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Acta Biomaterialia 4 (2008) 1455–1464

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Structural analysis of a series of strontium-substituted apatites

M.D. O’Donnell *, Y. Fredholm, A. de Rouffignac, R.G. Hill
Imperial College London, Department of Materials, South Kensington Campus, Exhibition Road, London SW7 2AZ, UK

Received 6 November 2007; received in revised form 26 March 2008; accepted 16 April 2008
Available online 3 May 2008

Abstract

A series of Sr-substituted hydroxyapatites, (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00, were made by a standard
wet chemical route and investigated using X-ray diffraction (XRD), Rietveld refinement and Raman spectroscopy. We report apatites
manufactured by two synthesis routes under 90 °C, and only the fully Sr-substituted sample had a small amount of an impurity phase,
which is believed to be strontium pyrophosphate. Lattice parameters (a and c), unit cell volume and density were shown to increase lin-
early with strontium addition and were consistent with the addition of a slightly larger and heavier ion (Sr) in place of Ca. XRD Lorentz-
ian peak widths increased to a maximum at x = 0.50, then decreased with increasing Sr content. This indicated an increase in crystallite
size when moving away from the x = 0.50 composition (d  9.4 nm). There was a slight preference for strontium to enter the Ca(II) site
1
in the mixed apatites (6 to 12% depending on composition). The position of the Raman band attributed to v1 PO3 4 at around 963 cm in
1
hydroxyapatite decreased linearly to 949 cm at full Sr-substitution. The full width at half maximum of this peak also correlated well
and increased linearly with increasing crystallite size calculated from XRD.
Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Raman; Apatite; Strontium; XRD; Rietveld

1. Introduction samples are typically only analysed by X-ray diffraction

It is known that strontium and other divalent cations
with a similar charge-to-size ratio to calcium can readily
substitute in the lattice of hydroxyapatite. Also it has been
reported that there is immiscibility in this system and com-
plete solid-solution cannot occur, although this may be due
to poor sample preparation [1]. Apatites have many appli-
cations, from optoelectronics [2] to waste immobilization
[3] and biomaterials [4]. Strontium is also beneficial for bio-
logical applications for bone regeneration due to the recent
success of treatments such as strontium ranelate [5], which
stimulates bone formation, decreases bone resorption and
reduces the risk of vertebral fractures in postmenopausal
osteoporosis. Both calcium- and strontium-hydroxyapatite
are hexagonal (space group P63/m) [6,7]. No complete sys-
tematic studies have been performed on this system manu-
factured by a wet chemical route to our knowledge, and
(XRD). Heijligers et al. [1] performed a structural study
of Sr–Ca apatites made by solid state synthesis using
XRD but had significant tristrontium phosphate present
for compositions above 80% Sr-substitution. Bigi et al.
looked at the structure of 0, 20 and 60% substitution of
Sr for Ca in hydroxyapatite [8].
Raman microspectrometry is powerful investigative
tool, as the probe is 10–100 times smaller than similar
micro-infrared spectroscopic techniques. It is useful for
biological samples due to its non-invasive and non-destruc-
tive nature, and fluorescence is minimized. No special sam-
ple preparation is required as the technique is performed in
reflection and hence artefacts from the preparation process
are eliminated. Complex studies can be performed, such as
at interfaces and line-scans of cross-sections. The func-
tional groups present in biological and synthetic apatites,

such as phosphate (PO3 4 ), hydroxyl (OH ), acidic phos-
phate (HPO4 ), carbonate (CO3 ) and fluoride (F), can
2 2

*
Corresponding author. Tel.: +44 20 7594 6814; fax: +44 20 7594 6757. be probed, and peak width, position and multiplicity corre-
E-mail address: m.odonnell@imperial.ac.uk (M.D. O’Donnell). lated with composition and structure.

1742-7061/$ - see front matter Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actbio.2008.04.018
1456 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464
The purpose of this study was to investigate the crystal-
line structure of a series of apatites, where Ca is progres-
sively substituted for Sr, by XRD, Rietveld refinement
and Raman spectroscopy.
2. Experimental
2.1. Synthesis
Strontium-substituted hydroxyapatites were synthesized
by a wet chemical route. Two reaction routes were used [9].
2.1.1. Route 1
Solution A preparation. Calcium nitrate 4-hydrate
(Ca(NO3)24H2O) and/or strontium nitrate (Sr(NO3)2) were
dissolved in 200 ml of distilled water. Table 1 gives the
weights used for each apatite composition. The pH of the
solution was adjusted to 11 using 30% ammonia solution,
then 400 ml of distilled water was added to the solution.
The solution was constantly stirred.
Solution B preparation. Diammonium hydrogen ortho-
phosphate ((NH4)2HPO4) was dissolved in 120 ml of dis-
tilled water. The amount of (NH4)2HPO4 used is given
in Table 1. The pH of the solution was adjusted to 11
using ammonia solution; however, no hydroxides precip-
itated, which have lower solubility than amide salts, tri-
calcium phosphate and apatite. Distilled water (160 ml)
was then added to the constantly stirred solution. The
solution was filtered using a Buchner funnel, as
described [9].
Solution A–solution B mix. Solution B was added drop-
wise to the constantly stirred solution A over a period of
approximately 2 h. The pH was kept at around 11. A pre-
cipitate formed and was stirred for 1 h, before being left
overnight. The precipitate was centrifuged and washed
twice with distilled water. Finally, the precipitate was dried
for 20 h at 85 °C. The dried material was crushed using a
Gyro-mill and sieved with a 38 lm sieve into coarse and
fine fractions.
2.1.2. Route 2
Solution A preparation. Calcium hydroxide (Ca(OH)2)
and strontium hydroxide (Sr(OH)2) were dissolved in
500 ml of distilled water. Table 2 gives the weights used
for each apatite composition.
Solution B preparation. Orthophosphoric acid solution
(85% H3PO4) was diluted in 500 ml of distilled water.
The amount of H3PO4 used is given in Table 2.
Table 1
Experimental weights (in g) for route 1 synthesis for the series (SrxCa1x)5(PO4)3OH, where x = 0.00 and 1.00
Sr (x) Ca(NO3)2  4H2O wt.% mol.%
1.00 – – – 42.34
0.50 23.62 38.95 31.25
0.25 35.42 57.27 46.87
0.00 47.23 74.87 62.50
Solution A–solution B mix. Solution B was added drop-
wise to the constantly stirred solution A over a period of
2 h. The pH of the mixture was adjusted to about 11 with
a 30% ammonia solution, if needed. The precipitate formed
was stirred for 1 h, before being left overnight. The precip-
itate was centrifuged and washed twice with distilled water.
Finally, the precipitate was dried for 20 h at 85 °C. The
dried material was powdered using a Gyro-mill and sieved
with a 38 lm sieve.
2.2. XRD
A Phillips powder diffractometer with a copper (Cu Ka)
X-ray source (Philips PW 1700 series diffractometer, Phi-
lips, Eindhoven, the Netherlands) was used to characterize
the glass samples. The powdered samples (<38 lm particle
size) were scanned between 2h values of 10 and 80° with a
step size of 2h = 0.04° in order to determine the crystal
structure of each apatite. This step size results in a d-spac-
ing deviation of around 0.009 Å at 20° 2h, consistent with
the errors reported in the refinement below. These param-
eters gave sufficient resolution for the refinement, with the
most intense peaks occurring in the 2h = 30–35° region.
XRD was then carried out and the results analysed using
software containing a database of standard diffraction files.
Rietveld refinement was performed with GSAS [10] and
EXPGUI [11] software using a 10-term shifter-Chebyschev
background function. Initial atomic coordinates and unit
cell dimensions were taken from previously published data
[6,7]. Parameters varied in the refinement were atomic
coordinates (x, y and z), unit cell parameters (a and c), dis-
placement parameters (Uiso), peak intensity scaling and
peak profile parameters related to particle size and stress.
For the mixed apatites, the fractional occupancies of both
divalent cation sites were initially set at the stoichiometric
values, then refined to total unity as there is some evidence
that strontium preferentially substitutes onto the Ca(II) site
[8]. To determine the Bragg peak widths, the Bragg reflec-
tion at around 2h = 25.9°, corresponding to the 0 0 2 hkl
reflection, was Lorentzian deconvoluted with Microcal Ori-
gin software.
2.3. Raman
The Raman system used consisted of a Renishaw RM
2000 spectrometer (Renishaw LC, UK) connected to a
Leica microscope with an objective (50). A 785 nm
300 mW line focus laser with 100 mW power at the sample
Sr(NO3)2 wt.% mol.% (NH4)2HPO4 wt.% mol.%
72.76 62.50 15.85 27.24 37.50
21.17 34.91 31.25 15.85 26.14 37.50
10.58 17.11 15.62 15.85 25.63 37.51
– – – 15.85 25.13 37.50
 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464 1457

Table 2
Experimental weights (in g) for route 2 synthesis for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00
Sr (x) Ca(OH)2 wt.% mol.% Sr(OH)2 wt.% mol.% H3PO4 wt.% mol.%
1.00 – – – 30.10 64.36 59.26 16.67 35.64 40.74
0.75 4.58 10.45 14.80 22.58 51.52 44.46 16.67 38.03 40.74
0.00 18.34 52.39 59.27 – – – 16.67 47.61 40.73

was used. This wavelength and 100% power was sufficient
to produce a high signal to noise ratio Raman spectrum.
The laser spot size was calculated to be 10 lm wide by
20 lm high and 40 lm deep. The spectrometer was set up
with a spectrometer slit of 50 lm and 8 CCD (charge-cou-
pled device) pixels. The powdered samples were placed on a
glass slide to collect the spectra. Ten 10 s spectra were
taken between Raman wave number shifts of 100 and
1500 cm1. Quartz was used as a calibration material with
the main Raman resonance peak at around 521 cm1.
Overlapping peak positions were obtained by Lorentzian
deconvolution using Microcal Origin software.
3. Results and discussion
3.1. XRD and Rietveld refinement
Fig. 1a shows the XRD traces of the Sr-substituted apa-
tites and Rietveld refinement. Traces were shifted on the
y-axis for display purposes. The fitting was good for all

a 3500

3000

2500
Intensity (a.u.)

2000

1500

1000

500

0
10 20 30 40 50 60 70 80
o
2-theta /

x=0.00 x=0.25 x=0.50 x=0.75 x=1.00

600

500

400
Intensity

300

200

100

-100
10 20 30 40 50 60 70 80
o
2-theta /
Data Fit Background Residual

Fig. 1. (a) XRD traces and Rietveld refinement of the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00: data points (XRD) and solid
lines (Rietveld); (b) Rietveld refinement for x = 0.50, with residual and positions of Bragg reflections.
1458 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464

samples, as demonstrated in the high R2 values (all >0.9,
not shown) indicating excellent correlation. Fig. 1b shows
a typical fit for the series for the x = 0.5 sample, also show-
ing the residual and background. The diffraction peaks
shift to lower 2h values with Sr-addition, indicating an
increase in d-spacings and hence lattice parameters. This
would be expected as Sr is slightly larger than Ca (118
and 100 pm for octahedral coordination [12]). Peak inten-
sity also increases with Sr-addition. This is to be expected
as Sr is heavier and contains more electrons than Ca, and
will therefore more effectively scatter X-rays, so there is a
general increase in crystallinity with Sr-addition (see
below).
Lattice parameters (a and c) increase linearly with Sr-
addition, as shown in Figs. 2 and 3, consistent with a larger
ion entering the apatite lattice. As a result of this, the unit
cell volume also increases linearly, as seen in Fig. 4. Density
calculated from the Rietveld refinement in Fig. 5 also
increases linearly with Sr-addition due to the replacement
of a heavier ion for Ca in the crystal structure (87.62 and
40.078 g mol1, respectively [12]), and the Ca-rich end of
the series agree well with previously published experimental
data on pure Ca-hydroxyapatites made by aqueous gel
casting [13] and sintering [14] and a low Sr-substitution
Ca-hydroxyapatite [15]. Due to a lack of published data
on pure Sr-hydroxyapatite and mixed Ca–Sr-hydroxyapa-
tite experimental densities, Fig. 5 shows the density of a
Yb-doped Sr-fluorapatite [2]. As F and OH have
approximately the same mass and ionic radii, the density
of these materials should not differ greatly from Sr-
hydroxyapatite. As Fig. 5 shows, there is good agreement
between the published and Rietveld data.
Crystal sizes, d, were calculated from the full width at
half maximum values (FWHMs) of the most intense Bragg
reflection at around 2h = 25.9°, corresponding to the 0 0 2
hkl reflection and using the formula equation shown below
in Eq. (1) [16]
0:9k
d¼ ð1Þ
w cos hx
where k is the wavelength of the X-rays (1.5406 Å), w is
the FWHM of the Bragg peak and hx the angle of the
Bragg reflection. The crystallite size decreased to a mini-
mum at around x = 0.5 then increased with Sr content
(Fig. 6). This is consistent with the observations of Li
et al. [17], who showed, with a series of three Sr–Ca apa-
tites (0.3, 1.5 and 15% Sr-substitution), that crystallite
size decreases as Sr-substitution approaches 15%. This
study did not report higher Sr-substitutions. It has been
indicated that strontium addition to hydroxyapatite

Table 3
Parameters from Rietveld refinement of the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00, with standard deviations
Sr Ca a / Å 2ra / Å c / Å 2rc / Å V / Å3 2rV / Å3 q/g.cm3 d / nm
0.00 1.00 9.411 0.004 6.877 0.003 527.5 0.378 3.163 17.55
0.25 0.75 9.505 0.007 6.950 0.006 543.8 0.648 3.384 11.37
0.50 0.50 9.596 0.004 7.054 0.004 562.6 0.452 3.692 9.38
0.75 0.25 9.659 0.005 7.182 0.004 580.3 0.740 3.897 12.94
1.00 0.00 9.777 0.003 7.288 0.003 603.3 0.472 4.068 20.50

9.80

9.75
y = 0.35x + 9.41
2
9.70 R = 0.99

9.65
a /Å

9.60

9.55

9.50

9.45

9.40
0.0 0.2 0.4 0.6 0.8 1. 0
Fraction Sr

Fig. 2. Variation in lattice parameter, a, for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00; error bars: +2r from Table 3.
 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464 1459

7.30

7.25 y = 0.42x + 6.86

2
R = 0.99
7.20

7.15

7.10
c /Å

7.05

7.00

6.95

6.90

6.85
0.0 0.2 0.4 0.6 0.8 1.0
Fraction Sr

Fig. 3. Variation in lattice parameter, c, for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00; error bars: ±2r from Table 3.

610
y = 75.25x + 525.88
600 2
R = 1.00
590

580

570
V / Å3

560

550

540

530

520
0.0 0.2 0.4 0.6 0.8 1.0
Fraction Sr

Fig. 4. Variation in unit cell volume for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00; error bars: ±2r from Table 3.

4.2

y = 0.93x + 3.18
4.0 2
R = 0.99

3.8
-3
ρ / g.cm

3.6

3.4

3.2

3.0
0.0 0.2 0.4 0.6 0.8 1.0
Fraction Sr
Rietveld Literature

Fig. 5. Variation in density for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00; error bars ±1%.
1460 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464

22
2
y = 37.73x - 34.74x + 17.57
20 2
R = 1.00
18

16
d / nm

14

12

10

8
0.0 0.2 0.4 0.6 0.8 1.0
x

Fig. 6. Variation in crystallite size from XRD Lorentzian peak widths for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00.

Table 4 1.00
Occupancies of M(I) and M(II) sites from Rietveld refinement
Site x (Sr)
Occupancy - Rietveld

0.00 0.25 0.50 0.75 1.00 0.75

Ca(I) 1.00 0.81 0.52 0.31 0.00
Sr(I) 0.00 0.19 0.48 0.69 1.00
Ca(II) 1.00 0.75 0.45 0.20 0.00 0.50
Sr(II) 0.00 0.25 0.55 0.80 1.00
Mean Sr 0.00 0.22 0.52 0.74 1.00
0.25

broadens the crystal size distribution, which contributes

0.00
to the improved mechanical strength of bone [17]. When
0.00 0.25 0.50 0.75 1.00
x = 0.5, the Sr–Ca apatite will be at its most disordered;
therefore it would be expected that the crystallite size ap- Sr content (x ) - stoichiometry
proaches a minimum.
Ca(I) Sr(I) Ca(II) Sr(II)
The Rietveld refinement gave a good fit with a slight
preference for strontium occupancy on the Ca(II) site, as 1.00
observed by Bigi et al. [8]. There is a 6 to 12% preference y = 1.01x - 0.01
of Sr for the M(II) site, with increasing preference as the 2
R = 1.00
Sr content (x ) - Rietveld

Sr content increases. The occupancies of the sites can be 0.75

seen in Table 4 and is plotted graphically in Fig. 7a, and
the correlation to the stoichiometric compositions agrees
well, as seen in Fig. 7b. 0.50

3.2. Raman spectroscopy

0.25
Figs. 8–10 show the Raman spectra of the apatites syn-
thesized in this study, normalized to the v1 PO3 4 band at
around 955 cm1 and shifted on the y-axis for presentation
0.00
purposes. It can be seen from the Raman spectra in Fig. 8
0.00 0.25 0.50 0.75 1.00
that there is a general shift to a lower wave number of
Raman bands with Sr-addition (see Table 5). The main Sr content (x ) - stoichiometry
Raman band at around 955 cm1 due to the v1 PO3 4 vibra- Fig. 7. (a) Occupancies of M(I) and M(II) sites and (b) mean Sr
tion decreases linearly with Sr-addition (see Figs. 8, 10 and compositions from occupancies.
 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464 1461

11). As the frequency of a Raman band is dependent on and the strength of the forces between the atoms/ions
lattice vibrations, the masses of the atoms/ions present define the position of the vibration. The frequency of the

Wavelength / nm
810 820 830 840 850 860
3
Normalised intensity (a.u.)

x=1.00
2

x=0.75

x=0.50
1

x=0.25

x=0.00

0
400 600 800 1000 1200
-1
Raman shift / cm

Fig. 8. Raman spectra for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00, with 782 nm excitation.

Wavelength / nm
812 814 816 818 820 822 824 826
0.40

0.35

x=1.00
Normalised intensity (a.u.)

0.30

x=0.75
0.25

x=0.50
0.20

0.15
x=0.25

0.10
x=0.00

0.05
400 450 500 550 600 650
-1
Raman shift / cm

Fig. 9. Raman spectra forth series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00, with 782 nm excitation (400–650 cm1 region).
1462 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464

Wavelength / nm
845 850 855 860
2.5

2.0
Normalised intensity (a.u.)

x=1.00

1.5

x=0.75

x=0.50
1.0

x=0.25
0.5

x=0.00

0.0
900 950 1000 1050 1100 1150
-1
Raman shift / cm

Fig. 10. Raman spectra for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00, with 782 nm excitation (900–1150 cm1 region).

Table 5
Raman band positions (in cm1) for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00
x v2 PO3
4 v4 PO3
4 P–O–P v1 PO3
4 v3 PO3
4 O–P–O
0.00 430, 446 580, 592, 609 – 963 1031, 1048, 1070 –
0.25 426, 447 579, 589, 606 – 958 1022, 1048, 1069 –
0.50 424, 443 582, 601 – 956 1034, 1051, 1064 –
0.75 425, 442 576, 585, 599 – 952 1027, 1044, 1065 –
1.00 422, 442 573, 581, 595 714, 738 949 1023, 1051, 1058 1051, 1058

965
y = -13.16x + 961.98
2
Position of PO4 v1 band / cm-1

R = 0.99
960

955

950

945
0.0 0.2 0.4 0.6 0.8 1.0
x
Fig. 11. Change in the v1 PO3
4 Raman band position for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75 and 1.00.
 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464
18
16
FWHM of PO4 v1 band / cm-1
14
12
10
6
8 10
Fig. 12. Change in the FWHM of v1 PO3
4 Raman band plotted against crystallite size for the series (SrxCa1x)5(PO4)3OH, where x = 0.00, 0.25, 0.50, 0.75
and 1.00.
vibration, f, can be described classically by a harmonically
oscillating ball and spring model, shown in Eq. (2), known
as the Szigeti relationship [18]
sffiffiffi
1 k
f ¼ ð2Þ
c l
where c is the velocity of light in a vacuum
(2.998108 m s1), k is the bond force constant (typically
in N m1) and l is the reduced mass of the two bonding
atoms (equal to m1m2/(m1 + m2)). As the bond strengths
of Ca–O and Sr–O are similar (bond enthalpies of 402.1
and 425.5 kJ mol1, respectively [19]), k would be expected
to be similar for both bonds. Therefore, as Sr is substituted
for Ca, l will increase, shifting f, and hence the Raman
shift to lower values as PO34 is associated with the heavier
Sr cation. In practice, this shift could be used to determine
the change in Sr in apatite compositions in future in vivo
and in vitro studies, in implant materials for example.
The following bands can be seen in all samples (Figs. 8–
10) and are tabulated in Table 5 [20]: two bands at around
430 cm1, attributed to v2 PO3 4 ; three bands around
590 cm1, attributed to v4 PO3 4 (except the x = 0.50 sam-
ple, where only two bands could be resolved); one band
at around 955 cm1, attributed to v1 PO3 4 ; and three bands
around 1050 cm1, attributed to v3 PO3 4 . In addition, two
bands were seen at around 725 cm1 for the pure Sr-
hydroxyapatite (x = 1.00). Unusually, for this sample the
intensity of the bands in the region of the normally weak
v3 PO34 vibrations were approximately half the strongest
v1 PO34 band. This spectral region contains the carbonate
vibration in apatite: 1100 cm1 for A-type carbonate
(OH) and 1070 cm1 for the more common B-type car-
bonate (PO3 4 ) [20]. However, these vibrations are weak
in biological apatites, which typically show carbonate con-
tents of between 2 (dental enamel) and 8% (dentine and
1463
y = -0.94x + 26.34
2
R = 0.90
12 14 16 18 20 22
d / nm
bone) relative to the v1 phosphate peak, and any carbonate
contamination from the reactants would be small. These
features could be due to a small amount strontium pyro-
phosphate impurity (Sr2P2O7), as Raman bands have been
previously reported in a series of phosphate glasses at
around 775 and 1070 cm1, identified as P–O–P and O–
P–O vibrations in P2 O4 7 dimmers, respectively [21], with
the latter band higher in intensity, as seen here. This impu-
rity is likely to be minor only, as one peak can be seen that
may correspond to this phase at 2h = 33.04° in Fig. 1 for
x = 1.00. This may be due to the 3 2 0 hkl reflection and
is the third most intense peak in Sr2P2O7 (space group
Pmna) [22]. The highest and second highest intensity peaks
are likely to be hidden in the strong apatite peaks.
Finally, the FWHM of the v1 PO3 band was plotted
4
against crystallite size from Table 3 and Fig. 6, and is
shown in Fig. 12. There is a good correlation between
crystal size and peak width, with linear broadening with
decreasing size, regardless of the composition. Again,
this could be used to estimate disorder in apatite
samples.
4. Conclusions
 A series of Sr-substituted hydroxyapatites were success-
fully synthesized by two routes under 90 °C with only
the fully substituted material containing a small impu-
rity, likely to be Sr2P2O7.
 Lattice parameters, unit cell volume and density
decreased linearly with strontium content, consistent
with addition of a larger, heavier ion.
 Crystallite size decreased with up to 25% substitution of
Sr then increased with higher content.
 There was a slight preference for Sr-occupancy of the
M(II) site (6 to 12%) in agreement with previous studies.
1464 M.D. O’Donnell et al. / Acta Biomaterialia 4 (2008) 1455–1464
 The v1 PO3 4 Raman vibration at around 963 cm1
decreased linearly with Sr-addition, indicating that this
could be used to accurately determine compositions of
solid-solution compounds.
 The FWHM of the v1 PO3 4 Raman band decreased lin-
early with crystallite size, which could also be used to
determine disorder in chemically dissimilar apatite
systems.
Acknowledgements
MDO would like to thank Dr. Molly Stevens, Dr. Gavin
Jell and Mr. Robin Swain at IC for use of the Raman
equipment and Dr. Stephen Skinner at IC for proofreading
the manuscript.
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