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Journal of the European Ceramic Society 33 (2013) 3445–3453

Dielectric and electrical conductivity properties of multi-stage spark plasma

sintered HA–CaTiO3 composites and comparison with conventionally
sintered materials
Ashutosh K. Dubey 1 , P.K. Mallik 1 , S. Kundu, B. Basu ∗
Materials Research Centre, Indian Institute of Science, Bangalore 560012, India
Received 13 March 2013; received in revised form 5 July 2013; accepted 13 July 2013
Available online 8 August 2013

Abstract
One of the different issues limiting the wider application of monolithic hydroxyapatite (HA) as an ideal bone replacement material is the lack
of reasonably good electrical transport properties. The comprehensive electrical property characterization to evaluate the efficacy of processing
parameters in achieving the desired combination of electroactive properties is considered as an important aspect in the development of HA-based
bioactive material. In this perspective, the present work reports the temperature (RT-200 ◦ C) and frequency (100 Hz–1 MHz) dependent dielectric
properties and AC conductivity for a range of HA–CaTiO3 (HA–CT) composites, densified using both conventional pressureless sintering in air as
well as spark plasma sintering in vacuum. Importantly, the AC conductivity of spark plasma sintered ceramics [∼upto 10−5 ( cm)−1 ] are found to
be considerably higher than the corresponding pressureless sintered ceramics [∼upto 10−8 ( cm)−1 ]. Overall, the results indicate the processing
route dependent functional properties of HA–CaTiO3 composites as well as related advantages of spark plasma sintering route.
© 2013 Elsevier Ltd. All rights reserved.

Keywords: Hydroxyapatite; Calcium titanate; Spark plasma sintering; Dielectric properties

1. Introduction as CaTiO3 and BaTiO3 attracted major scientific attention in

Hydroxyapatite (HA) is well known as a highly biocompat-
ible and bioactive ceramic that promotes bone growth in vivo.1
However, poor electrical and mechanical properties limit the
application of monolithic HA as an implant material for
orthopaedic applications. The addition of ceramic/metallic rein-
forcement (mullite, Ti) has been studied extensively to improve
the mechanical properties of HA.2–6 It is known that the natu-
ral bone is a piezoelectric material in vivo that generates the
electric potential upon the application of mechanical stress,
which helps in bone metabolism and growth.7,8 To this end,
it has been demonstrated that the electrical charges on bio-
material surfaces can enhance the osteobonding.9,10 The new
bone formation has been found to be significantly improved on
negatively charged surfaces.11 Because of high polarizability
and reasonable biocompatibility, few of the perovskites, such
∗ Corresponding author. Tel.: +91 80 2293 3256.
E-mail address: bikram@mrc.iisc.ernet.in (B. Basu).
1 These authors contributed equally to this work.
the context of the development of electroactive biomaterials.
Among these, CaTiO3 (CT) is reported as a good substrate for
apatite growth with the potential to enhance osseointegration
and osteoconduction.12,13
Despite significant bioactivity of HA, the development of
HA-based electrically active materials can provide the improved
functional response of the prosthetic implants. Also, reasonable
substrate conductivity facilitates better cell-to-cell signalling
processes involved in various cell fate processes (prolifera-
tion, differentiation etc.). In this context, our research group
recently reported the substrate conductivity dependent mod-
ulation of myoblast proliferation and differentiation on spark
plasma sintered HA–CaTiO3 composites in vitro.14 The present
work focuses on the evaluation of dielectric and electrical prop-
erties for a range of HA–CaTiO3 composites, synthesized using
innovative multi stage spark plasma sintering (SPS) as well as
conventional pressureless sintering routes.
The main advantage of using SPS technique over conven-
tional sintering route is to activate the different densification
mechanisms by enhancing the mass transport and diffu-
sion, which considerably reduces the processing time and

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3446 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453

Table 1
Multi-stage spark plasma sintering conditions and relative density of HA–CT
composites. All the powder compacts are held at each temperature for 5 min.
The pressure applied during sintering was 50 MPa, except for HA (30 MPa).
Composition Sample Sintering temperature (◦ C) Sinter density
designation (% ρth )

Pure HA HA 850 ◦ C/950 ◦ C/1100 ◦ C 99.4

Pure CT CT 950 ◦ C/1100 ◦ C/1200 ◦ C 98.2
HA-20 wt% HA20CT 950 ◦ C/1100 ◦ C/1200 ◦ C 99.3
CaTiO3
HA-40 wt% HA40CT 950 ◦ C/1100 ◦ C/1200 ◦ C 99.0
CaTiO3
HA-60 wt% HA60CT 950 ◦ C/1100 ◦ C/1200 ◦ C 99.3
CaTiO3
HA-80 wt% HA80CT 950 ◦ C/1100 ◦ C/1200 ◦ C 98.6
CaTiO3

Fig. 1. The heating profile of the HA–CaTiO3 powder compact during spark
plasma sintering.
temperature.15 The multistage SPS route, which involves hold-
ing the powder compact at one/two intermediate temperatures
prior to the final sintering temperature, has been demonstrated
to produce dense oxide and non-oxide ceramics.16–18 It can be
reiterated here that in the context of densification of HA-based
composites, SPS process inhibits grain growth, decomposi-
tion of HA phase as well as restricts the sintering reactions
between HA and reinforcement phase.19 Further, the dielec-
tric and electrical properties of spark plasma sintered HA–CT
composites have been compared with those of the pressure-
less sintered HA–CT composites to demonstrate the efficacy
of SPS route in achieving a better combination of functional
properties.
2. Experimental
2.1. Materials processing and microstructural
characterization
The starting powders of HA [Ca10 (PO4 )6 (OH)2 ] and crys-
talline calcium titanate (CaTiO3 ) were synthesized using wet
precipitation route 20 and mechanical activation of a mixture
of CaO and TiO2 (anatase), respectively.21 A range of HA–CT
composites were prepared by adding the varying amounts of
CaTiO3 (0, 20, 40, 60, 80,100 wt%) to HA. The powder mix-
ture with desired HA: CaTiO3 ratio was ball milled (Fritsch,
Pulverisette 1583, Germany) for 16 h using agate balls and
jars as grinding media, which allows homogeneous mixing as
well as reduces the initial particle size. The innovative multi-
stage spark plasma sintering technique (MSSPS) (Dr. Sinter,
Model 515S, SPS syntax Inc., Japan) was adopted to con-
solidate the composite powders. The powder compact was
held for 5 min at each of the temperatures of 950 ◦ C, 1100 ◦ C
and 1200 ◦ C, respectively, which was then followed by fur-
nace cooling (Fig. 1). However, the holding temperatures for
pure HA were 850 ◦ C, 950 ◦ C and 1100 ◦ C, respectively with
similar holding time. The heating rate was 100 ◦ C/min. The
pressureless sintering of HA–CT composites was performed
at 1400 ◦ C for 4 h in air with heating and cooling rates of
5 ◦ C/min, while pure HA was sintered in air at 1200 ◦ C for
2 h. Finally, all the HA–CT sintered samples were mirror
polished for microstructural, dielectric and electrical character-
ization.
The bulk density of the HA–CT composites was measured
using Archimedes’s principle. The theoretical density of the
composites has been calculated assuming the absence of any
reaction between the constituent phases. In order to deter-
mine the presence of different phases due to the dissociation
of HA or the reaction among constituent phases, the sintered
HA–CT composites were analyzed using XRD (Brucker Xpert
diffractometer) with Cu-K␣ radiation (λ = 1.54 Å). ´ The data
◦
were collected over the 2θ range of 20–80 with a scan speed
of 0.5◦ per min and a step size of 0.02◦ . The microstructure
of the etched samples was observed using scanning electron
microscope (SEM, FEI Quanta 200). The SPSed samples were
chemically etched using anhydrous citric acid and distilled water
in the ratio of 8:10 (by mass) with 2–3 drops of hydrofluoric
acid (HF) for about 5 min. The conventionally sintered sam-
ples were thermally etched at a temperature of 100 ◦ C lower
than the respective sintering temperature. For transmission elec-
tron microscopy (TEM) analysis, electron transparent ultrathin
samples of 0.1 ␮m or lower thickness were machined using ultra-
sonic disc cutter, which was then followed by dimpling and
precision ion polishing (PIPS, Gatan 691). The TEM (Tecnai
G2 ) was used at 200 kV.
In order to analyze the surface chemistry, selected SPSed
ceramics were examined using X-ray photoelectron spec-
troscopy (XPS, Thermo Scientific, model – Multilab 2000).
The measurement was performed using Al-K␣ radiation
(1486.6 eV). The binding energies were calibrated with respect
to C (1s) at 285 eV with a precision of (±0.1 eV). XPS results
were analyzed on the basis of binding energies of Ti2p, O1s and
Ca2s peaks.
2.2. Dielectric and electrical characterization
For dielectric and electrical measurements, the polished
samples of thickness 1–2 mm were coated with silver paste
 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453 3447

samples were heated at a heating rate of 2 ◦ C/min. The dielec-

tric constant (εr ) was calculated using the following formula,

C×d
εr =
ε0 A
where C, d and A are the capacitance, thickness and area of
the sample, respectively and ε0 is the dielectric constant of the
free space (=8.854 × 10−12 F m−1 ). The dissipation factor (D)
has been recorded directly from the instrument. AC conductivity
(σ ac ) was calculated using the following relationship,
G×d
σac = ( cm)−1
A
where G (=ωCD), d and A are the conductance, thickness and
area of the sample, respectively.
Fig. 2. XRD analysis of the spark plasma sintered HA–CT composites as well
as pure HA and CT. 3. Results

followed by curing, which acts as electrodes. The capacitance 3.1. Densification and microstructure
and dielectric loss were measured as a function of frequency
(100 Hz–1 MHz) from room temperature (RT) to 200 ◦ C by The sinter density data and the respective sintering condi-
precision impedance analyzer (Wayne Kerr 6500B, UK). The tions are provided in Table 1. It is clear that multi-stage SPS

Fig. 3. SEM images of polished and chemically etched microstructure of spark plasma sintered ceramics (a) pure CT, (b) HA80CT, and (c) pressureless sintered
HA40CT composite (thermally etched).
3448 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453

with total sintering duration of less than 30 min can result in

about 99% of theoretical density (ρth ) in the HA–CT composites
as well as in HA monolith. However, the pressureless sintering
of HA–CT composites revealed the maximum density of about
94% ρth at the optimal sintering temperature of 1400 ◦ C for
4 h.13 From the above, the efficacy of multi-stage SPS in den-
sifying HA–CT composites can be realized. Fig. 2 shows the
results of XRD analysis for all the SPSed samples. The traces
of TiO2 were found in the sintered samples, which might be due
to excess TiO2 , left during the mechanochemical synthesis of
CaTiO3 . Importantly, the XRD pattern of the SPSed samples
did not show any detectable presence of ␤-tricalcium phosphate
(␤-TCP). In all the composites, HA and CT are retained after
SPS processing. In contrast, the partial dissociation of HA to
␤-TCP as well as formation of other secondary phases, such as
CaO and TiO2 were observed in pressureless sintered HA–CT
composites.13 The pure HA generally decomposes into TCP
at temperature above 1300 ◦ C in air.22 However, the addition
of secondary phases as well as sintering in vacuum (such as
SPS) reduces the decomposition temperature of HA. The SPS
route inhibited the decomposition of HA into ␤-TCP due to
faster heating rate and lower sintering temperature. From SEM
images of polished and chemically etched spark plasma sin-
tered composites, as shown in Fig. 3(a) and (b), the presence of
grain sizes of 1–2 ␮m are observed in CT and HA80CT ceram-
ics. However, the SEM image [Fig. 3(c)] of thermally etched
microstructure of conventionally sintered HA40CT composite
revealed the biomodal distribution with grain sizes, character-
ized by coarser grains of 2–4 ␮m and finer grains of 1–2 ␮m.
The finer scale microstructural characteristic of HA–CT com-
posite was investigated using bright field (BF) TEM images.
Fig. 4 represents BF images of HA40CT and HA80CT compos-
ites. The predominant presence of HA and CaTiO3 is confirmed
using SAED pattern analysis of the microstructural phases (not
shown). The BF image acquired from CT grain in HA40CT com-
Fig. 4. Representative bright field TEM image of spark plasma sintered (a)
posite shows the presence of characteristics twins [see inset of
HA40CT and (b) HA80CT composites. The inset in (a) shows twinning mor-
Fig. 4(a)]. Irrespective of CT content, such twinning morphol- phology.
ogy is observed in all the HA–CT composites. It is also reported
that the twin width scales with grain size in HA-CaTiO3 sys-
tem. Considering SPS conditions, these twins are believed to of HA80CT, the dielectric relaxation seems to appear beyond
be deformation twins. It has been reported that the domain/twin our measuring frequency range. The other compositions show a
structure is a consequence of transformation from the parae- small variation in dielectric constant in the measured range of
lastic phase to the ferroelastic phase.23 The above observation temperature and frequency. In contrast, HA20CT, HA40CT and
therefore suggests that the CaTiO3 grains might be ferroelastic HA60CT composites follow a similar trend of decrease in the
in nature in HA–CT composites. dielectric loss at frequency below 1 kHz. At higher frequencies
(>10 kHz), almost frequency independent dielectric loss values
3.2. Dielectric properties are obtained.
Fig. 6 shows the variation of dielectric constant, dielectric
The variation of dielectric constant and loss with tempera- loss with temperature (RT-150 ◦ C) at a frequency of 1 MHz
ture and frequency for SPSed HA–CT composite samples are for pressureless sintered HA and HA–CaTiO3 composites.
shown in Figs. 5(a)–(d). The dielectric constant and loss val- Because of the differences in phase assemblage between spark
ues for pure CT and HA80CT are higher compared to pure HA plasma sintered and pressureless sintered samples, the different
and other grades of HACT composites. However, the dielectric polarization phenomena such as space charge and orientational
dispersion with frequency for CT and HA80CT suggested the polarizations also contribute at lower frequencies. Therefore, the
non-intrinsic origin of dielectric constants in these samples. The dielectric behaviour of the developed composites is compared
dielectric dispersion in CT is followed by the corresponding peak at 1 MHz frequency. Table 2 shows the comparison of dielectric
in loss curve, which represents the dielectric relaxation. In case behaviour for multistage spark plasma and pressureless sintered
 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453 3449

Fig. 5. The frequency and temperature dependent dielectric constant (a) and (b) and dielectric loss (c) and (d) for spark plasma sintered HA–CT composites as well
as pure CT and HA. A comparison of dielectric constant of HA–CT composites with Wiener bounds and logarithmic mixture rule at 1 MHz of frequency and room
temperature is also shown (e).

Table 2
Comparison of dielectric constant, loss and AC conductivity (measured at 27 ◦ C and 1 MHz) of pressureless (PS) and multistage spark plasma (SPS) sintered HA–CT
composites.
Composition Dielectric constant Dielectric loss AC conductivity ( cm)−1

PS SPS PS SPS PS SPS

HA 11.1 8.9 6 × 10−5 0.008 – –

HA-40 wt% CaTiO3 22.4 24.9 10−4 0.004 3.5 × 10−10 1.2 × 10−7
HA-60 wt% CaTiO3 34.2 22.4 0.004 0.007 8.0 × 10−8 3.2 × 10−7
HA-80 wt% CaTiO3 95.5 155.0 0.02 0.780 8.0 × 10−8 4.0 × 10−5
CaTiO3 ∼170(33) 490 ∼10−4(34) 1.006 ∼10−9(34) 10−3

HA–CT composites at room temperature (27 ◦ C) and at 1 MHz
frequency. Similar to the SPSed samples, the pressureless
sintered HA80CT composite shows the significantly higher
dielectric constant (95.5) and loss (0.02) values as compared
to other pressureless sintered composites. Except HA80CT, the
dielectric constant value in the pressureless sintered composites
does not vary significantly in the measured temperature range.
In contrast, the dielectric loss for these samples increases with
an increase in temperature. However, for HA80CT, it appears
to be constant in the temperature range of 50–150 ◦ C.
3450 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453
Fig. 6. Variation of dielectric constant (a) and dielectric loss (b) with temperature for pressureless sintered HA–CT composites. A comparison of dielectric constant
of HA–CT composites with Wiener bounds and logarithmic mixture rule at 1 MHz of frequency and room temperature is also shown (c).
From Figs. 5 and 6, the dielectric behaviour of spark plasma as
well as pressureless sintered HA and HA40CT samples appears
to be comparable. However, pressureless sintered HA60CT
ceramic shows a higher dielectric constant value as compared to
spark plasma sintered HA60CT composite. In contrast to spark
plasma sintered samples, the phase analysis of pressureless sin-
tered HA60CT revealed the formation of secondary phases, such
as CaO and ␤-TCP.13 The significantly higher values of dielec-
tric constant and loss have been obtained for SPSed HA80CT
composite as compared to the pressureless sintered HA80CT
sample.
3.3. AC conductivity property
Fig. 7 shows the variation of AC conductivity with temper-
ature at frequency of 1 MHz for SPSed as well as pressureless
sintered HA–CT composites. While the conductivity of SPSed
HA linearly increases in the measured temperature range,
the conductivity of HA20CT and HA40CT samples appear
to be independent of temperature. For HA60CT, the change
in conductivity with temperature is more significant for pres-
sureless sintered sample. The comparison of AC conductivity
for pressureless and multistage spark plasma sintered HA–CT
composites are shown in Table 2. For a given composite
composition, the conductivity of the SPSed samples is found
to higher than the respective pressureless sintered samples.
The spark plasma sintered HA80CT ceramic demonstrated the
highest value of conductivity due to high dissipation factor,
which increases further with increase in temperature.
4. Discussion
The dielectric properties of the composites can be explained
in the light of the existing theoretical models as well as in refer-
ence to the structural characteristics of the constituent ceramic
phases. HA is an ionic crystal with hydroxyl ion (OH− ) sublat-
tice as a series of one dimensional chain in the crystal lattice.
There are two types of calcium sublattices in HA lattice with one
having three fold rotational axis and other having equilateral
triangles about the c-axis with OH− ions at the centre of the
triangles. The ionic transport within the HA structure occurs by
OH− ion vacanc ies and diffusion of Ca2+ and PO4 3− ions under
the influence of applied electric field and temperature. This
causes a relative displacement of OH− ions with centre of posi-
tive (Ca2+ ) and negative (PO4 3− ) ions forming a chain segment.
Consequently, the displacement of OH− ions within HA lattice
creates a dipole parallel to the c-axis, which is greater than the
displacement of either Ca2+ or PO4 3− ions. However, the parallel
and perpendicular displacement of PO4 3− ions along the c-axis
is of the order of magnitude smaller than that of Ca2+ ions. All
these contribute towards the randomness of displacement in the
calcium sublattice as well as in structure of HA lattice.24 From
the above, it can be realized that the polarization of HA depends
on the number of lattice sites occupied by the OH− vacancies,
applied electric field, temperature, charge on the vacancy and the
 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453 3451

plasma sintering in vacuum. It is expected that [V]/[O] of SPSed

HA would be more than that in a conventional sintered HA in
ambient atmosphere. As a result, dielectric loss of SPSed HA is
more than that sintered in air (see Table 2).
Further, the experimental values of dielectric constant were
compared with the theoretical estimations using parallel and
series Wiener bounds 27 as well as the logarithmic mixture
rule,28

εc = υHA εHA + υCT εCT (3)

1 υ υ
= HA + CT (4)
εc εHA εCT

log εc = υHA log εHA + υCT log εCT (5)

where εc is the dielectric constant of the HA–CT composite,

υHA , υCT , εHA and εCT are the volume fractions and dielectric
constants of HA and CT, respectively. From Figs. 5(e) and 6(c),
it can be concluded that independent of the processing route,
the dielectric constant of the composites follow closely with the
series Weiner bound for CT content of ≤60 wt% in HA. One of
the possible reasons for this resemblance can be the lack of con-
nectivity among the high dielectric constant CaTiO3 phases.29
Also, the secondary phases formed (e.g., CaO, TiO2 , ␤-TCP
etc.) during the conventional processing of these composites
contribute to the effective dielectric constant of the composite.
The difference in conductivity property will now be
explained. With an increase in temperature, the dehydration
of chemically bound water causes ionic conduction due to the
movement of OH− ions and H+ proton along the columnar chan-
Fig. 7. Variation of AC conductivity with temperature for spark plasma sin- nels in HA crystals.30 The conductivity increases due to the
tered (a) as well as pressureless sintered (b) HA–CT composites at 1 MHz of presence of surface bound water and hydroxyl ions in HA, while
frequency. conductivity of pure CT and HA80CT composite is dominated
by ionic polarization.
interstice separation of chain segment along c-axis. The dielec- In case of monolithic CT, the mobility of O2− ions, located
tric constant, as measured with HA–CT composites, can at the face centred position in the crystal lattices of CaTiO3
therefore be related to the polarization of HA and this can be along c-axis contributes as the dominant conduction mecha-
expressed as25 : nism. It is particularly due to the presence of Ti3+ ions in SPSed
4πP CaTiO3 , as confirmed by XPS results (Fig. 8). Since CaTiO3 is
ε + iε = 1 + (1) retained predominantly in all SPSed samples and also because
E
SPSed samples exhibit better conductivity and dielectric prop-
where E is the periodic applied field, P is total polarization of erties, XPS analysis is carried out only on monolithic CaTiO3 .
the crystals, ε and ε are the real and imaginary components of It can be observed that the 2p3/2 peak at a binding energy of
dielectric constant, respectively. about 459 eV and a small shoulder peak at about 465 eV corre-
Also, the relative dielectric loss, ε of HA can be written sponds to the Ti3+ 2p1/2 .31 Moreover, no peak of the 2p3/2 and
in terms of OH− ion vacancy and oxygen concentrations in 2p1/2 appears at binding energies of 458 eV and 463 eV, which
hydroxyl ion sublattice as: corresponds to Ti4+ 2p peaks. This can be correlated with the
  fact that the colour of the CT samples in as-SPSed conditions
 A [V]
τ/2 [O]
ε = (2) were black, indicating that Ti4+ has been reduced to Ti3+ dur-
T [O] 1 + (
τ/2 [O])2
ing spark plasma sintering.32 Such a reduction of Ti4+ state to
where A is a constant, [V] and [O] are the vacancy and oxygen Ti3+ state generates vacancy in O2− sublattice. In the CaTiO3
impurity concentrations in OH– ion sublattice, respectively, ω structure, O2− ions occupy fourfold and eight fold positions.
and τ are the angular frequency and relaxation time for vacancy As a result, Ti3+ ions produce oxygen vacancies on eight fold
displacement. It is reported that high [V]/[O] (∼103 ) is respon- position sites, which lie in the same lattice plane. However, the
sible for the large values of dielectric loss in HA.26 It is to be four fold position of oxygen ions is independent of Ti3+ ion. It
noted that HA was sintered at 1100 ◦ C with multi stage spark is expected that O2− ion vacancies in both HA and CT lattices
3452 A.K. Dubey et al. / Journal of the European Ceramic Society 33 (2013) 3445–3453
Fig. 8. Plot of XPS results showing the binding energy of Ti2p, Ca2s, and O1s peaks, obtained from spark plasma sintered CT ceramic. Along Y-axis, XPS counts
(arbitrary units) are plotted.
are the dominant conduction mechanisms in the spark plasma
sintered composites.
As a concluding note, the present study unambiguously
confirms that the electrical transport properties of HA–CT com-
posites are significantly influenced with the addition of more
than 60 wt% CaTiO3 or more. For lower CT containing com-
posites, the functional properties are similar or marginally better
than HA matrix. The implication of the present experimental
results can be realized in terms of the significant increase in the
dielectric constant or conductivity of the spark plasma sintered
HA80CT composites as compared to the respective convention-
ally sintered composites. It may be worthwhile to mention that
the substrate conductivity is found to modulate the myoblast cell
functionality (both proliferation and differentiation) on the spark
plasma sintered HA-CaTiO3 composites in vitro.14 Also, spark
plasma sintered HA80CT composite is reported to exhibit early
stage osteogenesis than sintered HA in rabbit animal model.35
The results presented in this paper together with our recently
published papers therefore establish the motivation to develop
electroconductive composites for biomedical applications.
5. Conclusions
Based on the experimental work reported in the present study,
the following conclusions can be drawn,
a. From the impendence analysis, it is observed that the dielec-
tric constant and AC conductivity of HA–CaTiO3 composites
significantly increase for the higher amount (≥60 wt%)
of CaTiO3 addition to HA. Importantly, 80 wt% CaTiO3
addition to HA has significantly improved both, the dielec-
tric constant (155) and AC conductivity [∼10−5 ( cm)−1 at
1 MHz frequency] as compared to the lower CaTiO3 contain-
ing HA composites. A comparison between the spark plasma
and pressureless sintered HA–CT composite revealed a better
efficacy of SPS process to develop HA–CaTiO3 composites
with better electrical conductivity properties.
b. A comparison with the existing theoretical models revealed
that irrespective of processing route, the dielectric constant of
HA–CaTiO3 composites follow closely with Weiner (series)
model. The apparently large dielectric constant as well as
conductivity has been explained by the presence of Ti3+ ion
and oxygen vacancy in the spark plasma sintered materi-
als. Overall, spark plasma sintering is found to be a superior
processing route to develop HA–CaTiO3 composites with a
better combination of functional properties.
Acknowledgements
The use of precision impedance analyzer in the laboratory of
Prof. K. B. R. Varma is gratefully acknowledged. The authors
also thank Department of Science and Technology as well as
Department of Biotechnology for financial support.
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