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Induction suspension plasma sprayed biological-like hydroxyapatite coatings

Substituted hydroxyapatite coatings with different ions (Mg, Na, K, Cl, F) have been developed by the induction suspension plasma spray process. Suspensions were prepared with sol–gel. The main objective of this study was to demonstrate that induction suspension plasma spray technology possesses high material composition flexibility that allows as-sprayed coatings to closely mimic natural bone composition. Long-term in vitro behaviour of as-sprayed substituted coatings was evaluated with simulated body fluid. Data on the suspensions showed the formation of a pure hydroxyapatite phase. Transmission electron microscopy characterized various preparation stages of the suspensions. As-sprayed samples were distinguished by X-ray diffraction and scanning electron microscopy. Substituted elements were quantified by neutron activation. A well-crystallized hydroxyapatite phase was produced with concentration in various substitutions very close to natural bone composition. Ca/P and (Ca + Mg + Na + K)/P ratios provided evidence of the introduction of different cations into apatite structures. The immersion of samples into simulated body fluid led to the nucleation and growth of a flake-like octacalcium phosphate crystal layer at the surface of as-sprayed coatings after one week. Proof of octacalcium phosphate transformation and its partial dissolution and direct re-precipitation into apatite was disclosed by local energy dispersive spectroscopy and microstructure observation. Formation of a Ca/P ratio gradient from the precipitated layer surface to the as-sprayed coatings interface was observed after four weeks once the octacalcium phosphate crystals reached a critical size, resulting in the formation of a rich apatite layer at the interface after six weeks. A set of mechanisms has been proposed to explain these findings.