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Synthesis and Characteristics of K0.5Bi0.5TiO3 Ceramics

with Addition of CuO
a b b a
Hong-Qi Zhang , Fei Tong , Li-Hu Yi & Yu Liu
a
College of Mechanical and Electrical Engineering , Inner Mongolia Agricultural University ,
Inner Mongolia , China
b
Inner-Mongolia Electric Power Survey and Design Institute , Inner Mongolia , China
Published online: 10 Sep 2014.

To cite this article: Hong-Qi Zhang , Fei Tong , Li-Hu Yi & Yu Liu (2014) Synthesis and Characteristics of K0.5Bi0.5TiO3 Ceramics
with Addition of CuO, Materials and Manufacturing Processes, 29:10, 1168-1171, DOI: 10.1080/10426914.2014.941482

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 Materials and Manufacturing Processes, 29: 1168–1171, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 1042-6914 print=1532-2475 online
DOI: 10.1080/10426914.2014.941482

Synthesis and Characteristics of K0.5Bi0.5TiO3

Ceramics with Addition of CuO
Hong-Qi Zhang1, Fei Tong2, Li-Hu Yi2, and Yu Liu1
1
College of Mechanical and Electrical Engineering, Inner Mongolia Agricultural University, Inner Mongolia, China
2
Inner-Mongolia Electric Power Survey and Design Institute, Inner Mongolia, China

We sintered K0.5Bi0.5TiO3 ceramics by a solid-state reaction process with the addition of CuO. X-ray diffraction patterns indicate that the
synthesized K0.5Bi0.5TiO3 ceramics have the cubic perovskite phase. Scanning electron microscopy images show that the addition of CuO
has a marked influence on grain size and relative density of K0.5Bi0.5TiO3 ceramics. K0.5Bi0.5TiO3 ceramics have the smallest grain size and
highest relative density when the weight percentage addition of CuO is 2%. The results of temperature dependence of the dielectric constant
Downloaded by [Monash University Library] at 05:52 07 December 2014

of synthesized ceramics show that they have the highest value at a temperature of about 382
C. This behavior originates from the disordered
structure and fluctuations of composition in ferroelectric systems.

Keywords Ceramics; Dielectric; KBT-CuO; Microstructure.

INTRODUCTION sintering temperature. For the purpose of saving energy

The Restriction of Hazardous Substances Directive
(RoHS) on the applications of certain dangerous materi-
als in electrical and electronic equipment was adopted in
February 2003 by the European Union [1]. As a result,
the demand for environment-friendly materials has
increased, such as lead-free ceramics or crystals for the
application of piezoelectric devices, including NaNbO3
[2], Ba0.6Sr0.4TiO3 [3], KNbO3 [4], Na0.5Bi0.5TiO3 [5],
K0.5Bi0.5TiO3 [6], and KTa1  xNbxO3 [7]. Potassium bis-
muth titanate (K0.5Bi0.5TiO3, KBT) is a well-known
unleaded material having a piezoelectric effect. KBT is
an ABO3-type materials in which A-site ions can be
substituted, and shows perovskite-type ferroelectric
formation with tetragonal symmetry at ambient tem-
perature [8]. KBT materials often show relaxor-type fer-
roelectric properties, in which Na1þ and Bi3þ at A-sites
are disordered and have short-range=long-range order-
ing. Because of the remarkable electric performance
and high magnetic transition temperature (Tc, 380
C)
of KBT material, it is applied widely in various fields.
For example, KBT ceramics can be used in lead-free
piezoceramic cymbal actuators [9].
However, it is difficult to sinter KBT ceramics of high
density because Bi and K will volatilize at high sintering
temperatures (>1300
C). The volatilization of these
materials will yield inferior electrical properties of the
lead-free system [10, 11]. Attempts have been made to
reduce density, such as the addition of redundant Bi
and K, sintering in sealed crucibles, and lowering of
Received June 13, 2014; Accepted June 28, 2014
Address correspondence to Hong-Qi Zhang, College of
Mechanical and Electrical Engineering, Inner Mongolia Agricultural
University, Inner Mongolia 010018, China; E-mail: zhang_hongqi@
yeah.net.
consumption, it is better if we can sinter it at a lower
temperature. One common method is to add a sintering
aid when trying to lower the sintering temperature, such
as MgO, CuO, or MnO2 [12–15]. Also, the addition of
CuO or MgO can improve density and facilitate grain
growth in the sintering process [12, 15]. However, note
that excessive addition of CuO or MgO will lead to
unnatural growth of grains because of the formation
of liquidoids [16]. Based on this knowledge, we can con-
clude that the appropriate addition of materials in the
sintering process is very important. Herein, we report
on the synthesis of K0.5Bi0.5TiO3 ceramics through the
process of solid-state reaction with different weight per-
centages of CuO. We found that the addition of CuO
has obvious influence on the microstructure, grain size,
density, and dielectric constant of KBT samples
obtained.
EXPERIMENT
KBT was synthesized by the traditional solid-state
reaction technique. We used Bi2O3, Na2CO3, CuO, and
TiO2 as raw materials, the purities of which are all over
99%. The weight percentage of CuO was 1–4 wt%. On
the basis of stoichiometric ratio, raw materials were first
weighed, then raw materials were mixed in a planetary
ball mill with ethanol for 10 h. The mixture obtained
was dried at 100
C for 10 h, milled again for 10 h, and
sintered at 700
C for 4 h. The sintered mixture was
ball-milled and crushed into pellets. The diameter and
thickness of pellets are about 12 and 2 mm, respectively.
The pellets were sintered in a conventional muffle fur-
nace at 1000
C in air for 8 h. Then, the system was
cooled to room temperature naturally.
The crystallinity and phase purity of synthesized pow-
ders were examined by powder X-ray diffraction (XRD)

1168
 SYNTHESIS AND CHARACTERISTICS OF K0.5Bi0.5TiO3 1169

with an X-ray diffractometer (model D=max-cA, Rigaku,

Japan) using graphite monochromatized Cu Ka
irradiation (k ¼ 1.5405 Å). Thermogravimetric analysis
(TGA) and differential thermal analysis (DTA) were
detected using a ZRY-2P thermal analyzer. Scanning
electron microscopy (SEM) images were detected by
a Quanta 200 scanning electron microscope (Philips,
Netherlands). A layer of Aurum (Au) was sputtered on
the polished upper and lower surfaces of obtained
samples using ZHD-300M2 vacuum-coating equipment
(Technol, Beijing), which was used as top and bottom
electrodes for electrical measurements. The temperature
dependence of the dielectric constant was performed
on an LCR meter (HP-4284 A). The temperature was
increased from room temperature to 500
C by a combined
environmental chamber (9023) with a heating rate of
2
C=min. The frequency was 10 kHz. FIGURE 2.—TGA–DTA curves for KBT sample with the addition of 2 wt%
Downloaded by [Monash University Library] at 05:52 07 December 2014

CuO.
RESULTS AND DISCUSSION
The XRD patterns of KBT ceramics sintered at
1000
C for 8 h with different weight percentages of
The microstructure of KBT ceramics obtained is given
CuO are given in Fig. 1. All XRD patterns have peaks
in Fig. 3. The grain size of the synthesized samples
of (100), (101), (111), (200), and (211). These are
decreased and then increased when the different weight
characteristic diffraction patterns in the cubic perovskite
percentages of CuO were added. Grain size distributed
KBT, which is in accord with JCPDS card no. 36-0339.
from hundreds of nm to more than 4 mm when 1 wt%
Peaks related to CuO were not observed in XRD
of CuO was added. Grain size decreased when 2 and
patterns. These results show that KBT samples with high
3 wt% of CuO were added separately. In general, grain
crystallinity can be obtained under current synthesis
growth in ceramics is driven firstly by the motility of
conditions, and there is no formation of a second phase.
grain boundaries, which is governed there by ion dif-
Figure 2 shows the TGA–DTA curves of the KBT
fusion [17]. Impurities usually prohibit the movement
2 wt% CuO sample, which gives the thermal behavior
of grain boundaries and retard grain growth in ceramics
of the sample. In the DTA curve, four endothermic
peaks centered at 162
C, 387
C, 658
C, and 1091
C are
clearly observed. Also, there are obvious gravity
decreases at the corresponding temperatures in the TGA
curve. There are weak thermopositive and endothermal
peaks in the DTA curve at temperatures lower than
500
C. These are likely to have originated from the
dissolution of organics used in the milling process. The
endothermic band in the range 520–700
C indicates
there is the solid-state reaction in the mixture of Bi2O3,
Na2CO3, CuO, and TiO2.

FIGURE 1.—XRD patterns of KBT samples with different weight percen- FIGURE 3.—SEM images of KBT samples with different weight percen-
tages of CuO. tages of CuO (a) 1 wt%; (b) 2 wt%; (c) 3 wt%; (d) 4 wt%.
 1170
during sintering [18]. These results show that there are
obstacles to atomic diffusion because of the existence
of CuO within KBT ceramics. As a result, the grain
growth of KBT was restrained. However, there was
abnormal grain growth when the addition of CuO
reached a value of 4 wt%. The largest grain size was
more than 6 mm, possibly induced by the appearance
of the liquidoid in the sintering process because of the
higher weight percentage of CuO added.
According to the equation
qr ¼ ðqm =qt Þ  100; ð1Þ
the relative density (qr) can be calculated, where qm and
qt are the measured and theoretical densities, respect-
ively. The values of qr are 87.8%, 94.7%, 93.8%, and
88.3%, when the weights of CuO are 1, 2, 3, and
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4 wt%, respectively. It is known that relative density will
be higher when sintering temperature is higher if this is
lower than the critical temperature [19]. However,
relative density will decrease with increase in sintering
temperature, when that is higher than the critical tem-
perature. It is also known that the coarsening process
will predominate if the sintering temperature is higher
than the critical temperature, inducing a decrease in den-
sity [20]. In the experiment, the relative density of KBT
2 wt% CuO had a highest value when sintered at 1000
C
for 8 h. Further, the qr of samples with a fixed additional
weight percentage of 2 were 89.6%, 92.9%, and 90.5%
when they were sintered at 900
C, 1050
C, and 1100
C,
respectively, for 8 h. These results indicate when KBT
ceramics were sintered at 1000
C, the appropriate
additional level of CuO should be 2 wt%. We can now
maintain that the appropriate addition of CuO in the
sintering process decreases the required temperature
and increases densification.
Figure 4 shows the relation of dielectric constant
and temperature of KBT ceramics with the addition of
FIGURE 4.—The temperature dependence of dielectric constant of KBT
ceramics with different weight percentage of CuO. (a) 2 wt%; (b) 3 wt%;
(c) 4 wt%; (d) 1 wt%.
H.-Q. ZHANG ET AL.
different weight percentages of CuO. Temperature was
increased from room temperature to 500
C at a measur-
ing frequency of 10 kHz. The dielectric constant for all
samples shows obvious temperature dependence. First,
it increases when the temperature is lower than 382
C,
but the dielectric constant decreased when the tempera-
ture increased further. Obviously, the dielectric constant
behavior of KBT ceramics is of a diffuse type and all
samples had broad bands in the temperature range
350–420
C. The broad peak shoulders at about 382
C
indicate that there is a diffusion phase transition; this
is a common characteristic in solid solutions and
other disorder systems where the phase transition will
broaden [21]. The overlap of ferroelectric and non-
ferroelectric in some regions induces broad shoulders.
Also, in such systems, ferroelectric–paraelectric phase
transitions occur smoothly. Diffuse transitions exist over
the temperature zone of Tc. Ferroelectrics will show
distinctive dielectric and ferroelectric characteristics in
the temperature range of Tc. These phenomena originate
from disordered structure and fluctuations in compo-
sition in ferroelectric systems [22].
The dielectric constant of ferroelectric ceramics is
linked closely with the crystallite dimension and micro-
structure [23]. A large number of domains exist in grains
with different directions, which will suppress the dielec-
tric properties of samples. Smaller grain size will lead to
the presence of lower domains in grains [24]. Further,
the lower density of ceramics often suggests a lower
value of the dielectric constant. Induction of KBT
ceramics with the addition of 2 wt% CuO has the highest
value of dielectric constant. At the same time, stress will
be evident in the system when the ferroelectric ceramic is
cooled to room temperature (<Tc) [25]. If there are for-
mations of 90
domains with an appropriate arrange-
ment within the grains, the stresses will be abolished or
reduced. However, 90
domains are rejected if grain size
is fine. The rejection of 90
domains will induce large,
unrelieved stress, which finally suppresses dielectric
properties.
CONCLUSIONS
KBT ceramics were synthesized by a solid-state reac-
tion process with the addition of CuO. XRD results
show that the synthesized samples have a cubic perovs-
kite phase. The SEM results show that the addition of
CuO has a major influence on grain size and relative
density of KBT ceramics. KBT ceramics have the smal-
lest grain size and the highest relative density, when the
weight percentage of CuO added is 2%. There is abnor-
mal grain growth when the weight percentage of CuO
added reaches a value of 4 wt%, which may be induced
by the appearance of liquidoid in the sintering process.
Synthesized ceramics have the highest value of dielectric
constant at a temperature about 382
C. This behavior
originates from disordered structure and fluctuation in
composition in ferroelectric systems. Also, the grain size
and relative density of KBT ceramics have obvious
influences on electric properties.
 SYNTHESIS AND CHARACTERISTICS OF K0.5Bi0.5TiO3
FUNDING
This work is supported financially by the Natural
Science Foundation of NeiMengGu (2013MS0815).
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