Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

Christian, Jonathan H.; Foley, Bryan J.; Ciprian, Elodia; Darvin, Jason; Dick, Don D.; Hixon, Amy E.; Villa-Aleman, Eliel

doi:10.1016/j.jnucmat.2023.154596

Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

Journal Article · Sat Jun 24 00:00:00 EDT 2023 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2023.154596· OSTI ID:1993013

^[1]; ^[2]; Ciprian, Elodia ^[3]; ^[2]; ^[2]; ^[3]; Villa-Aleman, Eliel ^[2]

Savannah River National Laboratory (SRNL), Aiken, SC (United States); University of Notre Dame, IN (United States)
Savannah River National Laboratory (SRNL), Aiken, SC (United States)
University of Notre Dame, IN (United States)

The thermal decomposition of Pu(III) oxalate was analyzed by Raman microspectroscopy, infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. These data show that crystalline Pu₂(C₂O₄)₃•9H₂O progressively loses water and oxalate ligands as it is heated, which leads to a decrease in long-range lattice ordering, though minimal changes are observed in gross crystalline morphology. The onset of PuO₂ formation was observed between 200 - 250 °C. Thermal decomposition of oxalate ligands leads to the formation of CO₂ and plutonium oxalate-carbonate moieties, which had not been observed in previously published thermogravimetric measurements of Pu(III) oxalate. Formation of plutonium oxalate-carbonate moieties is believed to be associated with a change in the plutonium oxidation state from 3+ to 4+, which occurs prior to PuO₂ formation. The data provided herein demonstrate the rich spectroscopic nature of a rather underexplored, and technologically relevant, plutonium system. Ideally these results will further future investigations into the Pu(III) oxalate system both experimentally and computationally.

View Accepted Manuscript (DOE)

Research Organization:: Savannah River National Laboratory (SRNL), Aiken, SC (United States); Savannah River Site (SRS), Aiken, SC (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation; USDOE Office of Environmental Management (EM)

Grant/Contract Number:: 89303321CEM000080

OSTI ID:: 1993013

Report Number(s):: SRNL-STI-2023-00020

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 584; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
Calcination
Nonproliferation
Nuclear forensics
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Plutonium oxalate
Thermal degradation

Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

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References (37)

Figures / Tables (5)

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