Pitting corrosion interface potential

Interface Potential and Pit Initiation. It is generally accepted that pit initiation occurs when the corrosion potential or potentiostatically imposed potential is above a critical value that depends on the alloy and environment. However, there is incomplete understanding as to how these factors (potential, material, and environment) relate to a mechanism, or more probably, several mechanisms, of pit initiation and, in particular, how preexisting flaws of the type previously described in the passive film on aluminum may become activated and/or when potential-driven transport processes may bring aggressive species in the environment to the flaw where they initiate local penetration. In the former case, the time for pit initiation tends to be very short compared with the initiation time on alloys such as stainless steels. Pit initiation is immediately associated with a localized anodic current passing from the metal to the environment driven by a potential difference between the metal/pit environment interface and sites supporting cathodic reactions. The latter may be either the external passive surface if it is a reasonable electron conductor or cathodic sites within the pit. 

The chloride threshold for the initiation of pitting corrosion for a given structure depends on numerous factors [1, 8-10]. Major factors have been identified in the pH of concrete, i. e. the concentration of hydroxyl ions in the pore solution, the potential of the steel and the presence of voids at the steel/concrete interface. 

If the passive film cannot be reestablished and active corrosion occurs, a potential drop is established in the occluded region equal to IR where R is the electrical resistance of the electrolyte and any salt film in the restricted region. The IR drop lowers the electrochemical potential at the metal interface in the pit relative to that of the passivated surface. Fluctuations in corrosion current and corrosion potential (electrochemical noise) prior to stable pit initiation indicates that critical local conditions determine whether a flaw in the film will propagate as a pit or repassivate. For stable pit propagation, conditions must be established at the local environment/metal interface that prevents passive film formation. That is, the potential at the metal interface must be forced lower than the passivating potential for the metal in the environment within the pit. Mechanisms of pit initiation and propagation based on these concepts are developed in more detail in the following section. 

It is necessary to exceed the critical anodic potential (23) bd for the electrochemical breakdown of passivation by pitting and consists of these factors (i) presence of halides at the interface (ii) induction time for the initiation of the breakdown process, leading to localized conditions that may increase the localized corrosion current density (iii) development of favorable conditions inside the pits for propagation when the local sites become immobile and localized at certain sites. Electrochemical breakdown of some metal oxides is possible in the case of copper, lead, and tin cathodically to metal while ferric oxide is reduced to the ferrous ion in aqueous solutions. Zinc and aluminum oxides are not cathodically reducible and in these cases hydrogen is reduced. The vigorous evolution of hydrogen assisted by electron conducting zinc oxide can accelerate the breakdown of passivity. 

Al Corrosion The use of A1 as a cathode current collector in commercial Li-ion batteries is nearly ubiquitous [47]. A given electrolyte must passivate the electro-lyte-Al interface to prevent corrosive pitting of the current collector during cell cycling to high potential (>3.6 V vs. Li/Li+). 

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