Influence of Cr(III) on the formation and transformation of corrosion products of steel in marine environments

Abstract

A fundamental approach is used to better understand the influence of Cr on the resistance of low alloy steel to marine corrosion. It focuses on the formation and transformation of corrosion products of steel in seawater-like electrolytes. Fe(OH)2 precipitates are then prepared by mixing a solution of NaCl, Na2SO4·10H2O, FeCl2·4H2O or FeCl2·4H2O + CrCl3·6H2O (so that Cr = 8% and Fe = 92%), with a solution of NaOH. The initial concentration ratio of reactants, $$Q=\frac{2[{{{\rm{Fe}}}}^{2+}]+3[{{{\rm{Cr}}}}^{3+}]}{[{{{\rm{OH}}}}^{-}]}$$ , is set at Q = 0.88, 1, and 1.136. In a first approach, the obtained aqueous suspension is stirred, at a controlled temperature of 25 ± 0.5 °C, to be oxidized by air. The resulting oxidation product is characterized by XRD and Raman spectroscopy. In a second approach, the Fe(OH)2 precipitates are aged one week in suspension in anoxic conditions, filtered, mixed as a wet paste with glycerol and set as a thin compact layer on the sample holder of a X-ray diffraction system. The oxidation process of Fe(OH)2 is then monitored in situ during the acquisition of the X-ray diffractogram. The obtained results demonstrate that Cr(III) hinders the formation of green rust compounds, hence hindering the formation of γ-FeOOH, i.e., the main oxidation product of green rust compounds. The other oxidation pathways of Fe(OH)2, which lead to Fe3O4 or α-FeOOH, are thus favored. Nevertheless, Cr(III) favors mainly the solid state transformation pathway of Fe(OH)2, thus promoting α-FeOOH via the formation of poorly ordered Fe(III) oxyhydroxides, namely feroxyhyte and ferrihydrite.