| Abstract: | A mathematical model has been developed to describe the mass transport and electrochemical conditions in a corrosion fatigue crack in steel in 3.5% NaCl and in sea water for both freely corroding and anodic polarization conditions. Mass transport by advection (fluid flow induced by the movement of the crack walls), diffusion and ion migration was considered. Anodic and cathodic processes, hydrolysis reactions (including hydrolysis of alloying elements) and buffering reactions were included in the model. The pH value developed within the crack at a temperature of 5°C was between 7.0 and 8.5 for a wide range of conditions, with the maximum value controlled by the buffering associated with deposition of ferrous hydroxide. The lower pH values corresponded to relatively high ferrous ion concentration and were obtained for combinations of high R values (minimum/maximum load) and low frequencies for which convective mixing with the bulk solution was minimized. The presence of chromium in the steel at the 1 wt% level had only a small effect on the crack tip pH value in deep cracks but could lower the pH considerably (to about 4.0) in very shallow cracks (2.5 × 10−2 cm) if the potential was about −600 mV(SCE). The potential drop in the crack was relatively small (<30 mV) for a wide range of conditions at the free corrosion potential for structural steel in sea water ( −690 mV(SCE)) but increased markedly with anodic polarization with the effect most pronounced for deep cracks. Comparison of the model predictions with experimental measurements showed very good agreement with respect to crack tip pH and potential. |
