Current Applied Physics 15 (2015) 1521e1528

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Current Applied Physics

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Enhanced piezoelectric properties near the morphotropic phase

boundary in lead-free (1-x)(Bi0.5K0.5)TiO3-xBi(Ni0.5Ti0.5)O3 ceramics
Parkpoom Jarupoom a, Pharatree Jaita b, Rattikorn Yimnirun c, Gobwute Rujijanagul b, *,
David P. Cann d
a
Department of Industrial Engineering, Faculty of Engineering, Rajamangala University of Technology Lanna (RMUTL), Chiang Mai 50300, Thailand
b
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
c
School of Physics, Institute of Science, and NANOTEC-SUT Center of Excellence on Functional Nanomaterials, Suranaree University of Technology, Nakhon
Ratchasima 30000, Thailand
d
Materials Science, School of Mechanical, Industrial and Manufacturing Engineering, Oregon State University, Corvallis, OR 97331, USA

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

Article history: Lead-free piezoelectric ceramics of the composition (1-x)(Bi0.5K0.50)TiO3-xBi(Ni0.50Ti0.50)O3 or (1-x)BKT-

Received 29 June 2015 xBNiT (when x ¼ 0e0.20 mol fraction) were prepared by a conventional mixed-oxide method and sin-
Received in revised form tered at 1050  C for 4 h. The effects of BNiT content on the phase equilibria, and the dielectric, ferro-
18 August 2015
electric and piezoelectric properties were systematically investigated. High density sintered specimens
Accepted 1 September 2015
(5.71e6.12 g/cm3) were obtained for all compositions. X-ray diffraction patterns showed that all BKT-
Available online 8 September 2015
BNiT samples exhibited a single perovskite phase which confirms that BNiT and BKT formed a solid
solution up to x ¼ 0.20. A morphotropic phase boundary (MPB) separating a BKT-rich tetragonal phase
Keywords:
Morphotropic phase boundary
and a BNiT pseudo-cubic phase was identified over the compositional range 0.05 < x < 0.10, where
Piezoelectric responses enhanced electrical properties were observed. The optimum dielectric properties (εr ¼ 1710,
Binary system tand ¼ 0.036), ferroelectric properties (Pr ¼ 16.6 mC/cm2, Ec ¼ 22.5 kV/cm and Rsq ¼ 0.86) and piezo-
Lead-free ceramics electric properties (d33 ¼ 288 pC/N, Smax ¼ 0.22% and d*33 ¼ 313 pm/V) were observed with a relatively
high Tm ~ 304  C within this MPB region. Overall, these results indicate that the BKT-BNiT ceramic system
is a promising lead-free piezoelectric candidate for further development for actuator applications.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction PZT-based ceramics, making them viable candidates for numerous

applications. Among lead-free perovskite-based piezoelectric ma-
Pb(Zr,Ti)O3 (PZT) and related compositions have been the terials, bismuth potassium titanate, Bi0.5K0.5TiO3 (BKT) has been
mainstay for high performance actuators and transducers, owing to considered to be one of the most promising materials [5e11]. The
their superior piezoelectric properties and electromechanical compound BKT was first fabricated by Smolenskii et al. [5] in 1959.
coupling coefficients and their excellent dielectric properties [1]. It is a typical ferroelectric material with a stable perovskite struc-
However, these materials are disadvantageous with respect to the ture with tetragonal symmetry at room temperature and a rela-
environment and human health. In order to circumvent issues tively high Curie temperature (Tc) in range of 380e420  C [6,9].
related to lead toxicity, extensive research has been focused on the Ivanova et al. [10] also reported that BKT has a tetragonal structure
quest for alternate piezoelectric materials. Therefore, there has with lattice parameters of a ¼ 3.913 Å and c ¼ 3.993 Å at room
been a growing research interest in developing alternative lead- temperature. A transition into a pseudo-cubic phase was observed
free piezoelectric materials that can eventually replace the cur- at about 270  C, and a transition into a cubic phase was found at
rent lead-based materials [2e4]. around 410  C [10]. The piezoelectric coefficient (d33) of BKT was
Recently, many interesting lead-free based piezoelectric mate- measured to be 69.8 pC/N as reported by Hiruma et al. [11]. How-
rials have been reported that offer comparable properties to that of ever, it is difficult to prepare highly-dense BKT ceramics due to the
fact that secondary phases such as K2Ti6O13 are easily formed
during the sintering process at high temperatures. Moreover, the
* Corresponding author. piezoelectric properties of BKT are not generally high enough for
E-mail address: rujijanagul@yahoo.com (G. Rujijanagul). the most applications [12]. In order to further enhance the

http://dx.doi.org/10.1016/j.cap.2015.09.002
1567-1739/© 2015 Elsevier B.V. All rights reserved.
1522 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528

piezoelectric properties of BKT-related ceramics and to meet the 4 h dwell time with a heating/cooling rate of 5  C/min. An x-ray
requirements for typical actuator applications, it is necessary to diffractometer (Bruker, D8 Discover) was used to identify the phase
develop new BKT-based materials. Finding compositions near a of the ceramics. The bulk density was measured in accordance with
morphotropic phase boundary (MPB) between two ferroelectric Archimedes' method with ASTM standard C 373-88. For the elec-
end members with different crystal structures is a common strat- trical measurements, silver paste was used to form the electrodes.
egy for improving the piezoelectric properties of piezoelectric The dielectric properties were measured using an LCZ-meter
materials. Within this MPB region, the maximum polarization (Hewlett Packard 4192A) at frequencies of 10e1000 kHz. A ferro-
values are attainable which leads to enhancement of the electrical electric test system (Radiant technology) was used to measure the
properties [13]. Many BKT-based solid solutions such as BKT-BaTiO3 polarization-electric field (PeE) hysteresis data. For the piezoelec-
[14], BNT-BKT-LiTaO3 [15], BKT-LiNbO3 [16], and BKT-BiFeO3 [17,18], tric measurements, all samples were poled at 25  C in a stirred
thus have been fabricated and their MPB regions have been silicone oil bath by applying a DC electric field equal to 5 kV/mm for
investigated. However, further research new modified BKT systems 15 min. The low-field piezoelectric coefficient (d33) of each sample
are still necessary to obtain piezoelectric properties comparable to was measured using a d33-meter (KCF Technologies, S5865) at a
PZT. frequency of 50 Hz from samples aged 24 h. The room temperature
Bismuth nickel titanate (BNiT) is another promising lead-free strain-electric field (SeE) data were obtained using an optical
piezoelectric material [19]. However, BNiT is unstable when displacement sensor (Fotonic Sensor, MTI-2100) combined with
formed under normal atmosphere and normal pressure [20]. Choi Radiant ferroelectric test system.
et al. [21] reported that BNiT had a perovskite structure, and it
showed evidence of a pseudo-cubic phase when fabricated under 3. Results and discussion
high atmospheric pressures. Kitada et al. [22] fabricated single
phase Bi(Ni0.5Ti0.5)O3 under a high pressure of 6 GPa by using a After sintering, all compositions showed high densities over the
multianvil-type high-pressure apparatus. The P-E hysteresis data range of 5.71e6.12 g/cm3. However, the data clearly showed that a
on BNiT ceramics synthesized under high pressure for 30-days variation in the mole fraction of BNiT had a significant influence on
showed that this material presented a ferroelectric state with a sample density, i.e., the addition of BNiT caused an increase in
weak remanent polarization of Pr ¼ 0.30 mC/cm2 and a coercive field density (see Table 1). X-ray diffraction patterns of all ordinary
of Ec ¼ 9.1 kV/cm (measured at a maximum electric field of 30 kV/ calcined (1-x)BKT-xBNiT ceramics are shown in Fig. 1(a). The pat-
cm). Kitada et al. [22] also reported that the BNiT samples had a terns showed that all samples exhibited a single phase perovskite
multidomain structure and ferroelectricity on the basis of scanning structure. Dense samples were obtained for all compositions, which
nonlinear dielectric microscopy (SNDM) and P-E hysteresis loop also resulted in a single phase composition according to XRD
measurements. It is expected that this material is a multiferroic measurements. No impurity peaks, such as those of K2Ti6O13, could
material with possible application in multiple-valued logic and be detected thus confirming that the reagents completely reacted
optical isolator systems. to form the final perovskite phase [11,24]. This suggested that a
Recently, Bai et al. [23] reported that the binary system of (1-x) solid solution was obtained between BNiT and BKT during the
Bi0.5Na0.5TiO3-xBNiT exhibited reasonable piezoelectric properties calcination and sintering process. The solubility limit of BNiT in BKT
at the MPB (x ¼ 0.06 and 0.14). Furthermore, Choi et al. [21] found lattice is believed to be more than 20 mol% because no trace of any
that the BNiT-PbTiO3 system exhibited excellent piezoelectric secondary phases was detected within the detection limits of the
properties with a d33 of 250 pC/N at the MPB composition laboratory scale XRD instrument. This observation was also similar
(0.51BNT-0.49 PT sample). It is expected that BNiT can form a solid- to the Bi(Ni0.50Ti0.50)O3ePbTiO3 (BNiT-PT) binary system previously
solution with BKT resulting in improvement of the piezoelectric reported by Takenaka et al. [25] which reported that the maximum
properties. solubility limit of BNiT in PT was around 30e50%. The positions of
To our knowledge, the properties of BKT-BNiT ceramics has not all peaks slightly shifted towards higher 2q angles in comparison
been investigated before. Thus, the present research is aimed at with pure BKT. This is consistent with expectations given that the
fabricating ceramics within a new binary system based on (1-x) Ni2þ (0.69 Å) ion has a smaller ionic radii on the perovskite B-site
BKT-xBNiT and focused on the MPB region which would be ex- compared to Ti4þ (0.74 Å) [26], resulting in a change of unit cell size.
pected to show excellent piezoelectric properties as compared to X-ray analysis conducted over a narrow range of 2q ¼ 44e47
the unmodified BKT ceramics. The role of the BNiT mole fraction on range is shown in Fig. 1(b). The pure BKT phase could be indexed
the density, phase evolution, electrical properties (dielectric, according to a tetragonal unit cell which was matched with JCPDS
ferroelectric and piezoelectric) and the electric field-induced strain file number 36e0339 for the (Bi0.5K0.50)TiO3 tetragonal phase [11],
behavior of BKT ceramics were investigated and are discussed in which is consistent with the results observed earlier by Thongtha
detail. et al. [27]. In agreement with previously reported studies
[11,13e17,24], BKT samples had a tetragonal symmetry, as evi-
2. Experimental section denced by the splitting of (002)/(200) peaks at 2q ~ 46 and the
existence of a single (111) peak at 2q angle of approximately 40 . It
Within the binary system of (1-x)BKT-xBNiT (where x ¼ 0, 0.05,
0.10, 0.15 and 0.20) ceramics were prepared by a conventional
Table 1
mixed oxide method. Analytical grade reagents of Bi2O3 (99.9%), Physical and dielectric properties of (1-x)BKT-xBNiT ceramics sintered at 1050  C.
K2CO3 (99%), TiO2 (99.9%) and NiO (99.9%) were used as starting
x Density (g/cm3) c/a εra tand a
εmaxb Tm ( C)
materials. The raw materials were stoichiometrically weighed ac-
cording to the (1-x)BKT-xBNiT formula, and then vibratory milled 0 5.71 1.0141 1130 0.035 3500 351
0.05 5.86 1.0104 1680 0.039 4550 304
with yttrium stabilized zirconia media for 6 h in an ethanol solu-
0.10 5.93 1.0102 1710 0.036 3950 277
tion. The slurry was then dried in an oven. After drying, the ob- 0.15 5.95 1.0075 1670 0.039 3200 270
tained powder was calcined at 900  C for 2 h with a heating/cooling 0.20 6.12 1.0069 1410 0.042 3640 265
rate of 5  C/min. Afterward, 3 wt% of polyvinyl alcohol (PVA) binder a
Dielectric data obtained at room temperature and a frequency of 1 kHz.
were then mixed with the powders before being uniaxially pressed b
Dielectric data obtained at high temperature (25e500  C) and a frequency of
into discs. These pellets were then sintered at 1050  C for a 10 kHz.
 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528 1523

Fig. 1. X-ray diffraction patterns of (1-x)BKT-xBNiT ceramics sintered at 1050  C where

(a) 2q ¼ 20e80 and (b) 2q ¼ 44e47. Fig. 3. Plots of room temperature dielectric constant (εr) at a frequency of 1 kHz and
low-field piezoelectric coefficient (d33) as a function of BNiT content.

is worth noting that the addition of BNiT tended to change the

be 1130 with a tand value of 0.035. The addition of 5 mol% BNiT
crystal structure of the BKT ceramic. Splitting of the (002)/(200)
increased the εr value to 1680 while the dielectric loss was largely
peaks at 2q ~ 46 was observed for the samples contained 5e10 mol
unchanged. In this study, the composition 0.90BKT-0.10BNiT
% of BNiT. However, with a further increase in BNiT content up to
exhibited the maximum room temperature εr value of 1710. With
15e20%, the (200)T-(002)T diffraction peaks gradually merged into
further increase in BNiT content beyond 10 mol% a decrease in εr
a single peak. This suggested that there was a change from
was observed.
tetragonal symmetry in pure BKT to pseudo-cubic symmetry with
Fig. 4 displays the temperature dependence of the dielectric
the addition of BNiT [20] which can be seen clearly from the XRD
constant (εr) and dielectric loss (tand) for the (1-x)BKT-xBNiT ce-
patterns in Fig. 1(b). Therefore, a morphotropic phase boundary
ramics, measured at various frequencies. It can be seen that the εr
(MPB) separating tetragonal and pseudo-cubic phases may exist
versus temperature data for all samples were rather similar. The
over the composition range of 0.05 < x < 0.10, where the improved
dielectric trace showed a strong frequency dependence especially
electrical properties would be expected. In order to confirm the
for temperatures near the phase transition region. In this study,
appearance of the phase transition in more detail, the lattice pa-
pure BKT exhibited the highest transition temperature of 351  C,
rameters (a and c) and tetragonality ratio (c/a) values were calcu-
defined as the temperature at which the dielectric constant reached
lated from the XRD data. From the lattice constant analysis (Fig. 2),
a maximum value (Tm). This value is consistent with Tm data pre-
a decrease of tetragonality (c/a) value was observed with an in-
viously reported by Zuo et al. [16]. The Tm at the maximum
crease in the BNiT mole content which confirms the transformation
dielectric constant decreased with the addition of BNiT. Never-
from tetragonal to pseudo-cubic symmetry (for higher BNiT con-
theless, a broad dielectric maximum at Tm was observed which
centration of x > 0.10 samples). This also indicates a decrease in
could be attributed to a relaxor mechanism [28,29]. With increasing
lattice anisotropy for the BKT-BNiT system.
BNiT content up to x ¼ 0.20, the dielectric peak near Tm became
Plots of the room temperature dielectric constant (εr) at a fre-
more broad and exhibited a more significant frequency dispersion.
quency of 1 kHz and low-field piezoelectric coefficient (d33) as a
Furthermore, Tm shifted to lower temperatures with increasing
function of BNiT concentration are shown in Fig. 3. The dielectric
BNiT (see Fig. 4(f)).
data are also summarized in Table 1. The εr of pure BKT was found to
The polarization-electric field (PeE) hysteresis data for (1-x)
BKT-xBNiT ceramics are shown Fig. 5. The samples were subjected
to an external electric field of 70 kV/cm and a frequency of 1 Hz.
Higher values of applied voltage caused the samples to undergo
electrical breakdown. To verify the quantification of changes in the
hysteresis data, the loop squareness (Rsq) was calculated from the
equation of Rsq ¼ (Pr/Ps) þ (P1.1Ec/Pr) [30], where Pr is remanent
polarization, Ps is saturated polarization and Ec is coercive field. The
Rsq values are listed in Table 2. Pure BKT ceramic exhibited a weak
ferroelectric behavior with Pr ¼ 6.9 mC/cm2, Ps ¼ 18.7 mC/cm2,
Ec ¼ 23.9 kV/cm, and Rsq ¼ 0.62. The obtained data are in good
agreement with those reported in the literature [31]. The Pr, Ps and
Rsq values increased with increasing BNiT content and reached
maximum values of 16.6 mC/cm2, 31.7 mC/cm2 and 0.86, respectively,
for the composition x ¼ 0.05. However, Ec gradually decreased with
increasing BNiT content. The improvement in ferroelectric perfor-
mance was achieved for the x ¼ 0.05e0.10 compositions, suggest-
ing that this region is host to a transition region. Thus, the sample
near/or at the transition region enabled the dipole moments to
align more efficiently with electric field, resulting in higher polar-
Fig. 2. Plots of lattice parameter (a and c) and tetragonality (c/a) values as a function of izability and an increase in Pr, Ps, and Rsq values [32e34]. This seems
BNiT content of (1-x)BKT-xBNiT ceramics sintered at 1050  C.
1524 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528

Fig. 4. Temperature dependence on dielectric constant (εr) and dielectric loss (tand) of (1-x)BKT-xBNiT ceramics, measurement at various frequencies where (a) x ¼ 0, (b) x ¼ 0.05,
(c) x ¼ 0.10, (d) x ¼ 0.15 (e) x ¼ 0.20, and (f) plot of maximum temperature (Tm) as a function of BNiT content (Inset shows maximum dielectric constant as various BNiT content).

to be the main mechanism explaining the observed improvement earlier in (Bi1/2K1/2)TiO3 ceramics prepared with hot pressing (HP)
in ferroelectric properties similar to previous work on the system method by Hiruma et al. [11] who obtained a low-field d33 of
0.985(Bi0.5K0.5)TiO3-0.015LiNbO3 near the MPB composition stud- 69.8 pC/N. The low-field d33 rapidly increased with increasing BNiT
ied by Zuo et al. [16]. With a further increase in BNiT content greater content for compositions with x ¼ 0.05e0.10. The d33 values for
than 10 mol% the crystal structure transformed to pseudo-cubic these compositions were found to be in the range of 265e288 pC/N.
symmetry accompanied by a slight decrease in Pr, Ps, and Rsq This value was higher than that observed earlier in 0.985(Bi0.5K0.5)
[35e37]. TiO3-0.015LiNbO3 ceramics near the MPB composition studied by
The low-field d33 values of BKT-BNiT ceramics obtained after Zuo et al. [16] with a low-field d33 of 75 pC/N. The optimum
poling at room temperature at a field of 5 kV/mm for 15 min are properties closely correspond to the existence of the MPB in this
listed in Table 2. The variation in piezoelectric behavior with BKT-BNiT system located near x ¼ 0.05e0.10. Moreover, the
increasing BNiT content also showed a similar trend to that of the decrease of Ec value to around 20 kV/cm in comparison with that of
dielectric response (Fig. 3). The unmodified-BKT ceramic had a low- pure BKT ceramic (~24 kV/cm) was also observed. The decrease in Ec
field d33 of 118 pC/N. This value is higher than the value observed indicates an increase in domain mobility and therefore the
 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528 1525

Fig. 5. Polarization-electric field (P-E) hysteresis loops of (1-x)BKT-xBNiT ceramics sintered at 1050  C, measured at 70 kV/cm and a frequency of 1 Hz where (a) x ¼ 0, (b) x ¼ 0.05,
(c) x ¼ 0.10, (d) x ¼ 0.15, and (e) x ¼ 0.20.

Table 2
Ferroelectric and piezoelectric properties of (1-x)BKT-xBNiT ceramics sintered at 1050  C (DP ¼ Ps  Pr).

x Pr (mC/cm2) Ps (mC/cm2) DP (mC/cm2) Ec (kV/cm) Rsq d33 (pC/N) Smax (%) d*33 (pm/V)

0 6.9 18.7 11.8 23.9 0.62 118 0.10 137

0.05 16.6 31.7 15.1 22.5 0.86 265 0.20 287
0.10 8.6 25.4 16.8 20.3 0.79 288 0.22 313
0.15 7.3 23.7 16.4 18.4 0.65 219 0.16 234
0.20 7.2 23.6 16.4 15.9 0.55 135 0.10 149
1526 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528

enhancement of domain wall motion and improvement of piezo- measurement was conducted under a maximum electric field of
electricity would be expected for this composition [30]. However, 70 kV/cm and at a frequency of 0.1 Hz. Data on the maximum strain
with further addition of BNiT in compositions with greater than (Smax) and the normalized strain coefficient (d*33 ¼ Smax/Emax) are
10 mol% BNiT resulted in a decrease in the low-field d33 to values summarized in Table 2. Plots of Smax and d*33 as a function of BNiT
close to ~135 pC/N. This result was also similar to that observed content are shown in Fig. 7. As expected, it can be seen that the
previously by Ullah et al. [38,39]. Moreover, this decrease in variation of Smax with increasing BNiT content showed a similar
properties can be explained from the fundamental theory of fer- trend to that of the d*33 values. Pure BKT displayed a typical
roelectrics [40] in which d33 is proportional to the Pr value. For butterfly-shaped strain loop with Smax and d*33 values of 0.10% and
example, with the 0.80BKT-0.20BNiT composition, the Pr value 137 pm/V, respectively. These values are close to the earlier reports
decreased to around 7.2 mC/cm2 (see Table 2) which accompanied a in (Bi1/2K1/2)TiO3 ceramics prepared with hot pressing (HP) method
significant reduction in d33 [38e40]. by Hiruma et al. [11] who obtained d*33 of 135 pm/V. Large strain
Bipolar strain-electric field (SeE) data for (1-x)BKT-xBNiT ce- values were obtained in the MPB compositions with 0.05 < x < 0.10
ramics measured at room temperature are presented in Fig. 6. The with a value for Smax of 0.20e0.22% and d*33 of 287e313 pm/V. With

Fig. 6. Bipolar strain-electric field (SeE) of (1-x)BKT-xBNiT ceramics sintered at 1050  C, measured at room temperature, under an electric field of 70 kV/cm and a frequency of
0.1 Hz where (a) x ¼ 0, (b) x ¼ 0.05, (c) x ¼ 0.10, (d) x ¼ 0.15, and (e) x ¼ 0.20.
 P. Jarupoom et al. / Current Applied Physics 15 (2015) 1521e1528 1527

Nanomaterials, Suranaree University of Technology.

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