Chemical and structural effects of phosphorus on the corrosion behavior of ion beam mixed Fe-Cr-P alloys

An experimental program was conducted to determine the mechanisms by which phosphorus affects the corrosion and passivation behavior of Fe-Cr-P alloys. To identify separately the effects of structure and chemistry on the corrosion behavior, thin films of Fe-10Cr-xP (0≤x≤ 35 at.%) were prepared by ion beam mixing. Films with a phosphorus content greater than approximately 20 at.% were found to be entirely amorphous. Devitrification of the amorphous phase was accomplished by heating the samples to 450 °C in an inert environment. Standard polarization tests of the alloys in sulfuric acid (with and without Cl-) indicated that the films containing phosphorus were more corrosion resistant than Fe-10Cr, at both active and passive potentials. There was a monotonic relationship between the amount of phosphorus in the alloy and the corrosion resistance, with the open-circuit corrosion rate of Fe-10Cr-35P nearly four orders of magnitude lower than that of Fe-10Cr. Devitrification of the alloys had no significant effect on the corrosion rate, indicating that the primary effect of phosphorus is chemical in nature, and not structural. The passive oxides were depth-profiled using X-ray photoelectron spectroscopy, which indicated that phosphorus was a primary constituent, as phosphate. The presence of phosphate in the passive oxides reduced the overall corrosion rate directly, by suppressing anodic dissolution. The presence of phosphorus did enhance chromium enrichment in the oxide, but that was not thought to be the primary mechanism by which phosphorus increased the corrosion resistance.