Multiscale modelling of twinning in tin
Twinning is a displacive deformation mechanism characterized by a continuous deformation of the material. Although widely studied for other industrial materials such as titanium alloys, this inelastic mechanism remains poorly understood and incompletely modeled for complex crystallographic structures. However, due to the reduced number of symmetries in these structures, dislocation slip is insufficient to accommodate deformation in certain loading directions, requiring the activation of twinning. This is the case for tin, which has a tetragonal structure. In particular, twinning contributes significantly to the mechanical response of tin at high strain rates and low temperatures. At intermediate temperatures and strain rates, a competition between dislocation plasticity and twinning plasticity can occur, making it crucial to describe the coupling between these two phenomena. Proposing a better description of this coupling will shed new light on the experimental data available at CEA DAM. The objective of the thesis is to develop a multiscale approach, from molecular dynamics to continuum mechanics, validated by experiments, to converge on a model that describes the behavior of tin over a wide range of temperatures and strain rates.
Development of injectable adhesive hydrogels for the treatment of retinal tears
Retinal tears then detachment, a serious eye condition (20–25 cases per 100,000 in France each year), requires urgent surgery. Current treatments involve removing the vitreous, using gas as a tamponade agent, and sealing tears with laser. However, this method presents drawbacks, including patient restrictions (e.g., prolonged lying down) and complications (e.g., cataracts). Injectable hydrogels are being explored as alternative tamponade agents, but they do not display adhesive properties to suture the tears and laser treatment is still required. Surgical glues have also been tested, but cyanoacrylate-based adhesives are toxic, fibrin-based sealants are hard to use in the eye, and current hyaluronan (HA)-based materials lack sufficient stability and adhesion.
This PhD project aims to develop a sterile, injectable HA-based hydrogel with strong adhesive properties to seal retinal tears. Key requirements include biocompatibility, injectability (30G needle), tissue adhesiveness (1.5–3.7 N), and rapid delivery (within 1 hour). Our group has previously developed an injectable HA hydrogel with dynamic crosslinking, offering long-term stability, biocompatibility, and optical transparency. To confer it with tissue-adhesion properties, two strategies will be tested: (1) addition of tissue-adhesive tannic acid in the hydrogel formulation, or (2) grafting tissue-adhesive groups onto the HA backbone. The hydrogel will be tested for its biocompatibility and adhesiveness in preclinical eye models.
This innovative hydrogel could simplify retinal surgery, reduce complications, lower costs, and improve recovery. Beyond retinal repair, it may have applications in cornea surgery and other medical fields.
Study of Zn, Cr, Fe, Ni synergies on crystallisation in simplified glasses of nuclear interest
In France, nuclear power-plants used for electricity production generate high-level long-lived radioactive wastes through spent fuel reprocessing. These wastes are confined within a borosilicate glass matrix, whose structure allows for the incorporation at the atomic scale of a large number of elements, and which displays excellent long-term properties. The industry challenges are leading to changes in the nuclear fuel composition, which can thus induce a modification of the spent-fuel composition to be vitrified.
Chromium is as such an element of interest: its relatively low solubility in borosilicate glasses as well as its tendency to crystallise with other elements, such as iron, nickel and zinc, needs to be further investigated. This thesis aims to study the synergetic effect of Cr, Ni, Fe and Zn on crystallisation in simplified peralkaline glasses of nuclear interest in order to better comprehend affinities between these elements, thus identifying both the nature and quantity of the several crystalline phases which may form.
The PhD student will benefit from the recognised skills of the host laboratory in glass formulation as well as the study of their physico-chemical properties. All of the resources made available will enable a global approach to the subject, working on a fast-growing topic with major industrial and societal implications. The experience acquired during this interdisciplinary work will be useful in the field of materials.
TRANSIENT LIQUID PHASE SINTERING OF UOX AND MOX FUEL PELLETS
The subject is related to the manufacture of UOX and MOX fuels. The main objective is to identify dopant pairs that allow the formation of a transient liquid phase during the fuel sintering step. For this, phase diagram calculations using the CALPHAD method will have to be carried out, also taking into account the requirements related to the irradiation phase once the fuel is loaded into the reactor. The most promising pairs will then be evaluated in the context of the manufacture of a UOX fuel and a MOX fuel. The experiments to be carried out will essentially be: the preparation of a powdery material, the shaping by pressing of this material in the form of cylinders representative of fuel pellets and the study of the high-temperature sintering of these UOX and MOX formulation cylinders. After sintering, a very important step will be the characterization at the macroscopic and microscopic scales of these pellets. The first year of the thesis will take place at the CEA center in Cadarache. The next two will take place at the CEA site in Marcoule. The first year of the PhD will take place at the CEA Cadarache center within the ICPE Uranium Fuel Laboratory. The following two years will be spent at the INB Atalante facility on the CEA Marcoule site. The candidate will work in two facilities unique in Europe and will be able to develop experience working in a nuclear environment with a highly innovative approach that will lead to the publication of original scientific results.
INFLUENCE OF THE DRY GRANULATION ON THE MANUFACTURING OF SFR MOX FUELS
The subject is related to the manufacture of MOX U,Pu)O2 fuel for Fast Neutron Reactors. The current process integrates a co-grinding step of uranium and plutonium dioxides to generate a powder medium which is then shaped by uniaxial pressing to generate cylindrical fuel pellets which are then sintered at high temperature. The collected powder medium has poor flowability which limits the rates of shaping by pressing. The objective of the thesis is therefore to evaluate the impact of mechanical granulation of the powder medium on the flowability, the pressing step and the microstructure obtained after sintering. Dissolution tests in nitric acid will also be carried out on certain very specific microstructures. The thesis will be based on a formal experimental plan developed using specific software (JMP). The PhD will take place at the INB Atalante facility on the CEA Marcoule site. The candidate will work in a unique facility in Europe and will be able to develop expertise in working in a nuclear environment with a highly innovative approach that will lead to the publication of original scientific results.
Mechanical degradation of Solid Oxide Cells: impact of operating and failure modes on the performances
Solid oxide cells (SOCs) are electrochemical devices operating at high temperature that can directly convert fuel into electricity (fuel cell mode – SOFC) or electricity into fuel (electrolysis mode – SOEC). In recent years, the interest on SOCs has grown significantly thanks to their wide range of technological applications that could offer innovative solutions for the transition toward a renewable energy market. However, despite of all their advantages, the large-scale industrialization of this technology is still hindered by the durability of SOCs. Indeed, the SOCs remain limited by various degradation phenomena including mechanical damage in the electrodes. For instance, the formation of micro-cracks in the so-called ‘hydrogen’ electrode is a major source of degradation. However, the precise mechanism and the full impact of the micro-cracks on the electrode performances are still unknown. By a multi-physic modelling approach, it is proposed in this thesis (i) to simulate the damage in the microstructure of the electrode and (ii) to calculate its impact on the loss of performances. Once the model validated on dedicated experiments, a sensitivity analysis will be conducted to provide relevant guidelines for the manufacturing of improved robust and performant electrodes.
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.
Thermodynamic and experimental approach of the reactivity in multi-constituted Silicon-Metal-Carbon systems for ceramic brazing
The development of ceramic-based material assemblies plays a fundamental role in technological innovation in many engineering fields. The choice of materials and joining process must ensure a functional, reliable and durable assembly, whose properties comply with the specifications of the application.
The PhD thesis is part of the development of brazing alloys optimized for the joining of ceramics (primarily silicon carbide) considered for various applications in harsh environments, particularly in the field of energy. Indeed, the design of these materials requires a good knowledge of the reactivity at the liquid alloy / ceramic interface. In this context, the thesis will contribute to the development of a thermodynamic and experimental approach to predict and understand the reactivity in multi-constituted Si-Metal-Carbon systems. This work includes a study of the wetting and interfacial reactivity of selected alloys (wetting and brazing experiments, fine characterization of the interfaces by different techniques such as FEG-SEM, X-ray diffraction, TEM, XPS) with the support of thermodynamic modelling using the CALPHAD method. This highly experimental work will be carried out in a dynamic and collaborative environment.
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.
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.