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Investigation of the behavior of additive Yb2O3 in the anode during electrolysis is an important method for improving the corrosion resistance of the grain boundary to high-temperature molten salt electrolyte. The author examined the Yb content of cermets after both sintering and electrolysis and the experimental results showed that a dense layer of NiFe2O4-NiAl2O4-FeAl2O4 ceramic favorably formed on the surface of the anodes only if the electrolysis time was greater than 10 hours. Moreover, NiFe2O4, NiA2O4 and FeAl2O4 were produced and dissolved continuously as a result of the chemical and electrochemical corrosion that took place after the formation of the dense layer. As the electrolysis time was extended, Yb2O3 or YbFeO3 gradually dissolved into the electrolyte and primary aluminum as an impurity substance.