Atomic emission spectroelectrochemistry applied to dealloying phenomena II. Selective dissolution of iron and chromium during active-passive cycles of an austenitic stainless steel

Atomic emission spectroelectrochemistry was used to investigate selective dissolution of a 304 austenitic stainless steel sample in 2 M H₂SO₄. The partial dissolution rates of Fe, Cr, Ni, Mn, Mo, and Cu were measured as function of time during a series of potentiostatic triggered activation/passivation cycles. When first exposed to sulfuric acid solution, the steel sample was in a passive state with a total steady state ionic dissolution rate expressed as an equivalent current density of 10 μA cm⁻². A transition into the active and passive state could be triggered by cathodic (−700 mV vs. Ag/AgCl) and anodic (+400 to +700 mV vs. Ag/AgCl) potentiostatic pulses respectively of variable time. Excess Cr dissolution was observed during the activation cycle as compared to Fe and a depletion of Cr dissolution was observed during the passivation cycle. These results are interpreted in terms of the dissolution of a Cr rich passive layer during activation and selective dissolution of Fe, Mn, Ni and other elements to form a Cr rich passive layer during passivation. Quantitative analysis of the excess Cr showed that the residual film contained approximately 0.38 μg Cr/cm². Fe does not appear to be incorporated into the film at this early stage of passive film growth. Residual films of metallic nickel and copper were formed on the surface during the active period that subsequently dissolved during passivation.