Oxidation of ferritic–martensitic alloys T91, HCM12A and HT-9 in supercritical water

Abstract

The oxidation behavior of ferritic–martensitic (F–M) alloys in supercritical water (SCW) was studied in order to evaluate the suitability of these alloys for use in the Gen IV supercritical water reactor (SCWR) concept. A series of exposure tests in SCW were performed with three F–M alloys: T91, HCM12A, and HT-9. The effect of temperature was evaluated over the range of 400–600 °C and the dissolved oxygen concentration was controlled at <10 ppb (deaerated condition), 100 and 300 ppb. The oxidation behavior was determined from weight gain measurements along with oxide structure analysis. The results indicated that the oxidation rate was strongly dependent on temperature and followed an Arrhenius behavior. Activation energies for oxidation were 172, 177, and 189 kJ/mol for HT-9, HCM12A, and T91, respectively. The time dependence of the oxidation rate followed an exponential law with time exponents ∼0.3–0.42. Reduction in oxidation rate was observed at intermediate values (100–300 ppb) of dissolved oxygen concentration. The oxide formed on the alloy surface consisted of an outer layer of porous magnetite (Fe 3O 4) and an inner layer of iron chromium oxide, (Fe, Cr) 3O 4 with spinel structure. A transition region lies beneath the inner oxide in which the metal content increases to bulk values and the oxygen content decreases to nearly zero. Iron chromium oxide, (Fe, Cr)O, with the wustite structure was observed in the transition layer at 600 °C. The relatively good agreement between the activation energies for oxidation and that for grain boundary diffusion of oxygen support an oxidation mechanism based on short circuit oxygen diffusion to the oxide–metal interface.