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Abstract
Colloidal calcium hydroxyapatite (CaHAP) particles were modified with Ni2+, Cu2+, Co2+ and Cr3+ ions by ionexchange and coprecipitation. The CaHAPs doped with these ions were characterized by various methods including
FTIR, XPS, TEM and ICP. The atomic ratio, metal/(Ca+metal ), of the surface phase (X ) of the particles modified
s
with Ni2+ and Cu2+ by coprecipitation was much less than the atomic ratio of the whole particle (X ), while X of
w
s
the particles modified with Cr3+ approximated to their X . In the modification by ion-exchange, X was larger than
w
s
X except for the Ni2+-substituted samples where X was identical to X . The surface POH groups were decreased
w
s
w
by cation-exchange of the protons of the POH groups with Ni2+, Cu2+ and Co2+ in both the modification methods.
On the other hand, Cr3+ ions were doped in the surface phase by anion-exchange of the surface phosphate ions with
hydrated chromium hydroxide anions. 1998 Elsevier Science B.V. All rights reserved.
Keywords: Calcium hydroxyapatite; FTIR; Ion-exchange; Surface modification; XPS
1. Introduction
Calcium hydroxyapatite, Ca (PO ) (OH ) ,
10
46
2
abbreviated as CaHAP, is not only a main component of hard tissues, such as bones and teeth, but
also a material applied for bioceramics, adsorbents
and catalysts. The surface structure and properties
of CaHAP are fundamentally important in dental
and medical fields and the usage of this material.
Modification of the CaHAP surface is a technique
available for developing catalysts and adsorbents
with novel functions. Suzuki and coworkers have
found that Ca2+ of CaHAP can be exchanged
with various metal ions in aqueous media [19].
Hence, the surface structure and properties of
* Corresponding author. Fax: +81 729 78 3394;
e-mail: ishikawa@cc.osaka-kyoiku.ac.jp
CaHAP can be anticipated to be altered by ionexchange of Ca2+ with metal ions. It has been
reported that Cu2+, Ni2+ and Pb2+ doped into
CaHAP influence the catalytic activity of this
material [10,11]. Nevertheless, the surface structure of the metal-substituted CaHAP is poorly
understood. Information on the surface of modified CaHAP is requisite to give us new insights
into not only the mechanism involved in adsorption and catalysis on this material but also the
surface properties of bones and teeth contaminated
with metal ions. There are coprecipitation and ionexchange methods for modification of the CaHAP
surface with metal ions. These methods should
modify CaHAP in different manners; the coprecipitation changes both the surface and bulk structures
whilst the ion-exchange modifies mainly the surface
structure. Therefore, the employment of these two
0927-7757/98/$ see front matter 1998 Elsevier Science B.V. All rights reserved.
PII S0 9 2 7 -7 7 5 7 ( 9 8 ) 0 0 48 6 - 5
108
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
2. Experimental
2.1. Coprecipitation method
The CaHAP particles doped with Ni2+, Cu2+,
Co2+ and Cr3+ were prepared by coprecipitation.
Ca(NO ) and nitrates of the metals were dissolved
32
in 1 dm3 deionized-distilled water free from CO
2
at various atomic ratios, metal/(Ca+metal ), ranging from 0 to 0.1. The sum of the amounts of
Ca2+ and metal ions contained in the solutions
was held at 0.1 mol. H PO (0.060 mol ) was added
3 4
to the solutions and the solution pH was adjusted
to 9 by adding a 15 mol dm3 NH OH solution.
4
The resulting suspension was aged in a capped
Teflon vessel at 100C for 6 h. After the aging the
precipitates were filtered off, washed with 5 dm3
deionized-distilled water and finally dried in an air
oven at 70C. The obtained samples contained no
NH+ ion as confirmed by FTIR.
4
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
109
Fig. 1. TEM pictures of the particles formed by the coprecipitation with various metal ions at X
=0.03: (a) original sample; (b)
metal
Ni2+; (c) Cu2+; (d) Co2+; (e) Cr3+.
110
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
Fig. 2. Average lengths (open symbols) and widths (solid symbols) of the particles formed by the coprecipitation with various
metal ions vs. X
: %, & Ni2+; #, $ Cu2+; 6, + Co2+.
metal
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
111
Fig. 5. Metal contents of the coprecipitation products with various metal ions vs. X
: % Ni2+; # Cu2+; 6 Co2+; )
metal
Cr3+.
112
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
equilibrium, the samples were treated in the solutions at different concentrations of metal ions at
30C for various periods up to 24 h. Fig. 8 plots
the Co content determined by ICP on the treated
samples against the immersing time as a typical
example. As seen from this figure, the Co content
is constant after 5 min for the entire Co concentration of the treating solutions, proving that the
equilibrium is achieved after 5 min. Such a rapid
exchange has been reported on the exchange of
CaHAP with Cd2+, Zn2+ and Hg2+ [1]. Hence,
the ion-exchange period of the samples discussed
below was 5 min.
To compare the degree of ion-exchange, the
amounts of Ni2+, Cu2+, Co2+ and Cr3+ incorporated into the treated particles determined by ICP
are plotted against the concentration of these ions
in the treating solutions in Fig. 9. The contents of
all the metal ions in the particles are increased by
raising the concentration of the treating solution
up to 0.01 mol dm3. The exchangeability of these
divalent ions is in the order Cu2+>Co2+#
Ni2+, corresponding to the reported order
Cu2+>Zn2+>Co2+ [19] and Zn2+>Ni2+ [2]. As
seen in Fig. 9, at a high concentration of
0.1 mol dm3 the Cr content is larger than the
contents of the other ions. Therefore, Cr3+ can be
more easily incorporated into CaHAP than the
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M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
Fig. 11. Surface atomic ratios of P and O of the CaHAP particles modified by the exchange with various metal ions: %
Ni2+; # Cu2+; 6 Co2+; ) Cr3+.
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
115
116
M. Wakamura et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 107116
4. Conclusions
The surface of CaHAP particles could be modified by the coprecipitation and ion-exchange methods with divalent and trivalent metal ions. The
surface modification by the coprecipitation with
Ni2+, Cu2+ and Co2+ was less effective compared
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