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Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 739-743

Notes

Mechanochemical synthesis of sodium doped crystallinity, degradation behaviour and mechanical


hydroxyapatite powder properties1,2. Recent studies have also explored the
electrical properties of HA for sensor application.
Sharifah Adzilaa, c, Iis Sopyanb, *, Ramesh Singha, Mene et al.3 revealed possible application of
Erlani Pusparinid & Mohd. Hamdia hydroxyapatite as an efficient sensor for various
a molecules such as CO2, CH3OH, H2O and CH3I.
Department of Engineering Design and Manufacture, Faculty of
Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia Excellent biocompatibility and bioactivity of
b
Department of Manufacturing and Materials Engineering,
HA make this material useful in many clinical
Faculty of Engineering, International Islamic University Malaysia, applications. Some of its uses are as bone fillers in
50728 Kuala Lumpur, Malaysia orthopedics, maxillofacial surgery and stomatology.
Email: sopyan@iium.edu.my However, the use of HA for load bearing bone
c
Department of Materials Engineering and Design, Faculty of implants is limited due to its brittleness4. Substantial
Mechanical and Manufacturing Engineering, Universiti Tun efforts have been devoted by numerous research
Hussein Onn Malaysia, 86400 Johor, Malaysia groups to improve the psychochemical and
d
State Ministry for Research and Technology Republic of mechanical properties of synthetic HA. One of the
Indonesia, Jalan MH. Thamrin 8, Jakarta 10340, Indonesia strategies is by doping HA with metal ions such as
magnesium5-8, manganese4,9,10 and strontium11-13.
Received 30 November 2012; revised and accepted 10 May 2013 Traces of these metal ions are reported to alter the
Bioactive hydroxyapatite (HA) with nanosized spherical shape lattice parameters, the crystallinity, the dissolution
has been synthesized through mechanochemical synthesis of kinetics and other physical properties of apatite14.
calcium hydroxide and diammonium hydrogen phosphate. Sodium (Na) is well known to have an important
Sodium ion has been doped into HA by using sodium hydroxide effect on biological apatites since it plays a potential
precursor in a dry mixture of Ca(OH)2 and (NH3)2HPO4. Both
Na-free HA and Na-doped HA (1% - 9%) are characterized by
role in cell adhesion as well as in the bone
X-ray diffraction and Fourier transform infrared analyses. metabolism and resorption process. Sodium has
Reduction of the peak intensity and adsorption bands is observed been traced as an abundant element in natural
with increasing Na+ concentration in the Na-doped HA structure. bone and tooth mineral after calcium and
Increasing Na+ content expands the lattice parameters and unit phosphorous15. Even for humidity sensor application,
cell volume of HA, while the crystallite size and degree of
crystallinity decrease with increasing Na+ level. A mixture of rods
doping hydroxyapatite with sodium has greatly
and spheres are found in the Na+ doped HA. Characterization of improved its responsiveness to humidity condition16.
the obtained powder suggests that Na doped HA has a potential to Previous studies have been carried out on the
be used in clinical applications. preparation of sodium substituted HA through several
synthesis methods such as hydrolysis of monetite,
Keywords: Bioceramics, Hydroxyapatites, Doping, Sodium
doping, Calcium phosphate double decomposition, aqueous precipitation and
sol-gel method15,17,18,19. These studies have proved
Hydroxyapatite [Ca10(PO4)6(OH)2] (HA) is a calcium that sodium was incorporated into HA lattice at the
phosphate mineral which for long has been used as calcium sites. Nevertheless, the methods involved
bone substitute material. In natural bone, many steps as well as consumed several chemicals,
it exists along with organic collagen fibrils. The main leading to low purity of the final powder.
function of the inorganic mineral is to mechanically Till date there are no reports of synthesis of
support the body while maintaining the homeostasis Na-doped HA powder by mechanochemical synthesis.
by controlling release of calcium and other ions and Mechanochemical method is a simple method to
storing them in the body fluid. Besides calcium, synthesize powders especially in dry condition.
phosphate and carbonate, bone also contains a large Unlike the other methods, it does not entail drying,
number of other ions such as sodium, fluoride, filtering and calcination after synthesis. Hence, the
chloride, magnesium, strontium, zinc, copper and iron reactions from dry mechanochemical milling are
in various quantities. These species are known to faster with a low level of pollution by the mill
affect bone mineral characteristics, such as material20,21. In our previous study, the nanosize
740 INDIAN J CHEM, SEC A, JUNE 2013

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

The peak intensity of the PO43- group was reduced


with the increase of Na+ substitution up to
9%. However, the PO43- band at 1120 cm-1 is likely to
disappear at 7% and 9% Na+ substitution. The small
peak of OH- group at 630 cm-1 is clearly visible in
Na-free HA, which decreased as Na+ was substituted
into HA. The loss of OH- group can be seen in
7% and 9% Na+ substituted HA. The decrease of
PO43- and OH- groups is in tune with the XRD
patterns in term of the peak intensity. In addition, a
small trace of adsorbed water (H2O) was detected
around 3300 – 3600 cm-1. However, the synthesized
powders also exhibited trace levels of carbon and
nitrogen as detected at 1600 cm-1 and 2000–2300 cm-1
respectively. In comparison, Kannan et al.14 found
higher intensity of the elements of the residual
carbonate and nitrates from precipitate precursors.
The presence of these residual elements is merely due
to the adsorption of surrounding atmosphere and the
residual precursors during the synthesis process14. In
our previous report on Na-doped HA from sol-gel
technique19, we found the characteristic band of
inorganic carbonate ion at 1450 cm-1, for CO32- group;
it has been suggested that carbon from the organics
was not completely pyrolyzed and may instead be
incorporated in hydroxyapatite crystal. The band for
Fig. 2 – FTIR spectra of the Na-free HA and Na-doped HPO4 at 873 cm-1 assigned to a B-type carbonate of
HA powders. apatite19 was not found in the present study.

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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