Effect of LiOH, NaOH and KOH on corrosion and oxide microstructure of Zr-based alloys

Long-term corrosion test, SIMS analysis, and TEM microstructural study were carried out to investigate the corrosion characteristics and mechanism of Zr alloys in alkali hydroxides. The corrosion tests were performed in solutions of LiOH, NaOH, KOH, RbOH, and CsOH at 350 deg. C for 500 days. SIMS analysis was performed for the specimens prepared to have an equal oxide thickness. TEM studies on the specimens with an equal oxide thickness in various solutions in both pre- and post-transition regimes were also conducted. The corrosion rate in alkali hydroxide solutions was observed to decrease as the ionic radius of alkali cation was increased. The penetration depth of cation into the oxide decreases with increasing the ionic radius of cation. Even though the oxide thickness was equal, the different oxide morphologies were observed in specimens. Namely, in LiOH solution the oxide morphology was transformed early from columnar to equiaxed structure. However, in KOH solution the columnar structure was maintained up to post-transition regime. Based on the corrosion test, SIMS analysis, and microstructural study, the cation is considered to control the corrosion in a alkali hydroxide solution and its effect is dependent on the concentration of alkali and the oxide thickness. The slight acceleration of the corrosion rate at a low concentration is thought to be caused by cation incorporation into oxide while the significant acceleration at a high concentration is due to the transformation of oxide microstructure that would be induced by cation incorporation. KOH was shown not to affect significantly the corrosion and the hydrogen pickup of Zircaloy. Therefore, it has a potential for PWR application only from the point of view of Zircaloy corrosion. (author)