Plasma-sprayed hydroxyapatite+titania composite bond coat for hydroxyapatite coating on titanium substrate
A two-layer hydroxyapatite (HA)/HA+TiO2 bond coat composite coating (HTH coating) on titanium was fabricated by plasma spraying. The HA+TiO2 bond coat (HTBC) consists of 50 vol% HA and 50 vol% TiO2 (HT). The microstructural characterization of the HTH coatings before and after heat treatment was conducted by using scanning electron microscopy (SEM), electron probe microanalyser (EPMA), X-ray diffractometer (XRD) and transmission electron microscopy (TEM), in comparison with that of HT coating and pure HA coating. The results revealed that HA and TiO2 phases layered in an alternating pattern within the HTBC, and the HTBC bonded well to HA top coating (HAT coating) and Ti substrate. The as-sprayed HT coating consists mainly of crystalline HA, rutile TiO2 and amorphous Ca–P phase. The post-spray heat treatment at 650°C for 120 min effectively restores the structural integrity of HA by transforming non-HA phases into HA. It was found that there exists interdiffusion of the elements within the HTBC, but no chemical product between HA and TiO2, such as CaTiO3 was formed. The cross-sectional morphologies confirmed that there is a shift towards a relatively tighter bonding from the HAT coating/HTBC interface in the as-sprayed HTH coating to the HTBC/Ti substrate interface in the heat-treated HTH coating. On quenching the coatings into water, the surface cracking indicates more apparently the positive effect of the HTBC on the decrease of residual stress in HAT coating. The in situ surface cracking also suggests that the stress on the surface of the HTH coating is stable under subjection to a repetitious heat treatment. The toughening and strengthening of HTBC is thought to be mainly due to TiO2 as obstacles embarrassing cracking, the reduction of the near-tip stresses resulting from stress-induced microcracking and the decrease of CTE mismatch. In the HTH composite coating, the HAT coating is toughened by the decreased CTE mismatch with Ti through the addition of HTBC, which bonds well to the Ti substrate via its TiO2 hobnobbing with the Ti oxides formed on Ti substrate.
Journal: Biomaterials - Volume 25, Issue 18, August 2004, Pages 4393–4403