Materials Research Bulletin 70 (2015) 195–199

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Materials Research Bulletin

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

Relaxor behavior and complex impedance studies on

Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramics prepared by hydrothermal
method
Yuwen Liu, Yongping Pu * , Zixiong Sun, Qian Jin
School of Materials Science and Engineering, Shaanxi University of Science & Technology, Xi’an 710021, People’s Republic of China

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

Article history: Dense ceramics in the solid solution system, Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ (BCTZ–Fe3+) were prepared
Received 28 November 2014 by hydrothermal method assisted by microwave sintering. And the electrical properties were
Received in revised form 4 March 2015 investigated by the dielectric and impedance spectroscopies. The e–T/tan d–T curve revealed relaxor
Accepted 23 March 2015
behaviors below Curie temperature (TC) and a loss peak’s shifting to higher temperature with increasing
Available online 25 March 2015
frequency. Moreover, the BCTZ–Fe3+ ceramic exhibits only one loss peak which can be analyzed in terms
of the Maxwell–Wagner capacitor model at lower temperature, while the second peak related to the
Keywords:
space charge polarization between the ceramic and electrode appeared above 623 K. The impedance
A. Ceramics
B. Chemical synthesis
complex plane plots of BCTZ–Fe3+ ceramic turned into one semicircular arc at 473 K from a single line at
B. Piezoelectricity 373 K and then to two semicircular arcs at 573 K and 643 K, which were analyzed as four different
D. Dielectric properties equivalent circuits.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction were prepared by hydrothermal method and was assisted by MS

Over the past several decades, Ba1
xCaxTi1
yZryO3 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 [1–5]. The d33
of BCTZ ceramics have reached to over 600 pC/N [6], and in this
case any improvement is difficult 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 sol–gel 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 efficient 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, Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramics
* Corresponding author. Tel.: +86 29 86168133; fax: +86 29 86168137.
E-mail address: ivy_yw@outlook.com (Y. Pu).
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 (P–E loop
at room temperature) and higher temperature (multiple polariza-
tion 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
Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ 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 first dissolved in distilled water
respectively and then were mixed according to their stoichiomet-
ric. 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 BCTZ–Fe3+ 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

http://dx.doi.org/10.1016/j.materresbull.2015.03.054
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
196 Y. Liu et al. / Materials Research Bulletin 70 (2015) 195–199
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 P–E loop of the BCTZ–Fe3+ ceramic collected at an
ambient temperature of 297 K. The phase analysis identified a
monophase of tetragonal structure type with the lattice param-
eters a and c = 3.998 and 4.005 Å, respectively. The Fe3+ (0.785 Å)
probably occupied B-site of BCTZ ceramic for the closer ionic
radius to Ti4+ (0.605 Å) and Zr4+ (0.72 Å) than Ba2+ (1.61 Å) and Ca2+
(1.34 Å). 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
P–E 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 BCTZ–Fe3+ ceramic as a function of temperature measured at
frequencies of 1, 10, 100 and 1000 kHz, respectively. A peak with
Fig. 1. XRD pattern (a), SEM image (b), ferroelectric P–E loop (c) of the Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramic at room temperature.
Curie temperature (TC) of 326 K is detected due to the
ferroelectric–paraelectric phase transition (Tetragonal–Cubic).
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 BCTZ–Fe3+ 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/e–1/em) as a function of log(T–Tm) by fitting the Uchino
equation:
1 1 ðT
T m Þg

¼ 1<g<2 (1)
e em C
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 peak’s 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 Maxwell–Wagner and
Debye relaxation model. The permittivity exhibits an obvious drop
at low frequencies and seems temperature-independent at
 Y. Liu et al. / Materials Research Bulletin 70 (2015) 195–199 197

Boltzmann constant. The condition vpt p = 1 is fulfilled 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 fitting. The relaxation parameters E = 0.74 eV,
t 0 = 1.24  1014 s are obtained from the fitting 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:
 
4þ 2Fe 2FeTi þV O
3þ
2Ti ! (3)

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

the Maxwell–Wagner capacitor model, and The real and imaginary
parts of relative permittivity and tan d were calculated from the
following formula [15]:
e0
e1
e0 ¼ e1 þ (4)
1 þ v2 t 2

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

tan d for the Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramic measured at various frequen-
cies: (a). e–T; (b). tan d–T.

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 [8–13]. To
investigated the relaxation mechanisms of first peak, the thermally
activated parameters during relaxation process were calculated
using Arrhenius law:


E
t ¼ t 0 exp (2)
KBT
where t 0 is the pre exponential factor (or the relaxation time at
infinite temperature), E denotes the activation energy of the
relaxation process, T is the absolute temperature, and KB is the

Fig. 4. Frequency dependence of the dielectric permittivity and dielectric loss tan d
Fig. 3. Relaxor parameters of Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramic. for the Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramic measured at various temperatures.
198 Y. Liu et al. / Materials Research Bulletin 70 (2015) 195–199

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 first 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 d–T 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 BCTZ–Fe3+ ceramic measured at
373 K–673 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 infinite
resistance and can be considered as a capacitor. One single
Fig. 5. The Arrhenius plot of the dielectric relaxation peak from the frequency semicircular arc is gradually observed in sample measured at
spectra. The solid line is a result of linear least-square fitting. 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
vt ðeS
e1 Þ 1
e00 ¼ þ (5) elements connected in serial and two parallel RC elements
1 þ v2 t 2 vC0 ðR1 þ R2 Þ
connected in serial are established for it, respectively. The first
semicircular arc at higher frequency is related to the grain while

 the second to the electrode, and it can be also observed from
vt ðeS
e1 Þ s 1
tand ¼ þ (6) Fig. 6(b), (c) and (d) that the resistance of grain decreases with
eS þ e1 v2 t 2 ve0 e0 þ ðeS
e1 =1 þ v2 t 2 Þ
increasing from temperature. This behavior is also due to the
where es and e1 are the static and high-frequency permittivity, thermal ion polarization resulted from VO as discussed before.
respectively, t is the relaxation time of the composites, v is angular The second semicircular arc at lower frequencies is originating
frequency, C0 is the empty cell capacitance, R1 and R2 are from the contact between ceramic and electrode, for the resistance

Fig. 6. Complex impedance plots for the Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ ceramic measured at different temperatures.
 Y. Liu et al. / Materials Research Bulletin 70 (2015) 195–199 199

of electrode increases strongly with temperature. Thus, the two Talents Program of Chinese Education Ministry (NCET-11-1042),
parallel RC elements connected in serial at 400  C in Fig. 6(d) can be the Key Program of Innovative Research Team of Shaanxi
calculated as follows [14,15]: Province (2014KCT-06) and the International Science and
Technology Cooperation Project Funding of Shaanxi Province
1 1
Z ¼ þ ¼ Z 0
iZ 00 (7) (2012KW-06).
R
1
g þ ivC g R
1
e þ ivC e

References

Rg Re
Z0 ¼  2 þ
1 þ vRg C g 1 þ ðvRe C e Þ2
" # " #
Rg Re
Z 00 ¼ Rg   2 þ Re
1 þ vRg C g 1 þ ðvRe C e Þ2
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 Ba0.9Ca0.1Ti0.9Zr0.1O3–0.06Fe3+ 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 first loss peaks in tan d–f curve at
higher frequencies resulted from VO can be analyzed in terms of
the Maxwell–Wagner 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 BCTZ–Fe3+ measured
at 373–673 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
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