Int. J. Appl. Ceram. Technol.

, 5 [4] 401411 (2008)

DOI:10.1111/j.1744-7402.2008.02212.x

Ceramic Product Development and Commercialization

Synthesis and Characterization of Hydroxyapatite

Wollastonite Composite Powders by SolGel Processing
Martn A. Encinas-Romero* and Salvador Aguayo-Salinas
Departamento de Ingeniera Qumica y Metalurgia, Universidad de Sonora, Hermosillo, Sonora 83000,
Mexico

Santos J. Castillo
Departamento de Investigacion en Fsica, Universidad de Sonora, Hermosillo, Sonora 83000, Mexico

Felipe F. Castillon-Barraza
Centro de Ciencias de la Materia Condensada, Universidad Nacional Autonoma de Mexico, Ensenada
B.C. 22800, Mexico

Vctor M. Castano
Centro de Fsica Aplicada y Tecnologa Avanzada, Universidad Nacional Autonoma de Mexico, Santiago
de Queretaro, Queretaro 76000, Mexico

Composites of hydroxyapatitewollastonite were synthesized by a solgel route using calcium acetate and triethyl phosphate as precursors of hydroxyapatite and high-purity natural wollastonite added in ratios of 20, 50, and 80 wt%. These
composites were characterized by thermal analysis, X-ray diffraction, FT-IR and Raman spectroscopy, and scanning and
transmission electron microscopic techniques. Formation of hydroxyapatite occurs at a relatively low temperature, about
4201C, accompanied by calcium carbonate; wollastonite remains unreacted. The composites were purified by heat treatment to
a higher temperature and washed with hydrochloric acid and distilled water, to produce B-type carbonated hydroxyapatite
wollastonite composites as final products.

Introduction

This work was partially supported by PACAC UNISON-UNAM through project Px-864
and by CONACyT under scholarship 189156 to M. A. Encinas-Romero.
*maencinas@iq.uson.mx
r 2008 The American Ceramic Society

Hydroxyapatite Ca10(PO4)6(OH)2 has long been

recognized as a substitute material for bones and teeth in
orthopedics and dentistry due to its chemical and biological similarity to calcified human tissue. Moreover, its

402

International Journal of Applied Ceramic TechnologyEncinas-Romero, et al.

direct bonding capability to the surrounding tissues

characterizes it as an excellent biocompatible material
after implantation.1,2 Unlike other calcium phosphates,
hydroxyapatite does not break down under physiological conditions. It is thermodynamically stable and actively takes part in bone bonding, forming strong
chemical bonds with surrounding bone.3 For this reason, many processing routes have been developed for
synthesizing fine hydroxyapatite and sintering the reactive powders to form a dense ceramic. The most common approaches reported include precipitation, solidstate reaction, solgel methods, hydrothermal route,
emulsion and microemulsion techniques, mechanochemical reactions, and a combination of mechanochemical, hydrothermal, and ultrasonically assisted
reactions.4 In this respect, the solgel technique is an
effective method for the preparation of highly pure
powder due to the possibility of a strict control of the
process parameters. This method offers a molecular
mixing of calcium and phosphorus, capable of improving chemical homogeneity. Moreover, the high reactivity of the solgel powders allows a reduction of the
processing temperature and of any degradation phenomena during sintering.5
Various authors have reported the hydroxyapatite
synthesis by the solgel route using different calcium
and phosphate precursors, but the major limitations are
the drawbacks associated with hydrolysis of phosphates
and the higher cost of raw materials.6 Jillavenkatesa and
colleagues6,7 have reported the synthesis of hydroxyapatite powders using a solgel route with simple procedures and relatively inexpensive chemicals; difficulties
associated with the slow rates of hydrolysis of phosphates were overcome.
However, synthetic hydroxyapatite is essentially brittle; practice indicates that the use of hydroxyapatite without additives for implant production is inefficient due to
its low strength. One approach to solve this problem is to
combine it with a fracture-tough phase through a composite. Wollastonite CaSiO3 has been widely used as a
filler to fabricate composites with improved mechanical
properties.811 Moreover, it has also been used as a medical material for artificial bones and dental roots because of
its good bioactivity and biocompatibility.1214 Kokubo9
developed a clinically important glass ceramic (A/W-glass
ceramic) that contains apatite and b-wollastonite as reinforcing phases in a MgOCaOSiO2P2O5 glassy matrix.
The wollastonite phase in the A/W-glass ceramic consists
of a silica chain structure. This chain structure reinforces

Vol. 5, No. 4, 2008

the apatite crystals. Furthermore, the presence of

wollastonite in A/W-glass ceramic plays an important
role in the bioactivity of the glass ceramic. Greish and
Brown10 evaluated the effect of wollastonite on the mechanical and bioactive properties of the hydroxyapatite
Ca polycarboxilate composites prepared by hot pressure of
a powder mixture of tetracalcium phosphate, poly(acrylicco-itaconic), and wollastonite fibers. The presence of
wollastonite in this material improved some mechanical
properties and its bioactivity. Shumkova et al.11 prepared
hydroxyapatite by liquid-phase and solid-phase synthesis.
The products were mixed directly with natural wollastonite, introducing feldspar in the mixtures to reduce the
firing temperature. They found that controlling the ratio
of hydroxyapatitewollastonite components in ceramic
mixtures makes it possible to design bioceramic compositions having specified strength and porosity.
Wollastonite is unique among nonmetallic minerals
for its combination of white color, acicular (needle-like)
crystal shape, and alkaline pH. Natural wollastonite
grades are typically high in purity because most ores
must be beneficiated by wet processing and/or highintensity magnetic separation to remove accessory minerals.8 The application of extra-pure natural materials
makes it possible to reduce the cost of implant production. Furthermore, as distinct from synthesized materials,
natural wollastonite has a clearly expressed needle-shaped
habit with a ratio between the needle length and their
diameter equal to 1520 or more. This will presumably
facilitate the production of an interwoven reinforcing
mesh of wollastonite needles in the composite.11
The aim of the present work was to synthesize and
characterize, following the technique reported by Jillavenkatesa et al.,6 composites of hydroxyapatite
wollastonite by a solgel route, as an alternative to the
glass crystallization process and formulation of mixtures
by means of direct blended techniques, using calcium
acetate and triethyl phosphate as precursors of hydroxyapatite and high-purity natural wollastonite as a reinforcement element, whereas by a parallel study it will be
processed by sintering to produce dense materials to
evaluate their mechanical and bioactive properties.
Experimental Procedure
SolGel Synthesis

The composites of hydroxyapatitewollastonite

were prepared by solgel processing from calcium

www.ceramics.org/ACT

Synthesis and Characterization of HydroxyapatiteWollastonite Composite Powders

Table I. Chemical Composition of Wollastonite

s
NYAD M325, Produced by Minera NYCO S.A.
de C.V.15
Chemical composition
Component

CaSiO3
Typical value (%)

CaO
SiO2
Fe2O3
Al2O3
MnO
MgO
TiO2
K2 O
% wt loss (10001C)

46.25
52.00
0.25
0.40
0.025
0.50
0.025
0.15
0.40

acetate hydrate (Ca(C2H3O2)2, Sigma-Aldrich, Tokyo,

Japan), triethyl phosphate (PO(OC2H5)3, Sigma-Aldrich,
St. Louis, MO), and high-purity natural wollastonite,
s
NYAD M325 (CaSiO3, from NYCOs Pilares deposit
in Hermosillo, Sonora, Mexico), with 98.25% purity.
Tables I and II show the chemical analysis and typical
properties of the natural wollastonite used in this study.15
The amounts of the precursors reagents were chosen in
order to maintain the Ca/P molar ratio at 1.67 of stoichiometric hydroxyapatite, and the amounts of wollastonite were chosen in order to obtain 20, 50, and 80 wt%.
Table II. Typical Properties of Wollastonite NYAD
M325, Produced by Minera NYCO S.A. de C.V.15
Typical properties
Appearance
Morphology
Molecular weight
Specific gravity
Median particle size (mm)
Surface area (m2/g) (BET)
Refractive index
pH (10% slurry)
Water solubility (g/100 cm3)
Density (Ibs/cu.ft.)
Hardness Mohs
Coefficient of expansion (mm/mm/1C)
Melting point (1C)theoretical
Melting point (1C)ASTM D1857

Value
White
Acicular
116
2.9
9
1.3
1.63
9.9
0.0095
181
4.5
6.5  10 6
1540
1410

403

First, to produce about 1.0 g of pure hydroxyapatite

powder, 0.02 mol of calcium acetate was dissolved in
5 mL of ethanol by ultrasonic stirring, and then
0.012 mol of triethyl phosphate was added dropwise
to obtain a Ca/P molar ratio of 1.67. The mixture of
precursors was stirred for 12 h at 25301C by magnetic
stirring. The temperature was raised to 40451C and
maintained for 12 h, under continuous stirring. Then,
the temperature was held at 751C for 10 h, where gelation was observed. The gels were then dried at 1201C
for 10 h. To produce the composites, a suitable amount
of wollastonite to obtain 20 wt% (0.25 g), 50 wt%
(1.0 g), and 80 wt% (4.0 g) was suspended, by ultrasonic stirring, in a proper volume of ethanol to keep the
solid:liquid ratio at 1:2.25 (w/v) for all experiments.
Then the same procedure, as described previously,
was followed until the dried gels mixed with natural
wollastonite were obtained.
The dried gels were ground to a fine powder and
heat treated in a furnace at 10001C in air for 5 h; the
heating was done at a rate of 101C/min. Afterwards, the
samples were air-quenched to room temperature. To obtain the powdered materials purified, the samples were
dispersed in a 0.01M HCl solution and stirred for 2 h.
After stirring, each solution was filtered through a Whatman no. 42 filter paper, and the filtrate was washed repeatedly with distilled water. These solid residues were
dried at 1201C for 2 h. The obtained powders were characterized by X-ray diffraction (XRD), FT-IR and Raman
spectroscopy, and scanning and transmission electron
microscopy (SEM and TEM). The flow chart in Fig. 1
outlines the complete experimental procedure.
Characterization Techniques

Thermal analysis was used to detect changes occurring during the heat-treatment process. Thermogravimetric (TGA) and differential thermal analyses (DTA)
were carried out using a TA Instruments SDT 2960
Simultaneous DSC-TGA (New Castle, DE). Heating to
10001C was performed in an alumina crucible, with air
flow (23 cm3/min) at a rate of 101C/min. The samples
weight was 3 mg of dried gel. XRD analysis was carried
out by means of a Rigaku Miniflex powder diffractometer (Tokyo, Japan). CuKa radiation was used
(40 mA, 40 kV). The 2y range was from 101 to 801 at
a scanning speed of 21/min. For FT-IR absorption analysis, the samples in KBr pellets were analyzed in the
transmission mode using a Vector 33 Bruker FT-IR

International Journal of Applied Ceramic TechnologyEncinas-Romero, et al.

404

0.02 mol of
Ca(C2H3O2)2

0.012 mol of
PO(OC2H5)3

Suitable amount of
CaSiO3 suspended
in C2H5OH

Vol. 5, No. 4, 2008

TEM studies of the samples were done on a JEOL JEM2010F instrument. Sample specimens were prepared by
dispersing the powders in distilled water to form very
dilute suspensions. A drop of suspension was transferred
onto a carbon mesh supported on a conventional copper
microgrid.
Results

Stir vigorously at 25-30C for 12 hours

Stir at 40-45C for 12 hours

Hold the sample at 75C for 10 hours

Dry gel at 120C for 10 hours

Heat-treatment at 1000C in air

Figure 2 shows the TGA combined with DTA for

the dried gel of calcium acetate and triethyl phosphate
in ethanol, and the TGA/DTA trace for natural wollastonite from room temperature to 10001C. The dried
gel trace displays a thermal transition in the temperature
region 3804501C, which corresponds to a weight loss
of about 25 wt% with a strong exothermic peak at about
4201C. This weight loss is associated with the formation
of hydroxyapatite and calcium carbonate as calcite. A
further thermal process between 6001C and 7001C,
corresponding to a weight loss of about 20 wt%, accompanied by an endothermic peak at about 6501C,
could be due to the breakdown of calcium carbonate to
form calcium oxide and carbon dioxide, as reported by
Jillavenkatesa and colleagues.6,7 The wollastonite trace
does not exhibit any thermal transition in the whole
temperature range. Figure 3 shows the TGA plots for
samples of dried gels of calcium acetate and triethyl
phosphate in ethanol with different wollastonite

Wash with HCl 0.01M and distilled water and filter

0

200

400

600

800

1000
1.5

Dry residue at 120C in air for 2 hours and

characterize
Weight (%)

Fig. 1. Schematic flow chart for the solgel procedure for

synthesizing hydroxyapatitewollastonite composites.

1.0

90
80

0.5

70
0.0
60

spectrophotometer (Boston, MA) over the range 4000

400 cm 1. Raman characterization of the samples was
performed using a Dilor Labram Micro-Raman Spectrometer (Lille, France) with excitation radiation of
632.8 nm wavelength and a laser (HeNe) power of
20 mW, over the range 4000400 cm 1. The resolution
of the instrument is of the order of 1 cm 1.
Morphological studies of the samples were performed using a JEOL 5410LV SEM (Tokyo, Japan).

0.5

50
40
0

200

400
600
Temperature (C)

800

Temperature Difference (C/mg)

100

1.0
1000

Fig. 2. Thermogravimetric and differential thermal analyses trace

for samples from room temperature to 10001C at a heating rate of
101C/min. , dried gel of calcium acetate and triethyl phosphate
in ethanol; - - - - - - - -, natural wollastonite sample.

400

600

800

100

Weight (%)

(d)

90
80

70

70

(c)

60

(a)
50

(b)

40
0

200

400
600
Temperature (C)

800

200

400

600

800

1000
1.5

1.0

1.0

0.5

0.5

100

80

60

1000

(e)

90

1.5

Exo

200

405

Endo

Synthesis and Characterization of HydroxyapatiteWollastonite Composite Powders

50

Temperature Difference (C/mg)

www.ceramics.org/ACT

40
1000

0.0

0.0

(d)

(e)

(c)
(b)

0.5

0.5

(a)
1.0

1.0
0

200

400

600

800

1000

Temperature (C)

contents from room temperature to 10001C. In the

samples with 0 and 20 wt% of wollastonite, Fig. 3a and
b, respectively, no significant differences are observed,
both showing the two thermal processes explained previously, with similar weight losses. Nevertheless, when
the amount of wollastonite increases, these proportions
diminish, as observed in Fig. 3c and d. The same behavior is observed in the DTA trace for dried gels of
calcium acetate and triethyl phosphate in ethanol with
different percent by weight of wollastonite, as seen in
Fig. 4. Slight differences appear at temperatures where
exothermic and endothermic reactions occur. These reactions were observed between 4001C and 4201C, and
6501C and 7001C, respectively.
Figure 5 shows the XRD patterns for gel of calcium
acetate and triethyl phosphate in ethanol at several processing stages. Figure 5a corresponds to a dried gel at
1201C, where there is no evidence of hydroxyapatite
being present in the sample; the main peaks reveal
calcium acetate presence in a mixture of amorphous
phases. The presence of hydroxyapatite accompanied by
calcium oxide is confirmed in Fig. 5b, for a dried gel
upon heat treatment at 10001C. This gel was washed
with HCl 0.01M and distilled water to eliminate the
calcium oxide from the hydroxyapatite and calcium oxide mixture. The calcium oxide was converted to calcium chloride and dissolved in water to obtain only the
hydroxyapatite phase, as shown in Fig. 5c. However, the

Fig. 4. Differential thermal analysis plots for samples of dried gels

of calcium acetate and triethyl phosphate in ethanol with different
wt% of wollastonite: (a) 0 wt%, (b) 20 wt%, (c) 50 wt%, (d)
80 wt%, and (e) natural wollastonite sample.

peak at 29.31 and the overlapping of the (211) and

(112) planes at 2y  321 reveal carbonated hydroxyapatite presence in the final product.6,1618 Figure 6 shows
the same behavior, although the gel contains 20 wt% of
wollastonite. This fact demonstrates that the wollastonite remains unreacted. Figure 7 resumes the XRD

*
*
**
Relative Intensity (a.u.)

Fig. 3. Thermogravimetric analysis plots for samples of dried gels

of calcium acetate and triethyl phosphate in ethanol with different
wt% of wollastonite: (a) 0 wt%, (b) 20 wt%, (c) 50 wt%, (d)
80 wt%, and (e) natural wollastonite sample.

4X

**
* * ** *

**
*
* ****
*
* ** * ** ** * * * * *
* * * **
(c)

(b)

*
* * **

* * * ** * ****

(a)
10

20

30

40
50
2-Theta ()

60

70

80

Fig. 5. X-ray diffraction patterns for gel of calcium acetate and

triethyl phosphate in ethanol: (a) sample dried at 1201C, (b)
sample upon heat treatment at 10001C, (c) sample upon heat
treatment at 10001C and HCl treatment. Hydroxyapatite; J,
CaO; & , calcium acetate; c, carbonated hydroxyapatite.

International Journal of Applied Ceramic TechnologyEncinas-Romero, et al.

406

Vol. 5, No. 4, 2008

(a)

25%

4X

% Transmittance (a.u.)

Relative Intensity (a.u.)

(b)

20

30

40
50
2-Theta ()

60

70

80

Fig. 6. X-ray diffraction patterns for gel of calcium acetate,

triethyl phosphate, and 20 wt% wollastonite: (a) sample upon heat
treatment at 10001C, (b) sample upon heat treatment at 10001C
and HCl treatment. Hydroxyapatite; J, CaO; 1, wollastonite;
c, carbonated hydroxyapatite.

patterns for all materials with different percent by

weight of wollastonite.
Figure 8 shows the FT-IR spectra for several samples, including the composite with 20 wt% of wollastonite, in the range of 4000400 cm 1. Figure 8a, for a gel

** ** * **

(e)
*
* ** ** **** * * ***
*
* * * * * * * ***

Relative Intensity (a.u.)

*
*
*

(d)

(c)

(b)

(a)

10

20

30

40

50
2-Theta ()

60

70

(c)

(d)

(a)

10

(b)

80

Fig. 7. X-ray diffraction patterns for (a) natural wollastonite

sample, gel of calcium acetate, triethyl phosphate with different
wt% of wollastonite upon heat treatment at 10001C and HCl
treatment: (b) 80 wt%, (c) 50 wt%, (d) 20 wt% (e) 0 wt%.
Hydroxyapatite; 1, wollastonite; c, carbonated hydroxyapatite.

Wavenumber (cm )

Fig. 8. FT-IR spectra: (a) gel of calcium acetate and triethyl

phosphate in ethanol dried at 1201C, (b) natural wollastonite, (c)
gel of calcium acetate and triethyl phosphate in ethanol upon heat
treatment at 10001C and HCl treatment, (d) gel of calcium
acetate, triethyl phosphate, and wollastonite 20 wt% in ethanol
upon heat treatment at 10001C and HCl treatment.

of calcium acetate and triethyl phosphate in ethanol

dried at 1201C, shows the IR absorptions of calcium
acetate as a main component. Figure 8b shows the spectral characteristics of wollastonite from the natural sample. Fig. 8c and d shows dried gel upon heat treatment at
10001C and washed with HCl and distilled water without and with 20 wt% of wollastonite, respectively.
The FT-IR spectra can be divided into four regions:
peaks around 36503500 cm 1, 15001400 cm 1,
11001000 cm 1, and 650600 cm 1. The peaks observed around 3571 and 632 cm 1 arise from the
stretching and librational modes, respectively, of OH
ions. Bands between 1471 and 1414 cm 1 are due to the
carbonate IR absorption n3 mode. The n2 mode of carbonate also gives a sharp absorption at 870 cm 1. The
broad bands around 1000 cm 1 in Fig. 8b are different
from the bands around 1100 cm 1 in Fig. 8c. The former is mainly attributed to the silicate IR absorption,
while the latter is attributed to the phosphate IR absorption. The peaks at 1048 and 1090 cm 1 have been associated with the stretching n3 mode of the PO bonds,
and the 962 cm 1 band arises from the n1 symmetric
PO stretching vibrations mode of the PO34 group.
Bands at 603 and 571 cm 1 were caused by the triply
degenerate, n4 bending vibration of the PO34 group.
The clear presence of two peaks at 603 and 571 cm 1,
along the well-resolved peak at B632 cm 1, confirms
the presence of hydroxyapatite in the composites.6,1619

www.ceramics.org/ACT

Synthesis and Characterization of HydroxyapatiteWollastonite Composite Powders

Intensity (a.u.)

(a)

(b)
(c)

(d)
4000 3900 3800 3700 3600

1200

1000

800

600

400

Wavenumber (cm )

Fig. 9. Raman spectra: (a) gel of calcium acetate and triethyl

phosphate in ethanol dried at 1201C, (b) natural wollastonite, (c)
gel of calcium acetate and triethyl phosphate in ethanol upon heat
treatment at 10001C and HCl treatment, (d) gel of calcium
acetate, triethyl phosphate, and wollastonite 20 wt% in ethanol
upon heat treatment at 10001C and HCl treatment.

The presence of carbonate substituting in the phosphate

site is highlighted by the strong peaks at the wavenumbers of the B-type carbonated hydroxyapatite (1471,
1414, and 870 cm 1, n3b, n3a, and n2 of CO23 that replace PO34 ions in the hydroxyapatite lattice).20
Raman spectra of several samples in the range of
4000400 cm 1 are shown in Fig. 9. Figure 9a, for a gel
of calcium acetate and triethyl phosphate in ethanol
dried at 1201C, shows the Raman spectrum of calcium
acetate as a main component, in accordance with the
XRD and FT-IR analyses. Figure 9b shows the Raman
spectrum of wollastonite from the natural sample. In
Fig. 9c, the Raman spectrum for hydroxyapatite obtained from dried gel upon heat treatment at 10001C
and washed with HCl and distilled water shows the following bands. At 3573 cm 1 a band arises from stretching of the OH ions. The 1074 and 1052 cm 1 bands
arise from n3 PO34 , the very strong 962 cm 1 band
arises from n1 PO34 , the 590 and 579 cm 1 bands arise
from n4 PO34 , and the 447 and 431 cm 1 bands arise
from n2 PO34 . The strongest intensity CO23 band, n1,
for the B-type carbonated hydroxyapatite occurs at
1070 cm 1; this band is precluded by the strong intensity of the PO4 band at 1074 cm 1.6,18,19,2124 In
Fig. 9d, the Raman spectrum for the hydroxiapatite
wollastonite composite obtained from dried gel upon
heat treatment at 10001C and washed with HCl and

407

distilled water with 20 wt% of wollastonite shows a

similar behavior as the hydroxyapatite spectrum.
Figure 10a and b show the SEM micrographs of
dried gel upon heat treatment at 10001C and washed
with HCl and distilled water without and with 20 wt%
of wollastonite, respectively. It can be seen (Fig. 10a)
that the particles of hydroxyapatite are spherical and
submicrometric, with a tendency to agglomerate. In Fig.
10b, the particles of hydroxyapatite are agglomerated on
the surface of the wollastonita fibers. In addition, the
EDS spectra of the composites indicated that the materials were mainly composed of calcium, phosphorus,
oxygen, silicon, and a small fraction of carbon. Figure
10c and d show the TEM micrographs of dried gel upon
heat treatment at 10001C and washed with HCl and
distilled water without and with 20 wt% of wollastonite,
respectively. Figure 10c shows the typical shape of
hydroxyapatite grains and their hexagonal growth morphology.7,25 Almost all of the grains are between 50 and
100 nm in size. In Fig. 10d the grains of hydroxyapatite
appear inserted among the wollastonite fibers, with the
same shape and size as that observed during synthesis in
the absence of wollastonite. Figure 11a and b show the
selective area electron diffraction (SAED) image of dried
gel upon heat treatment at 10001C and washed with
HCl and distilled water without and with 20 wt% of
wollastonite, respectively. Figure 11a shows the typical
diffraction patterns of hydroxyapatite crystals, and
Fig. 11b shows the typical patterns of a polycrystalline
material.

Discussion
Hydroxyapatitewollastonite composites can be
synthesized using the solgel route by adequate heat
and mild acid treatments, using a simple procedure and
relatively inexpensive reagents. The results of this study
demonstrate that the as-synthesized gels obtained are a
mixture of residual calcium acetate and an amorphous
phase of any calcium phosphate, plus wollastonite, for
those samples that contain it. In the heat treatment for
these gels, the first step (for temperatures lower than
3801C) corresponds to the evolution of organic compounds formed by the reactions between the precursors
added to create the sol. The second step (about 4201C)
is representative of an exothermic reaction, indicating
the formation of hydroxyapatite in the early stages of
crystallization, accompanied with calcium carbonate as

408

International Journal of Applied Ceramic TechnologyEncinas-Romero, et al.

Vol. 5, No. 4, 2008

Fig. 10. (a) Scanning electron microscopic (SEM) image of gel of calcium acetate and triethyl phosphate in ethanol upon heat treatment at
10001C and HCl treatment, (b) SEM image of gel of calcium acetate, triethyl phosphate, and wollastonite 20 wt% in ethanol upon heat
treatment at 10001C and HCl treatment. (c) Transmission electron microscopic (TEM) image of gel of calcium acetate, triethyl phosphate in
ethanol upon heat treatment at 10001C and HCl treatment, (d) TEM image of gel of calcium acetate, triethyl phosphate, and wollastonite
20 wt% in ethanol upon heat treatment at 10001C and HCl treatment.

calcite, formed by the interaction between the evolved

organics and calcium present in the gels. In the third
step (upon reaching a temperature of approximately
6501C), the corresponding endothermic reaction indicates the breakdown of calcium carbonate to form calcium oxide, accompanied by the evolution of CO2.
Finally, with the acid treatment for the mixtures of calcium oxide, hydroxyapatite, and wollastonite obtained
upon heat treating at 10001C, calcium oxide is converted to calcium chloride. Owing to the higher solubility of
the latter in water, as compared with the negligible sol-

ubility of hydroxyapatite, calcium chloride is eliminated

from the final product: B-type carbonated hydroxyapatite and wollastonite.
Owing to the absence of peaks corresponding to the
carbonated hydroxyapatite in the XRD patterns of the
samples before acid treatment, it can be deduced the
formation of this compound occurs during acid treatment. The incorporation of carbonate replacing phosphate ions into the hydroxyapatite lattice is due to
residual carbonates because of their incomplete removal during heat treatment.6

www.ceramics.org/ACT

Synthesis and Characterization of HydroxyapatiteWollastonite Composite Powders

Fig. 11. (a) Selective area electron diffraction (SAED) image of

gel of calcium acetate and triethyl phosphate in ethanol upon heat
treatment at 10001C and HCl treatment, (b) SAED image of gel of
calcium acetate, triethyl phosphate, and wollastonite 20 wt% in
ethanol upon heat treatment at 10001C and HCl treatment.

409

Biological apatites present in natural bone, dentin,

and enamel contain different amounts of carbonate.
The B type is the preferential carbonate substitution
found in the calcified tissues of a variety of species.3 The
presence of CO3 2 in hydroxyapatite structure influences
the decomposition, sinterability, solubility, and biological reactivity of carbonated hydroxyapatite implant
materials. Therefore, the presence of carbonated
hydroxyapatite in the composites of this study can
give reliability in the present mechanical and bioactive
evaluations of sintered composites, for applications of
these materials.
This study also shows that natural wollastonite remains unreacted through all processing stages. The particles of synthesized hydroxyapatite agglomerate
homogeneously on the surface of the wollastonita
fibers, as shown in Fig. 12. Additionally, the different
amounts of wollastonite involved in the formation
of the composites do not affect the stages of synthesis
and the final characteristics, such as the structure and

Fig. 12. Scanning electron microscopic images of gel of calcium acetate, triethyl phosphate, and wollastonite 20 wt% in ethanol upon heat
treatment at 10001C and HCl treatment, at different magnifications.

International Journal of Applied Ceramic TechnologyEncinas-Romero, et al.

200

400

600

800

1000

1200

90

Exo

80

Endo

Weight (%)

100
1.0

0.5

70
0.0
60
0.5
50
40
0

200

400

600

800

1000

1200

Vol. 5, No. 4, 2008

Conclusions

1400
1.5
Temperature Difference (C/mg)

410

1.0
1400

Temperature (C)

Fig. 13. Thermogravimetric and differential thermal analyses

trace for samples from room temperature to 14001C at a heating
rate of 101C/min. , dried gel of calcium acetate and triethyl
phosphate in ethanol; - - - - - -, natural wollastonite sample.

morphology of hydroxyapatite produced. In all cases

well-crystallized, carbonated hydroxyapatite was obtained after acid treatment, showing early stages of
sintering while heating at 10001C.
In this kind of composites, the extent of the
fibermatrix interaction increases with increasing
proportions of wollastonite. Nonetheless, the fibers
can also interact with themselves. Other studies10,11
have reported that these interactions affect some of
the physical and mechanical properties due to effects
such as fiber pullout and debonding present in the
materials. The morphological characteristics of the
composites synthesized in the present study can avoid
direct fiber-to-fiber interaction because the fiber
surfaces are covered thoroughly by hydroxyapatite. Any
further treatment such as pressing and sintering
will produce materials with mostly fiberhydroxyapatite interactions.
A preliminary test to demonstrate the thermal stability (for sintering purposes) of composites synthesized
in this study is shown in Fig. 13. The DTA and TGA
traces for the dried gel of calcium acetate and triethyl
phosphate in ethanol and natural wollastonite show that
these compounds experience no significant decomposition upon heating within the range of 10001C and
14001C. This fact indicates that synthesized hydroxyapatite and natural wollastonite added to produce the
composites, both maintain their chemical integrity, even
under severe thermal conditions.

Hydroxyapatitewollastonite composites were synthesized using the solgel route with calcium acetate and
triethyl phosphate as hydroxyapatite precursors, and
high-purity natural wollastonite. Formation of hydroxyapatite in the composites occurs at a relatively low
temperature, about 4004201C, accompanied with calcium carbonate formation, while wollastonite remains
unreacted. The composites were purified by heat treatment to 10001C to decompose calcium carbonate into
calcium oxide, and then they were washed with hydrochloric acid and distilled water, to convert the calcium
oxide into calcium chloride and dissolve it in water.
Nonetheless, the XRD, FT-IR, and Raman analyses reveal the presence of B-type carbonated hydroxyapatite in
the final products. The particles of hydroxyapatite appear agglomerated homogeneously on the surface of
wollastonite fibers, showing spherical shapes and submicrometric size.
Acknowledgment
The authors are grateful to Dr. Eric M. Rivera and
Dr. Genoveva Hernandez from CFATA-UNAM, Ing.;
Francisco Rodrguez from CINVESTAV-Qro;
Dr. Francisco Brown, M. C. Hisila C. Santacruz, and
M. C. Eduardo A. Larios from DIPyM-UNISON, Ing.;
and Israel Gradilla and M. C. Eloisa Aparicio from
CCMC-UNAM for assistance in the characterization
and discussions.
References
1.
2.
3.

4.

5.

6.
7.

8.

L. L. Hench, Bioceramics: From Concept to Clinic, J. Am. Ceram. Soc., 74

[7] 14871510 (1991).
R. Z. LeGeros, Calcium Phosphate Materials in Restorative Dentistry: A
Review, Adv. Den. Res., 2 [1] 164180 (1998).
R. Z. LeGeros and J. P. LeGeros, Dense Hydoxyapatite, An Introduction to
Bioceramics. eds., L. L. Hench and J. Wilson. World Scientific, Singapore,
139180, 1993.
D. Choi and P. N. Kumta, An Alternative Chemical Route for the Synthesis
and Thermal Stability of Chemically Enriched Hydroxyapatite, J. Am.
Ceram. Soc., 89 [2] 444449 (2006).
G. Bezzi, G. Celotti, E. Landi, T. M. G. La Torretta, I. Sopyan, and
A. Tampieri, A Novel SolGel Technique for Hydroxyapatite Preparation,
Materi. Chem. Phys., 78 816824 (2003).
A. Jillavenkatesa and R. A. Condrate, SolGel Processing of Hydroxyapatite, J. Mater. Sci., 33 41114119 (1998).
A. Jillavenkatesa, D. T. Hoelzer, and R. A. Condrate, An Electron Microscopy Study of the Formation of Hydroxyapatite Through SolGel Processing, J. Mater. Sci., 34 48214830 (1999).
H. Fattah, Wollastonite: New Aspects Promise Growth, Ind. Miner., 11
2143 (1994).

www.ceramics.org/ACT
9.

10.

11.

12.

13.

14.
15.
16.

17.

Synthesis and Characterization of HydroxyapatiteWollastonite Composite Powders

T. Kokubo, A/W GlassCeramic: Processing and Properties, An Introduction to Bioceramics. eds., L. L. Hench and J. Wilson. World Scientific, Singapore, 7588, 1993.
Y. E. Greish and P. W. Brown, Characterization of Wollastonite-Reinforced
HApCa polycarboxylate Composites, J. Biomed. Mater. Res., 55 618628
(2001).
V. V. Shumkova, V. M. Pogrebenkov, A. V. Karlov, V. V. Kozik, and V. I.
Vereshchagin, HydroxyapatiteWollastonite Bioceramics, Glass Ceram., 57
910 (2000).
T. Yamamuro, A/W GlassCeramic: Clinical Applications, An Introduction
to Bioceramics. eds., L. L. Hench and J. Wilson. World Scientific, Singapore,
89103, 1993.
P. N. De Aza, F. Guitian, and S. De Aza, Bioeutectic: A New Ceramic
Material for Human Bone Replacement, Biomaterials, 18 12851291
(1997).
P. N. De Aza, F. Guitian, and S. De Aza, Bioactivity of Wollastonite Ceramics: In Vitro Evaluation, Scr. Metall. Mater., 31 10011005 (1994).
s
NYCO Minerals Inc. Premium Quality Wollastonite NYAD M325. NYCO
IN-299-04-01 Booklet, NYCO Minerals Inc., Willsboro, NY, 2001.
E. Landi, G. Celotti, G. Logroscino, and A. Tampieri, Carbonated
Hydroxyapatite as Bone Substitute, J. Eur. Ceram. Soc., 23 29312937
(2003).
A. S. Losarczyk, Z. Paszkiewicz, and C. Paluszkiewicz, FTIR and XRD
Evaluation of Carbonated Hydroxyapatite Powders Synthesized by Wet
Methods, J. Mol. Struct., 744747 657661 (2005).

411

18. M. Markovic and B. O. Fowler, Preparation and Comprehensive Characterization of a Calcium Hydroxyapatite. Reference Material, J. Res. Natl.
Inst. Stand. Technol., 109 553568 (2004).
19. P. N. de Aza, F. Guitian, and C. Santos, Vibrational Properties of Calcium
Phosphate Compounds. 2. Comparison between Hydroxyapatite and bTricalcium Phosphate, Chem. Mater., 9 916922 (1997).
20. G. Xu, I. A. Aksay, and J. T. Groves, Continuous Crystalline Carbonate
Apatite Thin Films. A Biomimetic Approach, J. Am. Chem. Soc., 123 [10]
21962203 (2001).
21. R. Cusco, F. Guitian, S. de Aza, and L. Artus, Differentiation between
Hydroxyapatite and b-Tricalcium Phosphate by Means of m-Raman Spectroscopy, J. Eur. Ceram. Soc., 18 13011305 (1998).
22. H. Tsuda and J. Arends, Orientational Micro-Raman Spectroscopy on
Hydroxyapatite Single Crystals and Human Enamel Crystallites, J. Dent.
Res., 73 [11] 17031710 (1994).
23. F. F. M. de Mul, M. H. J. Hottenhuis, P. Bouter, J. Greve, J. Arends, and J. J.
ten Bosch, Micro-Raman Line Broadening in Synthetic Carbonated
Hydroxyapatite, J. Dent. Res., 65 [3] 437440 (1986).
24. A. Antonakosa, E. Liarokapisa, and T. Leventourib, Micro-Raman and
FTIR Studies of Synthetic and Natural Apatites, Biomaterials, 28 3043
3054 (2007).
25. K. Hans-Joachim, E. F. Bres, D. Bernache-Assolant, and Z. Gunter, HighResolution Electron Microscopy and Convergent-Beam Electron Diffraction
of Sintered Undoped Hydroxyapatite, J. Am. Ceram. Soc., 80 [1] 3744
(1997).