Thermodynamic Modelling of Complex Oxides for Smart Sensors

The search for more efficient materials follows a pattern that has changed very little over the years, involving poorly automated phases of synthesis, characterization and measurement of functional properties. Although this pattern has proved its strength in creating knowledge bases, it remains ineffective because it is time-consuming and generally covers a reduced range of compositions. The project Hiway-2-mat (https://www.pepr-diadem.fr/projet/hiway-2-mat/) seeks to use high-throughput combinatorial approaches and develop autonomous configurations to explore the compositional spaces of complex oxide materials, with the aim of accelerating the discovery of materials for smart sensors. In this context, CALPHAD method is a valuable tool for materials exploration, as it can provide a number of useful insights into the role of oxidation state or oxygen partial pressure on phase stability, and on the degree of substitution of doping elements in an oxide matrix. The aim is to calculate phase diagrams of complex oxides based on available databases, either to better prepare combinatorial experiments, or to drive the autonomous robot on the fly, providing additional information for on-line characterization.
Your role will be to:
1)Perform thermodynamic simulations using CALPHAD method and Thermo-Calc Software to predict the stability range of a set of complex oxides (Ba/Ca/Sr)(Ti/Zr/Sn/Hf)O3 at different temperatures and oxygen partial pressures. In this step, the candidate will also perform a critical review of the thermodynamic data available in the literature.
2)Include key elements in the available database.
3)Develop a rapid screening method to search for the most promising compositions.
The candidate will work closely with the experimental platform development team to guide future trials and adapt the method to better meet the needs of large-scale production.

Hybrid ion exchangers for the traetment of radioactive organic liquids: molecular dynamics design assistance

The ECCLOR project (labelled 'Investissement pour le future') focuses on the treatment of radioactive organic effluents by developing porous materials capable of selectively eliminating alpha emitting ions. Research carried out at CEA has led to the design of hybrid materials with variable performance in capturing alpha emitters present in organic liquids. Understanding this performance at the molecular level is essential, but complex.
To address this challenge, this post-doctoral fellowship focuses on the use of classical molecular dynamics to rationalize these performances. The work will be carried out at the Marcoule research center's LILA laboratory, drawing on the expertise of teams specializing in the modeling of solid/liquid systems using classical molecular dynamics.
To support these simulations, experimental data may be provided by laboratories such as the Laboratoire des Procédés Supercritiques et de Décontamination (LPSD) and the Laboratoire de Formulation et Caractérisation des Matériaux minéraux (LFCM). The results obtained will be discussed at progress meetings and will be the subject of scientific publications.
In summary, this post-doctoral contract aims to couple theoretical approaches with experiment. Understanding the interactions within these materials at the molecular scale is essential to provide insights and improve the processes currently under study.

Modeling the corrosion behavior of stainless steels in a nitric acid media with temperature

Controlling the aging of equipment materials (mainly stainless steel) of the spent nuclear fuel reprocessing plant is the subject of constant attention. This control requires a better understanding of the corrosion phenomena of steels by nitric acid (oxidizing agent used during the recycling stages), and ultimately through their modeling.
The materials of interest are Cr-Ni austenitic stainless steels, with very low carbon content. A recent study on Si-rich stainless steel, which was developed with the aim of improving the corrosion resistance of these steels with respect to highly oxidizing environments [1 , 2 ]; showed that the corrosion of this steel was thermally activated between 40 °C and 142 °C with different behavior below and above the boiling temperature (107 °C) of the solution [3]. Indeed, between 40°C and 107°C, the activation energy is 77 kJ/mol and above boiling point, it is much lower and is worth 20 kJ/mol. This difference may be due to a lower energy barrier or a different kinetically limited step.
The challenge of this post-doctoral subject is to have a predictive corrosion model depending on the temperature (below and beyond boiling). With this objective, it will be important to analyze and identify the species involved in the corrosion process (liquid and gas phase) as a function of temperature but also to characterize the boiling regimes. This model will be able to explain the difference in activation energies of this Si-rich steel below and above the boiling temperature of a concentrated nitric acid solution but will also make it possible to optimize the processes of the factory where temperature and/or heat transfer play an important role.

Researcher in Artificial Intelligence applied to self-driven microfluidic

This postdoctoral position is part of the 2FAST project (Federation of Fluidic Autonomous labs to Speed-up material Tailoring), which is a part of the PEPR DIADEM initiative. The project aims to fully automate the synthesis and online characterization of materials using microfluidic chips. These chips provide precise control and leverage digital advancements to enhance materials chemistry outcomes. However, characterising nano/micro-materials at this scale remains challenging due to its cost and complexity. The 2FAST project aims to utilise recent advances in the automation and instrumentation of microfluidic platforms to develop interoperable and automatically controlled microfluidic chips that enable the controlled synthesis of nanomaterials. The aim of this project is to create a proof of concept for a microfluidic/millifluidic reactor platform that can produce noble metal nanoparticles continuously and at high throughput. To achieve this, feedback loops will be managed by artificial intelligence tools, which will monitor the reaction progress using online-acquired information from spectrometric techniques such as UV-Vis, SAXS, and Raman. The postdoctoral position proposed focuses on AI-related work associated with the development of feedback loop design, creation of a signal database tailored for machine learning, and implementation of machine learning methods to connect various data and/or control autonomous microfluidic devices.

Thermodynamic investigation of Metal-Insulator-Transition materials – The case of doped VO2 for smart windows applications

The present post-doc proposal aims to develop a specific thermodynamic database on the V-O-TM (TM=Fe,Cr) system by using the CALPHAD approach. The candidate will conduct experimental campaigns to obtain relevant data to feed the thermodynamic models. The candidate will mostly use the experimental equipment available at the lab (DTA, annealing furnaces, high temperature mass spectrometry, laser heating, SEM-EDS). In addition, the post-doc may participate to combinatorial high-throughput activities led by other laboratory of the Hiway-2-Mat consortium (e.g., ICMCB in Bordeaux), allowing a better connection between the CALPHAD simulation output and the accelerated characterization platform. The thermodynamic database will be then included in the autonomous research routine implemented in the material exploration path.

Study of cleavage brittle crack initiation sites in low alloy bainitic steels with segregations

Macro-segregations of alloy elements and impurities in heavy forged 16-20 MND5 components or Pressurized Water nuclear Reactors induces significant fluctuations of these mechanical properties, and in particular, of dynamic and fracture toughness. Such a macro-segregation occurs during the solidification of the ingot and can still be observed in the final component, even after significant discarding performed on purpose during the fabrication process.
Recent results have confirmed the essential role played by specific carbides located close to grain boundaries, even for moderately segregated materials. The main objective of this Post-Doctoral internship is to precisely study some clivage initiation sites on these alloys to determine the types of carbides and the cristallographic conditions that promote crack initiation. A statistical analysis will then be performed to identify the population of these carbides within the microstructure of the material. The experimental results will be used as entries of a local approach to brittle fracture model.

Agglomerate breakage model and homogenisation by DEM simulations: Calibration with tomographic micro-compressions in X ray beam line Soleil

Context:
The reference ceramic fabrication process involves three main stages: grinding, pressing, and sintering. Pellet compaction during pressing relies on three main densification steps rearrangements by motion, compaction by strain, and agglomerate fractures by compression. This research project aims to explore the influence of the pressing step on the microstructure behavior during the sintering process. The study focuses on a powder composed of agglomerates with a microstructure based on a homogeneous mix of TiO2-Y2O3, TiO2 for surrogate UO2 and Y2O3 for surrogate PuO2. Each agglomerate consists of unbreakable elementary particles included in breakable aggregates, synthesized using the Cryogenic Granulation Synthesis Process (CGSP) [1].
Recent investigations at the Anatomix X-ray beam line in the synchrotron Soleil [2] have validated the results of tomographic micro-compressions, aligning with Kendall's theory, Fig 1. The experiments involved one-way cyclic micro-compression tests on agglomerates subjected to a simple load and unload cycle until breakage. Tomographic post-treatments provided insights into porosities, crack initiation, and propagation. Several DEM simulation studies have also been used to explore agglomerate behavior under dynamic or quasi-static loading with and without breakage, however without fully calibrating the breakage model [3], [4], [5].

Study of the seismic behavior of piping systems using mechanical models of different degrees of fidelity

Piping systems are part of the equipment to which particular attention is paid as part of the safety review or design of nuclear installations. They are designed in accordance with codes, standards and regulations to withstand loads that occur or may occur over the life of a facility. These systems must therefore be designed to withstand accidental loads such as earthquakes. Feedback shows that piping systems generally behave well in the event of an earthquake. When failures are observed, they are more likely to be due to significant anchor movement, brittle materials, unwelded joints, corrosion, piping support failures, or seismic interactions. In practice, to be able to estimate the beyond design seismic behavior and the associated failure risks, the engineer can implement numerical models involving varying degrees of refinement depending on needs. This study consists of taking stock of the numerical modeling capabilities of piping systems under earthquake. For reasons of computational burden, global modeling based on beam elements is often favored, considering simplified material laws such as bilinear material laws with kinematic hardening. We know the “theoretical” limits of these models but it is difficult to have clear ideas about their real limits of applicability depending on the level of loading and the damage targeted. To make this assessment, we propose to interpret, using different numerical models involving different degrees of fidelity, the results of the experimental campaign carried out by the BARC and which was used for the MECOS benchmark (METallic COmponent margins under high Seismic loads).

Thermodynamic modelling of protective coating for solid oxide electrolysis cells

In the pursuit of a sustainable energy future, solid oxide electrolysis cells (SOECs) are a highly promising technology for producing clean hydrogen by electrolysis of water at high temperature (between 500 and 850°C). Although high operating temperature offers many benefits (high efficiency and low power consumption), it can lead to degradation of the interconnectors. Coatings are proposed to improve the long-term performance of interconnectors and reduce corrosion problems. The aim is to find the best coating candidates with high thermodynamic stability, high electrical conductivity and low cation diffusivity. In this context, you will join the LM2T team within the DIADEM Project (https://www.diadem.cnrs.fr/2023/03/29/atherm_coat/) for innovative materials.
Your role will be to:
1)Perform thermodynamic simulations using CALPHAD method and Thermo-Calc Software to predict the stability range of a set of coating candidates (e.g. spinel oxides and perovskites) and the possible decomposition reactions in different atmosphere conditions (temperature and oxygen partial pressure). In this step, the candidate will also perform a critical review of the thermodynamic data available in the literature.
2)To couple information obtained from CALPHAD calculations and the thermodynamic database to estimate the thermal expansion and electrical conductivity of the most promising compositions.
The candidate will work closely with the experimental team (ISAS/LECNA and UMR-IPV) producing the coatings to guide future trials and adapt the method to better meet large-scale production needs.

Study of aerosol transport through degraded materials

Radioactive Waste (RW) are produced during nuclear activities and are categorized as a function of their activities and their half-life in order to manage their conditioning, transport, storage… Mortar can be used in order to immobilize and/or create a safe barrier forming a Radioactive Waste Package (RWP) in order to protect the environment. It is important to study the efficiency of this mortar barrier for long term and safety assessment have to investigate the case of crack mortar formation as radioactive particles could then migrate in the cracks.
The LECD laboratory investigated this problematic by measuring the migration of CeO2 particle in mortar cracks using X-Ray microtomography. The cracks were synthesized by dissolving plastic molds (designed by 3D printing). This study showed the influence of particle interactions with tortuosity and roughness of the crack, but was limited to 40 µm particle diameter.
The aim of the postdoctoral work is to develop an experimental approach similar to the method developed to study the efficiency of HEPA filters, with particles of 0.05 - 5 µm diameter. Quantitative measurements will be performed on the particle flows on both sides of the cracked mortar sample. LECD has acquired an aerosol generator, a light-scattering aerosol spectrometer system for particle size analysis and concentration determination and an Universal Scanning Mobility Particle Sizers. The researcher will also develop modelling work using numerical tools as STARCCM+.
This project will be carried out under the format of an 12-month fixed-term contract at the Atomic Energy and Alternative Energies Commission (CEA), at the Cadarache site (Saint-Paul-lez-Durance, 13) at the Expertise and Destructive Characterization Laboratory (LECD) of the Expertise and Characterization CHICADE Service (SECC).
Contacts: ingmar.pointeau@cea.fr (R&D engineer) – Olivier.vigneau@cea.fr (Head of the Laboratory)

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