Journal of Alloys and Compounds 806 (2019) 11e18

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Structure and enhanced piezoelectric performance of BiScO3-PbTiO3-

Pb(Ni1/3Nb2/3)O3 ternary high temperature piezoelectric ceramics
Tian-Long Zhao a, Chunlong Fei a, Xianying Dai a, *, Jianjun Song a, Shuxiang Dong b, **
a
School of Microelectronics, Xidian University, Xi'an, 710071, China
b
Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, 100871, China

a r t i c l e i n f o a b s t r a c t

Article history: BiScO3-PbTiO3 based solid solutions are the most promising candidates in high temperature piezoelectric
Received 19 April 2019 application field. In this research, (1-x-y)BiScO3-xPbTiO3-yPb(Ni1/3Nb2/3)O3 (BS-xPT-yPNN) ternary high
Received in revised form temperature piezoelectric ceramics have been prepared by the traditional solid-state reaction methods
2 July 2019
and investigated in detail. X-Ray diffraction analysis shows that the system has a pure perovskite
Accepted 23 July 2019
Available online 24 July 2019
structure and the morphotropic phase boundary (MPB) region shifts to the low PT region with the
increasing PNN end member. The room temperature phase diagram has been drawn to predict the MPB
region and search for the optimal electrical properties of the BS-xPT-yPNN ternary solid solutions. The
Keywords:
High temperature
dielectric temperature spectra present typical diffuse phase transition characteristic caused by the
BiScO3-PbTiO3 production of chemical heterogeneities with the introduction of PNN. For the BS-xPT-0.025PNN system,
High piezoelectric performance the optimal properties of the piezoelectric coefficient d33 522 pC/N, planar electromechanical coupling
Piezoelectric ceramics factor kp 59.6%, remnant polarization Pr 39.2 mC/cm2, and the Curie temperature Tc 400
C are obtained
Diffuse phase transition for the BS-0.61PT-0.025PNN composition. Furthermore, the piezoelectric performance declines a little to
495 pC/N and 59% of the BS-0.60PT-0.05PNN composition with the increase of PNN content, which is also
equivalent to that of the unmodified BS-PT and other modified BS-PT such as the BS-PT-PZN system. All
these properties reveal that the BS-xPT-yPNN ceramics constitute a new family of high performance high
temperatures piezoelectric materials.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction such as Bi(Zn1/2Ti1/2)O3ePbTiO3, Bi(Mg1/2Ti1/2)O3ePbTiO3,

Nowadays, it is an urgent need for piezoelectric transducers,
sensors, and actuators that can be operated at severe environments,
such as high temperature often encountered in the automotive,
energy, and aerospace industry [1e4]. However, the most com-
mercial used piezoelectric materials (Pb(Zr, Ti)O3, PZT) are gener-
ally limited to the operating temperature of one half the Curie
temperature (Tc), approximately 150
C for PZT, which restricts
their applications in the extreme conditions [5].
Recently, bismuth-based perovskite solid solutions with the
formula Bi(Me)O3-xPbTiO3 (Me refer to the cations of valence þ3,
Sc, In, Yb et al.) have attracted growing interest due to their po-
tential alternatives to PZT in high temperature piezoelectric
application field. Many systems have been investigated in detail
* Corresponding author.
** Corresponding author.
E-mail addresses: xydai@xidian.edu.cn (X. Dai), sxdong@pku.edu.cn (S. Dong).
BiFeO3ePbTiO3, BiScO3-PbTiO3, and so on [6e11]. The binary (1-x)
BiScO3-xPbTiO3 (BS-PT) solid solutions are the most promising
candidates in these systems because that the Bi(Zn1/2Ti1/2)
O3ePbTiO3 solid solutions are hard to synthesize [11] and the
Bi(Mg1/2Ti1/2)O3ePbTiO3, BiFeO3ePbTiO3 will encounter the
conductive problem at high temperature [7,9]. In addition, the
piezoelectric properties (d33 ¼ 460 pC/N, kp ¼ 56%) are comparable
to the commercial piezoelectric materials PZT, whereas the Curie
temperature Tc (~450
C) is about 100
C higher than that of them
[5,10].
However, the BS-PT ceramics also face many challenges such as
the raw materials of scandium oxide are so expensive and limit
their commercial use by the high cost. To solve this problem, one
effective method is to generate a ternary system by importing in a
third component. This method has been proved that not only can
decrease the quantity of scandium oxide but also improve the
piezoelectric properties. Many third components have been
selected to form the BS-PT-ABO3 solid solutions, such as Pb(Cd1/
3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3, Pb(Mg1/3Nb2/3)O3, Pb(Sb1/2Nb1/2)O3,

https://doi.org/10.1016/j.jallcom.2019.07.286
0925-8388/© 2019 Elsevier B.V. All rights reserved.
12 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
LiNbO3, and so on [12e20]. All these new material systems possess
considerable electrical properties and high Curie temperature, for
example, the BS-PT-Pb(Zn1/3Nb2/3)O3 system exhibits the piezo-
electric performance (d33 ¼ 490 pC/N) together with the Curie
temperature Tc 417
C [13] and the BS-PT-Pb(Sb1/2Nb1/2)O3 system
shows the d33 of 553 pC/N and the Tc 384
C at the MPB composition
[15]. However, the content of the third component has a significant
influence on the electrical properties. As reported in the BS-PT-
Pb(Mg1/3Nb2/3)O3 system [14], it presents relaxor ferroelectric
properties when Pb(Mg1/3Nb2/3)O3 content reaches to 0.25 rather
than typical ferroelectric phase transition characteristic found in
the unmodified BS-PT system. The temperature of the dielectric
maximum (Tm) reduced from 450
C to 250
C which is the priority
for high temperature piezoelectric application. It can be concluded
that the content of the third component must be strictly controlled
to achieve the high Curie temperature and the considerable elec-
trical properties when designing the material compositions.
Pb(Ni1/3Nb2/3)O3 (PNN) as a classic relaxor end member, which
often used in PZT based systems, has also been introduced into the
BS-PT system to modified the electrical properties [21e27]. In 2013,
Wang et al. firstly reported that this ternary system with the for-
mula xPNN-(1-x)(0.30BS-0.70 PT) (x ¼ 0.28e0.38) exhibits the d33
of 490 pC/N and the Curie temperature Tc 171
C at the MPB
composition x ¼ 0.35 [26]. The introduction of much more PNN
reduces the phase transition temperature of this system and makes
it not suitable for high temperature piezoelectric application. Then
Meng et al. redesigned the material compositions by the formula of
xPNN-(1-x)(0.36BS-0.64 PT) with x range from 0.003 to 0.05 and
found that the d33 reach to 531 pC/N together with the Tc 417
C
when x ¼ 0.01 [27]. Though they obtained the enhanced piezo-
electric performance by this method, there was an obvious draw-
back that they could not get the accurate MPB region due to the
composition formula fixing the ratio of BS and PT. The proper
method is to fix the content of PNN and change the content of PT to
get an accurate MPB point, then we can achieve the accurate MPB
region by the variation of PNN content. The compositions formula
for this method is (1-x-y)BS-xPT-yPNN. However, this strategy will
take much time to experiment with the various material compo-
sitions. Therefore, we just select the PNN content y ¼ 0.025 and
0.05 in this research to explore the accurate MPB region for the BS-
PT-PNN ternary system and hope to achieve the high Curie tem-
perature and the considerable electrical properties. The PNN con-
tent selected here is because that the transition temperature will
reduce under 400
C with much more PNN introduced.
2. Experimental procedure
To explore the accurate MPB region for the BS-PT-PNN ternary
system, a series of (1-x-y)BiScO3-xPbTiO3-yPb(Ni1/3Nb2/3)O3(BS-
xPT-yPNN, y ¼ 0.025, x ¼ 0.60e0.63; y ¼ 0.05, x ¼ 0.58e0.62) ce-
ramics were synthesized by the traditional solid-state reaction
methods. The PT content range selected here may around the MPB
region based on the similar research of other BS-PT-ABO3 solid
solutions such as BS-PT-Pb(Zn1/3Nb2/3)O3 discussed before. Raw
materials of Bi2O3(99.8%), Sc2O3(99.99%), PbO(99%), TiO2(99.5%),
NiO(99%), and Nb2O5(99.9%) were selected and weighed in accor-
dance with the stoichiometric proportion and 3% Bi2O3 extra was
added to compensate the volatilization of bismuth in the sintering
process. Then the above oxide powder mixed with proper ethanol
together and was milled with agate balls in a polyethylene bottle
for 12 h. After dried and calcined at 800
C for 4 h, the mixture was
milled again in the same process to make the powder more fine and
uniform. Then the mixture was dried, ground and granulated with
the binder of polyvinyl alcohol (PVA). The above granulated powder
was pressed into pellets with the size in diameter 12.5 mm and
thickness 1.5 mm under the pressure of 120 MPa, and then were
sintered at 1050
Ce1100
C for 3 h with same composition powder
surrounded, the final size of the pellets is 10.5 mm in diameter and
1.0 mm in thickness.
The crystal structure was analyzed by X-ray diffraction tech-
nology (XRD) with Cu Ka radiation (l ¼ 1.5406, Rigaku D/Max 2500,
Japan). The fracture surface micromorphology was characterized by
scanning electron microscopy (SEM, Hitachi S-4800, Japan). Sam-
ples before electrical measurement were polarized for 20 min un-
der the applied electric field of 40 kV/cm in a silicone oil bath of
120
C. The piezoelectric coefficient d33 was obtained using a quasi-
static Berlincourt type meter (ZJ-3D, China). The electromechanical
coupling factor was calculated according to the resonance anti-
resonance method by the impedance analyzer (Agilent 4294A,
USA), and the dielectric spectra measurements were conducted
with the same instrument as a function of temperature. The po-
larization hysteresis (P-E) loops, current-electric curves (I-E) and
strain-electric curves (S-E) were measured using a ferroelectric
analyzer (aixACCT TF1000, Germany). Thermal annealing experi-
ments were conducted by holding the poled samples at various
temperatures for 1 h, and then measuring their d33 values after
cooling down to room temperature freely.
3. Results and discussion
Fig. 1(a and b) shows the room temperature X-ray diffraction
(XRD) patterns of BS-xPT-yPNN ceramics. A single-phase perovskite
structure has been detected and there is no evidence of a secondary
phase can be found, indicating that the PNN end member suc-
cessfully enters into the BS-PT solid solutions and generate a
ternary system. An evolution of the crystalline symmetry from
rhombohedral to tetragonal can be easily found in the BS-xPT-yPNN
ternary system according to the XRD patterns. When the value of y
is 0.025, that's to say for the BS-xPT-0.025PNN system, the crystal
structure presents a typical rhombohedral symmetry when
x ¼ 0.60 because of no splitting can be detected for all the diffrac-
tion peaks, and with increasing PT content, the (200) and (211)
diffraction peaks begin to broaden and have successfully split into
(002)/(200) and (112)/(211) peaks when x ¼ 0.62. The crystalline
structure transforms to tetragonal symmetry herein. It can be
concluded that the transformation from a rhombohedral to a
tetragonal symmetry happens in the compositional range of
0.60 < x < 0.62, and the morphotropic phase boundary (MPB) lo-
cates at x ¼ 0.61 vicinity. In a similar way, it can be found that the
MPB region locates at x ¼ 0.60 vicinity for the BS-xPT-0.05PNN
system from Fig. 1(b). By comparing the two MPB regions with that
of the BS-PT solid solutions, it can be concluded that the MPB region
of the BS-xPT-yPNN ternary system shifts to the low PT region by
the introduction of the PNN end member and the more PNN
introduced the larger the excursion.
According to the XRD patterns and the Bragg diffraction formula
2dsinq ¼ nl, we calculated the lattice parameters of the BS-xPT-
yPNN ceramics shown in Fig. 2(a and b). For the BS-xPT-0.025PNN
system shown as Fig. 2(a), it can be seen that the lattice parameters
change slightly with the increase of PT content. And for the
composition of PT content x ¼ 0.60, the lattice parameter a is equal
to c showing a typical characteristic of a rhombohedral symmetry
as discussed before. With the increase of PT content, the lattice
parameter a is no longer equal to c showing the tetragonal structure
generating from x ¼ 0.61. This phenomenon further confirms the
MPB location corresponding to the XRD patterns. In addition, we
calculated the c/a ratio shown in Fig. 2. It can be seen that the c/a
ratio increases with the variation of PT content, indicating that the
lattice structure symmetry being much more tetragonal. Similar
phenomenon can be found in the BS-xPT-0.05PNN system shown in
 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
Fig. 1. Room temperature XRD patterns: (a) BS-xPT-0.025PNN (b) BS-xPT-0.05PNN.
Fig. 2(b).
To further investigate the structure effect of PNN end number in
the BS-xPT-yPNN ternary solid solutions, we select the ceramic
sample with the same PT content, that's to say the BS-0.61PT-
0.025PNN, BS-0.61PT-0.05PNN, BS-0.62PT-0.025PNN, and the BS-
0.62PT-0.05PNN, and compare their XRD patterns shown in Fig. 3.
The selected (110) and (111) peaks shown in Fig. 3(b and c) clearly
present that the diffraction peaks shift towards low angle with the
increase of PNN content, indicating that the lattice parameter get
larger according to the Bragg diffraction formula. This variation of
the lattice parameter is also observed in Fig. 2, the enhanced lattice
parameter may be one reason for the MPB excursion in the BS-xPT-
yPNN ternary system discussed before.
The phase diagram of piezoelectric ceramics is important that
from which we can predict the MPB region of the solid solutions
and search for the optimal electrical properties at the MPB com-
positions. In this work, we have drawn the room temperature phase
diagram of the BS-xPT-yPNN ternary solid solutions shown as Fig. 4,
based on our present work and some previous experimental data.
The blue point and green point refer to the MPB compositions of the
BS-PT and the PNN-PT binary solid solutions [10,21], respectively.
And the red point and the hollow point refer to the MPB compo-
sitions of BS-xPT-yPNN ceramics with different PNN content [26].
13
Fig. 2. Lattice parameters and c/a ratio as a function of PT content: (a) BS-xPT-
0.025PNN (b) BS-xPT-0.05PNN.
Then the linear MPB of the ternary solid solutions can be predicted
as the dashed line in Fig. 4 to distinguish the phase of rhombohe-
dral and tetragonal at room temperature.
The fractured surfaces SEM photos of BS-xPT-yPNN ceramics
sintered at 1080
C are presented in Fig. 5. A dense microstructure
with strong interfacial joint and no obvious porosity can be
observed for all specimens, corresponding to the high relative
density of >96% measured by the Archimedes methods. The
average grain size is little changed with the same PNN content but
decreases from ~3.5 mm to ~2.5 mm with the increase of PNN con-
tent x from 0.025 to 0.05. In addition, the grain size of the BS-xPT-
yPNN ceramics is smaller than that of the pure BSePT ceramics
(~5 mm) [28]. These phenomena can be explained as two reasons.
One is that the grain growth is little relevant to the PT content in
this system, the other one is that the Nb5þ in the PNN end member
inhibits the grain growth as reported in many other BS-PT based
piezoelectric ceramics [12,13,29]. With the introduction of PNN end
member into BS-PT system, the average grain size reduce by the
inhibiting effect of Nb5þ ions. More PNN introduced, the grain size
more reduced.
Temperature dependence of the relative dielectric permittivity ε
and dielectric loss tan d at 1 kHz for the unpoled BS-xPT-yPNN ce-
ramics have been shown in Fig. 6(a and b), and the variation of Tc is
given in the inset. A single dielectric peak is detected for each
specimen, which corresponding to the Curie temperature Tc. From
the inset, it can be concluded that the Tc is very sensitive to the PT
content when the PNN content fixed, which almost linearly in-
creases from 390
C to 415
C with x increasing from 0.60 to 0.63 for
y ¼ 0.025 and 359
Ce402
C with x increasing from 0.58 to 0.62 for
14 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
Fig. 3. Selected XRD patterns of BS-xPT-yPNN ceramics.
Fig. 4. Phase diagram of BS-xPT-yPNN ceramics at room temperature.
y ¼ 0.05, respectively. Furthermore, the dielectric loss tan d is lower
than 0.1 from room temperature to 300
C, which is important for
high temperature piezoelectric applications.
To further investigate the effect on the dielectric properties of
Fig. 5. The fractured surfaces SEM photos of BS-xPT-yPNN ceramics sintered at 1080
C
(a) y ¼ 0.025, x ¼ 0.61, (b) y ¼ 0.025, x ¼ 0.62, (c) y ¼ 0.05, x ¼ 0.58, (d) y ¼ 0.05,
x ¼ 0.60.
PNN end number in the BS-xPT-yPNN system, the dielectric tem-
perature spectra measured at different frequency of 1 kHz, 10 kHz,
and 100 kHz for the selected BS-0.61PT-0.025PNN, BS-0.63PT-
0.025PNN, BS-0.60PT-0.05PNN, and the BS-0.62PT-0.05PNN ce-
ramics are shown in Fig. 6(cef). A typical diffuse phase transition
characteristic can be revealed as the peaks of dielectric maximum
are suppressed and become broader with the increasing measured
frequency, whereas the Curie temperature remains unchanged or
little changed, indicating that the BS-xPT-yPNN ceramics are in-
termediate between the normal ferroelectrics and relaxor ferro-
electrics. This may be attributed to the introduction of PNN which
lead to the production of chemical heterogeneities. Similar diffuse
phase transition behavior has been reported in many other BS-PT
based systems [12,13,15,30]. To study the diffuse phase transition
characteristic, Uchino had proposed a modified Curie-Weiss law as
follows [31]:
1 1 ðT  Tm Þg
 ¼
ε εm C
where ε refers to the dielectric permittivity, εm refers to the
maximum value of ε, T is the measured temperature, Tm is the
temperature where the εm locates, C is the Curie Weiss constant and
the g is the diffuseness coefficient which ranges between 1 and 2
for the normal ferroelectrics and ideal relaxor ferroelectrics,
respectively. The insets in Fig. 6 show the plot of ln(1/ε-1/εm) versus
ln(T-Tm). The values of g are calculated as 1.5865, 1.5704, 1.7397 and
1.7336 for BS-0.61PT-0.025PNN, BS-0.63PT-0.025PNN, BS-0.60PT-
0.05PNN, and the BS-0.62PT-0.05PNN ceramics, respectively,
which symbolize the diffuse phase transition behavior of BS-xPT-
yPNN ceramics. When the PNN content fixed, the diffuseness co-
efficient is reduced with the increasing PT content. It may be
attributed to that the tetragonal phase possesses better stabilities
than the rhombohedral phase. In addition, with the increase of PNN
content, the enlarged diffuseness coefficient indicates the gradual
increase of diffuse phase transition behavior, which can be ascribed
to the enhancement of chemical heterogeneities with much more
PNN content.
The detailed electrical properties of the BS-xPT-yPNN ceramics
measured at room temperature are summarized and listed in
Table 1. When the PNN content fixed, the optimal properties are
obtained at the MPB composition. For the PNN content y ¼ 0.025,
 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18 15

Fig. 6. (aeb) Temperature dependence of the relative dielectric permittivity ε and dielectric loss tan d at 1 kHz for the unpoled BS-xPT-yPNN ceramics, (cef) dielectric temperature
spectrum measured at 1 kHz, 10 kHz, and 100 kHz for the selected BS-0.61PT-0.025PNN, BS-0.63PT-0.025PNN, BS-0.60PT-0.05PNN, and the BS-0.62PT-0.05PNN ceramics.

Table 1
Room temperature piezoelectric and dielectric properties of BS-xPT-yPNN ceramics.

Material Phase structure Tc (oC) εT33 tand d33 (pC/N) kp (%) Ec (kV/cm) Pr (mC/cm2) Strain (%) h (%) Ref

PZT-5A MPB 365 1700 0.017 374 60.0 … … … … [5]

BS-0.64 PT MPB 450 2010 0.020 460 56.0 20 32 0.25 … [10]
BS-0.60 PT-PZN MPB 417 1540 0.024 490 57.4 28.5 40 … … [13]
BS-xPT-0.025PNN
x ¼ 0.60 R 390 2030 0.046 460 55.8 20.7 36.6 0.17 16.8
x ¼ 0.61 MPB 400 2216 0.049 522 59.6 19.3 39.2 0.22 16.2
x ¼ 0.62 T 408 2111 0.043 450 54.4 24.0 38.0 0.21 14.8
x ¼ 0.63 T 415 1980 0.027 380 50.2 27.0 32.2 0.19 13.6
BS-xPT-0.05PNN
x ¼ 0.58 R 359 2079 0.037 370 46.6 19.1 34.5 0.16 16.4
x ¼ 0.59 R 373 2017 0.049 460 53.1 21.1 37.8 0.20 17.6
x ¼ 0.60 MPB 385 2340 0.054 495 59.0 16.8 38.5 0.22 16.9
x ¼ 0.61 T 393 2237 0.052 465 55.2 18.9 38 0.18 12.1
x ¼ 0.62 T 402 2005 0.029 410 51.4 24.4 34 0.17 7.01
16 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
the optimal properties with the piezoelectric coefficient d33 of
522 pC/N and planar electromechanical coupling factor kp of 59.6%,
which superior to that of the unmodified BS-PT 460 pC/N and 56%,
are obtained for the BS-0.61PT-0.025PNN composition, and the
Curie temperature Tc remains at 400
C, just 50
lower than that of
the unmodified BS-PT. Furthermore, with the increase of PNN
content, the piezoelectric performance reduces a little maybe
resulting from the enlargement of lattice distortion. For the BS-
0.60PT-0.05PNN composition, the piezoelectric performance rea-
ches to 495 pC/N and 59%, respectively, which are still equivalent to
that of the unmodified BS-PT [10] and other modified BS-PT such as
the BS-PT-PZN [13] system.
Fig. 7(a and b) shows the room temperature P-E loops and I-E
loops of the BS-xPT-yPNN ceramics measured at 1 Hz. All P-E loops
go saturated and no obvious conductive problem can be detected
for each specimen under the driven field of 40 kV/cm, showing
good ferroelectric properties. It can be observed that there are two
apparent current peaks in the I-E loops for each specimen, indi-
cating typical ferroelectric type behavior which can be attributed to
the ferroelectric domain switching [32,33]. The maximum of the
leakage current during the measurement of ferroelectric properties
is only 1.23 mA, proving no obvious conductive problem existing
furthermore. The remnant polarization Pr and coercive field Ec
which of basic ferroelectric properties are obtained and drawn in
Fig. 7(c and d). As shown, when the PNN content remains un-
changed, the remnant polarization increases firstly and the opti-
mum is obtained at the MPB composition, then the Pr decreases
with the further increasing PT content. This phenomenon can be
ascribed to the improved polarization arising from the coexistence
of the rhombohedral and tetragonal phase in the MPB region.
Whereas the coercive field shows another trend as declining at first,
then increasing as the PT content further enlarged, which may be
the result of the harder domain switching in the tetragonal phase.
Fig. 7. (aeb) Room temperature P-E loops and I-E loops of BS-xPT-yPNN ceramics: (a) BS-xPT-0.025PNN (b) BS-xPT-0.05PNN, (ced) the variation of Pr and Ec of BS-xPT-yPNN
ceramics: (c) BS-xPT-0.025PNN (d) BS-xPT-0.05PNN
In addition, for the same PT content, the Pr reduces with the in-
crease of PNN content, which may be caused by the enlargement of
lattice distortion and diffuse phase transition behavior.
The unipolar S-E curves of the poled BS-xPT-yPNN specimens
were measured under the same driven electric field of 40 kV/cm
and shown in Fig. 8(a and b). A basically linear loop with a little
remnant strain was obtained for each specimen with the applied
field. As known, the electric field-induced strain may result from
both intrinsic and extrinsic contributions. The intrinsic part is
mainly given by the domains switching caused by the inverse
piezoelectric effect, while the extrinsic part refers to the strain
resulting from the movement of the domain walls and phase
boundaries [33,34]. The domain switching and movement process
under a high electric field can be partly reversible and partly irre-
versible. The main contribution to the electric field-induced strain
is from the reversible part, whereas the remnant strain maybe
result from the irreversible ones. Furthermore, the domain
switching under the driven electric field will induce complex
nonlinear and hysteretic behavior in the electric field-induced
strain. As shown in Fig. 8(a and b), the unipolar S-E curves for the
upward interval and downward interval of the applied electric field
do not coincide with each other. The strain hysteresis can be
described as follows:
DS
h¼  100%
Smax
where h is relative strain hysteresis, DS is the strain difference
between the upward and downward interval at the half maximum
electric field, and Smax is the strain at the maximum electric field.
The calculated h of the BS-xPT-yPNN ceramics are listed in Table 1. It
can be found that the relative strain hysteresis h ranges from 7.01%
to 17.6%, showing smaller strain hysteresis and better strain
 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
Fig. 8. Room temperature S-E curves of BS-xPT-yPNN ceramics: (a) BS-xPT-0.025PNN
(b) BS-xPT-0.05PNN
linearity characteristic than other BS-PT based piezoelectric ce-
ramics [35,36]. This is important for the design of the piezoelectric
actuator. In addition, it can be easily found that the strain increases
to the maxima 0.22% for the MPB composition, and then reduces a
little with the further increasing PT content when the PNN content
fixed, as the BS-xPT-0.025PNN system shown in Fig. 8(a). Similar
phenomenon can be found in the BS-xPT-0.05PNN system shown in
Fig. 8(b). All these can be ascribed to the enhanced polarizability
and domain wall mobility in the MPB region where existing large
numbers of thermodynamically stable polarization directions as 8
in the rhombohedral phase and 6 in the tetragonal phase [37].
Fig. 9 shows the thermal stability of the piezoelectric properties
for the MPB composition of BS-xPT-yPNN system, and the inset
gives the variation of relative d33 towards the depoling tempera-
ture. It can easily figure out that d33 remains almost unchanged
(over 90% of the value at the room temperature) before 200
C for
all samples, and the d33 keeps about 80% for BS-0.61PT-0.025PNN
and BS-0.60PT-0.05PNN composition at 250
C and 300
C,
respectively, indicating good thermal stabilities. But with the
further increase of annealing temperature, the d33 drops sharply
and reduces to be zero near the Curie temperature. Meanwhile, the
thermal stabilities of the ceramics weaken a little with the increase
of PNN content, which may be caused by the enlargement of lattice
distortion.
4. Conclusions
In summary, (1-x-y)BiScO3-xPbTiO3-yPb(Ni1/3Nb2/3)O3 (BS-xPT-
yPNN) ternary high temperature piezoelectric ceramics were
17
Fig. 9. Effect of thermal depoling on piezoelectric coefficient d33 of selected samples.
designed and prepared by traditional solid-state reaction methods.
XRD diffraction analysis demonstrates a pure perovskite structure
and the MPB shifts to the low PT region with the increase of PNN
end member content in this system. High temperature dielectric
behaviors show diffuse phase transition characteristic in BS-xPT-
yPNN ceramics and the diffuseness enlarges with the increase of
PNN content. The coexistence of the rhombohedral and tetragonal
phase at MPB composition presents the optimal properties of
piezoelectric coefficient d33 522 pC/N, planar electromechanical
coupling factor kp 59.6%, remnant polarization Pr 39.2 mC/cm2, and
the Curie temperature Tc 400
C for the BS-0.61PT-0.025PNN
composition in the BS-xPT-0.025PNN system. With the increase of
PNN content, the piezoelectric performance reduces a little and still
reaches to 495 pC/N and 59% of the BS-0.60PT-0.05PNN composi-
tion, which is also equivalent to that of the unmodified BS-PT and
other modified BS-PT such as the BS-PT-PZN system. All these
properties reveal that the BS-xPT-yPNN ceramics are a new ternary
system with high piezoelectric performance and the potential for
applications at the temperature of the order of 300
C.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 51802242, 11604251), the Natural
Science Foundation of Shaanxi Province (Grant No. 2019JQ-313),
and the 111 Project (No. B12026).
References
[1] S. Zhang, F. Yu, Piezoelectric materials for high temperature sensors, J. Am.
Ceram. Soc. 94 (2011) 3153e3170.
[2] J. Wu, X. Gao, J. Chen, C.-M. Wang, S. Zhang, S. Dong, Review of high tem-
perature piezoelectric materials, devices, and applications, Acta Phys. Sin. 67
(2018).
[3] C. Fei, T. Zhao, J. Zhang, Y. Quan, D. Wang, X. Yang, Q. Chen, P. Lin, D. Li,
Y. Yang, S. Dong, W. Ren, K.K. Shung, Q. Zhou, 0.36BiScO3-0.64PbTiO3 piezo-
electric ceramics for high temperature ultrasonic transducer applications,
J. Alloy. Comp. 743 (2018) 365e371.
[4] O.O. Ivashchuk, A.V. Shchagin, A.S. Kubankin, I.S. Nikulin, A.N. Oleinik,
V.S. Miroshnik, V.I. Volkov, Piezoelectric accelerator, Sci. Rep. 8 (2018).
[5] B. Jaffe, Piezoeletric Ceramics, Academic, london, 1971.
[6] C.J. Stringer, T.R. Shrout, C.A. Randall, I.M. Reaney, Classification of transition
temperature behavior in ferroelectric PbTiO3-Bi(Me'Me"])O3 solid solutions,
J. Appl. Phys. 99 (2006), 024106.
[7] A. Moure, M. Alguero  , L. Pardo, E. Ringgaard, A.F. Pedersen, Microstructure and
temperature dependence of properties of morphotropic phase boundary
Bi(Mg1/2Ti1/2)O3-PbTiO3 piezoceramics processed by conventional routes,
J. Eur. Ceram. Soc. 27 (2007) 237e245.
[8] Q. Zhang, Z. Li, F. Li, Z. Xu, X. Yao, Temperature dependence of dielectric/
18 T.-L. Zhao et al. / Journal of Alloys and Compounds 806 (2019) 11e18
piezoelectric properties of (1-x)Bi(Mg1/2Ti1/2)O3-xPbTiO3 ceramics with an
MPB composition, J. Am. Ceram. Soc. 93 (2010) 3330e3334.
[9] W.M. Zhu, H.Y. Guo, Z.G. Ye, Structural and magnetic characterization of
multiferroic (BiFeO3)1-x(PbTiO3)x solid solutions, Phys. Rev. B 78 (2008),
014401.
[10] R.E. Eitel, C.A. Randall, T.R. Shrout, S.E. Park, Preparation and characterization
of high temperature perovskite ferroelectrics in the solid-solution (1-x)
BiScO3-xPbTiO3, Jpn. J. Appl. Phys. 41 (2002) 2099e2104.
[11] M.R. Suchomel, P.K. Davies, Enhanced tetragonality in xPbTiO3-(1-x)Bi(Zn1/
2Ti1/2)O3 and related solid solution systems, Appl. Phys. Lett. 86 (2005)
262905.
[12] T.-L. Zhao, J. Chen, C.-M. Wang, Y. Yu, S. Dong, Ferroelectric, piezoelectric, and
dielectric properties of BiScO3-PbTiO3-Pb(Cd1/3Nb2/3)O3 ternary high tem-
perature piezoelectric ceramics, J. Appl. Phys. 114 (2013), 027014.
[13] Z.H. Yao, H.X. Liu, H. Hao, M.H. Cao, Structure, electrical properties, and
depoling mechanism of BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 high-temperature
piezoelectric ceramics, J. Appl. Phys. 109 (2011), 014105.
[14] C.J. Stringer, N.J. Donnelly, T.R. Shrout, C.A. Randall, E.F. Alberta,
W.S. Hackenberger, Dielectric characteristics of perovskite-structured high-
temperature relaxor ferroelectrics: the BiScO3-Pb(Mg1/3Nb2/3)O3-PbTiO3
ternary system, J. Am. Ceram. Soc. 91 (2008) 1781e1787.
[15] S.S. Zhang, Y. Yu, J.G. Wu, X.Y. Gao, C. Huang, S.X. Dong, Enhanced piezo-
electric performance of BiScO3-PbTiO3 ceramics modified by 0.03Pb(Sb1/2Nb1/
2)O3, J. Alloy. Compd 731 (2018) 1140e1145.
[16] Q.R. Hu, Y.P. Wang, L. Wu, J. Yin, L. Chen, G.L. Yuan, Y. Yang, Effects of LiNbO3
doping on the microstructures and electrical properties of BiScO3-PbTiO3
piezoelectric system, J. Mater. Sci. Mater. Electron. 29 (2018) 18036e18044.
[17] T.-L. Zhao, A.A. Bokov, J. Wu, H. Wang, C.-M. Wang, Y. Yu, C.-L. Wang, K. Zeng,
Z.-G. Ye, S. Dong, Giant piezoelectricity of ternary perovskite ceramics at high
temperatures, Adv. Funct. Mater. 0 (2019) 1807920.
[18] H.M. Qiao, C. He, Z.J. Wang, X.Z. Li, Y. Liu, X.F. Long, Improved electrical
properties of BaTiO3 modified BiScO3-PbTiO3 ceramics with high Curie tem-
perature, Ceram. Int. 43 (2017) 11463e11468.
[19] J.G. Chen, Y.J. Dong, J.R. Cheng, Reduced dielectric loss and strain hysteresis in
(0.97-x)BiScO3-xPbTiO3-0.03Pb(Mn1/3Nb2/3)O3 piezoelectric ceramics, Ceram.
Int. 41 (2015) 9828e9833.
[20] T.Y. Ansell, D.P. Cann, E. Sapper, J. Rodel, Thermal depolarization in the high-
temperature ternary piezoelectric system xPbTiO3-yBiScO3-zBi(Ni1/2Ti1/2)O3,
J. Am. Ceram. Soc. 98 (2015) 455e463.
[21] B. Fang, R. Sun, Y. Shan, K. Tezuka, H. Imoto, Phase transition, structural and
electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3ePbTiO3 ce-
ramics prepared by solid-state reaction method, J. Phys. Chem. Solids 70
(2009) 893e899.
[22] Y. Ye, H.T. Huang, L.M. Zhou, Y.W. Mai, Enhanced unipolar fatigue resistance in
ferroelectric Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared via glycerol-assisted
solid-state reaction, J. Am. Ceram. Soc. 94 (2011) 488e495.
[23] H. Tang, M.F. Zhang, S.J. Zhang, Y.J. Feng, F. Li, T.R. Shrout, Investigation of
dielectric and piezoelectric properties in Pb(Ni1/3Nb2/3)O3ePbHfO3ePbTiO3
ternary system, J. Eur. Ceram. Soc. 33 (2013) 2491e2497.
[24] J. Ma, W. Ma, Q. Li, X. Meng, B. Niu, Y. Guo, Low-temperature sintering and
piezoelectric properties of Pb(Fe2/3W1/3)O3eadded Pb(Zn1/3Nb2/3)O3ePb(Ni1/
3Nb2/3)O3ePb(Zr, Ti)O3 ceramics, J. Mater. Sci. Mater. Electron. 25 (2014)
3695e3702.
[25] J.-J. Zhou, K. Wang, J.-F. Li, X.-W. Zhang, H. Liu, J.-Z. Fang, Temperature-
dependent electrical properties of 0.5Pb(Ni1/3Nb2/3)O3e(0.5x)
PbTiO3exPbZrO3 piezoceramics near the morphotropic phase boundary,
J. Mater. Sci. Mater. Electron. 25 (2014) 2540e2545.
[26] D.L. Wang, Z.H. Jiang, B. Yang, S.T. Zhang, M.F. Zhang, F.F. Guo, W.W. Cao,
Enhanced electrical properties of novel Pb(Ni1/3Nb2/3)O3-BiScO3-PbTiO3
ternary system near morphotropic phase boundary, Jpn. J. Appl. Phys. 52
(2013) 101101.
[27] X. Meng, Q. Chen, H. Fu, H. Liu, J. Zhu, Influence of PNN on the structure and
electronic properties of BSPT ceramics, J. Mater. Sci. Mater. Electron. 29 (2018)
12785e12794.
[28] J. Chen, H. Shi, G. Liu, J. Cheng, S. Dong, Temperature dependence of dielectric,
piezoelectric and elastic properties of BiScO3-PbTiO3 high temperature ce-
ramics with morphotropic phase boundary (MPB) composition, J. Alloy. Comp.
537 (2012) 280e285.
[29] S. Chen, X.L. Dong, H. Yang, R.H. Liang, C.L. Mao, Effects of niobium doping on
the microstructure and electrical properties of 0.36BiScO3-0.64PbTiO3 ce-
ramics, J. Am. Ceram. Soc. 90 (2007) 477e482.
[30] J. Chen, T. Zhao, J. Cheng, S. Dong, Enhanced piezoelectric performance of
(0.98-x)Bi(Sc3/4In1/4)O3-xPbTiO3-0.02Pb(Zn1/3Nb2/3)O3 ternary high tempera-
ture piezoelectric ceramics, J. Appl. Phys. 113 (2013) 144102.
[31] K. Uchino, S. Nomura, L.E. Cross, R.E. Newnham, Soft modes in relaxor ferro-
electrics, Phase Transit 2 (1981) 1e6.
[32] J. Wu, A. Mahajan, L. Riekehr, H. Zhang, B. Yang, N. Meng, Z. Zhang, H. Yan,
Perovskite Srx(Bi1xNa0.97xLi0.03)0.5TiO3 ceramics with polar nano regions for
high power energy storage, Nano Energy 50 (2018) 723e732.
[33] G. Viola, T. Saunders, X. Wei, K.B. Chong, H. Luo, M.J. Reece, H. Yan, Contri-
bution of piezoelectric effect, electrostriction and ferroelectric/ferroelastic
switching to strain-electric field response of dielectrics, J. Adv. Dielec. 03
(2013) 1350007.
[34] Y. Tan, G. Viola, V. Koval, C. Yu, A. Mahajan, J. Zhang, H. Zhang, X. Zhou,
N.V. Tarakina, H. Yan, On the origin of grain size effects in Ba(Ti0.96Sn0.04)O3
perovskite ceramics, J. Eur. Ceram. Soc. 39 (2019) 2064e2075.
[35] H. Jia, X. Hu, J. Chen, Temperature-dependent piezoelectric strain and reso-
nance performance of Fe2O3-modified BiScO3-PbTiO3-Pb(Nb1/3Mn2/3)O3 ce-
ramics, J. Eur. Ceram. Soc. 39 (2019) 2348e2353.
[36] J. Chen, G. Jin, C.-M. Wang, J. Cheng, D. Damjanovic, Reduced dielectric loss
and strain hysteresis in Fe and Mn comodified high-temperature BiScO3-
PbTiO3 ceramics, J. Am. Ceram. Soc. 97 (2014) 3890e3896.
[37] C.A. Randall, N. Kim, J.-P. Kucera, W. Cao, T.R. Shrout, Intrinsic and extrinsic
size effects in fine-grained morphotropic-phase-boundary lead zirconate
titanate ceramics, J. Am. Ceram. Soc. 81 (1998) 677e688.