Insights into the fabrication and structure of plutonium pyrochlores

Finkeldei, S.; Stennett, M. C.; Kowalski, P. M.; Ji, Y.; de Visser-Týnová, E.; Hyatt, N. C.; Bosbach, D.; Brandt, F.

doi:10.1039/c9ta05795a

Title: Insights into the fabrication and structure of plutonium pyrochlores

Journal Article · 20 January 2020 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/c9ta05795a · OSTI ID:1592519

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Forschungszentrum Juelich (Germany); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Sheffield (United Kingdom)
Forschungszentrum Juelich (Germany); JARA High Performance Computing, Schinkelstrasse (Germany)
Nuclear Research and Consultancy Group (NRG) (Netherlands)
Forschungszentrum Juelich (Germany)

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725; AC02-98CH10886

OSTI ID:: 1592519

Alternate ID(s):: OSTI ID: 1669788

Journal Information:: Journal of Materials Chemistry. A, Vol. 8, Issue 5; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 15 works

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