Development of isotopic and elemental analysis methods on irradiated fuels for the reduction of sample quantities.
The objective of this postdoctoral research is to develop analytical methods for the overall reduction of sample quantities required for high-precision multi-element isotopic analysis (actinides and PF) of spent nuclear fuel, particularly through the use of novel "low-quantity" introduction methods on multi-collector ICPMS. These developments will notably reduce the amount of radioactive waste (consumables and effluents), the dose rate, and the exposure time of analysts/radioactive samples associated with this type of measurements.
To carry out this project, the candidate will conduct analytical developments in a controlled environment to minimize the quantities of elements required for analysis while maintaining or improving uncertainty levels compared to currently available methods.
Miniaturised analytical method dedicated to the screening of candidate molecules for the capture and removal of radionuclides
This project aims at developing a miniaturized multiplex device dedicated to the screening of the chelating ability of potential molecules for the decorporation of certain radionuclides (RN) from the nuclear power industry, for which current treatments are not satisfactory. The objective is to accelerate the identification of the most promising chelating molecules, while benefiting from the advantages of miniaturisation, such as the consumption of very small quantities of molecules and RN. In a previous project, a phosphated monolith of various lengths has been grafted in situ and characterised in capillaries of 100 µm internal diameter. The quantities of UO22+, Zr4+, Sr2+, Co2+, Cs+ and Ag+ immobilised on these monolithic phases have been measured online by coupling to an ICP-MS.Based on this work, the candidate will be responsible for developing and validating the miniaturised screening method with UO22+, for which data and chelating molecules are available, extending the approach primarily to Zr4+, Sr2+, Co2+, and to fabricate the microfluidic device incorporating parallel microchannels, in order to ultimately screen candidate molecules for distinct RNs in a single fluidic microsystem.
Thermodynamic study of photoactive materials for solar cells
The development of solar photovoltaic electricity generation requires the development of new materials for converting solar radiation into electron-hole pairs. Organic-inorganic hybrid perovskites (HOIPs) of the CsPbI3 type, with substitutions of Cs by formamidinium (FA) and/or methylammonium (MA) ions, have emerged as very promising materials in terms of performance and manufacturing. Substitutions of Cs with elements such as Rb, Pb with Sn, and I with Br are also being considered to improve stability or performance. The synthesis and optimization of the composition of layers of such materials require a better understanding of their thermodynamic equilibrium properties and stability. The objective is to construct a thermodynamic model of the Cs-Rb-FA-Pb-Sn-I-Br system. The project began with the ternary Cs-Pb-I system, which resulted in a paper [1]. The next step will focus on the ternary Cs-Pb-Br system, followed by the quaternary Cs-Pb-I-Br system. The approach uses the CALPHAD method, which focuses on building a database and an analytical formulation of the phases Gibbs energy, capable of reproducing thermodynamic and phase diagram data. A critical review of the data in the literature will enable this database to be initialized and the missing data will be evaluated by experiments and/or DFT calculations.
Microfluidics applied to the separation of actinides in nuclear samples by chromatography
The main objective of this post-doctoral position is to develop a method for separating the fission products, plutonium and uranium in nuclear samples by chromatography with a resin volume of 200 µL or less. This project is structured around three research axes.
The first one consists in optimising the miniaturised separation method. The resin packing protocol, the pressure applied during the separation and the eluant compositions will be studied by comparing the chromatograms and by calculating the associated decontamination factors. These developments will be carried out using simulated samples first, and then with plutonium-containing samples. Control over the redox adjustment step will be necessary to maximize the decontamination factors. A second development axis will focus on the conception of a user-friendly system, minimizing interventions in the glovebox in order to reduce the user's exposition to ionizing radiation. The experience of the laboratory in terms of experimental setup miniaturisation and micro-fabrication will be useful for this post-doctoral position. The third research axis consists in applying the developments of the first two axes to the determination of isotopic composition of nuclear samples by TIMS or MC-ICP-MS with a per-mil level of uncertainty in a radiation-controlled laboratory.
Experimental and Thermodynamic Modeling of Corium Phases Formed During Severe Nuclear Accidents (24 months)
During severe accidents in pressurized water reactors, uranium dioxide (UO2) fuel reacts with zirconium alloy cladding and the steel vessel, forming a mixture of liquid and solid phases known as "in-vessel corium". If the vessel ruptures, this corium interacts with the concrete raft, forming "ex-vessel corium". This phenomenon occurred in the Chernobyl and Fukushima severe accidents. To simulate these stages, multi-physics codes require accurate thermodynamic and thermophysical data for the various phases of corium. This project aims to fill the data gap through experimental measurements and modeling. The work will involve synthesizing samples, measuring liquidus/solidus temperatures and liquid phase densities, and characterizing samples using advanced techniques. Moreover, the laser heating setup combined with aerodynamic levitation (ATTILHA) used to acquire data will be improved. Experimental results will be compared with thermodynamic models (TAF-ID database), and discrepancies will be resolved using the CALPHAD method. Thermophysical data will also be validated using atomistic simulations and other measurement techniques.
Accelerated development of materials resistant to molten chloride salts
The accelerated development of materials is a major challenge for all industries, and corrosion resistance is all the more important for resource conservation issues. This project therefore aims to estimate the corrosion resistance of FeNiMnCr alloys in chloride salt for use in molten salt nuclear reactors, in collaboration with the University of Wisconsin, which has demonstrated extensive expertise in the accelerated development of materials for molten fluoride and chloride salt reactors. As part of this post-doc, dozens of samples of quaternary FeNiMnCr model alloys will be synthesised by additive manufacturing at the University of Wisconsin, varying the composition in order to map the entire composition tetrahedron as accurately as possible. These samples, with a NiCr model alloy corroded in a wide range of molten chlorides salt chemistries, will then be corroded at the CEA. The aim of these experiments is, on the one hand, to obtain a large database on the corrosion of FeNiMnCr alloys in a very short time (1.5 years) and, on the other hand, to screen the effect of a wide range of salt compositions on a model NiCr alloy. Finally, these experiments will make it possible to target the best materials for studying their corrosion mechanisms.
Development of a capillary electrophoresis microsystem hyphenated to ICP-MS for isotopic and elemental analysis
The precise and accurate determination of isotopic and elemental compositions of samples by mass spectrometry is paramount in several research fields such as geoscience, environmental science, biology or the nuclear field. In order to avoid spectral or non-spectral interferences, it is necessary to perform chemical separations steps prior to analysis by mass spectrometry. In most cases, those separations are performed by liquid chromatography. Electrokinetic separation methods are particularly suitable to perform those separations due to the small volume of sample required and the small volume of waste produced, in the nL and µL range, respectively.
The main objective of this post-doctoral work is to integrate electrokinetic separations, presently performed in a glass capillary, in an analytical microsystem. This analytical microsystem, based on the microfluidic technology, will be used for the separation of elements and has to be hyphenated to an MC-ICP-MS without degrading the separation. The output of this work is an automated device capable of increasing throughput while keeping the same analytical performance as the original method. For nuclear samples, the device will reduce the dose received and the production of waste associated with the analytical protocol.
Synthesis, Characterization, and Molecular Modeling of M-(A)-S-H
The main hydration product of Mg/silicate cements is magnesium silicate hydrate (M-S-H), whose composition evolves with time and environmental interactions [refs 1,2], with Mg/Si ratios ranging from 0.67 to 1.5, variable water content, and potential Al incorporation. Atomistic models of M-(A)-S-H remain largely unexplored [ref 4], and most of their properties are still unknown, making it difficult to establish composition–property relationships.
This project aims to elucidate the atomic-scale structure of (alumino)silicate magnesium hydrates (M-(A)-S-H) by combining experimental techniques and atomistic simulations, and to estimate their mechanical properties. The study will focus on M-(A)-S-H compositions relevant to nuclear applications or new low carbon cement matrices.
Impact of Microstructure in Uranium Dioxide on Ballistic and Electronic Damage
During reactor irradiation, nuclear fuel pellets undergo microstructural changes. Beyond 40 GWd/tU, a High Burnup Structure (HBS) appears at the pellet periphery, where initial grains (~10 µm) fragment into sub-grains (~0.2 µm). In the pellet center, under high temperatures, weakly misoriented sub-grains also form. These changes result from energy loss by fission products, leading to defects such as dislocations and cavities. To study grain size effects on irradiation damage, nanostructured UO2 samples will be synthesized at JRC-K, using flash sintering for high-density pellets. Ion irradiation experiments will follow at JANNuS-Saclay and GSI, with structural characterizations via Raman spectroscopy, TEM, SEM-EBSD, and XRD. The postdoc project will take place at JRC-K, CEA Saclay, and CEA Cadarache under expert supervision.
Thermochemical and thermodynamic study of chloride molten salts
In today’s climate emergency, access to clean and cheap energy is more important than ever. Several ways have been envisaged for several years now, but a number of technological issues still need to be overcome before they can be put into practice, as they represent breakthroughts. Whether for energy storage than for fourth generation nuclear reactors, molten salt environment used as coolant and/or as fuel is highly corrosive requiring a complexe choice of structural materials.
The aim of this subject proposed in the Corrosion and Materials Behavior Section is to study in depth the chemical properties of different chloride molten salts : the basic ternary salt (NaCl-MgCl2-CeCl3) but also the corrosion/fission/activation products that can be produced (MxCly with M=Cr, Fe, Te, Nd, Ni, Mo,…). The activity coefficients and solubility limits of these metallic elements will be determined using various techniques such as electrochemistry and Knudsen cell mass spectrometry. If required, this study can be completed by the phase transition temperature and heat capacity measurements using differential scanning calorimetry.