Behavior of thorium-uranium (IV) phosphate-diphosphate sintered samples during leaching tests. Part I - Kinetic study

Titre de la revue : Journal of Nuclear Materials Volume : 349 N° : 3 Pagination : 291-303 Date de publication : 01/03/2006

The dissolution of β-TUPD sintered samples was examined in various conditions of pH, temperature, concentrations of anions in the leachate and leaching flow rates. All the normalized dissolution rates were in the range 10-7 to 10-4 g m-2 day-1 even in very aggressive media, showing the good resistance of these ceramics to aqueous alteration. The first part of this paper describes several parameters exhibiting a significant influence on the normalized dissolution rate of the pellets prepared. Both the partial order relative to the proton concentration (n = 0.39-0.41) and the apparent activation energy (Eapp = 49 kJ mol -1) were found in good agreement with the data reported for powdered samples showing that the sintering process does not degrade the chemical durability of the ceramics. Moreover, due to the high thermodynamical constant of complexation of phosphate species for tetravalent uranium and thorium, the influence of other ligands such as nitrate, chloride or sulphate on the normalized dissolution rates was limited. Near the equilibrium, the increasing of the leaching time, the temperature or the leachate acidity led to the thorium precipitation at the surface of the pellets either in static or in dynamic conditions. Consequently, the dissolution became clearly incongruent and controlled by saturation processes which are described in the second part of this paper.