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Calcium phosphate has been studied as bone repair thermal and wet precipitation. Differences in the
materials for the last 80 years1. The use of calcium preparative routes lead to variations in morphology,
phosphate biomaterials, particularly hydroxyapatite stoichiometry, and level of crystallinity. Amongst
(HA) and tricalcium phosphate (TCP), has gained these methods, the most commonly used technique is
popularity due to their excellent biocompatibility, the precipitation technique involving wet chemical
bioactivity and osteoconductivity attributed to the reactions between calcium and phosphorus precursors
close chemical resemblance with the mineral under controlled temperature and pH conditions.
component of natural bone and teeth2,3. HA and TCP Other methods such as sol-gel, spray pyrolysis and
have been used, not only for bone implant substitute mechano-chemical method, have also been developed
materials1,2, but have also been identified for and well documented12,13. The advantage of the wet
applicability as drug delivery4, antiseptics5, food precipitation technique which involves aqueous solu-
supplements6, and hyperthermia treatment agents7,8. tion is that its by-product is mostly water and the
The potential of the material as anticancer agent has probability of contamination during processing is very
been investigated and it has been found that nanoscale low11. However, a long ageing time is required to al-
HA is effective in inhibiting cancer cells growth9,10. low the precipitation reaction to end, as keeping the
The success of calcium phosphate-based biomate- single ion concentration uniform during the precipita-
rials in biomedical application depends largely on the tion stage is very difficult14. Although many studies
availability of highly pure, crystalline HA with fine on apatite based calcium phosphate by wet precipita-
particle size, enabling improved biological and me- tion technique have been reported, the use of calcium
chanical properties. Intensive studies on calcium oxide as calcium precursor is rather scarce. In the pre-
phosphate involving a wide range of powder process- sent study, calcium oxide was reacted with ammo-
ing techniques have been carried out with the aim of nium di-hydrogen phosphate to yield HA through a
producing HA powder with well defined particle low temperature hydrothermal exchange reaction. In-
morphology11. Numerous synthesis techniques have vestigation on the effect of excess calcium precursor
been developed to produce HA such as solid state re- on the phase behaviour of the calcium phosphate is
action, microwave processing, pH shockwave, hydro- also presented.
ALQAP & SOPYAN: LOW TEMPERATURE HYDROTHERMAL SYNTHESIS OF CALCIUM PHOSPHATE CERAMICS 1493
The increase in the 630 cm-1 OH band until 1000oC the increase in intensity of the OH (librational) band
and decrease above 1000oC, accompanied by the in particular, and the characteristic companion peaks
appearance of 727 cm-1 P2O7 band which decreases at in general, with temperature. Even though P-OH or
1200oC, and also the appearance of PO4 peaks at 970 HPO4 bands are observed, the excess calcium pre-
and 945 cm-1 are all indicators of the biphasic CaP, vents the condensation reaction of HPO4 to P2O7 and
i.e., containing both HA and β-TCP. Therefore, it is water. As a result, the transformation from CDHA to
concluded that the 970 and 945 cm-1 bands may be β-TCP is not observed in the Ca-2 sample.
attributed to β-TCP. This is also supported by the fact While the three samples after calcination at 700 oC
that a decrease in resolution of the two peaks at 975 have the same spectra in general, but in more detail,
and 940 cm-1 was observed at 1200oC, indicating that the samples show a small difference in the region of
the appearance of β-TCP is likely during the 559-466 cm-1. Other PO4 peaks, i.e. ν4 or ν1 mode, tend
conversion process to another phase, which is most to show up. Hence, an adjustment of band position
probably α-TCP. between 545 and 559 cm-1 of the highest peak in
In the IR spectra of the sample Ca-2 calcined at transmittance of PO4 (ν4) which is observed in the
700-1200oC, the upper region, i.e., 4000-1300 cm-1, samples Ca-0 and Ca-1 at all heating temperatures is
shows the bands as observed in the samples Ca-0 and not seen in sample Ca-2. This suggests that the ap-
Ca-1 after calcination at 700oC; these disappear after pearance of PO4 (ν4) peak position has been affected
calcination at 800oC and above. The characteristic by calcium. After 800oC, P-OH or HPO4 which is ob-
peaks of Ca-2, in the region of 1250-400 cm-1, are served in sample Ca-0 condenses to form P2O7 and
also the same as those of the samples Ca-0 and Ca-1 H2O immediately at this temperature or even at lower
after calcination at 700oC. The 1020 cm-1 band of PO4 calcination temperatures but with longer dwell time as
(ν3) and 559 cm-1 band of PO4 (ν4) show the highest suggested by Markovic et al.15 Once P2O7 appears and
transmittance. These are accompanied by bands at OH disappears, the sample will have no more HA.
1089 cm-1 of PO4 (ν3), 958 cm-1 of PO4 (ν1), 875 cm-1 The presence of H2O as the by-product of the HPO4
of HPO4, 630 cm-1 of OH (librational) and 600 cm-1 of condensation reaction, or from water bonded to some
PO4 (ν4). However, the companion peaks as HA intermediates, or even from the atmosphere is likely
characteristic peaks as mentioned earlier increase in to affect the number of hydroxyl ions in the apatite
transmittance with the increase in calcination crystal. However, as the hydroxyl ions in HA crystal
temperatures and are stable up to 1100oC. The occupies a site slightly above or below the triangular
transmittance of these peaks reduces after calcination calcium plane, the replacement of hydroxyl, by
at 1200oC, indicating a change in phase. The carbonate for example, does not significantly affect
characteristic peaks differentiate the sample Ca-2 the overall crystal system. A significant change will
from the other two samples, Ca-0 and Ca-1. Here it is take place if carbonate is replaced by phosphate,
likely that HA exists as a single and stable phase at all leading to change in the a-lattice parameter22. Thus,
calcination temperatures, unless the X-ray data the presence of carbonate ions affects the order within
indicates β-TCP as trace. the apatite structure. This is thought to yield
The Ca-2 sample has a distinct IR pattern, and the disordered arrangement of phosphate ions that do not
main peaks are stable at all the calcination tempera- assemble in the expected hexagonal structure defining
tures. Particularly, the PO4 (ν1) remains as a single an ideal HA crystal system.
peak at 958 cm-1 and the PO4 (ν4) at 559 cm-1 is also X-ray analysis
stable. It is also interesting to note that the existence Figure 2 shows the X-ray patterns of the sample
of the CO3 and HPO4 bands in the range of 3800-1400 Ca-0 calcined at 700-1200oC. It shows the
cm-1 do not affect the stability of the bands at 1089, 700oC-calcined sample is totally different from those
1019, 958, 600 and 559 cm-1 of PO4 and at 630 cm-1 calcined at higher temperatures. The X-ray pattern
for OH, which was not been in the spectra of the Ca-0 indicates that the 700oC sample characterizes HA
and Ca-1 samples. All these six bands are characteris- peaks of low crystallinity, while at 800oC, the β-TCP
tics for HA as confirmed by the X-ray data. Thus, the peaks appear as the main phase. At 900oC and above,
sample Ca-2 has the IR spectra of the HA phase pat- HA appears again with very weak intensity. The
tern at all the higher temperatures. An increase in the X-ray pattern of 1200oC calcined sample suggests that
amount of HA is also observed here, as observed by the β-TCP is no longer stable in the sample Ca-0 as
1496 INDIAN J CHEM, SEC A, NOVEMBER 2009
its intensity decreases. It is likely to be transformed to the a-lattice parameters of the sample for 800, 900,
α-TCP. However, no α-TCP identified in the pattern 1000, 1100 and 1200°C are 10.446, 10.429, 10.429,
indicates that the transformation is just beginning. 10.468 and 10.429 Å respectively with an average of
One study has reported that the transformation to 10.440 Å; while for the c-lattices parameter these va-
α-TCP starts at 1160oC (ref. 17). lues are 37.375, 37.380, 37.380, 37.282 and 37.380 Å
Table 1 shows the main peaks within the range of respectively with an average of 37.359 Å. These
25-40o in 2θ for all the samples after calcination at average values are in good agreement with their
700oC and for comparison, data of HA according to standard values 10.429 and 37.380 Å, respectively.
JCPDS 09-0432. Table 1 suggests that one of the HA The parameter d of the sample Ca-0 arbitrarily taken
peaks, i.e., (112), of the sample Ca-0 is unresolved at 2θ = 25.782 and 34.398° gave the average values of
because the peak is too broad. In addition, the 2θ 3.461 and 2.601 Å, which are very close to the
positions shift to the left or to the right of the standard standard values, 3.453 and 2.605 Å, respectively.
HA positions. This suggests the appearance of Figure 3 shows the X-ray patterns of the sample
calcium-deficient hydroxyapatite. The fraction of Ca-1 calcined at 700-1200oC. It is observed that HA
crystalline phase (Xc) in the HA powders can be or calcium-deficient apatite peaks appear as a broad
evaluated by Eq.(2) (ref. 23), pattern such that the (112) peak is unresolved (see
Table 1). The fraction of crystalline phase (Xc) is
X c = 1 − V(112)/(300) / I (300) … (2)
Table 1 – The positions of main peaks of all the samples after calcination at 700oC
2θ (deg.)
(002) (102) (210) (211) (112) (300) (202) (310)
HA a 25.879 28.126 28.966 31.773 32.196 32.902 34.048 39.818
Ca-0 25.885 28.28 29.012 31.88 n.a. 32.64 34 39.65
Ca-1 25.869 28.2 28.925 31.957 n.a. 32.9 34.01 39.66
Ca-2 25.87 28.14 29.17 32.04 n.a. 32.88 34.035 39.595
a
According to JCPDS # 09-0432.
ALQAP & SOPYAN: LOW TEMPERATURE HYDROTHERMAL SYNTHESIS OF CALCIUM PHOSPHATE CERAMICS 1497
0.259. As the IR spectra show, the OH (librational) (i.e., 9.401 and 6.874 Å respectively) are lower than
band is clearly observed at higher calcination those of the HA standard (i.e., 9.418 and 6.884 Å
temperatures at 800-1200oC, leading to identifiable respectively). The a- and c-lattice parameters change
HA peaks in the X-ray spectra. The intensities of the with the CaO content. For the a- and c- lattice
HA peaks also increase with increase in temperature. parameters, it is observed that aCa-0 > aCa-1 = aTCP and
The fractions of crystalline phase (Xc) of the HA for cCa-0 < cCa-1 = cTCP for TCP phase; aCa-1 ≈ aHA > aCa-2
800, 900, 1000, 1100 and 1200oC are 0.443, 0.689, and cCa-1 > cHA > cCa-2 for HA phase, while the
0.786, 0.820 and 0.799 respectively. It is clear that a average values of atomic spacing shows the trend:
significant improvement in the crystalline fraction dCa-0 = dCa-1 > dTCP for TCP and dCa-1 > dHA ≈ dCa-2
does not occur after 1000oC. Figure 3 also indicates for HA. One reason for this trend in d is that
that β-TCP is the main phase at 800oC and above. The impurities (such as carbonate), play a role in
β-TCP intensities do not increase significantly from influencing the crystal system of the samples. Santos
800oC (500 cps) to 1100oC (520 cps), and decrease and Clayton20 have reported that carbonate
significantly at 1200°C (350 cps), although the substitution has a negative correlation with the
indication for β-TCP getting transformed to α-TCP a-lattice parameter. The value of parameters here
has not yet appeared. The average value of the a- and fluctuates suggesting that variation in carbonate
c-lattice parameters over 800-1200oC (i.e., 9.422 and has occurred due to uncontrolled atmosphere.
6.895 Å respectively) are closer to the standard values There may be another possible reason, i.e., the
for HA phase (i.e., 9.418 and 6.884 Å respectively) secondary phase which has been observed may
and identical to the standard for values TCP phase affect the crystal system. The contraction in the
(i.e., 10.429 and 37.380 Å respectively). There is no a-parameter is likely to be compensated by the
disruption of the lattice parameters in TCP. The a- or expansion in the c-parameter, and vice versa, such
c-lattice parameter of HA tends to fluctuate for that the ratio, c/a, is kept the same and, as a result, the
different temperatures although an increasing trend is atomic spacing of the samples is closer to that of the
also observed. For TCP, however, the value of standard.
parameters is constant over the range of 800-1200oC.
The X-ray patterns of the sample Ca-2 calcined at
700-1200oC (Fig. 4) show that the HA (112) is
unresolved at 700oC (see Table 1) indicating the
calcium-deficient hydroxyapatite phase. When
calcined at 800oC, the HA peaks appear as four peaks
in the range of 2θ = 31.77-34.05º, i.e., (211), (112),
(300), and (202). The fraction of HA crystalline phase
(Xc) increases with increase in temperature, i.e., 0.257,
0.651, 0.795, 0.889, 0.935 and 0.961 at 700, 800, 900,
1000, 1100 and 1200oC respectively. This
quantitatively proves that significant improvement in
the fraction of crystallinity can be obtained by
elevating the calcination temperature. The β-TCP is
still invisible at 700°C and appears when the sample
is calcined at 800oC but decreases in intensity with the
increased temperatures (Fig. 4). In the
1200oC-calcined sample, even the β-TCP peak is
insignificant. The single P-O band of 958 cm-1 (for ν1
PO4) and two P-O bands of 600 cm-1 and 559 cm-1
(both for ν4 PO4) as well as 630 cm-1 band for OH
(librational), are characteristic peaks for HA.
The HA phase of the sample Ca-2 is the main
phase of the sample. The average values of the a- and Fig. 4 – X-ray spectra of the sample Ca-2 calcined at temperatures
c- lattice parameters of Ca-2 over 700-1200°C of 700 -1200oC. [■ HA; ▲ TCP].
1498 INDIAN J CHEM, SEC A, NOVEMBER 2009
We have also carried out studies on 1 and 2 mole% It is noteworthy that the TG curves of the samples
excess of CaO with 0.125 mole CaO as the basis (7 g Ca-0 and Ca-1 show multiple losses, compared to the
CaO and 8.63 g NH4H2PO4) in 150 ml distilled water. single weight loss for sample Ca-2. The multiple
The principal difference between 1 and 10 mole% losses in the TG pattern are probably due to multipe
excess CaO samples is that the former, i.e., 1 mole% reactions. It is proposed that calcium hydroxide
excess has no HA and only β-TCP at all calcination appears from the reaction of CaO with water and,
temperatures employed where the β-TCP shows phosphoric acid (H3PO4) and ammonium hydroxide
around 600 cps of the main peak intensity (0210) for (NH4OH) from hydrolysis of ammonium dihydrogen
900°C calcination temperature. The latter, i.e., phosphate (NH4H2PO4). The reaction of calcium
10 mole% excess, has β-TCP and HA with the main hydroxide and phosphoric acid will then produce
peak intensity of β-TCP around 370 cps. There is no calcium dihydrogen phosphate (Ca(H2PO4)2) and
difference in the phase appearance between the 2 and water as shown in Eq. (3)25.
20 mole% excess CaO samples. Both give HA as
main phase with β-TCP as traces, however, the Ca(OH) 2 + 2H 3 PO 4 → Ca(H 2 PO 4 ) 2 + 2H 2 O … (3)
2 mole% excess sample has the HA main peak (211) Or, the unhydrolysed CaO will react with
intensity of around 850 cps, higher than that of phosphoric acid (Eq. 4).
20 mole% excess around 600 cps for 900°C
calcination temperature. CaO + 2H 3 PO 4 → Ca(H 2 PO 4 ) 2 + H 2 O … (4)
Thermogravimetry analysis of the samples Ca-0, The Ca(H2PO4)2 reacts readily with water to
Ca-1, and Ca-2 give information regarding the transform during heating to super-phosphate or
influence of excess CaO on reaction commencement monocalcium phosphate monohydrate
as observed from weight loss. The phase (Ca(H2PO4)2.H2O). This reacts with the remaining
transformations generally require heat as DT analyses calcium hydroxide to yield brushite (CaHPO4.2H2O)
indicate, except in the final stages when heat is (Eq. 5) 25.
released and the corresponding phase possibly begins
transforming to further phase at higher temperature. Ca(H 2 PO 4 )2 ⋅ H 2 O + Ca(OH) 2 → 2CaHPO 4 ⋅ 2H 2 O
The weight losses detected are mainly due to a + H 2 O … (5)
decrease in amount of O-H groups of intermediate
phase reaction. The common pattern in the TG curves The above calcium dihydrogen phosphate may also
of the three samples reveals four reaction sites in the decompose into monetite (CaHPO4) and phosphoric
ranges of 40-100oC, 100-250oC, 250-600oC and acid (Eq. 6).
600-800oC. These may be attributed to the loss of Ca(H 2 PO 4 ) 2 → CaHPO 4 + H 3 PO 4 … (6)
residual water for the first, water and ammonia
evaporations for the second and the third, and Ca(H2PO4)2 may react with ammonia to form
densification and crystallization for the fourth range. CaHPO4 (Eq. 7).
The TG curves show the difference in weight losses
until ~700oC, with the sample Ca-0 showing the Ca(H 2 PO 4 ) 2 + NH 3 → CaHPO 4 + NH 4 H 2 PO 4 … (7)
lowest and Ca-2 the highest loss. At around 700oC, it It is accordingly inferred that many overlapping
is seen that the temperature at which the weight loss reactions may occur since phosphoric acid and
occurs decreases and weight loss level increases with ammonium dihydrogen phosphate are produced at
the increase in excess calcium. It has been reported higher temperatures. Once the monetite or brushite is
earlier that the weight losses at ~700oC is probably formed, it decomposes into calcium pyrophosphate
due to removal of water as the by-product from the (Ca2P2O7) and water at 700-900oC (Eqs 8 & 9)25.
reaction of P2O74- ions with lattice OH- ions, forming
TCP24. However, this is not true in this study since the 2CaHPO 4 → Ca 2 P2 O7 + H 2 O … (8)
sample Ca-0, with the highest portion of TCP, 2CaHPO 4 ⋅ 2H 2 O → Ca 2 P2 O 7 + 4H 2 O … (9)
showed the least weight loss. It is suggested that the
loss is due to deviation from the stoichiometric This is probably the reason for the additional
reaction as the reaction using excess Ca precursor weight losses observed in the samples Ca-0 and Ca-1
removes more reactants. above 700oC. The calcium pyrophosphate may react
ALQAP & SOPYAN: LOW TEMPERATURE HYDROTHERMAL SYNTHESIS OF CALCIUM PHOSPHATE CERAMICS 1499
with CaO to form TCP (Ca3(PO4)2) at higher calcium compounds remaining in the solution before
temperature25, as observed by the P2O7 band at drying or aging. Unfortunately, the source of Ca2P2O7
727 cm-1 in the IR spectra at calcination temperature is not only one, as described above. The monetite and
above 800oC. However, the other intermediate phases brushite formed are also sources of calcium
are readily decomposed during heating into the pyrophosphate (Ca2P2O7) and water at 700-900oC and
subsequent phase at the given temperature and are not calcium hydroxide is the source of CaO. Thus,
observed in the X-ray patterns. possibly β-TCP and CaO appear at the subsequent
In X-ray patterns of all of the samples calcined at temperature.
700oC, the observed peaks are broad, showing its low
crystallinity. Such broad peaks can not merely be Conclusions
associated with less calcium in a sample because the In the above studies, calcium phosphate materials
samples Ca-1 and Ca-2 with excess calcium also with three different calcium contents, viz.,
show such broad peaks. It is suggested that the stoichiometric CaO (Ca-0), 10 mole% excess CaO
appearance of CDHA phase is not merely due to less (Ca-1), and 20 mole% excess CaO (Ca-2) with
calcium, but also due to incomplete transformation of 0.1 mole CaO as the base, have been successfully
HA. The TG–DTA curves suggest that the synthesized using CaO and NH4H2PO4 through low
transformation reaction is still in progress at 700oC as temperature hydrothermal process. The as prepared
the transformation is not complete above 700oC. powders have been dried, followed by calcination at
β-TCP appears replacing the CDHA after the sample 700-1200oC at 100oC interval. The difference in CaO
Ca-0 is calcined at 700oC; the β-TCP phase may content brought about difference in stability of the
come from decomposition of the CDHA as follows calcium phosphate phase over the different heating
(Eq. 10)17: regimes. The samples Ca-0, Ca-1 and Ca-2 have
been characterized as unstable, unstable and stable
Ca 9 (HPO 4 )(PO 4 )5 (OH) → 3Ca 3 (PO 4 ) 2 + H 2 O ... (10) phase respectively. The appearance of β-TCP is due to
calcium deficiency since its amount decreases with
In the sample Ca-1, β-TCP may be observed the increasing Ca content. Multiple reactions forming
due to the condensation of HPO42- upon heating into intermediates probably occur in the samples Ca-0 and
P2O74- and water as suggested elsewhere15,26. Ca-1 causing the thermal unstability of calcium
Simultaneously, P2O74- may react with O-H in the phosphate phase. The X-ray analysis shows different
presence of ionic calcium to form β-TCP as described lattice parameters in all the three samples. Even
in following reaction (Eq. 11). though all the samples have the c/a lattice ratio close
Ca 2 P2 O7 + 2OH − + Ca 2 + → Ca 3 (PO 4 ) 2 + H 2 O … (11) to that of the standard, the sample Ca-2 has the
closest the atomic spacing d.
However for the sample Ca-2, another explanation
for the very small β-TCP may be necessary because Acknowledgement
the P2O74- band is not observed in the IR spectra. A One of the authors, (ASFA), would like to thank
small amount of NH4H2PO4 may produce P2O5 during the Ministry of National Education, The Republic of
heating27 which reacts with CaO resulting in Ca2P2O7, Indonesia, for a scholarship, (No. 2865.33 &
and β-TCP is then obtained as the following sequence 2866.38/D4.4/2008).
of reactions shows (Eqs 12 & 13).
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