Advanced electrode materials by ALD for ionic devices

This work aims to develop Advanced ultrathin cunductive layers (<10nm) by ALD (Atomic Layer Deposition)for électrodes use(resistivity 100). The other challenge aims to reduce the ALD-based electrode layer thickness less than 5nm while still maintaining the advanced electric properties (resistivity in the mOhm range).
This work covers multiple aspects including inter alia ALD process, ALD precursors, Elementary characterization of intrinsec properties (physico-chemical, morphological and electrochemical) as well as integration on short loop 3D devices.

Experimental study of the behavior of fission gases in Fast Neutron Reactor fuels irradiated at low power.

With the emergence of new start-ups in the nuclear field, it is essential to extend the validation basis for Fast Neutron Reactor (FNR) fuel performance codes to lower linear power operating regimes, an area that has yet to be fully explored.
Given the lower temperatures reached in the fuel, the microstructure induced by irradiation is completely different from what is typically observed at higher linear power (formation of a central hole, columnar grains, etc.). These lower operating temperatures also lead to a decrease in fission gas release (FGR), which can cause significant gas swelling of the fuel. At the same time, low operating temperatures can also lead to an increase in the density of defects (dislocations) induced during irradiation (lower defect annealing efficiency), resulting in an indirect increase in fuel swelling.
It is therefore important to determine the density of dislocations in the fuel, as their ambivalent role shows that they can slow down the release of gases by trapping them and promoting their storage in intragranular bubbles, while also facilitating their migration if they form a connected network.
In order to improve our understanding of the phenomena involved and the models of fuel swelling under irradiation, it is essential to have experimental results such as the densities and sizes of Fission Gas (FG) bubbles and the densities of dislocations in these operating regimes.
The Laboratory for Fuel Characterization and Property Studies (LCPC) within the Research Institute for Nuclear Systems for Low-Carbon Energy Production (IRESNE), to which the PhD student will be affiliated, is equipped with state-of-the-art instruments recently acquired (TEM, SEM-FIB, SIMS, EPMA, XRD) for the study of irradiated materials allowing him to develop advanced experimental skills within the specific context of a Basic Nuclear Installation. This work will be carried out in close collaboration with the teams responsible for developing the multiphysics scientific computing tools of the PLEIADES software platform. It is clear that the skills acquired during the thesis will be valuable in a future career in both academia and industry. The doctoral student will also be able to promote their work to the international academic community and the industrial world through oral presentations and peer-reviewed articles.

Direct lithium extraction from brine through adsorption

The development of electric vehicles due to climate and the decision to turn towards a greener energy has increased sharply the demand of lithium over the past decade and will continue to escalate. Thus, lithium extraction projects are proliferating worldwide. Since mining presents a quite highly energy-consuming and polluting solution, alternative lithium sources like brine deposits or seawater are being currently investigated. In this study, we will focus on the approach of a direct lithium extraction from brine sources with different concentrations by adsorption. The first step will be to synthesize and characterize a wide range of materials as adsorbents, from classic oxides (LMO, LTO, etc) to functionalized hybrid porous materials (ZIFs, MOFs, etc). It is also intended to shape these materials with the help of an extruder, in order to enhance performances. Then, these materials will be evaluated both in static and dynamic conditions. Various parameters like the concentration of lithium, the presence of other cations and their concentration will be also evaluated and optimized so that we obtain a facile, efficient and selective process. The results of this study will be valorized through the deposit of patents and the submission of scientific articles along the whole duration of the thesis.

Lightweight and high-strength metamaterials with innovative architectures manufactured by additive manufacturing for constrained environments

Environmental constraints, rising raw material costs, and the need to reduce carbon footprints drive the development of more porous materials that combine lightness with mechanical strength. Such materials meet the requirements of strategic sectors including aerospace, space, transportation, energy, and high-performance physics instruments.

Mechanical metamaterials, composed of micro-lattice structures produced by 3D printing, offer a unique potential to address these challenges. By tailoring the topology of their internal networks, it becomes possible to achieve stiffness-to-density ratios higher than those of conventional materials and to adapt their architecture to target specific mechanical or functional properties.

This thesis is part of this wave of innovation. It aims to develop ultralight metallic metamaterials whose architecture is optimized to maximize mechanical performance while maintaining isotropy, ensuring predictable behavior using conventional engineering tools, including finite element analysis, numerical simulation, and multiscale approaches. The research builds on the recognized expertise of the CEA, particularly at IRAMIS and IRFU/DIS, in designing isotropic random metastructures and shaping them through metal additive manufacturing.

By combining numerical mechanics, advanced design, multi-process additive manufacturing, and in situ characterization, this thesis seeks to push the current limits of design and fabrication of complex metallic structures.

Acoustic imaging on irradiated fuel elements : from implementation to interpretation in terms of Metal/Ceramic interface

To improve the flexibility of civil nuclear reactors, many research programs are conducted by CEA in support of the French nuclear plants operator EDF and fuel fabricant FRAMATOME, specifically concerning the behaviour of fuel elements under irradiation.
The fuel elements consist of a metallic cladding and ceramic pellets. In case of power variations, the presence of a gap between the cladding and the pellets, and the bonding between them in case of contact, are fundamental for the mechanical strength of the fuel element.
To complete the current characterizations after irradiation of the pellet-cladding interface, the feasibility of a non-destructive method based on acoustic imaging has been studied and validated.
As a continuation of this first study, the objective of the thesis is to complete instrumentation of an operating measurement bench with the acoustic measurement chain. This bench is located in a cell which is dedicated to examinations of irradiated fuel elements.
The thesis work includes preparation and implementation of a qualification protocol of the acoustic chain, with images acquisitions on irradiated fuel elements. Acoustic signals processing will be developed to correct the effects of the external corrosion layer. Final expected results are images representing axial and azimuthal localization of the contact or gap between the cladding and the pellets, and the fraction of the bonding zones.
The PhD student will be based within IRESNE, an Institute of the CEA localized in Cadarache (in the south of France) which is specialized in the Research for Nuclear Systems for Low Carbon Energy Production. The work will take place in a nuclear installation which is equipped with various tools for multiscale characterization of the irradiated fuel from nuclear or experimental reactors.
This multidisciplinary work will be carried out in collaboration with a team from IES (Institute for Electronic and Systems - CNRS - Montpellier). This team is specialized in acoustic developments from probes to complete imaging systems.
Thanks to the resources and expertise of the two entities CEA and IES, the student will acquire solid skills in the fields of modeling, instrumentation and metrology. Results will be valorised in international publications and communications.

Chemo-mechanical modeling of the coupling between carbonation, rebar corrosion and cracking in cementitious materials

Rebar corrosion is one of the main causes of premature degradation of concrete infrastructures, including in the nuclear sector, where concrete is extensively used in containment structures and waste storage facilities. Carbonation, caused by the penetration of CO2 into the concrete, lowers the pH of the pore solution, promoting rebar corrosion. This corrosion leads to the formation of expansive products that can cause cracking in the material. The proposed thesis work, developed as part of a European collaborative project between CEA Saclay, École des Mines de Paris - PSL, and IRSN, aims to develop a numerical model to simulate these phenomena. The model combines a reactive transport code (Hytec) and a finite element code (Cast3M) to study the local effects of carbonation-induced corrosion on concrete cracking. This project will benefit from parallel experimental work to gather data for parameter identification and model validation. The first part of the research will focus on modeling the carbonation of cementitious materials under unsaturated conditions, while the second part will address the corrosion of rebar caused by the pH drop induced by carbonation. The model will describe the growth of corrosion products and their expansion, inducing stress within the concrete and potential microcracking.
This research project is aimed at a PhD student wishing to develop their skills in materials science, with a strong focus on multi-physical and multi-scale modeling and numerical simulations. The thesis will be carried out principally at CEA Saclay and at École des Mines de Paris – PSL (Fontainebleau).

Mechanical behavior of fourth-generation Li-Ion cells, study at the microstructure scale

Competition to increase the energy density of Li-Ion batteries is leading to the consideration of batteries with solid rather than liquid electrolytes. In this regard, sulfur-based electrolytes such as argyrodites are of great interest due to their high ionic conductivity and mechanical properties allowing a simpler manufacturing. Under the effect of lithiation/delithiation cycles, the silicium active particles embedded within this solid electrolyte cause volume variations that can damage the electrode and reduced its lifetime. This is why batteries with solid sulfide electrolytes only cycle properly when kept under pressure. The objective of this thesis is therefore to model these charge-discharge phases pf the battery at the microstructure scale representative of these new solid electrolyte electrodes. At the silicon particle scale, the work will consist of formulating a lithiation-delithiation model based on previous theoretical work and by comparison with available experimental data. Then, 3D models of electrode microstructures consisting of an argyrodite-type solid electrolyte and silicon particles will be established based on existing characterizations (SEM images). Finally, the microscopic mechanical model of lithiation-delithiation will be integrated on these microstructure models, studying in particular the effects of external mechanical loading on the intensity of mechanical interactions at the microstructure scale and the potential locations of damage. These simulation results will be compared with available measurements (macroscopic and local deformation measurements).
These studies will be carried out at CEA Cadarache within the Institute for Research on Nuclear Systems for Low-Carbon Energy Production (IRESNE), in close collaboration with the teams of the Laboratory for Innovation in New Energy Technologies and Nanomaterials (LITEN) at CEA Grenoble.
This framework will allow the PhD student to evolve in a stimulating scientific environment and to promote their research work both in France and abroad through conferences and publications in peer-reviewed journals.

Modeling of water ingression in a severe accident by separate effect testing

Nuclear energy is one of the pillars of the energy transition due to its low carbon footprint. It requires advanced safety studies, particularly regarding hypothetical severe nuclear accidents. These scenarios involve core meltdown and the formation of corium (molten radioactive material magma). Understanding corium behavior is a key element of nuclear safety.
At IRESNE institute of CEA Cadarache, the MERELAVA facility studies accident mitigation strategies by spraying water onto corium from above. A prototypical corium bath (containing depleted uranium) is cooled by water spraying under realistic conditions. This setup allows the study of complex interactions between corium, water, and the sacrificial concrete beneath.
In this context, the water ingression phenomenon plays a central role in corium cooling. During spraying, the solidified crust cracks, water seeps into the cracks and evaporates, significantly increasing the extracted heat flux compared to conduction alone. However, current models poorly describe this mechanism and struggle to predict its impact, mainly due to its highly multi-physical nature.
This thesis aims to study ingression through dedicated experiments on MERELAVA, to characterize the crust and to measure the ingression flux using 3D-printed representative matrices. The goal is to improve the existing physical model, with results compared to more complex experimental data. The thesis will primarily take place in the Severe Accidents experimental laboratory of the IRESNE institute. The candidate should have expertise in fluid mechanics and heat and mass transfer.

Development of functionalized supports for the decontamination of complex surfaces contaminated by chemical agents

In the case of contamination by a toxic chemical agent, treatment begins with rapid emergency decontamination. Those working in the field must take into account the risk of contamination transfer, in particular by wearing suitable protective clothing. These clothing, as well as the small equipment used, must then be decontaminated before considering undressing to avoid self-contamination. The procedure includes a “dry” decontamination phase generally by applying powders (often clays) which are then wiped off using a glove or sponge. However, this device does not neutralize chemical contaminants and the powder re-aerosolizes easily, so its use is limited to unconfined and ventilated environments. The objective of this thesis is to develop an alternative technology for the decontamination of complex surfaces (clothing, small equipment). We propose to study the functionalization of different supports (such as gloves, wipes, microfibers, sponges, hydrogels, etc.) by adsorbent particles (zeolites, ceramic oxides, MOFs, etc.). A preliminary bibliographic study will allow us to select the most suitable adsorbents and supports for the capture of model chemical agents. The work will focus on the preparation of the supports, and different ways of incorporation of the particles in/on these supports will be compared. The materials will be characterized (incorporation rate, homogeneity, mechanical strength, non-reaerosolization, etc.), then their transfer, sorption and inactivation properties will be evaluated with model molecules.

This subject is aimed at dynamic chemists, motivated by the multidisciplinarity (chemistry of mineral and/or polymer materials, solid characterization and analytical chemistry), and having a particular interest in the development of experimental devices. The candidate will work within the Supercritical Processes and Decontamination Laboratory at the Marcoule site, and will benefit from the laboratory's expertise in decontamination and the development of adsorbent materials, as well as the support and expertise of the ICGM institut in Montpellier on functional polymers and hydrogels. The student will interact with the laboratory's technicians, engineers, doctoral students and post-doctoral fellows. The doctoral student will be involved in the different stages of the project, the reporting and publication of its results, and the presentation of its work in conferences. He/She will develop solid knowledge in the fields of nuclear and environmental science, as well as in project management.

What mechano-thermal coupling is necessary for fast transients? Evaluation of the contributions of thermodynamics to irreversible processes.

The Laboratory for the Analysis of Radioelement Migration (LAMIR) at the Institute for Research on Nuclear Systems (IRESNE) of the CEA Cadarache has developed a set of measurement methods to characterize the release of fission products from nuclear fuel during transient thermal transients. For these transients, it is important to simulate the mechanical stresses associated with temperature changes that could lead to fracturing of the tested fuel samples . This thesis focuses on modeling hypothetical and very rapid accidental power transients. Its objective is to implement a new model based on the thermodynamics of irreversible processes (TIP).

The first part of this thesis will aim to validate the thermomechanical coupling model in TIP, which was proposed in our laboratory (https://www.mdpi.com/2813-4648/3/4/33). This will be an essentially analytical approach to establish the orders of magnitude of the various mechanisms involved. The second part will apply this formalism to experimental results obtained during rapid heating experiments using laser beams.

One of the main challenges of numerical simulation with TIP is calculating the temperature and stress fields simultaneously, rather than sequentially as in current models. We will start with a 1D program (in Python or another language) that will be progressively refined. Comparing the results obtained with TIP and with current models will help us identify situations in which TIP-specific couplings must be taken into account to achieve accurate predictions.

The PhD candidate will benefit from the support of experts in thermodynamics, mechanics, and programming. The research will lead to scientific publications and conference presentations. Owing to the diversity of the fields involved, this thesis topic offers excellent career prospects in both industry and academic research.

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