Bottom-up study of Ionic Transport in Unsaturated Hierarchical Nanoporous Materials : application to cement-based materials
Ion transport is critical in determining the durability of cement-based materials and, therefore, the extension of service life of concrete (infra)structures. Transport phenomena determine the containment capacity of concrete, which is crucial in the design and asset management of concrete infrastructures for energy production. Under most service conditions, concrete exists in unsaturated conditions. Anomalous transport has been associated with cement-based materials, and the reasons behind such deviations from the expected behavior of other porous materials may stem from nanoscale processes.
Research efforts have aimed to correlating material composition and microstructure to transport properties and durability. However, to date, the majority of predictive modeling of durability does not explicitly account for nanoscale processes, which are fundamental in determining transport properties. Recent advances have been made in quantifying the behavior of confined water in various phases present in cement systems. Calcium silicate hydrates (C-S-H) are the main hydrated phase in cement-based materials and present nanopores in the micro and mesopore range. The effects of desaturation remain however to be fully worked out. A fundamental understanding of transport processes requires a multiscale framework in which information from the molecular scale reverberates across other relevant scales (in particular, the mesoscale associated with C-S-H gel porosity (~nm), capillary porosity, and interfacial transition zone (~µm) up to the macroscopic scale of industrial application in cement-based materials).
The goal of this PhD work is to evaluate the ionic transport of chlorides, a critical species for the durability of concrete, under non-saturated conditions by combining small-scale simulations, multiscale modelling and experimentation in a bottom-up approach. The work will focus on the C-S-H. The project aims to characterize the effects of desaturation on the nanoscale processes driving transport of chlorides.
Development of an advanced grade of nano-reinforced austenitic steel for use under intense flux
Recent work has shown that it is possible to obtain ODS (Oxide Dispersion Strengthened) austenitic steels for use under intense flux. These new grades are beginning to be studied for nuclear applications around the world. They should have remarkable properties, particularly in terms of resistance to swelling under irradiation and creep, thanks to the addition of nano-reinforcements in exceptional density (10^23 to 10^24 m-3). These ODS steels are obtained by powder metallurgy, by co-grinding a metal powder with an oxide powder. The aim of this work is to succeed in manufacturing, using an innovative process, ODS austenitic steel cladding tubes. It will be necessary to master the recrystallization of these tubes, to propose a first critical evaluation by specifying the property/microstructure relationships and by evaluating, by irradiation with charged particles, the behavior under irradaition of this new material. The student will be trained in Scanning Electron Microscopy and the techniques that result from it (X-ray analysis, EBSD, etc.), in SAXS, in the performance and exploitation of mechanical tests. He will have to acquire good notions in Transmission Electron Microscopy and in Tomographic Atomic Probe. The understanding of the behavior under irradiation will be guided by simulations by cluster dynamics.
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.
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).
Online analysis of actinides surrogates in solution by LIBS and AI for nuclear fuel reprocessing processes
The construction of new nuclear reactors in the coming years will require an increase in fuel reprocessing capacity. This evolution requires scientific and technological developments to update process monitoring equipment. One of the parameters to be continuously monitored is the actinide content in solution, which is essential for process control and is currently measured using obsolete technologies. We therefore propose to develop LIBS (laser-induced breakdown spectroscopy) for this application, a technique well suited for quantitative online elemental analysis. As actinide spectra are particularly complex, we shall use multivariate data processing approaches, such as several artificial intelligence (AI) techniques, to extract quantitative information from LIBS data and characterize measurement uncertainty.
The aim of this thesis is therefore to evaluate the performance of online analysis of actinides in solution using LIBS and AI. In particular, we aim to improve the characterisation of uncertainties using machine learning techniques, in order to strongly reduce them and to meet the monitoring needs of the future reprocessing plant.
Experimental work will be carried out on non-radioactive actinide simulants, using a commercial LIBS equipment. The spectroscopic data will drive the data processing part of the thesis, and the determination of the uncertainty obtained by different quantification models.
The results obtained will enable publishing at least 2-3 articles in peer-reviewed journals, and even to file patents. The prospects of the thesis are to increase the maturity level of the method and instrumentation, and gradually move towards implementation on a pilot line representative of a reprocessing process.
Understanding and Modeling Laser Cutting Mechanisms for Dismantling
For over 30 years, the Assembly Technologies Laboratory (LTA) at CEA Saclay has been conducting research to develop innovative tools for the dismantling of nuclear facilities, by designing laser cutting processes to work in hostile environments. This technology is suitable to cut thick materials, either in air or underwater, and has proven particularly effective for dismantling operations due to its precision and ability to limit aerosol generation. Today, this technology is considered safe and reliable, thanks to the efforts achieved through the European project "LD-SAFE".
However, technical challenges remain, particularly the management of residual laser energy, which, by propagating beyond the cut piece, can damage surrounding structures.
Initial studies, including a PhD thesis, have made it possible to develop numerical models to predict and control this energy, yielding significant advancements. Nevertheless, technological challenges remain, such as handling thicker materials (>10 mm), cutting multi-plate configurations, and considering the addition of oxygen to improve cutting efficiency.
The objective of the PhD is to address these challenges and to gain a better understanding of the laser cutting process and the propagation of residual laser energy. The doctoral student will refine the numerical model to predict its impact on background structures, particularly for thick materials and multi-plate configurations. The work will include the development of a multiphysics model, validated by experiments, with a particular focus on the effect of oxygen, the creation of simplified models, and adaptation for use by operators.
The PhD will be conducted in collaboration between the Assembly Technologies Laboratory (LTA) at CEA Saclay and the Dupuy de Lôme Research Institute (IRDL - UMR CNRS 6027) at the University of South Brittany (Lorient).
Kinetics of segregation and precipitation in Fe-Cr-C alloys under irradiation : coupling magnetic, chemical and elastic effects
Ferritic steels are being considered as structural materials in future fission and fusion nuclear reactors. These alloys have highly original properties, due to the coupling between chemical, magnetic and elastic interactions that affect their thermodynamic properties, the diffusion of chemical species and the diffusion of point defects in the crystal. The aim of the thesis will be to model all of these effects at the atomic scale and to integrate them into Monte Carlo simulations in order to model the segregation and precipitation kinetics under irradiation, phenomena that can degrade their properties in use. The atomic approach is essential for these materials, which are subjected to permanent irradiation and for which the laws of equilibrium thermodynamics no longer apply.
The candidate should have a good background in statistical physics or materials science, and be interested in numerical simulations and computer programming. The thesis will be carried out at CEA Saclay's physical metallurgy laboratory (SRMP), in a research environment with recognised experience in multi-scale modelling of materials, with around fifteen theses and post-doctoral contracts in progress on these topics.
A Master 2 internship on the same subject is proposed for spring 2025 and is highly recommended.
Study of catalysis on stainless steels
The materials (mainly stainless steels) aging of the spent nuclear fuel reprocessing plant is the focus of an important R&D activity at CEA. The control of this aging will be achieved by a better understanding the corrosion mechanisms the stainless steels in nitric acid (the oxidizing agent used in the reprocessing steps).
The aim of the PhD is to develop a model of corrosion on a stainless steel in nitric acid as a function of temperature and the acid nitric concentration. This PhD represents a technological challenge because currently few studies exist on in situ electrochemical measurements in hot and concentrated nitric acid. The PhD student will carry out by coupling electrochemical measurements, chemical analyses (UV-visible-IR spectrometry...) and surfaces analyses (SEM, XPS,…). Based on these experimental results, a model will be developed, which will be incorporated in the future in a more global model of the industrial equipments aging of the plant.
The laboratory is specialized in the corrosion study in extreme conditions. It is composed of a very dynamic and motivated scientific team which has the habit to receive students.
Study of of the thermodynamic of K2CO3-CO2-H2O for the development of NET and SAF technologies
.Bioenergy with Carbon Capture and Storage (BECCS) uses biomass energy while capturing the carbon dioxide released by the process, resulting in negative emissions into the atmosphere. The reference process in Europe uses potassium carbonate but at atmospheric pressure [1], whereas its sequestration or hydrogenation into sustainable molecules requires high pressures.
The thesis consists in acquiring new thermodynamic and thermo-chemical data at high temperature/pressure [2] required for the energy optimization of such a process, and integrating them into a thermodynamic model.
The overall process will then be reassembled in order to quantify the expected energy gain.
The thesis will be carried out at the Thermodynamic Modeling and Thermochemistry Laboratory (LM2T), in collaboration with LC2R (DRMP/SPC) for the experimental part.
References :
[1]K. Gustafsson, R. Sadegh-Vaziri, S. Grönkvist, F. Levihn et C. Sundberg, «BECCS with combined heat and power: assessing the energy penalty,» Int. J. Greenhouse Gas Control, vol. 110, p. 103434, 2021.
[2] S. Zhang, X. Ye et Y. Lu, «Development of a Potassium Carbonate-based Absorption Process with Crystallization-enabled High-pressure Stripping for CO2 Capture: Vapor–liquid Equilibrium Behavior and CO2 Stripping Performance of Carbonate/Bicarbonate,» Energy Procedia, 2014
Effect of microstructure and irradiation on susceptibility to intergranular cracking of alloy 718 in PWR environment.
Alloy 718, a nickel-based alloy, is used in fuel assemblies for pressurized water reactors (PWRs). In service, these components are subjected to high mechanical stress, neutron irradiation and exposure to the primary environment. Usually, this alloy shows very good resistance to intergranular cracking. However, there are microstructural and/or irradiation conditions which, by modifying the mechanical properties and plasticity mechanisms, make the material susceptible to intergranular cracking in the primary PWR environment.
In this context, the aim of this thesis will be to study the influence of microstructure (via different heat treatments) and irradiation on deformation localization and susceptibility to intergranular cracking in primary PWR media.
To this end, two grades will be tested, one deemed sensitive and the other not. In-situ SEM tensile tests on samples whose microstructure has been previously characterized by EBSD will be carried out to identify the types of intra- and intergranular deformation localization and their evolution. The non-irradiated state will be characterized as the reference state. In addition, exposure and intergranular cracking tests in the primary medium (coupons, slow tension, etc.) will be carried out on both grades and at different irradiation levels. The microstructure as well as surface and intergranular oxidation of the specimens will be characterized by various microscopy techniques (SEM, EBSD, FIB and transmission electron microscopy).
This thesis constitutes for the candidate the opportunity to address a problem of durability of metallic materials in their environment following a multidisciplinary scientific approach combining metallurgy, mechanics and physico-chemistry and based on the use of various cutting-edge techniques available at the CEA. The skills that he will thus acquire can therefore be valued during the rest of his career in the industry (including non-nuclear) or in academic institutions.