Journal of Alloys and Compounds 624 (2015) 284–289

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Journal of Alloys and Compounds

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

Effect of pore content on diffuse phase transition behaviour of porous

0.5BaZr0.2Ti0.8O3–0.5Ba0.7Ca0.3TiO3 ceramics
W. Wang a,⇑, L.D. Wang a, W.L. Li a,b, D. Xu a, Y.F. Hou a, W.D. Fei a,⇑
a
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, PR China
b
National Key Laboratory of Science and Technology on Precision Heat Processing of Metals, Harbin Institute of Technology, Harbin 150001, PR China

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

Article history: The lead-free (1  x)BaZr0.2Ti0.8O3–xBa0.7Ca0.3TiO3 (BZT–xBCT) system has been well known as an alterna-
Received 21 May 2014 tive of lead based piezoelectric materials. Recently, this system has attracted new attentions for its poten-
Received in revised form 17 October 2014 tial applications in refrigeration. Benefit from the diffuse phase transition behaviour, it has the potential
Accepted 10 November 2014
to be used in a wide cooling temperature range. In this paper, porous BZT–0.5BCT ceramics have been
Available online 20 November 2014
prepared by using the glucose as pore form agency. And the effect of pore content on diffuse phase tran-
sition behaviour of porous BZT–0.5BCT ceramics has been studied. The results show that the pore content
Keywords:
increases with the glucose content increasing, and the diffuseness parameter decreased with the increase
Ceramics
Dielectric response
of pores. We suppose that the decrease of the diffuseness parameter are caused by the relieved of stress,
Diffusion because in porous ceramics internal stress could be relieved by pores. This result implies that the BZT–
Phase transitions 0.5BCT ceramics may have a stress-induced diffuse phase transition behaviour which is different from
Piezoelectricity the intrinsic ones.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introductions BZT–xBCT system, it has caused more and more concerns

Lead-free (1  x)BaZr0.2Ti0.8O3–xBa0.7Ca0.3TiO3 (BZT–xBCT)
ceramics have attracted much attention for its huge piezoelectric
response [1–4]. Liu and Ren [1] have reported that BZT–xBCT
ceramics exhibit very high piezoelectric coefficient of 620 pC/N at
morphotropic phase boundary (MPB), which is comparable even
with Pb(Zr, Ti)O3 (PZT). However, the Curie temperature (TC) for
the composition with the best piezoelectric properties (x = 0.5) is
relatively low (93 °C), thus restricting its applications [1]. Recently,
the diffuse phase transition of BZT–xBCT ceramics has been found
and attracted much attention [5], which results in good electroca-
loric (EC) effects [6–8]. Generally, the giant EC effect only exists in
a narrow temperature range around TC for the ferroelectrics that
have classical ferroelectric phase transition behaviour [9,10]. But
the temperature range of EC effect can be enlarged greatly in the
ferroelectrics with diffuse paraelectric to ferroelectric phase transi-
tion [11]. It is very important to design the Curie temperature and
diffusion transition behaviour of ferroelectrics for their applica-
tions of solid refrigeration.
Since the diffuse phase transition behaviour is important for
both the electrocaloric effect and the piezoelectric properties of
[5,8,12]. Bai et al. [8] have indicated that the EC effect and diffusion
transition behaviour are influenced by the composition in lead-free
BZT–xBCT ceramics, and the diffused phase transition has a signif-
icant impact on the cooling temperature range and the refrigera-
tion capacity of this system. Generally, the diffusion phase
transition can be evaluated by using diffuseness parameter (c)
[13]. However, the reported c values of BZT–xBCT ceramics are
scatted even for the ceramics with the same composition. For
example, c value of BZT–0.1BCT ceramic is reported as 1.47 by Sre-
enivas Puli et al. [5], and as 1.84 by Bai et al. [8], which implies that
the diffuse phase transition behaviour of BZT–xBCT ceramics may
be affected severely by the manufacturing processes or defects.
But the studies on this section are scarcely reported.
Generally, the important defect induced by the manufacturing
processes is the porosity. In this paper, porous BZT–0.5BCT ceram-
ics were designed to study the relationship between the diffuse
phase transition behaviour and the porosity. In addition, the micro-
structures of the porous BZT–0.5BCT ceramics have also been
studied.
2. Experimental

⇑ Corresponding authors. Tel.: +86 451 86413908. BZT–0.5BCT ceramic samples were prepared through a conventional solid oxide
E-mail addresses: spacexuanwu@163.com (W. Wang), wdfei@hit.edu.cn route, stoichioimetric quantities of BaCO3 (99%), TiO2 (98%), CaCO3 (99%) and
(W.D. Fei). BaZrO3 (99%) were mixed and ground by ball milling for 10 h with the addition

http://dx.doi.org/10.1016/j.jallcom.2014.11.066
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
 W. Wang et al. / Journal of Alloys and Compounds 624 (2015) 284–289
Fig. 1. XRD patterns of BZT–0.5BCT ceramics with different glucose contents.
of ethanol. After drying, the powder mixtures were calcined at 1250 °C for 3 h in air.
Then, the mixtures were ground again for 10 h. After drying, the powder mixtures
were sintered at 1350 °C for 3 h in air to get the powders with pure perovskite
structure. Then the glucose (as pore forming agent) was added into the powders
with different contents. The mixtures then were ground by ball milling for 4 h with
the addition of ethanol. After drying, the powder mixtures were mixed with PVA
binder (3 wt%) and pressed into pellets (10 mm diameter and 1 mm thick) under
uniaxial stress. The pellet samples were sintered at 1350 °C for 3 h in air. An Empy-
rean X-ray diffractometer (Panalytical) with Cu Ka radiation was used to reveal the
phase composition of the sintered samples. The microstructures of the sintered pel-
lets were examined by a HELIOS NanoLab 600i (FEI) scanning electron microscopy
(SEM). The investigations of porosity were performed using ‘‘Image-Pro Plus’’ com-
puter program. Silver electrodes were deposited on both sides of the pellet samples
by magnetron sputtering. The dielectric properties were measured as a function of
temperature (RT–200 °C) on a HP4294A Impedance Analyzer (Hewlett Packard).
Fig. 2. SEM images of porous BZT–0.5BCT ceramics with different glucose content, (a) 0 wt%, (b) 5 wt%, (c) 10 wt% and (d) 15 wt%.
285
Fig. 3. Porosity of BZT–0.5BCT ceramics with different glucose contents.
3. Results and discussion
3.1. Phase and microstructure
Fig. 1 shows the XRD patterns of the BZT–0.5BCT ceramic pellets
with different glucose contents. Only pure perovskite structure
phase can be found in the XRD patterns. Fig. 2 shows the SEM
images of porous BZT–0.5BCT ceramics. It can be seen that the size
and content of pores increase with the glucose content increasing.
Fig. 3 shows the relationship between the porosity and the glucose
content, it is seen that the ceramics without glucose added have a
pore content of 2%, this is because that the PVA burnt off during
sintering and leaving pores in the ceramics. And the porosity
increases with glucose content increasing, showing the adjustment
286 W. Wang et al. / Journal of Alloys and Compounds 624 (2015) 284–289
Fig. 4. The measured and fitted results of porous BZT–0.5BCT ceramics with different porosity, (a) 2%, (b) 4.5%, (c) 9%, (d) 12%, (e) peak positions versus porosity and (f) IR/
(IR + IT) versus porosity.
of the pores by the content of pore forming agent. Fig. 1 shows that
the peak shapes of the XRD patterns are different for the pellets
with different glucose contents. This result implies that the phase
compositions are different for the pellets with different glucose
contents. The phase composition of BZT–0.5BCT ceramics has been
well studied [1,4,14,15], and the (2 0 0)pc-reflections have been
generally employed to analyze the phase transition [5,16,17]. Here,
we also use the (2 0 0)pc-reflections to study the phase transitions
of porous BZT–0.5BCT ceramics with different pores. To further
confirm the phase composition, fine scan XRD measurements were
carried out for the (2 0 0)pc-reflections of porous BZT–0.5BCT
ceramics. The phase composition of BZT–0.5BCT ceramics are R
and T mixture phase [1,4,14,15], the (2 0 0)pc reflection of R phase
has one peak, and the (2 0 0)pc reflection of T phase has two peaks.
On the basis of that, R and T mixture phase model and the Gauss
function were used to fit the reflection profiles after automatic
back-ground removal and Ka2 stripping. The measured and fitted
results are shown in Fig. 4. As shown in Fig. 4a–d the measured
profiles can be well simulated by three peaks, respectively. Both
the peaks in the low and high angle side are the (0 0 2)pc peaks of
T phases, and the peaks in the middle angle are the (0 0 2)pc peaks
of R phases, respectively [1,18]. Fig. 4e shows the change of peak
positions and Fig. 4f shows the IR/(IR + IT) versus porosity of the
porous BZT–0.5BCT ceramics. From Fig. 4e it is seen that the peak
positions of all the three peaks shift to the lower side obviously
when the porosity increase from 2% to 4.5%, while these peaks
are not shift when the porosity increase from 4.5% to 12%. From
Fig. 4f it is seen that the IR/(IR + IT) basically remain unchanged
when the porosity increase from 2% to 4.5%, but decreases obvi-
ously when the porosity increase from 4.5% to 9%, and then remain
unchanged. This result could be explained as following. During the
manufacture process, internal stresses can be introduced in the
ceramics. Generally in the dense ceramics with small amounts of
pores, internal stress can be relieved by grain-boundary sliding
[19]. Also, in the ceramics with large amounts of pores, internal
stress is mainly relieved by pores [19]. Generally when the internal
press stress has been relieved, the XRD peaks are shifted to the
lower angle side, because the volume of the grains became larger.
This is the reason that the peak positions shift to the lower side
obviously when the porosity increase from 2% to 4.5%. And a
 W. Wang et al. / Journal of Alloys and Compounds 624 (2015) 284–289
Fig. 5. Temperature dependent dielectric constant of porous BZT–0.5BCT in the frequency range of 1–100 kHz with different porosity, (a) 2%, (b) 4.5%, (c) 9% and (d) 12%.
previous study [20] shows that the R ? T phase transition happens
under tensile stress, and the peak positions of these phases remain
unchanged. Which suggested that the R ? T phase transition could
happen in BZT–0.5BCT ceramics when the internal press stress
relived. And we suggest that this is the reason that the IR/(IR + IT)
decreases obviously when the porosity increase from 4.5% to 9%.
On the basis of above discussions, we can get the following results.
The residual press stress has been relieved by pores when the
porosity increase from 2% to 4.5%, and the grain volume of BZT–
0.5BCT increased in this stage. The residual press stress has still
been relieved when the porosity increase from 4.5% to 9%, and
the R ? T phase transition happens in this stage. The residual press
stress has been relieved completely after that, and then the grain
volume and phase composition of BZT–0.5BCT ceramics remain
unchanged.
3.2. Dielectric properties
To study the phase transition behaviours of porous BZT–0.5BCT
ceramics, the temperature-dependent dielectric constants in the
frequency range of 1–100 kHz were tested, as shown in Fig. 5. In
Fig. 5, obvious diffusion transition behaviour can be found for all
ceramic samples with different pore contents. In addition, the peak
temperatures of the curves in Fig. 5 are almost unchanged with fre-
quency for all samples studied in the present investigation, i.e. no
clear frequency dispersion can be observed. The above results indi-
cate that the diffusion transition is not a typical relaxor ferroelec-
tric with frequency dispersion.
Generally, the modified Curie–Weiss law has been used to
explain the dielectric behaviour of complex ferroelectric with dif-
fuse phase transition [21], described as following Eq. (1).
1 1 ðT  T m Þc
 ¼
e em C phase transition behaviour in epitaxial BaTiO3 thin films, which
287
where c is the diffuseness parameter, e the dielectric constant, em
the maximum dielectric constant, T the absolute temperature, Tm
the temperature at maximum dielectric constant, C the Curie–Weiss
constant. The c value between 1 and 2 gives the information on the
phase transition character. c= 1 represents the classical ferroelectric
phase transition, and c = 2 describes diffuse phase transition [13].
Fig. 6(a)–(d) shows the plot of ln[(1/e)  (1/em)] as a function of
ln(T  Tm) at 10 kHz in the temperature range of T > Tm, where,
the permittivity data were taken from the 10 kHz frequency to
avoid space charge contributions in the lower frequency range
[22]. Linear relationships between ln[(1/e)  (1/em)] and ln(T  Tm)
can be clearly found in Fig. 6(a)–(d), and c values can be obtained
from the above linear plots according to Eq. (1). The values of c
for the present porous BZT–0.5BCT are 1.74, 1.67, 1.60 and 1.60,
respectively, corresponding to different pore contents, which indi-
cates that the porous BZT–0.5BCT ceramics exhibits diffusion phase
transition characteristics [5,8,23,24].
The relations between c and the pore content are shown in
Fig. 6(e), it is seen that when the pore content is less than 9%, c
decreased with the increase of glucose content. But after that c sta-
bilized at 1.60 while the pore content increased from 9% to 12%.
This result indicates that the pore content influences the diffuse
phase transition behaviour remarkably, but the impact is limited
in a range.
3.3. Discussions
It has been reported that the Curie temperature of ferroelectrics
is related to internal stress [25,26]. And it has been reported that
the uneven distribution of stress lead to an uneven distribution
of TC and induced diffusion phase transition behaviour in ferroelec-
tric films [27,28]. Chattopadhyay et al. have reported the diffuse
ð1Þ
288 W. Wang et al. / Journal of Alloys and Compounds 624 (2015) 284–289

Fig. 6. linear fitted ln[(1/e)  (1/em)] as function of ln(T  Tm) for porous BZT–0.5BCT ceramics at 10 kHz. (a) BZT–0.5BCT (porosity = 2%), (b) BZT–0.5BCT (porosity = 4.5%), (c)
BZT–0.5BCT (porosity = 9%), (d) BZT–0.5BCT (porosity = 12%) and (e) c value versus porosity.

is related to the strain distribution in the films [29]. These results
suggested that besides the intrinsic DPT behaviour (e.g. which
caused by the local composition fluctuations [30]), there also
existed an stress-induced diffusion phase transition behaviour in
ferroelectrics. On the basis of the above studies, we suggest that
the difference of diffusion phase transition behaviour in the porous
BZT–0.5BCT ceramics were caused by the different stress distribu-
tion conditions. Normally, the stress effect in ceramics is not as
impressive as that in thin films [31,32], the stress induced diffusion
phase transition behaviours in the ceramics supposed to be much
smaller than that in thin films. But in this study the diffusivity
change is larger than expected (from c = 1.74 to c = 1.60). The rea-
sonable explanation is that the BZT–0.5BCT ceramics have nearly
isotropic free energy surface of MPB composition between differ-
ent phases [1]. Because of the isotropic free energy surface, the
phase composition and phase transition of the ceramics in the
vicinity of MPB composition are very sensitive to stress [33–35].
On the basis of above discussions, the phase transition behav-
iour against porosity can be explained as follows. The internal
stress and the stress-induced c value enhancement decrease with
the increasing of porosity. When the internal stress is small
enough, the stress-induced diffusion phase transition behaviour
disappeared and only remain the intrinsic diffusion phase transi-
tion behaviour, then the diffuseness parameter remain unchanged.
Our results also present the stress-induced diffusion phase transi-
tion behaviour may be remarkable in such ceramics that the phase
transitions are sensitive to stress.
In summary, the porous BZT–0.5BCT ceramics have been syn-
thesised by using the Glucose as pore form agency, and the dielec-
tric properties of the porous BZT–0.5BCT ceramics have been
 W. Wang et al. / Journal of Alloys and Compounds 624 (2015) 284–289 289

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