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Materials and Design 34 (2012) 148–154

Contents lists available at SciVerse ScienceDirect

Materials and Design


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

Sintering behavior of hydroxyapatite prepared from different routes


S. Ramesh a,⇑, C.Y. Tan b, R. Tolouei b, M. Amiriyan b, J. Purbolaksono a, I. Sopyan c, W.D. Teng d
a
Centre of Advanced Manufacturing & Material Processing (AMMP), Department of Engineering Design and Manufacture, Faculty of Engineering, University of Malaya,
50603 Kuala Lumpur, Malaysia
b
Ceramics Technology Laboratory, University Tenaga Nasional, 43009 Kajang, Selangor, Malaysia
c
Department of Manufacturing and Materials Engineering, Faculty of Engineering, International Islamic University Malaysia (IIUM), 50728 Kuala Lumpur, Malaysia
d
Ceramics Technology Group, SIRIM Berhad, 1 Persiaran Dato Menteri, 40911 Shah Alam, Malaysia

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

Article history: The sintering behavior of three different types of hydroxyapatite (HA) i.e. a commercial powder, HA(C), a
Received 20 June 2011 synthesized powder by wet chemical precipitation method, HA(W) and a synthesized powder by mech-
Accepted 5 August 2011 anochemical method, HA(M) were investigated over the temperature range of 1000–1350 °C. It has been
Available online 12 August 2011
revealed that the sinterability and mechanical properties of the synthesized HA(W) was significantly
higher than that of the HA(C) and HA(M). The optimum sintering temperature for the HA(W) samples
Keywords: was 1100 °C with the following properties being recorded: 99.8% relative density, Vickers hardness of
A. Engineering Ceramics
7.04 GPa and fracture toughness of 1.22 MPa m1/2. In contrast, the optimum sintering temperature for
C. Sintering
E. Mechanical
the HA(C) and HA(M) samples was 1300 °C with relative density of 98% and 95.5%, Vickers hardness of
5.47 GPa and 4.73 GPa, fracture toughness of 0.75 MPa m1/2 and 0.82 MPa m1/2 being measured. The pres-
ent research showed that the wet chemical precipitation reaction was beneficial in producing a highly
crystalline, high purity and single phase stoichiometric HA powder that is sinteractive particularly at
low temperatures below 1100 °C.
Ó 2011 Published by Elsevier Ltd.

1. Introduction prominent methods used to synthesize HA are the wet precipita-


tion method, mechanochemical technique, sol–gel technique and
Hydroxyapatite, Ca10(PO4)6(OH)2 (HA) material has been clini- hydrothermal method [4–6]. Although numerous studies on HA
cally applied in many areas of dentistry and orthopedics because synthesized via wet precipitation technique and mechanochemical
of its excellent osteoconductive and bioactive properties which is method were carried out, nevertheless, reports on the sinterability
due to its chemical similarity with the mineral portion of hard tis- of HA synthesized through these technique are rather scarce.
sues [1]. Bulk material, available in dense and porous forms, is used Therefore, the primary objective of the present work was to syn-
for alveolar ridge augmentation, immediate tooth replacement and thesize a well-defined, crystalline, pure hydroxyapatite (HA) phase
maxillofacial reconstruction [2]. Nevertheless, the brittle nature using two techniques, i.e. wet precipitation technique and mecha-
and the low fracture toughness (<1 MPa m1/2) of HA constraint nochemical technique. The sinterability of both synthesized
its scope as a biomaterial in clinical orthopaedic and dental appli- hydroxyapatite (HA) was evaluated and compared with a commer-
cations [3]. Hence, the development of an improved toughness HA cially available HA (Merck, Germany).
material is required. As a result, various studies have been carried
out to improve the mechanical properties of sintered HA [4].
The success of HA ceramic in biomedical application is largely 2. Methods and materials
dependent on the availability of a high quality, sintered HA that
is characterized having refined microstructure and improved In the current work, the HA powder used was prepared accord-
mechanical properties [4]. Intensive research in HA involving a ing to a novel wet chemical method, hereafter designated as
wide range of powder processing techniques, composition and HA(W) [7]. The method involve reacting calcium ion with phos-
experimental conditions have been investigated with the aim of phate ion based on a molar ratio of Ca/P = 1.67. The starting precur-
determining the most effective synthesis method and conditions sors used were commercially available calcium hydroxide Ca(OH)2
to produce well-defined particle morphology. Among the more (98% purity, BDH) and orthophosphoric acid H3PO4 (85% purity,
Merck) The prepared H3PO4 solution was then added dropwise into
the stirring suspension of Ca(OH)2 in distilled water. The titration
⇑ Corresponding author. Tel.: +60 3 7967 7671; fax: +60 3 7967 5330. process normally takes about 2 h. Throughout the titration process,
E-mail address: ramesh79@um.edu.my (S. Ramesh). the pH of the mixture was monitored and kept above 10.5 by the

0261-3069/$ - see front matter Ó 2011 Published by Elsevier Ltd.


doi:10.1016/j.matdes.2011.08.011
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S. Ramesh et al. / Materials and Design 34 (2012) 148–154 149

addition of ammonium (NH3) solution (25% concentration). NH3 powder consists of a mixture of fine powder particles ranging from
solution. The precipitate was allowed to settle down overnight be- 1 to 3 lm diameter and larger particles of 5–10 lm diameter. The
fore filtration. The filtered precipitate was rinsed three times by larger particles appear to be large agglomerates of loosely packed
using distilled water and then dried overnight in an oven. The dried smaller particles, resulting in a rough surface as shown in Fig. 1.
filtered cake was crushed and sieved to obtain a well-defined, The drying of the filter cake of synthesized HA could have resulted
highly crystalline HA powder. in less compaction of the precipitate and resulted in the formation
The HA powder synthesized by mechanochemical method in of soft agglomerates which was found to break easily using a very
the present work was prepared according to the method reported low pressing pressure of 1.3–2.5 MPa during powder compaction
by Rhee [8]. The starting precursors used were commercially avail- to form the green body. Due to the soft nature of the powders, at-
able calcium pyrophosphate, Ca2P2O7 (99.9% purity, Aldrich) and tempts to use higher pressures during uniaxial pressing the sam-
calcium carbonate, CaCO3 (99% purity, Aldrich). The mixture, in ples proved to be futile as powders lamination on the die surface
the mole ratio of Ca2P2O7:CaCO3 = 3:4, was milled for 8 h with a was observed and in some extreme cases, a layer of compacted
rotating speed of 170 rpm in a high-density polyethylene bottle powders separated immediately from the green body upon ejec-
using zirconia balls and distilled water as milling medium. Once tion from the mold.
milling was completed, the slurry was dried in oven at 150 °C for In contrast, although the particle size for powder synthesized by
24 h and then heat-treated at 1100 °C for 1 h. Finally the dried mechanochemical method ranges from 0.5 to 4 lm diameters, it
powder was sieved to obtain the HA powder, hereafter will be should be highlighted that the powder consists of hard agglomer-
known as HA(M). In order to evaluate the sinterability and perfor- ates as typically shown in Fig. 2. Additionally, ‘‘neck’’ formation
mance of different HA powders, a commercially available stoichi- could be observed between smaller particles as a result of the heat
ometric HA manufacture by Merck, Germany was also studied for treatment process carried out on this powder during the synthesis
comparison purpose, hereafter is known as HA(C). Green samples stage.
were fabricated by uniaxial compaction at about 1.3 MPa to On the other hand, the HA(C) powder consisted of a mixture of
2.5 MPa. The green compacts were subsequently cold isostatically small and large particles as shown in Fig. 3. The presences of soft
pressed at 200 MPa (Riken Seiki, Japan). This was followed by con- agglomerates could not be observed in the commercial powder
solidation of the particles by pressureless sintering performed in but instead the particles appeared to be large, up to 10 lm, and
air using a rapid heating furnace over the temperature range of seemed to be more compacted when compared to those observed
1000–1350 °C, with ramp rate of 2 °C/min. (heating and cooling) for the HA powder synthesized by the wet chemical method.
and soaking time of 2 h for each firing. All sintered samples were X-ray diffraction (XRD) analysis of the synthesized HA(W) and
then polished to a 1 lm finish prior to testing. HA(M) powders produced only peaks which corresponded to the
The calcium and phosphorus content in the synthesized HA standard JCPDS card no: 74-566 for stoichiometric HA as shown
powder were determined by using the Inductively Coupled Plas- in Figs. 4 and 5, respectively. The only difference in the XRD pat-
ma-Atomic Emission Spectrometry (ICP-AES) technique. The parti- terns of HA(W) and HA(M) powders before sintering was in the de-
cle size distributions of the HA powders was determined using a gree of crystallinity. The XRD patterns of HA(W) indicated that the
standard MicromeriticsÒ SediGraph 5100 X-ray particle size ana- powder was poorly crystalline as depicted by the broad diffraction
lyzer. The specific surface area of the powder was measured by peaks, which is a characteristic of HA prepared by an aqueous pre-
the Brunauer-Emmett-Teller (BET) method. The morphology of cipitation route. This observation is in agreement with that re-
the starting powder was examined using a Philips ESEM model ported by Gibson et al. [11] who found that calcination at higher
XL30 scanning electron microscope. The phases present in the temperature, as in the present case for HA(M) powders, would ex-
powders and sintered samples were determined using X-ray dif- hibit a narrower diffraction peaks and not a broad one as observed
fraction (XRD) (Geiger-Flex, Rigaku Japan). The bulk densities of for the HA(W) powder in the present work.
the compacts were determined by the water immersion technique In contrast, powders prepared by mechanochemical process
(Mettler Toledo, Switzerland). The relative density was calculated produced a diffraction pattern that indicated a highly crystalline
by taking the theoretical density of HA as 3.156 Mg m3 [2]. The material, with narrow diffraction peaks as a result of heat treat-
microhardness (Hv) of the samples was determined using the Vick- ment as typically shown in Fig. 5. It should be noted that HA could
ers indentation method (Matsuzawa, Japan). The indentation frac- only be obtained in this powder upon heat treatment at 1100 °C.
ture toughness (KIc) was determined from the equation derived by This is shown clearly in Fig. 5 where the XRD trace of the prepared
Niihara et al. [9]. powder before heat treatment produced peaks that corresponded
to the starting precursors (calcium carbonate and calcium pyro-
phosphate). Similarly, X-ray diffraction analysis of the commercial
3. Results and discussion powder, HA(C), produced only peaks which corresponded to the
standard JCPDS card no.: 74-566 for stoichiometric HA as shown
The Ca/P molar ratio determined by ICP-AES for the three pow- in Fig. 6.
ders varied slightly from 1.66 to 1.68, thus close to the stoichiom- After sintering in air atmosphere, the commercial HA compacts
etric value of 1.67 as shown in Table 1. Ozeki et al. [10] have were observed to have a distinct color change, i.e. from white (as-
emphasized the importance of the Ca/P ratio since any deviations received powder) to blue (as-sintered). The intensity of the blue
from the stoichiometric value would have an adverse effect on color was also observed to increase with increasing sintering tem-
the sintered properties of the hydroxyapatite body. The HA(W) perature, i.e. from light blue (1000 °C) to dark blue (1350 °C). It has
been reported by Yubao et al. [12] that most commercial HA pow-
ders contained small additions of impurities and the origin of the
Table 1
apatite blue color was due to the presence of Mn5+ or MnO3 4 ions
ICP-AES results of the starting HA powders.
at the PO34 sites in the apatite crystal structure. According to these
HA(W) HA(M) HA(C) authors, sintering at high temperature not only increases the
Color White White White intensity of oxidation in the oxidizing atmosphere, but also pro-
Calcium (% w/w) 38.9 38.3 37 vides enough energy for the oxidized manganese ion (Mn2+ to
Phosphorous (% w/w) 23.2 23 22
Mn5+) to migrate within the crystal lattice. This color change how-
Ca/P ratio 1.676 1.665 1.681
ever was not observed in both the synthesized HA(W) and HA(M)
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150 S. Ramesh et al. / Materials and Design 34 (2012) 148–154

5 µm

Fig. 1. SEM micrographs of HA(W) revealing the presences of loosely packed particles.

Neck formation

2.5 µm

Hard particles

Fig. 2. SEM micrographs of synthesized HA(M) revealing neck formation between particles and presences of hard particles.

The formation of secondary phases such as tricalcium phos-


phate (TCP), tetracalcium phosphate (TTCP) and calcium oxide
(CaO) was not detected throughout the sintering regime employed.
The result shows that the phase stability of HA was not disrupted
by the initial pressing conditions, sintering schedule and tempera-
ture employed. Similarly, Liao et al. [13] described that HA ceram-
ics would only start to decompose into secondary phases upon
sintering beyond 1350 °C.
The present results however are not in agreement with other
workers who found that decomposition of HA synthesized by
wet precipitation method starts at about 1300 °C [14]. Kothapalli
et al. [15] have reported that sintering at 1200 °C would caused
the HA to decomposed into a-TCP {Ca3(PO4)2}, b-TCP {Ca3(P2O8)}
10 µm and calcium oxide (CaO) according to the equation:

Ca10 ðPO4 Þ6 ðOHÞ2 ) 2Ca3 ðPO4 Þ2 þ Ca3 ðP2 O8 Þ þ CaO þ H2 O ð1Þ


Fig. 3. SEM micrographs of commercial HA(C) powders.
In the present work, decomposition of HA(W) was not observed
throughout the sintering regime employed. Additionally, no at-
tempt was made to control the sintering atmosphere and the sin-
compacts. These materials remained white regardless of sintering tering atmosphere was just plain air (not moisturized). The high
temperature. local humid atmosphere (i.e. the mean monthly relative humidity
The effect of elemental impurities on the sinterability of the falls within 70–90% all year around) could have played a role in
powders could not be confirmed by this study alone. The change hindering dehydroxylation in the HA matrix even at 1350 °C. In
in color in commercial HA was found to have negligible effect on addition, as HA was produced by wet chemical route and was
the HA phase stability as confirmed by XRD phase analysis of the not calcined prior to sintering, a significant amount of absorbed
sintered HA in the present work. The sintering of the synthesized water would probably remain in the structure. However, it is not
HA(W) compacts revealed the present of only HA phase as shown clear if the loss of water during sintering plays a role in suppressing
in Fig. 7. Similar results were observed for HA(C). dehydroxylation.
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S. Ramesh et al. / Materials and Design 34 (2012) 148–154 151

No sign of peaks corresponding

Fig. 4. Comparison of XRD patterns of synthesized HA(W) with the standard JCPDS card for stoichiometric HA.

Fig. 5. Comparison of XRD patterns of synthesized HA(M) powder before and after heat treatment at 1100 °C.

The XRD traces of hydroxyapatite synthesized via the mechano- employed is another important factor that could influence the sin-
chemical technique also revealed the present of only HA phase as tering behavior of HA. Kim et al. [18] synthesized HA powder by
indicated in Fig. 8. The present results obtained for the sintered mechanochemical method using water as the milling medium
HA(M) samples contradicted the findings of Mostafa [16]. In gen- and the milling time was set at 60 min. Nevertheless, the authors
eral, the author reported that the powder which was synthesized observed secondary phases in their HA matrix upon sintering.
using the same technique as the present HA(M) transformed par- The effects of sintering temperature on the sintered densities of
tially into b-TCP upon sintering at 1100 °C. In another work, Yeong the three HA compacts are shown in Fig. 9. All samples were
et al. [17] have also confirmed that the HA powder synthesized heated to the chosen sintering temperature at 2 °C/min. and, after
using mechanochemical method transformed partially into TCP a dwell time of 2 h, cooled to room temperature at 2 °C/min.
when sintered beyond 1200 °C. The difference in the results re- In general, the bulk density increases with increasing sintering
ported in the literatures as compared to the present work could temperature regardless of the type of powder studied. A small in-
be attributed to the milling medium used, the milling time and crease in density is observed before the onset of densification and
probably due to the high purity of the starting powders. The mill- this corresponds to the first stage of sintering, where necks are
ing medium used in the current work was water with a milling formed between powder particles. The second stage of sintering
time of 8 h. Rhee [8] has emphasized the importance of having corresponds to densification (onset of densification) and the re-
100% water content in the milling medium during the mechano- moval of most of the porosity. The onset of densification, indicated
chemical synthesis process. Yeong et al. [17] have synthesized by a sharp increase in the sintered density, for HA(M) and HA(C)
their HA powder using ethanol as the milling medium and this was between 1100 °C and 1200 °C. In the case for HA(W) samples,
could be the reason for obtaining secondary phases upon sintering sintering was carried out from 700 °C so as to determine the onset
due to insufficient H2O present in the medium to suppress decom- densification temperature. As shown in Fig. 9, this temperature
position activity in the HA structure. Additionally, the milling time was found to be between 900 °C and 1000 °C. Generally, sintering
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152 S. Ramesh et al. / Materials and Design 34 (2012) 148–154

Fig. 6. XRD signatures of as-received HA(C) powder.

Synthesized HA(W)

1350ºC
1300ºC
1250ºC
1200ºC
1150ºC
1100ºC
1050ºC
1000ºC

Fig. 7. XRD patterns of synthesized HA(W) sintered at various temperatures. All the peaks corresponded to that of stoichiometric HA.

above this range resulted in very low increase in density which is when sintered at the same temperature. As for HA(M), the highest
associated with the final stages of sintering where small levels of relative density of 98% could only be attained when the material
porosity are removed and grain growth begins. was sintered at 1350 °C. In general, the densification behavior of
The synthesized HA by wet precipitation method achieved a HA(W) was more superior to that of HA(M). This could be attrib-
final sintered density of 97–99% of theoretical density at uted to the higher BET surface area of 60.7 m2/g for HA(W) which
1050–1100 °C, whereas the commercial HA required a sintering promoted a large driving force for densification as compared to a
temperature of 1250–1300 °C to attain a similar density. In gen- low 2.7 m2/g for HA(M). Furthermore, the spherical nano particles
eral, these results indicate that HA synthesized by wet precipita- of HA(W) as observed within the larger agglomerates (Fig. 1)
tion method is more sinteractive than the commercial HA. The would have a higher heat transfer area and thus accelerate densi-
fact that HA(W) shows improved relative density as compared to fication upon sintering. In contrast, HA(M), which consists of hard
HA(C) could be attributed to the physical basis of the Herring agglomerates (Fig. 2), could have led to a lower packing density in
law of sintering [19], which suggests that the sintering rate at a gi- the green state and hence poor sintering behavior.
ven temperature is inversely proportional to the square of the The effect of sintering temperature on the Vickers hardness of
powder particle size. In the present study, the particle size mea- the three HA is shown in Fig. 10. Throughout the sintering temper-
sured using particle size analyzer for HA(W) and HA(C) were ature range studied, it can be noted that HA synthesized by the wet
1.78 ± 0.22 lm and 3.26 ± 1.53 lm, respectively. Thus, the smaller chemical precipitation method displayed superior hardness as
the particle size, the larger would be the BET surface area i.e. compared to HA synthesized by mechanochemical method and
60.7 m2/g for HA(W) as compared 28.4 m2/g for HA(C) and hence commercial HA. The hardness for HA(W) increased as the sintering
the easier would be for HA(W) powder to achieve high density temperature was increased and reached a maximum value of about
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S. Ramesh et al. / Materials and Design 34 (2012) 148–154 153

Fig. 8. XRD patterns of synthesized HA(M) sintered at various temperatures. All the peaks corresponded to that of stoichiometric HA.

100 1.2
Fracture Toughness (MPam 1/2)

95
1
Relative Density (%)

90
0.8
85

80 HA(W) 0.6
75 HA(M)
HA(C) 0.4 HA (W)
70 HA (M)
65 0.2 HA (C)

60 0
1000 1050 1100 1150 1200 1250 1300 1350 1000 1050 1100 1150 1200 1250 1300 1350
Sintering Temperature (ºC) Sintering Temperature (ºC)
Fig. 9. Effect of sintering temperature on the relative densities of HA(W), HA(M) Fig. 11. Effect of sintering temperature on the fracture toughness of HA.
and HA(C) samples.

in Fig. 10. This trend is similar for HA(M) which achieved a maxi-
8 mum hardness of 4.73 GPa when sintered at 1300 °C. Nevertheless,
7 a decreased of hardness was observed for both HA(C) and HA(M)
Vickers Hardness (GPa)

samples when sintered beyond 1300 °C.


6
The effects of sintering temperature on the fracture toughness
5 of compacts of three different HA powders are shown in Fig. 11.
4 In general, HA(W) exhibited better fracture toughness values as
compared to both HA(M) and HA(C) throughout the sintering tem-
3
HA (W) perature range studied. The synthesized HA(W) by wet precipita-
2 HA (M) tion method achieved maximum KIc value of 1.22 MPa m1/2 when
1 HA (C) sintered at 1100 °C. Further sintering at higher temperature would
cause a decreased in the toughness as shown in Fig. 11. In compar-
0 ison, both HA(M) and HA(C) could only achieved maximum KIc of
1000 1050 1100 1150 1200 1250 1300 1350
0.82 MPa m1/2 and 0.77 MPa m1/2, respectively when sintered at
Sintering Temperature (ºC) 1300 °C.
In general, the maximum KIc values for most HA reported in the
Fig. 10. Effect of sintering temperature on the Vickers hardness of hydroxyapatite.
literature varied between 0.96 MPa m1/2 and 1.0 MPa m1/2 [20–22].
Thus, the high value of 1.22 MPa m1/2 obtained in the present work
7.24 GPa when sintered at 1150 °C. Further sintering above 1150 °C for HA(W) when sintered at 1100 °C is very encouraging. It is be-
resulted in deterioration in the hardness. On the other hand, the lieved that this improvement in fracture toughness in the present
hardness of HA(C) started to increased sharply between 1100– HA(W) could be attributed to the improved properties of the
1250 °C and attained a maximum of 5.47 GPa at 1300 °C as shown starting synthesized HA powder.
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154 S. Ramesh et al. / Materials and Design 34 (2012) 148–154

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