Raman spectroscopic studies of defect structures and phase transition in hyper-stoichiometric UO2+x

Literature Information

Publication Date 2010-06-08
DOI 10.1039/B925495A
Impact Factor 3.676
Authors

Heming He, David Shoesmith


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Abstract

A method to determine the defect structures in hyper-stoichiometric UO2+x using a combination of XRD and Raman spectroscopy has been developed. A sequence of phase transitions, from cubic to tetragonal symmetry, occurs with increasing degree of non-stoichiometry. This sequence proceeds from a cubic phase through an intermediate t″-type tetragonal (axial ratio c/a = 1) phase to a final t-type tetragonal (c/a ≠ 1) phase. Four distinct structural defect regions can be identified in the stoichiometry range, UO2 to U3O7: (i) a random point defect structure (x (in UO2+x) ≤ 0.05); (ii) a non-stoichiometry region (0.05 ≤ x ≤ 0.15) over which point defects are gradually eliminated and replaced by the Willis 2 : 2 : 2 cluster; (iii) a mixture of Willis and cuboctahedral clusters (0.15 ≤ x ≤ 0.23); (iv) the cuboctahedral cluster (x ≥ 0.23). The geometry and steric arrangement of these defects is primarily determined by the concentration of the excess-oxygen interstitials.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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