STRUCTURAL ELUCIDATION OF SINTERED CARBONATE

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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

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