Phase transitions in U3O8−z: I, heat capacity measurements |
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Authors: | Keiji Naito Hideaki Inaba Seiichi Takahashi |
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Affiliation: | Department of Nuclear Engineering, Faculty of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan |
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Abstract: | The heat capacity of U3O8−z with various O/U ratios was measured in the range from 250 to 750 K, and λ-type heat capacity anomalies were found in each sample. The transition temperatures were 487 and 573 K for UO2.663, 490 and 576 K for UO2.656 and 508, 562 and 618 K for UO2.640. The entropy changes of the transitions were 0.44 and 0.39 J K−1mol−1 for UO2.663, 0.58 and 0.47 J K−1mol−1 for UO2.656 and 0.62, 0.51 and 0.25 J K−1mol−1 for UO2.640, increasing as O/U decreases. The enthalpy change due to the transition varied linearly with the transition temperature except for UO2.640, showing the presence of the same mechanism of phase transition among the samples with various O/U ratios. The mechanism of the phase transition was discussed on the assumption that the transition is originated from the order-disorder rearrangement of U5+ and U6+ with a consequent displacement of atoms, similarly to the case of U4O9−y. |
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