The degree of sensitization and susceptibility of intergranular corrosion of austenitic stainless steels are properly evaluated from immersion testing in acidic solutions as rapid screening methods. However, most of stainless steels are used in near-neutral pH environments, and the typical corrosion morphology in these environments is pitting. Acidification is known to occur inside pits due to the hydrolysis reaction of dissolving metal ions. Under practical service conditions around neutral pH such as seawater and river water, pitting is assumed to be closely related to the initiation of intergranular corrosion.

It is well-known that non-metallic inclusions, such as MnS, act as the initiation sites for pitting of stainless steels. Chiba et al. demonstrated that a small inclusion-free area on Type 304 indicated superior pitting corrosion resistance even in 3 M NaCl. ¹⁾ It would appear that MnS inclusions strongly affect pitting and intergranular corrosion of sensitized stainless steels.

To clarify the role of pitting at MnS inclusions in intergranular corrosion of sensitized Type 304 stainless steel (sensitized at 923 K), in situ observations were carried out during micro-scale anodic polarization in 1 M NaCl (pH 5.4). Micro-scale potentiodynamic anodic polarization was performed for a small area with a MnS inclusion at a sensitized grain boundary. Intergranular corrosion was initiated from the pit that was generated at the MnS inclusion located at the sensitized grain boundary. Acidification inside the pit probably caused intergranular corrosion due to the transition from passive to active state.

In 1 M NaCl, the depassivation pH values at the sensitized grain boundary with and without MnS inclusions were 1.0 and 0.4, respectively. It is likely that the dissolution of MnS accelerates the depassivation and promote the initiation pf intergranular corrosion. The dissolution products from MnS are supposed to accelerate depassivation of Cr-depleted regions.

1) A. Chiba, I. Muto, Y. Sugawara, N. Hara, J. Electrochem. Soc., 160, C511-C520 (2013).