Structural characterization of pulsed laser-deposited hydroxyapatite film on titanium substrate.

Pure, crystalline hydroxyapatite (HA) films with thicknesses of roughly 10 microns have been deposited on titanium substrate using the pulsed laser deposition (PLD) technique. Experimental results indicate that the structure and properties of the PLD-HA films varied with deposition parameters. The PLD process used in the present study did not induce significant amounts of calcium phosphate phases other than apatite, or significant changes in the behaviour of hydroxyl or phosphate functional groups. Broad face scanning electron microscopy showed that HA coating was comprised of numerous essentially spheroidal-shaped particles of different sizes, while the lateral morphology indicated that columnar and dome-shaped structures both existed in the film. Many pinholes and crevices observed on coating surfaces were linked to the original substrate surface crevices/craters. The adhesion strength of the coating, mostly in the range of 30-40 MPa, was found to be closely related to the fractography of the tested specimen. The fracture surfaces of specimens with higher bond strengths were usually accompanied by a higher degree of deformation and coating-substrate debonding, while the fracture of specimens with lower bond strengths occurred more frequently within HA coatings in a more brittle manner. The energy dispersive spectroscopy-determined Ca/P ratios of raw HA powder (1.78) and sintered HA target for PLD (1.79) were very close, indicating that the sintering process used in the present study essentially did not change the Ca/P ratio of HA. After the PLD process, the Ca/P ratio of the HA film increased to 1.99. Cross-sectional scanning electron microscopy-energy dispersive spectroscopy point analysis indicated that the value of the Ca/P ratio was significantly higher in the region near the surface, particularly near the coating-substrate interface, than in the coating interior.