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.
Surface technologies for enhanced superconducting Qubits lifetimes
Materials imperfections in superconducting quantum circuits—in particular, two-level-system (TLS) defects—are a major source of decoherence, ultimately limiting the performance of qubits. Thus, identifying the microscopic origin of possible TLS defects in these devices and developing strategies to eliminate them is key to superconducting qubit performance improvement. This project proposes an original approach that combines the passivation of the superconductor’s surface with films deposited by Atomic Layer Deposition (ALD), which inherently have lower densities of TLS defects, and thermal treatments designed to dissolve the initially present native oxides. These passivating layers will be tested on 3D Nb resonators than implemented in 2D resonators and Qubits and tested to measure their coherence time. The project will also perform systematic material studies with complementary characterization techniques in order to correlate improvements in qubit performances with the chemical and crystalline alteration of the surface.
Numerical modelling of large ductile crack progagation and assessment of margins comparing to engineering approach
Predicting failure modes in metal structures is an essential step in analyzing the performance of industrial components where mechanical elements are subjected to significant stress (e.g., nuclear power plant components, pipelines, aircraft structural elements, etc.). To perform such analyses, it is essential to correctly simulate the behavior of a defect in ductile conditions, i.e., in the presence of significant plastic deformation before and during propagation.
Predictive numerical simulation of ductile tearing remains an open scientific and technical issue despite significant progress made in recent years. The so-called local approach to fracture, notably the Gurson model (and its modified version GTN), is widely used to model ductile tearing. However, its use has limitations: significant computation time, simulation stoppage due to the presence of completely damaged elements in the model, and non-convergence of the result when the mesh size is reduced.
The aim of this thesis is to develop the ductile tear simulation model used at LISN so that it can be applied to large crack propagation on complex structures. It also aims to compare the results obtained with engineering methods that are simpler to implement.
Thermal Barrier Coatings with enhanced mechanical properties performed by plasma spraying
Increasing the performance of aircraft gas turbines requires improvements in the materials used in the combustion chamber and on the parts at the outlet of the chamber. Widely used in the aerospace industry, plasma spraying enables the application of low-conductivity ceramic coatings that provide a thermal barrier protection for metal parts. The mechanical stress observed require coatings that are increasingly resistant in mechanical terms. As a result, the thesis will focus on developing plasma-sprayed thermal barrier coatings with increased mechanical strength while maintaining good thermal insulation compared to the state of the art yttria stabilized zirconia thermal barrier coating currently used in gas turbine engines. For example, particular attention will be paid to toughness, which is the ability of a material to resist fracture in the presence of a crack. Factors that can influence toughness include composition, microstructure, and the addition of reinforcements. The use of original solutions, such as bio-inspired ones, is also a possibility.
Scaling Up Dislocation Dynamics Simulations for the Study of Nuclear Material Aging
Materials used in nuclear energy production systems are subjected to mechanical, thermal, and irradiation condition, leading to a progressive evolution of their mechanical properties. Understanding and modeling the underlying physical mechanisms involved is a significant challenge.
Dislocation Dynamics simulation aims to understand the behavior of the material at the crystal scale by explicitly simulating the interactions between dislocations, microstructure, and crystal defects induced by irradiation. The CEA, CNRS, and INRIA have been developing the NUMODIS calculation code for this purpose since 2007 (Etcheverry 2015, Blanchard 2017, Durocher 2018).
More specific work on zirconium alloys (Drouet 2014, Gaumé 2017, Noirot 2025) has allowed the validation and enhancement of NUMODIS's ability to handle these individual physical mechanisms by directly comparing them with experiments, through in situ tensile tests under a transmission electron microscope. However, these studies are limited by the current inability of the NUMODIS code to handle a sufficiently high and representative number of defects, and thus to obtain the mechanical behavior of the grain (~10 microns).
The objective of the proposed work is to implement new algorithms to extend the functionalities of the code, propose and test new numerical algorithms, parallelize certain parts still processed sequentially, and ultimately demonstrate the code's ability to simulate the deformation channeling mechanism in an irradiated zirconium grain.
The work will focus primarily on algorithms for calculating velocities, junction formation, and time integration, requiring both mastery of dislocation physics and the corresponding numerical methods. Algorithms for integration recently proposed by Stanford University and LLNL will be implemented and tested for this purpose.
Significant work will also be devoted to adapting the current code (hybrid MPI-OpenMP parallelism) to new computing machines that favor GPU processors, through the adoption of the Kokkos programming model.
Building on both previous experimental and numerical work, this study will conclude with the demonstration of NUMODIS's ability to simulate the channeling mechanism in an irradiated zirconium grain and to identify or even model the main physical and mechanical parameters involved.
At the interface between several fields, the candidate must have a good foundation in physics and/or mechanics, while being comfortable with programming and numerical analysis.
References:
1. Etcheverry Arnaud, Simulation de la dynamique des dislocations à très grande échelle, Université Bordeaux I (2015).
2. Blanchard, Pierre, Algorithmes hiérarchiques rapides pour l’approximation de rang faible des matrices, applications à la physique des matériaux, la géostatistique et l’analyse de données, Université Bordeaux I (2017).
3. Durocher, Arnaud, Simulations massives de dynamique des dislocations : fiabilité et performances sur architectures parallèles et distribuées (2018).
4. Drouet, Julie, Étude expérimentale et modélisation numérique du comportement plastique
des alliages de zirconium sous et après irradiation (2014).
5. Gaumé, Marine, Étude des mécanismes de déformation des alliages de zirconium
après et sous irradiation (2017).
6. Noirot, Pascal, Etude expérimentale et simulation numérique, à l'échelle nanométrique et en temps réel, des mécanismes de déformation des alliages de zirconium après irradiation (2025).
Rheology and Conduction of Functional Polymers for Embedded Electronics in 3D/4D Additive Manufacturing
This PhD project, conducted on the MAPP platform (CEA-Metz), focuses on the development of additive manufacturing (3D/4D) processes for the integration of smart materials. The aim is to overcome the limitations of traditional planar electronic architectures (PCBs, wafers) integration by enabling the direct-to-shape printing of electronic functions within 3D parts performed by Fused Deposition Modeling and Paste Extrusion Modeling. The research will address functional conductive polymers, composed of an organic matrix and metallic particles, whose conduction mechanisms (direct contact, tunneling effect, ionic conduction) are governed by the percolation threshold. The study will investigate the processing of these materials, their rheological and electrical behavior, and the exploitation of their resistive, piezoresistive and piezoelectric properties to design novel sensor (3D) and actuator (4D) functions. The doctoral candidate will benefit from advanced characterization facilities and the guidance of a multidisciplinary team with expertise in additive manufacturing, materials science, and microelectronics.
Synthesis of organic aerogels from polydicyclopentadiene derivatives
The study of inertial confinement fusion of the deuterium + tritium (DT) mixture has long been a research focus at the CEA. Experiments related to this topic, carried out within the Laser Mégajoule (LMJ) facility, require the use of materials with specific properties. This includes, among others, polymer foams (organic aerogels) used as pre-ignition targets. Such materials must combine very low density with sufficient mechanical strength to be compatible with the preparation process employed.
In this context, the objective is to develop CHx polymeric aerogels based on polydicyclopentadiene (pDCPD) and other polymers derived from ring-opening metathesis polymerization (ROMP), in order to produce materials that are (i) of low apparent density (target value in the project: below 50 mg/cc), (ii) homogeneous, (iii) exhibiting fine (open) nano-porosity, and (iv) machinable.
The proposed PhD work would focus on three main areas:
1. The synthesis of new (co-)monomers
2. The preparation of organic aerogels
3. The exploitation of data using AI (opportunity)
Effect of water radiolysis on the hydrogen absorption flux by austenitic stainless steels in the core of a nuclear pressurized water reactor
In pressurized water nuclear reactors, the core components are exposed to both corrosion in the primary medium, pressurized water at around 150 bar and 300°C, and to neutron flux. The stainless steels in the core are damaged by a combination of neutron bombardment and corrosion. In addition, radiolysis of the water can have an impact on the mechanisms and kinetics of corrosion, the reactivity of the medium and, a priori, the mechanisms and kinetics of hydrogen absorption by these materials. This last point, which remains unexplored, may prove problematic, as hydrogen in solid solution in steel can lead to changes in (and degradation of) the mechanical properties of the steel or induce premature cracking of the part. The pioneering work developed in this highly experimental thesis will focus on the impact of radiolysis phenomena on the mechanisms and kinetics of corrosion and, above all, hydrogen pick-up in 316L stainless steel exposed to the primary environment under irradiation. Hydrogen will be traced by deuterium, and neutron irradiation simulated by electron irradiation on particle accelerators. An existing permeation cell will be modified into a unique setup to allow in operando measurement by mass spectrometry of the deuterium permeation flux through a sample exposed to the simulated primary water under radiolysis conditions. The distribution of hydrogen in the material, as well as the nature of the oxide layers formed, will be analysed in detail using state-of-the-art techniques available at the CEA and in partner laboratories. The doctoral student will ultimately be required to (i) identify the mechanisms involved (corrosion and hydrogen entry), (ii) estimate their kinetics and (iii) model the evolution of hydrogen flux in the steel in connection with radiolysis activity.
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.
Understanding the mechanisms of oxidative dissolution of (U,Pu)O2 in the presence of Ag(II) generated by ozonation
The recycling of plutonium contained in MOx fuels, composed of mixed uranium and plutonium oxides (U,Pu)O2, relies on a key step: the complete dissolution of plutonium dioxide (PuO2). However, PuO2 is known to dissolve only with great difficulty in the concentrated nitric acid used in industrial processes. The addition of a strongly oxidizing species such as silver(II) significantly enhances this dissolution step—this is the principle of oxidative dissolution. Ozone (O3) is used to continuously regenerate the Ag(II) oxidant in solution.
Although this process has demonstrated its efficiency, the mechanisms involved remain poorly understood and scarcely documented. A deeper understanding of these mechanisms is essential for any potential industrial implementation.
The aim of this PhD work is to gain insight into the interaction mechanisms within the HNO3/Ag/O3/(U,Pu)O2 system. The research will be based on a parametric experimental study of increasing complexity. First, the mechanisms of generation and consumption of Ag(II) will be investigated in the simpler HNO3/Ag/O3 system. In a second phase, the influence of various parameters on the oxidative dissolution of (U,Pu)O2 will be examined. The results will lead to the development of a kinetic model describing the dissolution process as a function of the studied parameters.
At the end of this PhD, the candidate—preferably with a background in physical chemistry—will have acquired advanced expertise in experimental techniques and kinetic modeling, providing a strong foundation for a career in academic research or industrial R&D, both within and beyond the nuclear sector.