AbstractThe exposure of carbon steel in marine atmospheres can lead in certain circumstances to the formation of thick rust layers (containing a number of compact laminas) that are easily detached (exfoliated) from the steel substrate, leaving it unprotected and considerably accelerating the corrosion process. This deterioration phenomenon is of particular concern in steel infrastructures located close to the sea (civil constructions, bridges, etc.), whose service lifetime can be extraordinarily limited. High times of wetness of the metallic surface and high chloride ion deposition rates play a decisive role in the formation of this type of rust. Research has been carried out for 1 year in eight pure marine atmospheres with annual average chloride deposition rates of 70–1906 mg Cl^-/m² day. The studied carbon steels consisted of one mild steel, one conventional weathering steel (Corten A), and one high nickel (~3 wt.%) advanced weathering steel (AWS). The paper describes the environmental conditions that lead to the formation of these thick multilaminar rust layers and presents a characterisation study of this singular type of rust using a variety of analysis techniques: scanning electron microscopy/energy-dispersive X-ray spectroscopy, X-ray diffraction, Mössbauer spectroscopy, and transmission electron microscopy/electron diffraction. The Ni-AWS shows greater resistance to the occurrence of rust exfoliation.