The solid-state chemistry of uranium is essential to the nuclear fuel cycle. Uranyl nitrate is a key compound that is produced at various stages of the nuclear fuel cycle, both in front-end and backend cycles. It is typically formed by dissolving spent nuclear fuel in nitric acid or through a wet conversion process for the preparation of UF6. Additionally, uranium oxides are a primary consideration in the nuclear fuel cycle because they are the most commonly used nuclear fuel in commercial nuclear reactors. Therefore, it is crucial to understand the oxidation and thermal behavior of uranium oxides and uranyl nitrates. Under the ‘2023 Nuclear Global Researcher Training Program for the Back-end Nuclear Fuel Cycle,’ supported by KONICOF, several experiments were conducted at IMRAM (Institute of Multidisciplinary Research for Advanced Materials) at Tohoku University. First, the recovery ratio of uranium was analyzed during the synthesis of uranyl nitrate by dissolving the actual radioisotope, U3O8, in a nitric acid solution. Second, thermogravimetric-differential thermal analysis (TG-DTA) of uranyl nitrate (UO2(NO3)2) and hyper-stoichiometric uranium dioxide (UO2+X) was performed. The enthalpy change was discussed to confirm the mechanism of thermal decomposition of uranyl nitrate under heating conditions and to determine the chemical hydrate form of uranyl nitrate. In the case of UO2+X, the value of ‘x’ was determined through the calculation of weight change data, and the initial form was verified using the phase diagram for the U-O system. Finally, the formation of a few UO2+X compounds was observed with heat treatment of uranyl nitrate and uranium dioxide at different temperature intervals (450°C-600°C). As a result of these studies, a deeper understanding of the thermal and chemical behavior of uranium compounds was achieved. This knowledge is vital for improving the efficiency and safety of nuclear fuel cycle processes and contributes to advancements in nuclear science and technology.

Once discharged, spent nuclear fuel undergoes an initial cooling process within deactivation pools situated at the reactor site. This cooling step is crucial for reducing the fuel’s temperature. Once the heat has sufficiently diminished, two viable options emerge: reprocessing or interim storage. A method known as PUREX, for aqueous nuclear reprocessing, involves a chemical procedure aimed at separating uranium and plutonium from the spent nuclear fuel. This separation not only minimizes waste volume but also facilitates the reuse of the extracted materials as fuel for nuclear reactors. The transformation of uranium oxides through dissolution in nitric acid followed by drying results in uranium taking the form of UO2(NO3)2 + 6H2O, which can then be converted into various solid-state configurations through different heat treatments. This study specifically focuses on investigating the phase transitions of artificially synthesized UO2(NO3)2 + 6H2O subjected to heat treatment at various temperatures (450, 500, 550, 600°C) using X-ray Diffraction (XRD) analysis. Heat treatments were also conducted on UO2 to analyze its phase transformations. Additionally, the study utilized XRD analysis on an unidentified oxidized uranium oxide, UO2+X, and employed lattice parameters and Bragg’s law to ascertain the oxidation state of the unknown sample. To synthesize UO2(NO3)2 + 6H2O, U3O8 powder is first dissolved in a 20% HNO3 solution. The solid UO2(NO3)2 + 6H2O is obtained after drying on a hotplate and is subsequently subjected to heat treatment at temperatures of 450, 500, 550, and 600°C. As the heat treatment temperature increases, the color of the samples transitions from orange to dark green, indicating the formation of different phases at different temperatures. XRD analysis confirms that uranyl nitrate, when heattreated at 500 and 550°C, oxidizes to UO3, while the sample subjected to 600°C heat treatment transforms into U3O8 due to the higher temperature. All samples exhibit sharp crystal peaks in their XRD spectra, except for the one heat-treated at 450°C. In the second experiment, the XRD spectra of the heat-treated UO2 consistently indicate the presence of U3O8 rather than UO3, regardless of the temperature. Under an oxidizing atmosphere within a temperature range of 300 to 700°C, UO2 can be oxidized to form U3O8. In the final experiment, the oxidation state of the unknown UO2+X was determined using Bragg’s law and lattice parameters, revealing that it was a material in which UO2 had been oxidized, resulting in an oxidation state of UO2.24.

The stabilization technology for the damaged spent fuel is being developed to process the damaged fuel into sound pellet suitable for dry re-fabrication. It requires several treatments including oxidative decladding followed by reduction treatment for oxidized powder closely related to the quality of oxidized powders for pellet fabrication. For the development of operating condition for the reduction treatment, in this study, we evaluated the effect of air-cylinder based vertical shaking previously applied to oxidative decladding on powder reduction. For U3O8 of 50-100 g, the reduction test were applied with and without vertical shaking at 700°C under reduction atmosphere (Ar + 4%H2) and the concentration of hydrogen in effluent was measured to evaluate the reduction reaction. It was found that the vertical shaking system has allowed the reaction time of 50 g and 100 g U3O8 reduced by 33% compared to the test in static mode. Based on XRD analysis, the better crystallinity of the products was also achieved.