Effect of calcination temperature on neptunium dioxide microstructure and dissolution
Abstract
Comprehensive thermodynamic understanding of nuclear materials is paramount for long-term management of legacy nuclear waste and commercial spent nuclear fuel. Actinide oxides (AnO2(s)) are ubiquitous materials throughout the nuclear fuel cycle, yet existing thermodynamic data has noticeable discrepancies, creating uncertainty in environmental prediction of the fate of nuclear materials. The microstructure of actinide oxides, particularly neptunium (Np) and plutonium (Pu), is rarely investigated using high resolution electron microscopy, but such features may illuminate why differences in solubility measurements persist. The aim of this study was to synthesize NpO2(s) at varying calcination temperatures, characterize the materials using high resolution electron microscopy, and perform batch solubility studies to measure total dissolved Np as a function of calcination temperature. Here, the current work demonstrates the sizable differences in dissolution of NpO2(s) based on process conditions, such as the temperature at which the material is calcined and resultant particle size, and the need for more thorough evaluation of the microstructure of solid phases used to generate thermodynamic data of actinides.
- Authors:
-
- Clemson Univ., Anderson, SC (United States)
- Clemson Univ., Anderson, SC (United States); Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
- Publication Date:
- Research Org.:
- Clemson Univ., SC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1756008
- Alternate Identifier(s):
- OSTI ID: 1737655
- Grant/Contract Number:
- SC0012530; SC00012530
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Environmental Science: Nano
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 12; Related Information: https://doi.org/10.1039/D0EN00689K; Journal ID: ISSN 2051-8153
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 36 MATERIALS SCIENCE; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; 77 NANOSCIENCE AND NANOTECHNOLOGY; Neptunium dioxide; solubility; particle size; actinides
Citation Formats
Peruski, Kathryn M., and Powell, Brian A. Effect of calcination temperature on neptunium dioxide microstructure and dissolution. United States: N. p., 2020.
Web. doi:10.1039/d0en00689k.
Peruski, Kathryn M., & Powell, Brian A. Effect of calcination temperature on neptunium dioxide microstructure and dissolution. United States. https://doi.org/10.1039/d0en00689k
Peruski, Kathryn M., and Powell, Brian A. 2020.
"Effect of calcination temperature on neptunium dioxide microstructure and dissolution". United States. https://doi.org/10.1039/d0en00689k. https://www.osti.gov/servlets/purl/1756008.
@article{osti_1756008,
title = {Effect of calcination temperature on neptunium dioxide microstructure and dissolution},
author = {Peruski, Kathryn M. and Powell, Brian A.},
abstractNote = {Comprehensive thermodynamic understanding of nuclear materials is paramount for long-term management of legacy nuclear waste and commercial spent nuclear fuel. Actinide oxides (AnO2(s)) are ubiquitous materials throughout the nuclear fuel cycle, yet existing thermodynamic data has noticeable discrepancies, creating uncertainty in environmental prediction of the fate of nuclear materials. The microstructure of actinide oxides, particularly neptunium (Np) and plutonium (Pu), is rarely investigated using high resolution electron microscopy, but such features may illuminate why differences in solubility measurements persist. The aim of this study was to synthesize NpO2(s) at varying calcination temperatures, characterize the materials using high resolution electron microscopy, and perform batch solubility studies to measure total dissolved Np as a function of calcination temperature. Here, the current work demonstrates the sizable differences in dissolution of NpO2(s) based on process conditions, such as the temperature at which the material is calcined and resultant particle size, and the need for more thorough evaluation of the microstructure of solid phases used to generate thermodynamic data of actinides.},
doi = {10.1039/d0en00689k},
url = {https://www.osti.gov/biblio/1756008},
journal = {Environmental Science: Nano},
issn = {2051-8153},
number = 12,
volume = 7,
place = {United States},
year = {Mon Oct 19 00:00:00 EDT 2020},
month = {Mon Oct 19 00:00:00 EDT 2020}
}
Works referenced in this record:
Optimization of thorium oxalate precipitation conditions relative to derived oxide sinterability
journal, February 1981
- White, G. D.; Bray, L. A.; Hart, P. E.
- Journal of Nuclear Materials, Vol. 96, Issue 3
The solubility and colloidal behaviour of neptunium (IV)
journal, July 1989
- Moriyama, Hirotake; Pratopo, Mochammad Ilham; Higashi, Kunio
- Science of The Total Environment, Vol. 83, Issue 3
Neptunium(IV) hydrous oxide solubility under reducing and carbonate conditions
journal, January 1985
- Rai, Dhanpat; Ryan, Jack L.
- Inorganic Chemistry, Vol. 24, Issue 3
Thermodynamics of manganese oxides: Effects of particle size and hydration on oxidation-reduction equilibria among hausmannite, bixbyite, and pyrolusite
journal, August 2012
- Birkner, N.; Navrotsky, A.
- American Mineralogist, Vol. 97, Issue 8-9
Mobility of Aqueous and Colloidal Neptunium Species in Field Lysimeter Experiments
journal, January 2018
- Peruski, Kathryn M.; Maloubier, Melody; Kaplan, Daniel I.
- Environmental Science & Technology, Vol. 52, Issue 4
Long-term storage of spent nuclear fuel
journal, February 2015
- Ewing, Rodney C.
- Nature Materials, Vol. 14, Issue 3
High-temperature oxide melt calorimetry of oxides and nitrides
journal, August 2001
- Navrotsky, Alexandra
- The Journal of Chemical Thermodynamics, Vol. 33, Issue 8
The effect of precipitation and calcination parameters on oxalate derived ThO 2 pellets
journal, November 2017
- Wangle, Tadeas; Tyrpekl, Vaclav; Cagno, Simone
- Journal of Nuclear Materials, Vol. 495
Discrepancies in Thorium Oxide Solubility Values: Study of Attachment/Detachment Processes at the Solid/Solution Interface
journal, October 2010
- Vandenborre, Johan; Grambow, Bernd; Abdelouas, Abdessalam
- Inorganic Chemistry, Vol. 49, Issue 19
Solubility of plutonium hydroxides/hydrous oxides under reducing conditions and in the presence of oxygen
journal, October 2007
- Neck, Volker; Altmaier, Marcus; Fanghänel, Thomas
- Comptes Rendus Chimie, Vol. 10, Issue 10-11
Solubility of Neptunium(IV) Hydrous Oxide in Aqueous Solutions
journal, January 1996
- Nakayama, Shinichi; Yamaguchi, Tetsuji; Sekine, Keiichi
- Radiochimica Acta, Vol. 74, Issue s1
Size-Driven Structural and Thermodynamic Complexity in Iron Oxides
journal, March 2008
- Navrotsky, A.; Mazeina, L.; Majzlan, J.
- Science, Vol. 319, Issue 5870
The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14−
journal, January 2008
- Soderholm, L.; Almond, Philip M.; Skanthakumar, S.
- Angewandte Chemie International Edition, Vol. 47, Issue 2
Stability of grain boundary texture during isothermal grain growth in UO2 considering anisotropic grain boundary properties
journal, October 2015
- Hallberg, Håkan; Zhu, Yaochan
- Journal of Nuclear Materials, Vol. 465
Mechanistic aspects of thermal decomposition of thorium oxalate hexahydrate: A review
journal, June 2010
- Raje, Naina; Reddy, A. V. R.
- Thermochimica Acta, Vol. 505, Issue 1-2
Grain Boundary Corrosion and Alteration Phase Formation During the Oxidative Dissolution of UO 2 Pellets
journal, January 1996
- Wronkiewicz, David J.; Buck, Edgar C.; Bates, John K.
- MRS Proceedings, Vol. 465
Probing the local structure of nanoscale actinide oxides: a comparison between PuO 2 and ThO 2 nanoparticles rules out PuO 2+x hypothesis
journal, January 2020
- Bonato, Laura; Virot, Matthieu; Dumas, Thomas
- Nanoscale Advances, Vol. 2, Issue 1
Reaction mechanisms of the thermal conversion of Pu(IV) oxalate into plutonium oxide
journal, October 2007
- Vigier, N.; Grandjean, S.; Arab-Chapelet, B.
- Journal of Alloys and Compounds, Vol. 444-445
Stabilization of Plutonium Nano-Colloids by Epitaxial Distortion on Mineral Surfaces
journal, April 2011
- Powell, Brian A.; Dai, Zurong; Zavarin, Mavrik
- Environmental Science & Technology, Vol. 45, Issue 7
Ten-year results from unsaturated drip tests with UO2 at 90°C: implications for the corrosion of spent nuclear fuel
journal, October 1996
- Wronkiewicz, David J.; Bates, John K.; Wolf, Stephen F.
- Journal of Nuclear Materials, Vol. 238, Issue 1
Fabrication of Targets for Neutron Irradiation of Neptunium Dioxide
journal, October 1964
- Myrick, R. E.; Folger, R. L.
- Industrial & Engineering Chemistry Process Design and Development, Vol. 3, Issue 4
Solubility and hydrolysis of tetravalent actinides
journal, January 2001
- Neck, Volker; Kim, J. I.
- Radiochimica Acta, Vol. 89, Issue 1
Problems in the thermodynamics of the actinides in relation with the back-end of the nuclear fuel cycle
journal, May 1993
- Fuger, J.
- Journal of Nuclear Materials, Vol. 201
Kinetics of Reduction of Np(V) to Np(IV) by Platinum Black as Reduction Catalyst
journal, April 1992
- Nakamura, Tomotaka; Takahashi, Masanori; Fukasawa, Tetsuo
- Journal of Nuclear Science and Technology, Vol. 29, Issue 4
Actinide speciation in the environment
journal, June 2007
- Choppin, G. R.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 273, Issue 3
Role of Microstructure and Surface Defects on the Dissolution Kinetics of CeO 2 , a UO 2 Fuel Analogue
journal, April 2016
- Corkhill, Claire L.; Bailey, Daniel J.; Tocino, Florent Y.
- ACS Applied Materials & Interfaces, Vol. 8, Issue 16
Energetics of hydration on uranium oxide and peroxide surfaces
journal, June 2019
- Guo, Xiaofeng; Wu, Di; Ushakov, Sergey V.
- Journal of Materials Research, Vol. 34, Issue 19
Progress and new directions in high temperature calorimetry revisited
journal, April 1997
- Navrotsky, Alexandra
- Physics and Chemistry of Minerals, Vol. 24, Issue 3
Isothermal grain growth kinetics in sintered UO2 pellets
journal, December 1973
- Ainscough, J. B.; Oldfield, B. W.; Ware, J. O.
- Journal of Nuclear Materials, Vol. 49, Issue 2
Solubility of NpO2 • xH2O(am) in the Presence of Cu(I)/Cu(II) Redox Buffer
journal, January 1987
- Rai, Dhanpat; Swanson, J. L.; Ryan, J. L.
- Radiochimica Acta, Vol. 42, Issue 1
Calorimetry of nanoparticles, surfaces, interfaces, thin films, and multilayers
journal, January 2007
- Navrotsky, Alexandra
- The Journal of Chemical Thermodynamics, Vol. 39, Issue 1
The Aqueous Geochemistry of Neptunium: Dynamic Control of Soluble Concentrations with Applications to Nuclear Waste Disposal
journal, December 1999
- Kaszuba, John P.; Runde, Wolfgang H.
- Environmental Science & Technology, Vol. 33, Issue 24
Nanoscale Effects on Thermodynamics and Phase Equilibria in Oxide Systems
journal, July 2011
- Navrotsky, Alexandra
- ChemPhysChem, Vol. 12, Issue 12
Contribution of Energetically Reactive Surface Features to the Dissolution of CeO 2 and ThO 2 Analogues for Spent Nuclear Fuel Microstructures
journal, July 2014
- Corkhill, Claire L.; Myllykylä, Emmi; Bailey, Daniel J.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 15
Solubility of crystalline thorium dioxide
journal, January 2003
- Neck, V.; Altmaier, M.; Müller, R.
- Radiochimica Acta, Vol. 91, Issue 5
Plutonium dioxide particle properties as a function of calcination temperature
journal, March 1996
- Machuron-Mandard, Xavier; Madic, Charles
- Journal of Alloys and Compounds, Vol. 235, Issue 2
Alterations of thorium oxalate morphology by changing elementary precipitation conditions
journal, September 2017
- Tyrpekl, V.; Beliš, M.; Wangle, T.
- Journal of Nuclear Materials, Vol. 493
The plastic deformation of uranium oxides above 800° C
journal, April 1959
- Scott, R.; Hall, A. R.; Williams, J.
- Journal of Nuclear Materials, Vol. 1, Issue 1
The superplastic creep of uranium dioxide
journal, January 1979
- Chung, T. E.; Davies, T. J.
- Journal of Nuclear Materials, Vol. 79, Issue 1
Directed Synthesis of Crystalline Plutonium(III) and (IV) Oxalates: Accessing Redox-Controlled Separations in Acidic Solutions
journal, July 2009
- Runde, Wolfgang; Brodnax, Lia F.; Goff, George
- Inorganic Chemistry, Vol. 48, Issue 13
Aquatic chemistry and solubility phenomena of actinide oxides/hydroxides
journal, January 2002
- Fanghänel, Thomas; Neck, V.
- Pure and Applied Chemistry, Vol. 74, Issue 10
Production of Neptunium Dioxide
journal, October 1964
- Porter, J. A.
- Industrial & Engineering Chemistry Process Design and Development, Vol. 3, Issue 4