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RMC_AMC IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1082 (2018) 012025 doi:10.1088/1742-6596/1082/1/012025

XRD Analysis of Calcined Magnesium Substituted Biphasic

Calcium Phosphate (Mg-BCP)

N. A. Moslim1, N. Ahmad1 and S. R. Kasim1*

1
Biomaterials Niche Area, School of Materials and Mineral Resources Engineering,
Universiti Sains Malaysia, Penang, Malaysia.
*
[email protected]

Abstract. The incorporation of magnesium (Mg) in biphasic calcium phosphate (BCP) was
prepared through precipitation method. The concentration of added Mg was varied with respect
to calcium (Ca) precursor molarity as such Mg/Ca molar ratio were 0.05 and 0.1, while the
(Ca+Mg)/P ratio was maintained at 1.59 throughout the experiment to ensure that calcium
deficient apatite was formed. Precipitate obtained was aged for 24 h in ambient condition
followed by decantation, centrifugation and drying at 90°C overnight. The as-synthesized
powders were calcined at 600°C and characterized by X-ray diffraction (XRD) via Rietveld
refinement (X’Pert HighScore Plus software). Both as-synthesized and calcined Mg-BCP
powder contains hydroxyapatite (HA) and beta-tricalcium phosphate (β-TCP) phase with Mg
in its lattice. The substitution of Mg in calcium-deficient apatite resulted in the formation of
biphasic mixtures of β-TCP/HA after calcinations with shifted peaks β-TCP when compared to
reference β-TCP peaks. High deficiency of calcium in apatite enables more substitution of
magnesium thus stabilizing β-TCP phase when subjected to high temperature.

1. Introduction
For the past few decades, calcium phosphate-based bioceramics are materials of choice for bone tissue
engineering applications because of their composition similarity with bone mineral; which are
excellent bioactivity and osteoconductivity [1]. One of the most common calcium phosphate used in
biological applications is biphasic calcium phosphate (BCP) which contain the hydroxyapatite
(Ca10(PO4)6(OH)2, HA) and beta-tricalcium phosphate (Ca3(PO4)2, β-TCP) phases. Mixture of these
two phases ensures that BCP would have ideal biodegradability and biocompatibility compared to the
applications of HA or β-TCP alone in bone healing process. Lack of magnesium (Mg) in bone may
cause patient to suffer from osteoporosis disease [2] . Doping of calcium phosphate with required
amount of Mg gives improvement on mechanical and biological properties of BCP. Due to the smaller
size of Mg compared to calcium (Ca), it easily enter Ca lattice and controls the crystallization of HA,
affecting the stability of apatite [3]. The synthesis of Mg doped calcium apatites can be achieved
through different preparation route as such sol-gel, hydrothermal or precipitation method [4–5].
Current trend of studies focusing on the structural analysis of Mg doped BCP have been discussed
via X-ray powder diffraction (XRD) in parallel with Rietveld refinement. So, in this study, we focused
on the preparation of Mg substituted BCP through precipitation method as well as to investigate the
effect of Mg substitution on XRD peaks. The amount of Mg required for BCP doping usually in
between 1-3 wt% of total BCP wt%. Only a few papers have reported and studied magnesium doped
BCP obtained via this method.
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RMC_AMC IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1082 (2018) 012025 doi:10.1088/1742-6596/1082/1/012025

2. Experimental

2.1 Powder Preparation

The sources for calcium (Ca), phosphorus (P) and, magnesium (Mg) precursors are calcium nitrate
tetrahydrate (Ca(NO3)2.4H2O, Merck), diammonium hydrogen phosphate ((NH4)2HPO4, Merck) and
magnesium nitrate hexahydrate (Mg(NO3)2.6H2O, Merck) respectively. Pure biphasic calcium
phosphate (pure BCP) and Mg substituted BCP (Mg-BCP) samples were synthesized through
precipitation method. To prepare pure BCP powder, an appropriate amount of Ca(NO3)2.4H2O was
dissolved in water and stirred at the rate of 1000 rpm. (NH4)2HPO4 solution was slowly added into the
mixture through titration process in a fixed molar ratio (Ca+Mg)/P of 1.59 [6]. The pH of the mixture
was controlled between 10-11 with the addition of 25% ammonia solution (NH4OH). The precipitated
suspension was allowed to age to maturity for 24 h at room conditions. After aging, precipitates were
decanted and undergo centrifugation followed by drying at 90°C overnight. The dried cakes were
ground to fine powders using agate mortar and calcined at kept at 600°C in air for 2 h with heating rate
of 5°C/min.
To prepare Mg-BCP powders, same preparing approach of pure BCP was implemented with the
subsequent addition of Mg(NO3)2.6H2O whilst stirring. The Mg/Ca molar ratio was varied between
0.05 and 0.1 (coded M-MgBCP1.59 and H-MgBCP1.59 respectively). (NH4)2HPO4 solution was
added into mixture by titration with the same molar ratio of (Ca+Mg)/P as mentioned above. 25%
ammonia solution (NH4OH) was added to control pH at 10-11. Precipitated product was aged for 24 h
at room conditions, decanted, centrifugated and dried at 90°C overnight. The dried cakes were ground
to fine powders and kept for calcinations. All of the as-synthesized and calcined samples were
submitted for characterizations.

2.2 Characterization

The phase formation of the as-synthesized and calcined sample was characterized using X-ray
diffraction (XRD) with Rietveld refinement. X-ray diffraction spectra of the Mg doped BCP powders
were analysed over 2θ range of 10-70°C, copper Kα radiation (λ=1.5418Å), with a step scan of
2°/min. The accelerating voltage and current were 40kV and 30mA respectively. Crystallographic
identification of the synthesized phases was accomplished by comparing the experimental XRD
patterns to International Centre for Diffraction Data (ICDD); #98-010-2187 for hydroxyapatite (HA),
#98-000-5558 for monetite, and #98-000-0800, beta-tricalcium phosphate (β-TCP).

3. Results and discussion

3.1 As-synthesized powders

The XRD patterns for the as-synthesized powders are presented in Fig. 1 and Fig. 2. Both pure
biphasic calcium phosphate (BCP) and magnesium (Mg) substituted BCP powders indicated the
presence of HA except for the difference in phases and peak intensities. As can be seen in Fig.1, the
phase with highest intensity in pure BCP powder were monetite. This phase normally exists
predominantly before HA formation due to its high phase stability under acidic condition compared to
HA [7]. This condition being monitored through pH value (pH less than 5). Mg substitution is
characterized by the broad diffraction patterns which indicate the formation of calcium deficient HA;
which can be observed in Fig. 2. A little amount β-TCP phase can be found in the as-synthesized Mg
substituted BCP powders. Various study report that the diffraction pattern usually resembles that of
HA although the Ca/P molar ratio was not fixed at 1.67 [8].

2
RMC_AMC IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1082 (2018) 012025 doi:10.1088/1742-6596/1082/1/012025

Figure 1. XRD patterns of as-synthesized pure BCP powders

Figure 2. XRD patterns of as-synthesized BCP powders with different Mg concentrations

3.2 Calcined powders and formation of biphasic phases

Calcinations of the powders at 600°C as shown in Fig. 3 indicated the improvement in crystallinity by
the resolution of peaks when compared to the as-synthesized powders in Fig. 2. These peaks assigned
to the β-TCP phase are viewed by the difference in intensities which related to the level of calcium

3
RMC_AMC IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1082 (2018) 012025 doi:10.1088/1742-6596/1082/1/012025

deficiencies. Higher amount of β-TCP phase formed denotes the higher deficiencies of calcium in
powders [9]. Considering the substitution of Mg inside BCP lattice, there is slight shift in 2θ and d-
spacing in (0 2 1 0) plane of the highest intensity (refer Table 1). The 2θ for both Mg doped BCP
samples were higher than pure BCP sample with 31.2573° and 31.2591° for H-MgBCP and M-
MgBCP samples respectively; and 30.6063° for pure BCP sample. This shift is mainly caused by
stabilization effect of Mg when this ion (ionic radius ~0.65Å) being introduced into Ca ion (ionic
radius ~0.99Å) sites; thus resulted in peak displacement toward higher 2θ angles of β-TCP peaks.
However, there is no exact match found for the powders peaks with those β-TCP peaks. [5]. As for the
d-spacing of these three samples, pure BCP sample happen to have bigger d-spacing with 2.9186Å
compared to Mg doped BCP samples with 2.8591Å and 2.8593Å. It suppose that Mg substitute the Ca
sites in BCP lattice. While Mg ion have slightly smaller size than Ca ion, the substitution would
trigger lattice stresses which later causes an increase in d-spacing of Mg doped samples [10].

Ca10-x(Mg2P2O7)x/2(PO2)6-x(OH)2-x + x/2H2O (1-x)Ca10(PO4)6(OH)2 + 3x(CaMg2x/9)3(PO4)2

+ xH2O (Eqn. 1)

The above Eqn. 1 explains that the higher substitution of Mg in Ca sites is in parallel with the
transition of HA to β-TCP phase. Higher content of Mg causes HA phase to convert into β-TCP phase.
These cause high amount of β-TCP produce in heat treated Mg substituted BCP powder when
compared to heat treated pure BCP. It is correlated to the high amount of β-TCP formed in Mg
substituted powder compared to pure BCP powder as observed in Table 1. Small difference in the
values tabulated in Table 1 probably effect of different Mg concentrations substituted into β-TCP
phase. Quantitative determinations of the β-TCP/HA phase ratios of calcined pure BCP, M-
MgBCP1.59 and H-MgBCP1.59 powders were found to be 90.5/9.5, 99.2/0.8 and 98.7/1.3
respectively in phase compositional percentage obtained via Rietveld refinement.

Figure 3. XRD patterns of pure BCP and magnesium substituted BCP powders after calcined at 600°C

4
RMC_AMC IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1082 (2018) 012025 doi:10.1088/1742-6596/1082/1/012025

Table 1 Comparison of diffraction angle (2θ) and d-spacing values in XRD patterns of calcined samples

Sample 0 2 1 0 plane

2θ (°) d-spacing (Å)

Pure BCP 30.6063 2.9186
M-MgBCP1.59 31.2591 2.8591
H-MgBCP1.59 31.2573 2.8593

4. Conclusion

Mg substituted BCP with varying Mg content has been successfully synthesized through wet
precipitation method. After calcinations at 600°C, most of HA phase has been converted into ß-TCP
denotes the formation of biphasic mixtures. The addition of Mg in BCP structure causes lattice
contraction which can be observed from the larger 2θ of Mg doped BCP samples with 31.2591° and
31.2573° compared to the 2θ of pure BCP sample with 30.6063°. The effect of lattice contraction
which causes stresses in lattice was proved from the smaller d-spacing of Mg doped samples with
2.8591Å and 2.8593Å than pure BCP sample with 2.8592Å. The stresses is a result of the substitution
of Mg with smaller ionic size into the Ca sites with larger ionic size.

Acknowledgements

The authors are grateful to the Fundamental Research Grant Scheme (FRGS) from Ministry of
Education (MOE) for the financial support from the grant FRGS/203.PBAHAN.6071354.

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