JOURNAL OF MATERIALS SCIENCE LETTERS 8 (1989) 305 306

Hydrothermal synthesis of hydroxyapatite from calcium

pyrophosphate
TAKEO HATTORI, Y A S U H I K O IWADATE, T O M O Y O S H I KATO
Department of Synthetic Chemistry, Faculty of Engineering, Ch/ba University, 1-33 Yayoi-cho,
Chiba 260, Japan

Hydroxyapatite as well as tricalcium phosphate is calcium hydrogen orthophosphate, B-calcium phos-

known to be biocompatible with human bone and phate, and calcium pyrophosphate were formed in
tooth. Advances in biomaterials are occurring at an that order with increasing temperature, pressure, and
accelerated rate and much attention is being devoted soaking time. Attempts were made to synthesize the
to research and development of hydroxyapatite [1-3] hydroxyapatite powders hydrothermally from cal-
which can be used as implant material instead of cium pyrophosphate. The effect of NH 3 addition tO
metals, plastics, and other ceramics conventionally the sample solution on the shapes and dimensions of
available. Some reviews have been published concern- the powders obtained was also discussed.
ing hydrothermal synthesis of apatites [4, 5] in which Calcium pyrophosphate Ca2P207 with analytical
metal orthophosphates are usually utilized as starting reagent grade was used as a starting material (Kanto
materials, and the effects of additives such as SnO and Chemical Co. Inc., Tokyo, Japan). Hydrothermal syn-
bulky fatty acids on the apatite formation are also theses were performed using gold tube capsules, 3 mm
reported [6]. As described in the previous work [7], we outer diameter, 0.15 mm thick, and about 40 mm long.
have successfully prepared hydroxyapatite powder by Accurately weighed Ca2P207 was introduced into the
soaking calcium acetate and triethyl phosphate under capsule and then deionized water or NH4OH solution
hydrothermal conditions and found that the crystal having pH values of 11.8 to l 1.9 was poured over it
shapes of the powders obtained were needle-like in with a microsyringe, because the solubility of Ca2 P207
most cases, but granular under moderate conditions, in water at ambient temperature and pressure was
for example, 350°C and 30 MPa. The present work extremely low, in which the charging fraction was set
was initiated by the finding that three intermediate at 50% or 60%. Each sample encapsulated by arc-
compounds were formed in the above reaction: welding was placed in a pressure vessel made of a

N O
"4 ~q O

~
C~ ~ ml

2 Reference

csoo-c. 80 a. 96h

(450"C,70MPa,96h)-~
~ ~ ' - - - (450"C, 70MPa, 72h)

(450~C, 70MPa, 48h)

= - ~ (450"C, 70MPa, 24h) . _ 2 ~

Ca2P207

I I , I , I , I , I , t J , I I I , | , [ I
26 28 30 32 34 26 28 30 32 34"

28(CuK~)(deg) 2B (CuK~) (de@)

(a) Ca2P207-H20 system (b) Ca2P207-NH3-H20 system

Figure I XRD patterns of the products during the hydrothermalreaction. (a) Ca2P2OT-H20 system;(b) Ca2P2OT-NH3-H20 system.

0261-8028/89 $03.00 + .12 © 1989 Chapman and Hall Ltd. 305

Figure 2 Scanning electron micrographs of hydroxyapatite prepared from (a) Ca2P207-H20 system at 500°C, 80MPa, 9 6 h and (b)
Ca2P2OT-NH3-H20 system at 450 ° C, 70 MPa, 120 h.
cobalt-based wear-resistant alloy (Stellite 25, Nikkiso
Co. Ltd, Tokyo, Japan) and then heated at a rate of
l 0 ° C rain- 1. The inside of the vessel was at first filled
with water as a pressurizing medium. On heating to
the predetermined temperature, the pressure was
gradually applied, using a careful valve control, on the
basis of Kennedy's relation between temperature,
pressure, and volume for water [8]. The sample was
cooled by removing heat and pressure, i.e. by switch-
ing off the furnace, after it was soaked for a given
period at the desired temperature and pressure, The
powders obtained were fully dried at 110° C in an oven
for a day. The XRD patterns were recorded in the
range of 20 ° ~< 20 ~< 60 ° using CuKc~ radiation
monochromated with curved graphite on a diffrac-
tometer (Geiger-flex RAD-IIB, Rigaku Denki Co.,
Tokyo, Japan).
The XRD patterns of the powders obtained, cover-
ing 25 ° to 35 ° in 20, are illustrated in Fig. 1, where the
reference material is commercial hydroxyapatite
(Wako Pure Chemical Industries Ltd, Osaka, Japan)
reproducing the peak patterns catalogued in JCPDS
card no. 9-432 and Ca2P207 is the starting material. As
can be seen in Fig. la, Ca2P207 (Form I) [7] and a
small amount of hydroxyapatite were formed accord-
ing to the hydrothermal reaction at 450 ° C, 70 MPa,
and 24 h. As the soaking time increased, the yield of
apatite was observed to increase. Within the range of
experimental conditions used, the hydrothermal con-
ditions of 500 ° C, 80 MPa, and 96 h were needed to
attain pure hydroxyapatite powders. The apatite
powders possessed the following crystallographic fea-
tures in their formation process: (i) both (21 1) and
(3 0 0) planes tended to grow much more preferentially
than the (1 1 2) plane, which is different from the result
of the reference material; (ii) the relative X-ray intensity
of the (300) plane to the (21 1) plane was always
larger than unity. The latter finding was in contrast to
that in the previous work [7].
Addition of NH3 to the sample solution allowed the
reaction rate at high temperature and pressure to be
enhanced to some degree. In this case, pure hydrox-
yapatite had already been formed under conditions of
450°C, 70MPa, and 120h. Contrary to the XRD
patterns for the Ca2P2Ov-H20 system, Fig. lb shows
that the relative intensity of the (3 0 0) plane to the
(2 1 1) plane was invariably less than unity. This fact
306
was compatible with the result for the reference
material, but it seemed likely that the (1 1 2) plane was
in any event difficult to grow under the hydrothermal
conditions.
Scanning electron microscopy (SEM) was employed
to investigate the microstructures of the powders.
Fig. 2a indicates the hydroxyapatite powders
prepared from the Ca2P2OT-H20 system at 500°C,
80 MPa, and 96h, fe%aling the existence of elongated
grains with typical prism shapesl The averaged length
and width for the particles in this field, except the very
irregular ones which were too large or too small, were
about 25 and 5 #m, respectively. Fig. 2b shows the
apatite powders synthesized from the Ca2 P207-NH3-
H20 system at 450 ° C, 70 MPa, and 120h, indicating
that there existed a number of fine rice-like particles
(5 #m long and 3 #m thick) together with the small
elongated grains. In both systems, an increase of tem-
perature, pressure, or soaking time provoked growth
of the hydroxyapatite particles. The addition of NH3
to the sample solution was at first aimed at promoting
the hydrothermal reaction rate further, as it was not
more effective than had otherwise been expected.
However, it was proved to affect the crystallographical
nature of the hydroxyapatite powders.
Acknowledgements
The authors thank Professor M. Yamaguchi and Dr
K. Hashimoto for use of the SEM apparatus.
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Received 26 July
and accepted 6 September 1988