Materials Research Bulletin: Yuwen Liu, Yongping Pu, Zixiong Sun, Qian Jin

Materials Research Bulletin 70 (2015) 195199
Contents lists available at ScienceDirect
Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu
Relaxor behavior and complex impedance studies on

Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramics prepared by hydrothermal
method
Yuwen Liu, Yongping Pu * , Zixiong Sun, Qian Jin
School of Materials Science and Engineering, Shaanxi University of Science & Technology, Xian 710021, Peoples Republic of China
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 28 November 2014
Received in revised form 4 March 2015
Accepted 23 March 2015
Available online 25 March 2015
Dense ceramics in the solid solution system, Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ (BCTZFe3+) were prepared
by hydrothermal method assisted by microwave sintering. And the electrical properties were
investigated by the dielectric and impedance spectroscopies. The eT/tan dT curve revealed relaxor
behaviors below Curie temperature (TC) and a loss peaks shifting to higher temperature with increasing
frequency. Moreover, the BCTZFe3+ ceramic exhibits only one loss peak which can be analyzed in terms
of the MaxwellWagner capacitor model at lower temperature, while the second peak related to the
space charge polarization between the ceramic and electrode appeared above 623 K. The impedance
complex plane plots of BCTZFe3+ ceramic turned into one semicircular arc at 473 K from a single line at
373 K and then to two semicircular arcs at 573 K and 643 K, which were analyzed as four different
equivalent circuits.
2015 Elsevier Ltd. All rights reserved.
Keywords:
A. Ceramics
B. Chemical synthesis
B. Piezoelectricity
D. Dielectric properties
1. Introduction
Over the past several decades, Ba1xCaxTi1yZryO3 system
ceramics have been widely applied in the electronic industries
owing to their environment friendly and superior performances,
and till now this kind of ceramics are still extensively investigated
as lead-free piezoelectrics and relaxor ferroelectrics [15]. The d33
of BCTZ ceramics have reached to over 600 pC/N [6], and in this
case any improvement is difcult to obtain for this value might be a
bottleneck. The relaxation behavior with DTres = 15 C and g = 2.0
are also the limiting value of Ba0.90Ca0.10Zr0.25Ti0.75O3 with grain
size of 0.85 mm prepared by solgel method [7]. Thus, doping and
compositing could be the two optimism ways to improve the
dielectric properties of BCTZ system ceramics.
Moreover, almost all the synthetic methods of BCTZ system
ceramics were described as solid-state route in current literatures,
which may be a limitation of improving the performances.
Hydrothermal is a high efcient way for synthesizing powders with
homogeneous grain size and microwave sintering (MS) is specially
suitable for this kind of ceramics [8]. During the hydrothermal
process, the doping can be only achieved by using soluble salt as raw
materials. In present work, Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramics
* Corresponding author. Tel.: +86 29 86168133; fax: +86 29 86168137.

E-mail address: ivy_yw@outlook.com (Y. Pu).
http://dx.doi.org/10.1016/j.materresbull.2015.03.054
0025-5408/ 2015 Elsevier Ltd. All rights reserved.
were prepared by hydrothermal method and was assisted by MS

method with Fe3+ entering the lattice as ion form. In our earlier
exploration, Fe ion shown valence alternation during the sintering
process, which may lead to some special properties. And this
component shows advantages both at lower temperature (PE loop
at room temperature) and higher temperature (multiple polarization mechanisms at over 500 K). The dielectric spectroscopies were
employed to investigate the relaxor behavior and relaxation model,
and the impedance spectroscopies were shown to establish the
equivalent circuits.
2. Experimental
Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramics were prepared by
hydrothermal method and the BaCl22H2O (SCRC), CaCl2, TiCl4,
ZrOCl28H2O and Fe(NO3)3 were used as raw materials. All
these raw materials were chemically pure. BaCl22H2O, CaCl2
ZrOCl28H2O and Fe(NO3)3 were rst dissolved in distilled water
respectively and then were mixed according to their stoichiometric. The TiCl4 was added into the mixtures dropwise to obtain the
precursors. Finally the NaOH was added to regulated the pH > 14.
The precursors were put into the heating-autoclave, followed
by distilled water until the total volume reached to 80% of
the autoclave. The BCTZFe3+ powders were obtained after the
hydrothermal reaction carried out at 453 K for 10 h and then were
oven dried at 353 K for 2 h before washed by distilled water. After
196
Y. Liu et al. / Materials Research Bulletin 70 (2015) 195199
that, the powders were pressed into pellets of 12 mm diameter and

the green bodies were sintered at 1573 K for 10 min under
microwaves. Phase structure was examined using an X-ray
diffraction (D/max 2200 pc, Rigaku, Tokyo, Japan) with CuKa
radiation and the microstructure morphologies were obtained by
scanning electron microscopy (JEOL JSM-6390A JEOL Ltd., Tokyo).
Dielectric properties and impedance complex plots were measured
by Agilent 4980 A impedance analyzer.
3. Results and discussion
Fig. 1 shows the data of XRD pattern, SEM image, as well as
ferroelectric PE loop of the BCTZFe3+ ceramic collected at an
ambient temperature of 297 K. The phase analysis identied a
monophase of tetragonal structure type with the lattice parameters a and c = 3.998 and 4.005 , respectively. The Fe3+ (0.785 )
probably occupied B-site of BCTZ ceramic for the closer ionic
radius to Ti4+ (0.605 ) and Zr4+ (0.72 ) than Ba2+ (1.61 ) and Ca2+
(1.34 ). The no-splitting of (2 0 0)/(0 0 2) peak indicates the
coexistence of tetragonal and cubic phase. SEM image shows
well-sintered ceramics with grain sizes of 500 nm, which is a
much smaller grain size compared with other researches [3,7,9,11]
due to the synthesizing method of hydrothermal and fast
microwave sintering. The ferroelectric test exhibits well-saturated
PE loop with a Pr = 10.05 mC/cm2 EC = 4.88 kV/cm and weak switch
current density (<0.8 mA/cm2) at a frequency of 2 Hz. The
piezoelectric d33 value measured with the quasi-static method
equals 350 pC/N with the electromechanical coupling factor
kp = 0.38.
Fig. 2 shows the dielectric permittivity and dielectric loss (tan d)
of the BCTZFe3+ ceramic as a function of temperature measured at
frequencies of 1, 10, 100 and 1000 kHz, respectively. A peak with
Curie temperature (TC) of 326 K is detected due to the

ferroelectricparaelectric phase transition (TetragonalCubic).
The inset in Fig. 2(a) indicates a standard relaxor ferroelectric
with dispersion phase transition and dispersion frequency with
DTres = 278 K. And the loss peaks corresponding to TC can also be
observed in the inset of Fig. 2(b), which resulted from the ionic
polarization during the phase transition. To characterize the
relaxor behavior of BCTZFe3+ ceramic, the relationship between
inverse dielectric permittivity and temperature at 10 kHz is plotted
in Fig. 3, showing the T0 = 349 K and Tcm = 394 K. And the inset is the
plot of log(1/e1/em) as a function of log(TTm) by tting the Uchino
equation:
1
em
T T m g
1<g<2
C
(1)
where em refers to the maximum value of dielectric permittivity,

e to the dielectric permittivity at temperature T, Tm to the
temperature at the peak of the dielectric permittivity, C to the Curie
constant, and g to the diffuseness degree indicator, taking
the value between 1 (for a normal ferroelectric) and 2 (for a
complete diffuse phase transition) is calculated to be 1.69.
The loss peaks shifting toward higher temperature with the
increase in frequency emerged in Fig. 2(b) at high temperature as
well as the strong increasing of permittivity in Fig. 2(a) is
apparently a correlation of relaxation. What is more interesting, a
second loss peak is observed only in 1 kHz at 750 K. These
phenomenons can more conveniently be studied from the
frequency response of permittivity formalism measured at
different temperatures in Fig. 4, where the ferro-para transition
is excluded. The inset of Fig. 4(b) shows the MaxwellWagner and
Debye relaxation model. The permittivity exhibits an obvious drop
at low frequencies and seems temperature-independent at
Fig. 1. XRD pattern (a), SEM image (b), ferroelectric PE loop (c) of the Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic at room temperature.
197
Boltzmann constant. The condition vpt p = 1 is fullled at the peak

position, where v = 2pf is the angular frequency of measurement
and the subscript p denotes values at peak position. If we plot the ln
(vp) as a function of the reciprocal of peak temperature (Arrhenius
plots), a linear relation would be obtained according to Eq. (2). The
relaxation parameters E and t 0 can thus be deduced from the slope
and intercept of this line, respectively. Fig. 5 shows the Arrhenius
plots for the dielectric loss peak, where the solid line is the result of
a linear least-square tting. The relaxation parameters E = 0.74 eV,
t 0 = 1.24 1014 s are obtained from the tting line [14,15]. The
calculated E is not far from 0.7 eV which is the conduction activated
energy of the electrons from second ionization of oxygen
vacancies. Therefore, the conducting species in this temperature
range is likely to come from the second ionization of oxygen
vacancies (VO) as previous studies [16]. And the defect chemical
reaction of Fe3+ substitution for B-site ions is deduced as:

3
4 2Fe 2FeTi V O
2Ti

(3)
Thus, results of the rst loss peak should be analyzed in terms of

the MaxwellWagner capacitor model, and The real and imaginary
parts of relative permittivity and tan d were calculated from the
following formula [15]:
e0 e1
e0 e1
1 v2 t 2
(4)
Fig. 2. Temperature dependence of the dielectric permittivity and dielectric loss

tan d for the Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic measured at various frequencies: (a). eT; (b). tan dT.
f > 105 Hz. Seen from Fig. 4(b), a common loss peak at higher
frequencies is observed at all the temperatures corresponding to
the step decrease in permittivity in Fig. 4(a), and the second peak in
lower frequencies emerged at higher temperatures [813]. To
investigated the relaxation mechanisms of rst peak, the thermally
activated parameters during relaxation process were calculated
using Arrhenius law:

E
t t 0 exp
(2)
KBT
where t 0 is the pre exponential factor (or the relaxation time at
innite temperature), E denotes the activation energy of the
relaxation process, T is the absolute temperature, and KB is the
Fig. 3. Relaxor parameters of Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic.
Fig. 4. Frequency dependence of the dielectric permittivity and dielectric loss tan d
for the Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic measured at various temperatures.
198
Fig. 5. The Arrhenius plot of the dielectric relaxation peak from the frequency
spectra. The solid line is a result of linear least-square tting.
e00
vt eS e1
1
vC0 R1 R2
1 v2 t 2
tand
(5)
vt eS e1
s
1
eS e1 v2 t 2 ve0 e0 eS e1 =1 v2 t 2
(6)
where es and e1 are the static and high-frequency permittivity,

respectively, t is the relaxation time of the composites, v is angular
frequency, C0 is the empty cell capacitance, R1 and R2 are
resistances of the two dielectric components: grains and electrode,

respectively which will be discussed in further studies. And d is the
conductivity of the composites, and the e0 is the vacuum
permittivity. In this temperature range, both the thermal ion
polarization resulted from VO and the space charge polarization
between the ceramic and electrode exist, while the rst loss peak is
dominated by the thermal ion polarization. The second loss peak at
lower frequencies only exists at higher temperature, which is
corresponding to the second peak at 1 kHz in the tan dT curve, is
related to the space charge polarization (This kind of polarization
only exists at higher temperature for the resistance of electrode
increases with increasing temperature).
Complex impedance spectra of BCTZFe3+ ceramic measured at
373 K673 K are shown in Fig. 6. The four curves can be analyzed by
four different equivalent circuits: Sample measured at 373 K
exhibits one single line with a high slope, manifesting a innite
resistance and can be considered as a capacitor. One single
semicircular arc is gradually observed in sample measured at
473 K, can be analyzed by equivalent circuit of one parallel RC
element as previous study [15]. When the measuring temperature
is increased to 573 K and 673 K, one semicircular arc and a half
and two semicircular arcs are observed. One parallel RC and a C
elements connected in serial and two parallel RC elements
connected in serial are established for it, respectively. The rst
semicircular arc at higher frequency is related to the grain while
the second to the electrode, and it can be also observed from
Fig. 6(b), (c) and (d) that the resistance of grain decreases with
increasing from temperature. This behavior is also due to the
thermal ion polarization resulted from VO as discussed before.
The second semicircular arc at lower frequencies is originating
from the contact between ceramic and electrode, for the resistance
Fig. 6. Complex impedance plots for the Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic measured at different temperatures.
of electrode increases strongly with temperature. Thus, the two

parallel RC elements connected in serial at 400 C in Fig. 6(d) can be
calculated as follows [14,15]:
Z
1
R1
g ivC g
Z 0 iZ 00
R1
e ivC e
(7)
199
Talents Program of Chinese Education Ministry (NCET-11-1042),

the Key Program of Innovative Research Team of Shaanxi
Province (2014KCT-06) and the International Science and
Technology Cooperation Project Funding of Shaanxi Province
(2012KW-06).
References
Z0
Rg
Re

2
1 vRe C e 2
1 vRg C g
"
Z 00 Rg
Rg
1 vRg C g
#
2 Re
"
(8)
Re
1 vRe C e 2
#
(9)
where (Rg, Re) and (Cg, Ce) are the resistance and capacitance of
grain and electrode, respectively. Based on Eqs. (8) and (9) the
responses from the grains and grain boundaries are located at
1/(2pRgCg) and 1/(2pReCe), respectively. The semicircular arc
decreases with increasing temperature for the contact area
between grain and electrode makes more contributions to
increasing the permittivity and decreasing the resistance at higher
measuring temperature.
4. Conclusions
Lead-free Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic with average
grain size 500 nm have been prepared by hydrothermal method
and was well-sintered by microwave sintering. The sample showed
a relaxor ferroelectric with the coexistence of tetragonal and cubic
phase at room temperature. The rst loss peaks in tan df curve at
higher frequencies resulted from VO can be analyzed in terms of
the MaxwellWagner capacitor model. While the second peak at
lower frequencies was due to the space charge polarization
between the material and electrode, which is appeared at higher
temperatures. Four different equivalent circuits were established
to analyze the complex impedance spectra of BCTZFe3+ measured
at 373673 K and the resistance of grain decreases with increasing
temperature.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (51372144), the New Century Excellent
[1] Q. Lin, M. Jiang, D.M. Lin, Q.J. Zheng, X.C. Wu, X.M. Fan, Effects of
La-doping on microstructure, dielectric and piezoelectric properties of
Ba0.85Ca0.15Ti0.90Zr0.10O3 lead-free ceramics, J. Mater. Sci. 24 (2013)
734739.
[2] Y. Liu, W.C. Wang, J.Q. Huang, F. Tang, C. Zhu, Y.G. Cao, Dielectric properties
of giant permittivity NaCu3Ti3NbO12 ceramics, Cream. Int. 39 (2013)
92019206.
[3] T. Takenaka, H. Nagata, Current status and prospects of lead-free piezoelectric
ceramics, J. Eur. Ceram. Soc. 25 (2005) 26932700.
[4] S. Su, R.Z. Zuo, S.B. Lu, Z.K. Xu, X.H. Wang, L.T. Li, Poling dependence and
stability of piezoelectric properties of Ba(Zr0.2Ti0.8)O3(Ba0.7Ca0.3)TiO3
ceramics with huge piezoelectric coefcients, Curr. Appl. Phys. 11 (2011)
S120S123.
[5] R.Z. Zuo, X.S. Fang, C. Ye, Phase structures and electrical properties of new lead
free (Na0.5K0.5)NbO3(Bi0.5Na0.5)TiO3 ceramics, Appl. Phys. Lett. 90 (2007)
092904.
[6] W.F. Liu, X.B. Ren, Large piezoelectric effect in Pb-free ceramics, Phys. Rev. Lett.
103 (2009) 257602 4pp.
[7] X.G. Tang, H.L.W. Chan, Effect of grain size on the electrical properties of
(Ba, Ca)(Zr,Ti)O3 relaxor ferroelectric ceramics, J. Appl. Phys. 97 (2005)
034109.
[8] Z.X. Sun, Y.P. Pu, Z.J. Dong, Y. Hu, X.Y. Liu, P.K. Wang, M. Ge, Dielectric and
piezoelectric properties and PTC behavior of Ba0.9Ca0.1Ti0.9Zr0.1O3xLa
ceramics prepared by hydrothermal method, Mater. Lett. 118 (2014) 14.
[9] J. Wu, D. Xiao, W. Wu, Q. Chen, J. Zhu, Z. Yang, J. Wang, Role of roomtemperature phase transition in the electrical properties of (Ba, Ca)(Ti, Zr)O3
ceramics, Scripta. Mater. 65 (2011) 771774.
[10] Y.C. Lee, Y.Y. Yeh, P.R. Tsai, Effect of microwave sintering on the microstructure
and electric properties of (Zn, Mg)TiO3-based multilayer ceramic capacitors, J.
Eur. Ceram. Soc. 32 (2012) 17251732.
[11] C.Y. Tsay, K.S. Liu, I.N. Lin, Microwave sintering of (Bi0.75Ca1.2Y1.05)(V0.6Fe4.4)O12
microwave magnetic materials, J. Eur. Ceram. Soc. 24 (2004) 10571061.
[12] T. Chen, T. Zhang, G. Wang, J. Zhou, J. Zhang, Y. Liu, Effect of CuO on the
microstructure and electrical properties of Ba0.85Ca0.15Ti0.90Zr0.10O3
piezoceramics, J. Mater. Sci. 47 (2008) 46124619.
[13] P. Wang, Y.X. Li, Y.Q. Lu, Enhanced piezoelectric properties of (Ba0.85Ca0.15)
(Ti0.9Zr0.1)O3 lead-free ceramics by optimizing calcination and sintering
temperature, J. Eur. Ceram. Soc. 31 (2011) 20052012.
[14] J. Tao, Z.G. Yi, Y. Liu, M.X. Zhang, J.W. Zhai, Dielectric tunability dielectric
relaxation, and impedance spectroscopic studies on (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3
lead-free ceramics, J. Am. Ceram. Soc. 96 (2013) 18471851.
[15] N. Xu, Y.P. Pu, Z. Wang, Large dielectric constant and maxwell-wagner effects in
BaTiO3/Cu composites, J. Am. Ceram. Soc. 95 (2012) 9991003.
[16] Z. Wang, X.M. Chen, L. Ni, Y.Y. Liu, X.Q. Liu, Dielectric relaxations in
B(Fe1/2Ta1/2)O3 giant dielectric constant ceramics, Appl. Phys. Lett. 90
(2007) 102905.

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Materials Research Bulletin 70 (2015) 195199

Contents lists available at ScienceDirect

Materials Research Bulletin

Relaxor behavior and complex impedance studies on

* Corresponding author. Tel.: +86 29 86168133; fax: +86 29 86168137.

were prepared by hydrothermal method and was assisted by MS

Y. Liu et al. / Materials Research Bulletin 70 (2015) 195199

that, the powders were pressed into pellets of 12 mm diameter and

Curie temperature (TC) of 326 K is detected due to the

where em refers to the maximum value of dielectric permittivity,

Y. Liu et al. / Materials Research Bulletin 70 (2015) 195199

Boltzmann constant. The condition vpt p = 1 is fullled at the peak

Thus, results of the rst loss peak should be analyzed in terms of

Fig. 2. Temperature dependence of the dielectric permittivity and dielectric loss

Fig. 3. Relaxor parameters of Ba0.9Ca0.1Ti0.9Zr0.1O30.06Fe3+ ceramic.

Y. Liu et al. / Materials Research Bulletin 70 (2015) 195199

where es and e1 are the static and high-frequency permittivity,

resistances of the two dielectric components: grains and electrode,

Y. Liu et al. / Materials Research Bulletin 70 (2015) 195199

of electrode increases strongly with temperature. Thus, the two

Talents Program of Chinese Education Ministry (NCET-11-1042),

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