Oxygen Isotope and Fluorine Impurity Signatures during the Conversion of Uranium Ore Concentrates to Nuclear Fuel.

Within the front end of the nuclear fuel cycle, many processes impart forensic signatures. Oxygen-stable isotopes (δ18O values) of uranium-bearing materials have been theorized to provide the processing and geolocational signatures of interdicted materials. However, this signature has been minimally utilized due to a limited understanding of how oxygen isotopes are influenced during uranium processing. This study explores oxygen isotope exchange and fractionation between magnesium diuranate (MDU), ammonium diuranate (ADU), and uranyl fluoride (UO2F2) with steam (water vapor) during their reduction to UOx. The MDU was precipitated from two water sources, one enriched and one depleted in 18O. The UO2F2 was precipitated from a single water source and either directly reduced or converted to ADU prior to reduction. All MDU, ADU, and UO2F2 were reduced to UOx in a 10% hydrogen/90% nitrogen atmosphere that was dry or included steam. Powder X-ray diffraction (p-XRD) was used to verify the composition of materials after reduction as mixtures of primarily U3O8, U4O9, and UO2 with trace magnesium and fluorine phases in UOx from MDU and UO2F2, respectively. The bulk oxygen isotope composition of UOx from MDU was analyzed using fluorination to remove the lattice-bound oxygen, and then O2 was subsequently analyzed with isotope ratio mass spectrometry (IRMS). The oxygen isotope compositions of the ADU, UO2F2, and the resulting UOx were analyzed by large geometry secondary ion mass spectrometry (LG-SIMS). When reduced with steam, the MDU, ADU, and UO2F2 experienced significant oxygen isotope exchange, and the resulting δ18O values of UOx approached the values of the steam. When reduced without steam, the δ18O values of converted ADU, U3O8, and UOx products remained similar to those of the UO2F2 starting material. LG-SIMS isotope mapping of F impurity abundances and distributions showed that direct steam-assisted reduction from UO2F2 significantly removed F impurities while dry reduction from UO2F2 led to the formation of UOx that was enhanced in F impurities. In addition, when UO2F2 was processed via precipitation to ADU and calcination to U3O8, F impurities were largely removed, and reductions to UOx with and without steam each had low F impurities. Overall, these findings show promise for combining multiple signatures to predict the process history during the conversion of uranium ore concentrates to nuclear fuel.

Identification and Elemental Impurity Analysis of Heterogeneous Morphologies in Uranium Oxides Synthesized from Uranyl Fluoride Precursors.

The surface morphology characteristics of postenrichment deconversion products in the nuclear fuel cycle are important for producing nuclear fuel pellets. They also provide the first opportunity for a microstructural signature after conversion to gaseous uranium hexafluoride (UF6). This work synthesizes uranium oxides from uranyl fluoride (UO2F2) starting solutions by the wet ammonium diuranate route and a modification of the dry route. Products are reduced under a nitrogen/hydrogen atmosphere, with and without water vapor in the reducing environment. The crystal structures of the starting materials and resulting uranium oxides are characterized by powder X-ray diffraction. Scanning electron microscopy (SEM) and focused ion beam SEM with energy-dispersive X-ray spectroscopy (EDX) are used to investigate microstructural properties and quantify fluorine impurity concentrations. Heterogeneous distributions of fluorine with unique morphology characteristics were identified by backscatter electron imaging and EDX; these regions had elevated concentrations of fluorine impurities relating to the incomplete reduction of UO2F2 to UO2 and may provide a novel nuclear forensics morphology signature for nuclear fuel and U metal precursors.

Effect of Diel Cycling Temperature, Relative Humidity, and Synthetic Route on the Surface Morphology and Hydrolysis of α-U3O8.

The speciation and morphological changes of α-U3O8 following aging under diel cycling temperature and relative humidity (RH) have been examined. This work advances the knowledge of U-oxide hydration as a result of synthetic route and environmental conditions, ultimately giving novel insight into nuclear material provenance. α-U3O8 was synthesized via the washed uranyl peroxide (UO4) and ammonium uranyl carbonate (AUC) synthetic routes to produce unaged starting materials with different morphologies. α-U3O8 from UO4 is comprised of subrounded particles, while α-U3O8 from AUC contains blocky, porous particles approximately an order of magnitude larger than particles from UO4. For aging, a humidity chamber was programmed for continuous daily cycles of 12 "high" hours of 45 °C and 90% RH, and 12 "low" hours of 25 °C and 20% RH. Samples were analyzed at varying intervals of 14, 24, 36, 43, and 54 days. At each aging interval, crystallographic changes were measured via powder X-ray diffraction coupled with whole pattern fitting for quantitative analysis. Morphologic effects were studied via scanning electron microscopy and 12-way classification via machine learning. While all samples were found to have distinguishing morphologic characteristics (93.2% classification accuracy), α-U3O8 from UO4 had more apparent change with increasing aging time. Nonetheless, α-U3O8 from AUC was found to hydrate more quickly than α-U3O8 from UO4, which can likely be attributed to its larger surface area and porous starting material morphology.

Impact of Controlled Storage Conditions on the Hydrolysis and Surface Morphology of Amorphous-UO3.

The hydration and morphological effects of amorphous (A)-UO3 following storage under varying temperature and relative humidity have been investigated. This study provides valuable insight into U-oxide speciation following aging, the U-oxide quantitative morphological data set, and, overall, the characterization of nuclear material provenance. A-UO3 was synthesized via the washed uranyl peroxide synthetic route and aged based on a 3-factor circumscribed central composite design of experiment. Target aging times include 2.57, 7.00, 14.0, 21.0, and 25.4 days, temperatures of 5.51, 15.0, 30.0, 45.0, and 54.5 °C, and relative humidities of 14.2, 30.0, 55.0, 80.0, and 95.8% were examined. Following aging, crystallographic changes were quantified via powder X-ray diffraction and an internal standard Rietveld refinement method was used to confirm the hydration of A-UO3 to crystalline schoepite phases. The particle morphology from scanning electron microscopy images was quantified using both the Morphological Analysis of MAterials software and machine learning. Results from the machine learning were processed via agglomerative hierarchical clustering analysis to distinguish trends in morphological attributes from the aging study. Significantly hydrated samples were found to have a much larger, plate-like morphology in comparison to the unaged controls. Predictive modeling via a response surface methodology determined that while aging time, temperature, and relative humidity all have a quantifiable effect on A-UO3 crystallographic and morphological changes, relative humidity has the most significant impact.