Pitting corrosion

Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the creation of small holes in the metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading to very localised galvanic corrosion. The corrosion penetrates the mass of the metal, with a limited diffusion of ions. The mechanism of pitting corrosion is probably the same as crevice corrosion.

The more conventional explanation for pitting corrosion is that it is an autocatalytic process. Metal oxidation results in localised acidity that is maintained by the spatial separation of the cathodic and anodic half-reactions, which creates a potential gradient and electromigration of aggressive anions into the pit. For example, when a metal is present in an oxygenated NaCl electrolyte, the pit acts as anode and the metal surface acts as cathode. The localised production of positive metal ions in the pit gives a local excess of positive charge which attracts the negative chlorine ions from the electrolyte to produce charge neutrality. The pit contains a high concentration of MCl molecules which react with water to produce HCl, the metal hydroxide, and H+ ions, accelerating the corrosion process.In the pit, the oxygen concentration is essentially zero and all of the cathodic oxygen reactions take place on the metal surface outside the pit. The pit is anodic and the locus of rapid dissolution of the metal. The metal corrosion initiation is autocatalytic in nature however it's propagation isn't.

This kind of corrosion is extremely insidious, as it causes little loss of material with the small effect on its surface, while it damages the deep structures of the metal. The pits on the surface are often obscured by corrosion products.

Pitting can be initiated by a small surface defect, being a scratch or a local change in composition, or a damage to the protective coating. Polished surfaces display higher resistance to pitting.

Pitting Corrosion is defined by localised attack (microns - millimetres in diameter) in an otherwise passive surface and only occurs for specific alloy / environment combinations. Thus, this type of corrosion typically occurs in alloys that are protected by a tenacious (passivating) oxide film such as stainless steels, nickel alloys, aluminium alloys in environments that contain an aggressive species such as chlorides (Cl-). In contrast, alloy / environment combinations where the passive film is not very protective usually will not produce pitting corrosion. A good example of the importance of environment / alloy combinations is carbon steel. In environments where the pH is less than 10, carbon steel does not form a passivating oxide film and the addition of chloride results in uniform attack over the entire surface. However, at pH greater than 10 the oxide is very protecting and the addition of chloride results in pitting corrosion.

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