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 Mater. Res. Express 5 (2018) 095510 https://doi.org/10.1088/2053-1591/aad8a4

PAPER

Grain size effect on electric properties of novel BaTiO3/PVDF

composite piezoelectric ceramics
RECEIVED
29 May 2018
REVISED
31 July 2018
ACCEPTED FOR PUBLICATION
Bochao Zhou, Rui Li, Jun Cai, Jing Xu, Zhenhua Zhao and Jianzhong Pei
7 August 2018 School of Highway, Chang’an University, Xi’an, Shaanxi, 710064, People’s Republic of China
PUBLISHED
E-mail: peijianzhong@126.com
20 August 2018
Keywords: BaTiO3/PVDF composites, calcining, piezoelectric properties, dielectric properties

Abstract
Researches on barium titanate ceramics have been prosperous since its lead-free feature. In this paper,
we classified the BaTiO3 ceramics into four different groups to study the effect of grain size on the
electrical properties. According to the analysis of element, size distribution, conductivity, piezo-
electric, and dielectric properties, we found that group #3, compounded distribution where the
majority is small size, exhibited the best performance among four groups. The dielectric constant εr
and piezoelectric strain constant d33 of BaTiO3/PVDF composites reached the maximum values
which were 168.86 and 28pC/N, respectively, and dielectric loss tanδ maintained around 0.02.

1. Introduction

Since the Curies Brothers discovered piezoelectric effect in 1880, the piezoelectric materials have been developed
rapidly, which can be divided into piezoelectric single crystals, piezoelectric ceramics (polycrystalline),
piezoelectric polymers and piezoelectric composites according to the chemical composition and morphology
[1]. Due to the features such as simple preparation process, convenient composition control, excellent
piezoelectric performance, and low-cost. Lead-based piezoelectric ceramics are currently the most widely used
piezoelectric materials. As heavy metal element, the lead element has toxicity if into body, which would damage
the human nervous system severely. If it spread in the nature, it would pollute the ecological environment [2–6].
Zhang et al compared the performance of lead-free materials with leaded materials, it was concluded that
although the piezoelectric properties of lead-free materials are inferior to those of lead materials, there are
research properties on high-temperature properties [7]. Therefore, the research and development of the lead-
free piezoelectric ceramic, the eco-friendly material, is of great significance [8, 9].
As being the earliest discovered piezoelectric ceramic material, application of Barium titanate (BaTiO3)
ceramics is limited due to its low piezoelectric properties, low Curie temperature, and poor temperature
stability. In recent years, Japanese researchers Takahashi H, Karaki T et al have prepared high-voltage electrical
properties of BaTiO3 ceramics with the dielectric constant (d33) values of 360 pC/N, 480 pC/N, and 788 pC/N,
respectively [10–14]. Zhang et al adopted a conventional solid-state reaction method to optimize the preparation
process and obtained high-purity BaTiO3 ceramic with d33 up to 419 pC/N [15]. Recent research advances
indicated that BaTiO3-based piezoelectric ceramics have potentials to replace the lead-based piezoelectric
materials because of the high piezoelectric properties.
Many researches have shown that the grain size of ceramics plays a key role in its piezoelectric properties
[16–22]. The grain size of BaTiO3 ceramics has a significant effect on d33. It was found that the dielectric constant
of BaTiO3 increased with the decrease of the average grain size firstly, reached the maximum in the particle size
range of 0.8–1.1 micron, and then decreased rapidly as the grain size decreased in further. The same
phenomenon can also be observed within the piezoelectric material [23–25]. However, Ding, S H et al found that
the maximum value of d33 appeared at 8.9 μm, ranging from the ultra-fine powder particle sizes 0.56 to 120 μm
[26]. Those differences indicate that the processing conditions may have a significant effect on the piezoelectric
properties of BaTiO3 ceramics.

© 2018 IOP Publishing Ltd

Mater. Res. Express 5 (2018) 095510 B Zhou et al

Dong et al studied the effect of PZT particle size distribution on the electrical properties of PZT/PVDF
composites. The experimental results that when the fraction of compounded particles size was 70%, the
maximum piezoelectric strain constant was 75 pC/N [27]. The research on the grain size effect of piezoelectric
ceramics mostly focuses on single grain size. However, there is rare research on the compounded particle size
[28, 29]. At present, there are few studies focused on the influence of the grain size of piezoelectric ceramics on
the electrical properties of BaTiO3-based composites and the further exploration is needed [30–33].
In this paper, we proposed that BaTiO3 ceramic grain can be compositely distributed to form composites
material, through the method of particle size composition without changing the material of the raw materials.
PVDF was selected to form composites with BaTiO3 ceramic according to literatures [34–38]. This composites
material can improve the electrical properties of composites materials while improving their overall structural
properties. In this paper, the influence of the grain size of BaTiO3 ceramics on the composites is studied on the
micro-morphology and electrical properties. It would deepen the understanding of the grain size effect on the
influence mechanism of piezoelectric composites.

2. Experimental details

2.1. Materials
The BaTiO3 ceramics (ρ=6.017 g cm−3) with a specific grain size was custom-made by Fujian Quanzhou Qijin
New Materials Technology Co., Ltd, Fujian, China. The PVDF powders (ρ = 1.77 g cm−3, Tm = 167 °C) were
provided by Shanghai 3F New Materials Co., Ltd, Shanghai, China. All other chemical reagents used in this study
were provided by Shanghai Experiment Reagent Co., Ltd.

2.2. Preparation
Firstly, BaTiO3 ceramics were divided into four groups according to the grain size distribution: single grain size
of #1, whose ceramics grain size is around 100 μm, and #2, whose ceramic grain size is around 1 μm. For the
compounded grain size of #3, the percentage of small grain size is high while the percentage of large grain size is
low. The #4, the percentage of small grain size is low while the percentage of large grain size is high. Then, four
groups of BaTiO3 ceramics were calcined for three hours in an opened crucible, the calcining temperature was
950 °C and the heating rate was 5 °C min−1. BaTiO3 ceramics and PVDF powders were mixed with the solvent
of absolute ethanol for about 40 min and stove in oven at 80 °C. After that, BaTiO3/PVDF composites were
compressed into a disk of 13 mm in diameter and 1mm in thickness by the hot-press method with the pressures
of 25 MPa at 180 °C for 30 min. Finally, the samples were polarized in silicone oil at 120 °C for 30 min at
3 kV mm−1. These samples were taken out to conduct the performance test after being stewed for 24 h.
0.6BaTiO3/0.4PVDF composites with relatively high piezoelectric properties and good mechanical properties
were prepared.

2.3. Characterizations
The grain size distribution of the BaTiO3 ceramic grains were measured by a Malvern Mastersizer 2000 laser
particle size analyzer. Both the element analysis and microscopic appearance of the cross section (#1, #2, #3,
#4) of BaTiO3/PVDF composites were investigated by S-570 environmental scanning electron microscope. The
dielectric properties of BaTiO3/PVDF composite specimens with different grain size distributions (#1, #2, #3,
and #4) were analyzed by IM-3536 LCR meter, and the piezoelectric properties were measured by ZJ-3AN static
tester.

3. Results and discussion

3.1. Element analysis

As shown in figure 1, the main elements of BaTiO3 ceramics included C, O, Ba, and Ti and the element contents
are correspondingly 31.58%, 30.61%,28.11%, and 8.55%. Besides, the impurity element consists of Al, Si, Co,
etc. Compared with PZT ceramic whose lead content is more than 60%, BaTiO3 ceramics can be regarded as the
eco-friendly ceramic materials due to the non-existence of heavy metal element.

3.2. Analysis of grain size distribution of BaTiO3 ceramics

Figure 2 shows the different grain size distributions of BaTiO3 ceramics of #1, #2, #3, and #4. The grain size
distribution of #1 and #2 BaTiO3 ceramic grains are rather concentrate, and #1 is a large-grain-size BaTiO3
ceramic with an average size around 100 μm. The perovskite structure within #1 BaTiO3 ceramic is with higher
completeness due to the integral crystal structure, which leads to the strong continuity of the internal charge
carrier migration channel.

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 1. Element content of BaTiO3 ceramics.

Meanwhile, among the piezoelectric composite consist of large grain size, the interface area between the
ceramic phase and the polymer matrix is small in, so that the interfacial bonding defects of the two phases are
correspondingly small as well as the dielectric loss is low. However, the large-size crystal structure corresponds to
the larger domain length, resulting in the worse piezoelectric performance, while the large- size BaTiO3 ceramic
grains is of lower purity. Those impurities will also affect the piezoelectric properties of the composites. The #2
is a small grain size BaTiO3 ceramic with an average grain size around 1 μm. It has higher crystal purity, less
damage to the crystal structure in the process of compounding with the polymer, and smaller grain size makes
the polymer grip well and the compatibility of the substrate interface is better between ceramic phase and
polymer. At the same time, the smaller grain size corresponds to the smaller domain length, and the smaller the
domain length, the better the piezoelectric performance. However, small-size BaTiO3 ceramics are prone to
agglomerate, leading to the non-uniform distribution of ceramic grains and influence on the piezoelectric
performance. Otherwise, the smaller grain size has a larger specific surface area and a larger area of bonding with
the polymer, which is not conducive to charge carrier migration. Therefore, the grain size effect of BaTiO3
ceramics depends on the contribution of its various influencing factors to the performance, and there is no
absolute direct influence of the grain size on the performance.
The #3, #4 BaTiO3 ceramics are compounded grain size. For grain size distribution #3, the small-size grain
occupied the higher percentage while large-size grain occupied the lower percentage. For grain size distribution
#4, the small-size grain occupied the higher percentage while large-size grain occupied the lower percentage.
For those two types of grain size combinations, BaTiO3 ceramics performs a better filling effect in the polymer
matrix, large-grain ceramics form the space skeleton, small-grained ceramics are filled among them, and the
spatial structure forms a fuller combined effect. At the same time, this type of combination retains the
advantages of the complete perovskite structure of large grain size ceramic grains and avoids the defects of large
specific surface area of the small grains, a large area of contact with the polymer, and also increases the
transmission and transition continuity of charge between the ceramic grains.
Therefore, the combination and uniform distribution of grain size would theoretically improve the
structural composition of BaTiO3 ceramic as well as effectively enhance the electric properties. The performance
would be better than the piezoelectric composites with single-sized distribution.
Figure 3 is a sectional SEM image of BaTiO3/PVDF composites in different grain size distributions of
BaTiO3 ceramics. Figures 2(a)–(d) are SEM cross-sectional views of composite materials corresponding to grain
size distributions of #1, #2, #3, and #4, respectively. As shown in the figure, figures 3(a), (b) is a cross-
sectional view of BaTiO3/PVDF composite material composed of a single ceramic grain size. Figure 3(a) is a
cross-sectional view of composite material with large grain size. Large-grain ceramics are uniformly distributed
in the polymer and form a good space skeleton, the squeezing effect between the grains is rather strong.
However, since the grains have more angular contact, the uniform coating effect of the polymer is poor. The
structure is jammed while the whole structure is rather loose. Figure 3(b) is a cross-sectional view of composite
with small grain size. The ceramics is distributed in the polymer and the polymer is wrapped in a floc and
wrapped around the ceramic grains. The phenomenon of agglomeration is not obvious.
In figure 3, since the specific area of the grain is rather large and the ceramic grains cannot be fully coated by
polymer, there lead to certain deficit void of the interface. Figures 3(c) and (d) are cross-sectional views of
composites of BaTiO3/PVDF composites, respectively. Ceramics grains are distributed in the polymer matrix
and the polymer is coated on the outer surface of the grains. Large grains form the space skeleton structure and

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 2. Grain size distribution of BaTiO3 ceramics.

small grains of ceramic filled between them. In figure 3(c), there are many ceramics with small grains, so the
filling effect of small grains between large grains is better, but there is a certain phenomenon of agglomeration,
and the connection structure of small and large grains is coordinated. However, in figure 3(d), there are many
large-size grains, which are angularly inlaid with each other, and small grains are less. Small grains cannot be

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 3. Micro topography of BaTiO3/PVDF composite with different grain size distributions.

Figure 4. Conductivity diagram of BaTiO3/PVDF composite with different grain size distributions.

entirely filled between large grains. The voids between the interfaces are serious, and the overall structure of the
composite is relatively loose.

3.3. Conductivity
Figure 4 shows the relation between electric conductivity of BaTiO3/PVDF composites and the grain size
distribution of BaTiO3 ceramics. It can be seen from the bar graph that the conductivity σ of the BaTiO3/PVDF
composite composed of a single grain size distribution (#1, #2) is smaller than the σ of compounded grain size
(#3, #4). The composite with smaller grain size (#1) BaTiO3 ceramics has a higher σ than composites with
larger grain size (#2). This is because compounded the good overall structural continuity of the BaTiO3
ceramics with compounded grain size, with the large grain size forming a space skeleton the small grain size
filling in large grain size voids, and grains connected with each other, to increase the charge carrier mobility
transition channels, so the overall σ of the composites is higher. The composite grains with small grain size are
more angularly connected to each other, and the ceramic grains are uniformly distributed in the polymer, so the
movement distance between the charge carriers is shortened. The contact between the ceramic grains and the
corners is larger than that of the large grain size, and provides more channels for carrier transitions and
movements, and the impurity of large-grain ceramic crystal structure also affects the movement of charge
carriers. So, the conductivity of BaTiO3/ PVDF composites with smaller grain size is higher than that of larger
grain size.

3.4. Dielectric properties

Figure 5 shows relation between relative dielectric properties and BaTiO3 grain size distribution of
BaTiO3/PVDF composites. From figure 5(a), the εr value of BaTiO3/PVDF composites made from

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 5. Relation between dielectric properties and BaTiO3 grain size distribution of BaTiO3/PVDF composites at 1000 Hz. (a)
Relation between relative dielectric constant (εr) and BaTiO3 grain size distribution of BaTiO3/PVDF composite. (b) Relation between
dielectric loss (tan δ) and BaTiO3 grain size distribution in BaTiO3/PVDF composite.

compounded grain-size BaTiO3 ceramics, #3 and #4 both are higher than 160 and maximum up to 168.86. The
maximum εr value of BaTiO3/PVDF composites made from single grain-size BaTiO3 ceramics, #1 and #2, is
148.83. Comparing with #1 and #2 BaTiO3 ceramics, the dielectric properties of #3 and #4 BaTiO3 ceramics
have been improved after compounding the grain size without special treatment on the material of the ceramic
itself. The dielectric properties of BaTiO3/PVDF composites with #3 grain size distribution are higher than #4.
At the same time, it was found that the ceramics with smaller grain size are superior to ceramics with larger grain
sizes in the BaTiO3/PVDF composites. As shown in the figure, the εr value of the #2 grain size distribution is
better than that of the #1 grain size distribution. This is mainly because large-diameter ceramic materials have a
high internal porosity and a rather low purity, high content of those materials, which seriously affect the
polarization effect of piezoelectric ceramics. Moreover, the large grain size ceramic grains have the longer
domain lengths than the smaller grain size ceramic grains and many studies have shown that longer domains
correspond to lower electrical properties. From figure 5(b), it can be found that the tanδ value of the grain size
compounding composite is less affected, and the tanδ value is about 0.02, which indicates that the grain size
compounded method not only improves the overall εr value of the composite, but also have slight impact on the
tan δ value of the composite.
Figure 6 shows the trend of relative permittivity value (εr) of BaTiO3/PVDF composites made from BaTiO3
ceramics, #1, #2, #3, #4, with different grain size distributions at different test frequencies. As can be seen in
the figure 6, The εr values of BaTiO3/PVDF composites made from BaTiO3 ceramics with different grain size
distributions tend to decrease with increasing test frequency. Moreover, the εr value of BaTiO3/PVDF
composites made from compounded size (#3, #4) is higher than the εr value of composites made from single
size (#1, #2). When the test frequency f is lower than 10 k, the εr value of the composite shows a slight
decreasing trend with the increase of the test frequency, showing the better stability of frequency measurement.
When the frequency f is larger than 10 k, the εr value of the composite still decreases as the frequency becomes
larger, but this decreasing trend gradually become larger.
Figure 7 shows the trend of dielectric loss (tan δ) of BaTiO3/PVDF composites made from BaTiO3 ceramics,
#1, #2, #3, #4, with different grain size distributions varied with test frequencies. It is observed that the tanδ
value of the composite tends to increase as well as the test frequency, and its increasing trend increases gradually.
The trends of tanδ values of the composites with different grain size distributions are the same and have little
difference from each other. When the test frequency f>10 k, the tan δ value of the composites increase slightly

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 6. Relation between εr value-frequency curve and BaTiO3 grain size distribution of BaTiO3/PVDF composite.

Figure 7. Relation between tan δ value-frequency curve and grain size distribution of BaTiO3 in BaTiO3/PVDF composite.

with the increase of the test frequency, showing better frequency stability, and the value around 0.02, showing a
low dielectric loss and good frequency stability, which will produce lower Joule heat during production use.
When the test frequency f is larger than 10 k, the tan δ value of the composites still increase as the testing
frequency get increased, but its increasing trend changes significantly and gradually increases, which is also due
to the accumulation and migration of charge carriers.

3.5. Piezoelectric properties

Figure 8 shows the relationship between piezoelectric properties and the BaTiO3 grain size distributions,
piezoelectric strain constant d33 and piezoelectric voltage constant g33. From figure 8(a), BaTiO3 ceramic grain
size distribution can improve d33 value of composites obviously. It increased from 15 pC/N in the #1
distribution to 28 pC/N in the distribution #3, increased about 86.7%. At the same time, the d33 value of
BaTiO3/PVDF composite made from compounded size (#3, #4) is significantly higher than the d33 value of
composite made from single size (#1, #2). The piezoelectric properties of the small grain size distribution (#2)
of BaTiO3 ceramics are superior to the large grain size distribution (#1), and the increase is smaller by about
26.7%. This is because the large grain size BaTiO3 ceramics have the entire perovskite crystal structure, but larger
ferroelectric domain reduces the piezoelectric properties. The larger the pores of the ceramic grain size internal
structure, the greater the impurity content, leading to the less contact between the corners of the composite and
loose structure. These are not propitious to the performance of the piezoelectric properties. While the smaller
grain size distribution of BaTiO3 ceramics is evenly distributed in the polymer matrix. The polymer can achieve a
better coating effect with the smaller grain size, making the interface between the ceramic phase and the polymer
matrix have better compatibility. Eliminating of more interface defects and voids contributes significantly to the
polarization process of composites. This combination method has a great influence on the improvement of the
piezoelectric properties of the composite without changing the characteristics of the raw materials. As can be
seen in figure 8(b), the change in the g33 value of the BaTiO3/PVDF composite as the BaTiO3 ceramic grain size
distribution is the same as the d33 value. This is because the g33 value is determined by both the d33 value and the ε

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Figure 8. Effects of BaTiO3 grain size distribution on the piezoelectric of BaTiO3/PVDF composites. (a) Relation between piezoelectric
strain constants (d33) and BaTiO3 grain size distributions of BaTiO3/PVDF composite. (b) Relation between piezoelectric voltage
constants (g33) of BaTiO3/PVDF composites plotted against the grain size distribution of BaTiO3.

value. The g33 value is positively correlated with the d33 value of the BaTiO3/PVDF composite and negatively
related to the ε value of the composite. Therefore, the piezoelectric voltage constant also achieved a large value of
18.74 mV*m/N in the #3 distribution.

4. Conclusion

This paper selects 0.6BaTiO3/0.4PVDF composite with good piezoelectric properties. The grain size effect of the
ceramic in the composite was explored by adjusting the grain size composition of the ceramic phase. The
influence of the grain size and the different compounded grain size of the BaTiO3 ceramic on the composite
electrical properties was studied, drawing the following conclusion:

(1) Compared to BaTiO3 ceramics with a single size distribution (#1, #2), the BaTiO3/PVDF composites
made from the compounded grain size distribution (#3, #4) have the better ceramic grain connectivity, the
higher interlocking degree, and the denser microstructure.
(2) The BaTiO3/PVDF composites prepared by the compounded grain size distribution (#3, #4) have better
piezoelectric properties and dielectric properties than the single grain size distribution (#1, #2). The
relative permittivity εr increases from 143.26 in the #1 distribution to 168.86 in the #3 distribution,
increasing by approximately 17.9. The value of piezoelectric voltage constant d33 increases from 15pC/N of
#1 distribution to 28pC/N of #3 distribution, increasing about 86.7%, and the dielectric loss tanδ value
was at a low level around 0.02.
(3) The BaTiO3/PVDF composites with small size takes majority exhibit the better performances on electrical
properties than the large-size one. The relative permittivity εr increases from 143.26 with the large-grain size
distribution (#1) to 148.83 with the small-grain size distribution (#2). The piezoelectric voltage constant
d33 increases from 15pC/N of #1 distribution to 19pC/N of #2 distribution.

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Mater. Res. Express 5 (2018) 095510 B Zhou et al

Acknowledgments

This work was supported by the Special Fund for Basic Scientific Research of Central College of Chang’an
University (Nos. 300102218413, 310821153502 and 300102218405), the Department of Science &Technology
of Shaanxi Province (Nos. 2016 ZDJC-24 and 2017KCT-13).

ORCID iDs

Jianzhong Pei https://orcid.org/0000-0002-1994-5819

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