The effect of heating rate on the surface chemistry of NiTi.

The impact of the heating rate on the Ni content at the surface of the oxide layer of biomedical NiTi is explored. Heat treatment emulating common shape-setting procedures was performed by means of conventional and inductive heating for similar annealing time and temperature, applying various heating rates from ~0.25 K s(-1) to 250 K s(-1). A glow discharge optical emission spectroscopy method was established and employed to evaluate concentration profiles of Ni, Ti and O in the near-surface region at high resolution. The Ni content at the surface of the differently treated samples varies significantly, with maximum surface Ni concentrations of ~20 at.% at the lowest and ~1.5 at.% at the highest heating rate, i.e. the total amount of Ni contained in the surface region of the oxide layer decreases by >15 times. Consequently, the heating rate is a determinant for the biomedical characteristics of NiTi, especially since Ni available at the surface of the oxide layer may affect the hemocompatibility and be released promptly after surgical application of a respective implant. Furthermore, apparently contradictory results presented in the literature reporting surface Ni concentrations of ~3 at.% to >20 at.% after heat treatment are consistently explained considering the ascertained effect of the heating rate.

Effect of thermomechanical pre-treatment on short- and long-term Ni release from biomedical NiTi.

The effect of annealing and deformation on short-term (21days) and long-term (8months) Ni release from biomedical NiTi wires is studied. The deformation of annealed NiTi wires causes cracking and flaking of the surface oxide layer. Flaking of oxide particles does not uncover the Ni-rich layer underneath the surface oxide layer, since at sites where flaking occurs, a thin (∼25nm) layer of oxide remains on top of this Ni-rich layer. The number of cracks in the oxide and Ni-rich layer, respectively, increases with deformation, and intercrystalline crack propagation into the Ni-rich layer and the NiTi bulk is observed. In plastically deformed wires, the cracks may remain opened, providing access of immersion liquid to these zones. Characteristics and quantity of short-term Ni release are significantly affected by the pre-deformation, resulting in an up to 2 times higher total Ni release within the first 21days of deformed compared to annealed wires. Pre-deformation does not significantly influence long-term Ni release; all annealed and deformed samples exhibit similar long-term Ni release rates. The source of Ni during short-term release is the Ni contained in the surface zone of the oxide layer. For high pre-deformation, the Ni-rich layer is a second source for Ni. This second source is also the cause for Ni release in long-term immersion experiments.