The initiation site and morphology during the early stage of pitting on AISI 1045 carbon steel that has a microstructure of primary ferrite and pearlite were investigated in boric-borate buffer solutions with and without NaCl at pH 8.0. The pits initiated by micro-scale polarization were in the pearlite only and not in primary ferrite. In situ real-time observations during the micro-scale polarization of pearlite in a boric-borate buffer solution with 100 mM NaCl indicated that the pits were polygonal or rod-like in shape. In addition, it was found that the pit growth direction was the same as that of the pearlite lamellae that consisted of ferrite and cementite. Field-emission electron probe micro analysis detected segregated points of sulfur in the ferrite lamellae. On the basis of their etching behavior in 3% nital, the corrosion resistance of the cementite was estimated to be higher than that of the ferrite lamellar structure. Thus, pits readily initiated in the ferrite lamellae and proceeded along the ferrite lamellae. Ferrite-pearlite steel is widely used in the production of bars, plates, steel wires, etc.1-3 because of its high strength, ductility, toughness, wear resistance, and low cost.3-5 Pearlite has a lamellar structure that consists of ferrite and cementite (Fe 3 C) phases. A fine pearlite structure improves the mechanical properties of steels in terms of strength and ductility.6-8 While ferrite-pearlite steels exhibit excellent mechanical properties, their pitting corrosion resistance is relatively low. It is widely believed that the boundaries between the different phases act as initiation sites for localized corrosion in chloride environments.
9,10When ferrite-pearlite steel that does not undergo any surface treatment is exposed to chloride environments, the steel readily suffers from pitting corrosion. Although the steel is successfully protected from corrosion by coating and/or painting, to prolong their service life and improve their reliability, it is necessary to elucidate the initiation mechanism of pitting on ferrite-pearlite steel.The pitting corrosion process involves two stages: initiation and propagation.11 In chloride environments, pitting is initiated by a breakdown of the passive film on steel during a local active dissolution process that exposes the bare steel surface to the environment. This film-free dissolution involves the hydrolysis reaction of metal cations and results in acidification. Chloride ions migrate into the pit to maintain electrical neutrality, and the simultaneous accumulation of chloride ions combined with the high level of acidification accelerates the active dissolution inside the pit. There have been many reports about the propagation stage of pitting corrosion in ferrite-pearlite steels. A comparison of the active dissolution rates and the electrochemical properties of ferrite and cementite have been widely discussed. It is commonly believed that cementite has a lower dissolution rate than ferrite. Yumoto et al. synthesized stoichiometric Fe 3 C films with...