The passivation behavior of high purity iron and 1018 carbon steel in anhydrous propylene carbonate (PC) containing 0.5 M LiClO4or 0.5 M LiAsF6was studied. The air-formed film on Fe was stable and protective over a wide applied potential range in perchlorate solutions. Scratch tests showed that both bare Fe and steel passivate in the anhydrous PC solutions of either electrolyte by chemisorption of PC molecules below the oxidation potential of PC (PCox). At higher potentials, bare Fe passivates in PC/LiClO4via the formation of a Fe(ClO4)2salt film. The air-formed film on carbon steel was protective up to the PCoxpotential in either electrolyte. Above PCox, deterioration of the air-formed film on steel was associated with sulfide surface inclusions. Pits initiated and grew at these inclusion sites. Scratch tests showed slower repassivation of the bare steel by the Fe(ClO4)2salt film than on iron. Sulfides impeded this repassivation. Above PCox, neither the iron or the steel are passive in PC/LiAsF6solutions. The higher solubility of the Fe(AsF6)2salt prevents precipitation of a protective salt film. © 1991.
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