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Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized

by self-propagating combustion

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2008 Sci. Technol. Adv. Mater. 9 035003

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IOP PUBLISHING SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS
Sci. Technol. Adv. Mater. 9 (2008) 035003 (5pp) doi:10.1088/1468-6996/9/3/035003

Effect of metal-ion-to-fuel ratio on the

phase formation of bioceramic
phosphates synthesized by
self-propagating combustion
Swamiappan Sasikumar and Rajagopalan Vijayaraghavan
Materials Division, School of Science and Humanities, VIT University, Vellore 632 014,
Tamil Nadu, India
E-mail: [email protected]

Received 5 January 2008

Accepted for publication 14 May 2008
Published 1 September 2008
Online at stacks.iop.org/STAM/9/035003

Abstract
Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4 )6 (OH)2 ) is a well-known bioceramic
material used in orthopedic and dental applications because of its excellent biocompatibility
and bone-bonding ability due to its structural and compositional similarity to human bone.
Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid
as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen
phosphate serves as the source of phosphate ions. Reaction processing parameters such as
the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The
products were characterized by powder x-ray diffraction, which revealed the formation of a
hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra
showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology
of the particles was imaged by scanning electron microscopy, which also revealed that the
particles are of submicron size. Thermal analysis showed that the phase formation takes place
at the time of combustion. Surface area and porosity analysis showed that the surface area is
high and that the pores are of nanometer size. The mean grain size of the HAP powder,
determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to
determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found
to be 1 : 1.66.

Keywords: hydroxyapatite, bioceramic, tricalcium phosphate, tartaric acid

1. Introduction Therefore, the synthesis of biomimetic hydroxyapatite is

being intensely studied by various groups [5–9].
Hydroxyapatite is a member of the apatite family and has Self-propagating combustion synthesis (SPCS) is a rapid
almost the same chemical composition as human bone. and energy-saving technique often used [5, 6, 10] for the
Because of its biocompatibility and osteoconductive [1] preparation of metal oxides. During combustion metal nitrates
properties, it has many biological applications including as a act as conventional oxidants and organic compounds function
bone graft substitute [2, 3], a sustained-release drug delivery as fuels. SPCS is an exothermic redox reaction associated with
device [4] and for protein purification. However, biological nitrate decomposition and fuel oxidation, which releases an
apatite differs from pure and synthetically produced calcium enormous amount of heat energy. The nature of the fuel and
hydroxyapatite (HAP) in terms of stoichiometry, composition, the ratio of oxidizer to fuel control the exothermicity of the
crystallinity and other physical and mechanical properties. combustion.

1468-6996/08/035003+05$30.00 1 © 2008 National Institute for Materials Science Printed in the UK

Sci. Technol. Adv. Mater. 9 (2008) 035003 S Sasikumar and R Vijayaraghavan

It has been reported that carboxylic acids such as citric

1 M Ca(NO)3 1 M Tartaric acid
acid [5, 6], succinic acid [7], sucrose [8] and urea [9] can
solution
be used as fuels to synthesize hydroxyapatite by SPCS.
Thongtem et al [11] synthesized LiNiVO4 by this method
using tartaric acid as a fuel. They reported that the particle
sizes are in nanometer regime, whereas the same material pH is adjusted to 9.5 1 M (NH4)2HPO4
prepared using citric acid [12] with starch [13] as a using NH4OH (1:1) solution
complexing agent does not form nanocrystalline products.
Add dropwise
Lithium, being an alkali metal, forms a complex with tartaric @ 1 ml/min
acid. In this work, we have synthesized hydroxyapatite in Formation of white
nanocrystalline form using calcium, which is an alkaline-earth precipitate
metal and also can form a complex with tartaric acid. We
produced submicron-size particles of hydroxyapatite with
uniform morphology. The effect of the metal-ion-to-fuel ratio
on phase formation has also been investigated. Precipitate is dissolved
using conc. HNO3

2. Experimental work

2.1. Synthesis Stirred for 2 h

at 70 °C
An equal volume of 1 M calcium nitrate solution was added
to 1 M tartaric acid followed by thorough mixing using a
magnetic stirrer. The pH of the solution was then adjusted
to 9.5 by adding NH4 OH and water in a 1 : 1 ratio. A Yellow fluffy mass
stoichiometric amount of 1 M (NH4 )2 HPO4 solution was
added to the above mixture and the precipitated mixture of
phosphates was dissolved by adding concentrated HNO3 until
the pH became 1. The resultant solution was heated to 70 ◦ C Undergoes
and stirred until a transparent gel was formed. The gel was combustion at 220 °C
placed on a hot plate and the temperature was increased
gradually until the gel ignited. The precursor that formed was
calcined at 900 ◦ C for 2 h, which resulted in a pure white
Black precursor
microcrystalline hydroxyapatite sample referred to as TT1.
The procedure was repeated with a metal-ion-to-fuel ratio of
1 : 2 and the sample was named TT2 (refer flow chart).

2.2. Characterization Calcined at 900 °C

for 2 h
The phase purity of the synthesized hydroxyapatite samples
was analyzed using a Philips D-500 x-ray diffractometer
with Ni-filtered CuKα radiation. The chemical nature
White HAP powder
and molecular bond structure of the synthesized samples
were determined by FT-IR studies (Thermo Nicolet,
Avatar 330 FT-IR spectrometer, USA). The particle
Flowchart for the Synthesis of Microcrystalline Hydroxyapatite.
size and surface morphology was imaged using a
scanning electron microscope (Jeol, JSM – 5600 LV).
The Brunauer–Emmett-Teller (BET) technique was used to metal nitrate. Therefore, the reactivity and the product phases
analyze the specific average surface area of the hydroxyapatite formed by calcium nitrate with tartaric acid were investigated.
powders calcined at 700 and 900 ◦ C using a fully automated Tartaric acid plays a dual role in the synthesis; it
BET surface area analyzer (Micromeritics ASAP2020). The functions as a chelating agent and prevents the precipitation
thermal analysis of the charred gel was carried out at a heating of ions. A large amount of heat is released during the
rate of 20 ◦ C min−1 in air from room temperature to 1000 ◦ C combustion of tartarate gel, which produces intense local
using a thermal analyzer (V8.2 SDT Q600, TA Instruments, heating that assists the formation of hydroxyapatite. The
USA). addition of ammonium hydroxide and nitric acid promotes the
formation of ammonium nitrate, which increases the heat of
3. Results and discussion combustion.
The addition of tartaric acid to aqueous calcium nitrate
The rate of the combustion reaction depends on the ligand solution produces a colorless calcium tartarate solution, which
groups of the molecule and the compositional ratio of fuel to upon the further addition of the phosphate source and nitric

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Sci. Technol. Adv. Mater. 9 (2008) 035003 S Sasikumar and R Vijayaraghavan

Figure 1. TGA/DTA curves of precursor synthesized using a metal-ion-to-fuel ratio of 1 : 2.

acid forms a gel network of calcium–tartarate–phosphate at a decomposed tartarate–calcium–phosphate gel (carbonaceous

temperature of 80 ◦ C. The transparent gel, which undergoes product) present in the precursor. As there is no organic
autoignition at 220 ◦ C, forms a black precursor with the substance remaining to undergo combustion, there is no
evolution of a large amount of gases. The evolution of sharp exothermic peak in the DTA plot, showing that the
dark yellow fumes before ignition indicates the formation of crystallization of the calcium phosphate phase took place
nitrogen dioxide due to the oxidation of the gel matrix by during the combustion of the gel because the local temperature
nitrates. The swelling of the gel before ignition is due to the attained was very high.
evolution of carbon dioxide produced by the decomposition The XRD patterns of both TT1 (figure 2(a)) and TT2
of tartaric acid. (figures 2(b) and (c)) show sharp and well-defined XRD peaks
The temperature was measured using a thermometer until characteristic of hydroxyapatite. It was found that TT1 has
the gelation occurred. When the gel started to decompose, β-TCP as a secondary phase and that TT2 is single-phase. The
a thermocouple mounted close to the surface of the gel was formation of the β-TCP phase in TT1 may be either due to the
used to measure the temperature during combustion. For all inhomogeneous distribution of calcium and phosphate ions in
samples, the transformation of the solution to the gel state the gel matrix or due to the difference in energetics. However,
took approximately 2 h and the time necessary for the gel the former reason is more likely because the ratio of metal ions
to reach the autoignition temperature was about 20 min. The to phosphate ions determines the formation of hydroxyapatite.
combustion reaction took place within 1–2 min depending The stoichiometry of the reaction between calcium nitrate and
on the fuel ratio. The temperature increase of 70 ◦ C (from tartaric acid indicates that each mole of calcium ions requires
220 to 290 ◦ C) during combustion showed that intense local two moles of tartaric acid to form calcium tartarate, as given
heating occurs during combustion, which may promote the below.
phase formation in the precursor obtained after combustion.
Thermal analysis (figure 1) was performed for the Ca(NO3 )2 + 2C4 H6 O6 → (C4 H5 O6 )2 Ca + 2HNO3 .
precursor obtained after the combustion of the gel that was
used to form TT2 to determine the phase transformation and If the ratio of metal ions to tartaric acid is 1 : 1, then 50% of the
the reaction enthalpies. The precursor showed a significant calcium nitrate will not complex with the tartaric acid and will
weight loss in the temperature range of 50 to 540 ◦ C, remain as calcium nitrate. This may lead to the formation of
which is mainly due to the decomposition of organic an inhomogeneous distribution of calcium and phosphate ions
precursors, followed by further weight loss (5%) between in the gel matrix, leading to the formation of a β-TCP phase as
540 and 1000 ◦ C due to the removal of residual carbon. an impurity. The precursor calcined at the low temperature of
The broad exotherm seen in the DTA plot (figure 1) 500 ◦ C (figure 2(b)) formed the hydroxyapatite phase but with
between 50 and 500 ◦ C is due to the oxidation of the residual carbon, which was removed by calcining at 900 ◦ C

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Sci. Technol. Adv. Mater. 9 (2008) 035003 S Sasikumar and R Vijayaraghavan

Figure 3. FT-IR spectra of hydroxyapatite synthesized using

(a) metal-ion-to-fuel ratio of 1 : 1 followed by calcination at 900 ◦ C
(TT1) and (b) metal-ion-to-fuel ratio of 1 : 2 followed by calcination
at 900 ◦ C (TT2).

Figure 2. XRD patterns of hydroxyapatite synthesized using

(a) metal-ion-to-fuel ratio of 1 : 1 followed by calcination at 900 ◦ C,
(b) metal-ion-to-fuel ratio of 1 : 2 followed by calcination at 500 ◦ C
for 5 h and (c) metal-ion-to-fuel ratio of 1 : 2 followed by calcination
at 900 ◦ C for 2 h.

for 2 h to produce pure hydroxyapatite (figure 2(c)). This can

be observed from the results of thermal analysis (figure 1) as
Figure 4. SEM images of single-phase microcrystalline
there is a 5% weight loss between 500 and 1000 ◦ C. hydroxyapatite synthesized using metal-ion-to-fuel ratio of 1 : 2
The FT-IR spectra (figure 3) of the final powders (TT1 followed by calcination at 900 ◦ C.
and TT2) show a broad band at 3450 cm−1 , which is due
to moisture, and also a sharp peak at 3571 cm−1 due to
the stretching vibration of the OH− group present in the powders at 250 ◦ C for 2 h. Porosity analysis indicates that the
hydroxyapatite and a shoulder peak at 635 cm−1 due to the average pore diameter is approximately 22 nm. SEM images
bending vibration of the OH− group. The OH− vibrations are (figure 4) confirm the results of surface area analysis by
not observed in the TCP samples, but TT1 has an intense the BET method as they indicate that the particles are of
OH− peak, which is due to the presence of hydroxyapatite submicron size and highly porous. Bogdanoviciene et al [15]
as a major phase. Bending vibrations of the phosphate group prepared hydroxyapatite by the sol–gel method using tartaric
are observed at 473, 571 and 601 cm−1 , whereas stretching acid as a complexing agent and reported a microrod-shaped
vibrations of the phosphate group are observed at 962, 1044 morphology, whereas the SEM images (figure 4) of our
and 1089 cm−1 . The FT-IR spectra show that both the samples samples indicate agglomerated spherical particles. This shows
are biomimetic because a carbonate ion is substituted at the that a different processing method leads to a change in
phosphate site of hydroxyapatite, as indicated by the weak morphology, as expected.
bands of the carbonate group at 1465 cm−1 . The average crystallite size of the HAP powder
The specific surface area obtained for TT2 by the determined by the corrected Debye–Scherrer formula [16]
BET method is between 10 to 20 m2 g−1 for the powders relating the crystallite size, full-width at half-maximum of
calcined at 900 and 700 ◦ C. This agrees with the literature the peak, wavelength (0.154059 nm) and diffraction angle,
on the surface area [14] measurement of nanocrystalline is between 20 and 30 nm for TT2 irrespective of the
hydroxyapatite. Before the analysis, the adsorbed moisture calcination temperature. This is in accordance with the
on the fine powder surface was eliminated by preheating the BET measurements because there is little difference in

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Sci. Technol. Adv. Mater. 9 (2008) 035003 S Sasikumar and R Vijayaraghavan

the surface area of TT2 calcined at 700 and 900 ◦ C. The References
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