Probing the hydrolytic degradation of UF<sub>4</sub> in humid air

Foley, Bryan J.; Christian, Jonathan H.; Klug, Christopher A.; Villa‐Aleman, Eliel; Wellons, Matthew S.; DeVore, Michael A.; Groden, Nicholas; Darvin, Jason R.

doi:10.1039/d2dt00196a

Cited by 5 publications

(4 citation statements)

References 31 publications

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“…Finally, the reaction between UO 2 ms with ABF (eq ) yielded (NH 4 ) 2 UF 6 (Figure S6, Supporting Information). During this reaction, the spherical geometry was entirely lost, likely due to the susceptibility of tetravalent uranium fluoride to hydrolysis , combined with the agglomerating effect of NH 4 F U 3 O 8 ( s ) + 6 HF ( g ) + 1 2 O 2 ( g ) → 3 UO 2 F 2 ( s ) + 3 normalH 2 O ( g ) false( T = 250 0.25em C ° false) UO 2 F 2 ( s ) + 3 NH 4 normalF ( g ) → false( NH 4 false) 3 UO 2 F 5 ( s ) false( T = 250 0.25em C ° false) …”

Section: Resultsmentioning

confidence: 99%

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Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Jang,

Poineau

2024

ACS Omega

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Uranium microstructured materials with controlled size and shape are relevant to the nuclear industry and have found applications as targets for medical isotope production, fuels for nuclear reactors, standards for nuclear forensics, and energy sources for space exploration. Until now, most studies at the microscale have focused on uranium microspheres (oxides, nitrides, carbides, and fluorides), while micromaterials of uranium halides, carbides, and pnictides with other morphologies are largely unknown. A promising method to shape the morphology of uranium micromaterials is the replacement of O by F atoms in oxide materials using a solid−gas reaction. Here, with the aim to elaborate unexplored uranium fluoride micromaterials, the fluorination of uranium oxide (U 3 O 8 and UO 2 ) microspheres (ms), microrods (mr), and microplates (mp) in an autoclave at 250 °C with HF (g) (produced from the thermal decomposition of silver bifluoride (SBF)) and with ammonium bifluoride (ABF) was evaluated. We show that the reactions between U 3 O 8 mr and U 3 O 8 mp and SBF provided the most efficient way to elaborate mr and mp UO 2 F 2 micromaterials in a high yield (∼90%). The resulting UO 2 F 2 mr (length: 3−20 μm) and UO 2 F 2 mp (width: 1−7.5 μm) exhibited a well-defined geometry that was identical to that of the U 3 O 8 precursors. Agglomerated (NH 4 ) 3 UO 2 F 5 and UO 2 F 2 ms (2−3.5 μm) were prepared from the reaction of U 3 O 8 ms with ABF. It is noted that the reaction of UO 2 ms with SBF and ABF did not provide any uranium fluoride micromaterials. The successful preparation of uranium fluoride microstructures (ms, mr, and mp) developed here opens the way to novel actinide fluoride micromaterials.

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Section: Resultsmentioning

confidence: 99%

“…Finally, the reaction between UO 2 ms with ABF ( eq 4 ) yielded (NH 4 ) 2 UF 6 ( Figure S6 , Supporting Information). During this reaction, the spherical geometry was entirely lost, likely due to the susceptibility of tetravalent uranium fluoride to hydrolysis 28 , 40 combined with the agglomerating effect of NH 4 F …”

Section: Resultsmentioning

confidence: 99%

Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Jang,

Poineau

2024

ACS Omega

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“…Most of the research published in the open literature focuses on the science on uranium oxide, nitride, and carbide microspheres, while very little is known about uranium halide microspheres. So far, only UF 4 has been prepared as microspheres, and several reports contain images of commercially available UF 4 (International Bio-Analytical Industries, Inc.) microspheres (⌀ < 30 μm). − Currently, reports on uranyl halide microspheres ( i.e ., UO 2 X 2 ; X = F, Cl, Br) are limited, while UO 2 F 2 is an interesting material in the nuclear industry with remarkable significance.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Morphological Control of UO₂F₂Particulates

2023

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Uranium-based microspheres are of interest due to their potential applications as targets for medical isotopes production, as fuel for nuclear reactors, and as standardized materials for nuclear forensics. Here, for the first time, UO2F2 microspheres (1–2 μm) have been prepared from the reaction between UO3 microspheres and AgHF2 in an autoclave. In this preparation, a new fluorination method has been applied, and HF(g)produced in situ from the thermal decomposition of AgHF2 and NH4HF2was used as the fluorinating agent. The microspheres were characterized by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). Diffraction results indicated that the reaction performed with AgHF2 at 200 °C led to anhydrous UO2F2 microspheres, while at 150 °C, hydrated UO2F2 microspheres were obtained. Meanwhile, NH4HF2 led to the formation of contaminated products as driven by the formation of volatile species.

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“…Nondestructive spectroscopic determination of a nuclear materials age, physical and chemical characteristics, and process history is vital in determining material provenance for nuclear forensics and nuclear nonproliferation purposes. [1][2][3][4] Despite its simple face-centered cubic crystal structure, plutonium(IV) dioxide (PuO 2 ) demonstrates fascinating spectroscopic behavior due to its electronic band structure and its self-radiolysis that produces crystal lattice defects that increase with time. [5][6][7] In recent years, our group and others have used Raman spectroscopy to show how the intensity, position, and full width at half maximum (FWHM) of bands in the Raman spectrum of PuO 2 are significantly influenced by crystallinity, which itself is predominantly affected by alpha radiolysis, the calcination temperature employed during material production, and time elapsed because the material was last calcined/annealed.…”

Section: Introductionmentioning

confidence: 99%

The electronic Raman scattering spectrum of PuO₂

Villa‐Aleman

Dick

Christian

et al. 2022

J Raman Spectroscopy

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The Raman spectrum of PuO2 was measured up to 13,000 cm−1 with three different laser excitation wavelengths spanning the resonance (405 nm), near‐resonance (457 nm), and preresonance (514 nm) energy range. Approximately 26 never‐before‐seen bands were observed between 3500 and 13,000 cm−1. Given the very high energy of the Raman shifts of these bands and the relative insensitivity of their spectral position to the interrogating laser wavelength, they are believed to arise from an electronic origin. These bands are present in both freshly calcined and radiolytically aged PuO2, although a broad luminescence is observed in the aged material, which obscures many of the high frequency features. In situ laser annealing of the material attenuated this luminescence and allowed for clear observation of these never‐before‐seen spectral features. Discovery of these high‐energy bands presents a new way of identifying PuO2 for nuclear nonproliferation and forensics purposes.

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Probing the hydrolytic degradation of UF₄ in humid air

Abstract: When exposed to humid air over the course of two weeks, anhydrous UF4 undergoes surface corrosion to various O-bearing uranium complexes.

Cited by 5 publications

References 31 publications

Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Synthesis and Morphological Control of UO₂F₂Particulates

The electronic Raman scattering spectrum of PuO₂

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Probing the hydrolytic degradation of UF4 in humid air

Abstract: When exposed to humid air over the course of two weeks, anhydrous UF4 undergoes surface corrosion to various O-bearing uranium complexes.

Cited by 5 publications

References 31 publications

Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Tailoring Triuranium Octoxide into Multidimensional Uranyl Fluoride Micromaterials

Synthesis and Morphological Control of UO2F2Particulates

The electronic Raman scattering spectrum of PuO2

Contact Info

Product

Resources

About

Probing the hydrolytic degradation of UF₄ in humid air

Synthesis and Morphological Control of UO₂F₂Particulates

The electronic Raman scattering spectrum of PuO₂