The service life of vessels is closely dependent on the corrosion resistance of coated hull steel systems due to the harsh marine environment. In this work, the three-dimensional corrosion extension law of a defective epoxy coating/AH32 steel system in the initial stage was investigated by using micro-Raman spectrum, electron probe microscopic analysis, and X-ray photoelectron spectroscopy. Q235 steel was utilized as a contrast sample. The chemical composition of the AH32 steel was 0.183C, 0.199Si, 1.33Mn, 0.0896Cr, 0.007Mo, 0.0078Al, 0.005Cu, 0.0428P, 0.0258S, and Fe and that of Q235 steel was 0.0692C, 0.0981Si, 0.163Mn, 0.0219Cr, 0.001Mo, 0.0176Al, 0.008Cu, 0.0318P, 0.0318S, and Fe. Results showed that when the electrolyte solution reached the coating/metal interface through the defect, the corrosion of the AH32 steel substrate preferentially developed in the lateral direction. By contrast, the corrosion extension of the Q235 steel showed increased severity in the depth direction. This difference could be attributed to the protectiveness of the corrosion products that had formed at the defect. The oxidation of the Mn element in AH32 accelerated the formation of the protective rust layer of α-FeOOH, which retarded the further vertical penetration of the electrolyte solution into the steel. Therefore, corrosion initially occurred at the under-film area near the defect.
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