Crack initiation passive conditions

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... 

Fig- 7.73 Schematic representation of (a) passive film, (b) passive film rupture by stress-induced slip resulting in exposure of bare substrate, (c) crack initiation by anodic dissolution initiating crevice corrosion conditions before repassivation of exposed substrate, and (d) repassivation of exposed substrate before crack initiation. 

Figure 4 (a) Schematic representation of a a-N curve for CF crack initiation under passive conditions, (b) Comparison of experimentally and theoretically derived fatigue lives for the XI Cr MoNb 182 alloy in 30 g/L NaCl at 80°C [8]. 

Some films are termed "passive," for stainless steels or aluminum alloys, for instance. These films can play an important role in environment-sensitive crack initiation and fracture. Under thermodynamic equilibrium conditions, the film stability may be inferred from E =/(pH) diagrams, where E is the electrical potential related to the chemical free energy G by G = -nEF, and F is Faraday s number. At equilibrium, one can define the electrode potential (related to AG) and the current density I (I e here AG is the activation energy of dissolution). 

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 many of the alloy systems shovm in Table 1/ the stable configuration of the alloy surface is that it is filmed. Many of the alloys, e.g., stainless steels, Al, Ti, Zr and Mg alloys are only usable in such a condition. Such a consideration applies not only to these alloys covered with a thin passive film but also to those on which relatively thick films are formed. The possible mechcUiisms by which stress corrosion cracking occurs are concerned with reactions between unfilmed metal and the environment. Before consideration of these it is necessary to consider how these various types of film break down initially. While many of the alloys exhibit pitting, it is not necessary for pitting as such to precede crack propagation. Pitting is associated with static unstressed metals whereas cracking is associated with a metal whose surface is stressed. 

For some material-environment combinations it has been shown that accelerated anodic dissolution of yielding metal is the significant mechanism. This is the case for austenitic stainless steels in acidic chloride solutions. In these steels, plastic deformation is characterized by a dislocation pattern giving wide slip steps on the surface. For such systems, Scully [7.50] has proposed a model for initiation and development of stress corrosion cracks, which has been supported by other scientists [7.51]. The model in its simplest form is illustrated in Figure 7.52. A necessary condition is that flie surface from the beginning is covered by a passivating film (A). 

Under certain special environmental conditions, the passive films, which were described earlier in this Chapter, are susceptible to localized breakdown. Passivity breakdown may result in accelerated local dissolution (localized corrosion) of the metal or alloy. There are two (related) major forms of localized corrosion following passivity breakdown localized corrosion initiated on an open surface is called pitting corrosion, and localized corrosion initiated at an occluded site is called crevice corrosion. In the presence of mechanical stress, localized dissolution may promote the initiation of cracks. 

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