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Scripta Materialia 58 (2008) 10541057

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Phase stability and microstructure development

in hydroxyapatitemullite system
Shekhar Nath, Krishanu Biswas and Bikramjit Basu*
Department of Materials and Metallurgical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, UP, India
Received 13 November 2007; revised 16 January 2008; accepted 27 January 2008
Available online 5 February 2008

We report here the results of a transmission electron microscopy (TEM) study of hydroxyapatite (HAp)mullite composites.
TEM analysis, in combination with selected-area diraction pattern analysis, conrms the decomposition of HAp to tricalcium
phosphate, irrespective of mullite content. Importantly, the presence of sintering liquid residue of tetragonal gehlenite as well as
cubic CaO and rhombohedral Al2O3 has been observed in the investigated HAp composites. Based on the microstructural charac-
terization, the possible sintering reactions are discussed.
2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydroxyapatite; Composite; TEM; Microstructure

The last few decades have seen extensive eorts in
developing hydroxyapatite (HAp)-based composites.
The motivation for developing HAp-based composites
stems from the requirement to fabricate materials with
improved strength and toughness (toughness of pure
HAp < 1 MPa m0.5), while retaining good bioactivity.
Some of the widely studied HAp-based bioceramic com-
posites to date include HApalumina composite [1,2]
and HApzirconia [3,4] composite. A common phenom-
enon reported during sintering of HAp-based composites
is the decomposition of HAp due to dehydroxylation (re-
moval of OH ion). Such decomposition results in a
combination of HAp and dissociated tricalcium phos-
phate (TCP) phase, which is termed biphasic calcium
phosphate (BCP). In recent years, BCP-based ceramics
have received attention as an ideal bone substitute due
to their controlled biodegradation [5]. Literature reports
indicate that it is possible to alter the HAp:TCP ratio to
form BCP oering a combination of biodegradability
and stability.
Transmission electron microscopy (TEM) is a power-
ful experimental technique to investigate the microstruc-
ture of multiphase materials at small length scales,
which is essential for understanding the ner microstruc-
tural details and sintering mechanisms [6,7]. Chou et al.
* Corresponding author. Tel.: +91 5122597771; e-mail: bikram@iitk.
ac.in
[8] studied the microstructure of plasma-sprayed HAp
10 wt.% zirconia composite coating on Ti substrate
using TEM. They identied the presence of HAp, amor-
phous calcium phosphate, TCP, ZrO2 and CaZrO3 in
the investigated coatings. Xin et al. [9] examined the
in situ transformation of octacalcium phosphate
(OCP) to hydroxyapatite using TEM. They proposed a
new crystallographic orientation of HApOCP grains.
In addition to such reports, TEM analysis with electron
diraction has been used to study the synthesis, phase
identication and interface of several other HAp-based
composites [1013].
As part of our ongoing research activity [14,15] aimed
at developing lightweight biocompatible materials, the
choice of mullite as a ceramic reinforcement for HAp
matrix has been made in the present work. Mullite, an
important structural ceramic material, is a solid solution
of alumina and silica and has been investigated for a long
time as a refractory material [16]. Mullite (3Al2O3  2SiO2)
has lower density (3.05 g cm3) than Al2O3
(3.95 g cm3) or ZrO2 (6.1 g cm3), higher hardness
(15 GPa) than HAp (7 GPa) or ZrO2 (12 GPa) and
moderate fracture toughness (3 MPa m0.5). The present
paper addresses and assesses two important issues: (i) the
chemical interaction between HAp and mullite during
sintering; and (ii) HAp decomposition in the presence of
mullite. For this purpose, two specic composite compo-
sitions, i.e. HAp10 wt.% mullite and HAp30 wt.%
mullite, were pressureless sintered under identical condi-
tions (1350 C for 2 h in air).

1359-6462/$ - see front matter 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2008.01.045
 S. Nath et al. / Scripta Materialia 58 (2008) 10541057
For the present work, HAp was synthesized by a
widely reported solutionprecipitation route [17]. Com-
mercially available phase pure mullite (D30 0.67 lm,
D50 1.04 lm and D99 2.39 lm, KCM Corporation,
Japan) was used as ceramic reinforcement. In the pro-
duction of the composites, varying amounts of mullite
(10 and 30 wt.%) was ball milled with HAp for 16 h in
acetone using an agate ball as a milling medium. The
ball-milled powders were subsequently pressed in a
hydraulic uniaxial cold press to obtain green cylindrical
bodies (12 mm diameter) and sintered at 1350 C for 2 h
under normal atmospheric conditions (Nabertherm
Supercanthal, Germany). The heating rate was 5 C
min1. After the sintering processes, a typical sintered
disc was 12 mm thick. For phase identication, X-ray
diraction (XRD) analysis was carried out using Cu
Ka radiation (k = 1.5406 A ). Fourier transform infrared
analysis (FT-IR, Vortex 70, Bruker) of starting HAp
powder was carried out in the range of 400
4000 cm1. Detailed TEM analysis was performed using
a JEOL 2000 FXII microscope operated at 200 kV and a
Technai G30 microscope operated at 300 kV. The com-
positional analysis was performed by an energy
dispersive spectroscopy (EDS, Oxford Instruments)
attachment on the Technai G30. We will present here
representative results from our investigations.
Figure 1a presents the XRD spectra acquired from
polished surfaces of sintered HAp10 wt.% mullite and
HAp30 wt.% mullite composites (sintered at 1350 C
for 2 h) as well as ball-milled powder (HAp30 wt.%)
and starting calcined HAp powder. The XRD pattern
of pure HAp starting powder (Fig. 1a(i)) and HAp
Figure 1. (a) X-ray diraction pattern of pure HAp, starting powder
(i), ball-milled powder of HAp30 wt.% mullite composite mixture (ii),
HAp30 wt.% mullite composite sintered at 1350 C for 2 h in air (iii),
and HAp10 wt.% mullite composite sintered at 1350 C for 2 h in air
(iv). (b) FT-IR of pure calcined HAp starting powder.
1055
mullite ball-milled powder mix show characteristics
peaks of HAp and mullite phases (Fig. 1a(ii)). The
XRD pattern from HAp30 wt.% mullite (Fig. 1a(iii))
reveals the dominant presence of b-TCP, along with
detectable amounts of mullite, alumina, gehlenite, calcia
and HAp. In contrast, the major phases in HAp
10 wt.% mullite are a-TCP and HAp (see Fig. 1a(iv)),
which can be regarded as BCP composite. Also, the
X-ray diracted beam intensity corresponding to both
the CaP compounds are comparable. The other phases
could be identied are CaO and b-TCP. Therefore,
when the mullite content is increased from 10 to
30 wt.%, two distinct features can be noticed: (i) decom-
position of HAp to b-TCP is favored more at higher
mullite content; and (ii) this decomposition proceeds
through an intermediate stage of a-TCP at 10 wt.%
mullite addition. The other aspect is the presence of
CaO, Al2O3 and gehlenite, which are clearly the result
of sintering reactions. As far as the presence of b-TCP
at higher sintering temperature is concerned, it is possi-
ble that b-polymorphic structure is stabilized by either
SiO4
4 or Si
4+
or Al3+ ions from mullite phase or gehle-
nite (C2AS) or dispersed Al2O3 phase. Figure 1b repre-
sents the FT-IR plot of pure HAp starting powder. It
shows very strong characteristics of the OH stretching
vibration band at 3570 cm1 and a librational mode
band at 612 cm1.
Representative TEM images of HAp10 wt.% mullite
are shown in Figure 2. Figure 2a is a low-magnication
bright-eld image showing morphologies of the dierent
phases. The large grains are either HAp or transformed
TCP (23 lm) (labelled HAp or TCP, respectively).
The mullite phase can be easily identied by its typical
needle shape. The randomly oriented mullite needles
are 2 lm in size. The higher-magnication image
(Fig. 2b) of another region reveals the presence of a
grain boundary phase (labelled sintered product). The
selected-area diraction patterns (SADPs) from dierent
phases observed in the microstructure are also shown
and indexed in Figure 2. The SADP collected from mull-
ite needle (Fig. 2d) shows the orthorhombic symmetry
Figure 2. (a) Low-magnication TEM micrograph of HAp10 wt.%
mullite sintered at 1350 C showing typical mullite needles along with
the HAp phase. (b) Higher-magnication image showing the presence
of sintered product at the mulliteHAp interface. (ce) Electron
diractions patterns from HAp, mullite and a-TCP phase, respectively.
1056 S. Nath et al. / Scripta Materialia 58 (2008) 10541057

of the unit cell with lattice parameters of a = 0.755 nm,

b = 0.769 nm and c = 0.288 nm. Compositional analysis
using EDS does not reveal any appreciable composi-
tional change in unreacted mullite. The SADP from
HAp grain is shown in Figure 2c. It can be indexed using
the lattice parameters of hexagonal HAp (a = 0.943 nm
and c = 0.688 nm). The inset in Figure 2a is a high-res-
olution lattice fringe image from the HAp grain, show-
ing an atomic resolution image. Closer observation
reveals that the HAp grains are not clean, as a number
of defects are present. The above results are also in line
with the XRD analysis of HAp10 wt.% mullite. Similar
results are found from the electron-diraction patterns
obtained from the HAp30 wt.% mullite sample. It has
been observed during TEM observations that some of
the HAp grains have been transformed to a-TCP. Fig-
ure 2e shows a typical SADP recorded from one such
grain. This pattern can be indexed with monoclinic unit Figure 4. TEM micrograph of HAp30 wt.% mullite sintered at
cells (a = 1.289 nm, b = 2.728 nm and c = 1.522 nm), 1350 C for 2 h in air, showing (a) gehlenite around the mullite needle,
and a dislocation network in TCP grains, and (b) the presence of
corresponding to a-TCP.
alumina along with gehlenite ahead of mullite needles. (c) Parallel
The important result of the sintering of HAp with mullite needles bridging the TCP and HAp grains. (d) The SAD
mullite is the formation of the sintered product at the pattern taken from alumina grain, indicating the rhombohedral unit
interface of HAp and mullite needles. Figure 3 shows cell of alumina.
a bright-eld and a dark-eld view of such phase. The
corresponding SADP from this phase is shown in Figure
3c. The EDS pattern in Figure 3d indicates that the reac- bright-eld micrograph (Fig. 4a) shows a mullite needle,
tion phase contains Ca, Al, Si and O. In particular, gehlenite and also the dislocation network inside an
semiquantitative compositional analysis also reveals HAp grain. Such observations imply that HAp grains
that the average composition of the phase is Ca possibly undergo deformation during the sintering pro-
(1520 at.%), Al (2025 at.%), O (5060 at.%) and Si cess. Figure 4b reveals the alumina grains ahead of mull-
(35 at.%). In addition, the SADP can be indexed using ite needles. Figure 4d shows the SADP from Al3O3,
the lattice parameters of tetragonal gehlenite which can be indexed using rhombohedral alumina
(a = 0.759 nm and c = 0.490 nm). This, along with the (R3C, a = 0.472 nm and c = 1.282 nm). The presence
EDS analysis, further conrms that the phase is tetrag- of alumina has already been recorded from the XRD
onal gehlenite (2CaO  Al2O3  SiO2:C2AS). From the pattern (Fig. 1a). The other important characteristics
bright-eld and dark-eld image view shown in Figure of the sintered sample are shown in Figure 4c, which re-
3, it can be clearly seen that the HAp grains are partly veals three parallel mullite needles forming a bridge be-
wetted by gehlenite, which is a typical signature of li- tween HAp grains. This type of mullite dispersion in the
quid-phase sintering. HAp matrix is expected to enhance its mechanical prop-
Figure 4 reveals various microstructural features of erties. Indeed, preliminary mechanical property evalua-
sintered HAp30 wt.% mullite. The low-magnication tion reveals better indentation toughness of HAp30%
mullite (2.5 MPa m0.5), whereas the toughness of pure
HAp is always less than 1 MPa m0.5.
Another important aspect of the TEM investigation
is the presence of CaO. Figure 5 shows a bright-eld

Figure 3. Bright-eld (a) and dark-eld (b) view of HAp10 wt.%

mullite showing the sintered product wetting the HAp grain; (c) the Figure 5. (a) Bright-eld image of HAp10 wt.% mullite, showing the
corresponding SADP from the sintered product, which is identied as formation of CaO and gehlenite during the sintering process. (b) EDS
gehlenite; and (d) the EDS pattern recorded from the sintered product pattern recorded from the sintered product showing the presence of Ca
showing the presence of Ca, O, Al and Si. and O. (c) The corresponding SAD pattern from CaO.
 S. Nath et al. / Scripta Materialia 58 (2008) 10541057
image obtained from the sintered HAp10 wt.% mullite,
revealing dierent phases. The SADP obtained from
these phases is shown in Figure 5b. This diraction pat-
tern can be indexed using the lattice parameter of cubic
CaO (a = 0.481 nm). The EDS analysis (Fig. 5b), show-
ing a stronger presence of Ca and O, further conrms
the presence of CaO. Therefore, the presence of CaO
in the TEM investigation conrms that the decomposi-
tion reaction of HAp produces CaO along with TCP;
this can be explained by the following reaction:
2Ca5 PO4 3 OH 3Ca3 PO4 2 CaO H2 O 1
The formation of gehlenite (C2AS) and alumina
(Al2O3) at the grain boundary is the result of the limited
reaction of CaO with mullite. It can be recalled here that
SADP and TEMEDS analysis conrms the presence of
tetragonal C2AS (gehlenite). The reaction can be written
as
4CaO 3Al2 O3  2SiO2 22CaO  Al2 O3  SiO2 Al2 O3
2 Ceram. Soc. 17 (1997) 1361.
During sintering of HApmullite composites, CaO
reacts with mullite and rst forms ternary eutectic at
1170 C, according to the CaOAl2O3SiO2 ternary
phase diagram [18]. After sintering at 1350 C, the com-
posites contain C2AS (gehlenite), which has been identi-
ed from TEM diraction pattern analysis (Fig. 3c). It
should be noted here that the initial precursor mullite
particle was spherical in shape (spray dried); however,
needle-shaped mullite grains are recorded in sintered
ceramics (Figs. 4 and 5). It has been reported that mullite
grows with a grainy structure in the presence of certain
constraints [19]. This happens in the case of solid-state
sintering of pure mullite [20] and mullite-based compos-
ites [21]. However, in an unconstrained microstructure
(during liquid-phase sintering), due to the anisotropic
nature of growth of rhombohedral mullite, the mullite
grains can grow anisotropically [20,22,23], resulting in
elongated grains. In the present investigation, we believe
that the formation of the calciaaluminasilica liquid
phase helps the mullite phase to grow unidirectionally.
This type of elongated grain has been found to poten-
tially lead to better fracture toughness (crack deection)
due to its high aspect ratio [24].
The cell culture experiments on HApmullite com-
posites, using human osteoblast/osteosarcoma and
mouse broblast cell lines, reveal excellent cell adhesion
properties, similar to pure HAp, and the MTT assay test
also proves the same point quantitatively. Furthermore,
short-term implantation testing in rabbit for up to 12
weeks with HApmullite composites provides evidence
of bone regeneration as well as of the good histocompat-
ibility. Hence, this newly developed HApmullite com-
posite would be suitable for biomedical applications.
Based on experimental results, the following conclu-
sions can be drawn: (a) The sintering experiments at
1350 C clearly reveal that decomposition of HAp to
b/a-TCP is more favored with increase in mullite con-
tent. Interestingly, with an increase in mullite content
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1057
to 30 wt.% almost complete decomposition to b-TCP
was recorded; however, a noticeable amount of HAp
was retained in the HAp10 wt.% mullite composite.
(b) TEM observations, in combination with SADP
and EDS analysis, conrm the presence of a-Al2O3
(rhombohedral alumina) and tetragonal gehlenite
(C2AS) as the product of the sintering reactions. Also,
the gehlenite phase, being liquid at the sintering temper-
ature of 1350 C, promotes liquid-phase sintering.
Importantly, a bunch of mullite needles of aspect ratio
78 are dispersed in the sintering microstructures.
The authors thank Prof. K. Chattopadhyay for
allowing us to use the Technai TEM facility at IISC,
Bangalore, India, Prof. Rajendra K. Bordia for fruitful
discussions and Department of Biotechnology, Govern-
ment of India for nancial support.
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