Pitting Corrosion: Mechanism

For a defect-free "perfect" material, pitting corrosion is caused by the ENVIRONMENT (chemistry) that may contain aggressive chemical species such as chloride. Chloride is particularly damaging to the passive film (oxide) so pitting can initiate at oxide breaks.

The environment may also set up a differential aeration cell (a water droplet on the surface of a steel, for example) and pitting can initiate at the anodic site (centre of the water droplet).

For a homogeneous environment, pitting is caused by the MATERIAL that may contain inclusions (MnS is the major culprit for the initiation of pitting in steels) or defects. In most cases, both the environment and the material contribute to pit initiation.

The ENVIRONMENT (chemistry) and the MATERIAL (metallurgy) factors determine whether an existing pit can be repassivated or not. Sufficient aeration (supply of oxygen to the reaction site) may enhance the formation of oxide at the pitting site and thus repassivate or heal the damaged passive film (oxide) - the pit is repassivated and no pitting occurs. An existing pit can also be repassivated if the material contains sufficient amount of alloying elements such as Cr, Mo, Ti, W, N, etc.. These elements, particularly Mo, can significantly enhance the enrichment of Cr in the oxide and thus heals or repassivates the pit.

Source: http://www.corrosionclinic.com/types_of_corrosion/pitting_corrosion.htm