In Situ Monitoring of Pit Nucleation and Growth at an Iron Passive Oxide Layer by using Combined Atomic Force and Scanning Electrochemical Microscopy

Generation of single corrosion pits and insitu monitoring of pit growth on iron exposed to 0.5m NaCl solution was achieved by using combined atomic force and scanning electrochemical microscopy (AFM-SECM). Pits as small as 2.7m in diameter were formed at arbitrary locations on the substrate through the local generation of highly concentrated nitric acid in the vicinity of the AFM-SECM probe. Addition of nitrite ions to the environment, which act as corrosion inhibitors for iron, ensures passivation of the metal and hinders metal corrosion, despite exposure to the chloride-containing media. Localized acidification was achieved by oxidizing nitrite ions at the probe. Acidification in combination with the high chloride content in the solution led to a local rapid attack at the surface and pit generation below the AFM-SECM probe. Besides improved spatial resolution and precise control of the pit nucleation site, combined AFM-SECM allows simultaneous imaging of the generated pits by the AFM tip.