Chemical and mechanical properties of N-A-S-H aluminosilicates of geopolymer
Management of low- and medium-level nuclear waste relies primarily on cements, but their limitations with regard to certain types of waste (reactive metals, oil) require the exploration of new, more effective materials. Geopolymers, particularly those composed of hydrated sodium aluminosilicates (Na2O–Al2O3–SiO2–H2O, or N–A–S–H), appear to be a promising alternative thanks to their chemical compatibility with certain types of waste.
However, despite the growing interest in geopolymers, scientific obstacles remain: 1) The available thermodynamic data on N-A-S-H is still incomplete, making it difficult to predict their long-term stability via modeling, 2) The role of their atomic structure in regard to their reactivity remains unclear, and 3) The links between chemical composition (in terms of Si/Al ratio) and mechanical properties are not established, limiting the representativeness of the models created.
By combining experimentation and modeling in order to link atomic structure and properties, this thesis aims to obtain robust and novel data on the chemical and mechanical properties of N-A-S-H. The thesis is organized around three major objectives: 1) determining the impact of N-A-S-H composition on dissolution and establishing thermodynamic solubility constants, 2) characterizing their atomic structure (aluminols, silanols, and hydrated environments) using advanced NMR spectroscopy, and 3) linking their mechanical properties, measured by nanoindentation, to their structure and composition using molecular dynamics modeling.
Simulation of nuclear glass gels at the mesoscopic scale using a quaternary system.
This research work is part of studies conducted on the long-term behavior of nuclear glass used to immobilize radioactive waste and potentially intended for geological disposal. The challenge lies in understanding the mechanisms of alteration and gel formation (a passivating layer that can slow down the rate of glass alteration) by water and in predicting the kinetics of radionuclide release over the long term.
The proposed simulation approach aims to predict, at a mesoscopic scale, the maturation process of the gel formed during the alteration of glass by water using a ternary “phase field model” composed of silicon, boron, and water (leachate), to which aluminum will be added.
The underlying quaternary mathematical model will consists of a set of coupled nonlinear partial differential equations. These are based on Allen-Cahn and transport equations. The numerical solution of the associated equations is performed using the Lattice Boltzmann Method (LBM) programmed in C++ in the massively parallel LBM_saclay calculation code, which runs on several HPC architectures, both multi-CPUs and multi-GPUs.
The proposed research requires a solid foundation in applied mathematics and programming in order to develop the algorithms necessary for the correct resolution of the new system of strongly coupled equations.
Development of extracting systems for the isotopic enrichment of chlorine
Chlorine (Cl) is naturally composed of 76% 35Cl, which through neutron capture forms 36Cl, a long-lived gamma emitter (t1/2 = 301 000 years), and sulfur 36S, which accelerates corrosion phenomena, and 24% 37Cl with a drastically lower neutron capture section. A supply of 37Cl is therefore necessary in order to operate these reactors. Techniques currently exist that enable the enrichment of chlorine, such as ultracentrifugation, liquid-phase thermal diffusion, or laser isotope separation. The enrichment of chlorine by liquid-liquid extraction technics has been recently developed within CEA. The objective of the thesis is to identify and implement chemical systems allowing the 37Cl enrichment by a separative chemistry process. The thesis subject aims to identify on the basis of literature data initially, the families of ligands and, within these families, the best candidates for the 37Cl enrichment. Next, the synthesis and purification of the selected molecules will be carried out in the laboratory. Finally, the enrichment properties of the successfully synthesised ligands will be evaluated by separative chemistry, by quantification of chlorine isotopes using Inductively coupled plasma mass spectrometry (ICP-MS).
The thesis will be carried out at the recycling and energy recovery processes laboratory (LRVE) at the CEA in Marcoule.
The ideal candidate will be a Master's student in their second or third year of engineering school, studying chemistry, organic chemistry or analytical chemistry. The multidisciplinary nature of the skills acquired and the rigour developed by the student during the experiments undertaken will be valuable assets for the future PhD student.
New generation of organic susbtrates for power conversion
Recent advances in electric motors and associated power electronics have led to a significant increase in power density requirements. This increase in power density means smaller heat exchange surfaces, which amplifies the challenges associated with dissipating the heat generated by power electronics components during operation. In fact, the lack of adequate heat dissipation causes electronic components to overheat, impacting their performance, durability, and reliability. Other issues related to cost, repairability, and thermomechanical constraints call into question traditional ceramic-based insulating thermal interfaces. It is therefore imperative to develop a new generation of heat-dissipating materials that take the system environment into account.
The objective of this thesis is to replace the ceramic substrate in power module systems, whose main role is to act as the system's dielectric layer, with a thermally conductive organic matrix composite. The current substrate has well-known limitations (fragility, poor interface, cycling limit, cost). The organic substrate must have the highest possible thermal conductivity (>3 W/m.k) in order to dissipate the heat emitted properly, while also being electrically insulating with a breakdown voltage of approximately 3kV/mm. It must also have a coefficient of thermal expansion (CTE) compatible with that of copper in order to eliminate delamination phenomena during the cycling undergone by the device during its lifetime. The innovation of the doctoral student's work will lie in the use of highly thermally conductive (nano)fillers that will be electrically insulated (insulating coating) and can be oriented in a polymer resin under external stimulus.
The development of the electrical insulating shell on the thermally conductive core will be carried out using the sol-gel method. The synthesis will be controlled and optimized in order to correlate the homogeneity and thickness of the coating with the dielectric and thermal performance of the (nano)composite. The charge/matrix interface (a potential source of phonon diffraction) will also be studied. A second part will focus on grafting magnetic nanoparticles (MNPs) onto thermally conductive (nano)fillers. Commercial MNPs will be evaluated (depending on requirements, grades synthesized in the laboratory may also be evaluated). The (nano)composites must have rheology compatible with pressing and/or injection processes.
Study of plutonium oxalate formation mechanisms – Application to molten salt reactors
Molten salt reactors (MSRs) offer a promising alternative for sustainable nuclear energy production, thanks to their intrinsic safety and their ability to close the nuclear fuel cycle, notably through the use of a fast neutron spectrum. This type of reactor can use liquid chloride salts containing plutonium and other actinides as fuel. As part of the development of this nuclear pathway, the CEA supports the development of a PuCl3 production process. The synthesis of this chloride has already been carried out at small scale at the CEA and elsewhere in the world. Several starting materials can be used for the synthesis of the trichloride, notably plutonium metal, plutonium oxide and plutonium oxalate. The most industrially promising synthesis route is the oxalate route, because it can be transferred to the equipment already present at the La Hague site. This process consists of converting the oxalate into plutonium chloride via a gas–solid reaction with a chlorinating agent, such as HCl for example. However, the reaction mechanism and the decomposition of the oxalate in a chlorinated environment are still poorly understood. A detailed understanding of this transformation would make it possible to optimize operating conditions and facilitate the scale-up of this synthesis. The topic will initially focus on determining the reaction mechanism of Ce oxalate (a surrogate for Pu) to the chloride. Small-scale studies will be performed to identify the various reaction intermediates using analytical techniques such as X-ray diffraction (XRD), thermogravimetric analysis / differential thermal analysis (TGA/DTA) and analysis of the gases produced during the reaction. The kinetics as well as the enthalpy changes will also be studied in order to obtain key data for modelling a large-scale process. Subsequently, an optimization of the PuCl3 synthesis at the scale of a few tens of grams will be carried out. These studies will first be conducted under non-radioactive conditions on a surrogate to validate the experimental approach, before being transposed to radioactive conditions.
Effects of alpha decay on the alteration of nuclear glasses: simulation, understanding, and consideration in geochemical models
This Ph-D at the CEA on the alteration of nuclear glass is central to the challenges of sustainable radioactive waste management. The doctoral student will acquire expertise in materials and modeling, paving the way for exciting careers in research, engineering, or the nuclear industry. In deep geological storage, contact with groundwater can cause glass alteration, which is the main source of radionuclide release. The CEA is developing a multi-scale model that needs to be adapted to take into account the effects of glass self-irradiation. The aim of the thesis is to identify the mechanisms modified by irradiation and to parameterize the model. The doctoral student will conduct controlled irradiation experiments on non-radioactive glasses and compare them to ²44Cm-doped active glass. The structural and physicochemical changes induced will be characterized using various techniques (Raman, IR, NMR, SEM, TEM, DSC, etc.). Targeted alteration tests will be used to observe the impact of the level of damage on the kinetics of alteration. The results will be used to adjust and validate the predictive model under conditions representative of geological storage. The work will be carried out both in an active environment (shielded cells) and in an inactive laboratory. An M2 internship is available on the same subject. Profile: M2 or materials engineer, physical chemistry.
Study and Modelling of Tritium Speciation from the Outgassing of Tritiated Waste
Tritium, the radioactive isotope of hydrogen, is used as fuel for nuclear fusion, particularly in the ITER research reactor currently under construction in Cadarache (France). Its small size allows it to easily diffuse into materials, which will lead to the production of waste containing tritium after the operational phase of ITER.
To optimize the management of this tritiated waste, the CEA is developing technological solutions aimed at extracting and recycling tritium, as well as limiting its migration to the environment. The effectiveness of these solutions largely depends on the chemical form in which tritium is released. Experience from the outgassing of tritium from various types of waste indicates that it is released in two main chemical forms: tritiated hydrogen (HT) and tritiated water vapor (HTO), in varying proportions.
However, the mechanisms determining the distribution of tritium between these two species are not well understood. Several factors, such as oxygen and water concentrations, the nature and surface state of the waste, and the concentration of tritium, can influence this speciation.
The objectives of this thesis are as follows:
- To identify the phenomena affecting the speciation of tritium during the outgassing of tritiated waste.
- To conduct an experimental study to verify the proposed hypotheses.
- To develop a numerical model to predict the proportions of HT and HTO released, in order to optimize the management of this waste.
The thesis will be conducted within the IRESNE Institute (Institute for Research on Nuclear Systems for Low Carbon Energy Production) at the CEA site in Cadarache, in a laboratory specialised in tritium studies. The PhD candidate will work in a stimulating scientific environment and will have the opportunity to showcase their research work. The candidate must hold an engineering degree or a master’s degree in Chemical Engineering, Process Engineering, or Chemistry.
Bottom-up synthesis of nanographene and study of their optical and electronic properties
This project is part of an ANR project, which aims to synthesize perfectly soluble and individualized graphene nanoparticles in solution and incorporate them into spin electronics devices. To do this, we will draw on the laboratory's experience in synthesizing and studying the optical properties of graphene nanoparticles to propose original structures to several groups of physicists who will be responsible for studying the optical and electronic properties and manufacturing spin valve-type devices.
Tailored Peptide Ligands for Actinide Complexation: From Structure to Selectivity
The processes involved in the nuclear fuel cycle, such as the PUREX process designed to separate uranium and plutonium from fission products, rely on ligands capable of selectively complexing actinide cations to enable their extraction. The chemical functions carried by these ligands play a key role in determining both their affinity and selectivity toward metal cations. Studying the influence of these functional groups, such as carboxylic acids and phosphates, is therefore essential for the design of new extracting molecules, as well as for the development of decorporation strategies.
Over the past decade, cyclic peptides have been developed for their ability to complex uranyl ions with high selectivity over calcium. Organized in ß-sheet conformations, these peptides display a functional face bearing complexing groups (carboxylates, phosphates). Their amino acid composition can be tuned to finely adjust the chemical nature of the coordination site, making these cyclic peptides tailor-made molecular architectures for probing cation complexation. However, while their interaction with uranium is now well characterized, their ability to bind transuranic elements remains largely unexplored.
This PhD project aims to study the complexation of actinides such as plutonium and neptunium by various cyclic peptides. The combination of NMR spectroscopy and classical molecular dynamics simulations will provide detailed structural information on the formed complexes. Complementary techniques, including UV-Vis-nIR and EXAFS spectroscopies, ESI-MS mass spectrometry, and fluorescence spectroscopy, will deepen the characterization. By combining experimental and computational approaches, this work will enhance our understanding of ligand–actinide interactions while paving the way for the design of innovative extracting and decorporating molecules.
Investigation of autocatalysis phenomena occurring in nitric acid dissolution through electrochemical methods
The nuclear fuel recycling process, used at the La Hague plant in France, begins with the nitric dissolution of spent fuel, mainly composed of uranium and plutonium oxides. In a context of plant renewal and widespread of MOX fuel recycling, innovative new dissolution equipment are currently studied. The sizing of such devices is currently limited by the absence of a fully comprehensive model for the dissolution of mixed oxides, which is a highly complex reaction (three-phase involved, self-catalytic, heterogeneous attack, etc.). Despite substantial progress made in previous studies, a number of questions remain unanswered, particularly concerning the reaction mechanisms involved and the nature of the catalyst.
Electrochemical methods (cyclic voltammetry, electrochemical impedance spectroscopy, rotating electrode, etc.) have never been used to understand dissolution, yet they should prove relevant as already demonstrated by the studies carried out on this subject by CEA Saclay in the field of corrosion. Therefore, the aim of this thesis is to apply these experimental methods for the first time to the dissolution of nuclear fuels, through a phenomenological approach. To achieve this, the student will be able to rely on the teams and facilities of Saclay and Marcoule centers, specialized respectively in electrochemical methods for the corrosion studies and the physico-chemical modeling of dissolution.
This cross-disciplinary study, involving materials science, electrochemistry and chemical engineering, will follow a stimulating fundamental research approach, but will also take place in a highly dynamic industrial context. Initially, the work will be carried out on inactive model and noble materials (at the Saclay center), then on real materials containing uranium and/or plutonium (at the Marcoule center).