A total reflection X-ray fluorescence (TXRF) analysis method for direct compositional characterization of sintered and green (U,Th)O2 samples in different forms (e.g., pellets, powders, and microspheres) without sample dissolution has been developed for the first time. The methodology involves transfer of only a few nanograms of the sample on the TXRF sample support by gently rubbing the samples on supports or taking their tiny uniform slurry in collodion on the sample support, drying them to make thin film, and measuring the TXRF spectra of the specimens thus prepared. This approach minimizes the matrix effects. Uranium determinations from the TXRF spectra of such specimens were made with respect to thorium, considering it as an internal standard. Samples having uranium atom percent (at%) from 0 to 100 in (U,Th)O2 were analyzed for uranium in comparison to thorium. The results showed an average precision of 2.6% (RSD, 2σ, n = 8). The TXRF-determined results deviated from expected values within 5%. The TXRF results were compared with those of biamperometry with good agreement. The lattice parameters of the solid solutions were calculated using their XRD patterns. A good correlation between lattice parameters and TXRF-determined U at% and between TXRF-determined U at% and expected U at%, calculated on the basis of preparation of (U,Th)O2 solid solutions, was obtained. The developed method is capable of analyzing (U,Th)O2 samples directly with almost negligible sample preparation and is well suited for radioactive samples. The present study suggests that this method can be extended for the determination of U,Th and Pu in other nuclear fuel materials (e.g., nitrides, carbides, etc.) in the form of pellets, powders, and microspheres after suitable modifications in sample handling procedure.

No abstract

The study demonstrates the accomplishment of single step, direct supercritical fluid carbon dioxide (SC CO2) dissolution and extraction of uranium from crude matrices viz. yellow cakes (>90%) and rock phosphate ores (70%) employing adducts of trialkyl phosphates and nitric acid, thus avoiding free acid usage and eliminating number of process steps. Rock phosphate ore was made amenable for supercritical fluid extraction (SFE) system by unique strategy of pyrohydrolytic removal of fluorine. Pressure and temperature conditions, which were found to influence uranium extraction efficiency, were optimized at 150 atm. and 323 K. Two milliliter of adduct amount was found to be adequate. Adducts of branched alkyl phosphate, tri-isoamyl phosphate and tri-ethyl hexyl phosphate (TEHP), yield better purity in comparision to straight chain tri-butyl phosphate (TBP).