Improvement of the AmSel process for americium recovery within TRANSPARANT European project
Uranium and plutonium can already be industrially separated from spent nuclear fuels by the PUREX solvent extraction process. By recovering americium from a PUREX raffinate, the capacity of a deep geological repository can be increased by a factor of up to seven. This separation became feasible by ingeniously combining the selectivity of a suitable extracting agent (TODGA) and a water-soluble complexing agent (PrOH-BPTD). The former co-extracts americium, curium, and lanthanides into the organic phase, rejecting other fission products (FP). The development of this process, called AmSel, was already initiated during previous European projects but the selectivity could be further improved, especially the Cm/Am separation factor. In order to separate those elements, which have very close physico-chemical properties, both the lipophilic extractant molecule in the organic phase and the complexing agent in nitric acid medium should be optimized. Batch extraction tests will be performed in glove boxes in ATALANTE facility at CEA Marcoule with radionuclides of interest (241Am, 244Cm, 152Eu). The behavior of relevant fission products (e. g. Tc, Pd, Zr, Mo, Ru, Sr) both in extraction and stripping conditions will also be evaluated. Experiments using a simulated feed solution containing all elements (including americium) in nominal concentrations will validate the loading capacity and separation performances. The resistance towards radiolysis of the selective ligand used as Am stripping agent in the aqueous phase will be evaluated by in situ alpha irradiations with 241Am in nominal concentration. Degradation will be evaluated by ESI-MS measurements coupled with HPLC to both identify and eventually quantify degradation products and complexes formed with those compounds.
Development of new Potassium-ion cells with high performances and low environmental impact
Lithium ion batteries are considered as the reference system in terms of energy density and cycle life and will play a key role in the energetic transition, especially concerning electric vehicles. However, such a technology involves the use of a large amount of critical elements and active materials are synthesised using energy intensive processes.
In this way, our team is developing a new Potassium-ion batteries technology with high performances but with a low environmental impact.
For this innovative and ambitious project, CEA-LITEN (one of the most important research institute in Europe) is looking for a talented post-doctoral researcher in material chemistry. The post-doctoral position is opened for a young researcher with a high scientific level, interested by valorising her/his results through different patents and/or scientific publications.
Experimental and technological developments of a process for the mineralization of organic liquid waste by plasma
The ELIPSE process developed at the CEA allows the destruction of organic liquids by injection into a high-power plasma.
If the feasibility of destroying different organic components at flow rates of a few liters per hour has now been demonstrated, tests must now be further developed for reference organic liquids appropriately chosen according to existing deposits.
These studies, based on the characterization data of the chosen LORs, will aim to provide detailed process results obtained with the most representative operating conditions, to allow a complete and quantitative evaluation of the process. This will make it possible to establish operating, robustness and endurance data for the process.
This work will include the study of the behavior of radioelements in the process, which will be essential for the nuclearization study: this will involve studying the physico-chemical behavior of actinides during their processing via the use of inactive simulants.
Thermodynamic investigation of Metal-Insulator-Transition materials – The case of doped VO2 for smart windows applications
The present post-doc proposal aims to develop a specific thermodynamic database on the V-O-TM (TM=Fe,Cr) system by using the CALPHAD approach. The candidate will conduct experimental campaigns to obtain relevant data to feed the thermodynamic models. The candidate will mostly use the experimental equipment available at the lab (DTA, annealing furnaces, high temperature mass spectrometry, laser heating, SEM-EDS). In addition, the post-doc may participate to combinatorial high-throughput activities led by other laboratory of the Hiway-2-Mat consortium (e.g., ICMCB in Bordeaux), allowing a better connection between the CALPHAD simulation output and the accelerated characterization platform. The thermodynamic database will be then included in the autonomous research routine implemented in the material exploration path.
Modelling of uranium precipitation kinetics as a function of pH. Application to fluidized bed reactor
The Orano plant in Niger (Somaïr) precipitates its uranium concentrate in a fluidized bed reactor by adding sodium hydroxide. The concentrate obtained contains around 6% sodium which leads to converter penalties. Orano carried out tests at the end of 2019 on a fluidized bed in the laboratory to change the operating point of precipitation and preferentially form UO3 via a change in pH. To refine the management of the industrial unit, it is necessary to model the precipitation reactions of uranium. The candidate will have to propose and calibrate a competitive precipitation model for Na2U2O7 and UO3 based on the equilibrium constants and reaction kinetics, as a function of the pH within the reactor. In particular, the model should make it possible to understand the impact of pH on the distribution of the two main species identified in the concentrate: Na2U2O7 and UO3. This chemical model should serve as input to an existing physical model of the fluidized bed reactor. An extension of the model to other precipitation reagents, in particular magnesia, could also be studied.
Synthesis and structural analysis of reference uranium minerals for the identification of uranium-bearing phases in mining environment by TRLFS.
In the frame of the collaborative project between the ICSM , CEA and Orano, a study is conducted in order to detect and identify minerals containing uranium (VI) by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS). This technique showed its efficiency in order to identify the presence of uranyl in natural assemblies through the probing of the local environment of uranium. However, it requires the establishment of a database from synthetic and natural samples fully characterized. Therefore, in order to achieve this goal, we intend to synthesis, and thoroughly characterize a variety of compounds containing uranyl groups within the crystal structure. We can cite the families of oxi-hydroxide, sulfate, and silicates based compounds. Then, TRLFS spectra will be collected in order to complete the database and to evidence the impact of the local structure of uranyl cation on the intensity and the position of the emission bands. The obtained data will be also compared to a collection of natural samples.
Leaching foams to extract metals from electronic waste
The subject is part of the ANR "Foamex" project covering TRL from 1 to 5 and focussing on the development of recycling of some metals from a shred of electronic cards, this recycling being carried out in a fluid foam (minimization of the volume of solvents) that can be considered at the first level as a dynamic chromatography column. The principle is to use the foam as a reservoir containing an acid solution and specific oxidizing agents to dissolve and extract metals in the form of ionic species, a phenomenon enhanced by friction between bubbles and simultaneously to concentrate them via the fluid and mobile liquid/air interfaces by flow.
Structural characterization, reactivity and physico-chemical properties of Pu(IV) colloidal suspensions
Pu(IV) is known to be highly prone to hydrolysis leading to the formation of extremely stable Pu(IV) colloidal suspensions (known as intrinsic colloids). The lack of knowledge concerning the speciation and reactivity of these Pu colloids hinders the development of reliable models allowing to predict their behavior in industrial and environmental systems. The behavior of these colloidal species towards dissolution, complexation, or aggregation has been very poorly described in the literature. It thus appears essential to study and characterize Pu(IV) colloids and in particular their surface charge properties which ensure their stability and their interactions with their environment. This pioneering project in the nuclear field aims to study and characterize colloidal Pu(IV) suspensions whose size, concentration and dispersion medium can be controlled by our approaches. It comprises: (i) the preparation of intrinsic Pu(IV) colloidal suspensions and the study of their chemical and sonochemical reactivity; (ii) the electrophoretic characterization of various colloidal suspensions and the study of their behavior under the influence of an electric field; (iii) the characterization of their multi-scale structural properties by small and large angle scattering (SAXS / WAXS) coupled with EXAFS / XANES measurements (MARS line, SOLEIL synchrotron).
Design of new extractant molecules for uranium and plutonium separation
The subject of this postoctoral position is related to the optimization of the process used to separate uranium and plutonium from spent nuclear fuels. In the so called PUREX process currently in operation at La Hague reprocessing plant in France, the TBP (tri-n-butylphosphate) is used as extractant in the solvent extraction system. This molecule shows high affinity for uranium and plutonium at oxidation states VI and IV and allows to reach high decontamination factors versus fission products. Nevertheless, the separation of U from Pu requires the use of reducing and anti-nitrous reagents to allow the back-extraction of Pu(III). In order to improve the process, researches are under way to design new extractant molecules which would allow to separate U and Pu without redox chemistry and with high selectivity versus fission products (Ru, Tc, Cs, lanthanides, etc) and other actinides (especially Np). The objective of the postdoctoral associate will be to select the molecules, to determine synthesis routes and to perform their synthesis using equipment available in the LCPE laboratory (micro-wave, flash chromatography, NMR, HPLC-MS, GC-HRMS) at the CEA Marcoule.