Modelling/Simulation of the synthesis of anti-corrosion coatings using the MOCVD process for low-carbon energy production
The durability of materials used in many areas of energy production is limited by their degradation in the operating environment, which is often oxidising and at high temperature. This is particularly true of High Temperature Electrolysers (HTE) for the production of ‘green’ hydrogen, or the fuel cladding used in nuclear reactors to produce electricity. Anti-corrosion coatings can/should be applied to improve the lifespan of these installations, thereby conserving resources. A process for synthesising coatings using a reactive vapour route with liquid organometallic precursors (DLI - MOCVD) appears to be a very promising process.
The aim of this thesis is to model and simulate the DLI-MOCVD coating synthesis process for the two applications proposed above. Simulation results (deposition rate, deposit composition, spatial homogeneity) will be compared with experimental results from large-scale ‘pilot’ reactors at the CEA in order to optimise the model's input parameters. On the basis of this CFD simulation/experiments dialogue, the optimum conditions for deposition on a scale 1 component will be proposed. A coupling between CFD simulations and Machine Learning will be developed to accelerate the change of scale and the optimisation of scale 1 deposits.
Improving phase field damage models - Application to vitroceramic materials subjected to self-irradiation
The vitrification of nuclear waste is a solution currently adopted for the storage of nuclear waste. The vitroceramic materials considered for this application consist of a glass matrix and inclusions of crystalline phases. Rich in radioactive elements, these inclusions undergo self-irradiation resulting in their swelling, which may cause cracking of the glass matrix. It is necessary to know the maximum amount of inclusions below which the material does not crack. An experimental study on radioactive materials, produced and monitored over time, is excessively expensive and the development of a numerical approach could make it possible to better target the materials to be studied.
Following Gérald Feugueur's thesis work on the subject, which highlighted the difficulty of current models in dissociating crack initiation and propagation, the main goal is to develop and test an improved phase field model incorporating an elasticity-independent crack nucleation criterion, based on regularized models of softening plasticity. The model will be implemented using the finite element method (FEniCS code) and an alternative method using Fourier transforms (AMITEX code). Following cross-validation, the most efficient implementation will be selected for application to large-scale 3D microstructures. Close exchanges with CEA Marcoule will enable us to characterize the microstructure of the materials, and an experiment currently underway should enable us to analyze the potential cracking of these materials under self-irradiation.
Radiological large-scale accident dosimetry: use of EPR spectroscopy for population triage by measurements of smartphone screens
In the event of a large-scale radiological emergency involving sources of external irradiation, methods are needed to identify which members of the population have been exposed and require priority care. To date, there are no operational methods for such sorting. Smartphone touch screen lenses retain traces of ionizing radiation through the formation of so-called “radiation-induced” defects.Measuring and quantifying these punctual defects, in particular by electron paramagnetic resonance (EPR) spectroscopy, makes itpossible to estimate the dose deposited in the glass, and thus the exposure associated with irradiation. The thesis work proposed herefocuses in particular on the alkali-aluminosilicate glasses used in cell phone touch screens, which are currently the best candidates fordeveloping new measurement capabilities in the context of accidents involving large numbers of victims.
We will focus in particular on identifying point defects as a function of the glass model used in smartphones by simulating EPR spectra in order to optimize the proposed dosimetry method.
Development of highly reactive bio-based polyhydroxyurethanes for the substitution of isocyanates in polyurethanes
Polyurethanes are thermosetting materials with significant environmental impacts. They are primarily synthesized from isocyanates, which are highly hazardous substances (toxic, sensitizing, and some even classified as CMR - Carcinogenic, Mutagenic, or Reprotoxic) and are subject to REACH restrictions. In this context, polyhydroxyurethanes (PHUs) offer several advantages: (i) they are more easily bio-based compared to conventional PUs, (ii) their synthesis does not involve isocyanates, but (iii) instead allows for CO2 sequestration. However, the precursors used in the synthesis of PHUs (cyclic carbonates and amines) exhibit much lower reactivity than isocyanates, resulting in curing times that are currently incompatible with the temperatures and production rates required for this type of material.
Several research directions have been proposed to optimize PHU curing kinetics, focusing on the identification of (i) new cyclic carbonate and amine precursors chemically substituted at the a or ß positions of the reactive group, and (ii) new high-performance catalysts capable of activating both types of precursors used in synthesis.
In this context, the PhD candidate will be tasked with synthesizing new cyclic carbonate and amine precursors and studying their reactivity to identify the most favorable conditions for the synthesis of highly reactive PHUs. The results obtained during this work will then be analyzed using symbolic Artificial Intelligence models developed at CEA.
This PhD project is part of the PHURIOUS project, funded by the PEPR DIADEM program, which aims to integrate high-throughput synthesis and characterization techniques in polymer chemistry with digital tools, including DFT calculations, molecular dynamics simulations AI approaches.
High yield strength austenitic stainless steels for nuclear applications: numerical design and experimental study
The PhD thesis is part of a project that aims at designing new austenitic stainless steels grades for nuclear applications, which are specifically suitable to in-service conditions encountered by the components and to the manufacturing process. More precisely, the subject deals with bolt steels achieved by controlled nitriding of powders which are then densified by hot isostatic pressing. Indeed, current bolt steel grades may suffer from stress corrosion cracking, while nitriding allows to increase the chromium content, which is beneficial from that point of view.
The study will start by the definition of specifications and associated criteria, then CALPHAD calculations in the Fe-Cr-Ni-Mo-X-N-C system will be done to define promising compositions. Then, selected compositions will be supplied as powders. The behaviour of powders during nitriding will be studied and modelled. Samples will be nitrided, densified and heat treated. One grade will be then selected and fully characterised: mechanical properties and deformation mechanisms, corrosion behaviour. One important objective is to demonstrate the advantages of the new grade compared to the industrial solution.
CTC electrolyte pour LiS system
Lithium-Sulfur (Li-S) Batteries are among the most promising energy storage technologies for the fifth generation of batteries, often referred to as post-Li-ion. With a theoretical energy density five times higher than that of conventional Li-ion batteries and an abundant availability of sulfur, the Li-S system offers a unique potential to meet the growing demand for sustainable energy storage. However, current technology is limited by major challenges related to the dissolution of polysulfides in the electrolyte, leading to active sulfur loss, poor cycle life, and insufficient electrochemical performance. These limitations currently hinder the market deployment of this technology.
This thesis aims to explore an alternative approach based on an all-solid electrochemical sulfur conversion mechanism. To achieve this, a next-generation organic solid electrolyte developed in the laboratory will be implemented. This electrolyte features a unique lithium-ion conduction mechanism within a crystalline lattice, preventing polysulfide solubilization. The main objectives are:
1. To understand and control the ionic conduction mechanisms in these electrolytes.
2. To integrate this solid electrolyte into an innovative Li-S system.
3. To optimize the cathode structure for the solid-state mechanism and evaluate the electrochemical performance on a representative prototype scale.
The PhD candidate will use a wide range of characterization and analysis techniques to carry out this project:
• Formulation and characterization of the organic solid electrolyte: Techniques such as FT-IR and NMR to analyze chemical structures and identify the properties of synthesized materials (DSC, TGA, XRD, etc.).
• Electrochemical characterization: Analyses using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and symmetric cell cycling tests to study ionic conduction properties and electrolyte stability.
• Formulation and performance study of the cathode: Formulation of carbon/sulfur composites and sulfur cathodes integrating the solid electrolyte; galvanostatic cycling tests and advanced interface analyses to understand and optimize solid-state sulfur conversion.
The research will progress in three main phases:
1. Development and characterization of the solid electrolyte: Material development, analysis of conduction mechanisms, and optimization of ionic and mechanical properties.
2. Design and optimization of the cathode structure: Improving electrolyte/cathode interfaces for solid-state sulfur conversion.
3. Electrochemical performance evaluation: Experimental validation of prototypes through in-depth tests, including cyclability and power performance.
Development of a predictive power model for a photovoltaic device under spatial constraints
CEA is developing new cell and module architectures and simulation tools to assess the electrical performance of photovoltaic (PV) systems in their operating environment. One of these models, called CTMod (Cell To Module), takes into account not only the different materials making up the module, but also the different cell architectures. For space applications, the community wants to use terrestrial silicon-based technologies that can be integrated on flexible PVAs (Photovoltaic Assembly). The space environment imposes severe constraints. A relevant evaluation of performance at the start and end of a mission is therefore essential for their dimensioning.
The aim of this thesis is to correlate physical models of radiation-matter degradation in space with electrical models of photovoltaic cells. Performance degradations linked to the various electron, proton and ultraviolet (UV) irradiations of the space environment will be evaluated and validated experimentally. Linked to the CTMod Model, this new approach, never seen in the literature, will able to get a more accurate understanding of interactions between radiations and PVAs. These degradations result from non-ionizing energy deposition phenomena, quantified by the defect dose per displacement, and ionizing ones quantified by the total ionizing dose for protons and electrons. In the case of UV, the excitation of electrons in matter generates chain breaks in organic materials and colored centers in inorganic materials. Initially, the solar cell used in the model will be a Silicon cell, but the model can be extended to include other types of solar cell under development, such as perovskite-based cells.
For high-performance, safe, and long-lasting batteries: understanding the role of an additive in liquid electrolytes
The trade-off between performance, aging, and safety remains a major challenge for Li-ion batteries [1]. Indeed, the incorporation of certain additives into the 3rd-generation electrolyte aims to delay or reduce the consequences of thermal runaway, thus reducing the risk of fire or explosion. However, this approach can have negative effects on other key parameters, such as ionic conductivity [2,3]. Therefore, this thesis proposes to study the coupled effects of these additives in order to better understand and potentially predict their impact on each of these indicators.
At the beginning of this work, an additive will be selected to study its role in an NMC 811/Gr-Si chemistry and a 3rd-generation liquid electrolyte, in terms of performance, long-term stability, and safety. The additive will be chosen based on the state of the art and post-mortem analysis of commercial cells representative of the current market. In parallel, new commercial cells of a few Ah will be used. These will be equipped with a reference electrode, internal temperature measurement, and ionic conductivity monitoring. The cells will then be activated with the selected electrolyte at different additive concentrations. Electrochemical performance, along with chemical and morphological characterization of the materials present, will be studied. Key safety parameters (thermal stability, release of reducing gases, O2, released energy, flammability of the electrolyte) for these new cells will be measured at different additive concentrations. The internal instrumentation, including the reference electrode, will also be used innovatively to study the onset of thermal runaway under these conditions.
A full aging campaign will be conducted over a maximum period of one year. At regular intervals, a sample of cells will be studied to characterize the impact of aging on chemical, electrochemical, and morphological changes, as well as on key safety parameters. The most important mechanisms, along with simplified laws governing safety as a function of additive quantity and aging, will be proposed.
[1] Batteries Open Access Volume 9, Issue 8, August 2023, Article number 427
[2] Journal of Energy Storage 72 (2023) 108493
[3] Energy Storage Materials 65 (2024) 10313