Gilles Leturcq

Alteration of Cold Crucible Melter Titanate-Based Ceramics: Comparison with Hot-Pressed Titanate-Based Ceramic

Synroc ceramics were synthesized in an induction-heated cold crucible at laboratory scale (1 kg) from an oxide mixture, and at industrial prototype scale (45 kg) from Synroc previously produced by sintering under load at high temperature. After melting, both materials contained the major phases of Synroc-C. The chemical durability of both melted materials, as determined by static leaching of powder samples in initially pure water at 90°C with an SA/V ratio of 20000m −1 , was equivalent to that of conventional hot-pressed Synroc-C. Cerium, used in this investigation to simulate the presence of tri-and tetravalent actinides, was found in steady-state concentrations on the order of 1 ppb (i.e. NL(Ce) ≤ 10 −6 g·m −2 ). The concentration in the leachates was independent of the initial CeO 2 content of the Synroc (at least up to 10 wt%); moreover, it is similar to the results obtained with hot-pressed Synroc-C specifically formulated for conditioning long-lived actinides.

Leaching of zirconolite ceramics under H+ and He2+irradiation

Zirconolite is a candidate host material for conditioning minor tri- and tetra-valent actinides arising from enhanced nuclear spent fuel reprocessing and partitioning, which can be disposed in a geological repository for nuclear waste. Its chemical durability has been studied here under charged particle-induced radiolysis (He2+ and proton external beams) to identify possible effects on dissolution rates and mechanisms in pure water. Two geometries of experiments have been used to evaluate the influence of the following parameters: solid irradiation, Linear Energy Transfer (LET) at the interface and total deposited energy. Preliminary results on the elemental releases due to the enhanced dissolution of the zirconolite surface during charged particle-induced irradiation are first presented. Then, we focus on H2O2 production which is one of the major molecular species, created under water radiolysis, and likely to interact with the zirconolite surface. In presence of zirconolite, first results indicate an apparent consumption of the radiolytic hydrogen peroxide or its precursors compared to the production in pure water calculated from the primary yield GH2O2. The measured H2O2 concentration varies linearly with the total deposited energy in water over the irradiation duration (between 1 h and 6 h) and in the conditions of our experiments. Moreover, the H2O2 concentration decreases when the local density of the deposited energy close to the interface increases. Thus, we suggest that the mechanism(s) leading to the consumption of H2O2 or its precursors involve zirconolite surface reactions.

Enhancement of Zirconolite Dissolution Due to Water Radiolysis

Zirconolite is a candidate host material for conditioning minor tri- and tetra-valent actinides arising from enhanced nuclear spent fuel reprocessing and partitioning, in the case of disposal of the nuclear waste. Its chemical durability has been studied here under charged particle-induced radiolysis (He{sup 2+} and proton external beams) to identify the possible effects of water radiolysis on the dissolution rates in pure water and to describe the alteration mechanisms. Two experimental geometries have been used in order to evaluate the influence of the following parameters: solid irradiation, water radiolysis. In the first geometry the beam gets through the sample before stopping at the surface/water interface. In the second one the beam stops before the surface/water interface. Results on the elemental releases due to the enhanced dissolution of the zirconolite surface during charged particle-induced irradiation of water are presented. Under radiolysis, an increase of one order of magnitude is observed in the Ti, Zr and Nd elemental releases. No difference in the total elemental releases can be noticed when the solid is also irradiated. (authors)

Leaching of a zirconolite ceramic waste-form under proton and He2+ irradiation

Abstract In the hypothesis of a nuclear waste geological disposal, zirconolite is a candidate host material for minor tri- and tetra-valent actinides arising from enhanced nuclear spent fuel reprocessing and partitioning. Its chemical durability has been studied here under charged particle-induced radiolysis (He2+ and proton external beams) to identify possible effects on dissolution rates and mechanisms in pure water. Two experimental geometries have been used to evaluate the influence of the following parameters: solid irradiation and total deposited energy. Results on the evolution of the elemental releases due to the enhanced dissolution of the zirconolite surface during charged particle-induced irradiation of water are presented. Under radiolysis, elemental releases are first kinetically controlled. When the titanium and the zirconium releases reach (or exceed) their corresponding hydroxide solubility limits, the zirconolite dissolution becomes thermodynamically controlled.