Pitting corrosion

Pitting corrosion 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 localized galvanic corrosion. The corrosion penetrates the mass of the metal, with limited diffusion of ions. The mechanism of pitting corrosion is probably the same as crevice corrosion.

Pitting corrosion is a localized form of corrosion by which cavities or “holes” are produced in the material. Pitting is considered to be more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against. Corrosion products often cover the pits. A small, narrow pit with minimal overall metal loss can lead to the failure of an entire engineering system. Pitting corrosion, which, for example, is almost a common denominator of all types of localized corrosion attack, may assume different shapes. Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a semi-permeable membrane of corrosion products.

Passive metals, such as stainless steel, resist corrosive media and can perform well over long periods of time. However, if corrosion does occur, it forms at random in pits. Pitting is most likely to occur in the presence of chloride ions, combined with such depolarizers as oxygen or oxidizing salts. Methods that can be used to control pitting include maintaining clean surfaces, application of a protective coating, and use of inhibitors or cathodic protection for immersion service. Molybdenum additions to stainless steel (e.g. in 316 stainless) are intended to reduce pitting corrosion.
Pitting is initiated by:

a. Localized chemical or mechanical damage to the protective oxide film; water chemistry factors which can cause breakdown of a passive film are acidity, low dissolved oxygen concentrations (which tend to render a protective oxide film less stable) and high concentrations of chloride (as in seawater)

b. Localized damage to, or poor application of, a protective coating

c. The presence of non-uniformities in the metal structure of the component, e.g. nonmetallic inclusions.

Theoretically, a local cell that leads to the initiation of a pit can be caused by an abnormal anodic site surrounded by normal surface which acts as a cathode, or by the presence of an abnormal cathodic site surrounded by a normal surface in which a pit will have disappeared due to corrosion.

It is supposed by some that gravitation causes downward-oriented concentration gradient of the dissolved ions in the hole caused by the corrosion, as the concentrated solution is denser. This however is unlikely. The more conventional explanation is that the acidity inside the pit 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.

This kind of corrosion is extremely insidious, as it causes little loss of material with 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 protective coating. Polished surfaces display higher resistance to pitting.

A single pit in a critical point can cause a great deal of damage. One example is the explosion in Guadalajara, Mexico on April 22, 1992, when gasoline fumes accumulated in sewers destroyed kilometers of streets. The vapors originated from a leak of gasoline through a single hole formed by corrosion between a steel gasoline pipe and a zinc-plated water pipe. Firearms can also suffer from pitting, most notably in the bore of the barrel when corrosive ammunition is used and the barrel is not cleaned soon afterward. Deformities in the bore caused by pitting can greatly reduce the firearms accuracy. To prevent pitting in firearm bores, most modern firearms have a bore lined with chromium.