Accepted Manuscript

Structure and enhanced piezoelectric performance of BiScO3-PbTiO3-

Pb(Ni1/3Nb2/3)O3 ternary high temperature piezoelectric ceramics

Tian-Long Zhao, Chunlong Fei, Xianying Dai, Jianjun Song, Shuxiang Dong

PII: S0925-8388(19)32801-4
DOI: https://doi.org/10.1016/j.jallcom.2019.07.286
Reference: JALCOM 51574

To appear in: Journal of Alloys and Compounds

Received Date: 19 April 2019

Revised Date: 2 July 2019
Accepted Date: 23 July 2019

Please cite this article as: T.-L. Zhao, C. Fei, X. Dai, J. Song, S. Dong, Structure and enhanced
piezoelectric performance of BiScO3-PbTiO3-Pb(Ni1/3Nb2/3)O3 ternary high temperature piezoelectric
ceramics, Journal of Alloys and Compounds (2019), doi: https://doi.org/10.1016/j.jallcom.2019.07.286.

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 ACCEPTED MANUSCRIPT

Structure and enhanced piezoelectric performance of

BiScO3-PbTiO3-Pb(Ni1/3Nb2/3)O3 ternary high temperature
piezoelectric ceramics

Tian-Long Zhao 1, Chunlong Fei1, Xianying Dai 1*, Jianjun Song 1, Shuxiang Dong 2*

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1. School of Microelectronics, Xidian University, Xi’an 710071, China

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2. Department of Materials Science and Engineering, College of Engineering, Peking University,

Beijing 100871, China

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* Corresponding author Email address: xydai@xidian.edu.cn (X. Dai) and

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sxdong@pku.edu.cn(S.Dong)
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Abstract
BiScO3-PbTiO3 based solid solutions are the most promising candidates in high
temperature piezoelectric application field. In this research,
(1-x-y)BiScO3-xPbTiO3-yPb(Ni1/3Nb2/3)O3 (BS-xPT-yPNN) ternary high temperature
piezoelectric ceramics have been prepared by the traditional solid-state reaction

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methods and investigated in detail. X-Ray diffraction analysis shows that the system
has a pure perovskite structure and the morphotropic phase boundary (MPB) region

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shift 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

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the optimal electrical properties of the BS-xPT-yPNN ternary solid solutions. The
dielectric temperature spectra present typical diffuse phase transition characteristic

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caused by the production of chemical heterogeneities with the introduction of PNN.
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For the BS-xPT-0.025PNN system, the optimal properties of the piezoelectric
coefficient d33 522 pC/N, planar electromechanical coupling factor kp 59.6%, remnant
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polarization Pr 39.2 µC/cm2, and the Curie temperature Tc 400 oC are obtained for the
BS-0.61PT-0.025PNN composition. Furthermore, the piezoelectric performance
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declines a little to 495 pC/N and 59% of the BS-0.60PT-0.05PNN composition with
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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
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that the BS-xPT-yPNN ceramics constitute a new family of high performance high
temperatures piezoelectric materials.
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Key words:
high temperature; BiScO3-PbTiO3; high piezoelectric performance; piezoelectric
ceramics; diffuse phase transition;

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1. Introduction
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[1-4]. However, the
most commercial used piezoelectric materials (Pb(Zr, Ti)O3, PZT) are generally

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limited to the operating temperature of one half the Curie temperature (Tc),
approximately 150 °C for PZT, which restricts their applications in the extreme

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conditions[5].
Recently, bismuth-based perovskite solid solutions with the formula

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Bi(Me)O3-xPbTiO3 (Me refer to the cations of valence +3, Sc, In, Yb et.al.) have
attracted growing interest due to their potential alternatives to PZT in high

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temperature piezoelectric application field. Many systems have been investigated in
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detail such as Bi(Zn1/2Ti1/2)O3-PbTiO3, Bi(Mg1/2Ti1/2)O3-PbTiO3, BiFeO3-PbTiO3,
BiScO3-PbTiO3, and so on[6-11]. The binary (1-x)BiScO3-xPbTiO3 (BS-PT) solid
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solutions are the most promising candidates in these systems because that the
Bi(Zn1/2Ti1/2)O3-PbTiO3 solid solutions are hard to synthesize[11] and the
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Bi(Mg1/2Ti1/2)O3-PbTiO3, BiFeO3-PbTiO3 will encounter the conductive problem at

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high temperature[7, 9]. In addition, the piezoelectric properties (d33 =460 pC/N, kp
=56%) are comparable to the commercial piezoelectric materials PZT, whereas the
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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
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materials of scandium oxide are so expensive and limit their commercial use by the
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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,
LiNbO3, and so on[12-20]. All these new material systems possess considerable
electrical properties and high Curie temperature, for example, the

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BS-PT-Pb(Zn1/3Nb2/3)O3 system exhibits the piezoelectric performance (d33=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

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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

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unmodified BS-PT system. The temperature of the dielectric maximum (Tm) reduced
from 450 oC to 250 oC which is the priority for high temperature piezoelectric

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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

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electrical properties when designing the material compositions.
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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
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electrical properties[21-27]. In 2013, Wang et.al. firstly reported that this ternary
system with the formula xPNN-(1-x)(0.30BS-0.70PT) (x=0.28-0.38) exhibits the d33
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of 490 pC/N and the Curie temperature Tc 171 °C at the MPB composition x=0.35[26].
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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
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Meng et.al. redesigned the material compositions by the formula of

xPNN-(1-x)(0.36BS-0.64PT) with x range from 0.003 to 0.05 and found that the d33
reach to 531 pC/N together with the Tc 417 oC when x=0.01[27]. Though they
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obtained the enhanced piezoelectric performance by this method, there was an

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obvious drawback 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 compositions. Therefore,
we just select the PNN content y=0.025 and 0.05 in this research to explore the
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accurate MPB region for the BS-PT-PNN ternary system and hope to achieve the high
Curie temperature and the considerable electrical properties. The PNN content
selected here is because that the transition temperature will reduce under 400 oC with
much more PNN introduced.

2. Experimental procedure

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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=0.025, x=0.60-0.63;

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y=0.05, x=0.58-0.62;) ceramics were synthesized by the traditional solid-state reaction
methods. The PT content range selected here may around the MPB region based on

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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%),

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Sc2O3(99.99%), PbO(99%), TiO2(99.5%), NiO(99%), and Nb2O5(99.9%) were
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selected and weighed in accordance with the stoichiometric proportion and 3% Bi2O3
extra was added to compensate the volatilization of bismuth in the sintering process.
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Then the above oxide powder mixed with proper ethanol together and was milled with
agate balls in a polyethylene bottle for 12h. After dried and calcined at 800 oC for 4h,
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the mixture was milled again in the same process to make the powder more fine and
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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
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the size in diameter 12.5 mm and thickness 1.5 mm under the pressure of 120 MPa,
and then were sintered at 1050 oC -1100 oC for 3 h with same composition powder
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surrounded, the final size of the pellets is 10.5 mm in diameter and 1.0 mm in
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thickness.
The crystal structure was analyzed by X-ray diffraction technology (XRD) with
Cu Kα radiation (λ=1.5406, Rigaku D/Max 2500, Japan). The fracture surface
micromorphology was characterized by scanning electron microscopy (SEM, Hitachi
S-4800, Japan). Samples before electrical measurement were polarized for 20 min
under the applied electric field of 40 kV/cm in a silicone oil bath of 120 oC. The
piezoelectric coefficient d33 was obtained using a quasi-static Berlincourt type meter

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(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 polarization hysteresis (P-E) loops,
current-electric curves (I-E) and strain-electric curves (S-E) were measured using a

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ferroelectric analyzer (aixACCT TF1000, Germany). Thermal annealing experiments
were conducted by holding the poled samples at various temperatures for 1 h, and

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then measuring their d33 values after cooling down to room temperature freely.

3. Results and discussion

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Figure 1(a-b) shows the room temperature X-ray diffraction (XRD) patterns of
BS-xPT-yPNN ceramics. A single-phase perovskite structure has been detected and

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there is no evidence of a secondary phase can be found, indicating that the PNN end
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member successfully 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
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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=0.60 because
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of no splitting can be detected for all the diffraction peaks, and with increasing PT
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contents, the (200) and (211) diffraction peaks begin to broaden and have successfully
split into (002)/(200) and (112)/(211) peaks when x=0.62. The crystalline structure
transform to tetragonal symmetry herein. It can be concluded that the transformation
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from a rhombohedral to a tetragonal symmetry happens in the compositional range of

0.60 < x < 0.62, and the morphotropic phase boundary (MPB) locates at x = 0.61
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vicinity. In a similar way, it can be found that the MPB region locates at x = 0.60
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vicinity for the BS-xPT-0.05PNN system from Figure 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 shift 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 2dsinθ=nλ, we
calculated the lattice parameters of the BS-xPT-yPNN ceramics shown in Figure
2(a-b). For the BS-xPT-0.025PNN system shown as Figure 2(a), it can be seen that the
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lattice parameters change slightly with the increase of PT content. And for the
composition of PT content x = 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 = 0.61. This phenomenon further confirms the
MPB location corresponding to the XRD patterns. In addition, we calculated the c/a

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ratio shown in Figure 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.

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Similar phenomenon can be found in the BS-xPT-0.05PNN system shown in Figure
2(b).

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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,

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BS-0.62PT-0.025PNN, and the BS-0.62PT-0.05PNN, and compare their XRD patterns
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shown in Figure 3. The selected (110) and (111) peaks shown in Figure 3(b-c) clearly
present that the diffraction peaks shift towards low angle with the increase of PNN
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content, indicating that the lattice parameter get larger according to the Bragg
diffraction formula. This variation of the lattice parameter is also observed in Figure 2,
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the enhanced lattice parameter may be one reason for the MPB excursion in the
BS-xPT-yPNN ternary system discussed before.
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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
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properties at the MPB compositions. In this work, we have drawn the room
temperature phase diagram of the BS-xPT-yPNN ternary solid solutions shown as
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Figure 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
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binary solid solutions [10, 21], respectively. And the red point and the hollow point
refer to the MPB compositions of BS-xPT-yPNN ceramics with different PNN
content[26]. Then the linear MPB of the ternary solid solutions can be predicted as the
dashed line in Figure 4 to distinguish the phase of rhombohedral and tetragonal at
room temperature.
The fractured surfaces SEM photos of BS-xPT-yPNN ceramics sintered at 1080
o
C are presented in Figure 5. A dense microstructure with strong interfacial joint and
no obvious porosity can be observed for all specimens, corresponding to the high
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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 µm to ~2.5
µm with the increase of PNN content 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 BS–PT ceramics (~5
µm).[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 Nb5+

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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

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into BS-PT system, the average grain size reduce by the inhibiting effect of Nb5+ ions.
More PNN introduced, the grain size more reduced.

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Temperature dependence of the relative dielectric permittivity ε and dielectric
loss tan δ at 1 kHz for the unpoled BS-xPT-yPNN ceramics have been shown in

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Figure 6(a-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
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the inset, it can be concluded that the Tc is very sensitive to the PT content when the
PNN content fixed, which almost linearly increases from 390 oC to 415 oC with x
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increasing from 0.60 to 0.63 for y=0.025 and 359 oC to 402 oC with x increasing from
0.58 to 0.62 for y=0.05, respectively. Furthermore, the dielectric loss tan δ is lower
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than 0.1 from room temperature to 300 oC, which is important for high temperature
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piezoelectric applications.
To further investigate the effect on the dielectric properties of PNN end number
in the BS-xPT-yPNN system, the dielectric temperature spectra measured at different
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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 ceramics
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are shown in Figure 6(c-f). A typical diffuse phase transition characteristic can be
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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 intermediate between
the normal ferroelectrics and relaxor ferroelectrics. 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]:

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(T − Tm )
γ
1 1
− =
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 γ is the diffuseness coefficient which ranges between 1
and 2 for the normal ferroelectrics and ideal relaxor ferroelectrics, respectively. The

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insets in Figure 6 show the plot of ln(1/ε-1/εm) versus ln(T-Tm). The values of γ are
calculated as 1.5865, 1.5704, 1.7397 and 1.7336 for BS-0.61PT-0.025PNN,

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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

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ceramics. When the PNN content fixed, the diffuseness coefficient is reduced with the
increasing PT content. It may be attributed to that the tetragonal phase possesses

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better stabilities than the rhombohedral phase. In addition, with the increase of PNN
content, the enlarged diffuseness coefficient indicates the gradual increase of diffuse
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phase transition behavior, which can be ascribed to the enhancement of chemical
heterogeneities with much more PNN content.
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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,
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the optimal properties are obtained at the MPB composition. For the PNN content
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y=0.025, 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
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composition, and the Curie temperature Tc remains at 400 oC, just 50 degrees lower
than that of the unmodified BS-PT. Furthermore, with the increase of PNN content,
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the piezoelectric performance reduces a little maybe resulting from the enlargement of
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lattice distortion. For the BS-0.60PT-0.05PNN composition, the piezoelectric

performance reaches 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.
Figure 7(a-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
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apparent current peaks in the I-E loops for each specimen, indicating 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 Figure 7(c-d). As shown, when the

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PNN content remains unchanged, the remnant polarization increases firstly and the
optimum is obtained at the MPB composition, then the Pr decreases with the further

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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

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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. In addition, for the same PT content, the Pr

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reduces with the increase of PNN content, which may be caused by the enlargement
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of lattice distortion and diffuse phase transition behavior.

The unipolar S-E curves of the poled BS-xPT-yPNN specimens were measured
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under the same driven electric field of 40 kV/cm and shown in Figure 8(a-b). A
basically linear loop with a little remnant strain was obtained for each specimen with
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the applied field. As known, the electric field-induced strain may result from both
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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
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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
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partly reversible and partly irreversible. The main contribution to the electric
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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 Figure 8(a-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:

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∆S
h= × 100%
S max

where h is relative strain hysteresis, ∆S 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

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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 linearity

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characteristic than other BS-PT based piezoelectric ceramics[35, 36]. This is
important for the design of the piezoelectric actuator. In addition, it can be easily

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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

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fixed, as the BS-xPT-0.025PNN system shown in Figure 8(a). Similar phenomenon
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can be found in the BS-xPT-0.05PNN system shown in Figure 8(b). All these can be
ascribed to the enhanced polarizability and domain wall mobility in the MPB region
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where existing large numbers of thermodynamically stable polarization directions as 8

in the rhombohedral phase and 6 in the tetragonal phase[37].
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Figure 9 shows the thermal stability of the piezoelectric properties for the MPB
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composition of BS-xPT-yPNN system, and the inset gives the variation of relative d33
towards the depoling temperature. It can easily figure out that d33 remains almost
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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
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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
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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.

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4. Conclusions
In summary, (1-x-y)BiScO3-xPbTiO3-yPb(Ni1/3Nb2/3)O3 (BS-xPT-yPNN) ternary
high temperature piezoelectric ceramics were 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

PT
member content in this system. High temperature dielectric behaviors show diffuse
phase transition characteristic in BS-xPT-yPNN ceramics and the diffuseness enlarges

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with the increase of PNN content. The coexistence of the rhombohedral and
tetragonal phase at MPB composition presents the optimal properties of piezoelectric

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coefficient d33 522 pC/N, planar electromechanical coupling factor kp 59.6%, remnant
polarization Pr 39.2 µC/cm2, and the Curie temperature Tc 400 o
C for the

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BS-0.61PT-0.025PNN composition in the BS-xPT-0.025PNN system. With the
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increase of PNN content, the piezoelectric performance reduces a little and still reach
to 495 pC/N and 59% of the BS-0.60PT-0.05PNN composition, which is also
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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
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new ternary system with high piezoelectric performance and the potential for
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applications at the temperature of the order of 300 oC.

Acknowledgments
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This work was supported by the National Natural Science Foundations of China
(Grant No. 51802242, 11604251), the National Natural Science Foundation of
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Shaanxi Province (Grant No. 2019JQ-313), and the 111 Project (No. B12026).
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Table 1. Room temperature piezoelectric and dielectric properties of BS-xPT-yPNN ceramics

Phase Tc d33 kp Ec Pr Strain h
Material o
tanδ 2
Ref
structure ( C) (pC/N) (%) (kV/cm) (µC/cm ) (%) (%)

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

BS-0.64PT MPB 450 2010 0.020 460 56.0 20 32 0.25 … [10]

PT
BS-0.60PT-PZN MPB 417 1540 0.024 490 57.4 28.5 40 … … [13]

BS-xPT-0.025PNN

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x=0.60 R 390 2030 0.046 460 55.8 20.7 36.6 0.17 16.8

SC
x=0.61 MPB 400 2216 0.049 522 59.6 19.3 39.2 0.22 16.2

x=0.62 T 408 2111 0.043 450 54.4 24.0 38.0 0.21 14.8

x=0.63 T 415 1980 0.027 380 50.2 27.0 32.2 0.19 13.6

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BS-xPT-0.05PNN
x=0.58 R 359 2079 0.037 370 46.6 19.1 34.5 0.16 16.4
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x=0.59 R 373 2017 0.049 460 53.1 21.1 37.8 0.20 17.6
x=0.60 MPB 385 2340 0.054 495 59.0 16.8 38.5 0.22 16.9
x=0.61 T 393 2237 0.052 465 55.2 18.9 38 0.18 12.1
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x=0.62 T 402 2005 0.029 410 51.4 24.4 34 0.17 7.01

D
TE
C EP
AC

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Figure Caption
Fig.1 Room temperature XRD patterns: (a) BS-xPT-0.025PNN (b) BS-xPT-0.05PNN.
Fig.2 Lattice parameters and c/a ratio as a function of PT content: (a)
BS-xPT-0.025PNN (b) BS-xPT-0.05PNN.
Fig.3 Selected XRD patterns of BS-xPT-yPNN ceramics.

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Fig.4 Phase diagram of BS-xPT-yPNN ceramics at room temperature.
Fig.5 The fractured surfaces SEM photos of BS-xPT-yPNN ceramics sintered at

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1080 °C (a) y=0.025, x=0.61, (b) y=0.025, x=0.62, (c) y=0.05, x=0.58, (d) y=0.05,
x=0.60.

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Fig.6 (a-b) Temperature dependence of the relative dielectric permittivity ε and
dielectric loss tan δ at 1 kHz for the unpoled BS-xPT-yPNN ceramics, (c-f) dielectric

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temperature spectrum measured at 1 kHz, 10 kHz, and 100 kHz for the selected
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BS-0.61PT-0.025PNN, BS-0.63PT-0.025PNN, BS-0.60PT-0.05PNN, and the
BS-0.62PT-0.05PNN ceramics
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Fig.7 (a-b) room temperature P-E loops and I-E loops of BS-xPT-yPNN ceramics: (a)
BS-xPT-0.025PNN (b) BS-xPT-0.05PNN, (c-d) the variation of Pr and Ec of
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BS-xPT-yPNN ceramics: (c) BS-xPT-0.025PNN (d) BS-xPT-0.05PNN

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Fig.8 Room temperature S-E curves of BS-xPT-yPNN ceramics: (a)

BS-xPT-0.025PNN (b) BS-xPT-0.05PNN
Fig.9 Effect of thermal depoling on piezoelectric coefficient d33 of selected samples.
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(101)
(a)

(110)
(100)

(111)
Intensity(a.u.)

(211)
(001)

(200)

(112)
(102)
(210)
(002)

PT
x=0.63

x=0.62

RI
x=0.61

SC
x=0.60
20 30 40 50 60
2θ (degree)

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(101)

(b)
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(110)

M
(100)

(111)
Intensity(a.u.)
(001)

(211)
(200)

(112)
(002)

(210)
(102)

x=0.62
D
TE

x=0.61

x=0.60
EP

x=0.59

x=0.58
C

20 30 40 50 60
2θ (degree)
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Figure 1 Room temperature XRD patterns: (a) BS-xPT-0.025PNN (b)

BS-xPT-0.05PNN
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4.15 1.10
(a)
4.10 1.08
Lattice parameter (Å)

c
4.05
1.06

c/a ratio
PT
4.00
a 1.04

RI
3.95
1.02
c/a
3.90

SC
1.00
3.85
0.60 0.61 0.62 0.63

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PbTiO3 content x
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4.15 1.10
(b)
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4.10 1.08
Lattice parameter (Å)

c
D

4.05
1.06

c/a ratio
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4.00 a
1.04
EP

3.95
1.02

3.90 c/a
C

1.00
AC

3.85
0.58 0.59 0.60 0.61 0.62
PbTiO3 content x

Figure 2 Lattice parameters and c/a ratio as a function of PT content:

(a) BS-xPT-0.025PNN (b) BS-xPT-0.05PNN
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(a)

(110)

(111)

(211)
(001)
(100)

(200)

(112)
(002)

(102)
(210)
0.05-0.62
Normalized Intensity(a.u.)

0.025-0.62

PT
0.05-0.61

RI
0.025-0.61

SC
20 30 40 50 60
2θ (degree)

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(b) x=0.61 (c) x=0.62
(110)
(110)

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(111)
(111)

Normalized Intensity(a.u.)
Normalized Intensity(a.u.)

0.50PNN 0.50PNN
D
TE

0.25PNN 0.25PNN
EP

28 32 36 40 28 32 36 40
2θ (degree) 2θ (degree)
C

Figure 3 Selected XRD patterns of BS-xPT-yPNN ceramics

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PT
RI
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AN
M
D
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Figure 4 Phase diagram of BS-xPT-yPNN ceramics at room temperature.

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PT
RI
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Figure.5 The fractured surfaces SEM photos of BS-xPT-yPNN ceramics sintered at

1080 °C (a) y=0.025, x=0.61, (b) y=0.025, x=0.62, (c) y=0.05, x=0.58, (d) y=0.05,
D

x=0.60.
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27000 1.0 27000 405

1.0
415
(a) 410 24000 (b) 395
24000
405 385
0.8 21000 0.8
21000 400 375

Dielectric loss tanδ

Dielectric permittivity ε

Dielectric permittivity ε
395 18000

Dielectric loss tanδ

18000 365
390
0.6 15000 355 0.6
15000 0.60 0.61 0.62 0.63 0.58 0.59 0.60 0.61 0.62
y=0.05, x=0.58
y=0.025, x=0.60 12000 y=0.05, x=0.59
12000
y=0.025, x=0.61 0.4 y=0.05, x=0.60 0.4
9000
9000 y=0.025, x=0.62 y=0.05, x=0.61
y=0.025, x=0.63 6000 y=0.05, x=0.62
6000 0.2 0.2
3000

PT
3000
0
0 0.0 0.0
50 100 150 200 250 300 350 400 450 500 50 100 150 200 250 300 350 400 450 500
Temperature (°C)
Temperature (°C)

27000 27000

RI
-10 -10
(c) (d)
24000 24000

ln(1/ε -1/ε m)
Exprimental data -12 Exprimental data
ln(1/ε -1/ε m)

-12
Linear Fit Linear Fit
21000 -14 21000 -14
γ=1.5865 γ=1.5704
Dielectric permittivity ε

Dielectric permittivity ε
18000 -16 18000 -16

SC
-18 -18
15000 1 2 3 4 5 15000 1 2 3 4 5
ln(T-Tm) ln(T-Tm)
12000 12000

9000 9000
y=0.025, x=0.61 1 kHz y=0.025, x=0.63
1 kHz

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6000 10 kHz 6000 10 kHz
100 kHz 100 kHz
3000 3000
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0 0
50 100 150 200 250 300 350 400 450 500 50 100 150 200 250 300 350 400 450 500
Temperature (°C) Temperature (°C)
21000 27000
-10 -10
(e) (f)
24000
ln(1/ε -1/ε m)

18000 Exprimental data

ln(1/ε -1/ε m)
-12
M

Exprimental data -12

Linear Fit Linear Fit
-14 21000
-14
15000
Dielectric permittivity ε

γ=1.7397
Dielectric permittivity ε

-16 18000 γ=1.7336

-16

12000 -18 15000

1 2 3 4 5 -18
1 2 3 4 5
D

ln(T-Tm)
9000 12000 ln(T-Tm)

9000
6000 y=0.05, x=0.60 y=0.05, x=0.62
TE

1 kHz 1 kHz
6000
10 kHz 10 kHz
3000 100 kHz 3000 100 kHz
0 0
50 100 150 200 250 300 350 400 450 500 50 100 150 200 250 300 350 400 450 500
Temperature (°C) Temperature (°C)
EP

Figure.6(a-b) Temperature dependence of the relative dielectric permittivity ε and

dielectric loss tan δ at 1 kHz for the unpoled BS-xPT-yPNN ceramics, (c-f) dielectric
C

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
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BS-0.62PT-0.05PNN ceramics
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60 1.5 60 1.5
(a) (b)
40 1.0 40 1.0

µ C/cm2)
µ C/cm2)

Current(mA)
20 0.5 20 0.5

Current(mA)
Polarization(µ
Polarization(µ

0 0.0 0 0.0

-20 x=0.60 -0.5 -20 x=0.58 -0.5

x=0.61 x=0.59
x=0.62 x=0.60
-40 -1.0 -40 x=0.61 -1.0
x=0.63

PT
x=0.62
-60 -1.5 -60 -1.5
-40 -20 0 20 40 -40 -20 0 20 40

Electric Field(kV/cm) Electric Field(kV/cm)

RI
45 40
37
(c) (d)
39
40

SC
35
32
36
Pr (µ C/cm2)

Pr (µ C/cm2)
35
Ec (kV/cm)

Ec (kV/cm)
30
33 27
30

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25 30 22
25
AN
27
20 20 17

0.60 0.61 0.62 0.63 0.58 0.59 0.60 0.61 0.62

x PbTiO3
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x PbTiO3

Figure.7 (a-b) room temperature P-E and I-E loops: (a) BS-xPT-0.025PNN (b)
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BS-xPT-0.05PNN, (c-d) variation of Pr and Ec: (c) BS-xPT-0.025PNN (d)

BS-xPT-0.05PNN
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0.24 (a)
∆S
0.20 h= × 100%
Smax
Strain(%)
0.16
∆S at Emax/2
0.12

PT
x=0.60 Smax
0.08 x=0.61
x=0.62
x=0.63

RI
0.04

0.00

SC
0 10 20 30 40 50
Electric Field (kV/cm)

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0.24 (b)
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0.20

0.16
Strain(%)

0.12 x=0.58
x=0.59
D

x=0.60
0.08
x=0.61
TE

x=0.62
0.04
EP

0.00
0 10 20 30 40 50
Electric Field (kV/cm)
C

Figure.8 Room temperature S-E curves: (a) BS-xPT-0.025PNN (b) BS-xPT-0.05PNN

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BS-0.64PT
500 BS-0.61PT-0.025PNN
BS-0.60PT-0.05PNN

400
d33(pC/N)

PT
1.0
300
0.8
relative d33

0.6

200

RI
0.4

0.2

100 0.0

SC
0 100 200 300 400 500
° C)
Temperature(°

0
0 100 200 300 400 500

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Temperature (°C)
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Figure 9 Effect of thermal depoling on piezoelectric coefficient d33 of selected
samples.
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Highlights

1. The accurate MPB regions for BS-xPT-yPNN ternary system were investigated.

2. The MPB region shifts to the low PT region with the increase of PNN content.

3. Dielectric temperature spectra present diffuse phase transition characteristic.

PT
4. The optimal properties of d33 522 pC/N, kp 59.6% and Tc 400 oC are obtained.

RI
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