Similarly to IR,. Raman spectroscopy enables non-destructive analysis, thus giving ..... Infrared and Raman Spectra of Inorganic and Coordination Compounds.
Phosphorus Research Bulletin Vol.14 (2002), 47-56 STRUCTURAL ELUCIDATION OF SINTERED CARBONATE-CONTAINING HYDROXYAPATITES BY FT-RAMAN SPECTROSCOPY
TAKESHI MORIGUCHI and KAZUYUKI YANO Department of Chemistry, Saitama Medical School, machi, Iruma-gun, Saitama 350-0496, Japan SOUHEI
NAKAGAWA
and FUMIHIRO
981
Kawakado,
Moroyama-
KAJI
Department of Research and Development, Taihei Chemical Industrial 1-1 Takayasu, Ikaruga-cho, Ikoma-gun, Nara 636-0104, Japan
Abstract 400
Hydroxyapatites
and
to
1200•Ž,
give
the
spectra
translation The
v5,
band
were
and to
v6-v8
to the
in
shrinkage elucidation
magnesium
v1(PO4),
and
types
as
in the
well
The other
as
between
spectroscopy
v1(PO4)-v4(PO4),
several
these
intensities
the HAPs. study of
apatites
and
sintered
FT-Raman
bands
modes,
Raman
in
by
phosphate
carbonated
were
analyzed
four
and
changes
carbonate
were
in lattice
v2(PO4)+v5
the
volume structural and
typical
bands of
containing HAPs
indicating
notable
that
fluorinated
sintered
according
conclude
growth applied
(HAPs) the
intensities
changed
we
and
Co., LTD.,
OH
combination
bands.
ratio
R cp values
intensity
HAPs.
From
these
results,
possibly
reflect
the
particle
present substituted
forensic
Raman
study apatites
may such
be as
study.
INTRODUCTION
Hydroxyapatites biocompatible materials for
(HAPs) materials 1,
3,4
such
as
chromatography
HAPs
at
2
are for
surgical
tooth-brushing of
For
under
and
of
HAPsCa10(PO4)6-x(OH)2-y(CO3)x+y
this
report,
the
HAPs
decarboxylation
and
improvement (XRD).
of In
Received
the
order
August
to
Kaji
were
et
elucidate
28, 2002;
and
of
between by
with
the the
200
and
rise
in and
sintering
December -47-
on
to
thermal
to and
5, 2002
improve
of
FT-IR,
changes,there
process
6 of
changes
carbonate. the
and by
5
apatic
structural
reveal
temperatures
to
materials
sintering
1.2-4.8%
1200•Ž
compositional
packing
essential
contain
thermogravimetry
crystal
Accepted
is
applied
living-concerned
column
materials,
reported which
sintered
these
widely
daily
and
pressure
previously
and
therapies,
cosmetics,
production
al.7
dehydration HAPs
dental
atmospheric
crystallinity synthetic
rigidity.
synthesized
and
paste
peptides.
1000-1300•Ž
industrially
In
behaviors
of
crystallinity
X-ray
diffraction are
also
other
reports
8-42 about
IR
However,
no
Raman
Similarly
to
IR,
molecular
level
resembles
HAP
is
be
by
the
structure
of
the
HAPs
of with
relationship
such
groups,
bones
and
biological
16 these
the
carbonate
the
rise
between
HAPs
3-)
HAPs
in
and
medicinal
(substituted
to
characteristic
We
temperature,
structural
here
far.
giving
molecular the
on
structure
the
sintered
Therefore,
HAP-200) and
for
OH
PO4
patterns
spectral
difference
up
HAP-200 and
spectral Raman
we
sintered
HAP-100
report
spectral
has
study.
Since
have
and
data
and
so
thus
types,
15 Raman
HAPs.
reported
HAP
AB-type
seem
sintering
been
bonding
analysis.
and
biotic
analysis,
(HAP-100
compositions.
spectral
EXPERIMENTAL
PO4
have
tooth, 14, or
spectroscopic
for
HAPs
carbonate-containing
as
for
Raman
respectively, 7,
to
synthetic
useful
(substituted
carbonates,
since
syntheticor
non-destructive
functional
carbonate-containing
followed
B-type
as
sintered
sintered
enables
such
HAPs
to
synthetic
1200•Ž,
have
biotic
in
on
spectroscopy
addtion,
expected
analyses studies
information
to
investigated
spectral
spectroscopic
In
which
XRD
Raman
conformation. 13
to
and
in
the
3-)
due
changes HAPs,
and
changes.
SECTION
Materials HAPs, follows:
HAP-100
HAP-100
slurry,
and
anhydride
oven
cooling
it down
Raman
NIR
was
by
prepared
and
HAP-200
dropping by
(CO3
phosphoric
mixing
2-,
3.8%),
acid
slurries
of
into
calcium
were
prepared
as
a calcium
hydroxide
hydrogen
phosphate
carbonate.17
sample
Super to
(5g)
Burn
was
sintered
SBH-2305
room
for
one
(Motoyama
hour Co.,
between Ltd.,
400
Tokyo,
and
1200•Ž
Japan),
in
followed
an by
temperature.
spectroscopy Each
The
1.2%)
samples
HAP
electric
2-,
prepared
calcium
HAP Each
mm;
was
HAP-200 and
Sintering
(CO3
outer tube
sintered
HAP
diameter,
4
was
FT-Raman
inserted
sample mm; into
spectrometer
was
height, a holder System
directly 50
mm)
equipped 2000
-48-
loaded up
to
with
into 10
a quartz
mm
a concave
(Perkin-Elmer
height mirror Co.,
tube
(inner
from
the and
Wellesley,
diameter, tube
analyzed MA,
2
bottom. by USA).
an
Non-sintered as
HAPs
follows:
laser
angles,
180•‹; The
spectral Inc.,
IL,
the
The Raman
using
Windows
mounted
and up,
the
side
of
v 6-v 8 in
spectra
of
HAPs
Raman
shifts
v3(PO4),
the
stretching;
and than
patterns
were
spectral
pattern
the
both
pattern
broadened
sintered
cm-1,
draw
for
light
the
the
USA)
were scattering
corresponding
Macintosh
(SPSS
software
was
Spectrum
used.
those
a
motions
in for in
bands
mode 1200•Ž.
for in
the
pattern
non-sintered carbonate
and
and type
the
1200•Ž
v1(PO4)+v8
shown
and
HAPs, ions
but must
-49-
and TABLE
B,
v2(CO3), all
have
these
bands
disappeared
650
In
with
2a the
2b
as
other
spectrum
follows:
by
ones other and
in
decarboxylation.
in Large
indicates
v1(HPO4), absent
the
resembles
combination
1 further
in
spectral
HAP-100,
FIGURE
are
cm-1
different
2).
v4(CO3),
v2(PO4)+v5,
and
hand,
FIGURE
v2(PO4)+v7,
v2(PO4), symmetric
20
900
all
stretching;
bands
compared in
of HAPs
degenerate
in
Raman
assignment
v1(PO4),
(FIGURE
v1(PO4)+v8. A
other
the
19 v1(PO4),
follows:
and
v 5 and
non-sintered
between
HAP-200, is
v2(PO4)+v5
carbonate
The
at
In
of
v3(PO4),
On
up
band
and
bands,
observed
band
la.
v2(PO4)+v3(PO4),
19, 21 v1(CO3)
markedly
sintered
2,
by
significant
Similarly,
cases
as
state
zoomed
translation 18
the
solid The
was
Combination
combination
spectral
are
degenerate;
HAP-200.
HAPs
FIGURE
different
more
OH
phosphate
bands
1.
cm-1
FIGURE In
degenerate.
in
a new
these
100
rotation).
1. four
and
and
the
TABLE
of
and
in
in
FIGURE
clarify
shown
typical
bending
observed
except
the
were
to
analyzed
in
350
and
are in
were
shown
(translation
1200•Ž
bending
are
spectrum
indicate
in-plane
combination
at
conditions
analyzing
MA,
between
summarized
v2(PO4)+v7
v1(PO4)+v4(PO4),
libration
intensities,
spectra
modes
The
observed
lb,
to
TM 4.5
HAPs
original
at
spectra
observed
FIGURE
bands
is
out-of-plane
HAP-100
4
(ASCII)
Wellesley,
spectrum
each
v4(PO4).
v2(PO4)+v6,
each
sintered
v2(PO4),
v4(PO4),
files
band
Co.,
obtained
lattice
observed
and
resolution,
DeltaGraph
the
analysis
at 25•Ž.
text
software
compare
the
and
bands
1),
100;
carbonate-containing
notable
(FIGURE
into
The
DISCUSSION
picked in
method.
times,
converted
To
same
air-conditioned
graphic
non-sintered
were
the
scan
(Perkin-Elmer
spectroscopy,
bands
mW;
were
USA).
AND
by
temperature,
data by
Chicago,
RESULTS
200
measuring
spectral
for
analyzed
power,
figures
2000
were
the
OH HAPs
FIGURE
1
Raman spectra of non-sintered HAPs (a) HAP-100 and (b) HAP-200.
-50-
FIGURE
2
Raman
spectra
of
HAPs
HAP-200.
-51-
sintered
at
1200•Ž.
(a)
HAP-100
and
(b)
TABLE
1
Band (1200•Ž)
assignments HAP-100
of and
Raman
spectra
of
non-sintered
(NS)
and
sintered
HAP-200.
a This band possibly overlaps with one of the phosphate bands v 21). -52-
3(PO4) (see reference
TABLE 1 (to be continued from the previous page).
b
The as
The modes (translation and rotation) are related to all bands under 320 cm-1.
HPO4
2- ions
must
by
Greenfield
reported
never
observed
condensation covered
in of
with
the
Furthermore, to
combination
band 3.
In
reacted et
al. 22
FIGURE
HPO4 large
2- in
observe
2- in
Thereby,
the
although
the
HAPs.
analyzed
the
23
The
band a
to
for
for
sintered
between
the
-53-
the in
intensities
3-, and
H2O,
P2O7
4- was
to
P2O7 4- by
form
libration
400
must
and
1000•Ž
band
intensities of
PO4 ion
phosphate these
CO2,
pyrophosphate
OH
v2(PO4)+v7
in
give
possibility
as
changes 3a),
HAPs
band
such
HAPs
the
is
changes The
(FIGURE
there
bands
intensity
v2(PO4)+v5. HAP-100
withCO3
2
combination we
spectroscopy
FIGURE
have
both
have
by
v1(PO4) are
v1(PO4)
thermal been
Raman and
summarized and
v2(PO4)+v5
the in
increased
with
the
considerably these
rise
increased,
intensities
moderately clear
more
the
HAP-100
at
most
FIGURE
up
The
restricted
in
the
Over In
800•Ž.
5 can
also be
maximum
Over
HAPs
indicated
these
as in
800•Ž,
lattices
and
order
FIGURE
to
make
ratio
3.
In
given the
at
OH
strongly
Rep
case
predominant
R cp were
most
v1(PO4)
intensity
more
3b),
the
In
temperatures,
v1(PO4)
(FIGURE
the in
regarded
the
HAP-200
HAP-200,
values
At
900•Ž,
increased.
and
are
HAP-200.
900•Ž.
vigorously
5] / I [v1(PO4)]
for
to
HAP-100
v2(PO4)+v
to
decreased.
v2(PO4)+v5
v1(PO4).
1200•Ž
v2(PO4)+v5
between
mode
highly
mode.
the
I [v2(PO4)+v
up
consistent
while
other
and be
v2(PO4)
almost
combination the
temperature
the
difference
from
than
must
were
spectral
calculated
sintering
while
increased,
the
Rep>1,
in
of
mode 800•Ž
for
translation
collaborate
v5 with
24
3
Changes
in
(X)
phosphate
and
(b)
Raman
HAP-200.
intensities band
v1(PO4), NS
stands
of
(•œ)
and for
combination
(• )
these
band ratio
v2(PO4)+v5
R ep in
(a)
and
HAP-100
non-sintered.
We consider that the difference between HAP-100 and HAP-200 in spectral changes is ascribed to carbonate types in their apatic structure.
Decarboxylation occurs
at B-site (PO43- site) in HAP-100 and at both A- and B-sites (OH- and PO43- sites) in HAP-200.
In sintering of carbonated HAPs, decarboxylation causes the production of
stoichiometric HAP and calcium oxide. 7,25 Producing calcium oxide possibly means generating O2- ion and a hole ascribed to evolution of carbon dioxide in HAP lattice. 7, 26 Immediately after this, the hole may be dissolved by replacement of ions and volume shrinkage, and molecular motions such as translations and rotations by the constituent ions are to be strongly limited.
Therefore, in the case of AB-carbonated type HAP-200, -54-
the
OH
translation
finally
give
the
100.
The
possibly
appeared
and
was
extremely
the
highly
the
confirmed
that
volume
rather
Rep
the
drastically
the
explanation
growth of
values
in In
growth over
particle changes
in
have
found
that
decarboxylation
corresponding at
to
one
1200•Ž
1000•Ž.
in
HAP-
(FIGURE
OH
2b)
3 are
HAP-100,
the 700•Ž
to
volume
(R cp1),
(R cp>1).
structures
know
using
crystallinity
Therefore,
shrinkage
900•Ž In
lattice
HAP
work
v1(PO4).
v2(PO4)+v5.
useful
to
800•Ž
or
800•Ž, of
present of
as
was
at
volume
improvement such
as
the
which
started
the to
translation
such
FIGURE
over
crystal
phenomena causes
HAP,
growth
addition,
modes
of
of
particle In
these
bands
900•Ž
shrinkage
The
phosphate
from
growth
of
the
volume
possibly
combination
particle
reversed
overwhelms
over
restriction
go.
after
sintered
process.
Applying
strengthens
the
and
sintering
particle
shrinkage
than
in
of
than
HAP-200
growth
intensities
intensities
restricted
reason.
1000•Ž.
Raman
in
developed
over
directly
Raman
and
more
extremely
v2(PO4)+v5
bands
particle
method,
is
band
similar
a wet
the
shrinkage
the
reported
HAPs,
enhance
A-site
combination
by
shrank
carbonated
5 in
combination
27
by it
larger
other
Monma obtained
mode
Rep
is
shrinkage
can
be
used
for
HAPs.
CONCLUSIONS
We difference
in
the
is the
intensity
strong
connection From
structural
from with
as
the
person, benefit
of
12 the to
present
archaeological
cremated
growth
human
bone
v1(PO4) and
the
carbonated and
human
changing and
application, other
having
spectral
particle
of
of
HAPs
v2(PO4)+v5
fluoroapatite
structures
contemporary
Raman
viewpoint
such
deceased future
ratio
elucidation
apatites crystal
obtained
sintering
with
HAPs,
work
may and
remains
apatite
heat
patterns.
The
in
the
also
anthropological treated.
-55-
spectra
types ratio
of
can
R cp value,
sintered
reflect which
HAPs,
has
useful
for
shrinkage. work
is
probably in
treatment be
are
carbonate
volume
present
magnesium
different
applied sintering
are useful
expected to
studies,
be
other
process
dependent for
to
study. on
forensic in
substituted
the
study, which
Since
age
of
the
and
in
the
ancient
and
REFERENCES 1. H. Aoki, M. Akao, M. Toho, S. Hasegawa, and H. Ukegawa, Ceramics, 24, 614 (1989). 2. H. Nishina, J. Jpn. Orthop. Assoc., 63, 1237 (1989). 3. A. Slosarczyk, Interceram., 40, 148 (1991). 4. C. Fox, Cosmet. Toilet., 104, 27 (1989). 5. T. Kawasaki, S. Takahashi, and K. Ikeda, Eur. J. Biochem., 152, 361 (1985). 6. A. Krajewski, A. Ravaglioli, C. Fiori, and R. D. Casa, Biomater., 3, 117 (1982). 7. N. Matsuda, F. Kaji, S. Nakagawa, T. Uemura, and M. Watanabe, Inorg. Mater., 5, 398 (1998). 8. S. Baravelli, A. Bigi, A. Ripamonti, N. Roveri, and E. Foresti, J. Inorg. Biochem., 20, 1 (1984). 9. A. Krajewski, A. Ravaglioli, L. Riva di Sanseverino, F. Marchetti, and G. Monticelli, Biomaterials, 5, 105 (1984). 10. L. G. Ellies, D. G. A. Nelson, and J. D. B. Featherstone, J. Biomed. Mater. Res., 22, 541 (1988). 11. I. Mayer, S. Schneider, M. Sydney-Zax, and D. Deutsch, Calcif. Tissue Int., 46, 254 (1990). 12. J. L. Holden, J. G. Clement, and P. P. Phakey, J. Bone and Mineral Res., 10, 1400 (1995). 13. R. M. Gendreau, Trends in Anal. Chem., 5, 68 (1986). 14. R. A. Young, J. Dent. Res. 53, S193 (1974). 15. J. A. Timlin, A. Carden, M. D. Morris, R. M. Rajachar, D. H. Kohn, Anal. Chem., 72, 2229 (2000). 16. G. Bonel and G. Montel, C. R. Acad. Sci., 258, 1923 (1964). 17. N. Matsuda, F. Kaji, M. Watanabe, Phosphor. Res. Bull., 6, 345(1996). 18. D. C. O'Shea, M. L. Bartlett, and R. A. Young, Archs. Oral Biol., 19, 995 (1974). 19. D. G. A. Nelson and J. D. B. Featherstone, Calcif. Tissue Int._34, S69 (1982). 20. K.Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds 5th Edition, Part A (John Wiley & Sons, New York, 1997), p. 5. 21. G. Penel, G. Leroy, C. Rey, E. Bres, Calcif. Tissue Int., 63, 475 (1998). 22. D. J. Greenfield, J. D. Termine, and E. D. Eanes, Calc. Tissue Res., 14, 131 (1974). 23. A. Gee and V. R. Deitz, J. Am. Chem. Soc., 77, 2961 (1955). 24. K.Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 5th Edition, Part A (John Wiley & Sons, New York, 1997), p. 192. 25. J-C Labarthe, G. Bonel, and G. Montel, Ann. Chim., 8, 289 (1973). 26. S. E. P. Dowker and J. C. Elliott, J. Solid State Chem., 47, 164 (1983). 27. H. Monma, Kogyozairyo, 28, 101 (1980).
-56-
