Pitting corrosion passive films

The stainless steels contain appreciable amounts of Cr, Ni, or both. The straight chrome steels, types 410, 416, and 430, contain about 12, 13, and 16 wt % Cr respectively. The chrome—nickel steels include type 301 (18 wt % Cr and 9 wt % Ni), type 304 (19 wt % Cr and 10 wt % Ni), and type 316 (19 wt % Cr and 12 wt % Ni). Additionally, type 316 contains 2—3 wt % Mo which gready improves resistance to crevice corrosion in seawater as well as general corrosion resistance. AH of the stainless steels offer exceptional improvement in atmospheric conditions. The corrosion resistance results from the formation of a passive film and, for this reason, these materials are susceptible to pitting corrosion and to crevice corrosion. For example, type 304 stainless has very good resistance to moving seawater but does pit in stagnant seawater. 

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

Generally, pitting corrosion only occurs on passivated metals when the passive film is destroyed locally. In most cases chloride ions cause this local attack at potentials U > U q. Bromide ions also act in the same way [51], The critical potential for pitting corrosion UpQ is called the pitting potential. It has the same significance as in Eqs. (2-39) and (2-48). 

Pits occur as small areas of localized corrosion and vary in size, frequency of occurrence, and depth. Rapid penetration of the metal may occur, leading to metal perforation. Pits are often initiated because of inhomogeneity of the metal surface, deposits on the surface, or breaks in a passive film. The intensity of attack is related to the ratio of cathode area to anode ai ea (pit site), as well as the effect of the environment. Halide ions such as chlorides often stimulate pitting corrosion. Once a pit starts, a concentration-cell is developed since the base of the pit is less accessible to oxygen. 

Metals which owe their good corrosion resistance to the presence of thin, passive or protective surface films may be susceptible to pitting attack when the surface film breaks down locally and does not reform. Thus stainless steels, mild steels, aluminium alloys, and nickel and copper-base alloys (as well as many other less common alloys) may all be susceptible to pitting attack under certain environmental conditions, and pitting corrosion provides an excellent example of the way in which crystal defects of various kinds can affect the integrity of surface films and hence corrosion behaviour. 

Localised attack can, however, occur on a surface of metal that is apparently uniform, and this occurs particularly with the highly passive metals that depend on a thin invisible protective film of oxide for their corrosion resistance. In such cases submicroscopic defects in the passive film may form the sites at which pits are initiated, thus giving rise to a situation similar to that shown in Fig. 1.46. 

Crevice corrosion and pitting have a number of features in common, and it has been stated that pitting may be regarded as crevice corrosion in which the pit forms its own crevice however, whereas a macroscopic heterogeneity determines the site of attack in crevice corrosion, the sites of attack in pitting are determined by microscopic or sub-microscopic features in the passive film (5 Sections 1.3 and 1.5). 

As mentioned, corrosion is complexly affected by the material itself and the environment, producing various kinds of surface films, e.g., oxide or hydroxide film. In the above reactions, both active sites for anodic and cathodic reactions are uniformly distributed over the metal surface, so that corrosion proceeds homogeneously on the surface. On the other hand, if those reaction sites are localized at particular places, metal dissolution does not take place uniformly, but develops only at specialized places. This is called local corrosion, pitting corrosion through passive-film breakdown on a metal surface is a typical example. 

Corrosion, especially pitting corrosion, is a typical heterogeneous reaction composed of several processes. Usually, it is reduced to each elemental phenomenon, such as breakdown of passive film and substrate dissolution, which are treated separately to establish the theoretical and experimental bases of corrosion. 

The anions such as halogenides stimulate the active dissolution of zinc and tend to break down the passive film. Therefore, the effect of halogenide anions [267-270], thiocyanate [271], and sulfur-containing anions [272-274] in different media was studied. There are also anions that inhibit active dissolution and pitting corrosion, and this effect decreases in the... 

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. 

Hydrogen initiation of stress-corrosion cracking is indeed the probable mechanism. However, what has been given here is rather overgeneral. For example, the stress corrosion of alloys shows specificities that hint at unexplained factors. Passive films form at the bottom of pits and it is the breaking of these upon stress that sometimes causes cracks to spread. 

Figure 24 Schematic Evans diagram and polarization curve illustrating the origin of the negative hysteresis observed upon cyclic polarization for materials that do not pit. Line a represents the (unchanging) cathodic Evans line. Line b represents the anodic Evans line during the anodically directed polarization, while line c represents the anodic Evans line for the material after its passive film has thickened because of the anodic polarization. The higher corrosion potential observed for the return scan (E (back)) is due to the slowing of the anodic dissolution kinetics.

Pitting corrosion (Table 4.8) involves pit initiation (breakdown of passive film) followed by pit growth. The chloride ion induces pitting corrosion. Type 304 steel undergoes pitting more readily than Type 316 steel. The molybdenum in 316 steel is responsible for its reduced susceptibility to pitting corrosion. Type 316L steels contains... 

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