Raman and infrared spectra of plutonium (IV) oxalate and its thermal degradation products

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

doi:10.1016/j.jnucmat.2022.153574

Raman and infrared spectra of plutonium (IV) oxalate and its thermal degradation products

Journal Article · Thu Feb 17 00:00:00 EST 2022 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2022.153574· OSTI ID:1844185

Christian, Jonathan H. ^[1]; Foley, Bryan J. ^[2]; Ciprian, Elodia ^[3]; Dick, Don D. ^[2]; Said, Meena ^[4]; Darvin, Jason ^[2]; Hixon, Amy E. ^[3]; Villa-Aleman, Eliel ^[2]

Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Univ. of Notre Dame, IN (United States)
Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Univ. of Notre Dame, IN (United States)
Univ. of Notre Dame, IN (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

For over 80 years, plutonium dioxide has been routinely produced via thermal decomposition of hydrated plutonium(IV) oxalate. Despite the longstanding utility of this process, the chemical structures of starting materials and intermediates produced during this thermal conversion remain ill-defined. To help resolve this uncertainty, we measured high-resolution Raman and infrared spectra of Pu(C₂O₄)₂·6H₂O that was heated to 25, 100, 220, 250, 350, and 450 °C in air. Our measurements show that Pu(C₂O₄)₂·6H₂O has a rich vibrational spectrum with at least 15 Raman bands between 180 cm^-1 and 1900 cm^-1 and 9 infrared bands between 800 cm^-1 and 4000 cm^-1. As Pu(C₂O₄)₂·6H₂O is heated, water is liberated, and the oxalate ligand decomposes to produce plutonium oxycarbide species. When heated to 350 °C or higher, vibrational spectra are consistent with PuO₂ with some residual carbon-containing species. Full vibrational spectra, powder X-ray diffraction, and scanning electron microscopy measurements of Pu(C₂O₄)₂·6H₂O and its thermal degradation products are presented herein along with approximate assignments for observed spectral bands. These data can be used to validate and potentially improve existing computational models that describe the chemical structure of compounds produced during thermal degradation of plutonium (IV) oxalate. Given the utility of plutonium (IV) oxalate in synthesizing plutonium dioxide, these results are expected to provide value in the fields of nuclear fuel processing, nuclear nonproliferation, and nuclear forensics.

View Accepted Manuscript (DOE)

Research Organization:: Savannah River National Lab (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

Grant/Contract Number:: 89303321CEM000080

OSTI ID:: 1844185

Alternate ID(s):: OSTI ID: 1962941

Report Number(s):: SRNL--STI-2021-00434

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 562; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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