Titanium nitride has excellent corrosion and wear resistance properties, and has been used as a hard coating material on titanium hip prostheses. Analysis of explants reveals that calcium phosphate phases grow spontaneously and stick strongly on TiN-coated hip prosthesis heads, indicating a degree of bioactivity of the implant surface which is absent in standard uncoated titanium implants. We investigate the mechanism of TiN oxidation using spectroscopic and first principles molecular dynamics techniques. We find that the deposition of Ca2+ ions which is the first step of calcium phosphate nucleation is favoured by TiOxNy oxynitride surface phases. This is due to the presence of mixed-valence states of the surface Ti atoms which leads to localisation of negative charge on surface oxygens, promoting the adsorption of Ca2+ ions. These results indicate that nitridation and controlled oxidation of titanium implant surfaces can promote the in vivo formation of bone-like material.
