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11/16/2017 Pitting corrosion

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Pitting 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.

Suppose . . .that a small cavity exists in the surface of the metal into which oxygen cannot diffuse quickly. A
current will be produced between the unaerated area within the cavity, which will become anodic, and the
aerated part of the surface outside, which will be the cathode; soluble salt will be formed at the anodic surface
within the cavity, but this will not, of course, interfere with further anodic attack. At the mouth of the cavity
where the soluble metallic salt from the interior mixes with the alkali from the cathodic part outside, hydroxide
may be precipitated, but it will not put a stop to the anodic attack proceeding within. Since the rate of attack is
determined by the supply of oxygen to the whole surface outside the pit, and since it is all concentrated on the
small area within the pit, the rate at which the corrosion bores into the metal will be very great; . . . U.R. Evans,
1924

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11/16/2017 Pitting corrosion

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a semi-permeable
membrane of corrosion products. Pits can be either hemispherical or cup-shaped

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.

In the second case, post-examination should reveal the


local cathode, since it will remain impervious to the
corrosion attack as in the picture of an aluminum specimen
shown on the right. Most cases of pitting are believed to be
caused by local cathodic sites in an otherwise normal
surface.

Apart from the localized loss of thickness, corrosion pits can also be harmful by acting as stress risers. Fatigue
and stress corrosion cracking (SCC) may initiate at the base of corrosion pits.

One pit in a large system can be enough to produce the catastrophic failure of that system. An extreme example
of such catastrophic failure happened recently in Mexico, where a single pit in a gasoline line running over a
sewer line was enough to create great havoc to a city, killing 215 people in Guadalajara.

Example problem 6.4

Why would pitting corrosion be much more prone to provoke a catastrophic failure than uniform corrosion
generally does?

Some definitions

Pitting: corrosion of a metal surface, confined to a point or small area, that takes the form of cavities.

Pitting factor: ratio of the depth of the deepest pit resulting from corrosion divided by the average
penetration as calculated from weight loss.

Pitting resistance equivalent number (PREN): an empirical relationship to predict the pitting resistance
of austenitic and duplex stainless steels. It is expressed as PREN = Cr + 3.3 (Mo + 0.5 W) + 16N.

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Some examples

Pit depth measurement

Pitting corrosion causing leaks: pitted pot leaking water.

Sewer explosion due to corrosion: example of corrosion damages with shared responsibilities.

Corrosion pit shapes:pits with their mouth open or covered with corrosion products.

Pitting corrosion data:incidents of aircraft and helicopters.

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