Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

Villa-Aleman, Eliel; Christian, Jonathan H.; Darvin, Jason R.; Foley, Bryan J.; Dick, Don D.; Fallin, Brent; Fessler, Kimberly A. S.

doi:10.1177/00037028221145724

Title: Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

Journal Article · Thu Feb 16 00:00:00 UTC 2023 · Applied Spectroscopy

DOI: https://doi.org/10.1177/00037028221145724 · OSTI ID:1957665

Villa-Aleman, Eliel ^[1];

^[1];

^[1]

Savannah River National Laboratory, Aiken, SC, USA

Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu ₂ (C ₂ O ₄ ) ₃ •9H ₂ O and its thermal decomposition product, PuO ₂ . We analyzed a total of eight PuO ₂ samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu ₂ (C ₂ O ₄ ) ₃ •9H ₂ O features several broad bands that currently preclude detailed analysis. However, all PuO ₂ samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO ₂ was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO ₂ samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO ₂ can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO ₂ and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.

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Research Organization:: Savannah River National Lab (SRNL), Aiken, SC (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Environmental Management (EM)

Grant/Contract Number:: 89303321CEM000080

OSTI ID:: 1957665

Report Number(s):: SRNL-STI-2022-00401

Journal Information:: Applied Spectroscopy, Journal Name: Applied Spectroscopy Journal Issue: 5 Vol. 77; ISSN 0003-7028

Publisher:: SAGE PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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