RESUMEN
Carbon steel coupons were buried in a specific low-pH cement grout designed for radioactive waste disposal and left 6 months in anoxic conditions at 80 °C. The corrosion product layers were analyzed by µ-Raman spectroscopy, XRD, and SEM. They proved to be mainly composed of iron sulfides, with magnetite as a minor phase, mixed with components of the grout. Average corrosion rates were estimated by weight loss measurements between 3 and 6 µm yr-1. Corrosion profiles revealed local degradations with a depth up to 10 µm. It is assumed that the heterogeneity of the corrosion product layer, mainly composed of conductive compounds (FeS, Fe3S4, and Fe3O4), promotes the persistence of corrosion cells that may lead to locally aggravated degradations of the metal. New cement grouts, characterized by a slightly higher pH and a lower sulfide concentration, should then be designed for the considered application.
RESUMEN
Reinforcing clamps made of low alloy steel from the Metz cathedral and corroded outdoors during 500 years were studied by OM, FESEM/EDS, and micro-Raman spectroscopy. The corrosion product layer is constituted of a dual structure. The outer layer is mainly constituted of goethite and lepidocrocite embedding exogenous elements such as Ca and P. The inner layer is mainly constituted of ferrihydrite. The behaviour of the inner layer under conditions simulating the wetting stage of the RH wet/dry atmospheric corrosion cycle was observed by in situ micro-Raman spectroscopy. The disappearance of ferrihydrite near the metal/oxide interface strongly suggests a mechanism of reductive dissolution caused by the oxidation of the metallic substrate and was observed for the first time in situ on an archaeological system.