Passivity and pitting of carbon steel in chromate solutions

The passivity and pitting behavior of A516-70 carbon steel in chromate solutions were studied using electrochemical measurements. The anodic Tafel slopes in the active region show that carbon steel dissolution involves two mechanisms in this range: formation and further oxidation of a pre-passive film of Fe(OH)(2). The first current peak at - 0.228 V (Ag \ AgCl) in cyclic voltammograms is caused by the oxidation of the pre-passive film and the formation of a stable passive film of Cr3+ + Fe3+. The second peak at 0.612 V is ascribed to the oxidation of Cr3+ in passive film to Cr6+. The charge-transfer step at the electrode/solution interface controls the film formation and dissolution; the role of diffusion is negligible. Chromate ions play a prominent role in the formation of passive film, but hardly affect the stability of the passive state. More chromate ions in solution enhance the dissolution of Cr3+ at the second peak potential. Upon addition of chloride ions metastable pits are initiated, as indicated by a typical current transient: a quick current rise followed by a slow recovery. A maximum exists in the potential dependence of the pit initiation rate. Metastable pit growth is controlled by the ohmic potential drop mainly across the cover over the pits. Increasing potential is beneficial to the repassivation of metastable pits, as indicated by the decreasing average repassivation time. A pit stabilization criterion, the ratio of peak pit current to pit radius, must exceed 6 x 10(-2) A cm(-1) during pit growth to avoid repassivation in the present system. (C) 1999 Elsevier Science Ltd. All rights reserved.