To elucidate the pit initiation behavior of sensitized stainless steels, the anodic polarization of a single grain boundary was examined in 0.1 M NaCl (pH 5.4) at 298 K using a micro-electrochemical system. For Type 304 heat-treated at 923 K for 2 h, no pitting was initiated on a small area (ca. 100 μm × 100 μm) with a sensitized grain boundary without MnS inclusions. However, stable pitting was observed on the electrode area that was larger than ca. 200 μm × 200 μm. In situ microscopy revealed that the first step in corrosion was a spherical pit generated at a MnS inclusion at a sensitized grain boundary, and that intergranular corrosion started at the pit. The local depassivation of the Cr-depleted zone along the sensitized grain boundary was thought to be introduced by the dissolution of the inclusion. The co-existence of the MnS inclusion and the Cr-depleted zone was considered to be the critical factor in the pit initiation of sensitized stainless steels in NaCl solutions.
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