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Electrochemical synthesis and characterization of hydroxyapatite powders

Article  in  Materials Chemistry and Physics · September 2008

DOI: 10.1016/j.matchemphys.2008.03.045

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 Materials Chemistry and Physics 111 (2008) 137–142

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Electrochemical synthesis and characterization of hydroxyapatite powders

M.S. Djošić a , V.B. Mišković-Stanković b,∗ , S. Milonjić c ,
Z.M. Kačarević-Popović c , N. Bibić c , J. Stojanović a
a
Institute for Technology of Nuclear and Other Mineral Raw Materials, Franse d’Epere 86, 11000 Belgrade, Serbia
b
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box 3503, 11120 Belgrade, Serbia
c
Institute of Nuclear Sciences “Vinča”, P.O. Box 522, 11001 Belgrade, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: Electrochemical synthesis of hydroxyapatite powders was performed galvanostatically from homoge-
Received 12 November 2007 neous solution of Na2 H2 EDTA·2H2 O, NaH2 PO4 and CaCl2 at a concentration relationship Ca/EDTA/PO4 3−
Received in revised form 20 March 2008 of 0.25/0.25/0.15 M at current densities of 137 and 207 mA cm−2 and pH values of 9.0 and 12.0. The hydrox-
Accepted 27 March 2008
yapatite powders were characterized by X-ray diffraction, size distribution measurements, transmission
electron microscopy, scanning electron microscopy and thermogravimetric and differential thermal anal-
Keywords:
ysis. The influence of the electrochemical synthesis parameters, e.g. applied current density and pH value,
Biomaterials
on the phase composition, crystallite size, morphology and thermal characteristics of hydroxyapatite
Nanostructures
Differential thermal analysis
powders were investigated.
Electron microscopy © 2008 Elsevier B.V. All rights reserved.

1. Introduction The aim of this work was to prepare nanosized HA powders

using electrochemical method and to investigate the effect of
Calcium hydroxyapatite (HA), Ca10 (PO4 )6 (OH)2 , is one of the applied current density and solution pH value on the phase com-
calcium phosphate-based bioceramic material which makes the position, crystallite size, morphology and thermal characteristics
majority of the inorganic components of human bones and teeth. of obtained hydroxyapatite powders.
That makes the HA being the excellent material for clinical appli-
cations, e.g. implantation into the body [1]. As it is reported in the 2. Materials and methods
literature [2], the application of calcium phosphates depends on
the crystallite size of HA. 2.1. Electrochemical synthesis of hydroxyapatite powders
The preparation of hydroxyapatite powders with controlled
Electrochemical synthesis of hydroxyapatite (HA) powders was performed from
morphology, stoichiometry, crystallinity and, particularly, size in
homogeneous aqueous solution of Na2 H2 EDTA·2H2 O, NaH2 PO4 and CaCl2 at the
the nanometer range has the main role in production of bio- concentration relationship Ca/EDTA/PO4 3− of 0.25/0.25/0.15 M. All chemicals were
materials [3]. Various synthesis methods have been used for HA reagent grade (Sigma Aldrich Chemie) and used without further purification. The pH
powder production, e.g. solid-state reaction [4], chemical precipi- value of as received solution was 3.0, and then was changed to 9.0 and 12.0 by adding
tation method [5], formation of HA crystals on glass [6] or brushite appropriate amount of 10 M NaOH. The electrochemical cell was consisted of two
platinum rectangular electrodes (8 mm× 10 mm). The synthesis was performed gal-
[7], synthesis of nanocrystalline powders in simulated body fluid vanostatically at current densities, j, of 137 and 207 mA cm−2 , with constant stirring,
(SBF) [8], growth of HA crystal using the gel systems [9], sol–gel at room temperature during 3 h. The experimental conditions for four experiments
synthesis [10,11], surfactant templating method [12]. The possibil- are shown in Table 1.
ities of application for human tissue depend upon HA crystallite After 3 h of electrochemical synthesis, suspensions HA I, HA II, HA III and HA IV
were heated at 40 ◦ C until the dense precipitate was obtained. The precipitates were
sizes—130 nm × 30 nm for adult enamel, 20 nm × 4 nm for dentine
then washed with distilled water in centrifuge (10,000 rpm) until a negative reaction
and 25 nm × 3 nm for bone [2]. The properties such as bioactiv- on Cl− ions with AgNO3 was observed. Hydroxyapatite powders were obtained by
ity, dissolution range, resorption, etc. are close to those of natural drying for 48 h.
bones.
2.2. Characterization of hydroxyapatite powders

The phase composition and structure of the HA powders were determined by

X-ray diffraction (XRD) using an Enraf Nonius FR 590 Diffractometer with Cu K␣
∗ Corresponding author. Tel.: +381 11 3303 686; fax: +381 11 3370 387. radiation ( = 0.15418 nm). The diffraction intensity was measured by the scanning
E-mail address: [email protected] (V.B. Mišković-Stanković). technique in the range of 2 = 9–70◦ by a 0.05◦ step for 3 s per point.

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.03.045
138 M.S. Djošić et al. / Materials Chemistry and Physics 111 (2008) 137–142

Table 1 Table 2
Crystallite domain size of HA powders synthesized at different current densities and The values of average HA particle diameter and particle size distribution (PSD)
different pH values intensity of HA I suspension and HA I permeate

Sample pH value j (mA cm−2 ) D0 0 2 (nm) Size measurement HA I suspension HA I permeate

HA I 9.0 137 21.6 z-average diameter (nm) 583 6.07

HA II 12.0 137 23.4
PSD intensity
HA III 9.0 207 24.3
Peak 1: z, nm (Int.,%) 0.938 (95.3) 1.03 (90.9)
HA IV 12.0 207 22.4
Peak 2: z, nm (Int.,%) 331 (4.7) 1900 (9.1)

The hydroxyapatite particle size distribution was determined using a Zeta-sizer

The crystallite domain size was calculated using (0 0 2)
Nano ZS with 633 nm He–Ne laser (Malvern, UK). This instrument can measure
particle sizes from 0.6 nm to 6 ␮m. The microstructures of the HA powders were plane.
examined by scanning electron microscopy (SEM) using a JSM-35 (JEOL) instrument The X-ray diffraction patterns peaks (Fig. 1) are broadened due
and transmission electron microscopy (TEM). Transmission electron microscopy to the fine crystallite size [5]. That is in agreement with calcu-
(TEM) measurements of HA powder were carried out using a Philips EM 400 instru- lated crystallite domain size values, represented in Table 1. It can
ment with operating voltage 120 kV. Samples were prepared by placing a drop of
diluted aqueous HA suspension onto a carbon-coated copper grid. After the sample
be observed (Table 1) that crystallite domain size does not depend
was dried it was examined by TEM. significantly on pH value as well as on applied current density. How-
Differential thermal analysis (DTA) and thermogravimetric analysis (TG) were ever, the smallest crystallite size was obtained at lower pH value
carried out in air, using a SETARAM TG/DTA STSYS evolution—1750 system at heating and lower current density (sample HA I).
rate of 10 ◦ C/min and furnace cooling in the temperature range from 23 to 1400 ◦ C.
The mechanism of HA formation requires the liberation of Ca2+
ions from EDTA [14]:
3. Results and discussion
Ca(EDTA)2−  Ca2+ + EDTA4− (1)
3.1. XRD analysis the generation of OH– ions through water reduction:

X-ray diffraction analysis was performed to determine the 2H2 O + 2e− → H2 + 2OH− (2)
phase composition and structure of electrochemically synthesized
and ionic migration towards the electrodes, where precipitation of
hydroxyapatite powders.
HA occurs:
Fig. 1 represents the XRD patterns of HA powders synthesized
at pH 9.0 and j = 137 mA cm−2 (sample HA I, Fig. 1a), pH 12.0 and 10Ca2+ + 6PO4 3− + 2OH−  Ca10 (PO4 )6 (OH)2 (3)
j = 137 mA cm−2 (sample HA II, Fig. 1b), pH 9.0 and j = 207 mA cm−2
(sample HA III, Fig. 1c) and pH 12.0 and j = 207 mA cm−2 (sample 3.2. Particle size distribution
HA IV, Fig. 1d). The only detected crystalline phase in all samples
was hydroxyapatite, Ca10 (PO4 )6 (OH)2 . The particle size distribution (PSD) measurements were made
Using WinFit software [13], the crystallite domain using HA I suspension. The data presented in Table 2 are the average
size was calculated and the results are given in Table 1. of 10 runs.

Fig. 1. XRD pattern of HA powders synthesized at: (a) pH 9.0 and j = 137 mA cm−2 (sample HA I), (b) pH 12.0 and j = 137 mA cm−2 (sample HA II), (c) pH 9.0 and j = 207 mA cm−2
(sample HA III) and (d) pH 12.0 and j = 207 mA cm−2 (sample HA IV).
 M.S. Djošić et al. / Materials Chemistry and Physics 111 (2008) 137–142 139

Fig. 2. Particle size distribution of HA I suspension.

It is evident that the prepared HA I suspension was a high degree

polydisperse one. The average HA particles diameter is 583 nm.
However, based on PSD intensity, more than 95% HA particles have
an average diameter of ∼1 nm.
In order to separate HA particles of smaller diameters we have
performed ultrafiltration of HA I suspension using an Amicon cell,
model 8200, with a capacity of 200 cm3 and an effective membrane
area of 28.7 cm2 . The cell was supplied with a plasticized stirrer. An
Amicon Diaflo PM 10 polysulfone membrane with nominal molec-
ular weigh cut-off of 10,000 Da and apparent pore size diameter of
3.8 nm was used. The particle size distribution measurements were
made using HA I permeate and the obtained results are also given in
Table 2. The average diameter of HA particles in the HA I permeate
is 6.07 nm, and according to PSD intensity results more than 90%
HA particles are of an average diameter of ∼1 nm.
Size distributions by intensity for HA I suspension and HA I
permeate are presented in Figs. 2 and 3.

3.3. TEM analysis

The nanocrystalline nature of the derived powder was con-

firmed by TEM. Typical TEM images of permeate obtained after
double ultrafiltration of HA I suspension are presented in Fig. 4a
and b. It can be noticed that the primary particles are of nanometer
range, e.g. about 1 nm, according to existence of different contrast
on the TEM images. This result is in good agreement with the par-
ticle size distribution obtained using Zeta-sizer Nano ZS and XRD
analysis, which revealed that the particles were in the nanometer
size range.

3.4. SEM analysis

SEM micrographs of HA powders are shown in Fig. 5. All of

the investigated powders consist of big agglomerates which are
composed of fine crystallites. The spherule agglomerates can be Fig. 4. TEM micrographs of permeate obtained after double ultrafiltration of HA I
observed in the case of HA I and HA III (Fig. 5a and c), while the HA suspension.
II and HA IV present plate-like morphology (Fig. 5b and d). Accord-
ing to these results it could be proposed that the morphology of
agglomerates depends on the pH value of the solution. Namely, HA
powders obtained at lower pH values (HA I and HA III, pH 9.0) con-
pH (HA II and HA IV, pH 12.0) have the plate-like structure. In addi-
sist of spherule agglomerates, while HA powders obtained at higher
tion, it can be suggested that applied current density does not affect
the HA powder morphology.
The crystallite domain size of 21.6 nm for HA I, determined
by X-ray diffraction (Table 1), indicates that agglomerates were
formed through the drying process, which is confirmed by SEM
analysis (Fig. 5a). This proposition is in good agreement with
the literature where the nucleation-aggregation-agglomeration-
growth mechanism is proposed [15]. According to this mechanism,
particle formation occurs in the following steps: (a) nucle-
ation and growth to form crystallites in nanometric size
range, (b) aggregation of elemental nanocrystals by physical
Fig. 3. Particle size distribution of permeate obtained after double ultrafiltration of attractions and (c) further crystal growth to form stable agglom-
HA I suspension. erates.
140 M.S. Djošić et al. / Materials Chemistry and Physics 111 (2008) 137–142

Fig. 5. SEM micrographs of hydroxyapatite powders: (a) HA I, (b) HA II, (c) HA III and (d) HA IV.

3.5. DTA/TG analysis The TG curves of HA powders exhibit three weight loss stages.
The first stage was observed from 23 to about 80 ◦ C (Fig. 7a), with
DTA curves for HA powders are represented in Fig. 6. The first sharp peaks at DTG curves at 71, 63 and 76 ◦ C for samples HA I,
endothermic peak observed at DTA curves at about 80 ◦ C can be HA II and HA III, respectively (Fig. 7b). This stage corresponds to
attributed to desorption of water molecules adsorbed on the crys- desorption of water molecules adsorbed on the crystallite surface.
tallite surface. The subsequent strong exothermic peak at about The second stage of weight loss of the TG curves was observed
300 ◦ C results from the combustion of organic material [16], e.g. between 80 and 530 ◦ C (Fig. 7a), with sharp peaks at DTG curves
EDTA. Another exothermic peak appears at 1305 ◦ C, indicating at 301, 309 and 323 ◦ C for samples HA I, HA II and HA III, respec-
the decomposition of HA to anhydrous calcium phosphates such tively. This stage corresponds to the combustion of organic material
as tri-calcium phosphate (TCP), Ca3 (PO4 )2 . Namely, according to (EDTA) [16,19].
the literature [17,18] HA decompose to tri-calcium phosphate at The third stage of weight loss of the TG curves was observed
1200–1400 ◦ C. At 1280 ◦ C well crystallized HA and ␤-TCP exists between 530 and 1400 ◦ C (Fig. 7a), with peaks at DTG curves
[17], and at temperatures higher than 1350 ◦ C, ␤-TCP irreversibly (Fig. 7b) at around 930 and 1305 ◦ C, for all HA samples. The
transforms to ␣-TCP [18]. endothermic peak observed at around 930 ◦ C can be attributed to
The weight loss and temperatures associated with phase trans- the dehydroxylation of HA and formation of oxyhydroxyapatite,
formation were determined by thermogravimetric analysis. The Ca10 (PO4 )6 (OH)2−2x Ox x , where  is vacancy and x < 1 [20]. Next
TG curves of hydroxyapatite powders obtained in the temperature exothermic peak, recognized at 1305 ◦ C indicates the decompo-
range between 23 and 1400 ◦ C are shown in Fig. 7a, while Fig. 7b sition of HA to anhydrous calcium phosphate such as tri-calcium
represents the differential TG (DTG) curves. phosphate (TCP) [18].
 M.S. Djošić et al. / Materials Chemistry and Physics 111 (2008) 137–142 141

From DTA/TG analysis it can be concluded that parameters of

electrochemical synthesis of HA powders (applied current den-
sity and pH of the solution) do not effect significantly the weight
loss and temperatures associated with phase transformation during
thermal treatment.

4. Conclusions

Electrochemical synthesis of hydroxyapatite (HA) powders was

performed galvanostatically from homogeneous aqueous solution
of Na2 H2 EDTA·2H2 O, NaH2 PO4 and CaCl2 , at pH values of 9.0 and
12.0 and at current densities of 137 and 207 mA cm−2 . HA powders
were characterized by XRD, particle size distribution, TEM, SEM and
DTA/TG analysis.
The phase composition was determined by XRD and the only
detected crystalline phase in all samples was hydroxyapatite. The
crystallite domain size does not depend significantly on pH value
as well as on applied current density.
Fig. 6. DTA curves for hydroxyapatite powders HA I, HA II and HA III. Particle size distribution has proved HA I suspension to be high
degree polydispersed one. The average HA particles diameter is
583 nm. However, on the basis of PSD intensity results more than
95% HA particles have an average diameter of ∼1 nm. After ultrafil-
tration, the average diameter of HA particles in the HA I permeate
is 6.07 nm, and according to PSD intensity results more than 90%
HA particles have average diameter ∼1 nm. Based on TEM analy-
sis, the average size of the HA particles was found to be also in the
nanometer size range.
SEM analysis of electrochemically synthesized HA powders
shows that morphology of HA depends on the pH value of the solu-
tion. HA powders synthesized at lower pH value consist of spherule
agglomerates, while HA powders synthesized at higher pH value
have the plate-like structure. The applied current density does not
affect the HA powder morphology.
The thermal properties of HA powders, e.g. water desorp-
tion and phase transformation from hydroxyapatite to tri-calcium
phosphate, were analyzed by DTA/TG. It can be concluded
that parameters of electrochemical synthesis of HA powders
do not effect significantly the weight loss and temperatures
associated with phase transformation during thermal treat-
ment.

Acknowledgements

This research was financed by the Ministry of Science and Envi-

ronmental Protection, Republic of Serbia, contracts no. 142061,
142004, 141013, and TR 6723/B.

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