Pitting corrosion initiation time

Pitting corrosion always remains a worthy subject for study, particularly with reference to mechanism, and the problem conveniently divides into aspects of initiation and growth. For 6061 alloy in synthetic seawater, given sufficient time, pit initiation and growth will occur at potentials at or slightly above the repassivition potential . In an electrochemical study, it was found that chloride ions attack the passive layer as a chemical reaction partner so that the initiation process becomes one of cooperative chemical and electrochemical effects . 

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 failure time, however, incorporates both the time required for crack initiation and a period of slow crack growth so that the separate effect of the environment on each of these stages cannot be ascertained. (Some of the difficulty stems from the lack of a precise definition for crack initiation.) This difficulty is underscored by the results of Brown and Beachem [1] on SCC of titanium alloys. They showed that certain of the alloys that appeared to be immune to stress corrosion cracking in the traditional (smooth specimen) tests are, in fact, highly susceptible to environment-enhanced crack growth. The apparent immunity was explained by the fact that these alloys were nearly immune to pitting corrosion, which was required for crack nucleation in the same environment [1]. 

Initiation of pitting corrosion takes place when the chloride content at the surface of the reinforcement reaches a threshold value (or critical chloride content). A certain time is required from the breakdown of the passive film and the formation of the first pit, according to the mechanism of corrosion described above. From a practical point of view, the initiation time can be considered as the time when the reinforcement, in concrete that contains substantial moisture and oxygen, is characterized by an averaged sustained corrosion rate higher than 2 mA/m [8], The chloride threshold of a specific structure can be defined as the chloride content required to reach this condition of corrosion. 

Pits that reach a critical depth can act as crack initiation sites if they lead to a higher local stress intensity. The crack initiation time in this case corresponds to the incubation time of pits of a critical size. Alternatively, precipitation reactions at the grain boundaries can render an alloy sensitive to intergranular corrosion. The preferentially corroded grain boundary then serves as initiation site of a crack. Inclusions, preexisting microcracks, or other structural defects are also likely crack initiation sites. The crack initiation time, in this case, is defined as the time required for a crack to reach a detectable size. Crack initiation may also be the result of hydrogen formed by a corrosion reaction that may cause embrittlement of the metal or of successive ruptures of a passive film or tarnish layer, but these mechanisms are more important for the propagation than the initiation of cracks. Because of the multitude of possible crack initiation mechanisms, and because of the statistical nature of the phenomenon, it is not possible to predict the crack initiation time from first principles. 

The mechanisms that control crack initiation in corrosion fatigue are poorly understood. It is generally believed, however, that corrosion in its various forms (pitting, intergranular, acid, at inclusions etc.) plays a dominant role. The observed effect of the general corrosivity of the environment on the time to failure in Figure 11.46 supports this statement, because the results were obtained on non-precracked specimens and this kind of test provides mostly an indication of the crack initiation time. 

Electrochemical scanning techniques indicate the ability of a material to resist a given environment or repassivate after corrosion initiates. These tests can compare materials without waiting for pit initiation or for sufficient time to obtain measurable geneial corrosion rates. Although these tests can be done quickly, relating the results to long-term behavior in mill environments can require extensive expertise. 

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