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Pitting corrosion

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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 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.

[hide] 1 Mechanism 2 Susceptible alloys 3 Environment 4 Examples 5 See also 6 References

7 External


[edit] Mechanism

Diagram showing a mechanism of localized corrosion developing on metal in a solution containing oxygen

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[1]. 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.

[edit] Susceptible alloys

Alloys most susceptible to pitting corrosion are usually the ones where corrosion resistance is caused by a passivation layer: stainless steels, nickel alloys, aluminum alloys. Metals that are susceptible to uniform corrosion in turn do not tend to suffer from pitting. Thus, a regular carbon steel will corrode uniformly in sea water, while stainless steel will pit. Additions of about 2% of molybdenum increases pitting resistance of stainless steels.

[edit] Environment
The presence of chlorides, e.g. in sea water, significantly aggravates the conditions for formation and growth of the pits through an autocatalytic process. The pits becomes loaded with positive metal ions through anodic dissociation. The Cl ions become concentrated in the pits for charge neutrality and encourage the reaction of positive metal ions with water to form a hydroxide corrosion product and H+ ions. Now, the pits are weakly acidic, which accelerates the process. Besides chlorides, other anions implicated in pitting include thiosulfates (S2O32), fluorides and iodides. Stagnant water conditions favour 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: 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.

[edit] Examples

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

The collapsed Silver Bridge, as seen from the Ohio side

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.[2] 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.

Pitting corrosion can also help initiate stress corrosion cracking, as happened when a single eyebar on the Silver Bridge, West Virginia and killed 46 people on the bridge in December, 1967.[clarification needed]

[edit] See also

Corrosion Crevice corrosion Micro pitting Panel Edge Staining Stress corrosion cracking

[edit] References
1. ^ ASM Handbook, Volume 13, "Corrosion", ISBN 0-87170-007-7, ASM International, 1987 2. ^ "Sewer Explosion due to Corrosion". Corrosion Doctors.

[edit] External links

Pit Happens - Copper Corrosion in Household Plumbing. Pitting Corrosion - Corrosion Doctors [1] Pitting Corrosion Pitting Corrosion Theory Chemical explanation of pitting corrosion

Different Types of Corrosion - Recognition, Mechanisms & Prevention

Pitting Corrosion Recognition

What is pitting corrosion? Pitting Corrosion is the localized corrosion of a metal surface confined to a point or small area, that takes the form of cavities. Pitting is one of the most damaging forms of corrosion. Pitting factor is the ratio of the depth of the deepest pit resulting from corrosion divided by the average penetration as calculated from weight loss. This following photo show pitting corrosion of SAF2304 duplex stainless steel exposed to 3.5% NaCl solution.

Pitting corrosion forms on passive metals and alloys like stainless steel when the ultra-thin passive film (oxide film) is chemically or mechanically damaged and does not immediately re-passivate. The resulting pits can become wide and shallow or narrow and deep which can rapidly perforate the wall thickness of a metal.

ASTM-G46 has a standard visual chart for rating of pitting corrosion. The shape of pitting corrosion can only be identified through metallography where a pitted sample is cross-sectioned and the shape the size and the depth of penetration can be determined.

Mechanis ms
What causes pitting corrosion? 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. More details on the alloying effects can be found here.

Preventio n
How to prevent pitting corrosion? Pitting corrosion can be prevented through: Proper selection of materials with known resistance to the service environment Control pH, chloride concentration and temperature Cathodic protection and/or Anodic Protection Use higher alloys (ASTM G48) for increased resistance to pitting corrosion

For more details

More details on pitting corrosion are included in the following corrosion courses which you can take as in-house training courses, online courses or distance learning courses:

Corrosion and Its Prevention (5-day module) Corrosion and Its Prevention (2-day module)

Corrosion, Metallurgy, Failure Analysis and Prevention (3 days) Marine Corrosion, Causes and Prevention (2 days) Materials Selection and Corrosion (2 days) Stainless Steels and Alloys: Why They Resist Corrosion and How They Fail (2 days)