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hydroxyapatite powder was successfully synthesized Bragg’s diffraction angle (in degrees) and β is the
in the dry mechanochemical synthesis21. In this study, full-width at half-maximum (FWHM). The lattice
we wish to report our investigation on synthesis of parameters as well as the unit cell volume of the
the Na-doped HA through mechanochemical hydroxyapatite phase were determined with Bruker
synthesis method and characterisation by XRD, X’Pert Plus software. The crystallinity degree (Xc)
FTIR and TEM analyses. was calculated as Xc = 1 - (V112/300/I300), where I300 is
the intensity of (3 0 0) reflection of HA and V112/300 is
Experimental the intensity of the hollow between (1 1 2) and (3 0 0)
The precursors used for the synthesis of sodium reflections.
(Na) doped HA powder were commercially available The as-synthesized Na-free HA and Na-doped HA
calcium hydroxide (Ca(OH)2, R&M Chemicals, 98%), powders were characterized further by Fourier
diammonium hydrogen phosphate ((NH4)2HPO4, transform infrared (FTIR) (Perkin Elmer, model
Systerm, 98%) and sodium hydroxide (NaOH, R&M 100 spectrum series) in the wave number range of
Chemicals, 99%). 4000–380 cm-1. Morphology of the powders was
Ca(OH)2, (NH4)2HPO4 and NaOH, in the molar determined by transmission electron microscopy
ratio (Ca+Na):P::1.67:1 was milled in a planetary ball (TEM). Prior to TEM analysis, the powder sample
mill (Fristch) by using tungsten carbide vials was sonicated first in ethanol for 30 minutes.
(250 mL) and balls as milling medium. The powder
-to-ball mass ratio was fixed at 1:5. The rotation Results and discussion
speed and milling time were set at 370 rpm and 15 h The XRD patterns of mechanochemically
respectively based on our previous method21. The synthesized Na-free HA and Na-doped HA powders
interval pause was set for 1 h after every 1 h milling. are presented in Fig. 1. All the peaks of the
The reaction equation is described in Eq. 1, synthesized powders correspond to that of HA
(10 – x) Ca(OH)2 + xNa(OH) + 6(NH4)2HPO4 → (ASTM-JCPDS No. 09-0432) with different peaks
intensity. The broad diffraction peaks with various
Ca10-x Nax (PO4)6 (OH)2 + 12NH4OH + (6 – x) H2O widths were observed in all the synthesized powders.
where x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, is the molar Compared to Na-free HA, the intensity of HA at the
concentration of Na+. Table 1 shows the formulation main peaks; (211), (112) and (300), increased slightly
of sodium doped HA. in 1% to 5% NaHA. However, the intensity decreased
Phase analysis was carried out by X-ray diffraction with the increase of Na in 7%–9% NaHA. A similar
(XRD, Bruker) with Cu–Kα radiation (λ = 1.5406 Å) trend is also observed in the other peaks of HA
at 40 kV and 40 mA with diffraction angles of observed at (002), (122), (222), (123), (230), (231)
25° – 55° in 2θ and a step size of 0.02° per second. and (140). The increase and the decrease in intensities
All the samples were analyzed by referring to the of the Na-doped HA peaks as compared to those of
standards of the Joint Committee of Powder Na-free HA, implies that Na+ has been substituted into
Diffraction Standards (JCPDS) card number, 09-0432 HA. Ca2+ deficient-HA was formed with the decrease
for HA. The average crystallite size (D) of the of HA intensity at higher Na concentration in 7%–9%.
as-synthesized powders was calculated by using the Generally, Na+ doping does not cause significant
Scherrer equation, D = Kλ/β sin (θ), where K is the changes in HA phase as there is no secondary phase
shape factor of particles equal to 0.9, λ is the X-ray observed in the synthesized powders. Reports on
wavelength (1.5406 Å) for Cu–Kα radiation, θ is the as-precipitated powders prepared by other methods
Table 1 – Composition of sodium doped hydroxyapatite powders and the ratio of calcium and sodium to phosphorous
Sample Na (wt %) Molar conc. (mol%)
Ca P Na Ca/P (Ca+P)/P
Na-free HA 0.00 10.0 6.0 - 1.67 1.67
1%NaHA 0.23 9.9 6.0 0.1 1.65 1.67
3%NaHA 0.69 9.7 6.0 0.3 1.62 1.67
5%NaHA 1.15 9.5 6.0 0.5 1.58 1.67
7%NaHA 1.62 9.3 6.0 0.7 1.55 1.67
9% NaHA 2.09 9.1 6.0 0.9 1.52 1.67
NOTES 741
also gave diffraction pattern similar to that of HA phase in higher Na+ substitution at 7% and 9% NaHA
although the Ca/P ratio was less or greater than the may result in increase of HA dissolution or
stoichiometric molar ratio of 1.6714,19,22. Similar solubility23.
results are also reported for apatites with elements Ionic substitution generally affects the lattice
substituted in varying trace levels12,14. parameters in HA crystallographic sites depending on
Table 2 gives the crystallite size, degree of the size of the ions11. Table 2 shows that hexagonal
crystallinity, hexagonal lattice parameters of a-axis lattice parameters of a-axis and c-axis increases as the
and c-axis, and unit cell of volume of the Na+ doping increases to 9%. A similar trend is also
mechanochemically synthesized Na-free HA and observed in the hexagonal unit cell volume.
Na-doped HA powders. The crystallite size increased The increase in lattice parameters and unit cell
from Na-free HA (23.2 nm) to 1% NaHA (25.4 nm), volume is due to the larger ionic radius of Na+
but decreased as the Na+ composition increased from (1.02 Å) than Ca2+ (0.99 Å). The results show
5% (24.1 nm) to 9% (21.5 nm). The degree of that Na+ has been substituted into the Ca2+ site as
crystallinity also followed the trend of crystallite size the lattice parameters and the unit cell volume expand
which increased at 1% (0.58) but decreased from with Na+ concentration. Hexagonal lattice structure
5% to 9% NaHA (0.52 to 0.40). The decrease of of HA contains two types of calcium sites, Ca(I)
crystallite size and degree of crystallinity are reflected and Ca(II). Among ten calcium ions, 4-Ca(I) and
by the formation of Ca2+ deficient HA, exhibited 6-Ca(II) ions are located in HA lattice. Besides,
by the broad and low intensity of the HA peaks the elements that have ionic radii close to that of
seen in the XRD pattern. The less crystalline apatite Ca2+ are easily accepted into the apatite lattice24.
Previous studies have reported that a slight increase
in the c-axis parameter cause the increase in unit
cell volume for Na substituted apatite compared
to that of the pure HA. Na+ ion, which possesses an
ionic radius close to that of Ca2+ ion, shows
preference for substituting in the Ca(II) site14,25. Other
substitutions which possess ionic radius smaller
than that of Ca2+ cause the contraction of lattice
parameters and unit cell volume7 while ionic radius
greater than that of Ca2+ leads to the expansion of
lattice parameters12.
The functional groups of the synthesized powders
were determined by Fourier transform infra red
(FTIR). The existence of phosphate (PO43-) and
hydroxyl (OH-) bands as shown in Fig. 2, usually
confirms the formation of apatite. Here, the vibration
mode of PO43- group was observed at 574 cm-1
(O-P-O antisymmetric bending, ν4), 609 cm-1
Fig. 1 – XRD patterns of the Na-free HA and Na-doped (O-P-O bending, ν4), 966 cm-1 (P-O stretching, ν4),
HA powders. 1020 cm-1 and 1120 cm-1 (P-O stretching, ν3).
Table 2 – Crystallite size, lattice parameter (a and c) and unit cell volume (V) of the as-synthesized Na-free HA
and Na-doped HA powders
Na conc. Crystallite size Crystallinity degree a (Å) c (Ǻ) V (Ǻ 3)
(mol%) (nm) (Xc)
0 23.2 0.48 9.434 (± 0.002) 6.886 (±0.002) 1591.06 (±0.32)
1 25.4 0.58 9.433 (± 0.003) 6.885 (±0.002) 1593.11 (±0.47)
3 22.7 0.50 9.437 (±0) 6.890 (±0) 1594.13 (±0.01)
5 24.1 0.52 9.436 (± 0.002) 6.892 (±0.001) 1594.94 (±0.25)
7 21.0 0.45 9.444 (±0.002) 6.895 (±0.004) 1597.54 (±1.40)
9 21.5 0.40 9.445 (±0) 6.893 (±0.001) 1597.31 (±0.05)
742 INDIAN J CHEM, SEC A, JUNE 2013
Fig. 3 – TEM images of the (a) Na-free HA, (b) 1% NaHA, (c) 5% NaHA, (d) 7% NaHA, and, (e) 9% NaHA powders.
NOTES 743
Figure 3 displays the TEM morphology of the Institute of Research Management and Monitoring
particles from mechanochemically synthesized (IPPP) of University of Malaya, Malaysia, for
Na-free HA and Na-doped HA powders. Fig. 3(a) supporting this research through the grant
shows that the Na-free HA nanoparticles contained No. PS130/2010B.
only the sphere-like shapes. The rods like shapes start
to appear along with the sphere-like shapes
in 1% – 9% NaHA as shown in Fig. 3(b)–3(e). References
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The authors would like to thank Biomedical 26 Nasiri-Tabrizi B, Honarmandi P, Ebrahimi-Kahrizsangi R, &
Engineering Research Group of IIUM, Malaysia and Honarmandi P, Mater Lett, 63 (2009) 543.