Materials Letters 137 (2014) 128–131

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Enhanced relaxor ferroelectric behavior of BCZT lead-free ceramics

prepared by hydrothermal method
Yuwen Liu, Yongping Pu n, Zixiong Sun
School of Materials Science and Engineering, Shaanxi University of Science & Technology, Xi'an 710021, People's Republic of China

art ic l e i nf o a b s t r a c t

Article history: Ceramics in the solid solution system, Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ , were prepared via a hydrothermal
Received 24 July 2014 method and were assisted by microwave sintering, and the effects of Nd3 þ -doping on the electrical
Accepted 25 August 2014 properties of Ba0.9Ca0.1Ti0.9Zr0.1O3 were studied. All the samples showed single perovskite structure
Available online 3 September 2014
without a second phase, and a change from the rhombohedral phase to the coexistence of tetragonal and
Keywords: cubic phase occurred at x Z 0.025. The dielectric constant and dielectric loss both decreased with
Electroceramics increasing Nd3 þ content at 0.000 rx r 0.015 and the sample with x ¼0.020 showed giant permittivity
Ferroelectrics with higher dielectric loss. At x ¼ 0.025 and 0.030, the TC significantly decreased and the samples
Semiconductors exhibited optimistic relaxor behavior with excellent frequency dispersion. The Pr decreased with
increasing Nd3 þ content and the samples with x ¼0.025 and 0.030 showed P–E loops with lower
polarization loss. The piezoelectric constant (d33) measured at room temperature increased with
increasing Nd3 þ addition and exhibited the maximum value at x ¼0.025. The ferroelectric and piezo-
electric properties could not be detected at samples with x ¼ 0.020.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

Due to the excellent properties such as high d33 and kp, lead
zirconate titanates (PZT) began to be commercially used as piezo-
electric materials in many fields for over half a century. However,
considerable attention has been recently given to the development
of lead-free piezoceramics due to their environmental issues. For a
long period of time, the BaxCa1  xTiyZr1yO3 system as the leading
candidates, have attracted considerable attention and been con-
sidered as promising lead-free piezoelectric ceramics. Some donor
ions such as La3 þ have been frequently used to substitute the
piezoelectrics to increase the d33 or decrease the dielectric loss [1–
5]. However, there is little work on donor doping in the A-site such
as Nd3 þ of BCTZ ceramics and the most of BCTZ system ceramics
were synthesized by a conventional solid-state method. In this
case the hydrothermal method was used in this study to let the
Nd3 þ enter the lattice in ion form, which show advantages of
homogeneous grain size compared to other methods. It is well
known that the powders prepared by the soft chemical method
exhibited high nucleation activation energy; thus, the fast micro-
wave was applied in the sintering process [6,7].
n
Corresponding author. Tel.: þ 86 29 86168133; fax: þ 86 29 86168137.
Ba0.9Ca0.1Ti0.9Zr0.1O3 ceramics with Nd3 þ doping were pre-
pared by a hydrothermal method; the BaCl2  2H2O (SCRC),
CaCl2, TiCl4, ZrOCl2  8H2O and Nd(NO3)3 were used as raw materi-
als. BaCl2  2H2O, CaCl2, ZrOCl2  8H2O and Nd(NO3)3 were first
dissolved in distilled water separately and then were mixed.
The TiCl4 was added into the mixtures dropwise to obtain
the precursors. Finally the NaOH was added to regulate the
pH 414. The three precursors were put into the heating-auto-
clave; then, the distilled water was added until the total volume
reached  80% of the autoclave. The hydrothermal reactions were
carried out at 180 1C for 10 h and finally the three powders were
mixed and dried. After that, the powder was pressed into pellets of
12 mm diameter and the pellets were sintered at 1280 1C for
10 min under microwaves. The crystal structure was examined
by using an X-ray diffraction system (D/max 2200 pc, Rigaku,
Tokyo, Japan) with Cu Kα radiation. Dielectric and ferroelectric
measurements were measured by an Agilent 4980A impedance
analyzer and a ferroelectric analyzer (Premier II, Radiant, USA).
The ceramics were poled under a DC field of 4.5 kV/mm in a silicon
oil bath for 10 min at different temperatures and the d33 of the
poled ceramics was measured using a quasi-static meter d33 meter
(ZJ-4AN, China).

http://dx.doi.org/10.1016/j.matlet.2014.08.138
0167-577X/& 2014 Elsevier B.V. All rights reserved.
 Y. Liu et al. / Materials Letters 137 (2014) 128–131
(002)/(200)
(110)
(111)
30 40
Fig. 1. X-ray patterns of the Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ ceramics.
3. Results and discussion
Fig. 1 illustrates the X-ray diffraction patterns of Ba0.9Ca0.1
Ti0.9Zr0.1O3–xNd3 þ ceramics with different x, and all samples
possess pure perovskite structure without second phases. The
shifting of (200)/(002) peak towards higher degree of 2θ is due to
the decreasing of d caused by the Nd3 þ occupying the A-site for the
ion radius of Nd3 þ is similar to that of Ba2 þ and Ca2 þ , seen from
the smaller range of 44.3–46.11. Samples with 0.000rxr0.020
show single orthorhombic structure, which is characterized by the
broadening of the (200)/(002) peak and the coexistence of tetra-
gonal and cubic phase is detected at x¼0.025 and 0.030 [2,3].
Fig. 2 shows the temperature dependence of dielectric constant
and dielectric loss (a)–(g) and the relationship between x and
resistivity (h) of Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ ceramics, and it can
be also noted that all the ceramics have a broadened transition
peak.The Nd3 þ free sample shows a single TC peak while samples
of 0.005 rx r0.015 display two obvious polymorphic phase tran-
sitions corresponding to the orthorhombic to tetragonal (TO–T) and
tetragonal to cubic phase (TC) [4]. As the doping level of Nd3 þ
increases from 0.000 to 0.015, both the dielectric constant and the
dielectric loss decrease, suggesting that Nd ions enter the matrix of
the ceramics during the sintering process. Some novel phenom-
enon can be detected with further increasing x: x ¼0.020 sample
exhibits giant permittivity nearly 200,000, and judging from the
significant disparity of permittivities between different frequen-
cies, it can be assumed that the giant dielectric behavior results
from some relaxation polarizations with the addition of Nd3 þ . As
our earlier research proved [5], the defect chemical reactions of
Bi3 þ (donor doping) for A-site ions at higher x are represented as
2þ 2þ
3 þ Ba 3 þ Ca
⟹ NdBa þ e'; ⟹ NdCa þ e'
d d
Nd Nd
Relaxation polarizations such as dipole polarization and space
charge polarization caused by the emergence of e' cannot keep
pace with the electrical field of higher frequency, only making
contribution in the significant permittivity increase of samples at
f ¼1 kHz and f¼ 10 kHz. And in this case, the Ba0.9Ca0.1Ti0.9Zr0.1O3–
0.020Nd3 þ sample shows high dielectric loss due to the relaxation
polarizations which can be observed in Fig. 2(e) [6,7].
When the Nd3 þ addition is increased to 0.025 and 0.030, samples
exhibit much lower TC and excellent dielectric relaxation behavior
with optimistic frequency dispersion and diffused phase transition,
which can be used as relaxor ferroelectrics. The relaxation parameter
γ is calculated to be 1.63 and 1.71 respectively and is shown in the
inset of Fig. 2(f) and (g). That is probably due to the more
129
(220)/(202)
(211)
(210)
x=0.030
x=0.025
x=0.020
x=0.015
x=0.010
x=0.005
x=0.000
50 60 70 45 46
homogeneous grain size caused by higher concentration doping of
Nd3 þ in Ba0.9Ca0.1Ti0.9Zr0.1O3 ceramics. Fig. 2(h) indicates that the
resistivity of Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ exhibits the minimal value
at x¼0.020, for the new emerged e0 serving as carriers in ceramics.
The P–E loops (a) and the variations of the d33 (b) with different
x for the Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ ceramics are shown in Fig. 3.
Samples of 0.000 rx r0.015 exhibit typical P–E loops while the
ferroelectric properties cannot be detected at the x ¼0.020 sample
for the much lower resistivity, which is easily broken down under
a high voltage. When the Nd3 þ addition is increased to 0.025, the
ferroelectric properties are observed again in the ceramics and
x¼ 0.025 and 0.030 samples exhibit lower polarization loss, which
is characterized by the narrow P–E loops. Judging from the inset of
Fig. 3(a), both Pr and Ps decrease with increasing Nd3 þ content.
The piezoelectric constants (d33) measured at room temperature
increase with 0.000 rx r0.015 because of the enhancement of
MPB caused by the shifting of TO–T towards lower temperature,
and cannot be detected at x ¼0.020 for the same reason as the
ferroelectric properties. The samples of x ¼0.020 and 0.030 also
possess higher d33 because of the coexistence of tetragonal and
cubic phase [8,9].
4. Conclusions
Ba0.9Ca0.1Ti0.9Zr0.1O3 ceramics with different Nd3 þ addition (x)
were prepared via the hydrothermal process and were assisted by
microwave sintering, and the effects of Nd3 þ on the phase
transition and electrical properties of these ceramics were studied.
With Nd3 þ addition, a change from the rhombohedral phase to
the coexistence of tetragonal and cubic phases occurred at
xZ 0.025. Both dielectric constant and dielectric loss decreased
with increasing Nd3 þ content at 0.000 rx r0.015 while x¼ 0.020
sample shows giant permittivity, and samples of the x ¼0.020 and
0.030 are excellent relaxor ferroelectrics. d33 and Pr exhibit
opposite tendencies with the increase of x, and the ferroelectric
and piezoelectric properties cannot be detected at the x¼ 0.020
sample because of the much lower resistivity.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (51372144), the New Century Excellent
Talents Program of Chinese Education Ministry (NCET-11-1042),
the Key Program of Innovative Research Team of Shaanxi Province
130 Y. Liu et al. / Materials Letters 137 (2014) 128–131

Fig. 2. Temperature dependence of dielectric constant and dielectric loss (a)–(g) and the relationship between x and resistivity (h) for the Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ
ceramics: (a) x¼ 0.000; (b) x ¼0.005; (c) x ¼0.010; (d) x¼ 0.015; (e) x¼ 0.020; (f) x¼ 0.025; (g) x ¼0.030; and (h) relationship between x and resistivity.
 Y. Liu et al. / Materials Letters 137 (2014) 128–131 131

Fig. 3. The P–E loops and the variations of d33 with x for the Ba0.9Ca0.1Ti0.9Zr0.1O3–xNd3 þ ceramics with different x: (a) P–E loops and (b) d33–x curves.

(2014KCT-06) and the International Science and Technology Coop-
eration Project Funding of Shaanxi Province (2012KW-06).
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