名古屋工業大学学術機関リポジトリ Nagoya Institute of Tchnology Repository
Preparation of Calcium Phosphate Fibers for
Applications to Biomedical Fields
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journal or
publication title
volume
number
page range
year
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Toshihiro Kasuga, Akihiro Ichino, Yoshihiro
Abe
Journal of the Ceramic Society of Japan
100
1164
1088-1089
1992-08-01
http://id.nii.ac.jp/1476/00004154/
(c) 1992 The Ceramic Society of Japan
Journalof the CeramicSocietyof Japan 100 [8] 1088-1089 (1992)
Preparation
of Calcium
Ceramic letter
Phosphate
Fibers
to Biomedical
Toshihiro
KASUGA,
Akihiro
for Applications
Fields
ICKINO
and Yoshihiro
ABE
Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya-shi
466
生体 用 リン酸 カル シ ウ ム フ ァイバ ーの 調 製
春 日敏 宏 ・市 野 昭 弘 ・阿 部 良 弘
名古屋工業大学材料工学科, 466名 古屋市昭和区御器所町
[ Received
High-strength ƒÀ-calcium
applications
to
tracted
from
aqueous
glasses
solution.
tained
have
with
fields
high
of
Key-words:
ratios
1 to
Fibers,
for
of
with
new
tion. 8)
ex
heating
calcium
a dilute
crystalline ƒÀ-Ca(PO3)2
aspect
diameters
leaching
18, 1992; Accepted
successfully
products
by
The
fibers
were
crystallized
ultraphosphate
ics,
metaphosphate
biomedical
May
fibers
ranging
from
es
NaOH
30
metaphosphate,
and
low
wide
elastic
of
or
by
materials.
to
120
be
glasses
um
has
having
was
around
the
fibers
tremely
high
with
plies
that
the, ƒÀ-Ca(PO3)2
of
flexibility.
In
good
biocompatibility.
pected
that
fiber
In
by
are
of
the
work
matrix
we
im
at
the
and
system
found
is an
phosphate
of
pointed
fibers
with
ment
than
a
melt
advantageous
fibers
consist
that
an
to
asbestif
out,
high
aspect
the
Na2O-CaO-P2O5
medium
be
grown.
orm
for
the
6) The
NaCa
however,
NaCa(PO3)3
in
that
ratios
fibers
obtained
(PO3)3
are
crystal
straight
better
which
for
show
long
poly
phate
It
line
ions
Ca(PO3)2
changed
reinforce
taining
fibrilla
ysis
1088
The
during
Na+
revealed
ions
to
a
reheated
crystal
water
N NaOH
850
(DW)
were
used
fibers.
glass
powder
with
was
200ml
stirred
The
below
Distilled
were
in
in
the
at
of
the
60•‹-70•Ž
were
for
filtrated
pH
determined
the
were
that,
a
and
an
caused
at
by
glassy
X-ray
after
the
method.
stage
of
and
concentration
formed.
cou
initial
dissolution
no
of
inductively
the
treatment;
con
Ca2+, P5+
spectroscopic
rapidly
ion
the
function
of
ultraphosphate
Na+
and
as
by
emission
was
values
solution
concentrations
decreased
from
was
extract ƒÀ-Ca(PO3)2
change
atomic
phases.
2h.
cooled
powder
filled
as
was
The
into
ra
air.
where
which
for
and
glass
products
ions
value
1250•Ž
crystallized
were
plasma
pH
leaching,
fibers
. 7)-8)
in
molar
mixture
plate
0.1-0.5
resultant
ions
will
matrix
such
crystallization.
to
They
time,
the
in
The
mortar.
solutions.
of
are
fibrous ƒÀ
materials
at
crushed
of
1 shows
Na+
The
the
pulverised
150•Ž
leaching
glass
for
was
container
centration
ultraphos
fibers
raw
resultant
a tefron
Figure
CaO/
crystals
phases
from
a carbon
alumina
The
an
than
H3PO4.
The
48h
of
and
crucible
solutions
10g
dried
using
onto
solutions
into
of
of
CaO/P2O5=0.85
by
block
an
ratio
consist
ultraphosphate
and
for
using
pled
Griffith
with
a platinum
glass
molar
Tg.
calcium
leaching.
poured
600•Ž
the
preferentially
temperature.
leaching
is ex
ceramics.
is
in
was
around
Therefore, ƒÀ-Ca(PO3)2
prepared
4-72h.
ex
the
was
extraor
crystalli
durability
released
aqueous
leaching
composite
from
tem
is
is low
unity,
chemical
mixture
aqueous
put
prepared
phases
by
batch
rate
Ca2P6O17,
in
be
rate
which
3) The
crystals.
as
The
high-strength
new
crystallize
from
than
phase.
to
or
ex
glass-ceramic
for
re
glass
"stress-induced
of
less
poorer
lized
and
result
, it
slightly
able
at
2), 3)
exhibits
This
used
glassy
ƒÊm
400-600MPa
this
present
struc
a calci
4), 5) Therefore
be
as ƒÀ-Ca(PO3)2,
phate
room
crystalline, ƒÀ
70-120GPa.
can
the
leaching
of
addition,
such
melt
temperature
diameter
to
glasses,
is
melted
Ca(PO3)2
temperature.
fibers
hibits
biomaterials.
1ƒÊm
by
transition
growth
nucleation
Ca(H2PO4)2•EH2O
biomedical
a
of
strength
modulus
this
under
prepared
phosphate
glass
converted
P2O5
tio
phos
reheating
transition
ca.
bending
Young's
fibers
the
A
crystallized
composed
low
and
owing
phase
and
that
by
rod
glass
bulk
composite
produced
glass-ceramic
Ca(PO3)2
for
unidirectionally
glass
the
calcium
reported
fiber-reinfoced
metaphosphate
This
been
successfully
gradient
high
9) while
be
biocompatible
on
the
crystal
dinarily
biomaterials
reported
1) The
glass-ceramic
ture
The
zation",
Ca(PO3)2
effectively
into
glass-ceramics
It
nontoxic.
fibers
be
composition
below
(Tg).
much
proper
are
toughening
been
for
mechanical
strong,
and
1)-5)
is
for
have
required
materials
some
fibers
We
applications.
glass
the
polymer
mechanically
toxic.
phate
general,
been
can
Calcium
metaphosphate
temperatures
Glass-ceramics
biomaterials
have
introducing
The
should
not
In
ceramic
improved
the
at
perature
Glass-ceram
high-toughness
modulus
applications.
ties
around
glasses.
ultraphosphate
High-strength
fibers
CaO-P2O5
ob
Biomaterials
with
Long ƒÀ-Ca(PO3)2
even
5ƒÊm.
Calcium
June 16, 1992]
of
phos
crystal
remained
precipitates
diffraction
treatment
un
con
anal
in
0.5
N
Toshihiro KASUGA et al.
Journal of the Ceramic Society of Japan
Fig. 1. Ionic concentrations and pH values in the solutions.
DW: Treatment in distilled water.
NaOH(0.1N): Treatment in 0.1N NaOH aqueous solution,
NaOH(0.5N): Treatment in 0.5N NaOH aqueous solution.
100 [8]
1992
1089
Fig. 2. SEM photographs of calcium phosphate fibers.
(A) Fibers obtained by treatment in distilled water for 72h,
(B) Fibers obtained by treatment in 0.1 N NaOH aqueous solu
tion for 72h.
NaOH
solution
for 32h,
the crystallized
glass was
completely
dissolved
out, resulting
in the precipita
tion of hydroxyapatite.
After the treatments
in H2O
and 0.1N NaOH solution,
new precipitates
were not
detected.
However,
the changes
in ion concentra
tions of the solutions
imply the formation
of a small
amount
of calcium
phosphate
compounds
such as
CaHPO4 and hydroxyapatite.
Figures
ray
The
fibers
by
the
er
in
3
are
showed
On
as
that
released
the
other
in
diameter
tic
carriers
for
substitute.
posite
or
We
materials
reported
fibers
are
a near
30-120.
to
These
of
1
3)
bioab
morphogene
treatments
such
porosity.
is
of
available
fabricated
Fiber
matrix
Fiber-B
bone
for
3,
the
ratios
Fig. 3. X-ray diffraction patterns of the fibers.
(A) Fibers obtained by treatment in distilled water for 72h,
(B) Fibers obtained by treatment in 0.1 N NaOH aqueous solu
tion for 72h.
phases.
2 and
from
stabilize
already
matrix
Figs.
aspect
cushions
with
in
the
which
have
of ƒÀ-Ca(PO3)2
the
in
medicaments
biomedical
analy
crystals
Fiber-A.
high
that
diffraction
Ca2P6O17
extracted
with
with
proteins
fillers
shown
comparison
is expected
sorbable
as
larg
NaOH-treat
crystals
from
successfully
5ƒÊm
of
fibrous
completely
obtained
are
by
X-ray
amount
some
hand,
more
phases
It
Fiber-B).
a small
fibers
Fiber-A)
those
X
respectively.
The
as
to
and
fibers,
shape.
compared
not
is
in
photographs
the
(denoted
in Fiber-A;
are
SEM
of
straight
diameter
exist
show
patterns
(denoted
sis
be
and
DW-treatment
ment
-B
2
diffraction
as
and
4)
to
a periodontal
the
5)
6)
fiber-com
materials
will
future.
7)
References
1)
2)
M. Nagase, Y. Abe, M. Chigira and E. Udagawa, Biomateri
als, 13, 172-75 (1992).
Y. Abe, M. Hosoe, T. Kasuga, H. Ishikawa, N. Shinkai, Y.
Suzuki and J. Nakayama, J. Am. Ceram. Soc., 65, C189-90
(1982).
8)
9)
Y. Abe, T. Kasuga, H. Hosono and K. de Groot, J. Am. Cer
am. Soc., 67, C142-44 (1984).
C. P. A. T. Klein, Y. Abe, H. Hosono and K. de Groot,
Biomaterials, 5, 362-64 (1984).
idem, ibid, 8, 234-36 (1987).
E. J. Griffith, "Proc. 1981 Intern'l Conf. Phos. Chem.", Ed.
by L. D. Quin and J. G. Verkade, American Chemical Society,
Washington D.C. (1981) pp. 361-65.
T. Ngo, R. L. Hansen, J. A. Hinkebein, A. R. Henn, M. M.
Crutchfield and E. J. Griffith, Phos. Res. Bull., 1, 87-100
(1991).
A. R. Henn and P. B. Fraundorf, J. Mater. Sci., 25, 3659-63
(1990).
Y. Abe, T. Arahori and A. Naruse, J. Am. Ceram. Soc., 59,
487-90 (1976).