Studies on the primary and secondary residues from the dissolution of high-burnup nuclear fuels

To clarify the composition of residues from the dissolution of high-burnup nuclear fuels a sample with a burnup of 4.5 GWd and a two year cooling period was studied with the help of REM-EDX. In a parallel experiment an inactive simulator of a solution was subjected to a similar chemical treatment. The residues which resulted from this were analysed analogously. As a result of the results the chemistry of the following compounds in HNO3 were studied: MoO3, ZrMo2O5(OH)2x2H2O, the oxide of antimony as well as Sb4O4(OH)2(NO3)2, PdO.xH2O, Ag2Se, Ag2Te, and CsTcO4. Of special interest here were the solubility and precipitation formation of these compounds as well as the influence of a high (ca. 1 mol/l) concentration of uranium on these characteristics. With high radiation doses to the simulated solution a radiolytical reduction of Pd2+ was established and was studied more closely with pure Pd(NO3)2 solutions. In primary dissolution residues the presence of the radionuclides Ru-106, Ag-110m, Sb-125, Cs-134, and Cs-137 was γ-spectrometrically proven. The residue was made up primarily of an element combination of Mo and Ru. As other components Rh, Pd and Tc appear in an alloy as the so-called ε phase, which already has to be present in the fuel, because this phase was not exhibited in the similarly handled simulator. Zirconium molybdate was not identified in the real feed slurries, but was definitely present in the precipitation of the simulated feed solution. The analysis of the primary residues also showed pure zirconium particles, presumably from the zirconium alloy of the fuel cans, as well as undissolved fuel particles. The precipitation from the fuel solution was made up of agglomerates of the smallest particles of the ε phase, upon which silver halogenides were crystallized. Radiochemically reduced Pd was also found. (orig./RB)