Materials Research Bulletin 66 (2015) 16–25

Contents lists available at ScienceDirect

Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Ba(Cu0.5W0.5)O3-induced sinterability, electrical and mechanical

properties of (Ba0.85Ca0.15Ti0.90Zr0.10)O3 ceramics sintered at low
temperature
Xiaolian Chao * , ZhongMing Wang, Ye Tian, Yanzhao Zhou, Zupei Yang *
Key Laboratory for Macromolecular Science of Shaanxi Province, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062,
Shaanxi, PR China

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

Article history: A low sintering temperature is achieved for (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 (BCZT) piezoelectric ceramics
Received 26 April 2014 using Ba(Cu0.5W0.5)O3 (BCW) as a sintering aid. The effects of the BCW content on the density, phase
Received in revised form 12 October 2014 structure, electrical and mechanical properties are investigated. The addition of BCW content
Accepted 6 February 2015
significantly improves the sinterability of the BCZT ceramics, which results in a reduction of the
Available online 9 February 2015
sintering temperature from 1450
C to 1220
C and an improvement in both the piezoelectric and
mechanical properties. The BCZT ceramics with x = 0.8 wt.% BCW sintered at 1220
C exhibits outstanding
Keywords:
piezoelectric, dielectric and mechanical properties: d33 = 541 pC/N, kp = 49%, Qm = 107, er = 5405, tan
A. Ceramics
C. X-ray diffraction
d = 0.014 and Tc = 78
C. The ceramics also exhibit higher hardness (78 MPa) and higher fracture toughness
D. Electrical properties (4.7 MPa m1/2). These results indicate that the BCZT–BCW lead-free ceramics sintered at low
D. Microstructure temperatures are promising for high temperature piezoelectric applications.
D. Piezoelectricity ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction ceramics could be reduced if a liquid-phase is formed during

Lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 (BCZT)-based piezoelec-
tric ceramics have attracted considerable interest because of their
excellent piezoelectric properties and environmental friendliness
[1,2]. The piezoelectric coefficient d33 (620 pC/N) of this system
sintered at above 1450
C has been reported, which is comparable
to that (500–600 pC/N) of Pb(Zr, Ti)O3 (PZT) based piezoelectric
ceramics [3–5]. Some attempts have been made to improve the d33
value of lead-free piezoelectric ceramics and the origin of this large
piezoelectricity, such as by ion substitution, new preparation
techniques, the introduction of additives and the construction of
the coexistence of two or more phases [6–10]. Nevertheless, low-
temperature sintering and the electrical properties of BCZT-based
piezoelectric ceramics are seldom reported.
Although this type of the ceramics displays good properties,
further investigation is needed to lower the sintering temperature
of the ceramics to reduce compositional variation, energy
consumption and fabrication costs. In addition, low-temperature
sintering can have several advantages, such as the reduction of
energy consumption [11]. The sintering temperature of the
* Corresponding authors. Tel.: +86 29 81530718; fax: +86 29 8153 0702.
E-mail addresses: chaoxl@snnu.edu.cn (X. Chao), yangzp@snnu.edu.cn (Z. Yang).
the sintering process. It is well known that the addition of a
sintering aid is an effective approach to reduce the sintering
temperature and improve the density of piezoelectric materials
[12,13]. In the related literature, a sintering temperature of 1350–
1400
C has been achieved for BCZT-based ceramics while
maintaining good properties with the addition of CuO, however,
the sintering temperature remains relatively high [14,15]. Perov-
skite-type Ba(Cu0.5W0.5)O3 (BCW) exhibits a strong ferroelectricity,
a high Curie temperature and a low melting temperature (730
C).
The addition of BCW has also been demonstrated to be very
effective in improving the piezoelectric properties of PZT ceramics
[16]. However, no systematic investigations have been performed
on the effects of BCW on the low-temperature sintering and
electrical properties of BCZT ceramics to date.
During multilayer piezoelectric device operation, the piezo-
electric device induced damage and piezoelectric device quality
are related to the mechanical properties of the host materials [17].
To date, only a few groups have investigated the mechanical
properties of these ceramics. The mechanical properties of
piezoelectric materials are very important for equipment design
and practical use [18,19]. However, few studies have reported that
strongly enhanced mechanical properties can be obtained from
BCZT ceramics with the addition of BCW content. In this study, our
objective is to reduce the sintering temperature of BCZT ceramics

http://dx.doi.org/10.1016/j.materresbull.2015.02.022
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
and while maintaining a high-piezoelectric activity. BCW-doped
BCZT ceramics are fabricated to systematically investigate the
effect of the BCW content on the sintering temperature, phase
structure, density, electrical and mechanical properties (hardness
and fracture toughness). The underlying physical mechanisms are
addressed in this study.
2. Experiment
2.1. Sample preparation
(Ba0.85Ca0.15)(Zr0.10Ti0.90)O3–xBa(Cu0.5W0.5)O3 ceramics (x = 0.0,
0.4, 0.8, 1.2, 1.6, 2.0 and 3.0 wt.%) were synthesized using a
conventional solid-state sintering process. BaCO3 (99%), CaCO3
(99%), ZrO2 (99%), TiO2 (98%), CuO (99.5%), and WO3 (99%) powders
were used as starting raw materials. Ba(Cu0.5W0.5)O3 does not need
to be synthesized. The powders were weighed according to the
stoichiometric composition. The mixed powders were dried and
then calcined at 1100
C for 6 h. The calcined powders were mixed
with 5 wt.% polyvinyl alcohol (PVA) solution and then uniaxially
pressed into pellets with a diameter of 1.5 cm under 100 MPa. After
burning out PVA at 500
C, the samples were sintered at 1180, 1220,
1260, 1300 and 1340
C for 4 h in air. Sliver paste was fired on both
faces of the samples at 850
C for 30 min to form electrodes.
2.2. Characterization
The sintered ceramics were examined by X-ray powder
diffraction analysis using a Cu Ka radiation (DMX-2550/PC,
Rigaku, Japan) to determine the crystalline phase at room
temperature. For the measurement of the electrical properties,
[(Fig._1)TD$IG]
Fig. 1. XRD patterns of the BCZT ceramics with various BCW contents sintered at 1220
C for 4 h.
17
both sides of the sintered samples were polished. The tempera-
ture-dependent dielectric constant was obtained with an LCR
meter (Agilent, E4980A) connected to a computer-controlled
temperature chamber by measuring the capacitance at 1, 10, 100,
100 kHz. For the temperature-dependent polarization–electric
field (P–E) hysteresis and strain measurements, the top electrode
was connected to a high voltage amplifier (Model 610E, Trek, USA)
for the electrical loading. Before the piezoelectric properties
measurements, the samples were poled for 30 min at room
temperature with an electric field of 4 kV/mm. The piezoelectric
coefficient d33 was measured using a quasistatic piezoelectric
meter (ZJ-3d, Institute of Acoustics Academic Sinica, Beijing,
China). The electromechanical coupling coefficient kp was deter-
mined using the resonance and anti-resonance technique using an
impedance analyzer (HP/Agilent Model 4294A).
Hardness measurements were performed at room temperature
on an HXD-1000 tester with a diamond indenter under a 300 N
load for 15 s. Fracture toughness tests were conducted at room
temperature using a PC-1036PC material tester at a testing rate of
0.5 mm/min.
3. Results and discussion
3.1. Phase formation
Fig. 1 presents the XRD patterns of the BCZT ceramics with
various BCW contents sintered at 1220
C for 4 h. The positions of
the diffraction peaks can be used to evaluate the structural order at
long range or the periodicity of the material. The BCZT phase is
confirmed by comparing the XRD patterns with the respective
JCPDS card No. 50-0346. All the diffraction peaks can be assigned to
 18 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
[(Fig._2)TD$IG]

Fig. 2. The density and SEM images of the BCZT ceramics sintered at various temperatures as a function of the BCW content.

the perovskite structure in the ceramics with x = 0.0–2.0 wt.%. In SEM images of the 0.80 wt.% BCW-modified specimen sintered at
addition, when x  3.0 wt.% BCW, the TiO2 phase begins to appear, 1220
C reveals that the bodies are fully densified with fairly
confirmed by JCPDS card No. 21-1276 [20]. To clearly analyze the uniform microstructures, as illustrated in Fig. 2(b).
phase structure of all the ceramics, the enlarged XRD patterns with Fig. 3 displays the water-solid contact angle of the surface of
2u ranging from 44
to 46
and from 64
to 67
are presented in untreated samples with various BCW contents as a function of
Fig. 1(b) and (c), respectively. The compositions with x  0.8 wt.% time. The methods for the measured densification of the ceramics
exhibit a rhombohedral (R) structure [21]. The (2 0 0) and (0 0 2) and the liquid-solid contact angle in water have been described.
diffraction peaks of the BCZT ceramics gradually emerge with The liquid–solid contact angle is used as an index for the
increasing BCW content (x  1.2 wt.%), where both (2 2 0) and wettability or hydrophobicity: density of the ceramics. The water
(2 0 2) diffraction peaks almost appear, confirming the involve- enters the ceramics readily, which indicates that water entry is not
ment of a phase transition. Therefore, the coexistence of tetragonal restrained by the lack of pores of the ceramics. A drop of water was
and rhombohedral phases occurs for the BCZT ceramics with rapidly applied and remained at the surface of the ceramics. The
x = 0.8 wt.% at room temperature, demonstrating that the ceramics contact angle was marked every 1 s. As illustrated in Fig. 3, by
lie at the morphotropic phase boundary (MPB) [22,23]. Because the increasing the time, the contact angle decreases gradually from
peaks shift to higher angles, it is assumed that (Ti, Zr)4+ is 86.8
to 0
, which spend 330 s for the ceramics with x = 0.00 wt.%,
substituted by Cu2+ and W6+, suggesting a change of the unit cell indicating that the drop of water has seeped into the ceramics
volume. This change may be due to the formation of complete solid through the pores. In other words, the intake time of a drop of
solutions between the BCW content and the BCZT ceramics, which water is 330 s for the ceramics with x = 0.00 wt.%. The intake time is
leads to a distortion of the crystal lattice. The addition of the BCW 708 s at x = 0.8 wt.%, and then decreases to 672 s at x = 1.6 wt.%. The
solid solution promotes the substitution of the Ba2+/Ca2+ and/or Zr4 reduced porosity of the ceramics delays the intake time, indicating
+
/Ti4+ B site of the perovskite structure more effectively than the that the ceramics with x = 0.8 wt.% is dense. In addition, the inset of
addition of raw metal oxides, and then increases structure defects Fig. 3 shows that the contact angle left (CA left) and contact angle
and decreases the barrier among domains. The formation of the right (CA right) for the compositions (x = 0.0 wt.% 0.8 wt.% and
BCW solid solution is beneficial to the diffusion of ions and 1.6 wt.%) are measured. With increasing BCW, CA left and CA right
reduction of the BCZT sintering temperature. increase gradually, reaching maximum values of CA left (92.2
) and
CA right (92.1
) at x = 0.8 wt.%, and then decreasing. The variation
3.2. Densification behavior contact angle in Fig. 3 is consistent with the relative density in
Fig. 2.
Fig. 2 presents the density and SEM images of the BCZT ceramics
sintered at different temperatures as a function of the BCW
content. Fig. 2(a) clearly demonstrates that higher densities of all
[(Fig._3)TD$IG]
the ceramics are obtained in the sintering temperature range from
1220
C to 1260
C, demonstrating that the addition of BCW
sintering aids to BCZT ceramics reduces the sintering temperature
by 200
C. The maximum value of 5.58 g/cm3 is obtained for the
0.80 wt.% BCW-modified BCZT ceramics sintered at 1220
C. By
adding BaCO3, CuO and WO3 with low melting points, the liquid
formation promotes the sintering of BCZT ceramics and results in
an increase in the density of the ceramics. However, with
increasing the BCW content, the density decreases. This finding
may be due to a larger amount of this liquid phase accumulating at
the grain boundaries, thus resulting in voids and inhibiting
densification. It is apparent that adding a small amount of BCW
causes the generation of oxygen vacancies is beneficial to the mass
transport in the ceramics during sintering, which is responsible for
the enhanced grain growth behavior, sinterability and bulk density
of the suitable BCW-doped specimens sintered at low temperature.
Therefore, the addition of BCW plays an important role in the
Fig. 3. The water-solid contact angle of the surface of untreated samples with
improvement of the density of BCZT-based ceramics. The surface different BCW contents as a function of time.
 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25 19

3.3. Temperature dependence of the dielectric behavior of the ceramics
Fig. 4 plots the temperature dependence of the dielectric
behavior for the BCZT ceramics with different BCW contents
measured at 0.1, 1, 10 and 100 kHz, respectively. The tetragonal-
cubic phase transition (TC) is observed in these ceramics, while the
coexistence of two phases cannot be clearly observed in the
temperature range involved except for the ceramics with x = 0.80,
1.2 and 1.6 wt.%. The coexistence of two phases near room
temperature is usually beneficial to the improvement in the

[(Fig._4)TD$IG]

Fig. 4. Temperature dependence of the dielectric behavior of the BCZT ceramics with varuous BCW contents measured at 0.1, 1, 10 and 100 kHz, respectively: (a) x = 0.0 wt.%,
(b) x = 0.4 wt.%, (c) x = 0.8 wt.%, (d) x = 1.2 wt.%, (e) x = 0.16 wt.%, (f) x = 2.0 wt.%, and (g) x = 3.0 wt.%.
20 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
[(Fig._5)TD$IG]
piezoelectric properties of the ceramics [22]. In addition, all the
ceramics possess a low dielectric loss in the present work, and the
peaks of the dielectric constant versus temperature become much
broader with increasing the BCW content.
The temperature dependence of the dielectric constant (a) and
em, tan d, Tc (b) for the BCW-doped BCZT ceramics is shown in Fig. 5.
As observed in Fig. 4(a), two obvious phase transitions corre-
sponding to the rhombohedral-tetragonal transition (Trt) at 38
C
and tetragonal-cubic transition (Tc) at 80
C are observed for the
samples with x = 0.0–1.6 wt.%. Trt and Tc shift to below room
temperature with increasing the BCW content, indicating its
tetragonal structure at room temperature, which is consistent with
the XRD results in Fig. 1. Usually, the Trt located below room
temperature is beneficial to the temperature stability of the BCZT-
based ceramics [3,5]. The results are in agreement with the results
in the literature [23]. It has been reported that a decrease in the
Curie temperature could be attributed to the valence mismatch
[16]. It is expected from the tolerance factors that small ions (r(R3
+
) < 0.87 Å) will occupy the B site, large ions (r(R3+) > 0.94 Å) will
occupy the A site, and intermediate ions will occupy both sites with
different portioning for each ion. Considering Ba2+ (r = 1.34 Å), Cu2+
(r = 0.72 Å) and W6+ (r = 0.62 Å), it is concluded that Cu2+ and W6+
occupy the B site, resulting in deformation in the ABO3 lattice and a
change of oxygen vacancies. However, when BCW content becomes
high, for example at 0.8 wt.%, the deformation cannot be ignored
and the structure of the ceramics becomes un-stable. Therefore,
with increasing the BCW content, the structure changes from the
tetragonal phase to the cubic phase at lower temperature, thus
Fig. 5. Temperature dependence of dielectric constant (a) and em, tan d,Tc (b) for the resulting in a decrease of Tc in this work. The Tc values of BCZT–
BCW-doped BCZT ceramics. xBCW ceramics with x = 0.0, 0.4, 0.8, 1.2, 1.6, 2.0 and 3.0 wt.% are 83,
81, 78, 70, 67, 60 and 44
C, respectively. Fig. 5(b) displays the
maximum dielectric constant (em), maximum dielectric constant

[(Fig._6)TD$IG]

Fig. 6. Plots of the inverse dielectric constant as a function of temperature at 10 kHz for the BCTZ–xBCW (x = 0.0–3.0 wt.%) ceramics.
 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25 21

Table 1
The Curie–Weiss temperature (To), the temperature above which the dielectric constant follows the Curie–Weiss law (Tcw), deviation (DTcm), and the Curie–Weiss constant (C)
for samples at 1 kHz and 100 kHz.

Samples (wt.%)

0.0 0.4 0.8 1.2 1.6 2.0 3.0

1 kHz 100 kHz 1 kHz 100 kHz 1 kHz 100 kHz 1 kHz 100 kHz 1 kHz 100 kHz 1 kHz 100 kHz 1 kHz 100 kHz
To (
C) 54 65 51 48 54 67 54 71 40 73 42 68 3 13
Tcw (
C) 95 98 90 92 98 92 87 90 83 79 71 81 60 69
DTcm (
C) 10 16 8 11 20 14 16 19 16 13 11 21 13 23
C(105) (
C) 4.52 4.62 4.98 4.59 9.59 3.53 8.83 2.61 5.36 2.29 3.76 1.89 4.96 3.57

(tan d) and Curie temperature (Tc) of specimens as a function of the increase of the relaxor behavior. The variation tendencies of the To,
BCW content. The maximum dielectric constant (13456 at Tcw, C and DTcm data of the specimen are similar between 1 kHz and
x = 0.00 wt.%) first decreases and then starts to increase at 100 kHz.
x = 0.4% in Fig. 4(b). em of the ceramics increases to 18197 at The deviation from the Curie–Weiss law can be defined by DTcm
x = 1.6 wt.% and then decreases with increasing BCW contents from as follows:
1.6 to 3.0 wt.%. Tan d exhibits a transverse “S” trend, and reaches a
minimum value of 0.0129 at x = 1.2 wt.%, which is consistent with DT cm ¼ T cw  T m ; (2)
the temperature dependence of the dielectric constant (er) in where Tcw denotes the temperature from which the dielectric
Fig. 5(a). As mentioned before, when (Cu0.5W0.5)4+ substitutes for constant starts to follow the Curie–Weiss law, and Tm represents
Zr4+ and Ti4+ at B sites, the lattice will be distorted less as the the temperature at which the dielectric constant reaches the
fraction of Ba2+ in the larger A sites decreases, making the phase maximum. As is shown in Fig. 6 and Table 1, Tcw gradually
transition at lower temperatures possible. Therefore, the formation decreases from 95
C to 60
C with increasing x from 0.00 to 3.0 wt.
of the coexistence of two phases near room temperature is %. DTcm is found to increase from 10
C to 20
C for x = 0.0, 0.40 and
beneficial to enrich the properties of BCZT-based ceramics. 0.80 wt.%, which is associated with the increased dielectric
It is of great interest to note that the dielectric peaks at Tc for all diffuseness and enhanced relaxor behavior when BCW is mixed
the ceramics are relatively broad, indicating the characteristic of into BCZT ceramics. After reaching the maximum of 20
C when
the diffuse phase transition from the tetragonal phase to the cubic x = 0.80 wt.%, DTcm gradually decreases to 13
C for the composi-
phase. It is well known that the dielectric constant of a normal tions with BCW ranging from 0.80 wt.% to 3.0 wt.%, respectively.
ferroelectric should follow the Curie–Weiss law when the
temperature exceeds the Curie temperature: [(Fig._8)TD$IG]
C
e¼ ðT > T m Þ; (1)
T  To
where C is the Curie–Weiss constant and To is the Curie–Weiss
temperature. The plot of the inverse dielectric constant versus
temperature at 1 kHz is presented in Fig. 6. It is observed that the
dielectric constant of BCZT ceramics slightly deviates from the
Curie–Weiss law with increasing BCW contents. To, Tcw, C and DTcm
obtained by the Curie–Weiss law for all specimens at 1 kHz and
100 kHz are listed in Table 1. To finally decreases from 54
C to
28
C with increasing x from 0.00 to 3.0 wt.%. By increasing x to
0.08 wt.%, C rapidly increases to 9.59  105
C, indicating an obvious
[(Fig._7)TD$IG]

Fig. 7. Ln[(em  e)/e] as a function of ln(T  Tm) for BCZT ceramics with different Fig. 8. (a) P–E loops, (b) Pr and Ec values as a function of BCW content of the BCZT
BCW contents at 1 kHz. ceramics sintered at 1220
C and measured at room temperature.
 22 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
This result indicates that the diffuse phase transition behavior has
been enhanced firstly and then reduced with the increase of the
BCW content.
The dielectric behavior of complex ferroelectrics with a diffuse
phase transition can be explained by the modified Curie–Weiss law
[24],
em ðT  T m Þg
¼1þ ; produce polar nano-regions. These polar nano-regions are isolated
e 2
ð2D Þ
where em is the maximum value of the dielectric constant at the
phase transition temperature Tm, and g (1 < g < 2) is the degree of
the diffuseness, which is a constant used to express the diffuseness
degree of the phase transition. When g = 1, the materials with this
type of phase transition belong to normal ferroelectrics; when
1 < g < 2, the materials are relaxor ferroelectrics; when g = 2, the
materials are ideal relaxor ferroelectrics. To eliminate space-
charge polarization contributions at high temperatures and lower
measurement frequency, herein, the 1 kHz data are selected. It is
found that the dielectric permittivity of the BCZT ceramics with
different BCW contents obviously deviate from the Curie–Weiss
law. Ln[(em  e)/e] as a function of Ln(T  Tm) for BCZT ceramics
with different BCW contents at 1 kHz is plotted in Fig. 7. It can be
observed that a linear relationship is obtained by linear fitting of
the experimental data. The diffuseness exponent g of all the
ceramics is between 1 and 2 for the ceramics with x < 2.0 wt.%,
which indicates that these compositions show intermediate
relaxor-like behavior between normal and ideal relaxor ferro-
electrics and the phase transition of all ceramics exhibits a diffuse
character. When x = 3.0 wt.%, the g value is 2.001, which is higher
than 2, indicating that these ceramics are not ferroelectrics, which
is consistent with the results of Fig. 6. The relaxor behavior in the
BCZT ceramics with different BCW contents should be attributed to
[(Fig._9)TD$IG]
Fig. 9. (a) d33, kp and (b) Qm, er, tan d of BCZT ceramics as a function of BCW content.
the cationic disorder induced by both A-site and B-site sub-
stitutions, such as (Cu0.5W0.5)4+ ions entering the six fold
coordinated B-site (Zr, Ti)4+, and Ba2+ ions entering the A-site of
the perovskite structure to substitute for (Ba, Ca)2+. Heterovalent
substitution induces quenched random electric fields because of
the local charge imbalance and the local elastic fields in BCZT-
derived systems. The fields hinder long-range ordering and
and frustrated in BCZT ceramics with different BCW contents, and
are then embedded in the disordered matrix, which has also been
demonstrated by Zheng and co workers [25–27]. The results are in
accordance with the previous XRD analysis.
3.4. Electrical properties of the ceramics
Fig. 8(a) illustrates the typical polarization levels versus applied
electrical field (P–E) hysteresis loops of BCW-modified BCZT
ceramics sintered at 1220
C and measured at room temperature.
Fig. 8(a) demonstrates that the P–E hysteresis loops become much
slimmer when BCW additives are mixed into the BCZT ceramics.
Fig. 8(b) depicts the remnant polarization (Pr) and coercive field
(Ec) of the ceramics as a function of the BCW content. According to
Fig. 8(b), with increasing the BWC content, Pr first decreases, then
increases and reaches the maximum value of 10.59 mC/cm2 when
x = 0.8 wt.% as increasing the BCW content, indicating that the
ceramics with x = 0.8 wt.% are the easiest to pole. Moreover, further
[(Fig._10)TD$IG]
Fig. 10. P–E loops and current of 0.80 wt.% doped-BCZT ceramics sintered at 1220
C
as a function of temperature.
 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25 23

increasing the BCW content beyond 0.8 wt.% causes sudden drops
in the Pr values, which can be attributed to BCW segregation at
boundaries which inhibits the movement of domain walls. In
addition, it can be observed that Ec of the ceramics markedly
decreases from 0.33 kV/cm to 0.13 kV/cm as increasing the BCW
content. The ceramics with x = 0.80 wt.% possess a large Pr
(10.59 mC/cm2) and a relatively large Ec (0.23 kV/cm). Because
BCW doping is expected to increase the defect concentration either
at the A- or B-site of the ABO3 lattice, a direct interaction of these
defects with the domain walls is expect [28,29]. Increasing the
BCW content affects the polarizability and reduces the Ec values
due to the doping effect and the decrement of the lattice
parameters. A lower Ec value is advantageous in the fabrication
of high-density and low-operation-voltage sensors and actuators
[30]. As observed in Fig. 8(b), the piezoelectric constant (d33),
electromechanical coupling factor (kp) and Pr change with the BWC
content increases, reaching the maximum values at the same time,
and then droping simultaneously. Therefore, we strongly confirm
that the enhanced d33 and kp are related to their ferroelectric
properties. Moreover, the dense microstructure is also partly
responsible for the enhanced piezoelectric properties observed in
this work [14].
Fig. 9(a) gives the piezoelectric properties (d33 and kp) of the
BCZT ceramics with different BCW contents. By increasing the BCW
content, the d33 and kp values of the ceramics initially increase, and
then begin to decrease at x = 3.0 wt.%. The peak values of
d33 = 544 pC/N and kp = 0.49 can be obtained from the BCZT-
0.8 wt.% BCW samples. In addition, Fig. 9(b) gives the mechanical
quality factor (Qm), dielectric constant (er) and dielectric constant
(tan d) of BCZT ceramics with different BCW contents. er of the
ceramics increases from 4248 to 8205 with increasing BCW
content. As increasing the BCW content, Qm and tan d value of the
ceramics initially decrease, and then begin to increase. Minimum
values of Qm = 59 at x = 1.6 wt.% and tan d = 0.014 at x = 0.8 wt.% are
obtained. The above discussions support the analysis of the phase
structure in Figs. 1, 4 and 5, confirming that Tr–t of the ceramics in
the MPB regions with x = 0.80 wt.% is closer to room temperature,
resulting in an enhancement of d33 and kp in the ceramics sintered
at 1220
C. Moreover, during sintering, the presence of the BCW
liquid phase enhances the density and reduces the sintering
temperature, which leads to a decrease of the energy loss and
improvement of the electrical properties. And the dense micro-
structure also contributes parameter to the enhancement in the
electrical properties of the BCZT–xBCW ceramics in Fig. 2. The
similar results were also obtained in the literature [31].
ceramics, as observed in Fig. 10(b). An applied electric field can lead
to a change in the surface charges of the sample. One contribution
is from the ferroelectric domain switching, which can be
represented by the sharp increase in the displacement currents.
Ec can be determined from the current peak position (maximum
current), which decreases with the measuring temperature, as
shown in the inset of Fig. 10(b).
Fig. 11 illustrates the bipolar electric-field-induced strain of the
0.8 wt.% doped-BCZT ceramics as a function of the measuring
temperature. As observed in Fig. 11(a), the ceramics all exhibit the
typical butterfly-shaped curve of ferroelectrics. The hysteresis,
which is caused by the domain switching and phase transition
induced by the electric field is very large. From Fig. 11(a), the
bipolar maximum strain of the ceramics is 0.82%, which is obtained
at T = 30
C, and then significantly decreases from 0.82% to 0.71%
with the increasing of the temperature. Generally speaking, a large
electric-field-induced strain means a large piezoelectric response.
The results for the electric-field-induced strain are consistent with
the d33 values measured using the quasistatic method. Moreover,
the largest d33 (544 pC/N) value is also obtained at T = 30
C. With
increasing the temperature from 40
C to 90
C, strain values of the
ceramics initially increase, and then begin to decrease at T = 50
C.
The peak values of the stain (0.79%) are obtained at 50
C for the
0.80 wt.% doped composition near the rhombohedral side of the
MPB boundary. Because the structural activities for the compo-
sitions in the biphase coexistent regions are high, the phase
transition from the rhombohedral ferroelectric phase to the
tetragonal phase, accompanied by the mobility and polarization
of ions, can occur easily. This structural transition is very beneficial
in enhancing the strain properties. It can also be seen in Fig. 11(b)
that d33 decreases from 544 pC/N to 67 pC/N for the ceramics with
increasing the measuring temperature from 30
C to 90
C. The
lattice distortion and domain switching induced by electric field
contribute to the measured strain. Meanwhile, only lattice
[(Fig._1)TD$IG]

3.5. Temperature stabilities of the electrical properties of the ceramics

To obtain further details on the ferroelectric properties and

depolarization mechanism of the ceramics, P–E hysteresis loops
and the current of 0.80 wt.% doped-BCZT ceramics at different
temperatures were measured under an electric field of 3.2 kV/mm,
as shown in Fig. 10. All the ceramics exhibit a typical ferroelectric
P–E loop at room temperature, which is much slimmer between
30
C and 90
C. It can be seen from Fig. 10(a) that the P–E hysteresis
loops are more predominant at lower temperatures, and higher
temperatures lead to constriction in the loops. According to the
inset of Fig. 10(a), as the measured temperature increases from
30
C to 90
C, the ceramics present remnant polarization (Pr)
values of 9.81, 8.80, 8.09, 7.81, 3.51 1.45 and 0.92 mC/cm2 as well as
Ec values of 2.68, 2.19, 2.01, 1.81, 1.03, 0.85 and 0.63 kV/cm,
respectively. Ec of the ceramics decreases with the measured
temperature from 30
C to 90
C; thus, poling is facile due to the
low Ec. As the applied electric field is ramped to approximately
0.65–2.4 kV/cm, the currents exhibit a sharp increase, demon- Fig. 11. The strain and piezoelectric properties of 0.80 wt.% doped-BCZT ceramics
strating the occurrence of polarization switching in the BCZT sintered at 1220
C as a function of temperature.
24 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
distortion contributes to the d33 value measured by the quasistatic
method. Ec of the ceramics in Figs. 8 and 10 decreases with
increasing the measuring temperature; therefore, the domain
switches more easily. The joint action of lattice distortion and
domain switching results in the largest strain being obtained in the
0.80 wt.% doped-BCZT ceramics induced by the measuring
temperature.
It has been well known that the morphotropic phase boundary
(MPB) plays an important role in the improvement of piezoelectric
properties in PZT based piezoelectric ceramics [32]. The piezo-
electric properties of the ceramics near the MPB region reach
maximum values. As we know, the MPB of a specific material
depends only on its composition, while the polymorphic phase
boundary (PPB) is dependent not only on its composition but also
on the temperature. In this work, the R–T phase transition makes
the dielectric property peak at the corresponding temperature, as
shown in Figs. 4 and 5. This finding is in good agreement with the
PZT-based single crystals with rhombohedral-tetragonal MPB
reported by Zhang and co workers [33,34]. Because the R–T phase
boundary of PMN-PT, PMN-PZT, and PIN-PMN-PT single crystals is
well known to be an MPB, rather than a PPB, similar to KNN-based
piezoelectric ceramics, the BCZT ceramics studied in this work may
also exhibit a morphotropic character. However, it has been
reported that the piezoelectric properties of the BCZT-based
ceramics exhibit a strong temperature dependence [35]. Therefore,
compared with pure BCZT ceramics, the ceramics with x = 0.8 wt.%
BCW shift the rhombohedral-tetragonal phase transition to near
room temperature (40–50
C), and may possess more possible
polarization states, which results in the improvement of the
piezoelectric and dielectric properties at room temperature.
However, inappropriate distortion is also introduced by replacing
W6+ with Cu2+, which leads to the deterioration of the piezoelectric
properties. Furthermore, the real nature of the phase boundary in
the BCZT ceramics requires systematic investigations in the future.
3.6. The mechanical properties of the ceramics
The hardness and fracture toughness of the ceramics sintered at
1220
C for 4 h as a function of the BCW content are plotted in Fig.12.
It is apparent from Fig.12 that the hardness increases with increasing
the BCW contents, and falls to half of the free pore ones when BCW is
0.80 wt.%. Therefore, a reduction of the bending strength occurs with
increasing the BCW content from x = 0.00 wt.% to x = 0.80 wt.%. Both
the hardness and fracture toughness peaked at 78 MPa and
4.7 MPa m1/2, respectively, when the BCW concentration was
0.80 wt.%. In addition, with increasing the BCW content, a fine-
[(Fig._12)TD$IG]
Fig. 12. Hardness and fracture toughness of BCZT ceramics with different BCW
contents.
grained and relatively uniform microstructure is obtained at
x = 0.80 wt.%, which is very beneficial for practical applications as
it is known that a fine-grained and homogenous microstructure can
lead to an increase in the density and mechanical strength for
piezoelectric ceramics, as observed in Fig. 2(b).
4. Conclusions
BCZT lead-free piezoelectric ceramics with various BCW contents
were prepared using the conventional solid state sintering method.
The phase structure, microstructure, dielectric properties and
ferroelectric properties of the BCZT ceramics as a function of the
BCW content were investigated in this study. The results demon-
strated that the addition of BCW content not only decreased the
sintering temperature but also retained the optimum electrical
properties. The sintering temperature of BCZTcan be decreased from
1450 to 1220
C with the addition of BCW. The coexistence of
tetragonal and rhombohedral phases (MPB) was identified for the
BCZT ceramics at x = 0.8–1.6 wt.%, as confirmed by the XRD patterns
and the temperature dependence of the dielectric behavior. The
degree of relaxor behavior increased with increasing the BCW
content. Due to the existence of MPB and the relaxor behavior, the
optimum electrical properties of d33 = 541 pC/N, kp = 49%, Qm = 107,
er = 5405, tan d = 0.014 and Tc = 78
C were obtained in 0.8 wt.% BCW-
doped BCZT ceramics. The introduction of the diffusion mechanism
into BCZT ceramics improved the temperature stability of the
piezoelectric properties, which was useful in other material
systems. In addition, the hardness (78 MPa) and fracture toughness
(4.7 MPa m1/2) of the ceramics were obtained because of the
improved density by BCW additives. These results indicated that
appropriate BCW additives can significantly improve the electrical
and mechanical properties of BCZT ceramics. The present study
demonstrated that (Ba0.85Ca0.15Ti0.90Zr0.10)O3–0.8 wt.% Ba
(Cu0.5W0.5)O3 ceramics with a lower sintering temperature were
promising candidates for lead-free piezoelectric applications.
Acknowledgements
This work was supported by National Science Foundation of
China (NSFC) (Grant Nos. 51107077 and 51172136), the Fundamen-
tal Research Funds for the Central Universities (Program Nos.
GK201305013, GK201301002, GK201102003, GK201101004 and
GK201403006), Science and Technology Program of Shaanxi
Province and Xi'an City (Grant Nos. 2013K09-26 and CXY1342
(4)), Fundamental Research Funds of Experimental Technology for
Shaanxi Normal University (Program No. SYJS201219).
References
[1] D. Damjanovic, A. Biancoli, L. Batooli, A. Vahabzadeh, J. Trodahl, Appl. Phys.
Lett. 100 (19) (2012) 192907.
[2] J.G. Wu, D.Q. Xiao, W.J. Wu, Q. Chen, J.G. Zhu, Z.C. Yang, J. Wang, Scripta Mater.
65 (2011) 771–774.
[3] J.H. Gao, D.Z. Xue, Y. Wang, D. Wang, L.X. Zhang, H.J. Wu, S.W. Guo, H.X. Bao, C.
Zhou, W.F. Liu, S. Hou, G. Xiao, X.B. Ren, Appl. Phys. Lett. 99 (2011) 092901.
[4] K. Chung, D. Lee, J. Yoo, Y. Jeong, H. Lee, H. Kang, Sens. Actuators A: Phys. 121
(2005) 142–147.
[5] Y. Tian, L.L. Wei, X.L. Chao, Z.H. Liu, Z.P. Yang, J. Am. Ceram. Soc. 96 (2) (2013)
496–502.
[6] J.G. Wu, D.Q. Xiao, W.J. Wu, Q. Chen, J.G. Zhu, Z.C. Yang, J. Wang, J. Eur. Ceram.
Soc. 32 (2012) 891–898.
[7] M.C. Ehmke, F.H. Schader, K.G. Webber, J. Rodel, J.E. Blendell, K.J. Bowman, Acta
Mater. 78 (2014) 37–45.
[8] C.Y. Chang, H.I. Ho, T.Y. Hsieh, C.Y. Huang, Y.C. Wu, Ceram. Int. 39 (2013)
8245–8251.
[9] J.G. Wu, A. Habibul, X.J. Cheng, X.P. Wang, B.Y. Zhang, Mater. Res. Bull. 48 (2013)
4411–4414.
[10] J.P. Praveen, K. Kumar, A.R. James, T. Karthik, S. Asthana, D. Das, Curr. Appl.
Phys. 14 (2014) 396–402.
 X. Chao et al. / Materials Research Bulletin 66 (2015) 16–25
[11] I.Y. Kang, I.T. Seo, Y.J. Cha, J.H. Choi, S. Nahm, T.H. Sung, J.H. Paik, J. Eur. Ceram.
Soc. 32 (2012) 2381–2387.
[12] H.I. Hsiang, C.S. Hsi, C.C. Huang, S.L. Fu, Mater. Chem. Phys. 113 (2009) 658–663.
[13] X.L. Chao, D.F. Ma, R. Gu, Z.P. Yang, L.R. Xiong, J. Alloys Compd. 49 (2010)
1698–1702.
[14] T. Chen, T. Zhang, C. Wang, J.F. Zhou, J.W. Zhang, Y.H. Liu, J. Mater. Sci. 47 (2012)
4612–4619.
[15] Y.R. Cui, X.Y. Liu, M.H. Jiang, Y.B. Hu, Q.S. Su, H. Wang, J. Mater. Sci. 23 (2012)
1342–1345.
[16] X.L. Chao, Z.P. Yang, L.R. Xiong, Z. Li, J. Alloys Compd. 509 (2011) 512–517.
[17] A.A. Kaminskii, M. Akchurin, R.V. Gainutdinov, K. Takaichi, Crystallogr. Rep. 50
(2005) 869–873.
[18] X.R. Hou, S.M. Zhou, T.T. Jia, H. Lin, H. Teng, J. Eur. Ceram. Soc. 31 (2011) 733–
738.
[19] B. Yu, K.M. Liang, S.R. Gu, Ceram. Int. 29 (2003) 695–698.
[20] T.K. Lea, D. Flahaut, H. Martinez, T. Pigot, H.K.H. Nguyen, T.K.X. Huynh, Appl.
Catal. B: Environ. 144 (2014) 1–11.
[21] A.A. Bokov, Z.G. Ye, J. Mater. Sci. 41 (1) (2006) 31–52.
[22] Q. Gou, J.G. Wu, A.Q. Li, B. Wu, D.Q. Xiao, J.G. Zhu, J. Alloys Compd. 521 (2012)
4–7.
25
[23] Y. Tsur, T.D. Dunbar, C.A. Randall, J. Electroceram. 7 (2001) 25–28.
[24] W.F. Liu, X.B. Ren, Phys. Rev. Lett. 103 (25) (2009) 257602.
[25] M.P. Zheng, Y.D. Hou, F.Y. Xie, J. Chen, M.K. Zhu, H. Yan, Acta Mater. 61 (2013)
1489–1498.
[26] H.Q. Fan, W.Q. Jie, C.S. Tian, L.T. Zhang, H.E. Kim, Ferroelectrics 269 (2002)
33–38.
[27] H.L. Du, W.C. Zhou, F. Luo, D.M. Zhu, S.B. Qu, Y. Li, Z.B. Pei, J. Appl. Phys. 104
(2008) 034104.
[28] R.S. Nasar, M. Cerqueira, E. Longo, J.A. Varela, A. Beltran, J. Eur. Ceram. Soc. 22
(2002) 209–218.
[29] R. Eitel, C.A. Randall, Phys. Rev. B 75 (2007) 094106.
[30] S. Zhang, R.E. Eitel, C.A. Randall, T.R. Shrout, E.F. Alberta, Appl. Phys. Lett. 86
(2005) 262904.
[31] W.H. Li, X.Y. Liu, J.F. Ma, Y. Wu, Y.R. Cui, J. Mater. Sci.: Mater. Electron. 24 (5)
(2013) 1551–1555.
[32] D. Damjanovic, J. Am. Ceram. Soc. 88 (2005) 2663.
[33] S. Zhang, S.M. Lee, D.H. Kim, H.Y. Lee, T.R. Shrout, Appl. Phys. 90 (2007) 232911.
[34] X.Z. Liu, S.J. Zhang, J. Luo, T.R. Shrout, W. Cao, J. Appl. Phys. 106 (2009) 074112.
[35] X.J. Cheng, J.G. Wu, X.P. Wang, B.Y. Zhang, J.G. Zhu, D.Q. Xiao, X.J. Wang, X.J. Lou,
Appl. Phys. Lett. 103 (2013) 052906.