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Pitting Corrosion: Mechanism

Pitting corrosion is a localized form of corrosion that leads to small holes or pits in metals. It occurs for specific alloy and environment combinations where the alloy forms a protective oxide film. Chloride ions are a common cause of pitting corrosion as they can penetrate this film and cause localized breakdown. Pits grow inward in a limited area while the surrounding metal remains intact. A single pit can cause significant damage, such as compromising the integrity of pipelines or structural components.

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95 views4 pages

Pitting Corrosion: Mechanism

Pitting corrosion is a localized form of corrosion that leads to small holes or pits in metals. It occurs for specific alloy and environment combinations where the alloy forms a protective oxide film. Chloride ions are a common cause of pitting corrosion as they can penetrate this film and cause localized breakdown. Pits grow inward in a limited area while the surrounding metal remains intact. A single pit can cause significant damage, such as compromising the integrity of pipelines or structural components.

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Carlos Bustamante
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© © All Rights Reserved
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Pitting corrosion

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Severe pitting corrosion problems caused by chloride ions on a truss beam of the Nandu River Iron
Bridge (Hainan Province, China) leading to the complete rupture of a metallic element.
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 (oxidation reaction) while an
unknown but potentially vast area becomes cathodic (reduction reaction), leading very
localized galvanic corrosion. The corrosion penetrates the mass of the metal, with a limited
diffusion of ions.
Another term arises, pitting factor, which is defined as the ratio of the depth of the deepest pit
(resulting due to corrosion) to the average penetration, which can be calculated based on the
weight loss.

Contents

 1Mechanism
 2Susceptible alloys and environment combinations
 3Engineering failures due to pitting corrosion
 4See also
 5References
 6External links

Mechanism[edit]
Diagram showing a mechanism of localized corrosion developing on metal in a solution containing
oxygen
The more conventional explanation for pitting corrosion is that it is an autocatalytic process.
Metal oxidation results in localized 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.[1] For example, when a metal is present in an oxygenated
sodium-chloride electrolyte, the pit acts as anode and the metal surface acts as cathode. The
localized 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 metal (Me) chloride (MeCl n) which hydrolyzes with water to
produce the corresponding metal hydroxide (Me(OH) n), and n H+ and n Cl– ions, accelerating
the corrosion process.[2] 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.[3] The metal corrosion initiation is autocatalytic in
nature however its propagation is not.
This kind of corrosion is often difficult to detect and so 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 the alloy composition (or local
impurities, e.g. metallic sulfide inclusions such as MnS or NiS), or a damage to the protective
coating. Polished surfaces display a higher resistance to pitting. [citation needed]

Susceptible alloys and environment combinations[edit]


Pitting corrosion is defined by localized attack, ranging from microns to millimeters in diameter,
in an otherwise passive surface and only occurs for specific alloy and environmental
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, aluminum alloys in
environments that contain an aggressive species such as chlorides (Cl –) or thiosulfates (S2O32–).
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
alloy/environment combinations is carbon steel. In environments where the pH value is lower
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 (alkaline) the oxide is
protective and the addition of chloride results in pitting corrosion. [citation needed]
Besides chlorides, other anions implicated in pitting
include thiosulfates (S2O32−), fluorides and iodides. Stagnant water conditions favor pitting.
Thiosulfates are particularly aggressive species and are formed by partial oxidation of pyrite, or
partial reduction of sulfate. Thiosulfates are a concern for corrosion in many industries handling
sulfur-derived compounds: sulfide ores processing, oil wells and pipelines transporting soured
oils, kraft paper production plants, photographic industry, methionine and lysine factories.
Corrosion inhibitors, when present in sufficient amount, will provide protection against pitting.
However, too low level of them can aggravate pitting by forming local anodes.
Engineering failures due to pitting corrosion[edit]

A corrosion pit on the outside wall of a pipeline at a coating defect before and after abrasive blasting.

The Silver Bridge collapsed into the Ohio River as a result of stress corrosion cracking.


A single pit in a critical point can cause a great deal of damage. One example is the explosion
in Guadalajara, Mexico on 22 April 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.[4]
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 afterwards. Deformities in
the bore caused by pitting can greatly reduce the firearm's accuracy. To prevent pitting in
firearm bores, most modern firearms have a bore lined with chromium.[citation needed]
Pitting corrosion can also help initiate stress corrosion cracking, as happened when a
single eyebar on the Silver Bridge in West Virginia, United States failed and killed 46 people on
the bridge in December 1967.[5]

See also[edit]
 Corrosion
 Corrosion engineering
 Crevice corrosion
 Micro pitting
 Panel edge staining
 Stress corrosion cracking

References[edit]
1. ^ ASM Handbook, Volume 13, "Corrosion", ISBN 0-87170-007-7, ASM International,
1987
2. ^ "Pitting corrosion". substech.com. 21 July 2015. Retrieved  4 December  2020.
3. ^ Princeton.edu, pitcorrosion.
4. ^ "Sewer Explosion due to Corrosion". Corrosion Doctors.
5. ^ Silver Bridge Collapse, Corrosion Doctors, read May 13, 2016

External links[edit]
 "Different types of corrosion: generalized corrosion, pitting corrosion, galvanic
corrosion, MIC corrosion". corrosionclinic.com. Retrieved 4 December 2020.

https://en.wikipedia.org/wiki/Pitting_corrosion

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