Stress corrosion passive metals

The arbitrary division of behaviour has been made because of the extreme behaviour of some chemicals that initiate small areas of attack on a well-passivated metal surface. The form of attack may manifest itself as stress-corrosion cracking, crevice attack or pitting. At certain temperatures and pressures, minute quantities of certain chemicals can result in this form of attack. Chloride ions, in particular, are responsible for many of the failures observed, and it can be present as an impurity in a large number of raw materials. This has led to the development of metals and alloys that can withstand pitting and crevice corrosion, but on the whole these are comparatively expensive. It has become important, therefore, to be able to predict the conditions where more conventional materials may be used. The effect of an increase in concentration on pitting corrosion follows a similar relationship to the Freundlich equation where... 

In the previous analysis, homogeneous current distribution has been assumed but, on many occasions, corrosion occurs with localized attack, pitting, crevice, stress corrosion cracking, etc., due to heterogeneities at the electrode surface and failure of the passivating films to protect the metal. In these types of corrosion processes with very high local current densities in small areas of attack, anodic and cathodic reactions may occur in different areas of disparate dimensions. 

Stainless steels exhibit the best resistance to corrosion when the surface is oxidized to a passive state. This condition can be obtained, at least temporarily, by a so-called passivation operation in which the surface is treated with nitric acid and then rinsed with water. Localized corrosion can occur at places where foreign material collects, such as in scratches, crevices, or comers. Consequently, mars or scratches should be avoided, and the equipment design should specify a minimum of sharp comers, seams, and joints. Stainless steels show great susceptibility to stress corrosion cracking. As one example, stress plus contact with small concentrations of halides can result in failure of the metal wall. 

Alkalis Most metals are protected by a passive oxide in mildly alkaline solutions, but the protective oxide will redissolve in strong alkali to form oxy-anions of the metal, allowing corrosion to occur. For carbon steels, the region of corrosion in alkali is very limited, but it can lead to the serious problem of caustic stress corrosion cracking (SCC). 

Stress corrosion cracking is a form of localized corrosion, where the simultaneous presence of tensile stresses and a specific corrosive environment prodnces metal cracks [157, 168]. Stress corrosion cracking generally occnrs only in alloys (e.g., Cn-Zn, Cu-Al, Cu-Si, austenitic stainless steels, titaninm alloys, and zirconinm alloys) and only when the alloy is exposed to a specific environment (e.g., brass in ammonia or a titaninm alloy in chloride solutions). Removal of either the stress on the metal (which must have a surface tensile component) or the corrosive environment will prevent crack initiation or cause the arrest of cracks that have already propagated. Stress corrosion cracking often occurs where the protective passive film breaks down. The continual plastic deformation of the metal at the tip of the crack prevents repassivation of the metal surface and allows for continued localized metal corrosion. 

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