ARTICLE IN PRESS

Physica B 405 (2010) 2799–2802

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Physica B
journal homepage: www.elsevier.com/locate/physb

Sol–gel synthesis of nanostructured hydroxyapatite powder in presence of

polyethylene glycol
A. Ruban Kumar, S. Kalainathan n
School of Advanced Sciences, VIT University, Vellore-632 014, Tamil Nadu, India

a r t i c l e in fo abstract

Article history: A study on the morphological changes of nanostructured hydroxyapatite in presence of polyethylene
Received 30 January 2010 glycol synthesized by sol–gel technique is presented. Equimolar solutions of Ca(NO3)2  4H2O and
Received in revised form (NH4)2HPO4 dissolved in ethanol were used in the synthesis at 85 1C. Polyethylene glycol is added as an
27 March 2010
organic modifier. The product was sintered at 400, 750 and 1100 1C. The XRD and FTIR results indicated
Accepted 30 March 2010
the presence of amorphous hydroxyapatite in as dried gel precursor and single phase HAP was obtained
after heat treatment at 1100 1C at 4 h. SEM images of the precursor appear agglomerated leaving sub
Keywords: micrometric pores between them and the small particles seen embedded in each agglomerated cluster
Nanostructured with an average diameter of 50–70 nm. At high temperatures the more flexible polyethylene glycol
Hydroxyapatite
molecules induced the orientation growth which leads to the formation of HAP platelets.
Scanning electron microscopy
& 2010 Elsevier B.V. All rights reserved.

1. Introduction nanofibers [12], plates [13], nanoparticulates [14] and nanorods

Hydroxyapatite (Ca10(PO4)6  (OH)2, HAP) is the most ubiqui-
tous calcium phosphate that has assumed substantial interest and
importance because of its chemical similarity to the natural
calcium phosphate mineral present in biological hard tissues.
Different clinical applications involve repair of bone defects, bone
augmentation, as well as coatings for metallic implants [1,2]. The
important requirement of a material designed for bone substitu-
tion and/or repair, is the ability to create a bond with the host
living bone [3]. Hence, researchers have tried to customize its
properties such as bioactivity, mechanical strength, solubility and
sinterability by controlling its composition, morphology and
particle size [4,5]. The chemical, structural and morphological
properties of synthetic hydroxyapatite can be modulated by
varying the method and conditions of synthesis. There are several
different synthetic methods used to generate HAP as reported in
the literature including chemical precipitation [6], hydrothermal
techniques [7], sol–gel [8], solid state and mechano-chemical
methods [9,10].
Among the alternative methods, sol–gel approaches have
attracted much attention recently because of its well known
advantages, which include homogeneous molecular mixing, low
processing temperature, the ability to generate nano-sized
particles and the tremendous flexibility to generate nanocrystal-
line powders, bulk amorphous monolithic solids and thin films
[11]. In the morphology-controlled synthesis of hydroxyapatite
n
Corresponding author.
E-mail address: kalainathan@yahoo.com (S. Kalainathan).
[15], several organic modifiers are used such as ethylene glycol
[13], cetyltrimethylammonium bromide (CTAB) [12,16], polyvinyl
alcohol [16], citric acid [17] and ethylenediamminetetraacetic
acid (EDTA), [18] etc.
The present work carried out elaborates on size controlled
synthesis of nanostructured hydroxyapatite by sol–gel method
using calcium nitrate tetra hydrate and di-ammonium hydrogen
phosphate as starting materials with the aid of polyethylene
glycol (MW 600) as modifier. The explanation about the effect of
the polyethylene glycol on size-controlled synthesis of hydro-
xyapatite is attempted.
2. Materials and methods
The flow chart shown in Fig. 1 outlines the experimental
procedure used to generate the HAP powder described in this
study. The starting materials used in the synthesis of
hydroxyapatite were analytical grade reagents calcium nitrate
tetra hydrate and di-ammonium hydrogen phosphate. Calcium
nitrate tetra hydrate was dissolved in 50 mL of ethanol and
rapidly added to a 50 mL solution containing di-ammonium
hydrogen phosphate under stirring. The concentration of the
reactants was varied to obtain a Ca/P molar ratio of 1.67. About 5%
of polyethylene glycol was added along with the mixture. The
resultant sol–gel was continuously stirred at a constant pH of 10
(pH was kept constant by adding NH4OH solution) and at a
constant temperature of 85 1C for 4 h. After allowing the product
to cool, it was kept inside the oven at 40 1C overnight. The product

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.03.067
 ARTICLE IN PRESS
2800 A. Ruban Kumar, S. Kalainathan / Physica B 405 (2010) 2799–2802

Ca (NO3)2.4H2O 2500

211
Hydroxyapatite at 1100°C
5% Polyethylene
(NH4)2HPO4 2000
glycol

Intensity (cps)

300
Sol-Gel (pH>10) 1500

112
Heating at 85°C

1000

213
002

222
202

310
Gelation 40°C
(12 hours)

321
500

002
312
210

410
402
102

311
212
301

203
Sintering

113
200
111

320
Powder at 400 °C 0
(2 hours)
20 25 30 35 40 45 50 55
Sintering
2θ (deg)
Powder at 750 °C
Fig. 2. XRD pattern of HAP sintered at 1100 1C.
(2 hours)

Sintering
2500
Powder at 1100°C PEG-HAP at 1100°C

211
(4 hours)
2000
Fig. 1. Flow chart.

300
Intensity (cps)

was sintered for 2 h at 400 1C, again at 750 and 1100 1C for 4 h in 1500
stagnant air as shown in the flow chart.

112
The X-ray powder diffraction analysis was carried out by means
of a Siemens ED-5005 diffractometer with Cu Ka radiation 1000
002

213
222
(l ¼1.5405 Å). The 2y range was from 201 to 551 at a scanning

310
202
speed of 0.21/min. The patterns due to different phases were

321
312
500

004
210

402
compared with the ASTM standards. The samples were further

410
102

301
characterized by FT-IR spectroscopy in the range of 400–4000 cm  1

400
311
200
111

212

113

320
using Thermo Nicolat, Avatar 330 (ESP) FTIR spectrometer by KBr
0
pellet technique. Morphological investigation of the samples
was performed using a JEOL-JSM-6510 Scanning Electron
20 25 30 35 40 45 50 55
Microscope 20 kV. The samples were sputter-coated with gold prior
2θ (deg)
to examination.
Fig. 3. XRD pattern of HAP using PEG sintered at 1100 1C.

3. Results and discussion

experimental conditions. The diffraction peaks particularly in the
planes (0 0 2), (2 1 1), (1 1 2) and (3 0 0) are high and narrow
The reaction of Ca(NO3)2  4H2O with (NH4)2HPO4 in ethanol
implying that the HAP crystallizes well.
results in formation of a gel. The resultant gel is translucent
because of the concentration. The sintered samples at various
temperatures were characterized for structural confirmation. 3.1.2. FTIR analysis
The FTIR spectra of the washed HAP and HAP using
polyethylene glycol as modifier are shown in Fig. 4. The bands
3.1. Chemical structure
at 3570 and 632 cm  1 belong to the vibration of hydroxyl (O–H)
group, the bands at 1089, 1044 and 960 cm  1 are the
3.1.1. XRD analysis
characterization of phosphate stretching vibration and
The XRD patterns of hydroxyapatite and hydroxyapatite using
the bands observed at 601, 570 and 473 cm  1 are due to the
polyethylene glycol as modifier, were taken at various tempera-
phosphate being in vibration. From the IR analysis, the
tures (as prepared, 400 and 750 1C). The patterns indicate the
precipitated powders are proved to be hydroxyapatite [19,20] in
presence of amorphous hydroxyapatite. The broaden peaks reveal
nature. The presence of polyethylene glycol in hydroxyapatite
that the particles sizes are very small in the range of 50–70 nm.
does not play any role in the structural deformation of
The X-ray patterns collected on the powders after heat treatment
hydroxyapatite, meaning that naked HAP crystallites were
at 1100 1C for 4 h in stagnant air exhibit single phase of HAP. Fig. 2
prepared.
shows the X-ray patterns of HAP at 1100 1C. The X-ray patterns of
HAP using PEG at 1100 1C are shown in Fig. 3. These patterns are
in good agreement with the ASTM data (JCPDS no. 09-0432) for 3.2. Morphology and particle size
hydroxyapatite. No characteristic peaks of impurities, such as
calcium hydroxide and calcium phosphates were observed, Fig. 5 shows the SEM micrographs of HAP using polyethylene
meaning that phase pure HAP was prepared under the present glycol as modifier by sol–gel method at 85 1C. The as-dried gel

A. Ruban Kumar, S. Kalainathan / Physica B 405 (2010) 2799–2802
b
% Transmittance
3500 3000 2500 2000 1500
Wave numbers (cm-1)
Fig. 4. FTIR spectra of the (a) pure hydroxyapatite and (b) hydroxyapatite using
polyethylene glycol.
Fig. 5. SEM micrographs of HAP using polyethylene glycol at 85 1C.
precursor appears to be agglomerated leaving sub micrometric
pores between them and small particles are seen embedded in
each agglomerated cluster with an average diameter of 50–70 nm.
These pores are beneficial for the circulation of the physiological
fluid throughout the coatings when it is used as a biomaterial in
bone implantation. In Fig. 6 (a), the powder obtained after heat
treatment at 1100 1C for 4 h in stagnant air exhibits the
morphology of sintered platelets. Individual platelets are seen
and the size is also increased considerably. Whereas the pure HAP
sintered at 1100 1C for 4 h in stagnant air exhibits the morphology
of spherical structure as shown in Fig. 6(b).
The role of polyethylene glycol in the morphological changes is
explained as follows: Polyethylene glycol exhibits in flexura chain
state and contains numerous ether bonds (–O–). The flexibility of
the polyethylene glycol molecules in aqueous solution increases
with increasing temperature. Therefore, at high synthesis tem-
perature, the more flexible polyethylene glycol molecules induce
the axis orientation growth of HAP via an interaction between the
ether bonds of polyethylene glycol and HAP nanocrystallites,
resulting in the formation of HAP platelets with large size. On the
other hand, at a lower synthesis temperature, the less flexible
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1000 500
Fig. 6. (a) SEM micrographs of HAP using polyethylene glycol at 1100 1C and
(b) SEM micrographs of pure HAP at 1100 1C.
polyethylene glycol colloids should be responsible for the
formation of the nanostructured HAP.
4. Conclusion
HAP plate-like crystals were successfully obtained by ethanol
based sol–gel method. Calcium nitrate tetra hydrate and di-
ammonium hydrogen phosphate were used as starting materials
and polyethylene glycol was added as organic modifier at low
synthesis temperature of 85 1C. This method provides the
synthesis of pure, porous stoichiometric HAP at 85 1C at alkaline
pH via an alcohol based sol–gel process. Flexura chain state and
numerous ether bonds presented in polyethylene glycol induce
the axis orientation growth of HAP via an interaction between the
ether bonds of polyethylene glycol and HAP nanocrystallites,
resulting in the formation of HAP nanoparticles. The image of the
precursor appears agglomerated leaving sub micrometric pores
between them with small particles seen embedded in each
agglomerated cluster. These pores will help the material to attain
more biocompatibility and enables the circulation of physiological
fluids. At 1100 1C for 4 h, more flexible polyethylene glycol
molecules induced the orientation growth which leads to the
formation of HAP platelets with an average size of 50–70 nm. The
 ARTICLE IN PRESS
2802 A. Ruban Kumar, S. Kalainathan / Physica B 405 (2010) 2799–2802
XRD studies reveal pure crystalline HAP and the FTIR spectra
confirm the functional groups of hydroxyapatite. The crystal-
linities of the resultant nanostructured HAP increased with
increasing synthesis temperature.
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