Electrochemical studies were made in aqueous LiCl, MgCl2, and MgBr2 solutions and in ZnCl2/KCl molten salt to clarify the corrosion reactions related to stress corrosion cracking (SCC) of austenitic stainless steel and to better define environmental variables critical to the occurrence of chloride SCC. Type 304 stainless steel electrodes were employed, with complementary SCC tests made with U-bend Type 304 stainless steel specimens. Several conclusions critical to an understanding of the mechanism of chloride SCC resulted from these investigations: (1) SCC was observed in concentrated MgBr2 solutions, (2) H2O must be present in the electrolyte, as SCC did not occur in dry molten ZnCl2/KCl, and (3) H2 evolution from corroding specimens may be facilitated by anodic polarization. Present studies do not support a model equating crack propagation with stress assisted anodic dissolution. Rather, evidence is presented that hydrogen evolution at the crack tip occurs and is a critical precursor to crack initiation and propagation. A model of SCC requiring hydrogen evolution at the crack tip is proposed, with emphasis being placed on the effect of anodic reactions within the crack in maintaining high acidity near the crack tip. Recent publications suggest that the role of evolved hydrogen in SCC may be related to formation of hydrogen induced martensitic platelets along paths of crack propagation.
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