1/2)O3 ceramics. Transmission electron microscopy (TEM) results confirm the existence of MPB, where
Keywords:
the rhombohedral and tetragonal phases coexist. The results of thermal expansion analysis show a low
A. Ceramics
D. Ferroelectricity
thermal expansion and stability of this material. The optimal high temperature piezoelectric ceramic is
D. Piezoelectricity obtained by the composition of 0.05BZZ–0.34BS–0.61PT.
ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction applications are restricted due to either limited solid solubility or

inferior piezoelectric properties.
Over the past decades, technological advancements in the fields In 1996, the PbTiO3–Bi(Zn1/2Zr1/2)O3 system had been
of materials engineering and systems integration have led to the addressed by Gridnev et al. [7]. They found Zinc ion (0.38 Å) has
demand for piezoelectric actuators and sensors applied at high a larger off-center displacement than Ti ion (0.32 Å) for 0.75PT–
temperatures, especially in the aerospace, automotive and energy 0.25BZT due to the strong hybridization of the 4s and 4p orbitals of
industries [1–3]. However, significant loss of polarization and Zn with the 2p orbitals of O atoms [12]. The X-ray diffraction (XRD)
mechanical stress occurs in the conventional piezoelectric results showed that all the (1  x)PbTiO3–xBi(Zn1/2Zr1/2)O3 com-
materials based on Pb(Zr1xTix)O3 (PZT) composition (Curie positions with x > 0.3 revealed two phase products. In our previous
temperature Tc = 386 8C) at temperatures lower than 200 8C [4]. research, we found that the coercive field (Ec) can reach 85 kV/cm
Recently, PbTiO3–Bi(Me)O3 type ferroelectric ceramics (Me are (x = 0.2) and it is hard to be poled by electrical field [13]. In this
cations with an average valence of 3+) have received great interest study, the ceramics of (1  x  y)PbTiO3–xBiScO3–yBi(Zn1/2Zr1/
due to their characteristic structures combined with potential 2)O3 near the MPB (x = 0.34, y = 0.05; x = 0.30, y = 0.10), where the
piezoelectric applications at high temperatures. Eitel et al. tetragonal, rhombohedral phases and the domain walls were
reported that PbTiO3–BiScO3 possesses excellent piezoelectric recognized by XRD analysis, were prepared by solid-state method.
properties near the morphotropic phase boundary (MPB) (x = 0.64) The temperature dependence of polarization and strain of bipolar
(piezoelectric coefficient, d33 = 460 pC/N, planar coupling coeffi- electric loading were investigated by P–E and S–E loops.
cient, kp = 0.56, and Tc = 450 8C) [5,6]. Although a series of PbTiO3– Furthermore, the second harmonic generation (SHG) measure-
Bi(Me)O3 materials have been studied extensively, e.g. PbTiO3– ment is required to study the polar change of materials with
Bi(Zn1/2Zr1/2)O3 [7], PbTiO3–BiInO3 [8], PbTiO3–BiGaO3 [9], temperature. The ferroelectric properties were analyzed by the
PbTiO3–Bi(Mg1/2Ti1/2)O3 [10], PbTiO3–Bi(Mg1/2Zr1/2)O3 [11], their SHG measurements from room temperature (RT) to 450 8C.

2. Experimental

The materials of PbTiO3–BiScO3–Bi(Zn1/2Zr1/2)O3 (abbreviated

* Corresponding author at: Department of Chemistry, University of Science and
Technology Beijing, Beijing 100083, China. Tel.: +86 10 62334200;
as PT–BS100x–BZZ100y) ceramics were prepared by the conven-
fax: +86 10 62332525. tional solid-state reaction. Analytical reagent oxides and carbo-
E-mail address: [email protected] (X. Xing). nates were used as precursors: PbO, Bi2O3, TiO2, ZrO2, Sc2O3, and

0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2013.02.002
 H. Kang et al. / Materials Research Bulletin 48 (2013) 2006–2009 2007

ZnCO3. The raw materials were accurately weighed and then 3. Results and discussion
milled in the alcohol media for 12 h by planetary milling. After
calcination at 860 8C for 5 h, the sintered powders were ball ground The XRD patterns of powders of PT–xBS–BZZ5, (0.29  x  0.35)
again. The dried and sintered powders were subsequently pressed at RT are shown in Fig. 1a. All the samples exhibit pure perovskite
into pellets in a diameter of 10 mm with a thickness of 1 mm. phase. When the value of x is larger than 0.35, it is indexed in a
Those pellets were then sintered at 1050–1150 8C for 2 h. rhombohedral symmetry where no apparent splitting of peaks
XRD (Rigaku) analysis at room temperature was performed to such as {2 0 0} can be detected. Tetragonal phase is observed for
reveal the crystal structures. The temperature dependence of x  0.33 as displayed by the splitting of {1 0 0} and {2 0 0} peaks. It
crystal structure of PT–BS34–BZZ5 ceramics was further studied indicates that a phase transformation from tetragonal to rhombo-
from room temperature up to 600 8C (TTRIII). The data were hedral can be detected in the compositional range of
collected in a 2u angular range of 208–608 using a step (0.028) 0.33  x  0.35. By increasing the content of PbTiO3, it is evident
scanning mode with the step duration of 5 s. that the relative intensity of the (2 0 0) peak near 2u = 458 indicates
The sintered pellets were grounded and polished to a thickness the phase transformation from tetragonal to rhombohedral
of 0.6 mm and then all pellets were coated with silver paste for structure. The MPB is located around the composition of PT–
electrical properties measurements. The polarization and longitu- BS34–BZZ5, where the value of piezoelectric property can reach
dinal strain vs. electric field hysteretic loops were characterized by 420 pC/N. Fig. 1b shows the XRD patterns of the PT–BS34–BZZ5 at
a ferroelectricity analyzer (TF Analyzer 1000) at a frequency of RT to 600 8C (interval: 100 8C). In the temperature range of RT–
1 Hz. The measurement was performed from room temperature to 400 8C, PT–BS34–BZZ5 mainly preserves its tetragonal structure,
200 8C with an interval of 40 8C. Before collecting the data, the indicating a good stability property of vertical MPB. Its piezoelec-
sample was held at each temperature for 30 min to minimize tric property could have a high thermal stability due to the absence
thermal fluctuation. In order to investigate the small-signal of phase transformation below Tc. This is consistent with the
piezoelectric coefficient d33, samples were poled at 60 8C under results from dielectric measurement. However, when temperature
an electric field of 60 kV/cm for a dwelling time of 15 min, and then is further increased to 500 8C, the peaks show a symmetrical
cooled down to room temperature under the applied electric field. character indicating the phase of cubic perovskite. The transfor-
The piezoelectric coefficient d33 was measured after poling 24 h mation from the tetragonal to cubic phase takes place in the
with a piezo-d33 meter (China Academy of Acoustics, ZJ-3). The temperature range of 400–500 8C. The reason for this phase
temperature-dependent dielectric constant and loss tangent were transition can be well understood by the measurements of
determined by an impedance analyzer (HP4294A, Hewlett- temperature-dependent dielectric constant.
Packard Company, Palo Alto, CA) in a frequency range of 103– Fig. 2 shows the transmission electron microscopy (TEM)
106 Hz from room temperature to 500 8C. observation of the PT–BS34–BZZ5 ceramic. In Fig. 2a, the typical

Fig. 1. (a) XRD patterns of PbTiO3–BiScO3–Bi(Zn1/2Zr1/2)O3 at RT. (b) Temperature dependence of XRD patterns of PT–BS34–BZZ5.

Fig. 2. Transmission electron microscopy images of PT–BS34–BZZ5.

2008 H. Kang et al. / Materials Research Bulletin 48 (2013) 2006–2009

Fig. 3. (a) Temperature dependence of P–E loops of PT–BS34–BZZ5. (b) Ec of PT–BS34–BZZ5 at different temperature at 60 kV/cm. (c) Temperature dependence of S–E unipolar
loops for PT–BS34–BZZ5 at 60 kV/cm. (d) Temperature dependence of small signal d33 coefficient of PT–BS34–BZZ5.

tetragonal domain configuration including a grain of 1808 and 908 field piezoelectric coefficient under uni-polar drive, d33ðuniÞ for PT–
domain walls appears. The 1808 domain wall resembles a winding BS34–BZZ5. A linear increase in strain and d33ðuniÞ was observed up
path and the 908 domain wall is ribbon-like [14]. Similarly, we can to 200 8C. The highest strain was obtained at 200 8C. At room
also observe the rhombohedral phase in Fig. 2b [15]. It also temperature, more non-1808 domains are piezoelectrically active
confirms the existence of MPB in this material. The multi-domain due to lower internal stress in the rhombohedral. However, as
structure and high polarity at temperatures below 200 8C facilitate temperature increases, the barrier to domain wall motion
the polarization enhancement with temperatures, which is decreases and the non-1808 domains become increasingly
promising for the future applications of this ceramic. piezoelectrically active [17]. The highest d33ðuniÞ was 475 pm/V
The temperature dependence of P–E loops from RT to 200 8C for at 200 8C.
PT–BS34–BZZ5 is plotted in Fig. 3a. The ceramic shows the In Fig. 4a, the temperature dependence of dielectric constant
hysteretic behavior of a normal ferroelectric material and the was measured at various frequencies for the ceramic with
saturated loops are obtained either at RT or at high temperatures. It composition of PT–BS34–BZZ5. The Curie temperature (Tc) was
is interesting to find that the Pr value increases and the Ec value located at 410 8C. The dielectric loss can be greatly restricted not
decreases with temperatures. It can be attributed to an increase in only at RT but also in the high temperature region; especially with
domain switching, because the motion of domain walls becomes the frequency above 1 kHz. The low dielectric loss in the
easier as Tc is approaching. This general behavior is comparable to a temperature range of RT–500 8C provides a foreground for high
related study in PbTiO3–Bi(Mg1/2Ti1/2)O3 piezoceramics which temperature applications.
display a high remnant polarization and a high coercive field at RT, The second harmonic generation measurements also confirm
together with a greatly enhanced Pr and weakened Ec as the dependence of polarizations on temperature. As well known,
temperature increases [16]. The highest Pr (40 mC/cm2) and ferroelectrics all display a second harmonic generation (SHG)
lowest Ec (10 kV/cm) are obtained at 200 8C. The internal stress effect, which is very sensitive to the symmetry-breaking that
imparted by the rhombohedral structure is consequently lower occurs during the change of temperature. In Fig. 4b, the
than that of the tetragonal structure. Therefore non-1808 domain ferroelectric ceramic of PT–BS34–BZZ5 clearly shows that a
walls are relatively free to move; resulting in a lower Ec and an considerable strong SHG effect appears below 200 8C, and
increase in Pr. The observed value of Ec from the temperature in decreases sharply at temperatures above 200 8C. The SHG effect
inverse proportion was shown in Fig. 3b. Fig. 3c presents the strain still can be observed at 350 8C, it means the sample still has
with electric field from room temperature to 200 8C exhibited by ferroelectricity.
poled PT–BS34–BZZ5 ceramic at 60 kV/cm under unipolar drive. At In Fig. 4c, a dilatometric measurement on PT–BS34–BZZ5
a given field, the strain displayed by the sample approaching Emax ceramic was taken to characterize the apparent thermal expansion
was lower than the strain departing Emax due to strain hysteresis. of materials from room temperature to 800 8C. Dilatometric
Fig. 3d shows the temperature dependence of % strain and high heating and cooling cycles for the ceramic demonstrate the
 H. Kang et al. / Materials Research Bulletin 48 (2013) 2006–2009 2009

Fig. 4. (a) Dielectric constant and loss tangent of PT–BS34–BZZ5. (b) and second-order nonlinear effective coefficient. (c) Dilatometric curves of ceramic bars of PT–BS34–
BZZ5.

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