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@INPROCEEDINGS{Schreinemachers:893763,
author = {Schreinemachers, Christian and Bollen, Olivier and
Leinders, Gregory and Tyrpekl, Václav and Modolo, Giuseppe
and Verwerft, Marc and Binnemans, Koen and Cardinaels,
Thomas},
title = {{H}ydrolysis of uranium({VI}), neodymium({III}) and
cerium({III}/{IV}) by thermal decomposition of urea},
reportid = {FZJ-2021-02818},
year = {2021},
abstract = {<p><strong>Abstract</strong></p> <p>Uranium dioxide is used
as conventional fuel for the production of energy by nuclear
$fission.\ Even$ though the front-end of the nuclear
fuel cycle is well known, studies to investigate
$alternative\ fabrication$ routes to prepare precursors
for oxidic uranium-based fuels are ongoing. The
precipitation induced by thermal decomposition of urea has
been demonstrated for several metals $(e.g.\ Ti,$ Ni,
Cu, Zn, Ce, Th), and a modified hydrothermal approach has
been applied to $precipitate\ ammonium$ diuranate (ADU)
from a solution containing uranyl ions.</p> <p>Within this
study, we investigated the hydrolysis behaviour of uranyl
and lanthanide $mixtures\ to$ support the development
$of\ $ alternative fabrication routes for transmutation
fuel, such as sol-gel processes. The lanthanides Nd and Ce
acted as surrogates for the actinides Am and
$Pu,\ respectively.$ We specifically sought out
parameters for the hydrolysis of uranyl ions induced
$by\ thermal$ decomposition of urea at ambient
pressure. Moreover, the hydrolysis behaviour of
$Nd(III),\ Ce(III)$ and Ce(IV), as well as mixtures of
the lanthanide- and uranyl ions, was investigated
$using\ the$ conditions determined for uranyl.
Hydrolysis experiments were carried out at 90 $\°C$ and
100 $\°C\ for$ <em>n</em>(urea)
$:\ <em>n</em>(UO<sub>2</sub><sup>2+</sup>)$ ratios of
$26\ and$ 52. The solution was sampled during the
$precipitation\ reaction$ to monitor its pH and certain
samples were analysed applying UV/VIS
$spectroscopy\ and$ inductively coupled plasma mass
spectrometry, while powder X-ray diffraction and
$scanning\ electron$ microscopy were applied to
characterise the precipitates.</p> <p>Uranyl ions hydrolysed
between pH 5.1 and pH 5.5 and the experimental conditions
$impacted\ the$ reaction kinetics significantly. A
temperature increase from 90 $\°C$ to 100 $\°C$
reduced the time $to\ finish$ the precipitation by
about 66 $\%,$ whereas a doubling of the urea content
decreased the $reaction\ time$ by about 33 $\%.$ ADU
precipitates of different composition (<em>x</em>
UO<sub>3</sub> $\·$ <em>y</em> NH<sub>3</sub>
$\·$ <em>z</em> H<sub>2</sub>O) $formed\ under$
the applied conditions. For trivalent Nd and Ce, a
comparable pH evolution and $lanthanide\ carbonate$
hydroxide (<em>Ln</em>CO<sub>3</sub>OH) products were
observed, whereas tetravalent Ce hydrolysed at
$a\ lower$ pH forming CeO<sub>2</sub>. The
precipitation behaviour was confirmed for solutions
containing $binary\ mixtures$ of uranyl and lanthanide
cations, while a simultaneous precipitation of Nd(III) and
Ce(III)<br> was observed for ternary U/Nd/Ce compositions.
For the latter, a partial incorporation of the
$<em>Ln\ </em>phase$ into the ADU phase was observed,
whereas the precipitation in the presence of
$Ce(IV)/CeO<sub>2</sub>\ led$ to the formation of three
separate phases. In this contribution we will report and
discuss $the\ experimental$ results.</p>},
month = {Jun},
date = {2021-06-29},
organization = {Uranium Science 2021, virtual event
(UK), 29 Jun 2021 - 1 Jul 2021},
subtyp = {Other},
keywords = {uranium (Other) / neodymium (Other) / cerium (Other) /
ammonium diuranate (Other) / ADU (Other) / Nuclear fuel
fabrication (Other) / Co-conversion (Other) / GenIV (Other)
/ pH (Other) / XRD (Other) / SEM (Other)},
cin = {IEK-6},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {1411 - Nuclear Waste Disposal (POF4-141) / GENIORS - GEN IV
Integrated Oxide fuels recycling strategies (755171)},
pid = {G:(DE-HGF)POF4-1411 / G:(EU-Grant)755171},
typ = {PUB:(DE-HGF)6},
doi = {10.5281/ZENODO.5034714},
url = {https://juser.fz-juelich.de/record/893763},
}