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The passive state of three commercial highly alloyed austenitic stainless steels is studied by voltammetric, contact electric resistance and impedance measurements in 0.5 M sulphate solutions (pH 2-7). The three materials self-passivate and are susceptible to transpassive dissolution. The electric properties of the passive films formed are only slightly dependent on alloy composition. The impedance response can be interpreted as due to both the electronic properties of a thin semiconductor film of variable stoichiometry and the ionic defect migration through that film limiting the metal dissolution rate in the passive state. A range of kinetic, transport and structural parameters characterising the passive film and its interfaces with the underlying alloys and the electrolyte solution are determined by a quantitative comparison of the Mixed-Conduction Model to the experimental steady-state current and impedance data in a wide potential range. The relevance of the parameter values and the prospects of using the proposed approach to predict the steady-state metal dissolution rate and thus the general corrosion behaviour of stainless steels are discussed

Conduction mechanism in passive films on austenitic stainless steels in sulphate solutions