Electrochemical behavior of surface films formed on Fe in chromate solutions

Abstract The stability of passive films formed on Fe in K 2 Cr 2 O 7 solutions during exposure at open-circuit potential or by potential cycling is studied in a chromate-free solution. The electrochemical behavior of chromate-passivated Fe is investigated with cyclic voltammetry combined with LASER light reflectance measurements which allow an in situ determination of the thickness of the iron oxide film. The electrochemical behavior of chromate-passivated Fe in chromate-free solutions strongly depends on passivation treatment. Passivation of iron by immersion at open-circuit in chromate solution leads to a passive film, in which both Fe and Cr species dissolve almost independently of the presence of the other one: Fe oxide by reductive dissolution and Cr oxide by oxidative dissolution in the corresponding potential regions. Passivation of iron by potential cycling in chromate solutions leads to much less loss of the otherwise soluble oxidized chromate and reduced ferrous species in subsequent electrochemical experiments (trapping in a protective film). Concerning the dissolution behavior, the film formed on iron by cycling in chromate solution behaves similarly as the passive film on Fe–17Cr alloy. However, the remnant passive film after reductive or oxidative dissolution on the Fe–Cr alloy is of truely protective nature as compared to the films formed on iron in chromate solutions, which show only a small contribution to the potential drop.