Mechanisms preferential corrosion

Attack at welds due to bacteria is possible, but it is not nearly so common as is often supposed. Because of residual stresses, microstruc-tural irregularities, compositional variation, and surface irregularities, welds show a predisposition to corrode preferentially by most corrosion mechanisms. Attack is common along incompletely closed weld seams such as at butt welds in light-gauge stainless steel tubing (Fig. 6.9A and B). Attack at carbon steel welds may occur. Figure 6.10 shows a severely corroded carbon steel pipe from a service water sys-... 

In principle the selective dissolution of the less noble component of a singlephase alloy would perhaps be expected and is in fact observed (dezincification of an a-brass, etc.) even though the details of the mechanism by which it occurs is not yet fully understood. In contrast, the preferential attack of the less noble phase of a two-phase alloy is not only expected and observed —the mechanism by which it occurs in practice is also quite clear. Selective dissolution of the more active phase of a two-phase alloy is best exemplified by the graphitic corrosion (or graphitisation) of grey cast iron. 

A corrosion-inhibiting admixture is a chemical compound which, when added in small concentrations to concrete or mortar, effectively checks or retards corrosion. These admixtures can be grouped into three broad classes, anodic, cathodic and mixed, depending on whether they interfere with the corrosion reaction preferentially at the anodic or cathodic sites or whether both are involved [48]. Six types of mechanisms, viz. anodic (oxidizing passivators), anodic (non-oxidizing passivators), cathodic, precipitation... 

Unmixed zones. All methods of welding stainless steel with a filler metal produce a weld fusion boundary consisting of base metal that has been melted, but not mechanically mixed with filler metal and a partially melted zone in the base metal. An unmixed zone has the composition of base metal, but the microstructure of an autogenous weld. The microsegregation and precipitation phenomena characteristic of autogenous weldments decrease the corrosion resistance of an unmixed zone relative to the parent metal. Unmixed zones bordering welds made from overalloyed filler metals can be preferentially attacked when exposed on the weldment surface.14,61... 

In the first group, emerging persistent slip bands (PSBs) are preferentially attacked by dissolution. This preferential attack leads to mechanical instability of the free surface and the generation of new and larger PSBs, followed by localized corrosion attack, resulting in crack initiation. Under passive conditions, the relative rates of periodic rupture and reformation of the passive film control the extent to which corrosion reduces fatigue resistance. When bulk oxide films are present on a surface, rupture of the films by PSBs leads to preferential dissolution of the fresh metal that is produced.102... 

Corrosion by dealloying is common in brasses here the zinc component of the alloy is preferentially removed. Brasses with high proportions of the P phase are especially prone to this type of attack. The mechanism appears to be corrosion of both copper and zinc from the metal the zinc passes into solution but the copper is re-deposited with a porous structure of low strength. Aluminium bronzes also suffer dealloying of the aluminium component if incorrectly heat treated. Other metals which may be preferentially dissolved from their alloys are manganese from copper-manganese, nickel from copper-nickel, copper from either copper-silver or copper-gold, and tin from tin-lead (solders). It is evident from this list that it is the component which is anodic to the alloy which is removed. 

Dealloying occurs when one component of an alloy is lost preferentially. Thus, brass is an alloy of zinc (a rather active metal) and copper (a rather noble metal). Consequently, the zinc tends to be lost in preference to the copper. Often the copper will form a seal over the surface, preventing further corrosion, but if conditions do not allow this, then the corrosion can penetrate into the component, removing most of the zinc. The result is a porous copper component, which has little mechanical strength, and the problem is often discovered when the component fractures. Similarly, one component of a two-phase alloy can... 

The mechanism of poultice corrosion is shown diagramatically in Figure 4. Corrosion initially occurs uniformly over the whole metal surface. However, as the process continues, the oxygen reduction cathodic reaction may become restricted to a band near the surface where oxygen is readily available. Corrosion of metal then takes place preferentially slightly below the band. The pH rises in the cathodic reaction area due to an increase in hydroxyl ion concentration while the anodic area decreases in pH due to the hydrolysis of metal chloride reaction products. 

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