Atomic emission spectroelectrochemistry applied to dealloying phenomena: I. The formation and dissolution of residual copper films on stainless steel

The rates of elemental dissolution were measured for a 304 stainless steel containing 0.19% Cu in real time during linear sweep voltammetry experiments using the atomic emission spectroelectrochemistry (AESEC) method. The results demonstrate that Fe, Cr, Ni, Mn, and Mo dissolve simultaneously leaving a residual copper film that inhibits the steel dissolution. The formation and dissolution of the copper film leads to the appearance of two peaks in the anodic dissolution transient, one due to inhibition of steel by residual copper and the other due to the formation of the passive film. The addition of NaCl to the electrolyte results in a marked increase in the intensity of the second dissolution peak, while hardly affecting the first peak. This is interpreted in terms of the lowering of copper dissolution potential by chloride ions due to the stabilization of CuCl₂⁻. A simple phenomenological kinetic model is used to simulate the variation of dissolution rate with potential.