Insights into the fabrication and structure of plutonium pyrochlores
Abstract
Rare earth zirconates, such as Nd2Zr2O7, crystallise with the pyrochlore structure and are a group of materials which have been suggested as potential nuclear waste forms for actinide immobilisation. In this work, a new hydroxide co-precipitation route is presented to investigate the incorporation of Pu into Nd2Zr2O7. The plutonium content was varied between 5 and 10 mol% and the structural uptake and Pu oxidation state were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The experimental findings were complemented by DFT ab initio calculations. For all the incorporation mechanisms studied PuO2 was used as the reference reactant state to allow for a direct comparison between the possible Pu uptake scenarios. Analysis of the experimental data suggests that Pu(IV) cations substitute for Nd(III) cations leading to structural distortion of the pyrochlore A-sites. The computed solution energies and bond-distances corroborate the experimental findings and indicate that the excess charge is balanced via the introduction of oxygen at formerly vacant sites.
- Authors:
-
- Forschungszentrum Jülich, Institute of Energy and Climate Research – IEK-6, Nuclear Waste Management and Reactor Safety, 52425 Juelich, Germany
- University of Sheffield, Department of Materials Science and Engineering, UK
- Nuclear Research and Consultancy Group (NRG), Research & Innovation, The Netherlands
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1592519
- Alternate Identifier(s):
- OSTI ID: 1669788
- Grant/Contract Number:
- AC02-98CH10886; AC05-00OR22725
- Resource Type:
- Published Article
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Name: Journal of Materials Chemistry. A Journal Volume: 8 Journal Issue: 5; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., and Brandt, F. Insights into the fabrication and structure of plutonium pyrochlores. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9TA05795A.
Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., & Brandt, F. Insights into the fabrication and structure of plutonium pyrochlores. United Kingdom. doi:10.1039/C9TA05795A.
Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., and Brandt, F. Tue .
"Insights into the fabrication and structure of plutonium pyrochlores". United Kingdom. doi:10.1039/C9TA05795A.
@article{osti_1592519,
title = {Insights into the fabrication and structure of plutonium pyrochlores},
author = {Finkeldei, S. and Stennett, M. C. and Kowalski, P. M. and Ji, Y. and de Visser-Týnová, E. and Hyatt, N. C. and Bosbach, D. and Brandt, F.},
abstractNote = {Rare earth zirconates, such as Nd2Zr2O7, crystallise with the pyrochlore structure and are a group of materials which have been suggested as potential nuclear waste forms for actinide immobilisation. In this work, a new hydroxide co-precipitation route is presented to investigate the incorporation of Pu into Nd2Zr2O7. The plutonium content was varied between 5 and 10 mol% and the structural uptake and Pu oxidation state were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The experimental findings were complemented by DFT ab initio calculations. For all the incorporation mechanisms studied PuO2 was used as the reference reactant state to allow for a direct comparison between the possible Pu uptake scenarios. Analysis of the experimental data suggests that Pu(IV) cations substitute for Nd(III) cations leading to structural distortion of the pyrochlore A-sites. The computed solution energies and bond-distances corroborate the experimental findings and indicate that the excess charge is balanced via the introduction of oxygen at formerly vacant sites.},
doi = {10.1039/C9TA05795A},
journal = {Journal of Materials Chemistry. A},
number = 5,
volume = 8,
place = {United Kingdom},
year = {2020},
month = {2}
}
DOI: 10.1039/C9TA05795A
Web of Science
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