j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230

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

Densification behaviour of nanocrystalline

hydroxyapatite bioceramics

S. Ramesh a,∗ , C.Y. Tan a , S.B. Bhaduri b , W.D. Teng c , I. Sopyan d

a Ceramics Technology Laboratory, University Tenaga Nasional, 43009 Kajang, Selangor, Malaysia
b School of Materials Science & Engineering, Clemson University, Clemson, SC 29634, USA
c Ceramics Technology Group, SIRIM Berhad, 40911 Shah Alam, Selangor, Malaysia
d Department of Manufacturing and Materials Engineering, Faculty of Engineering,

International Islamic University Malaysia, Malaysia

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

Article history: The sinterability of nanocrystalline hydroxyapatite (HA) particles by microwave sinter-
Received 6 June 2007 ing was compared with conventional pressureless sintering. The results revealed that
Received in revised form microwave heating was effective in producing a useful HA body in a very short sinter-
10 November 2007 ing cycle without disrupting the HA phase stability. The maximum hardness of 7.21 GPa
Accepted 6 December 2007 and 6.38 GPa was obtained for HA sintered at 1050 ◦ C by the conventional method and
1150 ◦ C by microwave sintering, respectively. The maximum fracture toughness measured
for the microwave-sintered and conventional-sintered HA was 1.45 MPam1/2 at 1050 ◦ C and
Keywords: 1.22 MPam1/2 at 1000 ◦ C, respectively. Although the relative density of microwave-sintered
Hydroxyapatite HA was slightly lower than the conventional-sintered HA throughout the sintering regime
Bioceramic employed, taking into account of the heating and soaking periods, the time taken by
Sintering microwave sintering to achieve a relative density of 96.5% was about 3% of the time con-
Mechanical properties sumed for samples sintered by the conventional heating. Microwave heating was found to be
an effective technique to produce a useful HA body for clinical applications without causing
grain coarsening.
© 2007 Elsevier B.V. All rights reserved.

1. Introduction studies have been carried out to improve the mechani-

Hydroxyapatite, Ca10 (PO4 )6 (OH)2 (HA) material has been clin-
ically applied in many areas of dentistry and orthopaedics
because of its excellent osteoconductive and bioactive prop-
erties which is due to its chemical similarity with the mineral
portion of hard tissues (Hench, 1998; Afshar et al., 2003;
Suchanek and Yoshimura, 1998; Aoki et al., 1987; Metsger et
al., 1982).
One of the major concern with HA is the low fracture
toughness, i.e. <1 MPam1/2 of the sintered body (Gabriel Chu et
al., 2002; Muralithran and Ramesh, 2000). As a result various
cal properties of sintered HA (Suchanek and Yoshimura,
1998; Rodrı́guez-Lorenzo et al., 2002; Kokubo et al., 2003).
These include the development of new powder process-
ing/synthesis techniques and composition modification. The
ultimate goal is to identify the most appropriate synthesis
method and conditions to produce well-defined particle mor-
phology (Suchanek and Yoshimura, 1998; Aoki et al., 1987;
Metsger et al., 1982; Gabriel Chu et al., 2002; Muralithran and
Ramesh, 2000; Rodrı́guez-Lorenzo et al., 2002; Kokubo et al.,
2003) that is sinter active at low temperatures to produce body
that exhibits high mechanical properties.

∗
Corresponding author. Tel.: +60 3 89287282; fax: +60 3 89212116.
E-mail address: ramesh@uniten.edu.my (S. Ramesh).
0924-0136/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2007.12.027
222 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230
One of the critical controlling parameter that requires
attention during the processing of hydroxyapatite is the selec-
tion of a suitable sintering method to obtain a solid, high
density HA body that is characterized by having fine-grained
microstructure. The most commonly used sintering tech-
nique is the conventional pressureless sintering (CPS) in air
atmosphere. This method of densification normally requires
high temperature, slow heating rate and long holding time to
produce >99% dense HA body with large-grained microstruc-
ture and low mechanical properties (Metsger et al., 1982;
Muralithran and Ramesh, 2000).
In contrast, sintering by microwave heating has been
reported to be a viable processing technique to produce a
dense HA body that possessed fine microstructure coupled
with improved mechanical properties (Agrawal et al., 1992;
Fang et al., 1994; Yang et al., 2002; Vijayan and Varma, 2002).
For instance Yang et al. (2002) prepared green compacts of
stoichiometric HA synthesized by the chemical precipitation
method. The sintering behaviour of the synthesized HA was
compared by microwave heating at 1050–1100 ◦ C for 5–10 min
in a 10 kW, 2.45 GHz microwave furnace and conventional
heating at 1100 ◦ C for 1 h. SEM investigation performed on
the fracture surface indicated that the microwave-sintered HA
had very fine grain sizes, in the range of 0.3–0.5 ␮m, as com-
pared to 3–5 ␮m observed for the conventional-sintered HA.
The authors inferred that the finer grain size and higher den-
sities of the microwave-sintered HA observed in their work
was due to the higher efficiency of microwave heating. This
can be attributed to the rapid and uniform generation of heat
within the body instead of being transferred from outside the
body as in the conventional sintering (Sutton, 1989). Although
microwave sintering (MS) has great potential in fabricating
dense body, there are concerned regarding the stability of HA
phase (Fang et al., 1994).
The objective of the present paper was to compare the
effect of microwave sintering with that of conventional
method on the densification behaviour and mechanical prop-
erties of synthesized nanocrystalline hydroxyapatite.
2. Experimental details
In the present work, the nanocrystalline hydroxyapatite pow-
der was prepared according to a wet chemical precipitation
method from aqueous medium involving calcium hydroxide
and orthophosphoric acid (Ramesh, 2004). The resulting pre-
cipitate was filtered, washed, dried and then ground to a fine
powder.
The specific surface area of the powder was measured
by the Brunauer–Emmett–Teller (BET) method. Nitrogen gas
adsorption analysis was performed on a Coulter SA 3100
Analyzer. The calcium-to-phosphorous (Ca/P) ratio of the
synthesized powder was determined by inductively coupled
plasma-atomic emission spectrometry (ICP-AES) analysis.
The as-received HA powder was isostatic pressed at
200 MPa into rectangular and discs samples. These samples
were then sintered by conventional method and microwave
technique over the temperature range of 1000–1300 ◦ C.
The conventional pressureless sintering was performed
using a rapid heating box furnace (ModuTemp, Australia). The
green compacts were sintered in air atmosphere at a ramp
rate of 2 ◦ C/min and soaking time of 2 h was employed for each
firing cycle.
The microwave sintering was carried out using a
microwave furnace (M.M.T., Knoxville, TN) provided with a
variable power output magnetron source capable of operat-
ing from 0 kW to 3 kW at 2.45 GHz. The cavity is large and
overmoded, thus ensuring mixing of the microwave modes
and resulting in a homogeneous field distribution. The HA
compacts were sandwiched between two SiC susceptors and
surrounded with alumina fiber before sintering. In this pro-
cess, the sintering schedule for all samples was kept constant
at duration of 30–35 min. The temperature of the samples was
measured via a pyrometer (Model M77, Mikron Corp.) and the
power of the microwave system adjusted accordingly to main-
tain the required temperature.
All the sintered disc samples were polished to a 1 ␮m
surface finish prior to testing. Phase analyses by X-ray diffrac-
tion (XRD: Rigaku Geiger-Flex, Japan) of synthesized powder
and polished compacts were carried out at room temperature
using Cu K␣ radiation at a scan speed of 0.5◦ /min and a step
scan of 0.02◦ . The microstructural evolution of the sintered
samples was performed by scanning electron microscopy
(SEM: Philips XL30). The sintered grain size of polycrystalline
HA was determined from the SEM micrographs using the line
intercept method (Mendelson, 1969).
The bulk density of sintered samples was determined by
the Archimedes technique. The relative density was calcu-
lated by taking the theoretical density of HA as 3.156 g cm−3 .
The microhardness (Hv ) and fracture toughness (KIc ) of the
samples were determined using the Vickers indentation
method. The indentation load (<200 g) was applied and held
in place for 10 s. Five indentations were made for each sam-
ple and the average value was taken. The indentation fracture
toughness was determined from the equation derived by
Niihara (Niihara, 1985):
 c −1.5
0.5
KIc = 0.203 (Hv )(a) (1)
a
where Hv is the Vickers hardness, a the half diagonal of the
indentation, c the radial crack dimension measured from the
centre of the indent impression, i.e. c = L + a and L is the crack
length.
3. Results and discussion
3.1. HA powder characteristics
The properties of the synthesized HA powder is shown in
Table 1. The estimates of crystal size from the XRD peak broad-
ening based on Scherrer’s formula (Cullity and Stock, 2001)
for the HA powders taken at the most prominent peaks were
Table 1 – Properties of synthesized HA powders
Ca/P molar ratio 1.67 ± 0.02
Colour White
SBET 71.2 m2 /g
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230 223

Fig. 1 – Comparison of XRD patterns of synthesized HA with the standard JCPDS card for stoichiometric HA.

10.8 nm at (2 1 1) reflection corresponding to diffraction angle
2 = ∼31.9◦ and 31.9 nm at (0 0 2) reflection corresponding to
diffraction angle 2 = ∼25.9◦ . Thus, the HA primary particles
consisted of extremely fine precipitates.
X-ray diffraction analysis of the synthesized HA powder
produced only peaks which corresponded to the standard
JCPDS for stoichiometric HA as shown in Fig. 1. Secondary
phases such as tricalcium phosphate (TCP), tetracalcium
phosphate (TTCP) and calcium oxide (CaO) were not evident in
the synthesized powder. This is consistent with the Ca/P ratio
obtained for the powder (Table 1). Additionally, the XRD pat-
tern of the synthesized powder was in good agreement with
that of enamel of a human tooth as shown in Fig. 2.
3.2. HA phase stability
The sinterability of the HA powder under both sintering condi-
tions, the microwave sintering and conventional pressureless
sintering were compared in terms of HA phase stability, rel-
ative density, Vickers hardness, fracture toughness and grain
size measurement.
The XRD analysis of all the samples, regardless of sintering
method, fired between 1000 ◦ C and 1300 ◦ C indicated no sec-
ondary phases were present in the HA lattice. Further evidence
of the high temperature phase stability of the material was
obtained by sintering at higher temperature of 1350 ◦ C. The
phase analysis as shown in Fig. 3 for both the MS-HA and CPS-
HA compacts showed no sign of HA decomposition, and the
phases present in the lattice was in good agreement with the
JCPDS card number 74-566 for stoichiometric HA. The results
obtained in this study are comparable to the results reported
by Muralithran and Ramesh (Muralithran and Ramesh, 2000)
for the effect of sintering temperature on the phase stability
of synthetic HA. These authors found that decomposition of
HA started at 1400 ◦ C and sign of melting of the material was
observed at 1450 ◦ C.

Fig. 2 – A good agreement was observed between the XRD traces of the synthesized HA powder with that of a human tooth.
224 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230
Fig. 3 – Comparison of XRD patterns between microwave-sintered and conventional pressureless sintered HA at 1350 ◦ C. All
diffraction peaks belong to the HA phase.
In general, high temperature sintering of HA can lead to the
partial thermal decomposition of HA into TCP and/or TTCP.
The thermal decomposition is accompanied in two steps,
i.e. dehydroxylation and decomposition (Wang et al., 1998;
LeGeros and LeGeros, 1993). Wang and Chaki (1993) and Gu
et al. (2002) reported that the dehydroxylation phenomenon
could be observed by comparing the XRD peaks position of
the sintered material with that of the standard JCPDS data for
stoichiometric HA.
In the present work, XRD peak shifting was observed
mainly for the conventional pressureless sintered HA com-
pacts as typically shown in Fig. 4. The peak shifting for CPS-HA
was found to vary significantly between 0.08◦ and 0.16◦ when
compared to less than 0.06◦ for MS-HA.
The dehydroxylation phenomenon observed for the CPS-
HA is consistent with the findings of other workers (Wang and
Chaki, 1993; Gu et al., 2002; Kijima and Tsutsumi, 1979; Santos
et al., 1991; Zhou et al., 1993; Ruys et al., 1995). Although the
dehydroxylation phenomenon in HA is still unclear, a general
consensus that has been reached in the reported literatures
is that dehydroxylation neither collapse the HA structure nor
is responsible for the declined in mechanical properties when
sintered at elevated temperatures.
In the present work, decomposition of HA was not observed
in both the conventional-sintered and microwave-sintered
compacts. The processing route employed to synthesize the
HA crystallites could have resulted in the retention of absorbed
water in the HA lattice. However, it is not clear if the loss of
water during sintering plays a role in suppressing dehydroxy-
lation.
Van Landuyt et al. (1995) studied the effects of sinter-
ing temperature (1200–1500 ◦ C) on the densification behaviour
of stoichiometric HA, and their XRD results showed a simi-
lar observation to both the CPS-HA and MS-HA produced in
this study for temperatures between 1000 ◦ C and 1350 ◦ C. The
authors found that conventional sintering under air atmo-
sphere resulted in a slight dissociation of the HA phase only
after 8 h of holding at 1300 ◦ C, whereas the stability of the HA
phase was maintained in the structure after sintering for 3 h
at 1450 ◦ C. This observation prompted them to believe that the
dissociation of HA occurred by a nucleation and growth mech-
anism, involving an incubation period which decreased with
increasing sintering temperature.
If an incubation period is one of the factor governing the
decomposition of HA, then the rapid sintering by microwave
would be beneficial in suppressing the dissociation of the OH
ions and thus preventing decomposition of the HA phase. This
could explained the observation made in the present work
since no decomposition as well as minimal degree of XRD peak
shifting was observed upon microwave sintering.
3.3. Bulk density
The effects of CPS and MS on the densification of HA compacts
are shown in Fig. 5. In general, both the bulk density variation
of the HA samples sintered by conventional and microwave
methods increases with increasing sintering temperature but
at different rates. The onset of densification, indicated by a
sharp increase in the sintered density, for both sintering meth-
ods was between 1000 ◦ C and 1100 ◦ C. Nevertheless, the bulk
density of the CPS-HA was higher than the MS-HA throughout
the sintering regime investigated.
The conventional-sintered material achieved a relative
density of 96% when sintered at 1000 ◦ C and exhibited above
99% of theoretical density when the temperature increased
to above 1100 ◦ C. In contrast, the microwave-sintered ceramic
exhibited a lower value of 90–91% when sintered at 1000 ◦ C
and achieved above 96% of theoretical value when sintered
at 1100 ◦ C. The maximum value of 98% theoretical density
was attained for compacts that were microwave-sintered at
1300 ◦ C. These results are in good agreement with that in the
reported literature for microwave-sintered HA (Agrawal et al.,
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230 225

Fig. 5 – Comparison between the relative density of MS-HA

and CPS-HA as a function of sintering temperature.

sive of heating, soaking and cooling to room temperature) as a

Fig. 4 – XRD signatures of HA phase taken at the three most
prominent diffraction angles for compacts fired at
1000–1300 ◦ C. Peak shifting was evident for CPS-HA.
1992; Fang et al., 1994; Yang et al., 2002; Vijayan and Varma,
2002).
Although the bulk density of the microwave-sintered HA
is lower than the conventional pressureless sintered material,
the benefit and effectiveness of microwave sintering can be
viewed in the context of the time taken to achieve the respec-
tive bulk density shown in Fig. 5. This advantage is shown in
Table 2 which compares the total sintering time taken (inclu-
function of sintering temperature by both sintering methods
to achieve the respective densities.
Taking into consideration of the attained densities based
on the total time of sintering as shown in Table 2, the benefi-
cial effect of microwave heating in promoting densification of
HA can be realized. For example, a relative density of 96% is
achievable by CPS at 1000 ◦ C whereas a higher temperature of
1100 ◦ C was required by microwave sintering to achieve a simi-
lar relative density. However, this small difference of sintering
temperature is offset by the very short sintering time required,
i.e. microwave sintering took a fraction of less than 3% of the
total time taken by the conventional pressureless sintering to
achieve 96% relative density when sintered at 1000 ◦ C.
The densification of ceramics in a solid state sintering is
a process of pore elimination, accomplished by a diffusion
process through the transfer of matter from the particle vol-
ume or from the grain boundary between particles (Kingery
et al., 1976). Thus, in the present work, it can be suggested
that grain boundary diffusion between the HA particles was
substantially enhanced during the microwave sintering.
Sutton (1989) and Rahaman (1995) explained that volumet-
ric heating in the microwave sintering is a consequence of a
series of losses. In general, when microwaves penetrate and
propagate through a dielectric material, the internal fields
generated within the affected volume induce translational
motions of the free and bound charges and, rotate charge
complexes such as dipoles. The resistance of these induced

Table 2 – Total sintering time taken to achieve the respective sintered density based on the two different sintering
techniques
Sintering temperature (◦ C) CPS MS

Relative density (%) Time taken (min) Relative density (%) Time taken (min)

1000 96.8 1090 90.8 29.4

1050 98.4 1140 95.2 30.4
1100 99.0 1190 96.5 31.4
1150 99.0 1240 96.7 32.4
1200 99.0 1290 96.6 33.4
1250 99.1 1340 97.0 34.4
1300 99.0 1390 98.0 35.4
226 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230

Fig. 6 – SEM images of (a) CPS-HA and (b) MS-HA surfaces fired at 1000 ◦ C.

motions due to inertial, elastic and frictional forces causes
losses and in turn attenuates the electric field. As a con-
sequence of these losses, volumetric heating results. These
principles should be applicable to the microwave sintering of
HA. In particular, the hydroxyl in the HA structure could have
played a role in causing losses and thus promoting densifica-
tion of HA in a short sintering time.
3.4. Microstructural evolution and grain size
The microstructural evolution of the conventional pressure-
less sintering and microwave sintering HA at 1000 ◦ C is shown
in Fig. 6.
It can be noted that the CPS-HA (Fig. 6a) exhibited an almost
dense microstructure that correspond to a relative density of
96.8% if compare to the MS-HA (Fig. 6b) which had remnant
porosity (∼9%) remaining in the structure after sintering at
1000 ◦ C.
However, as the sintering temperature was increased
beyond 1150 ◦ C, all the microwave-sintered samples exhibited
very little porosity as shown in Fig. 7d–f. The SEM results cor-
related well with the measured density (Fig. 5), in particular
for the conventional pressureless sintered HA which showed
that almost full densification was accomplished when com-
pacts sintered >1050 ◦ C. Increasing the sintering temperature
beyond 1050 ◦ C resulted in grain growth and the CPS-HA exhib-
ited larger grain sizes than the microwave-sintered HA for the
same sintering temperatures (Fig. 8).
In general, the finer grain size clearly indicates that the
sintering regime employed for microwave processing did not
promote extensive grain growth even when sintered at high
temperature of 1350 ◦ C as shown in Fig. 9.
The variation in average grain sizes with sintering tem-
perature is presented in Fig. 8. HA samples sintered by the
conventional and microwave methods exhibited a similar
grain size trend with increasing temperature from 1000 ◦ C to

Fig. 7 – Microstructural evolution of CPS-HA (a–c) and MS-HA (d–f) when sintered at 1150 ◦ C (a, d), 1250 ◦ C (b, e) and 1300 ◦ C
(c, f).
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230
Fig. 8 – Average grain size variation with sintering
temperature for CPS-HA and MS-HA.
1200 ◦ C, i.e. the grain sizes of both the CPS-HA and MS-HA
increased slowly with sintering temperature. It is interesting
to note that in this temperature regime, the rates of grain
growth of both conventional-sintered and microwave-sintered
HA were almost similar. However, as the temperature was
increased further, above 1200 ◦ C, the rate of grain growth for
the conventional pressureless sintered HA increased rapidly
as compared to the microwave-sintered ceramic. The grain
size of the CPS-HA increased by a factor of >5 from 1.54 ␮m
(1200 ◦ C) to 8.78 ␮m (1300 ◦ C) whereas the grain size of MS-HA
increased by a factor of about 2.4 from 0.86 ␮m to 2.08 ␮m when
the temperature increased by 100 ◦ C from 1200 ◦ C.
A similar observation was noted for the HA sintered at
1350 ◦ C as shown in Fig. 9. The measured grain sizes for the
ceramics sintered at 1350 ◦ C were 12.4 ␮m for the CPS-HA
and 2.77 ␮m for the MS-HA, respectively. These results clearly
demonstrate another useful advantage of microwave sintering
in preventing grain growth when sintered at high tempera-
tures. This is important, since material with smaller grain
size would normally result in enhanced mechanical proper-
ties when compared to the same material having a larger grain
size.
Although a fully dense body was not attained in the present
work, a useful HA body that has the potential for clinical
implant has been produced by microwave sintering in the
shortest possible sintering time. The low degree of porosity, i.e.
<10%, in the microwave-sintered HA compacts in the present
work would be an added benefit when implanted in living
body. According to the literature, HA ceramics in porous form
(porosity up to 60%) has been widely used successfully as bone
substitutes (Akao et al., 1981; Hench, 1991; Liu, 1997; Yuan et
Fig. 9 – SEM micrographs of HA sintered at 1350 ◦ C by (a) conventional pressureless sintering and (b) microwave sintering.
227
Fig. 10 – Effect of sintering temperature on the fracture
toughness of HA sintered by the conventional method
(CPS-HA) and microwave technique (MS-HA).
al., 1998; Vaz et al., 1999; Duan et al., 2002). In general, it is per-
ceived that the pores provide a mechanical interlock leading to
firmer fixation of the material (Suchanek and Yoshimura, 1998;
Flautre et al., 2001). In addition, bone tissue grows well into the
pores and thus increasing the strength of the HA implant (Hing
et al., 1997; Lu et al., 1999; Rivera-Munoz et al., 2001).
3.5. Fracture toughness and Vickers hardness
The effect of sintering temperature on the fracture tough-
ness (KIc ) of synthesized HA sintered by the conventional
and microwave technique is shown in Fig. 10. The results
show that the fracture toughness of the HA sintered by
the conventional method decreases almost linearly with
increasing sintering temperature, i.e. from a maximum
value of 1.22 ± 0.08 MPam1/2 at 1000 ◦ C to a minimum of
0.91 ± 0.05 MPam1/2 for sintering at 1300 ◦ C. On the other hand,
the average toughness of microwave-sintered HA was found
initially to increase with density and grain size from an
average value of 1.24 MPam1/2 to 1.45 MPam1/2 and thereafter
decrease almost linearly with further increase in grain size,
i.e. down to 0.96–1 MPam1/2 when sintered at 1300 ◦ C despite
having high relative density of 98%.
The minimum fracture toughness obtained for both the
conventional-sintered and microwave-sintered HA was in
agreement with the values reported in the literature for syn-
thetic HA samples sintered up to 1300 ◦ C (Muralithran and
Ramesh, 2000; Van Landuyt et al., 1995; De With et al., 1981). In
general, the maximum KIc values for most HA reported in the
literature varied between 0.96 MPam1/2 and 1 MPam1/2 . Thus,
228 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230
Fig. 11 – Vickers hardness of HA sintered at various
temperatures by the conventional and microwave methods.
the high values of 1.22 MPam1/2 and 1.45 MPam1/2 obtained in
the present work for CPS-HA and MS-HA, respectively were
encouraging. It is believed that this improvement in fracture
toughness in the present HA could be attributed to both the
improved properties of the synthesized HA powder as well as
the improved sinterability of these powders with limited grain
growth during microwave sintering.
The effect of sintering temperature on the Vickers hard-
ness of HA sintered by both the conventional method and
microwave technique is shown in Fig. 11. The hardness of both
HA increases with sintering temperature and peaked at a cer-
tain value at a particular temperature and then decreases with
further increase in the temperature up to 1300 ◦ C. For sintering
below 1150 ◦ C, the hardness of HA sintered by the conventional
pressureless sintering method was higher than the equivalent
microwave-sintered material. However, sintering at 1150 ◦ C
and above, both the CPS-HA and MS-HA exhibited a similar
trend with almost identical hardness values being attained at
the same temperature. This is an advantage since it is possible
to attain comparable hardness by microwave heating the HA
ceramic in minutes rather than in hours as in the conventional
pressureless sintering method.
The lowest hardness value was measured for HA compacts
sintered at 1000 ◦ C in both the conventional and microwave
sintering methods. The conventional-sintered HA exhibits
a large increase in hardness from 5.72 ± 0.21 GPa at 1000 ◦ C
to a maximum value of 7.21 ± 0.17 GPa at 1050 ◦ C. Further
sintering, however was detrimental as the hardness of the
CPS-HA decreased almost linearly with increasing temper-
ature. On the other hand, the hardness of MS-HA start to
increase sharply between 1000 ◦ C and 1050 ◦ C and then grad-
ually between 1050 ◦ C and 1150 ◦ C to attain a maximum value
of 6.38 ± 0.20 GPa at 1150 ◦ C as shown in Fig. 11.
Based on the density results in Fig. 5, the CPS-HA exhib-
ited a rapid increase in relative density from 96.8% at 1000 ◦ C
to 98.4% and 99% at 1050 ◦ C and 1100 ◦ C, respectively. Simi-
larly, the relative density of the MS-HA increased from 90.8%
at 1000 ◦ C to 95.2% and 96.7% at 1050 ◦ C and 1150 ◦ C, respec-
tively. This increase in density in both the CPS-HA and MS-HA
is clearly reflected in the improved hardness with increasing
sintering upto 1050 ◦ C and 1150 ◦ C, respectively as shown in
Fig. 12.
Fig. 12 – Variation in hardness with sintered density for
MS-HA and CPS-HA compacts.
The results clearly show the effect of sintered density
on the hardness of HA ceramics, and that the hardness of
CPS-HA was greater than MS-HA for lower sintering tempera-
tures, where it achieves higher sintered densities. The results
obtained in this study however were not in agreement with the
general trend of hardness increases with increasing sintering
temperature as reported by other workers (Van Landuyt et al.,
1995; Gibson et al., 2001; Lu et al., 1998; Yeong et al., 2001).
In the present study, it was found that the hardness of
both HA decreased with increasing sintering temperature
beyond the point at which maximum hardness was obtained
(i.e. >1050 ◦ C for conventional pressureless sintered HA and
>1150 ◦ C for microwave-sintered HA as shown in Fig. 12),
although the densities of these compacts above this tem-
perature range were still high, i.e. 99% for the CPS-HA and
above 96% for MS-HA. This decreased in hardness observed for
both the CPS-HA and MS-HA when sintered above 1050 ◦ C and
1150 ◦ C, respectively could not be due to bulk density effect
but rather can be interpreted as due to a grain size effect as
shown in Fig. 13.
As can be noted from Fig. 13, the hardness of both the
CPS-HA and MS-HA increases with grain size and reached
a maximum value at a certain grain size limit (dc ) before
decreasing further with increasing grain size resulting from
sintering at higher temperatures. The results obtained in the
Fig. 13 – Vickers hardness dependence on the grain size of
hydroxyapatite.
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 2 0 6 ( 2 0 0 8 ) 221–230
present work suggest that below some critical grain size of dc
the hardness is governed by bulk density. In contrast, above
dc the bulk density is not the controlling parameter but rather
grain growth. This is evident from Fig. 13, where the dc for the
conventional-sintered (CPS-HA) and microwave-sintered (MS-
HA) hydroxyapatite are ∼0.5 ␮m and ∼0.2 ␮m, respectively.
4. Conclusions
The sinterability of nanocrystalline HA by microwave sintering
was studied and compared with that of conventional pressure-
less sintering method. The XRD patterns of the microwave
sintering and conventional pressureless sintering HA com-
pacts that were fired between 1000 ◦ C and 1300 ◦ C, respectively
corresponded to that of stoichiometric HA. Decomposition
of HA phase was not observed throughout the sintering
regime employed. However, substantial grain coarsening was
observed in the conventional-sintered HA when compared to
compacts sintered via microwave method, particularly for sin-
tering above 1200 ◦ C.
The fracture toughness values obtained for CPS-HA was
lower compared to MS-HA, with maximum average value
of 1.45 MPam1/2 being attained for microwave compacts at
1050 ◦ C. The maximum average hardness of 7.21 GPa and
6.38 GPa was measured for CPS-HA and MS-HA sintered at
1050 ◦ C and 1150 ◦ C, respectively.
Regardless of sintering methods, there is a definite correla-
tion between hardness and grain size in the present HA. The
hardness of HA would start to decrease at a certain critical
grain size limit despite exhibiting high bulk density.
Acknowledgements
This work was supported by the Ministry of Science, Technol-
ogy and Innovation of Malaysia (Grant No. 03-02-03-SF0073).
The authors would like to thank Dr. M.G. Kutty and J. Jok-
isaari for technical support, Clemson University for microwave
facility, SIRIM and TNBR for providing support with testing
equipment.
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