Effect of Cr, Mo, and W Contents on the Semiconductive Properties of Passive Film of Ferritic Stainless Steels

This study investigated the influence of Cr, Mo, and W alloying elements incorporated into ferritic stainless steel on the characteristics of passive films formed under acidic chloride conditions. Electrochemical assessments demonstrated that increasing the amounts of Cr, Mo, and W reduces passive current density and enhances polarization resistance. Through XPS analysis, it was determined that the passive film exhibits a double-layer structure, consisting of an inner layer rich in metal oxides and an outer layer containing metal oxy-anions. Mott–Schottky analysis indicated the presence of both p-type and n-type semiconducting properties. To clarify the effect of these alloying elements on the passive films at the surface of stainless steel, this work introduces a new parameter termed the “Bipolar Index,” defined as |p-type slope| + |n-type slope|. With higher Cr, Mo, and W contents, the bipolar index increases, reflecting modifications in the semiconductive behavior. Consequently, the point defect concentration within the passive film decreases, causing a reduction in passive current density and a rise in polarization resistance.