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Application of Transient Electrochemical Methods to Characterize Passive Oxide Layers

Duplex passive films electroformed on Co and Pb electrodes were studied by combined voltammetry and potentiostatic current transient techniques. The influence of anodizing time at different potentials as Well as effects due to surface layer thickness can be discussed on the basis of electroreduction reaction models. Both electroreduction processes fit in the secondary passivity range a two stage electrochemical mechanism associated with the bilayer structure of the passive films. The particular nature of each of the anionic species of the electrolyte towards the surface films leads to characteristic features in the current transients. Hence, ageing promotes modifications in the passive layers, which without changing the oxidation state present several structural configurations. The ageing processes appear as an apparent increasing irreversibility of the electroreduction reaction.