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HYDROTHERMAL SYNTHESIS OF CRYSTALLINE

HYDROXYAPATITE ULTRAFINE PARTICLES
a a a
E. SADA , H. KUMAZAWA & Y. MURAKAMI
a
Department of Chemical Engineering , Kyoto University , Kyoto, 606, Japan
Published online: 25 Apr 2007.

To cite this article: E. SADA , H. KUMAZAWA & Y. MURAKAMI (1991) HYDROTHERMAL SYNTHESIS OF CRYSTALLINE
HYDROXYAPATITE ULTRAFINE PARTICLES, Chemical Engineering Communications, 103:1, 57-64, DOI:
10.1080/00986449108910862

To link to this article: http://dx.doi.org/10.1080/00986449108910862

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HYDROTHERMAL SYNTHESIS OF
CRYSTALLINE HYDROXYAPATITE ULTRAFINE
PARTICLES
E. SADA,? H. KUMAZAWA and Y. MURAKAMI
Department of Chemical Engineering
Kyoto University
Downloaded by [New York University] at 18:39 07 May 2015

Kyoto 606, Japan

(Received September 7, 1990; i n f i ~form
l lanunry 28, 1991)

Crystalline hydroxyapatite ultrafine particles were synthesized hy hydrothermal treatment of the same
~owdersDreDared hv mixing aqueous solutions of Ca(N0-), and (NHAHPO. with a stoichiometric
iatio of ~a i o P (1:67) at room temperature. The rd~ationiof the p & A e size and shape to such
operating conditions as hydrothermal temperature, Ca(NO,), concentration, stirring speed and
treatment time were investigated systematically. A mechanism of particle growth was proposed.
KEYWORDS Hydroxyapatite Ultrafine particle Hydrothermal synthesis X-ray diffraction.

INTRODUCTION

Calcium hydroxyapatite, Ca,,(PO,),(OH), (normally called hydroxyapatite)

which is the chief constituent of bone and tooth, has been used as a component
material suitable for living bodies. But hydroxyapatite is not strong in itself, and
hence sintered bodies of hydroxyapatite powders have been widely used. The
microstructures developed during the sintering of the powders are determined to
a large extent by the powder characteristics such as mean particle size and size
distribution. Normally, fine particles with a narrow size distribution are required.
For example, it has been reported that by use of hydroxyapatite powders of less
than 50 nm in size, the dense sintered body can be yielded. Also, hydroxyapatite
powders with exact stoichiometry must be formed, because calcium deficit apatite
converts to Ca3(P04), during calcination.
Hydroxyapatite precipitates in an aqueous mixed solution of Ca(NO& and
(NH&HPO, with a stoichiometric ratio of Ca to P (1.67), but is apt to become
Ca-deficit apatite. Recently, it has been reported that crystalline hydroxyapatite
powders are synthesized by hydrothermal treatment of such precipitates (Ioku el
al., 1988). In the present work, thus, the same ultrafine powders prepared by
such a wet method were treated under hydrothermal conditions to form
crystalline hydroxyapatite particles. The relations of the particle size and shape to
such operating conditions as hydrothermal temperature, Ca(NO,)* concentration,

t To whom correspondence should be addressed.

57
 58 E. SADA, H. KUMAZAWA AND Y. MURAKAMI
stirring speed and treatment time were investigated systematically. A mechanism
of particle growth was proposed.

EXPERIMENTAL SECTION

An aqueous solution of Ca(NO,), and an aqueous solution of (NH4),HP04 were

mixed together. Before both solutions were mixed together, pH values of them
were adjusted at 10 with ammonia. The concentration of (NH4),HP04 ranged
from 0.10 to 0.25 mol/L. The concentration of Ca(N03), was varied from 1.67 to
0.418 mol/L so that the molar ratio of Ca to P might be kept at a stoichiometric
ratio of hydroxyapatite (1.67). In a mixed solution, precipitates are formed. In
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the course of precipitation, a great decrease in pH results. The precipitate is

noncrystalline gel-like hydroxyapatite composed mainly of Ca-deficit apatite. An
aqueous suspension of such apatite was adjusted at pH 10 again. A 50 cm3 of the
suspension was put in a beaker made of polyfluorine resin (teflon), and the
beaker was set in the autoclave. The rate of rise-in-temperature leading to a
specified hydrothermal temperature was CC/min. The temperature of hydrother-
mal treatment ranged from 100 to 200°C. The stirring speed of the autoclave was
varied to 200 rpm. The hydrothermal treatment was continued until 20 hours had
elapsed.
Prepared ultrafine particles were rinsed with distilled water several times and
dried at about 100°C in an oven. Afterwards, the particles were observed by
means of a scanning electron micrograph (Hitachi, S-510). The crystallite size of
ultrafine hydroxyapatite powders was estimated from the line broadening (half
value breadth) of the X-ray diffraction peak in terms of Sherrer's equation (Klug
and Alexander, 1974). The crystallite size in the c-direction was calculated from
the half value breadth of the diffraction peak on the (002) face (28 = 25.8"), while
the size in the a-direction was calculated from that on the (300) face (28 = 32.9").
The directions of a- and c-axis here are defined as in Figure 1. The crystallite

FIGURE 1 Schematic diagram of hydroxyapatite single crystal.

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 60 E. SADA, H. KUMAZAWA AND Y. MURAKAMI
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0
20 25 30 35 4 0 4 5 50 55
28 a n g l e (deg)

FIGURE 3 X-ray diffraction patterns o f hydroxyapatite ultrafine particles as prepared at room

temperature (a), synthesized hydrothermally at 100°C (b) and 200°C (c).
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HYDROTHERMAL SYNTHESIS OF HYDROXYAPATITE

61
 62 E. SADA, H. KUMAZAWA AND Y. MURAKAMI
In Figure 5, the variation of the crystallite sizes with treatment time is
presented. The sizes in the direction of a - and c-axis increase until about two
hours have passed. It is judged that the particle growth occurs only in this period.
In the region of longer treatment, the size in the direction of a-axis remains
almost unchanged and the size in the direction of c-axis slightly decreases with
time. It implies that the crystallization in the direction of c-axis is promoted in
such a long treatment, that is, the packing of atoms in the crystals becomes dense
in that direction.
Figure 6 indicates the effect of stirring speed on the crystallite sizes in both
directions. The crystallite size in the direction of a-axis is almost independent of
the stirring speed, whereas the size in the direction of c-axis decreases a little with
increasing stirring speed below 100 rpm, and above 150 rpm, it decreases with an
increase in stirring speed. Such a variation of the size in the c-axis is considered to
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reflect the rate of agglomeration in the early stage of hydrothermal treatment.

The agglomeration rate is apt to be increased with increasing stirring speed.
Next, the effect of concentrations of raw materials on the crystallite size was
investigated, where the ratio of concentration of Ca(NO& to that of

n , rpm
FIGURE 6 Dependences of crystallite sizes in a- and c-axis and aspect ratio on stirring speed.
 HYDROTHERMAL SYNTHESIS OF HYDROXYAPATITE 63
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FIGURE 7 Dependences of crystallite sizes in a- and c-axis and aspect ratio on Ca(NO,),
concentration.

(NH4)2HP04was maintained at a value of stoichiometric ratio (1.67). Figure 7

shows the relations of Ca(NO,), concentration to crystallite sizes in both axes.
The size in the direction of a-axis is found to be almost independent of the
concentration, while the size in the direction of c-axis increases slightly with
increasing concentration.

CONCLUSION
Crystalline hydroxyapatite ultrafine particles were synthesized by hydrothermal
treatment of the same ultrafine powders prepared at room temperature. As the
hydrothermal temperature rises, crystallization is promoted and the crystallite
size increases. In the early stage of hydrothermal treatment, crystallites grow.
Afterwards, the crystallite size in the direction of c-axis decreases slightly with
time. The crystallite size in the direction of a-axis is almost independent of
stirring speed, whereas the size in the direction of c-axis slightly increases with
increasing stirring speed.
 64 E. SADA, H. KUMAZAWA AND Y. MURAKAMI
NOMENCLATURE

a crystallite size in the direction of a-axis, nm

c crystallite size in the direction of c-axis, nm
n stirring speed, rpm
r aspect ratio defined by c l a
0 diffraction angle, degree

REFERENCES

Ioku, K., Yoshimura, M., and Somiya, S., Nippon Kagakukairhi, 1565 (1988).
Klug, H.P., and Alexander. L.E.,X-Ray Diffraction Procedures, p. 618, John Wiley and Sons, New
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York (1974).