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@ARTICLE{Uygur:1016797,
author = {Uygur, Selim and Delville, Rémi and Schreinemachers,
Christian and Leinders, Gregory and Vanhove, Nico and Van
Renterghem, Wouter and Verwerft, Marc and Vleugels, Jozef},
title = {{C}ation-heterogeneity in internally gelated
{U}$_{1-z}${C}e$_{z}${O}$_{2-x}$, 0.15 ≤ $z$ ≤ 0.3
microspheres},
journal = {Journal of nuclear materials},
volume = {587},
issn = {0022-3115},
address = {Amsterdam},
publisher = {Elsevier Science},
reportid = {FZJ-2023-03781},
pages = {154749 -},
year = {2023},
abstract = {Internal gelation of aqueous mixtures of metal (M = Ln, An)
nitrate with Uranyl Nitrate is generally assumed to yield
cation homogeneity and a fluorite type single phase
U1-zMzO2±x solid solution. As-sintered (U,Ce)O2 internally
gelated microspheres, manufactured with target z values up
to 0.3 using Ce(NO3)3, were observed to exhibit systematic
peak broadening and splitting at higher 2θ angles in their
X-Ray diffraction (XRD) patterns, correlating with
increasing z≥0.15. This was interpreted as an unexpected
departure from a single phase material. Thermogravimetry was
used to make an initial assessment whether these peak
anomalies were caused by an oxygen hypostoichiometry.
Results indicated global oxygen stoichiometry for all
compositions. The subsequent detailed characterization study
via Electron Probe Micro Analysis of cross-sections of the
as-sintered microspheres revealed the systematic presence of
spherical Ce concentration gradients, as well as µm-sized
highly Ce-enriched features. EDS and TEM studies on focused
ion beam lamellae extracted from the cross-sections of
as-sintered microspheres revealed a hexagonal Ce4.67(SiO4)3O
minor phase manifesting as single grain precipitates and
clusters uncovering the presence and critical role of
Silicon as an unexpected contaminant and Ce-scavenger from
surrounding (U,Ce)O2 grains. Characterization at
intermediate heat treatment steps revealed that the
systematic U/Ce heterogeneity features are already present
post-gelation and are independent of the superimposed trace
Ce-Si-O phase. This work constitutes the first systematic
cation distribution study on cross-sections of (U,Ce)O2±x
microspheres, executed on a series of compositions, using a
combination of elemental mapping techniques.},
cin = {IEK-6},
ddc = {620},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {1411 - Nuclear Waste Disposal (POF4-141)},
pid = {G:(DE-HGF)POF4-1411},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001086750800001},
doi = {10.1016/j.jnucmat.2023.154749},
url = {https://juser.fz-juelich.de/record/1016797},
}