Chemical durability of hollandite ceramic for conditioning cesium

Abstract

The aqueous corrosion behavior of Cs-doped hollandite ceramic (BaCs 0.28Fe 0.82Al 1.46Ti 5.72O 16) was studied using several different static experimental protocols, with leachants of varying pH, and at different surface area to volume ratios, for periods ranging from six months to three years. All leach tests were carried out at 90 °C. X-ray diffraction (XRD) and scanning electron microscopy (SEM), coupled with energy dispersive X-ray spectroscopy (EDS), were used to characterize the surfaces of the hollandite before and after leaching. The most pronounced elemental releases, and corresponding changes to surface composition and microstructure, was evident at low pH, in particular pH 1. Cs and Ba releases were highest at low pH, with surface alteration exhibited by the formation of secondary rutile (prevalent at pH 1) and Al- and Ba-depleted hollandite (prevalent at pH 2). After rapid initial Cs release, the alteration rate was extremely low over the pH range from 2 to 10, as well as in pure water experiments with a sample-surface-area-to-solution-volume ratio ranging from 0.1 cm −1 to 1200 cm −1. The rates were about 10 −5 g m −2 d −1, corresponding to alteration thicknesses of a few nanometers per year. Higher rates (5 × 10 −3 g m −2 d −1) were observed only under very acidic conditions (pH 1). Congruency in Cs and Ba releases occurred only at pH 1, with incongruency between the two elements increasing with increasing pH. There were no apparent solubility constraints on Cs releases regardless of the SA/ V ratio, whereas geochemical modeling suggested that Ba releases could have been affected by the formation of BaCO 3, particularly at high SA/ V ratios. Extended leaching (with the leachant renewed once after 261 days of leaching) confirmed the high durability of hollandite with altered thicknesses of less than one nanometer per year over the last two years. Whilst Cs depletion of the hollandite surface was evidenced when leachates were replenished with the fresh deionised water, the presence of a soluble Ba-bearing secondary phase was inferred.