Furthering the understanding of silicate-substitution in α-tricalcium phosphate: An X-ray diffraction, X-ray fluorescence and solid-state nuclear magnetic resonance study

• Published in: Acta biomaterialia 2014-03, Vol.10 (3), p.1443-1450
• Main Authors: Duncan, J., Hayakawa, S., Osaka, A., MacDonald, J.F., Hanna, J.V., Skakle, J.M.S., Gibson, I.R.
• Format: Article
• Language: English
• Subjects: 29Si; 31P; Bioceramics; Ca3(PO4)2; Calcium Phosphates - chemistry; Inclusions; Line broadening; Magnetic Resonance Spectroscopy; NMR spectroscopy; Phosphates; Rietveld; Silicates - chemistry; Silicon; Silicon - chemistry; Spectrometry, X-Ray Emission; X-Ray Diffraction; X-ray fluorescence; X-rays
• ISSN: 1742-7061; 1878-7568
• DOI: 10.1016/j.actbio.2013.11.014

High-purity (SupT) and reagent-grade (ST), stoichiometric and silicate-containing α-tricalcium phosphate (α-TCP: ST0/SupT0 and Si-TCP x=0.10: ST10/SupT10) were prepared by solid-state reaction based on the substitution mechanism Ca3(PO4)(2-x)(SiO4)x. Samples were determined to be phase pure by X-ray diffraction (XRD), and Rietveld analysis performed on the XRD data confirmed inclusion of Si in the α-TCP structure as determined by increases in unit cell parameters; particularly marked increases in the b-axis and β-angle were observed. X-ray fluorescence (XRF) confirmed the presence of expected levels of Si in Si-TCP compositions as well as significant levels of impurities (Mg, Al and Fe) present in all ST samples; SupT samples showed both expected levels of Si and a high degree of purity. Phosphorus (31P) magic-angle-spinning solid-state nuclear magnetic resonance (MAS NMR) measurements revealed that the high-purity reagents used in the synthesis of SupT0 can resolve the 12 expected peaks in the 31P spectrum of α-TCP compared to the low-purity ST0 that showed significant spectral line broadening; line broadening was also observed with the inclusion of Si which is indicative of induced structural disorder. Silicon (29Si) MAS NMR was also performed on both Si-TCP samples which revealed Q0 species of Si with additional Si Q1/Q2 species that may indicate a potential charge-balancing mechanism involving the inclusion of disilicate groups; additional Q4 Si species were also observed, but only for ST10. Heating and cooling rates were briefly investigated by 31P MAS NMR which showed no significant line broadening other than that associated with the emergence of β-TCP which was only realised with the reagent-grade sample ST0. This study provides an insight into the structural effects of Si-substitution in α-TCP and could provide a basis for understanding how substitution affects the physicochemical properties of the material.