Trends Biomater. Artif.

Organs, and
Preparation Vol 19(2), pp 57-62 (2006)
Characterization 57
http://www.sbaoi.org
of Microcrystalline Hydroxyapatite Using Sol Gel Method

Preparation and Characterization of Microcrystalline Hydroxyapatite Using

Sol Gel Method

U. Vijayalakshmi* and S. Rajeswari

Department of Analytical Chemistry

University of Madras
Guindy Campus, Chennai-600 025
E-mail: lakesminat@yahoo.com

Hydroxyapatite ceramics have been recognized as substitute materials for bone and teeth in orthopaedic and
dentistry field due to their chemical and biological similarity to human hard tissue. On implantation, the bioactive
materials induce specific tissue response which results in the formation of a bonding interface between the
implant and the natural bone tissue. Calcium phosphate is used as biomaterials such as synthetic bone graft,
drug carrier and coating on metal prosthesis (in hip endoprosthesis and dental implants). Sol Gel technique has
been developed and employed to prepare various materials because it has main advantage of easy control of
chemical composition and low temperature synthesis that are very important for thin film formation. In this
work, microcrystalline hydroxyapatite powder was synthesized from calcium acetate and tri ethyl phosphate
in water and ethanol medium. The hydrolysis rate of tri ethyl phosphate in water and alcoholic medium was
examined. The pH and gelation time of the batch containing with and without water was examined. The effect
of calcinations on powder properties was studied. The XRD analysis was used to examine the phase
transformation of hydroxyapatite at different temperature. At particular temperature calcium carbonate was
observed and upon acid treatment the calcium carbonate peak at 29.399o was minimized and a stoichiometric
hydroxyapatite was examined. The functional group change of hydroxyapatite at different temperature was
observed by FT- IR spectroscopy. The morphological feature of the raw and sintered samples was examined.
The synthesized powder was characterized through FT-IR, XRD and SEM analysis.

Introduction temperature conventional processes. This

Materials, which are introduced in medical
practice for reconstruction and replacement of
the diseased and damaged human bones, are
called "Biomaterials". According to the tissue
response behaviour at the implant interface,
biomaterials have been divided in to inert,
resorbable and bioactive materials. Among
these bioceramics, hydroxyapatite ceramic is a
biocompatible and bioactive material that can
be used to restore damaged human calcified
tissue. The use of sol gel routes to form a
bioactive hydroxyapatite layer on metal
substrates has recently attracted in the
biomedical field. The sol gel method represents
the low temperature way of the production of
glasses, ceramic and composite materials with
better purity and homogeneity than high
process has been used to produce a wide range
of compositions (mostly oxides) in various
forms, including powders, org/inorg hybrids,
fibers, coating, thin films, monoliths and porous
membranes. One of the most attractive features
of the sol gel process is that it can produce
compositions that cannot be created by the
conventional methods. The mixing level of the
solution is retained in the final product.
In sol gel chemistry, the metal alkoxides convert
to amorphous gels of metal oxides through
hydrolysis and condensation reactions. Only
limited attempts have been reported on the sol
gel processing of hydroxyapatite material (1-4).
The alkoxide solution route has been proven to
be a good way to synthesis materials in different
shapes such as films, fibers and powders (5).
58 U. Vijayalakshmi and S. Rajeswari
It has been reported that the materials prepared
with the sol gel process are efficient calcium
phosphate absorbents in in vitro and in vivo
studies (6-8). While those of the same
composition prepared by traditional methods
at high temperature are biologically inert (9),
hydroxyl groups present on the sol gel process
can be responsible for the bioactivity of these
materials (10).
In the present investigation, tri ethyl phosphate
and calcium acetate were used to develop a
hydroxyapatite phase with simple procedures.
The synthesized amorphous calcium
phosphate powder can be sintered into a pure
hydroxyapatite ceramic. The chemical and
phase behaviours of the ACP powder have been
examined after the thermal treatment. The pH
and gelation time of the batch containing with
and without alcohol was examined. Many
reports have been focused on the sol gel
derived hydroxyapatite and that showed the
presence of secondary phase like calcium oxide
and pyrophosphate. But in our study, we didn't
see any calcium oxide peak instead we have
calcium carbonate peak. This CaCO 3 is
minimised by acid treatment. The synthesized
sample was characterised through FT-IR, XRD
and SEM analysis.
Methods and Materials:
Calcium acetate and tri ethyl phosphate was
used as calcium and phosphorous precursors
respectively. Solution preparation was
conducted in a moisture free atmosphere
because of the hygroscopic nature of the
reactants. High purity calcium acetate was
dissolved in water. The phosphate solution was
added drop wise into the calcium containing
solution with the aid of a magnetic stirrer to
obtain a Ca : P ratio of 1.67 and the resultant
mixture was stirred for additional 10min at
ambient temperature. Preparation was carried
out in a nitrogen atmosphere glove box. The
solution was allowed to age for the period of 24
hrs. During this stage pH and gelation time of
the sols was observed. The formed gels were
then dried at 120 o C for 16hrs. The same
procedure was carried out in the presence of
ethanol medium.
The dried powder was sintered at 900 oC for
2hrs. The resultant powder was washed with
0.01M HCl and washed with water to eliminate
the calcium carbonate and it was filtered
through filter paper then the resultant powder
was dried at 120oC for 3hrs.
Characterization of gel:
Fourier transform infrared spectroscopy
(FT-IR)
The FT-IR spectral studies were conducted
using Hitachi 270-50 spectrophotometer by KBr
disks in the range of 4000-400 cm-1
X-Ray Diffraction (XRD)
Sintered gel was powdered and the XRD
spectrum was recorded using SEIFERT JSO-
DEBYEREX-2002 using a step size of 0.02o. The
scan rate of 1o Per minute and a scan range
between 10-60o in flat plate geometry with Cu
radiation was performed.
Scanning Electron Microscope (SEM)
The samples were investigated with a
scanning electron microscope (Philips 501
model) to investigate the powder morphology
and microstructure of the powders.
Chemical analysis
The phase constitution and the chemical
homogeneity of the sample were examined by
quantitative chemical analysis via EDTA titration,
gravimetry. The molar Ca/P ratio was found to
be 1.67, which indicates the formation of
hydroxyapatite.
Results and Discussion:
Organic phosphorous derivatives of various
ester functional group exhibit different hydrolysis
rate upon exposure to water and alcoholic
medium. The hydrolysis rate can be monitored
by testing its pH values. After preparation of the
sols, pH =11.25 was detected for the aqueous
based sol and pH=9.47 was observed for the
ethanol based sol. Decrease in pH values was
monitored after aging in an oil bath for 24hrs.
The pH values of aging precursors were
measured and the values before and after aging
are summarized in Table 1. The decrease in
pH values after aging indicating hydrolysis of
TEP. Upon aging the hydrolysis products form a
complex with Ca2+ ions dissolved in the solution.
Both the sols were transformed into clear and
 Preparation and Characterization of Microcrystalline Hydroxyapatite Using Sol Gel Method 59

Table 1. pH values of aging precursors before and after aging

Medium pH Before Aging pH After Aging

Without Alcohol 11.25 10.01

Ethanol 9.47 8.47

transparent solution. The viscosity of the sols FT-IR Spectroscopy:

was increased after the solvents were removed
The FT-IR spectra of as prepared powder with
during heating at 60oC. After cooling the viscosity
and without treated powders are shown in Fig
of the sols was further increased for both
1(a, b, c). FT-IR spectrum of the raw sample
viscous sols. Further heating causes removal
showed a strong band at 3390cm -1 was
of the solvents accompanied by thermal
associated to the O-H stretching vibration of
dehydration and condensation in the formation
hydrogen bonded molecules. The IR bands at
of more (-Ca-O-P-) bonds in the dried gels.

Fig 1a. FT-IR Spectra for the raw and sintered sample (Before Acid Treatment)

Fig 1b. FT-IR Spectra for the raw and sintered sample (After Acid Treatment)

Fig 1c. FT-IR Spectra for the raw and sintered sample in ethanol medium
60 U. Vijayalakshmi and S. Rajeswari

1430 and 870cm-1 corresponded to the CO32- with carbonate substitution. The peaks at
groups. These vibrations are characteristic of a 3650cm -1 are associated with adsorbed
carbonate groups engaged in an amorphous hydrate. The triplet with well resolved bands at
solid. The amorphous solid had a strong band 1096, 1085 and 1056 cm -1 was identical to
at 1060, 570 and 606cm -1 which were phosphate band. The triply degenerate bending
associated to the P-O vibration modes vibration of the PO43- ions at 570, 602, and
respectively. The other featureless peaks are 632cm -1 was indicated of the presence of
associated to the PO43- band in the disordered hydroxyapatite phase.
manner.
XRD pattern:
The sample heated at 900oC was exhibited a
Figure 2 showed the XRD spectrum for the
strong characteristic peak with respect to
treated and untreated samples in water and
hydroxyapatite. When the temperature
ethanol medium. XRD patterns of the as
increased the carbonate bands became less
synthesized powder showed the presence of
intense and the stretching and vibrational
an amorphous phase. The sample heated at
modes of OH- groups became more intense.
900oC showed broad peaks of an apatite phase.
The peak at 1430cm-1 was minimized but not
When the temperature was increased, the
negligible. From the figure, it was confirmed that
apatite peaks became sharper, because of
the hydroxyapatite constitute of calcium
crystal growth. Alternatively, calcium carbonate
carbonate after thermal treatment at 900oC.
peak at 29.399o was present together with HAP
In order to eliminate the carbonate groups from phase; however, the β-TCP phase was not
the hydroxyapatite powder acid treatment was detected at any temperature. Also, the CaO peak
performed. The sintered hydroxyapatite at 37.469o and 54.029o was not detected at any
particles were suspended in a 0.01M temperature. The presence of hydroxyapatite
hydrochloric acid medium and stirred for 3 hrs was confirmed by a strong diffraction peak at
with the aid of magnetic stirrer. After acid
treatment, the resultant slurry was filtered and
dried in an oven for 3hrs at 80oC. Then the dried
powder was analysed by FT-IR, XRD and SEM.
Figure 1b and 1c represents the FT-IR Spectra
of the sample after acid treatment. The acid
treated samples had a strong band at
873,1430cm -1 that was indicative of the
carbonate ion substitution. But after the
treatment the intensity of carbonate band was
decreased. These spectra suggest that
hydroxyapatite samples used in our study are
Fig 2a. As prepared powder in water medium

Fig 2b. XRD Pattern for the sample with and without acid treatment in Water medium
 Preparation and Characterization of Microcrystalline Hydroxyapatite Using Sol Gel Method 61

Fig 2c. XRD Pattern for the sample with and without acid treatment in Ethanol medium

31.773 o (211) plane. The accompanying two of aggregates is decreased after calcinations
peaks at 32.196 and 32.902 o of equal of the sample at 900 o C. The collapse of
intensities were also detected. aggregate was more obvious for the sample
after acid treatment, which results in the
After acid treatment, the carbonate peak at
formation of a large particles network.
29.399o was minimized. The powder patterns
do not indicate any peaks corresponding to
CaO. The calcium carbonate peak was
minimized and the intensity of hydroxyapatite
peaks at 211, 112, 300 plane was increased.
The crystallization of the carbonate
hydroxyapatite was prepared. From the figure,
the secondary impurity phases such as CaO
and β-TCP were not detected at the sintered
samples.
Scanning Electron Microscope (SEM):
Microstructural changes were commensurate
with thermal crystallization as shown in Figure
3. The morphology of the as prepared sample
showed needle like crystal particles. The size (3b) Sintered powder without treatment

( 3c) Sintered powder with treatment

(3a) As prepared powder in water medium
62 U. Vijayalakshmi and S. Rajeswari

Conclusion:
Hydroxyapatite can be synthesized using the
sol-gel route with proper heat and acid
treatment. There will be no significant
differences observed for the powder with and
without alcohol medium excluding the pH and
gelation time. The powder calcined at higher
temperature did not show any secondary
phases like CaO, Ca2P2O7, β-TCP respectively.
The acid treated powder showed a higher
resolved HAP peaks at 211,112,300 planes
respectively. The acid consumes all the
dissolvable impurities. The calcium carbonate
(3d) Sintered powder with treatment in peak at 29.399o was minimized by mild acid
ethanol medium washing method.

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