Chemical and electrochemical conditions within stress corrosion and corrosion fatigue cracks

In the area of environment assisted cracking, literature aimed at understanding the chemical and electrochemical conditions at/near the crack tip establishes that the crack tip is occluded and not well represented by bulk conditions. A review of the relevant literature, both modeling and experimental, is presented here and shows that crack tip conditions are determined by the balance between high metal ion concentrations resulting from crack tip anodic reactions and subsequent hydrolysis, mass transport (including ion migration, diffusion, and advection), and electrochemical polarization of the bold surface, which determines the extent of anodic and cathodic reactions occurring in the crack environment. Under both freely corroding conditions and anodic polarizations, the crack tip pH decreases with increasing polarization above the freely corroding condition, most often leading to a very acidic crack environment. Under sufficient cathodic polarization, the crack tip pH increases. Because of high-anion and -cation concentrations in the crack environment, an IR drop down the crack exists, leaving the crack tip relatively unpolarizable. Ion migration enhances the occluded nature of the crack tip by supplying anions from the bulk solution to maintain electroneutrality at the crack tip. Diffusion to counteract this concentration gradient is minimal and only plays a role in crack tip conditions at very small crack lengths. When cyclic loading conditions are encountered, the occluded nature of the crack tip can be counteracted by advection; although, the role decreases with decreasing f and increasing R, essentially as corrosion fatigue conditions approach those of stress corrosion cracking.