High temperature dissolution of ferrites, chromites and bonaccordite in chelating media

Different methods have been employed world wide for the decontamination of reactor coolant system surfaces. The success of a decontamination process mainly depends on the oxide dissolution efficiency of the decontamination formulation. Among the oxides, Fe₃O₄ undergoes easy dissolution in organic acid media at normal temperatures. However, dissolution of chromites and mixed ferrites is not that easy in organic chelant media at normal temperatures even in the presence of redox reagents. Hence, a high temperature process was attempted for the dissolution of ferrites and chromites. A re-circulation system consisting of an autoclave, pump, heat exchanger etc. all lined with teflon was used for carrying out high temperature dissolution experiments. This study describes the high temperature dissolution kinetics of Fe₃O₄, NiFe₂O₄, and Cr₂O₃. Nitrilotriacetic acid (NTA), a well known solvent for metal oxides, was applied at temperatures ranging from 80 to 180^oC. About six fold increase in dissolution rate was observed for Fe₃O₄ in this temperature range. Effect of N₂H₄ on oxide dissolution was studied. Lower dissolution rates were observed for Fe₃O₄ and NiFe₂O₄ in the presence of hydrazine. Oxide dissolution efficiency of other chelating agents like EDTA, PDCA etc. and the effect of reducing agents like oxalic acid and ascorbic acid on high temperature dissolution also has been studied. The effect of incorporation of boron and zinc in the iron and chromium oxides has also been studied. Bonaccordite (Ni₂FeBO₅) has been observed in the fuel deposits of pressurized Water Reactors especially in the AOA affected plants. Zinc ferrite/chromite are formed in reactors adopting zinc injection passivation technique to control radiation field. Bonaccordite and zinc ferrite/chromite formed over the reactor coolant system structural materials are also difficult to dissolve by the reagents used in chemical decontamination processes. Sample of bonaccordite was prepared by solid state route by heating stoichiometric mixtures of Hematite, Nickel Oxide and Boric acid at 900_oC for 24 Hours. The phase purity of Bonaccordite formed was confirmed by XRD and Laser Raman Spectroscopy. Studies carried out in the Teflon lined autoclave indicated that boron and zinc containing oxides/ ferrites can be dissolved more easily at elevated temperatures (>140_oC) as compared to normal temperatures (80 - 100_oC). The effect of variation of temperature, concentration of chelating agent, presence of reducing agents has also been studied. High temperature corrosion study of carbon steel (CS) and stainless steel in all the above chelating medium in the presence and the absence of reductants has been carried out. About 60% reduction in corrosion rate was observed for CS in NTA medium in the presence of N₂H₄ at 160^oC and at pH 6.5. However, at the same temperature and pH, in the absence of N₂H₄, corrosion rate of CS was decreased drastically. With increase in temperature, dissolution rate of chromium oxide also increased considerably. The effectiveness of high temperature process was substantiated by using oxide covered specimen prepared under simulated BWR water chemistry conditions. (author)