Localized corrosion experimental polarization

Experimental studies usually yield good agreement between the rates of corrosion obtained from polarization resistance measurements and those derived from weight-loss data, particularly if we recall that the Tafel slopes for the anodic and the cathodic processes may not be known very accurately. It cannot be overemphasized, however, that both methods yield the average rate of corrosion of the sample, which may not be the most critical aspect when localized corrosion occurs. In particular it should be noted that at the open-circuit corrosion potential, the total anodic and cathodic currents must be equal, while the local current densities on the surface can be quite different. This could be a serious problem when most of the surface acts as the cathode and small spots (e.g., pits or crevices) act as the anodic regions. The rate of anodic dissolution inside a pit can, under these circumstances, be hundreds or even thousands of times faster than the average corrosion rate obtained from micro polarization or weight-loss measurements. 

A correlation has been between pitting potential and pitting in the field the tendency to form pits naturally at open circuit increases as the experimentally determined pitting potential decreases [51]. The difference between E-p and E, which is related to the extent of hysteresis in a cyclic potentiodynamic polarization curve, has also been considered to be a measure of the susceptibility to localized corrosion [3,52]. Issues associated with this interpretation have been reviewed [53]. 

The described behavior applies only if crack propagation involves anodic dissolution at the crack tip. If local hydrogen embrittlement is the cause of cracking, there is no lower hmit, since the crack tip is not blunted by corrosion. Figure 11.18 shows experimental measurements taken on a steel specimen, subjected to cathodic polarization at two different potentials, in artificial seawater. The results indicate that hydrogen embrittlement of the metal occurs under these conditions. 

---