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.