Trends Biomater. Artif.

Organs, Vol 19(2),

pp 81-83
(2006)
Synthesis
of Hydroxyapatite
that Mimic Bone Minerology

81
http://www.sbaoi.org

Synthesis of Hydroxyapatite that Mimic Bone Minerology

T.V. Thamaraiselvi, K. Prabakaran and S. Rajeswari
Department of Analytical Chemistry
University of Madras
Guindy Campus, Chennai 600 025
Biomimetic hydroxyapatite (HAP) that resemble human bone in composition and structure was synthesised
using calcium nitrate dihydrate and diammonium hydrogenphosphate dissolved in synthetic body fluid (SBF).
The chemical analyses of the powders were carried out by atomic absorption spectroscopy, titrimetry,
gravimetry and spectrophotometry. The synthesised samples were characterised by fourier transform
spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) techniques.

Introduction
Synthetic hydroxyapatite [HAP, Ca10(PO4)6(OH)2]
has assumed substantial interest and importance because of its chemical similarity to the
natural Ca phosphate mineral present in biological hard tissue [1, 2]. Considering the numerous applications of calcium phosphate compounds in biomedical fields, various synthesis
techniques have been developed. These include
mechanochemical synthesis [3], combustion
preparation [4], electrophoretic deposition [5],
sol-gel procedure [6,7], hydrothermal synthesis
[8,9] and precipitation from aqueous solution
[10]. In the present investigation, the precipitation of bioactive hydroxyapatite, similar to biological mineralisation, in simulated body fluid
(SBF), a solution with ion concentrations and a
pH value similar to those of human plasma [11]
was explored. The synthesised HAP powder was
characterised by FT-IR, XRD and SEM techniques. The results revealed the nanocrystallinity
and phase purity of the synthesised powder. The
presence of magnesium and sodium were identified by AAS.
Experimental

Synthesis of biomimetic hydroxyapatite

A solution of 0.125M Ca(NO3)2.4H2O (AR grade)
prepared in SBF, whose composition is elicited

in Table 1 [12]was used as the calcium source,

the pH of which was raised to 9 using 1:2 solutions of aqueous ammonia and SBF respectively.
A solution of 0.75M (NH4)2HPO4 (AR grade) prepared in SBF was added drop wise to the calcium source under constant stirring until it
reached the physiological pH of 7.4. The reaction temperature was maintained at 37C. The
resulting product was centrifuged, washed thoroughly with double distilled water and dried in
air oven at 80C. The dried cakes were powdered using mortar and pestle. The powders
were then sintered at various temperatures for
characterisation.
Atomic absorption spectroscopy (AAS) was employed for the chemical analysis of Na and Mg in
Table 1. Ion concentration of SBF solution [12]
Ion

Concentration, mM

Na

142.0

Cl

125.0

HCO3-

27.0

5.0

Ca2+

2.5

HPO42-

1.0

24

SO

0.5

Mg2+

1.5

82

T.V. Thamaraiselvi, K. Prabakaran and S. Rajeswari

the powders sintered at 900 C. Fourier transform infrared (FT-IR) was used to determine the
nature of functional groups of the synthesised
HAP. All IR spectra were obtained at 4000-400cm1
with a SHIMADZU model 8300 FT-IR system.
The X-ray diffraction studies were carried out to
determine the phase composistion and crystallinity using RICHSEIFERT model 3000, Germany.
Scans were made over the range 2 = 10-70 in
increments of 0.01. The powder morphology
and microstructure were determined by using
scanning electron microscopy (SEM), with a
Philips 501 model system.
Results and Discussion
The Ca/P ratios of the synthesised samples
were found to be 1.65. Chemical analysis of the
sintered samples for Mg and Na revealed
0.033% and 0.09%, respectively. Figure1a, b and
c depicts the FT-IR spectra of HAP powders
heated at 80 C, 700 C and 900 C respectively.
The spectra show the characteristic peaks of
absorbed water, hydroxyl, phosphate and car-

bonate species. The broad peak around 3250

cm-1 to 3500 cm-1 for the sample at 80 C corresponds to the adsorbed water [13]. The spectrum clearly indicates a peak at 1640 cm-1 (bending mode n2), which is attributed to the presence
of water associated with HAP [14,15]. The absorption bands at 1460 cm-1 and 875 cm-1 suggest the presence of CO3-, which is supposed to
have come from SBF and atmosphere during
the precipitation process [16-18]. The total intensity of these bands gets decreased for the
samples calcined at 700 and 900 C. This confirms the elimination of CO3- ion at higher temperatures. Also, bands at 630 cm-1 and 3572
cm-1 (Figure 1b and c) assigned to the OH- ion
were not clearly visible for the sample heated at
80 C. The absorption bands at 1040, 1093, 962
and 571 cm-1 detected in the spectra are attributed to the PO42- ion.
Figure 2a and b depict the XRD patterns for the
as received and sintered samples, respectively.
The XRD pattern of the sample sintered at 900
C for 6h show sharp lines indicating the crystalline nature of the sintered samples. The stron-

(a)
(a)

(b)
(b)

(c)

Fig. 1. FT-IR spectra of HAP heated at (a) 80 C,

(b) 700 C and (c) 900 C

Fig. 2. XRD pattern of HAP (a) as-received and

(b) sintered at 900 C

Synthesis of Hydroxyapatite that Mimic Bone Minerology

(a)

83

JCPDS file No. 09-432 of calcium hydroxyapatite. The XRD pattern clearly indicated the absence of -TCP phase. Size of the crystallites
responsible for the Bragg reflection of the (002)
and (003) planes determined using Sherrer relationship was found to be 68 nm and 69 nm,
respectively [19]. A typical SEM of the as received
powders and sintered powders are given in Figure 3a and b, respectively. These powders displayed a significant level of agglomeration.
Conclusions

(b)
Fig. 3. SEM micrographs of HAP dried at (a) 80 C
and (b) 900 C

gest peaks in the XRD pattern were characteristic of pure HAP and closely matched with the

Biomimetic hydroxyapatite was successfully

synthesised by using calcium nitrate dihydrate
and diammonium hydrogenphosphate dissolved in synthetic body fluid (SBF). FT-IR, XRD
and SEM studies confirm the formation of HAP.
The chemical analysis of the sintered sample
shows the presence of Mg and Na, which elicits
that the HAP synthesised was biomimic in nature.
Acknowledgement
The authors are thankful to the University Grants
Commission (UGC) for rendering financial support to carry out this work.

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