First stages of siderite crystallisation during CO2 corrosion of steel evaluated using in situ synchrotron small- and wide-angle X-ray scattering

We use in situ synchrotron small-and wide-angle X-ray scattering (SAXS/WAXS) to demonstrate that the formation of crystalline siderite (FeCO3) during the corrosion of steel in CO2-saturated brine - a problem of practical interest relating to the growth of protective scales on the interior surface of oil and gas production pipelines - is preceded by the formation of a colloidal precipitate in the solution and an amorphous surface layer, both assumed to be amorphous ferrous carbonate. Grazing incidence SAXS shows instantaneous film formation upon the application of an anodic potential, followed by development of a separate population of particles at later times, then by the formation of crystalline species, observed by WAXS. These observations can be interpreted in terms of crystal nucleation within the amorphous surface layer. Traces of Cr3+ in the solution significantly accelerate the precipitation rate of the colloidal precursor and accelerate the appearance of the crystalline scale. We speculate on the significance of these observations for the nucleation, growth and morphology of the corrosion scale and hence its protectiveness.