J. Am. Ceram. Soc.
, 95 [2] 445–448 (2012)
Journal
Investigation of Phase Structure and Electrical Properties of Doped
PMN–PZT Ceramics Prepared by Different Methods
Li Wang, Ruihong Liang, Chaoliang Mao, Min Gao, Gang Du, Fei Cao,
Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China
The doped 0.25Pb(Mg1/3Nb2/3)O3–0.40PbTiO3–0.35PbZrO3
(PMN–PZT) ceramics with pure perovskite phase were pre-
pared by one-step oxide-mixed method and conventional colum-
bite method. The phase structure and electrical properties were
systematically investigated. Crystallites of the ceramic fabri-
cated by the oxide-mixed method are partially oriented with the
c-axis, while samples prepared from columbite method are ran-
domly oriented. This crystalline orientation enabled better elec-
tric properties, especially a higher piezoelectric coefficient d33
of 760 pC/N and electromechanical coupling factor kp of 69%.
Materials fabricated from the oxide-mixed method are attrac-
tive for high-performance piezoelectric actuator and this simple
method may have a great prospect in industrial production.
I. Introduction
L EAD-BASED perovskite-type solid solutions consisting of
ferroelectric and relaxor materials have attracted a great
fundamental and practical interest due to their excellent
dielectric, piezoelectric, and electrostrictive properties.1,2
Among the lead-based materials, lead magnesium niobate–
lead zirconate titanate (PMN–PZT) system has been exten-
sively studied for actuator and sensor applications for its
high piezoelectricity and fairly large strain.3–5
In general, PMN–PZT ceramics with pure perovskite struc-
ture were synthesized by conventional columbite precursor
method.6–8 In this method, the precursor of MgNb2O6 was
first synthesized by calcining the wet-mixed powders of
MgCO3 and Nb2O5 at a temperature. Then, Pb3O4, TiO2,
ZrO2, and MgNb2O6 powders were mixed and calcined to
form a pervoskite-phase PMN–PZT. Afterward, some changes
were made on this method. Villegas et al.9 synthesized PMN–
PZT powders by calcining the mixture of PbO, PZT, and
MgNb2O6, where PZT and MgNb2O6 were prepared previ-
ously. Jiansirisomboon et al.10 and Yimnirun et al.11 prepared
PMN–PZT from calcining mixed PMN and PZT powders, in
which PMN powder was obtained from the columbite method
and PZT by mixed oxides method. The above methods are
complex and it is difficult to control the impurity in industrial
production. In addition, the PMN–PZT system prepared by
the conventional columbite precursor method has a common
piezoelectric coefficient d33 of 200–600 pC/N.7,12–15 However,
S. Bose—contributing editor
Manuscript No. 30231. Received August 26, 2011; approved October 23, 2011.
This work was financially supported by National High Technology Research and
Development Program of China (“863” program, 2009AA03Z108) and Shanghai tech-
nology innovation program (9595810900).
†
Author to whom correspondence should be addressed. e-mail: xldong@sunm.
shcnc.ac.cn
445
DOI: 10.1111/j.1551-2916.2011.04974.x
© 2011 The American Ceramic Society
Genshui Wang, and Xianlin Dong†
there are few reports on the simple fabrication of PMN–PZT
ceramics and the relevant properties.16,17
In our present study, the doped PMN–PZT ceramics with
pure perovskite structure were successfully fabricated by the
one-step oxide-mixed method. Partially oriented crystalline
microstructure has been developed from the method and this
crystalline orientation enables a superior piezoelectricity. In
addition, the phase structure and electrical properties of the
ceramics prepared by the oxide-mixed method and conven-
tional columbite method were systematically investigated.
II. Experimental Procedure
Ceramics with composition of Pb0.92Sr0.06Ba0.02(Mg1/3
Nb2/3)0.25Ti0.40Zr0.35O3 (PMN–PZT) were prepared both by
oxide-mixed method (sample hereafter denoted as S1) and
conventional columbite precursor method (sample hereafter
denoted as S2). In the oxide-mixed method, reagent-grade
powders of Pb3O4, SrCO3, BaCO3, MgCO3·5H2O, Nb2O5,
TiO2, ZrO2 were used as raw materials. These materials were
mixed together and ball-milled for 8 h. Then, they were
calcined at 650°C for 1 h and 850°C for 2 h. As for the
columbite precursor method, first, the columbite precursor
MgNb2O6 was synthesized by mixing MgCO3·5H2O and
Nb2O5 powders and then calcined at 1200°C for 4 h. Next, the
powders of Pb3O4, SrCO3, BaCO3, TiO2, ZrO2, and MgNb2O6
were weighed and wet ball-milled. Then, the mixed powders
were also calcined at 650°C for 1 h and 850°C for 2 h. The cal-
cined powders obtained from the two methods were separately
ground and ball-milled again for 24 h to fine powders. A poly-
vinyl alcohol was added to the dried powders. The powders
were then pressed into disks of 12 mm in diameter and ~2 mm
in thickness. The green pellets were burned out at 800°C for
1 h and then sintered at 1260°C for 2 h. For the properties
measurement, the samples were polished to 1 mm thickness
and coated with silver paint as electrodes. Afterward, the sam-
ples were heat-treated at 700°C for 30 min to ensure the con-
tact between the electrodes and the ceramic surfaces.
The phase structures of specimens were examined by X-ray
diffraction using CuKa radiation (D/MAX-2550V, Rigaku,
Tokyo, Japan). Microstructure of ceramics was observed by
SEM (Model JSM-6700F; JEOL, Tokyo, Japan). The dielec-
tric properties were measured using an inductance–capaci-
tance–resistance (LCR) meter (HP 4284A; Hewlett-Packard,
Kobe-shi, Japan). The piezoelectric properties were measured
after the samples were poled in silicon oil and aged in air for
24 h.
III. Results and Discussion
(1) Phase Structure
The XRD patterns of PMN–PZT ceramics fabricated by the
two methods are shown in Fig. 1. It can be seen that the
446 Rapid Communications of the American Ceramic Society Vol. 95, No. 2

Fig. 1. XRD patterns of S1: samples made by one-step oxide-mixed

method and S2: samples made by conventional columbite method.

pure perovskite structure was obtained through both the

methods. The most distinct difference is the crystalline orien-
tation which has been displayed through (001) and (002)
peaks. The S1 exhibits stronger (00l) diffraction peaks in
comparison with S2, which is randomly oriented. These
observations demonstrate that the crystalline-oriented micro-
structure has been developed from the oxide-mixed method.
To compare the orientation degree of S1 and S2, the relative
intensity of (00l) was calculated according to the simple
equation I(00l)/I(110). The values were 0.18 and 0.07, respec-
tively. The ratio of S1 to S2 is greater than 2.5. This result
indicated that the crystallites of ceramics prepared by oxide-
mixed method are more oriented with the c-axis in compari-
son with that of the columbite method.
Fig. 2. Temperature and frequency dependences of dielectric
(2) Dielectric Properties properties of S1 and S2.
The dielectric properties of the two samples as functions of
temperature T and frequency f are shown in Fig. 2. It can be
seen that both of the dielectric peaks shift to higher tempera-
tures when the frequency increased. The maximum value of
the dielectric constant decreases with increasing frequency.
The dielectric properties of S1 and S2 exhibit a typical relax-
or characteristic.
To compare the dielectric constants e of the two samples
in detail, e–T curves of them at 1 kHz frequency are pre-
sented in Fig. 3. It was found that e of S1 is larger than that
of S2, especially in the vicinity of Tc (phase transition tem-
perature). Initially, we considered the difference of e arose
from the grain size effect. However, SEM results illustrated
that the grain sizes of S1 and S2 are nearly the same.
According to above analyzed results, crystallites in S1 are
partially oriented with the c-axis while that of S2 are ran-
domly oriented. The crystalline orientation in S1 may lead to
higher dielectric constant, which was also found in other
materials, such as BNT ceramics.18

Fig. 3. Temperature dependence of dielectric properties of S1 and

(3) Piezoelectric Properties
The piezoelectric coefficient d33, electromechanical coupling
factor kp, and electromechanical quality factor Qm of the
two samples as function of poling temperature are shown in
Fig. 4. The error bars represent the standard deviation.
When the samples were polarized at 30°C, optimal piezoelec-
tric properties can be obtained. For sample S1, a high d33 of
760 pC/N, as well as a high kp of 69% was obtained. For
sample S2, the two property values decreased. The superior-
ity in piezoelectricity of S1 could be attributed to the crystal-
line orientation with c-axis. The more crystallites along with
(00l) orientation would facilitate the polarization of S1, and
then enable better piezoelectric properties than that of S2. By
S2 at 1 kHz frequency.
the way, Qm of S1 is a little smaller than that of S2. This is
common that materials possessing bigger kp always have
smaller Qm. As we can see, the values of d33 and kp of S1 are
considerably higher compared with reported values of
208 pC/N and 28% in Ref. [7]. Therefore, the PMN–PZT
ceramics prepared by the simple oxide-mixed method possess
an advantage for actuator applications.
Figure 5 shows the field-induced longitudinal strain behav-
iors of the two samples. It can be seen that under low electric
field, S1 can reach a higher strain. While at high electric field,
February 2012 Rapid Communications of the American Ceramic Society 447

Fig. 4. Piezoelectric coefficients d33 (a), electromechanical coupling factor kp, and quality factor Qm (b) as a function of poling temperature for
S1 and S2.

Fig. 5. Field-induced longitudinal field-induced strain behaviors for

S1and S2.

S2 has a little higher strain. The results can be explained by

following formula19: 2
SðEÞ ¼ dE þ ME þ . . .
where S(E) is the field-induced strain and E is the level of
applied electric field. The coefficient “d” describes the revers-
ible piezoelectric response. The latter one “M” is the electro-
strictive coefficient, which is larger in relaxor ferroelectrics
than normal ferroelectrics. From the above formula, it can
be inferred that the larger strain of S1 under low electric field
could be attributed to its higher d33. At high electric field,
the strain may be dominated by the diffuseness degree of the
material. To obtain the value of diffuseness c, the fitting of
ln (ɛrm/ɛr  1) vs ln (T  Tm) is presented in Fig. 6.
The value of c can vary from 1 for normal ferroelectrics
with a normal Curie–Weiss behavior, to 2 for completely Fig. 6. Variation of ln (ɛrm/ɛr  1) vs ln (T  Tm) of S1 and S2.
relaxor ferroelectrics.20–22 It can be found that c of S2 is a
little bigger than that of S1, which may result in a higher
electrostrictive coefficient “M”. This little higher “M” tion enables S1 a higher dielectric constant and better piezo-
enabled S2 a bit larger strain at high electric field. From electric properties, especially a higher d33 of 760 pC/N and
Fig. 5, the maximum strain of S1 can reach 0.224% at kp of 69%. The PMN–PZT ceramics with preferable piezo-
40 kV/cm, which is sufficiently high for actuator applica- electricity prepared by this simple oxide-mixed method
tions.8,23 possess an advantage for actuator applications.

IV. Conclusions References

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bite method (S2). The crystalline-oriented microstructure has
been developed from the oxide-mixed method. This orienta-
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