Multiscale electrochemical analysis of the corrosion of titanium and nitinol for implant applications

•Direct screening of differences in the surface reactivity of the passive layers formed on pure titanium and nitinol.•Distinct effect of polarization on the passive layers.•Detection of nickel soluble species released from corrosion pits.

Surface electrochemical activity of titanium and nitinol biomaterials in naturally aerated Ringer’s physiological solution was investigated using potentiodynamic polarization and scanning electrochemical microscopy (SECM) techniques. SECM was operated in feedback and redox competition modes as a function of potential applied to the substrate. The kinetics of the electron transfer rate on both materials was characterized by mathematical modelling of the Z-approach curves monitored under feedback conditions. The rate constant values greatly depended on the characteristics of the passive layers formed over the metals under potentiostatic control. A more insulating film was found on nitinol when biased at low polarizations, resulting in smaller tip current increments during tip approach to the investigated surface under positive feedback and competition operation modes. However, at higher anodic polarizations, nitinol passive layers experience breakdown, and therefore tip current values reflect the release of metal cations from the biomaterial surface.

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