13C isotopic labeling to decipher the iron corrosion mechanisms in a carbonated anoxic environment

Abstract A two‐step corrosion experiment was performed on a ferritic steel (Armco) in a synthetic solution representing the Callovo–Oxfordian at 120°C. After the development of a carbonated corrosion product layer (CPL) during the first 15 days of the experimental step, corrosion front progression was investigated using 13 C marked carbonate species during the second 15 days experimental step. CPL was characterized at each step, in terms of morphology (scanning electron microscopy), composition (energy‐dispersive spectroscopy), and structure (µ‐Raman). 13 C corrosion product locations were analyzed by time‐of‐flight secondary ion mass spectrometry. Results evidenced that after a step of generalized corrosion, iron corrosion continues locally at the metal/CPL interface. These results suggest that although a protective siderite layer formed on the iron surface after 15 days, a local dissolution of the carbonate layer at the M/CPL interface occurred. A galvanic effect is developed between the bared surface (anode) and the covered one (cathode). This activates iron oxidation. The precipitation of carbonate corrosion products to the metal/CPL interface is possible by the diffusion of 13 CO 3 2− ions from the bulk through the siderite layer.