The cathodic processes localized to iron rich intermetallic phases on commercial aluminum alloys during corrosion in neutral chloride environments are controlled by the structural and compositional changes occurring on these phases in a locally stable alkaline environment. These phenomena are investigated by conventional electrochemical techniques on synthetically grown Al
3Fe crystals. The surface of the crystals is enriched by metallic iron at E<-1.175 V
SCE as a result of selective aluminum dissolution. In the potential range -1.175<E<-0.72 V
SCE, the surface is essentially passive to oxidation resulting from the successive formation of an adsorbed FeOH and the bulk oxides Fe(OH)
2 and Fe
3O
4 with increasing potential. In the range -0.72<E<-0.66 V
SCE, a transpassive behavior is observed, characterized by the selective dissolution of aluminum and oxidation of enriched iron into an unprotective oxide, possibly FeOOH. At higher potentials, the surface passivates again by Fe
2O
3 formation. The significance of these results on aluminum alloy corrosion is discussed. In addition to their role as cathodes, it is argued that these compounds may be contributing directly to pit initiation and the determination of the pitting potential on aluminum alloys.
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