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.
Towards a Method for characterizing the electrokinetic Properties of Particles in water at high Temperatures
In the field of industry and particularly energy, liquid water circuits are omnipresent. Fluids, by interacting with pipes made from metal alloys, inevitably lead to the formation of corrosion products.
Predicting the behavior of small particles (order of magnitude of µm) is therefore of particular interest. Indeed, due to their size, the behavior of the latter is governed by forces of electrical origin responsible for their adhesion to the surfaces. The electrokinetic properties and in particular the surface potential thus control the fate of the particle and can be defined using the zeta potential. This quantity characterizes a solid/solution couple and takes into consideration both the particle and its surface chemical properties as well as the solution where the particle is located.
If the characterization of the zeta potential at room temperature is quite widespread, its determination at high temperature is today confined to a few examples (theses by C. Cherpin 2022 [1] and M. Barale 2006 [2], studies of VTT [3] and EDF with the University of Besançon 2002 [4] and the EPRI patent 1994 [5]). The CEA (LC2R) has developed an innovative measurement method currently being patented to explore poorly developed experimental techniques based on theoretical hypotheses to be confirmed.
Through multi-physics (flow, temperature, chemistry, electrochemistry, etc.) and multi-scale (microscopic particles influencing a macroscopic state) approaches, the objective of the thesis is therefore to carry out measurements of the surface properties of particles in water at high temperature depending on the physicochemical conditions (pH, RedOx and temperature), to adapt existing models or propose new ones then validate them with experimental data.
The data thus obtained is intended to feed the simulation codes in order to better understand and control the aging of the circuits.
[1] C. Cherpin, PhD, 2022, Modelling the behaviour of colloidal corrosion products in the primary circuit of Pressurized Water Reactors
[2] M. Barale, PhD, 2006, Etude du comportement des particules colloïdales dans les conditions physico-chimiques du circuit primaire des réacteurs à eau sous pression
[3] E. Velin, Master’s Thesis, 2013, The effect of Temperature on the Zeta Potential of Magnetite Particles in Ammonia, Morpholine and Ethanolamine Solutions
Learning Interpretable Models for Stress Corrosion of Stainless Steels Exposed in the Primary Environment of PWRs
Stress corrosion cracking (SCC) of austenitic alloys in water-cooled nuclear reactors is one of the most significant component degradation phenomena. SCC occurs due to the synergistic effects of tensile stresses, environment and material susceptibility. For reactor life extension, understanding this mechanism is essential. The methodology most frequently employed to investigate SCC cracking is an experimental one, requiring lengthy and costly tests of several thousand hours. Furthermore, the considerable number of critical parameters that influence susceptibility to SCC cracking and coupling effects have resulted in test grids increasing in length and complexity. This thesis proposes a novel approach based on the use of interpretable models that are driven by the artificial intelligence of fuzzy logic. The aim is to reduce the length and cost of research activities by focusing on relevant tests and parameters that can improve environmental performance. The key issues here will be to add the performance of artificial intelligence to the experimental approach, with the aim of defining susceptibility domains for the initiation of SCC cracks as a function of the critical parameters identified in the model, and providing data for the development of new materials by additive manufacturing. The thesis will develop a numerical model that can be used as guidance in decision-making regarding the stress corrosion mechanism. The future PhD student will also carry out experimental work to validate this new numerical approach.
Synthesis, characterization and modeling of (Mn,Co)3O4 thin films applied to corrosion layers and spintronics
Spinel-type transition metal oxides (AB2O4) appear spontaneously during the generalized corrosion of steels or alloys in aqueous or gaseous environments at high temperatures. This spinel phase forms a continuous corrosion layer and thus regulates corrosion processes by controlling conductivity and material transport between the material and the oxidizing medium. They are also applied voluntarily as protective coatings against degradation phenomena. In particular, the Mn-Co-O spinel system is very promising as protective conductive layers on ferritic stainless steel used to fabricate interconnects in solid oxide fuel cells for green hydrogen production. The composition of the spinel phase determines the protective performance of the coatings. This feature is particularly delicate for materials used in high-temperature electrolyzers, as electronic transport must be optimal (high electrolysis), but must not be accompanied by material transport (low cation diffusion).
In contrast, electronic transport properties of spinel-type transition metal oxides are generally not well understood. Measurements are made on complex corrosion layers (or coatings) of variable composition, low crystallinity, complex microstructure and low thickness. Furthermore, spinel oxides exhibit magnetic properties and composition-dependent cationic disorder that are usually ignored, even though they have a strong impact on electronic transport. The properties highlighted here are the ones that also hold significant importance within the field of spintronics. Thus, tuning the chemical composition of these spinel-structured oxides (normal, inverse or mixed) offers a wide range of magnetic (ferrimagnetic, antiferromagnetic) and electronic (semimetallic, semiconductor, insulator) properties. In particular, CoMn2O4 is expected to exhibit a complex magnetic configuration [1], mainly related to the arrangement of Co2+ and Mn3+ cations in interstitial sites, which needs to be analyzed in detail. Unlike corrosion layers, these physical studies require the synthesis of thin films of well-controlled composition and high crystallinity.
The aim of the thesis is to build up knowledge of physicochemical and structural properties of (Mn,Co)3O4 in order to contribute to the elaboration of Mn-Co-O phase diagrams and electronic transport models based on the relationship between order/disorder, magnetic properties and resistivity of (Mn,Co)3O4. Eventually, the whole (Fe,Cr,Mn,Co)3O4 system will be also considered. The study will be carried out on thin films of perfectly controlled composition and high crystallinity, and will be enhanced by numerical simulations. The experimental and theoretical work will be based on the results of previous studies on (Ni,Fe,Cr)3O4 epitaxial thin films [2,3].
The thesis will be divided as follows:
- Growth of thin films and multilayers by MBE (Molecular Beam Epitaxy) (J.-B. Moussy)
- Spectroscopic characterization using XPS (X-ray photoemission spectroscopy) (F. Miserque)
- Fine structure characterization by DRX and X-ray absorption (XMCD) (P. Vasconcelos)
- Modeling of core-level spectra (XPS, XAS and XMCD) and atomistic modeling (A. Chartier)
- Magnetic characterization by SQUID/VSM magnetometry and electric transport characterization (J.-B. Moussy)
[1] Systematic analysis of structural and magnetic properties of spinel CoB2O4 (B= Cr, Mn and Fe) compounds from their electronic structures, Debashish Das, Rajkumar Biswas and Subhradip Ghosh, Journal of Physics: Condensed Matter 28 (2016) 446001.
[2] Stoichiometry driven tuning of physical properties in epitaxial Fe3-xCrxO4 thin films, Pâmella Vasconcelos Borges Pinho, Alain Chartier, Denis Menut, Antoine Barbier, Myrtille O.J.Y. Hunault, Philippe Ohresser, Cécile Marcelot, Bénédicte Warot-Fonrose, Frédéric Miserque, Jean-Baptiste Moussy, Applied Surface Science 615 (2023) 156354.
[3] Elaboration, caractérisation et modélisation de films minces et multicouches à base d’oxydes (Ni,Fe,Cr)3O4 appliquées à la corrosion et à la spintronique, A. Simonnot, thèse en cours.
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.
Mesoscopic simulations and development of simplified models for the mechanical behaviour of irradiated concrete
In nuclear power plants, the concrete biological shield serves as a support for the reactor vessel and as a protective shield against radiation. Over the long term, prolonged exposure to neutron radiation can cause the concrete aggregates to expand through amorphisation, leading to micro-cracking and degradation of its mechanical properties. This is an important issue in studies aimed at extending the life of power plants. At the mesoscale, these phenomena can be modelled by separating the behaviour of the aggregates, the cementitious matrix and the interfacial transition zones. However, it is difficult to describe the initiation and propagation of microcracks in such complex heterogeneous multi-cracked systems. The aim of this thesis, carried out as part of a Franco-Czech ANR project, is to develop a high-performance numerical simulation tool for analysing the effects of neutron irradiation on concrete at the mesoscopic scale. A coupled thermo-hydro-mechanical approach will be used in which the behaviour of the matrix will take into account shrinkage, creep and micro-cracking. The simulations will be validated using experimental data obtained on tested samples, and the numerical tool will then be used to estimate the impact of various factors on the behaviour and performance of concrete subjected to neutron irradiation.
This research project is aimed at a PhD student wishing to develop their skills in materials science, with a strong focus on multiphysical and multiscale modelling and numerical simulations.
Study of the corrosion behaviour in NaCl-MgCl2-CeCl3 of a nickel-based alloy in the presence of fission products (Te, S) for molten salt reactor
Access to clean and affordable energy seems more crucial than ever in the current context of climate emergency. Several avenues have been explored for years, but many technological barriers remain to be overcome in order to realise them, as they represent significant technological breakthroughs. Whether it's for energy storage or 4th generation nuclear reactors, the molten salt medium used as a heat transfer fluid and/or fuel is highly corrosive, making the choice of structural materials very complex.
The objective of the proposed PhD project within the Service of Corrosion and Material Behaviour (S2CM) is the comprehensive study of the behaviour of promising nickel-based alloys in the NaCl-MgCl2-CeCl3 ternary system, representative of the salt used in the French molten salt reactor concept, at 600°C. By "comprehensive", this refers to everything from specimen preparation to the multi-scale and multi-technique characterisation of corrosion products. This topic has therefore a strong experimental character and focuses on understanding corrosion mechanisms. The influence of fission products, such as tellurium or sulphur, on corrosion mechanisms will be specifically studied.
Predicting thermodynamic properties of defects in medium-entropy alloys from the atomic scale through statistical learning
The properties and behaviour of materials under extreme conditions are essential for energy systems such as fission and fusion reactors. However, accurately predicting the properties of materials at high temperatures remains a challenge. Direct measurements of these properties are limited by experimental instrumentation, and atomic-scale simulations based on empirical force fields are often unreliable due to a lack of precision.This problem can be solved using statistical learning techniques, which have recently seen their use explode in materials science. Force fields constructed by machine learning achieve the degree of accuracy of {it ab initio} calculations; however, their implementation in sampling methods is limited by high computational costs, generally several orders of magnitude higher than those of traditional force fields. To overcome this limitation, two objectives will be pursued in this thesis: (i) to improve active statistical learning force fields by finding a better accuracy-efficiency trade-off and (ii) to create accelerated free energy and kinetic path sampling methods to facilitate the use of computationally expensive statistical learning force fields.
For the first objective, we improve the construction of statistical learning force fields by focusing on three key factors: the database, the local atomic environment descriptor and the regression model. For the second objective, we will implement a fast and robust Bayesian sampling scheme to estimate the anharmonic free energy, which is crucial for understanding the effects of temperature on crystalline solids, using an adaptive bias force method that significantly improves convergence speed and overall accuracy.We will apply the methods developed to the calculation of free energy and its derivatives, physical quantities that give access to the thermo-elastic properties of alloys and the thermodynamic properties of point defects. To do this, we will use algorithmic extensions that allow us to sample a specific metastable state and also the transition paths to other energy basins, and thus to estimate the free energies of formation and migration of vacancy defects. The thermodynamic quantities calculated will then be used as input data for kinetic Monte Carlo methods, which will make it possible to measure the diffusion coefficients in complex alloys as a function of temperature.
One aim will be to try to relate the atomic transport properties to the complexity of the alloy. Since our approach is considerably faster than standard methods, we will be able to apply it to complex alloys comprising the elements W, Ti, V, Mo and Ta at temperatures and compositions that have not been studied experimentally.
Superlattices for the characterization of diffusion under irradiation at the atomic scale
Metal alloys used in nuclear applications are subjected to relatively low temperatures (below 450°C) for long periods of time (more than 10 years). At these temperatures, the kinetics of the diffusion-controlled microstructure transformations are slow. The appearance of certain undesirable phases, likely to embrittle the material, can occur after several years of service. Therefore, diffusion coefficients play a crucial role as input data for modeling the evolution of these microstructures using phenomenological models. However, experimental determination of diffusion coefficients at low temperatures (T < 600°C) is extremely tricky, especially because of the need to characterize nanometric diffusion lengths, a difficulty made all the more difficult in the presence of irradiation.
With the development of chemical analysis by transmission electron microscopy (TEM) and atom probe tomography (APT), it is now possible to experimentally access very small diffusion lengths and thus determine low-temperature diffusion coefficients using superlattices, which consist of stacking nanometric layers of different chemical compositions. We can even characterize the effect of irradiation on diffusion by performing ion irradiations, enabling us to simulate the changes caused by neutron irradiation without activating the materials. The aim of this thesis is to develop a methodology and characterize diffusion under and outside irradiation in a ternary system of interest (Ni-Cr-Fe), representative of the steels and high-entropy considered in the nuclear industry.
This thesis is an opportunity to work with cutting-edge experimental techniques, in close collaboration with a team of theoretician in the same department, as well as with teams specializing in the development of superlattices at UTBM in Belfort and CINAM in Marseille.
Behavior of nanocavities under mechanical loading: from understanding physical mechanisms to homogenizing nanoporous materials
Nanocavities - typically a few nm to a few tens of nm in size - are often observed in metals, for example in high-temperature applications due to the condensation of vacancies or in metal alloys used in nuclear reactors due to irradiation. The presence of these nanocavities degrades the mechanical behaviour of materials and contributes to fracture. It is therefore necessary to determine the physical mechanisms associated with the behaviour of these nanocavities under mechanical loading and to obtain homogenised models describing the macroscopic behaviour of these nanoporous materials. The results available in the literature remain limited to date, particularly with regard to the representativeness of the simulations carried out and the models proposed for the applications of interest. This includes for example considering crystal defects surrounding the cavities, the effect of cyclic loading and the localisation of nanocavities at grain boundaries. The objectives of this thesis are therefore to determine the behaviour of nanocavities under mechanical loading and the associated physical mechanisms by considering realistic situations with respect to applications, to develop physically-based analytical models to describe the behaviour of nanocavities under mechanical loading, and finally to propose homogenised models adapted to nanocavities that can be used to simulate the failure by growth and coalescence of cavities. The targeted applications are those related to metal alloys under irradiation, but the elements of understanding obtained and the models developed could be used in a broader context. In order to achieve these objectives, Molecular Dynamics (MD) simulations will be performed, analysed from the elastic theory of dislocations and used to propose relevant homogenised models for nanoporous materials.