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.