Influence of Si substitution on the reactivity of α-tricalcium phosphate.

Silicon substituted calcium phosphates have been widely studied over the last ten years due to their enhanced osteogenic properties. Notwithstanding, the role of silicon on α-TCP reactivity is not clear yet. Therefore, the aim of this work was to evaluate the reactivity and the properties of Si-α-TCP in comparison to α-TCP. Precursor powders have similar properties regarding purity, particle size distribution and specific surface area, which allowed a better comparison of the Si effects on their reactivity and cements properties. Both Si-α-TCP and α-TCP hydrolyzed to a calcium-deficient hydroxyapatite when mixed with water but their conversion rates were different. Si-α-TCP exhibited a slower setting rate than α-TCP, i.e. kSSA for Si-TCP (0.021g·m-2·h-1) was almost four times lower than for α-TCP (0.072g·m-2·h-1). On the other hand, the compressive strength of the CPC resulting from fully reacted Si-α-TCP was significantly higher (12.80±0.38MPa) than that of α-TCP (11.44±0.54MPa), due to the smaller size of the entangled precipitated apatite crystals.

Chitosan/apatite composite beads prepared by in situ generation of apatite or Si-apatite nanocrystals.

The objective of this work was to develop nanocrystalline apatite (Ap) dispersed in a chitosan (CHI) matrix as a material for applications in bone tissue engineering. CHI/Ap composites of different weight ratios (20/80, 50/50 and 80/20) and with CHI of different molecular weights were prepared by a biomimetic stepwise route. Firstly, CaHPO(4).2H(2)O (DCPD) crystals were precipitated from Ca(CH(3)COO)(2) and NaHPO(4) in the bulk CHI solution, followed by the formation of CHI/DCPD beads by coacervation. The beads were treated with Na(3)PO(4)/Na(5)P(3)O(10) solution (pH 12-13) to crosslink the CHI and to hydrolyse the DCPD to nanocrystalline Ap. This new experimental procedure ensured that complete conversion of DCPD into sodium-substituted apatite was achieved without appreciable increases in its crystallinity and particle size. In addition, composites with silicon-doped Ap were prepared by substituting Na(3)PO(4) by Na(2)SiO(3) in the crosslinking/hydrolysis step. Characterization of the resultant composites by scanning electron microscopy, X-ray powder diffraction (XRD), thermal analysis and Fourier transform infrared spectroscopy confirmed the formation, within the CHI matrix, of nanoparticles of sodium- and carbonate-substituted hydroxyapatite [Ca(10-x)Na(x)(PO(4))(6-x)(CO(3))(x)(OH)(2)] with diameters less than 20nm. Relatively good correspondence was shown between the experimentally determined inorganic content and that expected theoretically. Structural data obtained from its XRD patterns revealed a decrease in both crystal domain size and cell parameters of Ap formed in situ with increasing CHI content. It was found that the molecular weight of CHI and silicate doping both affected the nucleation and growth of apatite nanocrystallites. These effects are discussed in detail.