Elsevier, Electrochimica Acta, (104), p. 274-281, 2013
DOI: 10.1016/j.electacta.2013.04.109
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In this paper, an ion micro dispenser (IMD) was used to initiate a single pit by generating chloride anions above a 316L stainless steel electrode in either H2SO4 or HClO4 electrolyte. The current variations with respect to time provided an unambiguous characterization of the single pit evolution. Different pit shapes were observed depending on both the nature of the electrolyte and potential applied to the electrode. Substituting SO42− for ClO4− gave smaller (in diameter) but deeper pits at the early stage of pitting. However, when using a different setup that allows the sustaining of the pit propagation with a continuous supply of Cl−, the deeper pits were observed in HClO4 rather than H2SO4. The formation of an iron sulphate salt film at the bottom of the pit by precipitation of dissolution products in H2SO4 slowed down the corrosion rate. At high potentials, the repassivation mechanism outweighed the metal dissolution in the ClO4− containing solution.