X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)

Wayne, David M.; Stritzinger, Jared T.; Casella, Amanda J.; Sweet, Lucas E.; Corbey, Jordan F.; Garcia, Daniel J.; Wylie, E. Miller; Tandon, Lav; Olson, Angela C.; Rim, Jung Ho

doi:10.1007/s10967-021-07810-z

X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF₄)

Journal Article · Wed Jun 23 00:00:00 EDT 2021 · Journal of Radioanalytical and Nuclear Chemistry

DOI:https://doi.org/10.1007/s10967-021-07810-z· OSTI ID:1827569

^[1]; ^[1]; Casella, Amanda J. ^[2]; Sweet, Lucas E. ^[2]; Corbey, Jordan F. ^[2]; Garcia, Daniel J. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

A 30 year-old PuF₄ sample consisting of brown powder (PuF₄-b) and pink granules (PuF_4-p) was analyzed. X-ray diffraction shows the bulk is comprised of three compounds: PuF₄, PuO₂, and PuF₄·1.6H₂O. Broadening of PuF₄ XRD peaks suggests possible α-damage. After annealing at 650 °C, crystalline PuF₄ and PuO₂ remain. Thermogravimetric analysis and differential scanning calorimetry—with simultaneous evolved gas analysis—of the separated PuF₄-p and PuF₄-b components reveal a distinct sequence of reactions. Dehydration occurs between ~ 90 and 300 °C. Exothermic annealing of the α-damage occurs in two stages: at 350–355 °C and at 555–558 °C. Hydrofluoric acid, fluorine and helium desorb during the first exotherm. Above 700 °C, PuF₄ reacts with PuO₂, resulting in oxygen release and mass loss.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1827569

Alternate ID(s):: OSTI ID: 1818130
OSTI ID: 23046643

Report Number(s):: LA-UR--20-20067

Journal Information:: Journal of Radioanalytical and Nuclear Chemistry, Journal Name: Journal of Radioanalytical and Nuclear Chemistry Journal Issue: 2 Vol. 329; ISSN 0236-5731

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Energetics of radiation damage in natural zircon (ZrSiO4) Ellsworth, Susan; Navrotsky, Alexandra; Ewing, Rodney C. Physics and Chemistry of Minerals, Vol. 21, Issue 3 https://doi.org/10.1007/BF00203144	journal	July 1994
Phase relations in the system LiF-PuF3 Barton, C. J.; Strehlow, R. A. Journal of Inorganic and Nuclear Chemistry, Vol. 18 https://doi.org/10.1016/0022-1902(61)80381-3	journal	March 1961
The oxide chemistry of plutonium in molten fluorides and the free energy of formation of PuF3 and PuF4 Bamberger, C. E.; Ross, R. G.; Baes, C. F. Journal of Inorganic and Nuclear Chemistry, Vol. 33, Issue 3 https://doi.org/10.1016/0022-1902(71)80476-1	journal	March 1971
Review of major plutonium pyrochemical technology Moser, W. Scott; Navratil, James D. Journal of the Less Common Metals, Vol. 100 https://doi.org/10.1016/0022-5088(84)90062-6	journal	July 1984
Radiation damage in nuclear materials Matzke, Hj. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 65, Issue 1-4 https://doi.org/10.1016/0168-583X(92)95010-O	journal	March 1992
Alpha-decay damage and aqueous durability of actinide host phases in natural systems Lumpkin, Gregory R. Journal of Nuclear Materials, Vol. 289, Issue 1-2 https://doi.org/10.1016/S0022-3115(00)00693-0	journal	February 2001
Halides Of The Actinide Elements Katz, Joseph J.; Sheft, Irving Advances in Inorganic Chemistry and Radiochemistry, Vol. 2, p. 195-236 https://doi.org/10.1016/S0065-2792(08)60190-9	book	January 1960
New scenario for the accumulation and release of radiation damage in rock salt and related materials den Hartog, H. W.; Vainshtein, D. I.; Dubinko, V. I. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 191, Issue 1-4 https://doi.org/10.1016/S0168-583X(02)00548-7	journal	May 2002
Hydration of plutonium oxide and process salts, NaCl, KCl, CaCl2, MgCl2: effect of calcination on residual water and rehydration Smith, D. M.; Neu, M. P.; Garcia, E. Waste Management, Vol. 20, Issue 7 https://doi.org/10.1016/S0956-053X(00)00014-3	journal	November 2000
Zircon grain selection reveals (de)coupled metamictization, radiation damage, and He diffusivity Ault, Alexis K.; Guenthner, William R.; Moser, Amy C. Chemical Geology, Vol. 490 https://doi.org/10.1016/j.chemgeo.2018.04.023	journal	June 2018
Electrochemical behavior of plutonium fluoride species in LiF-CaF2 eutectic melt Claquesin, Julien; Lemoine, Olivier; Gibilaro, Mathieu Electrochimica Acta, Vol. 301 https://doi.org/10.1016/j.electacta.2019.01.169	journal	April 2019
Apatite (U–Th)/He thermochronometry using a radiation damage accumulation and annealing model Flowers, Rebecca M.; Ketcham, Richard A.; Shuster, David L. Geochimica et Cosmochimica Acta, Vol. 73, Issue 8 https://doi.org/10.1016/j.gca.2009.01.015	journal	April 2009
Influence of radiation damage on titanite He diffusion kinetics Baughman, Jaclyn S.; Flowers, Rebecca M.; Metcalf, James R. Geochimica et Cosmochimica Acta, Vol. 205 https://doi.org/10.1016/j.gca.2017.01.049	journal	May 2017
Annealing kinetics of radiation damage in zircon Ginster, Ursula; Reiners, Peter W.; Nasdala, Lutz Geochimica et Cosmochimica Acta, Vol. 249 https://doi.org/10.1016/j.gca.2019.01.033	journal	March 2019
Moisture and surface area measurements of plutonium-bearing oxides Crowder, Mark L.; Duffey, Jonathan M.; Livingston, Ronald R. Journal of Alloys and Compounds, Vol. 488, Issue 2 https://doi.org/10.1016/j.jallcom.2009.09.161	journal	December 2009
Thermodynamic properties and phase diagrams of fluoride salts for nuclear applications Beneš, O.; Konings, R. J. M. Journal of Fluorine Chemistry, Vol. 130, Issue 1 https://doi.org/10.1016/j.jfluchem.2008.07.014	journal	January 2009
On the fluorination of plutonium dioxide by ammonium hydrogen fluoride Claux, Benoit; Beneš, Ondřej; Capelli, Elisa Journal of Fluorine Chemistry, Vol. 183 https://doi.org/10.1016/j.jfluchem.2015.12.009	journal	March 2016
Helium diffusion in uranium and plutonium oxides Ronchi, C.; Hiernaut, J. P. Journal of Nuclear Materials, Vol. 325, Issue 1 https://doi.org/10.1016/j.jnucmat.2003.10.006	journal	February 2004
Evolution of spent nuclear fuel in dry storage conditions for millennia and beyond Wiss, Thierry; Hiernaut, Jean-Pol; Roudil, Danièle Journal of Nuclear Materials, Vol. 451, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2014.03.055	journal	August 2014
A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product Orr, R. M.; Sims, H. E.; Taylor, R. J. Journal of Nuclear Materials, Vol. 465 https://doi.org/10.1016/j.jnucmat.2015.06.058	journal	October 2015
Radiation damage and annealing in plutonium tetrafluoride McCoy, Kaylyn; Casella, Amanda; Sinkov, Sergey Journal of Nuclear Materials, Vol. 496 https://doi.org/10.1016/j.jnucmat.2017.08.005	journal	December 2017
Probing He bubbles in naturally aged and annealed δ-Pu alloys using ultra-small-angle x-ray scattering Jeffries, J. R.; Hammons, J. A.; Willey, T. M. Journal of Nuclear Materials, Vol. 498 https://doi.org/10.1016/j.jnucmat.2017.10.058	journal	January 2018
Synthesis of plutonium trifluoride by hydro-fluorination and novel thermodynamic data for the PuF3-LiF system Tosolin, A.; Souček, P.; Beneš, O. Journal of Nuclear Materials, Vol. 503 https://doi.org/10.1016/j.jnucmat.2018.02.037	journal	May 2018
Radiation damage effects of crystal Pei, Yu; Chen, Xiaofeng; Yao, Dongmin Radiation Measurements, Vol. 42, Issue 3 https://doi.org/10.1016/j.radmeas.2007.02.071	journal	March 2007
The Chemical Thermodynamic Properties of Plutonium Compounds Oetting, Franklin L. Chemical Reviews, Vol. 67, Issue 3 https://doi.org/10.1021/cr60247a002	journal	June 1967
Spectroscopic studies of .alpha.-induced radiation damage in divalent metal fluorides Exarhos, Gregory J. The Journal of Physical Chemistry, Vol. 86, Issue 20 https://doi.org/10.1021/j100217a027	journal	September 1982
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
Quantification of actinide α-radiation damage in minerals and ceramics Farnan, Ian; Cho, Herman; Weber, William J. Nature, Vol. 445, Issue 7124 https://doi.org/10.1038/nature05425	journal	January 2007
The preparation and some properties of plutonium fluorides Dawson, J. K.; Elliott, R. M.; Hurst, R. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9540000558	journal	January 1954
The hydrated tetrafluorides of uranium and plutonium Dawson, J. K.; D'Eye, R. W. M.; Truswell, A. E. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9540003922	journal	January 1954
A new mechanism for radiation damage processes in alkali halides Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I. Journal of Applied Physics, Vol. 86, Issue 11 https://doi.org/10.1063/1.371639	journal	December 1999
Cerium tetrafluoride. II. The system cerium tetrafluoride-cerium trifluoride Asker, Wj; Wylie, Aw Australian Journal of Chemistry, Vol. 18, Issue 7 https://doi.org/10.1071/CH9650969	journal	January 1965
Characterization and modelling of helium bubbles in self-irradiated plutonium alloys Schwartz *, A. J.; Wall, M. A.; Zocco, T. G. Philosophical Magazine, Vol. 85, Issue 4-7 https://doi.org/10.1080/02678370412331320026	journal	February 2005
Radiation damage in Nacl Groote, J. C.; Seinen, J.; Weerkamp, J. R. W. Radiation Effects and Defects in Solids, Vol. 119-121, Issue 2 https://doi.org/10.1080/10420159108220844	journal	November 1991
Seeing is believing: Visualization of He distribution in zircon and implications for thermal history reconstruction on single crystals Danišík, Martin; McInnes, Brent I. A.; Kirkland, Christopher L. Science Advances, Vol. 3, Issue 2 https://doi.org/10.1126/sciadv.1601121	journal	February 2017
Radiation damage from long-term alpha particle bombardment of silicates – a microfocus XRD and Fe K -edge XANES study Bower, W. R.; Pearce, C. I.; Droop, G. T. R. Mineralogical Magazine, Vol. 79, Issue 6 https://doi.org/10.1180/minmag.2015.079.6.20	journal	November 2015
Microscopic effects of self-radiation damage in ²⁴⁴ Cm-doped LuPO ₄ crystals Luo, J. S.; Liu, G. K. Journal of Materials Research, Vol. 16, Issue 2 https://doi.org/10.1557/JMR.2001.0056	journal	February 2001
Radionuclide Decay Effects on Waste Glass Corrosion Wronkiewicz, D. J. MRS Proceedings, Vol. 333 https://doi.org/10.1557/PROC-333-083	journal	January 1993
Self-Radiation Damage in Actinide Host Phases of Nuclear Waste Forms Weber, W. J.; Wald, J. W.; Matzke, Hi. MRS Proceedings, Vol. 44 https://doi.org/10.1557/PROC-44-679	journal	January 1984
TEM study of alpha-damaged plutonium and americium dioxides Wiss, Thierry; Dieste-Blanco, Oliver; Tacu, Anca Journal of Materials Research, Vol. 30, Issue 9 https://doi.org/10.1557/jmr.2015.37	journal	March 2015
Characterization of radiation damage in ceramics: Old challenge new issues? Simeone, David; Costantini, Jean Marc; Luneville, Laurence Journal of Materials Research, Vol. 30, Issue 9 https://doi.org/10.1557/jmr.2015.77	journal	April 2015
Zircon (U-Th)/He Thermochronometry Reiners, P. W. Reviews in Mineralogy and Geochemistry, Vol. 58, Issue 1 https://doi.org/10.2138/rmg.2005.58.6	journal	January 2005
Helium diffusion in natural zircon: Radiation damage, anisotropy, and the interpretation of zircon (U-Th)/He thermochronology Guenthner, W. R.; Reiners, P. W.; Ketcham, R. A. American Journal of Science, Vol. 313, Issue 3 https://doi.org/10.2475/03.2013.01	journal	March 2013

Similar Records

X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)

Journal Article · Mon Aug 02 00:00:00 EDT 2021 · Journal of Radioanalytical and Nuclear Chemistry · OSTI ID:1818130

Preparation of plutonium tetrafluoride

Technical Report · Sun Jul 01 00:00:00 EDT 1973 · OSTI ID:4936082

THE REACTION OF PuF$sub 4$ WITH OXYGEN

Journal Article · Thu Nov 30 23:00:00 EST 1961 · J. Inorg. & Nuclear Chem. · OSTI ID:4811027

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
annealing
differential scanning calorimetry
evolved gas analysis
plutonium tetrafluoride
radiation damage
thermal analysis

X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)

Citation Formats

References (43)

Similar Records

Related Subjects

X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF₄)