Surface structure and properties of biomedical NiTi shape memory alloy after Fenton's oxidation

Fenton's oxidation is traditionally used to remove inorganic and organic pollutants from water in waster water treatment. It is an advanced oxidation process in which H2O2 is catalytically decomposed by ferrous irons into hydroxyl radicals (*OH) which have a higher oxidation potential (2.8V) than H2O2. In the work reported here, we for the first time use Fenton's oxidation to modify the surface of biomedical NiTi shape memory alloy (SMA). The influences of Fenton's oxidation on the surface microstructure, blood compatibility, leaching of harmful Ni ions and corrosion resistance in simulated body fluids is assessed using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma mass spectrometry, electrochemical tests, hemolysis analysis and the blood platelet adhesion test. The mechanical stability of the surface titania film produced by Fenton's oxidation as well as their effects on the shape memory behavior of the SMA are studied by bending tests. Our results show that Fenton's oxidation produces a novel nanostructured titania gel film with a graded structure on the NiTi substrate without an intermediate Ni-rich layer that is typical of high-temperature oxidation. Moreover, there is a clear Ni-free zone near the top surface of the titania film. The surface structural changes introduced by Fenton's oxidation improve the electrochemical corrosion resistance and mitigate Ni release. The latter effects are comparable to those observed after oxygen plasma immersion ion implantation reported previously and better than those of high-temperature oxidation. Aging in boiling water improves the crystallinity of the titania film and further reduces Ni leaching. Blood platelet adhesion is remarkably reduced after Fenton's oxidation, suggesting that the treated SMA has improved thrombo resistance. Enhancement of blood compatibility is believed to stem from the improved hemolysis resistance, the surface wettability and the intrinsic electrical characteristics of the titania film. The titania film produced by Fenton's oxidation has good mechanical stability and does not adversely impact the shape memory behavior of NiTi. Our work suggests that Fenton's oxidation is a promising low-temperature, low-cost surface modification method for improving the surface properties of biomedical NiTi SMA.