Influence of chromium doping of UO2 fuel on fission product speciation under accidental conditions
The development of nuclear reactors is part of a drive to improve safety, with, for example, the deployment of nuclear fuels with improved properties in terms of their behavior under accident conditions, the so-called E-ATF (Enhanced Accident Tolerant Fuel). Industrial operator FRAMATOME is developing the Cr2O3-doped UO2 fuel as E-ATF. However, very little data is available on the behavior of fission products from Cr-doped fuel under accident conditions.
This thesis proposes to develop a synthesis process for Cr-doped UO2 fuel that simulates irradiated fuel, in order to study the behavior of the elements (Cr and fission products) at different temperatures and under different oxygen partial pressures. The methodology is based on an experimental approach combining synthesis of model materials and in-depth chemical characterization, complemented by a theoretical approach (thermodynamic calculations) enabling thermal sequences to be dimensioned and the proposed reaction mechanisms to be confirmed.
The thesis will be carried out at CEA Cadarache (France), within IRESNE (Research Institute on Nuclear Systems for Low-Carbon Energy Production). The PhD student will be hosted in a laboratory dedicated to the study of uranium-based compounds in the Department of Fuel Studies (DEC). Depending on the densification processes chosen, experiments of various duration may be carried out in other laboratories in France or Europe.
The PhD student will have the opportunity to learn advanced characterization techniques for ceramic materials, gain access to experiments on large-scale instruments (synchrotron) and take part in exchanges with the academic community(CNRS, Universities, JRC). He or she will be able to promote his work through publications and participation in conferences.
At the end of this thesis, the PhD student will have acquired skills in materials science and solid state characterization that he/she will be able to use in various materials fields, as well as experience in the nuclear environment of interest to the nuclear industry.
Development of an automated and miniaturised system for the isotopic analysis of nuclear samples
Miniaturisation, which is the process of reducing an object’s, a method’s or a function’s dimensions while preserving or even upgrading its performances as compared to the classical scale, has a particular interest in the field of analytical chemistry for nuclear applications. Indeed, most of the analyses are performed in gloveboxes where miniaturisation and automation are a direct solution to the need for reduced doses and waste volumes. This PhD aims at developing a miniaturised and automated system, in a glove box, for performing high-precision isotopic measurements. This system will use capillary electrophoresis (CE) hyphenated with a nuclearised multicollector ICP-MS (MC-ICP-MS). During this PhD, the student will make use of micro-machining machines and 3D printers to develop an ergonomic system which will then be coupled to last generation MC-ICP-MS instruments available in our laboratory. The project will be focused on the conception of the automated system and its integration in the glove box, and on the further development of the existing CE method in order to perform isotopic and elemental analyses with nuclear samples. This PhD is hosted in a laboratory internationally recognized for its ability to carry out high precision isotopic measurements. An analytical chemistry curriculum is expected and a Master 2 internship is available before this PhD.
Redox behavior of technetium in the innovative PUMAS process: kinetic and speciation study
Technetium (Tc), an artificial radioactive element, makes up about 6% of the fission products in spent nuclear fuel. The PUREX process is used to separate uranium and plutonium from other fission products. However, Tc is co-extracted with these actinides, requiring an additional stripping step. In this stage, a stabilizing agent, hydrazinium nitrate (NH), is used, but due to its toxicity and CMR classification (Carcinogenic, Mutagenic, Reprotoxic), it is being replaced by less toxic alternatives such as oximes. Although promising, oximes exhibit slower stripping kinetics compared to NH. In the context of the PUMAS process, this thesis aims to understand the complex redox mechanisms of Tc and the kinetic differences between oximes and NH. The PhD student will study the reduced forms of Tc and analyze the reduction kinetics in the presence of U(IV) and anti-nitrous agents. A methodology will be developed to characterize the oxidation states of Tc, and reaction rate constants will be determined as a function of temperature and reactant concentrations.
The candidate will work closely with the supervising team to develop autonomy, adaptability, and the ability to propose innovative ideas. By the end of this journey, the candidate will have gained not only advanced technical skills but also abilities in project management, collaborative work, and scientific writing and communication. These competencies will provide strong prospects for a career in academic research or industry.
Molecular Dynamics Simulation of Plutonium(IV) in Solution
With the revival of nuclear power in France, the CEA is playing a key role in the nuclear industry of the future. In this context, engineers and researchers are mobilised to meet the growing needs of this industry. Plutonium is a key element in the nuclear fuel cycle. Acquiring molecular data is crucial to optimising and rationalising the mechanisms involved in separating this element.
Plutonium(IV) is one of the most common cationic forms in the nuclear fuel cycle. Its study by theoretical chemistry presents difficulties both in ab initio modelling (occupied f-block orbitals) and in classical atomistic simulations. In classical molecular dynamics simulation, the models necessarily require the addition of the polarisation effect, and sometimes even the addition of charge transfer, in order to reproduce the system's behaviour correctly. As a result, classical simulations containing plutonium (IV) are almost completely absent from the scientific literature. In addition, the speciation of this cation is sensitive to the acidity of the medium, which has to be taken into account in the simulations, adding a further difficulty.
The aim of this thesis is to use molecular dynamics (classical and ab initio) to simulate solutions containing plutonium, taking into account the effect of acidity. The PhD student will be faced with two main issues: the choice or development of a force field for the Pu4+ cation, and the design of a method for including acidity in the solutions. A crucial step in the process will be to compare the results with the available experimental data in order to conclude on the ability of the models to reproduce the experimental data. This thesis will be carried out in a multidisciplinary laboratory, combining experimental chemistry and theoretical modelling, while conducting both applied and fundamental research.
Impact of solvent nanostructure on uranium precipitation: a physicochemical approach for nuclear recycling
Recycling nuclear fuel is a major challenge to ensure a sustainable energy future. The CEA, in partnership with Orano and EDF, has been developing a new process for separating plutonium-rich fuels for several years. The goal is to replace the current TBP/TPH system with a redox-free process, better suited for the reprocessing of MOX or fast neutron reactors (FNR).
In this context, this thesis proposes to study the behavior of organic solvents loaded with uranium to understand and prevent the formation of precipitates, a phenomenon that could impact the performance of industrial processes. The scientific approach will focus on the supramolecular scale and compare different monoamides to evaluate the effect of alkyl chains on the physicochemical properties and nanostructure of the solutions.
The candidate should hold a Master's degree (Master 2) in chemistry, physical chemistry, or materials science. Skills in analytical chemistry, spectroscopy (NMR, FTIR), and scattering techniques (SANS, SAXS) will be highly valued. By joining this project, you will become part of the CEA's cutting-edge laboratories (ICSM/LTSM and DMRC/SPTC/LILA), equipped with world-class facilities for studying radioactive samples. You will benefit from multidisciplinary supervision, including opportunities for international collaborations. This thesis represents a major scientific challenge with direct industrial applications, offering you valuable experience in the field of nuclear separation and processing technologies.
Topological and altermagnetic materials: what power can be extracted from the anomalous Hall effect?
The major argument to promote the development of spin electronics and topological materials is the low power dissipation when using spin degrees of freedom and transverse configurations such as Hall configurations. Indeed, in the case of a topological phase, the generated effective magnetic field is expected not to dissipate. However, such an assertion must be the subject of a theoretical description in the context of a realistic electronic device in steady state. The aim of the thesis is to determine the useful power of these devices, in a study that is both experimental and theoretical.
In this context, the definition of the useful power is an open problem. Indeed, the thermodynamics of this type of non-equilibrium system involves cross effects between the degrees of freedom of the electric charge carriers, those of the spin of these carriers, as well as those of the magnetization. The non-equilibrium cross effects are described in a very general way by the famous Onsager reciprocity relations. We have developed a variational method to establish the steady state of a Hall bar and the power dissipated in a load circuit, as a function of the load resistance and the Hall angle. An unexpected result predicts the existence of a maximum ("maximum power transfer theorem"). Preliminary measurements based on the anomalous Hall effect have recently validated the prediction. This experimental confirmation allows us to establish a thesis project that aims to reproduce the measurements on a large set of materials (metals, semiconductors, oxides) and in particular magnetic topological materials, called altermagnetic.
In addition, a ferromagnetic resonance study (called spin pumping) will involve thermoelectric effects, whose dissipative properties, measured on an adjacent load circuit, remain to be determined.
Radiolytic Degradation of N,N-dialkylamides: Effects on Metal Complexation
N,N-dialkylamides (or monoamides) are promising extractant molecules for the development of new processes for nuclear fuel reprocessing. In this context, these extractant molecules are exposed to radiolysis caused by ionizing radiation from radionuclides, which leads to the formation of new compounds through the breaking or modification of chemical bonds. Such changes in solution composition can alter the extractive properties, particularly in terms of efficiency and selectivity.
This thesis aims to study the impact of radiolysis on the speciation of actinide-ligand complexes in solution, in order to improve the understanding of the phenomena observed under ionizing radiation. We propose an approach combining experimental studies (chromatographic and spectroscopic techniques) with theoretical calculations (such as bond dissociation energies, identification of probable radical attack sites, stability of metal-ligand complexes, etc.) to describe the molecular speciation of species in solution. Organic compounds formed during radiation and the metallic complexes will be characterized to evaluate the modifications caused by radiation.
Modeling of Critical Heat Flux Using Lattice Boltzmann Methods: Application to the Experimental Devices of the RJH
The Lattice Boltzmann Methods (LBM) are numerical techniques used to simulate transport phenomena in complex systems. They allow for the modeling of fluid behavior in terms of particles that move on a discrete grid (a "lattice"). Unlike classical methods, which directly solve the differential equations of fluids, LBM simulates the evolution of distribution functions of fluid particles in a discrete space, using propagation and collision rules. The choice of the lattice in LBM is a crucial step, as it directly affects the accuracy, efficiency, and stability of the simulations. The lattice determines how fluid particles interact and move within space, as well as how the discretization of space and time is performed.
LBM methods exhibit natural parallelism properties, as calculations at each grid point are relatively independent. Although classical CFD methods based on the solution of the Navier-Stokes equations can also be parallelized, the nonlinear terms can make parallelism more difficult to manage, especially for models involving turbulent flows or irregular meshes. Therefore, LBM methods allow, at a lower computational cost, to capture complex phenomena. Recent work has shown that it is possible, with LBM, to reproduce the Nukiyama cooling curve (boiling in a vessel) and thus accurately calculate the critical heat flux. This flux corresponds to a mass boiling, known as the boiling crisis, which results in a sudden degradation of heat transfer.
The critical heat flux is a crucial issue for the Jules Horowitz Reactor, as experimental devices (DEX) are cooled by water in either natural or forced convection. Therefore, to ensure proper cooling of the DEX and the safety of the reactor, it is essential to ensure that, within the studied parameter range, the critical heat flux is not reached. It must therefore be determined with precision.
In the first part of the study, the student will define a lattice to apply LBM methods on an RJH device in natural convection. The student will then consolidate the results by comparing them with available data. Finally, exploratory calculations in forced convection (from laminar to turbulent flow) will be conducted.
Study of the amorphous intermediate states during the precipitation of actinides oxalate
Growing energy needs and the climate emergency require a rapid transition to completely carbon-free energy, by mixing renewable energies and sustainable nuclear power. In this context, the precipitation of plutonium and uranium in the form of oxalate constitutes a key step in the industrial process of recycling spent fuel. A detailed understanding of the crystallization mechanisms of these oxalates thus constitutes a major challenge for better management of these operations.
However, it is now widely accepted that ions in solution assemble into crystals via a series of non-crystalline transient states, which fundamentally contradicts all classical nucleation theories used in precipitation models. In particular, we have demonstrated in recent years that rare earth oxalate crystals (Eu, Nd, Ce, Tb), some used to experimentally simulate the recycling of uranium and plutonium, form via liquid, reagent-rich nanodroplets which separate from the aqueous solvent. This behavior modifies the view hitherto retained for the precipitation of these oxalates and leads us to question the behavior of actinide oxalates.
The aim of this thesis is to confirm or refute that transient mineral droplets also form during the formation of uranium and plutonium oxalates, and to determine whether crystallization transients impact the precipitation models used to calibrate the recycling process of nuclear fuel. This study will not only impact precipitation processes used in recycling, but will also advance a fundamental question about long-debated “non-classical” crystallization.
Dislocation glide in body-centered-cubic high-entropy alloys
High entropy alloys are single-phase multi-component solid solutions, all elements being present in high concentrations. This class of materials has significant improvements in mechanical properties over "conventional" alloys, particularly their high strength at high temperature. It is commonly accepted that good mechanical performance comes from the interactions of dislocations with the alloying elements and that at high temperature interstitial impurities or interstitial doping, such as oxygen, carbon or nitrogen, play a preponderant role. The study of plasticity in concentrated alloys with a body-centered cubic crystal structure in the high temperature range therefore constitutes the objective of this PhD thesis. The associated technological challenges are important, these alloys being promising structural materials, notably for nuclear applications where operating temperatures above room temperature are targeted.
This work aims to understand and model the physical mechanisms controlling the mechanical strength of these alloys at high temperature, by considering different concentrated alloys of increasing complexity and by using atomistic simulations, in particular ab initio electronic structure calculations. We will first focus on the binary alloy MoNb before extending to the ternary alloys MoNbTi and MoNbTa and studying the impact of oxygen impurities on plastic behavior of these alloys. We will model the dislocation cores and analyze their interaction with interstitial and substitutional elements in order to determine the energy barriers controlling their mobility. Based on these ab initio results, we will develop strengthening models notably allowing us to predict the yield strength as a function of temperature and alloy composition.
This work will be carried out within the framework of the DisMecHTRA project funded by the French National Research Agency, allowing in particular to compare our strengthening models with the data from the experiments which are planned in the project (mechanical tests and transmission electron microscopy), and which will be carried out by the other partners (CNRS Toulouse and Thiais). The PhD thesis, hosted at CEA Saclay, will be co-supervised by a team from CEA Saclay and MatéIS (CNRS Lyon).