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Effects of Potential on the Electrical Conductivity of a Solution within a Crevice of Stainless Steel in High-temperature Water

This study investigates the effects of potential [electrochemical corrosion potential (ECP)] on the water chemistry within a crevice of stainless steel in 288°C water containing Cl<sup>-</sup> major anionic impurities. In situ measurements of the electrical conductivity of a solution within a 15-μm-gap crevice (<i>σ</i><sub>crev</sub>) were conducted using small sensors installed at different crevice depths. The ECP at the external surface of the crevice specimen (<i>E</i><sub>ext</sub>) was controlled by the dissolved oxygen concentration in the bulk water. An increase in <i>E</i><sub>ext</sub> from approximately −0.49 V (versus a standard hydrogen electrode at 288°C) to −0.12 V resulted in an increase in <i>σ</i><sub>crev</sub> from 12 to 160.3 μS∙cm<sup>-1</sup> at 21 mm from the crevice mouth. FEM analysis taking into account the electrochemical reaction quantitatively reproduced this behavior. Cl<sup>-</sup> was considered to be the major anionic species transported into the crevice in this potential range. A further increase in <i>E</i><sub>ext</sub> up to 0.3 V led to a decline in <i>σ</i><sub>crev</sub>. An increase in the flux of oxidizing (O<sub>2</sub> and HCrO<sub>4</sub><sup>-</sup>) and alkalizing species (OH<sup>-</sup>) into the crevice was considered the cause of this behavior.