Can the Point Defect Model Explain the Influence of Temperature and Anion Size on Pitting of Stainless Steels

The pitting behaviours of 304L and 316L stainless steels were investigated at $3^{\circ}C$ to $90^{\circ}C$ in 1 M solutions of NaCl, NaBr and NaI by potentiodynamic polarization. The temperature dependences of the pitting potential varied according to the anion, being near linear in bromide but exponential in chloride. As a result, at low temperatures grades 304L and 316L steel are most susceptible to pitting by bromide ions, while at high temperatures both stainless steels were more susceptible to pitting by small chloride anions than the larger bromide and iodide. Thus, increasing temperature appears to favour attack by smaller anions. This paper will attempt to rationalise both of the above findings in terms of the point defect model. Initial findings are that qualitatively this approach can be reasonably successful, but not at the quantitative level, possibly due to insufficient data on the mechanical properties of thin passive films.