In situ monitoring of electroactive species by using the scanning electrochemical microscope. Application to the investigation of degradation processes at defective coated metals

The scanning electrochemical microscope (SECM) is a non-optical scanning microscopic instrument capable of imaging highly localized electrical currents associated with charge transfer reactions occurring in the vicinity of the surface of coated metals. The SECM tip operates as working microelectrode in an electrochemical cell under potentiostatic control. Microelectrode current and position is recorded as the tip is scanned very near a coated sample at a constant Z height, and variations in the faradaical current measured at selected tip potential values can be related to changes in the local concentration of electroactive species involved in corrosion reactions occurring at the substrate. Carbon steel samples coated with polyurethane in which a holiday was produced prior to immersion in different aqueous electrolytes were investigated with this technique. The release of Fe(II) ionic species into the solution phase from local anodic sites, as well as the consumption of dissolved oxygen at the corresponding cathodic locations was successfully monitored.