Current Applied Physics 12 (2012) 748e751

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Current Applied Physics

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Structural and dielectric properties in the (Ba1
xCax)(Ti0.95Zr0.05)O3 ceramics

Wei Li*, Zhijun Xu, Ruiqing Chu, Peng Fu, Guozhong Zang
College of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, China

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

Article history: Lead-free (Ba1
xCax)(Ti0.95Zr0.05)O3 (x ¼ 0.05e0.40) (BCZT) ceramics were prepared by solid-state reac-
Received 21 July 2011 tion technique. XRD results show that the samples in the composition range of 0.05  x  0.25 exhibit
Received in revised form pure perovskite structures and undergo a polymorphic phase transitions from orthorhombic to tetrag-
30 October 2011
onal phase around room temperature. The biphasic structures are detected at x  0.30 and the dielectric
Accepted 31 October 2011
peaks become broad and dielectric constants decrease with increasing Ca content. Ca replacement at Ba
Available online 9 November 2011
site leads to diffuseness, whereas Ca occupancy at Ti site leads to decrease of the Tc.
Ó 2011 Elsevier B.V. All rights reserved.
Keywords:
Lead-free ceramics
Dielectric properties
Structure
Titanates

1. Introduction
Ferroelectric materials of perovskite-class with formula ABO3
have received considerable attention in electromechanical, elec-
tronic and microwave applications due to the outstanding perfor-
mances of piezoelectric, pyroelectric, electro-optic, and dielectric
properties [1e3]. With the recent growing demand of global
environmental protection, the restriction of the use of certain
hazardous substances in electrical and electronic equipment
(RoHS) directive bans the placing on the EU market of new elec-
trical and electronic equipment containing more than agreed levels
of lead in 1 July 2006. Many researchers have greatly focused on
lead-free ceramics to replace the lead-based ceramics [1e5].
Barium titanate (BaTiO3) is one of the most widely studied lead-free
piezoelectric materials. As the temperature declines, it undergoes
a paraelectric-ferroelectric phase transition from a cubic to
a tetragonal structure at 130  C and two more ferroelectric poly-
morphic transitions: tetragonal to orthorhombic at 0  C and
orthorhombic to rhombohedral at
90  C, respectively [6,7].
ABO3 perovskite has different A-site and B-site dopants (where
A ¼ Ca, Sr, La; B ¼ Nb, Ta, Zr, Sn, Mn) to modify the electrical prop-
erties [8e12]. These kinds of solid solution have been, and continue
to be, of interest for investigation, not only because of their various
applications, but also for their interesting dielectric and ferroelectric
behaviors. In particular, compositionally modified BaZrxTi1
xO3
* Corresponding author. Tel./fax: þ86 6358230923.
E-mail address: liwei_727@yahoo.cn (W. Li).
(BZT) received much attention due to the tunable structure and
electrical properties to specific applications [13]. The polymorphic
phase transition (PPT) temperatures (rhombohedral e ortho-
rhombic T1, orthorhombic e tetragonal T2 and tetragonal e cubic Tc)
move closer with increasing Zr content in the BaZrxTi1exO3 ceramics
and merge near room temperature at the composition of x ¼ 0.15.
Further increase of the Zr content, especially for x > 0.25, the
samples show broad dielectric peaks with frequency dispersion, i.e.,
ferroelectricerelaxor behavior [14,15].
Modified barium titanate compositions are widely used in
multilayer ceramic capacitor (MLCC) due to their high dielectric
constant and low loss. BaTiO3eCaZrO3 ceramics have been used for
Y5V-type MLCC exhibiting a large magnitude of dielectric constant
(εr) of 15,000 [16,17]. Wang et al. [18] reported that high electro-
strictive strain of 0.22% was obtained near the solubility limit in the
side of composite (x ¼ 0.23) in the Ba(1ex)CaxTiO3 ceramics. Pur-
wanto et al. [19] reported that the optical properties were evaluated
by doping of Ba(1ex)CaxTiO3 nanoparticles with Pr3þ ions. The
structural and dielectric properties of the ternary system BaTiO3
(BT)eCaTiO3 (CT)eSrTiO3 (ST) were systematically studied by
Zhang et al. [1,20,21]. On the other hand, Zhang et al. [17] reported
the (Ba0.95Ca0.05)(Ti0.88Zr0.12)O3 ceramics sintered in N2 attained
a piezoelectric coefficient d33 ¼ 200 pC/N and higher dielectric
constants ε r of 1900. Zheng et al. [22] reported the CuO-modified
Ba(Ti0.9625Zr0.0375)O3 ceramics possessed good piezoelectric
performance of d33 ¼ 300 pC/N and weak temperature dependence
between
25 and 55  C. Ren et al. [23] reported that the
Ba(Ti0.8Zr0.2)O3e(Ba0.7Ca0.3)TiO3 showed a surprisingly high
piezoelectric coefficient of d33 ¼ 620 pC/N, which even exceeded

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.10.013
 W. Li et al. / Current Applied Physics 12 (2012) 748e751 749

state reaction technique, respectively. Raw materials of BaCO3

110

(99.0%), CaCO3 (99.0%), ZrO2 (99.0%) and TiO2 (99.5%) were ball

002
200
* CaTiO3

002
200

211
111 milled with addition of alcohol, which were then dried and calcined

202
at 1200  C for 4 h. Thereafter, calcined powders were remixed and

210
* x=0.40
* *
pressed into 12 mm-diameter pellets and sintered at 1450  C for 4 h
x=0.35 in air. Sample structure and phase development were examined by
Intensity(a.u.)

using an X-ray diffraction meter with a Cu Ka radiation

x=0.30 (l ¼ 1.54178Å) (D8 Advance, Bruker Inc., Germany). Microstructures
of powders and ceramics were characterized by using a scanning
x=0.25
electron microscope (JSM-5900, Japan). Dielectric properties were
x=0.20 measured by using the precision impedance analyzer (4294A Agi-
x=0.15 lent Inc., USA) controlled by a computer at 100 kHz with the testing
x=0.10 temperature ranged from room temperature to 150  C.
x=0.05

30 40 50 60 70 44 45 46 47
3. Results and discussion
2 Theta /(Degrees)

Fig. 1. X-ray diffraction patterns of the (Ba1
xCax)(Ti0.95Zr0.05)O3 ceramics at x ¼ 0.05,
0.10, 0.15, 0.20, 0.25, 0.30, 0.35 and 0.40.
that of many soft PZTs. This system may provide a new recipe for
designing excellent piezoelectric and dielectric materials. In
previous we reported the piezoelectric properties of (Ba1
xCax)
(Ti0.95Zr0.05)O3 (x ¼ 0.02e0.20) ceramics [24]. In this work we focus
on the structure and dielectric properties of the lead-free (Ba1
x-
Cax)(Ti0.95Zr0.05)O3 ceramics with the x range from 0.05 to 0.40.
2. Experiment
The (Ba1
xCax)(Ti0.98Zr0.02)O3 ceramics at x ¼ 0.05, 0.10, 0.15,
0.20, 0.25, 0.30, 0.35 and 0.40 were prepared by conventional solid-
Fig. 1 shows the XRD patterns of the (Ba1
xCax)(Ti0.95Zr0.05)O3
ceramics with different compositions. It can be seen that the
samples (x < 0.30) show pure perovskite structure, suggesting that
Ca and Zr diffuse into the BaTiO3 lattice to form a homogeneous
solid solution. With increasing x, diffraction peaks of the BCZT
ceramics shift to a larger 2q, showing that the lattice parameters
decrease with Ca addition. Because the ionic radius of Ca2þ (1.34 Å)
is smaller than that of Ba2þ (1.61 Å) [1], Ca2þ substitution could lead
to the shrinkage of crystals and the decrease of lattice parameters.
The maximum solubility of [Ca2þ/Ba2þ] in the CaTiO3eBaTiO3
system is 23% [1,19], whereas Ca2þ concentration is near 30% in this
BCZT system. Evolution of the secondary phase, which marked “*”
in Fig. 1, can be observed for the samples at x  0.3. The secondary
phase represents orthorhombic CaTiO3 (CT) (PDF card#:82e0229)
and its peak intensity increases with increasing Ca content. It can be

Fig. 2. SEM micrographs of the (Ba1
xCax)(Ti0.95Zr0.05)O3 ceramics: (a) x ¼ 0.10, (b) x ¼ 0.20, (c) x ¼ 0.30, (d) x ¼ 0.40.
750 W. Li et al. / Current Applied Physics 12 (2012) 748e751

Fig. 2 shows SEM micrographs of the BCZT ceramics at x ¼ 0.10,

12000 x ¼ 0.20, x ¼ 0.30 and x ¼ 0.40, respectively. It is clearly shown
x=0.05
x=0.10 that the Ca modified BCZT ceramics exhibit coarse grain size. The
10000 x=0.15 BCZT ceramic at x ¼ 0.10 possesses bimodal grain microstructure
x=0.20 and the grain size is in the range of 4e10 mm. At x ¼ 0.20, the size
x=0.25 distribution becomes uniform, yielding a homogeneous and dense
Dielectric constant

8000
x=0.30 microstructure However, further increase of Ca content (x ¼ 0.30
x=0.35 and x ¼ 0.40) makes the microstructure inhomogeneous and the
6000 x=0.40 grain boundary blurry. This result indicates that improved
microstructure of the BCZT ceramics could be performed at
x ¼ 0.20. It should be attributed to a solid solution of the BCZT
4000
ceramics with x up to 0.30 and a diphasic strain of the BCZT
ceramics at x  0.30.
2000 Dielectric constants of the BCZT ceramics as a function of
temperature at 100 kHz are shown in Fig. 3. As can be seen, two
0
obvious phase transitions corresponding to the ortho-
20 40 60 80 100 120 140 rhombicetetragonal at 40  C and tetragonalecubic at 110  C,
Temperature( C)
o respectively, are observed for the samples at x ¼ 0.05. As Ca content
increases up to 0.20, the orthorhombicetetragonal transition shifts
Fig. 3. Temperature dependence of dielectric constant for the (Ba1exCax)(Ti0.95Zr0.05)O3 towards lower temperature and cannot be observed above room
ceramics at x ¼ 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35 and 0.40 measured at 100 kHz. temperature. This result indicates that at room temperature the
structure of BCZT ceramics changes gradually from orthorhombic to
tetragonal symmetry with increasing Ca content, which agrees
concluded that the solubility limit of the BCZT ceramics lie around with the discussion in XRD pattern. It can be observed that Ca
x ¼ 0.30. addition causes a negligible change of the Curie point between
The 2q range from 44 to 47 is chosen for refinement to x ¼ 0.05 and x ¼ 0.30, but a rapid downward shift for further
understand the phase transformation exactly. At room tempera- increase of Ca content (x  0.30). On the other hand, the maximal
ture, the BCZT ceramics at x ¼ 0.05 possess orthorhombic phase relative dielectric constants decrease and the dielectric peaks
[13,24], which is characterized by a single peak of (200) at around become broad with increasing Ca content (x  0.30). There are
2q of 45 . The BCZT ceramics become tetragonal structures [14,24], some possible reasons for the phenomena. It is shown in this article
featured with splitting of the (002)/(200) peaks at around 2q of 45 , that the replacement of Ba2þ by Ca2þ reduces the lattice constant
with increasing Ca content (0.10  x  0.25). When x ¼ 0.25, the with increasing hydrostatic pressure and moves the PPT down-
BCZT ceramics possess tetragonal phase only. However, biphasic wards. Meanwhile, the dielectric peaks at Curie temperature
structure of the tetragonal BCZT and orthorhombic CT coexist with become broad with the increase of Ca content. That may be the
the increase of Ca content (x  0.3). diffuseness of the phase transition in the BCZT ceramics, as is

1kHz
12000 1 kHz
10 kHz
a 12000
10kHz b
100 kHz 100kHz
10000 10000
Dielectric constant
Dielectric constant

8000 8000

6000 6000

4000 4000

2000 2000

0 0
20 40 60 80 100 120 140 20 40 60 80 100 120 140
o
Temperature ( C)
o
Temperature ( C)

12000 1kHz 12000

10kHz c 1 kHz
10 kHz
d
100kHz 100 kHz
10000 10000
Dielectric constant

Dielectric constant

8000 8000

6000 6000

4000 4000

2000 2000

0 0
20 40 60 80 100 120 140 20 40 60 80 100 120 140
o o
Temperature ( C) Temperature ( C)

Fig. 4. Temperature dependence of dielectric constant for the (Ba1
xCax)(Ti0.95Zr0.05)O3 ceramics: (a) x ¼ 0.10, (b) x ¼ 0.20, (c) x ¼ 0.30 and (d) x ¼ 0.40 measured at 1 kHz, 10 kHz
and 100 kHz.
 W. Li et al. / Current Applied Physics 12 (2012) 748e751 751

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