Characteristics, apatite-forming ability and corrosion resistance of NiTi surface modified by AC anodization

NiTi samples were anodized in the non-sparking regime using AC voltage in a solution containing calcium and phosphate ions (solution Ca-P). The as-anodized samples were subsequently treated hydrothermally in water (sample A-W-NiTi) or in solution Ca-P (sample A-CaP-NiTi). Thin-film X-ray diffractometry (TF-XRD) analysis confirmed the existence of anatase in the hydrothermally treated samples, but not in the as-anodized sample, while hydroxyapatite (HA) was detected only in sample A-CaP-NiTi. Cross-sectional micrograph by scanning-electron microscopy (SEM) revealed that the thickness of the modified surface layer formed on sample A-CaP-NiTi was ∼200 nm. X-ray photoelectron spectroscopy (XPS) analysis showed that the Ni concentrations at the surface of sample A-W-NiTi and sample A-CaP-NiTi were in the order of 0.4 and 0.3 at.%, respectively, which were about an order of magnitude lower than that for bare NiTi. Both Ca and P were present in the surface layer on as-anodized NiTi and sample A-CaP-NiTi, but negligible on sample A-W-NiTi, as determined from XPS composition depth profiling. Immersion tests in a conventional simulated body fluid (SBF) of the Kokubo type to study apatite-forming ability showed that growth of apatite was induced on A-W-NiTi and much more abundantly on A-CaP-NiTi, but not on bare NiTi and as-anodized NiTi, suggesting that the presence of anatase and HA is favorable for apatite growth. The apatite-forming ability of the samples in the present study may be ranked in ascending order as: bare NiTi < As-anodized NiTi < A-W-NiTi < A-CaP-NiTi. Polarization tests in Hanks' solution recorded significant increase in corrosion resistance due to anodization and further increase was obtained via hydrothermal treatment. The present study thus shows that anodization followed by hydrothermal treatment is a simple method to form a potentially bioactive and at the same time corrosion resistant surface layer on NiTi.