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Solution Combustion Synthesis of Calcium

Hydroxyapatite Nanoparticles
a a a
Samir K. Ghosh , Someswar Datta & Sujit K. Roy
a
Central Glass and Ceramic Research Institute Kolkata—700 032
Published online: 04 Nov 2014.

To cite this article: Samir K. Ghosh, Someswar Datta & Sujit K. Roy (2004) Solution Combustion Synthesis
of Calcium Hydroxyapatite Nanoparticles, Transactions of the Indian Ceramic Society, 63:1, 27-32, DOI:
10.1080/0371750X.2004.11012125

To link to this article: http://dx.doi.org/10.1080/0371750X.2004.11012125

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 Solution Combustion Synthesis of Calcium
Hydroxyapatite Nanoparticles
Samir K. Ghosh, Someswar Datta and Sujit K. Roy
Central Glass and Ceramic Research Institute
Kolkata - 700 032
Nanoparticles of calcium hydroxyapatite, Ca 10(P0 4)s(OHh, (HA)
an important material for biomedical applications and other
non-medical uses were synthesized by combustion in the
aqueous system Ca-nitrate-diammonium hydrogen orthophos-
phate-urea. The combustion behaviour and phase evolution with
respect to the Ca/P atom ratio in the starting materials were
investigated. Single-phase hydroxyapatite particles were
obtained when the Ca/P ratio in the starting batch was 1.75. Below
this ratio the products contained mainly hydroxyapatite and
tricalcium phosphate (Ca 3 (P04 ) 2 , TCP), the relative abundance
of these phases being dependent upon the batch composition.
In all these cases, the particles were equiaxed, nanosized (60-
Downloaded by [Northeastern University] at 10:05 08 January 2015
130 nm) and occurred as easily dispersible soft agglomerates of
sizes ranging from 0.1 to larger than 100 pm. The products were
characterized for phase contents, particle size distribution and
morphology.
Introduction
With the growth in medical science and advancements
in surgical techniques, there is an increasing demand for
artificial bone implants. This happens due, on one hand, to
a limited supply of auto-graft material and, on the other,
the health risks associated with the use of allografts. 1
Hydroxyapatite (HA), having the chemical formula
Ca10(P04) 6(0Hh, is the major constituent of teeth and
bones. Synthetic hydroxyapatite has commanded exten-
sive attention in the last several years as material for
medical implants. 2-4 From the point of view of biocompati-
bility, hydroxyapatite seems to be the most appropriate
choice for hard tissue replacement implants. It shows
excellent biocompatibility with hard tissues and also with
skin and muscle tissues. Moreover, HA can directly bond
to the bone. 5 Hydroxyapatite powder and granules have
been used for bone grafting and augmentation while dense
as well as porous blocks have found application as
implant material in the field of dentistry and orthopaedics. 6
Unfortunately, its low fracture toughness (0.8-1.2 MPa.
m112 ) and flexural strength (<130 MPaf currently restrict its
use to small unloaded implants, powders, coatings and
low-loaded porous implants. 8 · 9 The non-medical applica-
tions of HA include packing media for column chromatog-
raphy, gas sensors, catalysts, and host material for lasers. 10
According to its chemical formula, stoichiometric HA
should have the Ca/P atom ratio of 1.67. The stability
limit of the apatitic structure in HA has been the subject
of a number of studies, covering a rather wide range of
compositions. 11 · 12 The apatitic crystal structure can be
preserved with Ca/P ratios as low as 1.5 which are called
calcium-deficient or non-stoichiometric. These materials
exhibit thermal instabilities at characteristic temperatures. 13
A variety of methods have been employed to enhance
the strength of HA. These include: modification in the
VOL. 63 (1) JANUARY- MARCH 2004
powder processing route, addition of dopants, and the use
of hot pressing technique. Different sintering regimes were
also studied to improve its toughness. 14 Preparation of HA
ceramics with superior mechanical properties is possible if
the starting HA powder is stoichiometric. 5 With a
hyperstoichiometric material (i.e., Ca/P > 1.67), GaO forms
during sintering, and the substoichiometric composition (Cal
P<1.67) yields 13- or a-tricalcium phosphate (Ca3(P04 ) 2 ,
TCP). Since the presence of TCP increases biodegrad-
ability of the HA ceramics, its occurrence is generally
avoided. However, HA!TCP composites are sometimes
used to control their biological performance by suitably
changing the biodegradation rate of the composite implant
through a careful control of the HA 1 TCP ratio. 15·16
Materials with microstructural features less than 100
nm in dimensions are known as nanomaterials and have
been proven to possess novel properties. 17 Monolithic
nanocrystalline ceramics can normally be fabricated from
nanocrystalline powders and these could become relatively
ductile if ultrafine grain sizes can be achieved on sintering
at increased temperatures. Besides, HA has hexagonal
crystal structure and its coefficient of thermal expansion is
anisotropic that makes the ceramic prone to microcracking
as the grain size increases, causing degradation of the
structure. Therefore, it is important to obtain a final grain
size below a critical size less than 1.5 Jim for sintered HA
to improve its fracture toughness. 18
Reaction-processing methods involving combustion
techniques are currently being pursued as a quick, straight-
forward way to synthesize homogeneous, very fine,
crystalline, and weakly agglomerated multi-component
materials, without the need for intermediate calcination
and decompositon steps. Certain variants of these methods
are also reported to favour a strict control of product
stoichiometry. 19
Solution Combustion
The solution combustion method involves an exother-
mic, usually very rapid and self-sustaining chemical reac-
tion between the desired metal salts, preferably nitrates,
and a suitable organic fuel, such as urea, in an aqueous
solution and the reaction is initiated at a fairly low tem-
perature.20 The important aspect of this oxidation-reduc-
tion (redox) reaction is that the heat required to sustain the
chemical reaction and accomplish the compound synthesis
is provided by the reaction itself and not by an external
source. A large amount of gases is formed that burn with
the appearance of an incandescent flame and may attain
high temperatures, often exceeding 1000°C.
27
 Conventionally, this technique consists of preparing a
stoichiometric mixture of the required cations and the
organic fuel in the desired amount of water, bringing it to
boil until ignition occurs whereby a self-sustaining and
rather fast combustion reaction takes off, at the end of which
a dry, usually crystalline, fine oxide powder is obtained.
Water-soluble nitrate salts of the desired metal ions and
urea are the most common starting materials for the solution
combustion processing. The combustion of metal nitrates
-urea mixtures in water solution usually occurs as a self-
propagating and non-explosive exothermic reaction.
Thermochemical concepts used in propellant chemistry
constitute the principle of this method. The composition of
a fuel-oxidizer mixture is important in the field of propellants
and explosives for a variety of reasons, and needs to be
expressed by an index or parameter that would clearly
indicate its relation to stoichiometry of the mixture, that is,
if it is fuel-lean, stoichiometric, or fuel-rich. Jain et a/. 21
introduced a simple method of calculating the oxidizing to
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reducing nature of the mixture, irrespective of whether the
elements are present in the oxidizer or the fuel components
of the mixture. Those authors also showed that, for a stoi-
chiometric mixture, the magnitude of the total composition
of oxidizing and reducing elements is closely related to the
heat of reaction (or the difference in the proportionately
summed up bond energies of the products and the reac-
tants), calculated thermodynamically from the heats of
formation of the constituent batch materials.
According to the concepts of the propellant chemistry,
the gaseous products of combustion reaction are C0 2, H20
and N2. This leads to the consideration that the elements
C and H are reducing elements with the corresponding
valences of +4 and + 1, oxygen having the valence of -2
serves as the oxidizing element, and nitrogen has zero
valence. The extrapolation of this concept to processing
of ceramic oxides by solution combustion means that
metals are considered as reducing elements with their re-
spective stable valences. The stoichiometric composition
of the redox mixture for the synthesis is calculated on the
basis of the total oxidizing and reducing valences of the
oxidizer and of the fuel, in order to release the maximum
amount of energy for the reaction.
Besides urea (CON 2H 4 ), a variety of organic fuels
have been used that include tetraformal triazine (TFTA,
C4H 16 N60 2), 22 carbohydrazide (CON 4 H6)23 · 24 or maleic hy-
drazide (C 4H4 N20 2f 5 that differ in their total valences, that
is, +6, +28, +8 and + 16, respectively ("reducing power")
and the amount of gases they generate. The amount of
gases generated by one mole of fuel ranges from 15 moles
for TFTA to only 4 moles for urea. 26 This obviously influ-
ences the characteristics of the reaction product. The non-
isothermal reaction releases larger amounts of gases that
dissipate more heat, thereby preventing the oxides from
sintering. The coincident sintering effect in the higher tem-
perature reactions may result in a loss of submicron nature
of the powder particles. However, the product tends to be
microporous and less crystalline. Considering the hazard
and difficulty in synthesis of these fuels, urea seems to be
the most convenient fuel to use because it is cheap and
28
readily available commercially, and generates the highest
temperature, which may lead to the production of prema-
turely sintered particle agglomerates in highly exothermic
systems. Metal nitrates are the preferred salts because
they are soluble in water whereby better mixing is achieved
and uniformity of the product results. The water of crystal-
lization does not affect the total valences of the nitrates
and are, therefore, irrelevant for the chemistry of the solu·
tion combustion technique.
The aqueous combustion reaction is governed by a com-
bination of microscopic chemical kinetics and macroscopic
heat and mass transfer; accordingly, the reaction tempera-
ture and the reaction time are the two important factors that
govern the phase formation during the synthesis process.
It is expected that increasing the reactant concentration and
heat of reaction and reducing the heat losses through con-
vection and radiation to the surroundings will facilitate the
propagation of the reaction. 27 This can be achieved by ad-
JUSting the nature and content of the fuel, solution loading,
volume of gases formed and the furnace temperature.
The credit of developing this method of synthesis goes
to Kingsley and Patil 20 who demonstrated its use in the
preparation of high-purity and also doped a-alumina pow-
ders. Subsequently, Patil and co-workers, as also others
successfully used this method of material synthesis in pre-
paring a variety of single and mixed oxides, ranging from
zirconia toughened alumina (ZTA) to superconductors,
using various fuels mentioned earlier. 20 ·22- 25 This technique,
being quick and energy-efficient, has attracted much inter-
est and has been profitably utilized in the synthesis of a
number of advanced materials. 28 - 33
In the present study, the technique of solution combus-
tion in aqueous Ca-nitrate-urea system containing diammo-
nium hydrogen orthophosphate is employed in order to
obtain a homogeneous, porous, easily dispersible, crys-
talline powder of calcium hydroxyapatite. The feasibility of
producing nano-crystalline particles and the thermal be-
haviour of HA during synthesis with regard to initial Ca/P
atom ratio in the solutions are also investigated.
Experimental
In this study, calcium nitrate tetrahydrate (Ca(N03h.
4H 20), diammonium hydrogen phosphate (DAP,
(NH 4hHP0 4) and urea (CO(NH 2h), were used as raw
materials. Aqueous solutions of these salts were used in
the experiments and urea was added to the mixed solution
as a solid. Concentrated HN0 3 was used to regulate the
pH of the experimental batches. The characteristics of the
raw materials and their solutions are given in Table I. The
stoichiometric composition of the mixtures is calculated on
the basis of total oxidizing and reducing valences of the
oxidizer and that of the fuel. At the exact equivalence of
oxidizer and fuel valences the mix is considered stoichio-
metric and energy release is at the maximum. Here the
elements Ca, H, and C are considered as reducing ele-
ments with their corresponding valences of +2, + 1 and +4
respectively and divalent oxygen serves as the oxidant.
The valence of nitrogen (N 2) is considered as zero (0).
Following this procedure, the calculated total valences of
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 Table I : Raw materials the particle size distribution were ascertained by photon
correlation spectroscopy (Mastersizer 2000, Malvern, UK).
Materials Source Purity(%) ·concentration
Infrared spectra of the powder samples were collected in
Ca-nitrate s.d. fine chem. 99 1.73 M the range of 4000 cm- 1 - 400 cm- 1 by Fourier Transform
Infra-Red (FTIR) spectrometer (Perkin-Elmer, Model1615)
DAP Sarabhai Chern 97 1.63 M
in the transmission mode. The particle morphology and
Urea Glaxo (Qualigens) 99 Solid addition the agglomerate structure were investigated using a scan-
HN0 3 Merck 99.95 14M ning electron microscope (SEM) (leo 430i).

the raw materials are: calcium nitrate tetra hydrate (-1 0),
diammonium hydrogen phosphate (+6) and urea (+6). Al-
though the positive total valence (+6) of OAP suggests fuel
characteristics, it is to be noted that DAP does not act as a
fuel and its participation in the reaction is akin to that of a
diluent and utilizes redox heat for subsequent HA synthe-
sis. Therefore, the use of additional fuel and/or oxidizer
will be required if the HA-synthesis is to be accomplished
during combustion. Further, to assist formation of a large
volume of gases during reaction and synthesis of nano-
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Results and Discussion
The characteristics of the products obtained by solution
combustion technique in Ca-nitrate-diammomium hydrogen
phosphate-urea system with respect to different Ca/P
ratios are given in Table Ill.
The appearance of white incandescent flame, produc-
tion of a large volume of gases, short reaction duration
and foamy nature of the reaction product together indicate
that HA is produced by the combustion process. This
method of synthesis progresses through the stages of

particles, fuel-rich compositions were employed. It was
seen earlier that fuel-rich mixtures ignited easily, the high
temperature was sustained longer, and the combustion
resulted in crystalline as-prepared compounds. 34
The experimental batches were prepared by combin-
ing the reactant salt solutions in different volume ratios to
vary the Ca/P atom ratios and are displayed in Table II.
The required volumes of aqueous solutions of 1.73(M)
Ca(N0 3) 2 .4H 2 0 and 1.63(M) (NH 4 hHP0 4 were added into
a 250 cm 3 Pyrex beaker. The resulting white precipitate
was dissolved by adding 3 cm 3 of concentrated nitric acid.
A predetermined amount of urea was added to the clear
solution, and following homogenization by stirring with a
magnetic stirrer for 30 min at room temperature, the beaker
containing the solution was introduced into a muffle fur-
nace preheated to 600°C. When placed in the furnace, the
mixed solution soon started to boil, underwent dehydra-
tion and decomposition and a large volume of gases con-
taining oxide of nitrogen and traces of ammonia evolved.
The mass then frothed and swelled to yield foam, where a
llnme appeared and produced incandescence. The entire
process required less than 20 min with flame duration of
nearly one minute. The as-synthesized products were typi-
cally voluminous, fluffy foam-like mass that occupied a large
volume. The resulting soft-agglomerated mass was read-
ily ground manually in an agate mortar/pestle into fine pow-
der and was thoroughly characterized. X-ray diffraction
patterns of the combustion products were recorded to study
the phase formation (Philips Analytical, X'Pert, 1830, Hol-
land). The median diameter of the powder particles and
Table II : Batch compositions
Sample Molar Amount of
ldentifi· ratio Ca-Nitrate DAP Urea HN03
cation of Ca/P (g) (g) (g) (ml)
HA-1 1.75 8.80 2.80 14
HA-2 1.67 8.80 2.94 14
HA·3 1.45 8.80 3.39 14
dehydration, decomposition and ignition leading to the
exothermic self-sustaining reaction. At the completion of
the reaction, the fuel converts completely into gases and
the solid product Ca-hydroxyapatite forms according to the
following relation:
30Ca(N0 3h4H 20 + 18(NH 4hHP04 + 50CO(NH 2 h +
270 2 = 3Ca 10 (P0 4 ) 6 (0H) 2 +50C0 2 +
298H 20 + 98N 2 •• (1)
The total heat required for the synthesis of the hydroxy-
apatite phase is supplied mainly by the combustion reac-
tion of urea-nitrate mixture and may be described by the
following equation.
2CO(NH 2 ) 2 + 30 2 = 2C0 2 + 4H 2 0 + 2N 2 •• (2)
Although it is assumed that the gaseous products of
solution combustion are carbon dioxide, moisture, and ni-
trogen only, in practice it was found that oxides of nitrogen
and ammonia evolved at various stages of this reaction.
This makes the calculation of the stoichiometric mixture a
difficult task and it appears that working with a fuel-rich
composition is preferable.
It will be seen from the results given below that in the
present study nanometric HA particles were obtained. The
preparation of nanocrystalline materials using fuel-rich
batch materials is in contradiction to the results of Hong et
a/. 35 who observed increased grain growth and loss of sur-
face area with increased urea contents during wet chemical
combustion synthesis of Cao 5 Sr0 .5Zr4 P60 24 (CSZP). The
results were attributed to the longer flame duration. This
discrepancy between these two results may be attributed
to the differences in the experimental procedures adopted.
pH In the present study, the use of dilute solutions of reactants,
furnace temperature of 600°C, and evolution of larger vol-
ume of gases during reaction that prevented sintering of
the product nuclei aided the formation of nanometer-sized
3 3.5
particles. On the other hand, Hong et a/. 35 combusted a
3 3.5 slurry that might have caused heterogeneous nucleation
3 3.5
of the phosphate phase on the solid sites present and fa-
cilitated growth of the limited number of nuclei. Moreover,

VOL. 63 (1) JANUARY- MARCH 2004 29

 Table Ill : Characteristics of the hydroxyapatite materials formed by solution combustion synthesis

Specimen Ca/P atom Phase content by XRD SEM Particle Size

identity ratio
HA TCP Others Morphology Size Dgo Dso 010
vol% vol% vol% (nm) (pm) (pm) (pm)

HA-1 1.75 -100 - - Isometric 60-150 28.29 3.99 0.21

spherical
particles
HA-2 1.67 85.1 14.8 0.1 Isometric 70-100 36.05 3.98 0.23
spherical
particles
HA-3 1.45 30.1 42.7 27.2 Isometric 60-130 47.27 6.83 0.23
spherical
particles

it is possible that a specific composition of the gaseous
atmosphere enhanced coarsening of CSZP grains. Such
grain-growth effects were noted by Roy 36 and by Readey
eta/. 37 during sintering of oxides in reactive atmospheres.
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patite phase. It is seen that post-synthesis thermal treat-
ments are not essential for the desired phase formation.
However, depending on the initial Ca/P ratio the products

contain various quantities of tricalcium phosphate, (~­

Results of X-ray diffraction for the as-synthesized pow- Ca3(P04h, ~-TCP) as the associated phase. Essentially
ders prepared by the solution combustion route and having full conversion to single phase Ca-hydroxyapatite is
different Ca/P atom ratios in the starting batch compositions achieved only for the powder prepared from the batch
are presented in Fig. 1. The as-prepared materials are all HA-1 having Ca/P ratio of 1. 75. An increase in calcium
highly crystalline and contain mainly the desired hydroxya- content relative to phosphorus in the lattice of this hydroxy-
apatite material is indicated by the presence of a small
peak at 29.39° in the XRD pattern. Hing et a/. 1 also
D=HA observed an additional peak at 37.4° (CaO) in the XRD
• =TCP pattern of Endobon, a commercial hydroxyapatite material
o = CaC0 3
produced from natural cancellous bone. This is expected,
a as hydroxy-apatite is known to accommodate a consider-
able range of lattice substitutions at both the A (OW) and
Ca/P = 1.75 B (P043-) sites. FT-IR analysis shows that this as-synthe-
a sized product was essentially B-type carbonate substituted
a apatite. Bone mineral is believed to be primarily a B-type
a carbonate substituted apatite. 1 The occurrence of both the
HA and TCP phases in the products from HA-2 and HA-3
may indicate the mechanistic mode of solution combustion
process. Fanovich et a/. 13 carried out a survey on the sta-
>
l- a bility aspects of apatite structure in non-stoichiometric HA
Ui having compositions of 1.67 > Ca/P > 1.50 and concluded
z a
w that these ceramics partially decompose to ~-Ca3 (P0 4 h at
1- a Ca/P = 1.67
!:: temperatures above 800°C. The phase transformation from
D
~- to a-Ca3 (P0 4)2 takes place subsequently at tempera-
tures higher than 1200°C. 38 Thus, it is suggested that dur-
ing combustion HA is formed first which then decomposes
to yield TCP. The absence of a-phase indicates that the
temperature reached during synthesis is lower than
1200°C. The flame temperature could then be assumed to
Ca/P = 1.45 be between 1oooo and 1200°C. The relative abundance of
the phases is calculated from the integrated intensities of
the major peaks and the products of combustion of HA-2
and HA-3 are found to contain ~-TCP in amounts of 14.8
and 42.7% by volume, respectively. Thus, it is observed
that the variation in the nominal Ca/P atom ratio in the batch
25 30 35 40 45 50 materials may serve as a powerful tool to control the phase
29 (degree) contents of the products. In all the cases, the products
Fig. 1 - XRD spectra of combustion synthesized consist of soft agglomerates that could be dispersed by
hydroxyapatite powders. easy mechanical means.

30 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 Figure 2 displays the FTIR spectra of the as-synthe- ent sizes. These are built up of small ultimate particles, the
sized powders obtained from the batches containing dif- size of which is nearly 100 nm. The combustion process
ferent proportions of Ca-nitrate and diammonium hydro- yields fine, uniform equi-axed particles as a result of the
gen phosphate solutions. The characteristic features of the fast chemical reaction at high temperature in situ in a
HA-phase, namely, the P0 4 -bands at 1046, 954, 600 and viscous, homogeneous medium.
569 cm· 1 and OH-stretching mode at 3431 cm- 1 are clearly The morphology of the powder particles and the struc-
present in all the three products. The presence of co; ture of particle agglomerates are essentially similar in the
group is indicated by the simultaneous occurrence of a products derived from the three batches, HA-1, HA-2, and
peak at 877 cm- 1 and a broad band at 1385-1443 cm- 1 HA-3, but these have small differences in the size of the
especially in the batches HA-2 and HA-3. On the basis of ultimate particles. Figure 4 depicts the scanning electron
FTIR results, it can be further inferred that the products micrograph of as-prepared HA-1 product. The agglomerates
from HA-1 and HA-3 batches are essentially free of the
nitrate group whereas its presence (1385 cm- 1) may be
indicated in the specimens of HA-2 which is the stoichio-
metric hydroxyapatite.
The results of direct measurement of particle size dis-
tribution of the as-prepared powders by photon correlation
spectroscopy are shown in Fig. 3. The distribution is multi-
modal, showing the occurrence of agglomerates of differ-
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• =C02 (air)
Ca/P =1.75

Ca/P = 1.67
Fig. 4 - Scanning Electron micrograph of "as-synthesized"
hydroxyapatite powder. [HA-1; Ca/P = 1.75]

are highly porous and are composed of fine isometric par-

ticles having narrow size distribution. The particle size is
estimated to be of 60-150 nm. Small variation of ultimate
particle size with Ca/P ratio is noted and estimated sizes
for HA-2 and HA-3 provide the values of 70-1 00 nm and
60-130 nm, respectively. The reaction produces a powder
with morphology similar to the foam-like structure present
in the boiled viscous solution, and due to high volume
4000 3000 2000 1000 400
cm· 1
reduction of the solid phase, particles are distributed in the
Fig. 2- FTIR spectra of as-synthesized hydroxyapatite cellular walls of the foam. Also, as the gases escape
powders of different Ca/P ratios in starting solutions. instantaneously, they leave a porous network of the nucle-
ated HA-particles, preventing their coarsening. Therefore,
the highly porous, foam-like structure of HA-materials

~
Ca/P =1.75 suggests the inherent nature of the chemical reaction
100[ - - Ca/P =1.67 associated with the presence of large amount of gases,
c ------- Ca/P =1.45 high temperature, and short reaction period.
w 80
:::;
:> Conclusions
...J
~ 60 Nano-sized, crystalline powders of calcium hydroxy-
w apatite and of hydroxyapatite I tricalcium phosphate com-
>
~
...J
40 posites could be produced by the solution combustion
:> method using fuel-rich batches. Variation in the contents
:::;
:> 20 of calcium nitrate and diammonium hydrogen orthophos-
(J
phate in the starting materials is found to be a way to control
0 the phase composition of the composite products. Consi-
dering the dependence of thermal stability of hydroxyapa-
0.01 0.1 10 100 tite phase on the Ca/P atom ratio in the range of 1.45 to
PARTICLE DIAMETER (Jim) 1.67, it is suggested that in the solution combustion pro-
Fig. 3- FTIR spectra of as-synthesized hydroxyapatite cess HA is formed initially that undergoes transformation
powders of different Ca/P ratios in starting solutions. to TCP and yields the composite materials.

VOL. 63 (1) JANUARY- MARCH 2004 31

 Acknowledgements: The authors wish to thank Dr. H. S. Maiti, Di-
rector, Central Glass and Ceramic Research Institute, Kolkata for his
keen interest and constant encouragement. The help of Dr. A. K.
Chakrabarty for XRD, of Dr. B. Karmakar for FTIR, of Dr. Mahua Ghosh
for PSD, and of Mr. A. Mandai for SEM is deeply appreciated. The
technical help rendered by the personnel of Glass-Ceramic Coating
Division is gratefully acknowledged. SKR is currently working as a
CSIR Emeritus Scientist.
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