Corrosion characteristics and oxide microstructures of Zircaloy-4 in aqueous alkali hydroxide solutions

Abstract

The corrosion characteristics of Zircaloy-4 have been investigated in various aqueous solutions of LiOH, NaOH, KOH, RbOH and CsOH with equimolar M + and OH − at 350°C. The characterization of the oxides was performed using transmission electron microscope (TEM) and scanning electron microscope (SEM) on the samples which were prepared to have an equal oxide thickness in pre-transition and post-transition regimes. At a low concentration (4.3 mmol) of aqueous alkali hydroxide solutions, the corrosion rates decrease gradually as the ionic radius of cation increases. At a high concentration (32.5 mmol), the corrosion rate increases significantly in LiOH solution and slightly in NaOH solution, but in the other hydroxide solutions such as KOH, RbOH and CsOH, the corrosion rate is not accelerated. Even if the specimens have an equal oxide thickness in LiOH, NaOH and KOH solutions, the oxide microstructure formed in the LiOH solution is quite different from those formed in the NaOH or the KOH solutions. In the LiOH solution, the oxides grown in the pre-transition regime as well as in the post-transition regime have an equiaxed structure including many pores and open grain boundaries. The oxides grown in the NaOH solution have a protective columnar structure in the pre-transition regime but an equiaxed structure in the post-transition regime. On the other hand, in the KOH solution, the columnar structure is maintained from its pre-transition regime to the post-transition regime. On the basis of the above results, it can be suggested that the cation incorporation into zirconium oxide would control the oxide microstructure, the oxide growth mechanism at the metal–oxide interface and the corrosion rate in alkali hydroxide solutions.