Pitting corrosion breakdown

The critical breakdown potential, which is the positive potential limit of stability of the oxide film. At this potential and more positive potentials, the oxide film is unstable with respect to the action of anions, especially halide ions, in causing localised rupture and initiating pitting corrosion. 

As mentioned, corrosion is complexly affected by the material itself and the environment, producing various kinds of surface films, e.g., oxide or hydroxide film. In the above reactions, both active sites for anodic and cathodic reactions are uniformly distributed over the metal surface, so that corrosion proceeds homogeneously on the surface. On the other hand, if those reaction sites are localized at particular places, metal dissolution does not take place uniformly, but develops only at specialized places. This is called local corrosion, pitting corrosion through passive-film breakdown on a metal surface is a typical example. 

Corrosion, especially pitting corrosion, is a typical heterogeneous reaction composed of several processes. Usually, it is reduced to each elemental phenomenon, such as breakdown of passive film and substrate dissolution, which are treated separately to establish the theoretical and experimental bases of corrosion. 

Regions characterized by large anodic overpotentials. Under such conditions, complete passivation and severe oxidation of most metal surfaces occurs. A breakdown of passive oxide layers and pitting corrosion is observed for transition-metal model systems. In this section are considered also the surfaces of electropositive metals such as aluminum. 

The influence of several anions such as perchlorate [259], halogenide [267-270], sulfate ions [272, 273], and their concentration on breakdown of the passive layer and pitting corrosion was also analyzed. 

These tests focused on the determination of a materials resistance to localized (pitting) corrosion. To accomplish this goal, three types of electrochemical experiments were conducted (cyclic polarization, electrochemical scratch, and potenti-ostatic holds) to measure several key parameters associated with pitting corrosion. These parameters were the breakdown potential, EM, the repassivation potential, Etp, and the passive current density, tpass. 

Pitting corrosion (Table 4.8) involves pit initiation (breakdown of passive film) followed by pit growth. The chloride ion induces pitting corrosion. Type 304 steel undergoes pitting more readily than Type 316 steel. The molybdenum in 316 steel is responsible for its reduced susceptibility to pitting corrosion. Type 316L steels contains... 

FIGURE 22.26 Schematic polarization curves for anodic metal dissolution, passivation, passivity breakdown, pitting corrosion, and transpassivation Eb = film-breakdown potential and Ep]l — pitting potential. 

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. 

Alloys, used at high temperatures, obtain their protection from a dense and adherent oxide layer formed on the metal surface. The corrosive attack of metals and alloys in molten salts is due to the solubility of oxide scales by basic and acidic dissolution. This breakdown of the passive film gives rise to accelerated metal consumption by enhanced oxidation (Hot Corrosion). The phenomenon is closely related to pitting corrosion of metals and alloys in aqueous solutions. 

---