Behavior of thorium-uranium(IV) phosphate-diphosphate sintered samples during leaching tests. Part II. Saturation processes

Sintered pellets of thorium-uranium (IV) phosphate-diphosphate solid solutions (beta-Th4-xUx(PO4)(4)P2O7, beta-TUPD) were altered in several acidic media. All the results reported in the first part of this paper confirmed the good chemical durability of the samples. The evolution of the normalized weight loss showed that, in several media, thorium quickly precipitates in a neoformed phosphate-based phase while uranium (IV) is released in the leachate due to its oxidation into the uranyl form. The characterization of neoformed phases was carried out through several techniques involving grazing XRD, infrared and mu-Raman spectroscopies, EPMA, SEM and TEM. SEM micrographics showed that the dissolution mainly occurs at the grain boundaries, leading to the break away of the grains: only the first 15 mu m are altered for 2 months in 10(-1) M HNO3. From EPMA and BET measurements, neither the chemical composition nor the specific surface area are significantly modified. Near equilibrium, two neoformed phases were observed and identified by grazing XRD and/or mu-Raman spectroscopy at the surface of the leached pellets: one is found to be amorphous and progressively turns into the crystallized thorium phosphate-hydrogenphosphate hydrate (TPHPH). From the results obtained, a chemical scheme of the dissolution of beta-TUPD sintered samples is proposed. The behavior of the actinides in the gelatinous phase appears mainly driven by their oxidation state: thorium remains in the tetrapositive state and is quickly and quantitatively precipitated while uranium (IV) is oxidized into uranyl then released in the leachate. The Th-precipitation as TPHPH first appears scattered then covers the entire surface of the pellet, inducing a delay of the actinides release in the leachate. Both phases act as protective layers and should induce the significant delay of the release of actinides (Th, U) to the biosphere. (c) 2005 Elsevier B.V. All rights reserved.