Abstract
The structure–activity relationship of three oxyphosphonate inhibitors differing in heteroatom type (C, N, S) was examined to clarify their influence on the pitting corrosion resistance of ferritic–martensitic steel EP-450 in chloride media. Gravimetric tests in 10% FeCl3, supported by surface microscopy and adsorption analysis, showed that EP-450 is highly susceptible to localized attack, with pits nucleating preferentially at carbide-enriched, chromium-depleted regions. Addition of dimethyl(1-hydroxycyclohexyl)phosphonate reduced the corrosion rate from 49 to 33 mm/year at 2.0 g/L, corresponding to ≈33% protection, while the nitrogen-containing dimethyl[1-(2-ethoxyethyl)-4-hydroxypiperidin-4-yl]phosphonate produced the largest decrease in mass loss, exceeding a 55% reduction under identical conditions. The sulfur-bearing dimethyl(4-hydroxytetrahydro-2H-thiopyran-4-yl)phosphonate afforded an intermediate effect. Adsorption analysis for the cyclohexyl derivative suggested mixed physisorption–chemisorption with limited surface coverage, while heteroatom substitution (N or S) is consistent with a change in adsorption configuration and interfacial packing that can yield a more compact protective layer. The observed inhibition efficiency increased in the sequence C < S < N, which is interpreted empirically in terms of heteroatom-dependent adsorption geometry and film integrity rather than conjugation-driven activation of the P=O group.