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CERAMICS
INTERNATIONAL
Ceramics International 41 (2015) S481–S486
www.elsevier.com/locate/ceramint

Dielectric, mechanical, and microstructural characterization

of HA–BST composites
S. Inthonga, T. Tunkasiria, G. Rujijanagula, K. Pengpata, C. Kruea-Inb, U. Intathac, S. Eitssayeama,n
a
Department of Physics and Materials science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Faculty of Science and Technology, Chiang Mai Rajabhat University, Chiang Mai 50300 Thailand
c
School of Science Mae Fah Luang University, Chiang Rai 57100, Thailand
Received 26 October 2014; accepted 14 March 2015
Available online 31 March 2015

Abstract

Hydroxyapatite (HA) is an excellent inorganic biomaterial and has various applications because its structure is similar to the inorganic matrix
of human bone and dental enamel. In this present study, the HA–(Ba0.7Sr0.3)TiO3; HA–BST composites were synthesized by a solid state reaction
technique. The phase, densification, microstructure, mechanical and dielectric properties of HA–BST composites sintered at 1350 1C were
investigated. The HA–BST composite showed an increase in densification, Vickers hardness, Young's modulus and fracture toughness with
maximum value as 3.42 g/cm3, 5.01 GPa, 161.70 GPa, and 1.48 MPa m1/2, respectively. The average grain size was decreased from 12.09 μm for
a reference HA sample to 1.14 μm for the 30 wt% BST in HA–BST composites. The dielectric constant as a function of temperature and
frequency tend to increase with increasing BST contents.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: B. Composites; C. Dielectric properties; C. Mechanical properties; D. Apatite

1. Introduction significantly accelerate or decelerate bone-like crystal growth on

Many intensive studies have investigated the properties of
calcium phosphate with the objective of using in orthopedic and
dental applications in the future. The investigation revealed several
interesting properties such as good bioactivity, biocompatibility,
high wear resistance, osteoconductivity and the mineral component
similarity with nature mineral in bone and teeth [1–6]. However,
calcium phosphate has many forms and phase such as hydro-
xypatite (HA), biphasic calcium phosphate (BCP), beta tricalcium
phosphate (β-TCP), alpha tricalcium phosphate (α-TCP), and
unsintered apatite (AP), which are dependent on fabrication process
conditions [7]. Recently, electrical properties such as dielectric,
ferroelectric and conductivity of HA have been of interest because
these properties are linked to bioactivity property [3,8–11]. These
relations are interesting for many researches. Since Yamashita et al.
[9] reported that the induced surface charge of polarized HA can
n
Corresponding author.
E-mail address: sukum99@yahoo.com (S. Eitssayeam).
the surface deposition in simulated body fluid (SBF), depending on
electric polarization conditions, types and volume of surface charge
which are connected with dielectric properties. For improving
electrical and mechanical properties, the modified HA was focused
to study by doping and synthesizing composites with HA such as
Fe-doping [12], Cd-doping [7] and HA–ZrO2 [13], HA–Sr [14],
HA–BaTiO3 [15], HA CaTiO3 [16]. Especially, HA–BaTiO3 and
HA–CaTiO3 have been presented as a good substrate for apatite
growth with high osseointergration and osteoconction [15,17].
Therefore, the properties of hydroxyapative–perovskite composites,
only non-toxic chemical compound, are highly potential for
HA application due to their high polarizability and reasonable
biocompatibility.
BSTs (BaxSr1
xTiO3, 0oxo1) are ferroelectric materials
that have high dielectric, low dielectric loss and spontaneous
polarization. The temperature of changing ferroelectric phase to
paraelectric phase was determined by the substitution of Ba2 þ by
Sr2 þ in the A-site of perovskite structure (ABO3). Among BSTs,
Ba0.7Sr0.3TiO3 has a phase transition temperature of about 40 1C,

http://dx.doi.org/10.1016/j.ceramint.2015.03.205
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S482 S. Inthong et al. / Ceramics International 41 (2015) S481–S486
which is a high dielectric constant (εr  13,000) [18–20]. Th-
erefore, this material has high dielectric and still ferroelectric
phase at close to normal human body temperature.
Detailed literature survey reveals the new bone formation
has been found to be significantly improved on polarized
surface. For this significant context, many electroactive bio-
materials have been developed [15,17]. To our literature
reviews, a composite of HA–Ba0.7Sr0.3TiO3; HA–BST has
not yet been synthesized and their properties have not been
reported. Consequently, the effects of BST in HA–BST
composites were investigated and discussed compared with
other previous reports in this work.
2. Experimental
The nanocrystallinity of HA was performed by peroxide-
based route, with control pH at 9. Calcium nitrate solution
(Ca(NO3)2  4H2O, Sigma-aldrich), ortho-phosphoric acid 85%
(Merck) and hydrogen peroxide solution 30% (Qrec) were
used as the stating reagent. During the chemical reaction, the
solution pH of the control was at a constant value of 9 by
adding ammonium hydroxide solution 30% (J.T. Baker). The
obtained powders of HA are in the nano-range ( 60 nm). The
BST powders were prepared by conventional solid state
processing. The reagent grades of BaCO3 (99.9%, Sigma-
aldrich), SrCO3 (99.9%, Sigma-aldrich), and TiO2 (99.9%,
Sigma-aldrich) were used as starting material. The mixed
powers were calcined at 1150 1C for 4 h. The obtained powers
had perovskite structure and particle size about 0.9 μm. For the
preparation of the composite, the HA–xBST composites were
prepared by adding various amounts of BST contents with
x=0, 5, 10, 15, 20, 25, and 30 wt% in HA. The mixed powers
were ball milled in isopropanol for 24 h. This slurry was dried
and sieved to form homogeneous powders. These mixed
powders were then granulated using polyvinyl alcohol (PVA)
3 wt% organic binder and formed into discs, typically 10 mm
in diameter and 2 mm in thickness by cold uniaxial pressing.
The resulting discs were sintered in air at a temperature of
1350 1C in a step of 100 1C/hour (with soaking time of 3 h).
The polish of these ceramics was examined via an X-ray
diffractometer with Cu Kα radiation to check the phase
formation. Density of samples was measured using the
Archimedes method. The surface morphology and elemental
composition of the samples were then analyzed using a
scanning electron microscope (SEM) equipped with an energy
dispersive X-ray (EDX). Average grain size was determined
using the intercept method. Mechanical properties were studied
on a polished surface using a micro-hardness tester. For
dielectric measurements, the ceramics were coated with silver
paste electrodes on both sides of the pellets and the dielectric
property was measured using an impedance analyzer.
3. Results and discussion
Fig. 1 shows the XRD patterns of a reference HA, and
HA–BST composites ceramics. All studied samples were
analyzed by comparison of peak location to JCPDS database
Fig. 1. XRD analysis of HA–BST composite as well as a reference HA.
reference pattern spectra. The HA, α-TCP, and β-TCP phases
were detected in a reference HA and all HA–BST composi-
tes samples with reference numbers 09-0432, 09-0348, and 09-
0169 for HA, α-TCP, and β-TCP phases, respectively. It
should be noted that the decomposition of HA was observed
in reference HA and HA–BST composites. This result is in
agreement with previous reports [21,22]. In general, HA phase
transformation during thermal treatment consists of two
processes, which are dehydroxylation and decomposition.
Dehydroxylation to oxyhydroxyapatite proceeds at temperature
about 850–900 1C through the following equation [21]:
Ca10 ðPO4 Þ6 ðOHÞ2 -Ca10 ðPO4 Þ6 ðOHÞ2
2x Ox þ xH2 O ð1Þ
For above 900 1C, the decomposition process of HA can be
found according to the reaction in the following equation [22]:
Ca10 ðPO4 Þ6 ðOHÞ2 -2Ca3 ðPO4 Þ2 þ Ca3 ðP2 O8 Þþ CaO þ H2 O
ð2Þ
However, the perovskite structure of BST in HA–BST compo-
sites was shown at x4 5 wt%, according to JCPDS reference no.
01-089-0274. The intensity of BST structure peaks is increased
associated with BST contents in HA–BST composites. However,
phases of BST with xr 5 wt% cannot be observed due to the
infinitesimal of BST contents were nearly a limit of this XRD
instrument. The morphology and composition of BST were
analyzed by SEM and EDX as show in Fig. 3. The morphology
form of SEM showed clearly two phases in the matrix of the HA–
BST surface, i.e., HA phase and BST phase. The phase of HA and
BST was determined by EDX analysis. The spectra corresponding
to HA showed a peak corresponding to that of phosphorus and
calcium as shown in x¼ 15 wt% BST. The EDX pattern of small
grain size in a matrix of HA–BST composites at x¼ 10 wt%
showed a peak corresponding to the major elements present in
composites (Ba, Sr, and Ti) as expected from BST grain.
In this work, reference HA and HA–BST composites
samples were sintered with different sintering temperatures
for optimum sintering temperature condition. All samples were
 S. Inthong et al. / Ceramics International 41 (2015) S481–S486
Fig. 2. Bulk density and average grain size as a function of BST in the
HA–BST composite.
sintered at 1350 1C for 3 h, which produced the den-
sest ceramic samples. The bulk density of the as-sintered
HA–BST composites is shown in Fig. 2. It was observed that
the bulk density was increased from 2.98 g/cm3 to 3.42 g/cm3
for a reference HA to 30 wt% BST in HA–BST composites.
The increase of density in HA–BST may be because the
theoretical density of the constituent compounds of BST
(5.69 g/cm3) [18] is higher than that of HA (3.16 g/cm3 by
assuming the absence of any reaction between the constituent
phases), which is a normal phenomenon of density of
composite ceramics. This result indicated that the BST
promoted the densification of HA–BST composites.
The studied samples' surface morphology of HA–BST compo-
sites is shown in Fig. 3. The microstructure of all studied samples
showed dense ceramics without any cracks and fewer pores at the
grain boundaries. SEM analysis revealed that BST additions
produced a notable decrease in grain size of HA–BST composites.
An average value of grain size was determined by the intercept
method as shown in Fig. 2. The average grain sizes of the studied
samples decreased from 12.09 μm for a reference HA sample to
1.14 μm for the x¼ 30 wt% BST in HA–BST composites. This
result indicated that the addition of BST inhibited grain growth of
this composite. Moreover, both intergranular and intragranular
structures can be observed in HA–BST composites, which is
predominated by the intergranular structure. This phenomenon is
mostly found in the composites. During HA grain growth, residual
pores were removed throughout the sinter of the HA matrix.
Simultaneously, BST particles were trapped in the grain boundaries
(intergranular structure). This result is similar to the work reported
by Dubey et al. [16,17]. Therefore, the partial intergranular was
increased on increasing the BST contents. It should be noted that
the intergranular second phase small grain size acts to reduce the
grain size and pore and thus reinforces the grain boundaries.
The mechanical properties of the studied samples were
studied using Vickers hardness, Young's modulus and fracture
toughness. The mechanical properties of HA–BST compo-
sites are listed in Table 1. The results revealed that the
mechanical properties depended on the BST contents in the
HA–BST composites. The Vickers hardness values increased
from 4.35 GPa for a reference HA sample to 5.01 GPa for
x ¼ 30 wt% BST in HA–BST composites. Young's modulus of
samples increased with increasing BST content up to
S483
maximum at x ¼ 25 wt% BST (161.70 GPa) and then
decreased. Similarly, the trend of fracture toughness is mostly
Young's modulus values. The highest value was recorded at
1.48 MPa m1/2 for x ¼ 25 wt% BST. It should be noted that
mechanical properties such as Vickers hardness, Young's
modulus and fracture toughness have greatly increased, which
is comparison a reference HA. The increasing of hardness and
fracture strength can be explained by grain size reduction and
matrix grain boundary reinforcement [27]. However, the
decrease of Young's modulus and fracture toughness at x ¼ 30
wt% BST may due to the increase of BST producing an
increasing inhomogeneous structure and pore in the HA matrix
as shown in the SEM micrograph. However, the previous
reports [22,23] by other authors who studied a group of
calcium phosphate bioceramics demonstrated that the decom-
position of HA to TCP can lead to a significant decrease in
mechanical strength. The grain sizes increased on increasing
the temperature in the decomposition temperature range. For
our studies, the mechanical properties and grain sizes of the
HA–BST composites are mainly because of BST contents.
These results are similarly found in other composites of HA as
mentioned in Sprio et al. and Silava et al. [24,25].
The variation in the dielectric constant of HA–BST compo-
sites under investigation was measured as a function of
temperature between 30 1C and 200 1C. Fig. 4(a) shows plots
of dielectric constant versus temperature for reference HA and
HA–BST composites at 1 MHz. And the inset of Fig. 4(a)
shows temperature-dependent dielectric constant curve of BST
ceramics. It is revealed that dielectric constant increased on
increasing the BST contents. Moreover, in the high frequency,
the dielectric constant is weakly dependent on this temperature
range. The characteristics of dielectric constant curve for the
HA–BST composites agreed well with the work carried out by
Dubey et al. [16,28]. This result may be due to the develop-
ment of interfacial polarization in the presence of HA and BST
phases in composites with different electrical conductivities.
Fig. 4(b) shows the dielectric constant as a function of
frequency for reference HA and HA–BST composites. The
dielectric constant exhibited frequency dispersion in which
higher dielectric constants at lower frequencies are due to the
presence of conductivity and different polarizations types in
this material. Fig. 4(c) shows a comparison of dielectric result
with the theoretical estimations using parallel, series Wiener
bounds [28] and the logarithmic mixture rule [28], following
the equation
εc ¼ υHA εHA þ υBST εBST ð3Þ
1 υHA υBST
¼ þ ð4Þ
εc εHA εBST
log εc ¼ υHA log εHA þ υBST log εBST ð5Þ
where εc is the dielectric constant of the HA–BST composites,
υHA and υBST are the volume fractions of HA and BST, and εHA and
εBST are the dielectric constants of HA and BST, respectively. The
calculated dielectric constant was 12.58 for HA and 8102.47 for
BST ceramics, respectively. The dielectric constant of the
S484 S. Inthong et al. / Ceramics International 41 (2015) S481–S486

Fig. 3. Selected SEM images and EDX analysis of the microstructures of the HA–BST composite.

composites follows closely the series Weiner bound, which is was studied by Dubey et al.[29]. They reported that the cell could
similar to the result of HA–CaTiO3 composite for CaTiO3 less than easily proliferate in the proximity of the composites of HA-40 wt%
60 wt% [16]. In addition, the relation of the biocompatibility BaTiO3 and HA-40 wt% CaTiO3 ceramics, for which the
(in vitro) and electrical properties of HA–BaTiO3 and HA–CaTiO3 room-temperature dielectric constants (1 kHz) were 18.7 and
 S. Inthong et al. / Ceramics International 41 (2015) S481–S486 S485

22.7, respectively. It should be noted that the dielectric constants of were in the range of 2.98–3.42 g/cm3 and 12.09–1.14 μm,
HA–BST composites are nearly these dielectric values, which is respectively. The density of composites increased as a function
higher than the dielectric constant of dry human bone (9.2 at of BST contents while the average grain size decreased. In
1 kHz) [29]. addition, the mechanical and dielectric data indicated that BST
effectively improved both of these properties. The highest
4. Conclusions Vickers hardness and room temperature dielectric constants
(1 kHz) are 5.01 GPa and 32.87 for x ¼ 30 wt% BST, respec-
The composite of HA–BST ceramics was successfully tively. The highest values of Young's modulus  161.70 GPa
fabricated using conventional solid state processing with and fracture toughness  1.48 MPa m1/2, respectively, were
optimum sintering temperature at 1350 1C. This study inves- obtained for the sample with x¼ 25 wt% BST. Based on these
tigated the physical, mechanical and dielectric properties of results, this study suggests that BST had a significant effect on
these composites. All samples showed a decomposition of HA the properties of HA–BST composites.
in this sintering temperature. Density and grain size values
Table 1 Conflict of interest
The mechanical properties of HA–BST composites.
We declare that we do not have any commercial or associative
wt% BST Vickers hardness Young's modulus Fracture toughness interest that represents a conflict of interest in connection with the
(GPa) (GPa) (MPa m1/2)
work submitted.
0 4.35 30.73 0.59
5 4.56 59.10 0.66
10 4.62 80.80 0.91 Acknowledgment
15 4.69 78.67 1.04
20 4.79 110.50 1.28 The authors would like to thank Research and Researchers for
25 4.96 161.70 1.48 Industries (RRI) under the Thailand Research Fund (TRF), the
30 5.01 96.69 1.11
National Research University Project (NRU) under Thailand's
Human – 3–30 [25] 2–4 [26]
bone office of the Higher Education Commission (OHEC), Faculty of
Science, Chiang Mai University and Graduate School Chiang

Fig. 4. Temperature dependence of dielectric constant at 1 MHz (a) and frequency dependence of dielectric constant measured at 37.5 1C (b) as a function of BST.
A comparison of dielectric constant of HA–BST composites with theoretical estimation of Wiener bounds and logarithmic mixture rule at 30 1C and 1 MHz.
S486 S. Inthong et al. / Ceramics International 41 (2015) S481–S486
Mai University, Thailand, and National Research Council of
Thailand (NRCT) for financial support.
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