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Transactions of The Indian Ceramic Society
Transactions of The Indian Ceramic Society
Transactions of The Indian Ceramic Society
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
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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) powder processing route, addition of dopants, and the use
an important material for biomedical applications and other of hot pressing technique. Different sintering regimes were
non-medical uses were synthesized by combustion in the
aqueous system Ca-nitrate-diammonium hydrogen orthophos-
also studied to improve its toughness. 14 Preparation of HA
phate-urea. The combustion behaviour and phase evolution with ceramics with superior mechanical properties is possible if
respect to the Ca/P atom ratio in the starting materials were the starting HA powder is stoichiometric. 5 With a
investigated. Single-phase hydroxyapatite particles were hyperstoichiometric material (i.e., Ca/P > 1.67), GaO forms
obtained when the Ca/P ratio in the starting batch was 1.75. Below during sintering, and the substoichiometric composition (Cal
this ratio the products contained mainly hydroxyapatite and
P<1.67) yields 13- or a-tricalcium phosphate (Ca3(P04 ) 2 ,
tricalcium phosphate (Ca 3 (P04 ) 2 , TCP), the relative abundance
of these phases being dependent upon the batch composition. TCP). Since the presence of TCP increases biodegrad-
In all these cases, the particles were equiaxed, nanosized (60- ability of the HA ceramics, its occurrence is generally
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130 nm) and occurred as easily dispersible soft agglomerates of avoided. However, HA!TCP composites are sometimes
sizes ranging from 0.1 to larger than 100 pm. The products were used to control their biological performance by suitably
characterized for phase contents, particle size distribution and
changing the biodegradation rate of the composite implant
morphology.
through a careful control of the HA 1 TCP ratio. 15·16
Introduction Materials with microstructural features less than 100
With the growth in medical science and advancements nm in dimensions are known as nanomaterials and have
in surgical techniques, there is an increasing demand for been proven to possess novel properties. 17 Monolithic
artificial bone implants. This happens due, on one hand, to nanocrystalline ceramics can normally be fabricated from
a limited supply of auto-graft material and, on the other, nanocrystalline powders and these could become relatively
the health risks associated with the use of allografts. 1 ductile if ultrafine grain sizes can be achieved on sintering
Hydroxyapatite (HA), having the chemical formula at increased temperatures. Besides, HA has hexagonal
Ca10(P04) 6(0Hh, is the major constituent of teeth and crystal structure and its coefficient of thermal expansion is
bones. Synthetic hydroxyapatite has commanded exten- anisotropic that makes the ceramic prone to microcracking
sive attention in the last several years as material for as the grain size increases, causing degradation of the
medical implants. 2-4 From the point of view of biocompati- structure. Therefore, it is important to obtain a final grain
bility, hydroxyapatite seems to be the most appropriate size below a critical size less than 1.5 Jim for sintered HA
choice for hard tissue replacement implants. It shows to improve its fracture toughness. 18
excellent biocompatibility with hard tissues and also with Reaction-processing methods involving combustion
skin and muscle tissues. Moreover, HA can directly bond techniques are currently being pursued as a quick, straight-
to the bone. 5 Hydroxyapatite powder and granules have forward way to synthesize homogeneous, very fine,
been used for bone grafting and augmentation while dense crystalline, and weakly agglomerated multi-component
as well as porous blocks have found application as materials, without the need for intermediate calcination
implant material in the field of dentistry and orthopaedics. 6 and decompositon steps. Certain variants of these methods
Unfortunately, its low fracture toughness (0.8-1.2 MPa. are also reported to favour a strict control of product
m112 ) and flexural strength (<130 MPaf currently restrict its stoichiometry. 19
use to small unloaded implants, powders, coatings and
low-loaded porous implants. 8 · 9 The non-medical applica- Solution Combustion
tions of HA include packing media for column chromatog- The solution combustion method involves an exother-
raphy, gas sensors, catalysts, and host material for lasers. 10 mic, usually very rapid and self-sustaining chemical reac-
According to its chemical formula, stoichiometric HA tion between the desired metal salts, preferably nitrates,
should have the Ca/P atom ratio of 1.67. The stability and a suitable organic fuel, such as urea, in an aqueous
limit of the apatitic structure in HA has been the subject solution and the reaction is initiated at a fairly low tem-
of a number of studies, covering a rather wide range of perature.20 The important aspect of this oxidation-reduc-
compositions. 11 · 12 The apatitic crystal structure can be tion (redox) reaction is that the heat required to sustain the
preserved with Ca/P ratios as low as 1.5 which are called chemical reaction and accomplish the compound synthesis
calcium-deficient or non-stoichiometric. These materials is provided by the reaction itself and not by an external
exhibit thermal instabilities at characteristic temperatures. 13 source. A large amount of gases is formed that burn with
A variety of methods have been employed to enhance the appearance of an incandescent flame and may attain
the strength of HA. These include: modification in the high temperatures, often exceeding 1000°C.
reducing nature of the mixture, irrespective of whether the volume of gases formed and the furnace temperature.
elements are present in the oxidizer or the fuel components The credit of developing this method of synthesis goes
of the mixture. Those authors also showed that, for a stoi- to Kingsley and Patil 20 who demonstrated its use in the
chiometric mixture, the magnitude of the total composition preparation of high-purity and also doped a-alumina pow-
of oxidizing and reducing elements is closely related to the ders. Subsequently, Patil and co-workers, as also others
heat of reaction (or the difference in the proportionately successfully used this method of material synthesis in pre-
summed up bond energies of the products and the reac- paring a variety of single and mixed oxides, ranging from
tants), calculated thermodynamically from the heats of zirconia toughened alumina (ZTA) to superconductors,
formation of the constituent batch materials. using various fuels mentioned earlier. 20 ·22- 25 This technique,
According to the concepts of the propellant chemistry, being quick and energy-efficient, has attracted much inter-
the gaseous products of combustion reaction are C0 2, H20 est and has been profitably utilized in the synthesis of a
and N2. This leads to the consideration that the elements number of advanced materials. 28 - 33
C and H are reducing elements with the corresponding In the present study, the technique of solution combus-
valences of +4 and + 1, oxygen having the valence of -2 tion in aqueous Ca-nitrate-urea system containing diammo-
serves as the oxidizing element, and nitrogen has zero nium hydrogen orthophosphate is employed in order to
valence. The extrapolation of this concept to processing obtain a homogeneous, porous, easily dispersible, crys-
of ceramic oxides by solution combustion means that talline powder of calcium hydroxyapatite. The feasibility of
metals are considered as reducing elements with their re- producing nano-crystalline particles and the thermal be-
spective stable valences. The stoichiometric composition haviour of HA during synthesis with regard to initial Ca/P
of the redox mixture for the synthesis is calculated on the atom ratio in the solutions are also investigated.
basis of the total oxidizing and reducing valences of the
oxidizer and of the fuel, in order to release the maximum Experimental
amount of energy for the reaction. In this study, calcium nitrate tetrahydrate (Ca(N03h.
Besides urea (CON 2H 4 ), a variety of organic fuels 4H 20), diammonium hydrogen phosphate (DAP,
have been used that include tetraformal triazine (TFTA, (NH 4hHP0 4) and urea (CO(NH 2h), were used as raw
C4H 16 N60 2), 22 carbohydrazide (CON 4 H6)23 · 24 or maleic hy- materials. Aqueous solutions of these salts were used in
drazide (C 4H4 N20 2f 5 that differ in their total valences, that the experiments and urea was added to the mixed solution
is, +6, +28, +8 and + 16, respectively ("reducing power") as a solid. Concentrated HN0 3 was used to regulate the
and the amount of gases they generate. The amount of pH of the experimental batches. The characteristics of the
gases generated by one mole of fuel ranges from 15 moles raw materials and their solutions are given in Table I. The
for TFTA to only 4 moles for urea. 26 This obviously influ- stoichiometric composition of the mixtures is calculated on
ences the characteristics of the reaction product. The non- the basis of total oxidizing and reducing valences of the
isothermal reaction releases larger amounts of gases that oxidizer and that of the fuel. At the exact equivalence of
dissipate more heat, thereby preventing the oxides from oxidizer and fuel valences the mix is considered stoichio-
sintering. The coincident sintering effect in the higher tem- metric and energy release is at the maximum. Here the
perature reactions may result in a loss of submicron nature elements Ca, H, and C are considered as reducing ele-
of the powder particles. However, the product tends to be ments with their corresponding valences of +2, + 1 and +4
microporous and less crystalline. Considering the hazard respectively and divalent oxygen serves as the oxidant.
and difficulty in synthesis of these fuels, urea seems to be The valence of nitrogen (N 2) is considered as zero (0).
the most convenient fuel to use because it is cheap and Following this procedure, the calculated total valences of
the raw materials are: calcium nitrate tetra hydrate (-1 0), Results and Discussion
diammonium hydrogen phosphate (+6) and urea (+6). Al- The characteristics of the products obtained by solution
though the positive total valence (+6) of OAP suggests fuel combustion technique in Ca-nitrate-diammomium hydrogen
characteristics, it is to be noted that DAP does not act as a phosphate-urea system with respect to different Ca/P
fuel and its participation in the reaction is akin to that of a ratios are given in Table Ill.
diluent and utilizes redox heat for subsequent HA synthe- The appearance of white incandescent flame, produc-
sis. Therefore, the use of additional fuel and/or oxidizer tion of a large volume of gases, short reaction duration
will be required if the HA-synthesis is to be accomplished and foamy nature of the reaction product together indicate
during combustion. Further, to assist formation of a large that HA is produced by the combustion process. This
volume of gases during reaction and synthesis of nano- method of synthesis progresses through the stages of
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particles, fuel-rich compositions were employed. It was dehydration, decomposition and ignition leading to the
seen earlier that fuel-rich mixtures ignited easily, the high exothermic self-sustaining reaction. At the completion of
temperature was sustained longer, and the combustion the reaction, the fuel converts completely into gases and
resulted in crystalline as-prepared compounds. 34 the solid product Ca-hydroxyapatite forms according to the
The experimental batches were prepared by combin- following relation:
ing the reactant salt solutions in different volume ratios to 30Ca(N0 3h4H 20 + 18(NH 4hHP04 + 50CO(NH 2 h +
vary the Ca/P atom ratios and are displayed in Table II. 270 2 = 3Ca 10 (P0 4 ) 6 (0H) 2 +50C0 2 +
The required volumes of aqueous solutions of 1.73(M) 298H 20 + 98N 2 •• (1)
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 The total heat required for the synthesis of the hydroxy-
was dissolved by adding 3 cm 3 of concentrated nitric acid. apatite phase is supplied mainly by the combustion reac-
A predetermined amount of urea was added to the clear tion of urea-nitrate mixture and may be described by the
solution, and following homogenization by stirring with a following equation.
magnetic stirrer for 30 min at room temperature, the beaker 2CO(NH 2 ) 2 + 30 2 = 2C0 2 + 4H 2 0 + 2N 2 •• (2)
containing the solution was introduced into a muffle fur-
nace preheated to 600°C. When placed in the furnace, the Although it is assumed that the gaseous products of
mixed solution soon started to boil, underwent dehydra- solution combustion are carbon dioxide, moisture, and ni-
tion and decomposition and a large volume of gases con- trogen only, in practice it was found that oxides of nitrogen
taining oxide of nitrogen and traces of ammonia evolved. and ammonia evolved at various stages of this reaction.
The mass then frothed and swelled to yield foam, where a This makes the calculation of the stoichiometric mixture a
llnme appeared and produced incandescence. The entire difficult task and it appears that working with a fuel-rich
process required less than 20 min with flame duration of composition is preferable.
nearly one minute. The as-synthesized products were typi- It will be seen from the results given below that in the
cally voluminous, fluffy foam-like mass that occupied a large present study nanometric HA particles were obtained. The
volume. The resulting soft-agglomerated mass was read- preparation of nanocrystalline materials using fuel-rich
ily ground manually in an agate mortar/pestle into fine pow- batch materials is in contradiction to the results of Hong et
der and was thoroughly characterized. X-ray diffraction a/. 35 who observed increased grain growth and loss of sur-
patterns of the combustion products were recorded to study face area with increased urea contents during wet chemical
the phase formation (Philips Analytical, X'Pert, 1830, Hol- combustion synthesis of Cao 5 Sr0 .5Zr4 P60 24 (CSZP). The
land). The median diameter of the powder particles and results were attributed to the longer flame duration. This
discrepancy between these two results may be attributed
Table II : Batch compositions
to the differences in the experimental procedures adopted.
Sample Molar Amount of pH In the present study, the use of dilute solutions of reactants,
ldentifi· ratio Ca-Nitrate DAP Urea HN03 furnace temperature of 600°C, and evolution of larger vol-
cation of Ca/P (g) (g) (g) (ml) ume of gases during reaction that prevented sintering of
the product nuclei aided the formation of nanometer-sized
HA-1 1.75 8.80 2.80 14 3 3.5
particles. On the other hand, Hong et a/. 35 combusted a
HA-2 1.67 8.80 2.94 14 3 3.5 slurry that might have caused heterogeneous nucleation
HA·3 1.45 8.80 3.39 14 3 3.5
of the phosphate phase on the solid sites present and fa-
cilitated growth of the limited number of nuclei. Moreover,
it is possible that a specific composition of the gaseous patite phase. It is seen that post-synthesis thermal treat-
atmosphere enhanced coarsening of CSZP grains. Such ments are not essential for the desired phase formation.
grain-growth effects were noted by Roy 36 and by Readey However, depending on the initial Ca/P ratio the products
eta/. 37 during sintering of oxides in reactive atmospheres.
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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]
~
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.
[MS received August 14, 2003; revised copy received September 30, 2003)