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.
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.
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.
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.
Optimizing phytotechnologies for the remediation of contaminated nuclear sites
CEA is recruiting a postdoctoral researcher for a research project aimed at optimizing phytotechnologies for the remediation of contaminated nuclear sites. This research is part of the risk management and remediation of contaminated soils, in particular those resulting from the decommissioning of nuclear facilities. The aim of the project is to develop an advanced mechanistic model of soil-plant transfers, in order to gain a better understanding of contaminant mobility in lightly contaminated soils, and to optimize the use of suitable plants to stabilize these contaminants.
Modeling the corrosion behavior of stainless steels in a nitric acid media with temperature
Controlling the aging of equipment materials (mainly stainless steel) of the spent nuclear fuel reprocessing plant is the subject of constant attention. This control requires a better understanding of the corrosion phenomena of steels by nitric acid (oxidizing agent used during the recycling stages), and ultimately through their modeling.
The materials of interest are Cr-Ni austenitic stainless steels, with very low carbon content. A recent study on Si-rich stainless steel, which was developed with the aim of improving the corrosion resistance of these steels with respect to highly oxidizing environments [1 , 2 ]; showed that the corrosion of this steel was thermally activated between 40 °C and 142 °C with different behavior below and above the boiling temperature (107 °C) of the solution [3]. Indeed, between 40°C and 107°C, the activation energy is 77 kJ/mol and above boiling point, it is much lower and is worth 20 kJ/mol. This difference may be due to a lower energy barrier or a different kinetically limited step.
The challenge of this post-doctoral subject is to have a predictive corrosion model depending on the temperature (below and beyond boiling). With this objective, it will be important to analyze and identify the species involved in the corrosion process (liquid and gas phase) as a function of temperature but also to characterize the boiling regimes. This model will be able to explain the difference in activation energies of this Si-rich steel below and above the boiling temperature of a concentrated nitric acid solution but will also make it possible to optimize the processes of the factory where temperature and/or heat transfer play an important role.
Design and accelerated testing of corrosion FOSs for reinforced concrete structures
Corrosion of steel reinforcement is the main pathology threatening the durability of civil engineering structures. Today, structures are mainly monitored by means of periodic visual inspections or even auscultation (corrosion potentials, ultrasonic measurements, core sampling, etc…), which are not very satisfactory. There is therefore a need for instrumentation capable of detecting the initiation and location of corrosion of reinforcement in concrete and ensuring long-term monitoring (several decades or more). In the context of Civil Engineering (CE) structures, Optical Frequency-Domain Reflectometry (OFDR) appears to be a suitable metrological solution because of its centimetre resolution and measurement range (70 metres in the standard version, i.e. several thousand measurement points along an optical fibre).
Content of work: The aim will be to adapt the design of this fibre optic sensor (FOS) to increase its durability and then to verify its applicability in the laboratory. Initially, the person recruited on a fixed-term research contract will be asked to work on the durability of the connexion between the optical fibre and the armature. Two different methods are envisaged: plasma torch spraying of ceramic powders and sol-gel. Both of these processes prevent the galvanic coupling because they involve insulating materials (ceramics) and are already deployed in industry in various civil and military fields. Secondly, test specimens equipped with the FOS will be tested in the laboratory according to classic civil engineering situations, i.e. localised corrosion (pitting induced by exposure to chloride ions) and uniform corrosion (generalised corrosion induced by carbonation of the embedding concrete). OFDR acquisitions will be carried out periodically over time in parallel with conventional metrology (potential, etc.).