Electrochemical impedance spectroscopy is used to monitor the long-term stability (up to 150 days) of mechanically polished commercial pure titanium, Ti6Al4V, Ti6Al7Nb, and CoCrMo alloys in 0.1M sodium sulfate and fetal bovine serum. A capacitive spectrum in the frequency range from 10(-3) to 10(5) Hz is always found and the impedance spectra can be fitted by a simple parallel RC circuit with a constant phase element. The open circuit potential observed in serum is always more cathodic and the polarization resistance (R(p)) is higher than that recorded in sodium sulfate solutions. The observed variation of the equivalent capacitance in serum bovine suggests that an adsorption layer of organic molecules develops on the electrode surface and it is responsible for both the decrease in open circuit potential and the higher R(p), because it hinders the oxygen evolution reaction and the charge transfer responsible for the passive film dissolution (or growth). Among the alloys studied, Ti6Al4V displayed the highest steady-state values of R(p) both in serum and in sodium sulfate.
The onset of pitting corrosion at MnS inclusions on 304 stainless steel in 1 M NaCl was studied with and without applied mechanical stress with use of microelectrochemical cells. Polarization curves of areas ͑100 m diam͒ without inclusion showed no pitting at potentials below that of oxidation evolution; stress had no effect on the corrosion behavior. Areas containing five round inclusions of about 4 m in size showed stable pitting at about 400 mV; the effect of stress shifted the pitting potential to values that were 150 mV more negative. Polarization curves measured on large deep MnS inclusions showed active pitting. Curves of areas with single large, shallow MnS inclusions showed multiple current transients during dissolution of the inclusion without stress, but the metastable events did not initiate stable pitting. The dissolution of shallow MnS inclusion did not form a deep microcrevice between the MnS and stainless steel matrix. However, under applied stress, cracks were formed within the shallow MnS inclusion and active pitting occurred. To explore whether such cracks might serve to generate locally high concentrations of aggressive species, the pH and chloride concentration inside a crack were simulated using a finite difference model. For experimental conditions where stable pitting was observed, the simulations predicted that the solution composition at the base of a typical 13 m deep crack correspond to a pH of around 2, and a chloride concentration of about 6 M led to stable pitting.
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