Corrosion of ferritic-martensitic steels and nickel-based alloys in supercritical water

The corrosion behavior of ferritic/martensitic (F/M) steels and Ni-based alloys in supercritical water (SCW) has been studied due to their potential applications in future nuclear reactor systems, fossil fuel power plants and waste treatment processes. 9∼12% chromium ferritic/martensitic steels exhibit good radiation resistance and stress corrosion cracking resistance. Ni-based alloys with an austenitic face-centered cubic (FCC) structure are designed to retain good mechanical strength and corrosion/oxidation resistance at elevated temperatures. Corrosion tests were carried out at three temperatures, 360°C, 500°C and 600°C, with two dissolved oxygen contents, 25 ppb and 2 ppm for up to 3000 hours. Alloys modified by grain refinement and reactive element addition were also investigated to determine their ability to improve the corrosion resistance in SCW.;A duplex oxide structure was observed in the F/M steels after exposure to 25 ppb oxygen SCW, including an outer oxide layer with columnar magnetite grains and an inner oxide layer constituted of a mixture of spinel and ferrite phases in an equiaxed grain structure. An additional outermost hematite layer formed in the SCW-exposed samples when the oxygen content was increased to 2 ppm. Weight gain in the F/M steels increased with exposure temperatures and times, and followed parabolic growth kinetics in most of the samples. In Ni-based alloys after exposure to SCW, general corrosion and pitting corrosion were observed, and intergranular corrosion was found when exposed at 600°C due to formation of a local healing layer. The general oxide structure on the Ni-based alloys was characterized as NiO/Spinel/(CrxFe 1-x)2O3/(Fe,Ni). No change in oxidation mechanism was observed in crossing the critical point despite the large change in water properties.;Corrosion resistance of the F/M steels was significantly improved by plasma-based yttrium surface treatment because of restrained outward diffusion of iron by the yttrium oxide particles distributed along grain boundaries. Grain refinement by shot peening or equal channel angular pressing mitigated the corrosion of F/M steels in SCW by development of a Cr-rich inner oxide layer and/or chromium oxide layer that acts as an effective diffusion barrier. The improvement is attributed to the enhanced diffusion of chromium through a high density grain boundary network due to grain refinement, and varies depending upon the chromium content in alloys and the SCW exposure times.