Crack initiation film formation mechanisms

In neutral solutions the application of cathodic polarisation prevents crack initiation and this could be taken to indicate that hydrogen embrittlement is not the operative mechanism, since the discharge and entry of hydrogen might be expected to fracture the specimen more readily. The beneficial effect of cathodic polarisation has been interpreted , however, to result from more rapid film repair in the alkaline catholyte generated by the cathode reaction. The film serves as a barrier to rapid hydrogen entry. Consistent with this is the observation that in an environment of low pH (e.g. 10 N HCl) where film formation would not be expected, cathodic polarisation has no effect upon crack propagation. 

This is the case for magnesium and calcium electrodes whose cations are bivalent. The surface films formed on such metals in a wide variety of polar aprotic systems cannot transport the bivalent cations. Such electrodes are blocked for the metal deposition [28-30], However, anodic processes may occur via the breakdown and repair mechanism. Due to the positive electric field, which is the driving force for the anodic processes, the film may be broken and cracked, allowing metal dissolution. Continuous metal dissolution creates an unstable situation in the metal-film and metal-solution interfaces and prevents the formation of stable passivating films. Thus, once the surface films are broken and a continuous electrical field is applied, continuous metal dissolution may take place at a relatively low overpotential (compared with the high overpotential required for the initial breakdown of the surface films). Typical examples are calcium dissolution processes in several polar aprotic systems [31]. 

To consider this sequential nature of crack formation, the condition that the propagating segments of the forming cracks advance in unison is relaxed. Instead, it is assumed that a periodic array of cracks first forms in the film at spacing 2A the mechanics of formation of this initial array is not an issue in this discussion. After these cracks are fully formed and their... 

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