Study of the thermomechanical properties of solid hydrogen flows
IRIG's Department of Low Temperature Systems (DSBT) is developing several research themes around cryogenic solid hydrogen and its isotopes. The applications of this research range from the production of renewable micrometre-sized solid hydrogen targets for the generation of high-energy protons for laser-plasma acceleration, to the formation and injection of millimetre- or centimetre-sized hydrogen ice cubes for the supply and control of plasma in fusion reactors using magnetic or inertial confinement. A cross-cutting issue in these applications is the need for a detailed understanding of the mechanical properties of solid hydrogen, in order to gain a better understanding of the physics of extrusion and target production, as well as the formation and acceleration of icicles for injection into fusion plasmas.
The subject of this thesis focuses on the study of solid hydrogen extrusion under pressure. Using this technology, the DSBT has been developing several cryostats for over 10 years, enabling the production of ribbons of solid hydrogen, ranging in size from a few millimetres to a few tens of micrometres, extruded at speeds of a few millimetres per second.
The main objective of the research is to gain a better understanding of extrusion mechanisms to enable the development of numerical predictive tools for extrusion system design. This experimental thesis will be based on cryogenic rheometry using a capillary rheometer and/or a duvet experiment developed during a previous thesis. This study will be carried out in collaboration with the Laboratoire de Rhéologie et Procédés at Grenoble Alpes University.
Chiral Superconductors and Thermal Transport
In this PhD project, we intend to probe two well-known unconventional superconductors with thermal transport, through an original approach combining macroscopic and microscopic probes. These superconductors are UPt3 and UTe2, chosen because they address two issues currently under hot debate in the international community, that could strongly benefit from this new approach. UPt3 addresses the question of topological superconductivity, while UTe2 requires a clear identification of its spin-triplet superconducting order parameter.
Topological superconductivity is an active subject on the theoretical side and because of its potential interest in the field of quantum engineering. However, unambiguous experimental results are scarce, and we intend to focus here on UPt3, the first ever superconductor demonstrating the existence of transitions between superconducting phases, together with convincing evidences for chiral superconductivity. The goal is to probe predictions on the existence of an anomalous (zero field) thermal Hall effect, which would arise from the chiral edge currents.
A new approach is proposed, combining a newly designed set-up for the macroscopic measurement of thermal conductivity and thermal Hall effect, together with a microscopic probe realizing Scanning Thermal Spectroscopy. This will be realized thanks to a collaboration between two labratories in Grenoble: a team Pheliqs, mastering high quality crystal growth of these systems together with low temperature thermal transport measurements, and two teams in Néel, experts in Scanning SQUID microscopy and microscopic thermal measurements down to sub-Kelvin temperatures.
With this project, the PhD student will acquire very broad skills, ranging from sample preparation, low temperature instrumentation, and major actual issues in the field of quantum materials.
Reactive neural network potentials: optimization of dataset construction and application to mechanochemical reactions
The spontaneous decomposition of organic molecules during synthesis, handling, or storage causes significant safety issues in the field of energetic materials. Besides thermal activation, recent studies suggest that intramolecular deformations, such as those induced by shock waves, significantly influence chemical reactivity and may alter decomposition mechanisms.
Molecular-level studies of these phenomena present significant challenges because they require both quantum-level accuracy for bond breaking and formation and the inclusion of condensed phase effect.
To bridge this gap, we propose the development and application of machine learning-based interatomic potentials (MLIPs),
In particular, we aim to significantly advance methodologies for building reactive structural datasets, specifically tailored to complex thermal and mechanochemical reactions with multiple decomposition pathways. Leveraging these improved datasets, we will develop MLIPs to study molecular decomposition under varying temperature and pressure conditions. Besides the safety concerns inherent to energetic molecules, the tools and knowledge developed during the project are expected to be of great value to the mechanochemistry community who currently lacks a molecular-level understanding of transformations in mechanochemical systems.
Micro-needles functionalized with aptamers for the optical detection of cortisol
Compact, wearable medical devices, by offering autonomous and continuous monitoring of biomarkers, open the way to precise monitoring of pathologies outside of care centers and to a personalized therapeutic approach. The thesis project aims to develop wearable sensors based on microneedles (MNs) made of biomaterials for the minimally invasive detection of cortisol in the interstitial fluid (ISF) of the skin. Cortisol is one of the important biomarkers of physical and psychological stress, and is linked to the development of chronic diseases. ISF, a very rich source of biomarkers, offers an alternative to blood as a minimally invasive biofluid for cortisol quantification, and can be continuously analyzed by microneedle devices. Thus, swelling microneedles made of crosslinked biopolymer hydrogel have been developed at CEA-Leti over the last three years for ISF collection and analysis. The objective of the project will be to functionalize the hydrogel with a cortisol-sensitive aptamer molecular beacon, whose fluorescence will be activated in the specific presence of this metabolite, drawing on the expertise of the DPM NOVA team. Wearable optical sensors based on cortisol-sensitive MN patches will be designed, exploring two configurations: MN patches entirely made of hydrogel, and hybrid MN patches comprising an optical waveguide biopolymer and a cortisol-sensitive hydrogel coating. Different needle/waveguide shapes will be explored to optimize the fluorescence detection performance of the biosensors. The ability of the devices to puncture a skin model, sample artificial ISF, and detect the target will also be evaluated. The study will include biocompatibility tests, as well as a comparison with current methods for measuring serum cortisol by immunoassay.
Development of highly reactive bio-based polyhydroxyurethanes for the substitution of isocyanates in polyurethanes
Polyurethanes are thermosetting materials with significant environmental impacts. They are primarily synthesized from isocyanates, which are highly hazardous substances (toxic, sensitizing, and some even classified as CMR - Carcinogenic, Mutagenic, or Reprotoxic) and are subject to REACH restrictions. In this context, polyhydroxyurethanes (PHUs) offer several advantages: (i) they are more easily bio-based compared to conventional PUs, (ii) their synthesis does not involve isocyanates, but (iii) instead allows for CO2 sequestration. However, the precursors used in the synthesis of PHUs (cyclic carbonates and amines) exhibit much lower reactivity than isocyanates, resulting in curing times that are currently incompatible with the temperatures and production rates required for this type of material.
Several research directions have been proposed to optimize PHU curing kinetics, focusing on the identification of (i) new cyclic carbonate and amine precursors chemically substituted at the a or ß positions of the reactive group, and (ii) new high-performance catalysts capable of activating both types of precursors used in synthesis.
In this context, the PhD candidate will be tasked with synthesizing new cyclic carbonate and amine precursors and studying their reactivity to identify the most favorable conditions for the synthesis of highly reactive PHUs. The results obtained during this work will then be analyzed using symbolic Artificial Intelligence models developed at CEA.
This PhD project is part of the PHURIOUS project, funded by the PEPR DIADEM program, which aims to integrate high-throughput synthesis and characterization techniques in polymer chemistry with digital tools, including DFT calculations, molecular dynamics simulations AI approaches.
Elucidation of the homarine degradation pathway in the oceans
Context:
Primary biological production in the oceans exerts significant control over atmospheric CO2. Every day, phytoplankton transform 100 million tonnes of CO2 into thousands of different organic compounds (1). Most of these molecules (as metabolites) are biologically labile and converted back into CO2 within a few hours or days. The climate-carbon feedback loops mediated by this reservoir of labile dissolved organic carbon (DOC) depend on this network of microbes and metabolites. In other words, the resilience of the ocean to global changes(such as temperature rise and acidification) will depend on how this network responds to these perturbations.
Because of its short lifespan, this pool of labile DOC is difficult to observe. Yet these microbial metabolites are the most important carbon transport pathways in the ocean and are assimilated by marine bacteria as sources of carbon and energy. Knowledge of the main metabolic pathways (from genes to metabolites) is therefore essential for modelling carbon flows in the oceans. However, the diversity of these molecules remains largely unexplored and many of them have no annotated biosynthetic and/or catabolic pathways. This is the case for homarin (N-methylpicolinate), an abundant compound in the oceans. Homarine content can reach 400 mM in the marine cyanobacterium Synechococchus (2) and this ubiquitous organism contributes between 10 and 20% of global net primary production (3).Because of its abundance, homarine is probably an important metabolite in the carbon cycle.
Project:
In this thesis project, we aim to elucidate the homarine degradation pathway in the oceans.
Ruegeria pomeroyi DSS-3 is a Gram-negative aerobic bacterium and a member of the marine Roseobacter clade. Its close relatives account for around 10-20% of the bacterial plankton in the mixed coastal and oceanic layer (4). In the laboratory, DSS-3 can use homarine as its sole carbon source but to date, there is no information on the genes and catabolites involved in this process.
Comparative analysis of RNAseq experiments conducted on DSS-3 cultures grown with homarine or glucose (control) as a carbon source will enable us to identify the candidate genes involved in the degradation pathway. This pathway will also be studied using a metabolomic approach based on liquid chromatography coupled with very high resolution mass spectrometry. The difference in profile between DSS-3 metabolomes from cells grown on glucose as a carbon source and those from cells grown on homarine will help to detect catabolites in the pathway. Finally, the candidate genes will be cloned for recombinant expression in E. coli, the corresponding proteins purified and their activity characterized in order to reconstruct the entire homarine degradation pathway in vitro.
Analysis of the expression of these genes in data from the Tara Oceans project (5) will be the first step towards a better understanding of the role of homarine in the carbon cycle.
References :
(1) doi.org/10.1038/358741a0
(2) doi.org/10.1128/mSystems.01334-20
(3) doi.org/10.1073/pnas.1307701110
(4) doi.10.1038/nature03170
(5) https://fondationtaraocean.org/expedition/tara-oceans/
Wetting dynamics at the nanoscale
Wetting dynamics describes the processes involved when a liquid spreads on a solid surface. It's an ubiquitous phenomenon in nature, for example when dew beads up on a leaf, as well as in many processes of industrial interest, from the spreading of paint on a wall to the development of high-performance coating processes in nanotechnology. Today, wetting dynamics is relatively well understood in the case of perfectly smooth, homogeneous model solid surfaces, but not in the case of real surfaces featuring roughness and/or chemical heterogeneity, for which fine modeling of the mechanisms remains a major challenge. The main goal of this thesis is to understand how nanometric roughness influences wetting dynamics.
This project is based on an interdisciplinary approach combining physics and surface chemistry. The PhD student will conduct systematic model experiments, combined with multi-scale visualization and characterization tools (optical microscopy, AFM, X-ray and neutron reflectivity, etc.).
Thanks to the complementary nature of the experimental approaches, this thesis will provide a better understanding of the fundamental mechanisms of energy dissipation at the contact line, from the nanometric to the millimetric scale.
Understanding the signals emitted by moving liquids
Elasticity is one of the oldest physical properties of condensed matter. It is expressed by a constant of proportionality G between the applied stress (s) and the deformation (?): s = G.? (Hooke's law). The absence of resistance to shear deformation (G' = 0) indicates liquid-like behavior (Maxwell model). Long considered specific to solids, shear elasticity has recently been identified in liquids at the submillimeter scale [1].
The identification of liquid shear elasticity (non-zero G') is a promise of discoveries of new solid properties. Thus, we will explore the thermal response of liquids [2,3], exploit the capacity of conversion of mechanical energy into temperature variations and develop a new generation of micro-hydrodynamic tools.
At the nanoscopic scale, we will study the influence of a solid surface in contact with the liquid. It will be a question of studying by unique methods such as Inelastic Neutron Scattering and Synchrotron radiation, the dynamics of the solid-liquid interface using Very Large Research Facilities such as the ILL or the ESRF, as well as by microscopy (AFM). Finally, we will strengthen our collaborations with theoreticians, in particular with K. Trachenko of the Queen Mary Institute "Top 10 Physics World Breakthrough" and A. Zaccone of the University of Milan.
The PhD topic is related to wetting, macroscopic thermal effects, phonon dynamics and liquid transport.
Analysis of solid oxide cell degradation by transmission electron microscopy and atomic probe tomography
Nowadays, high-temperature electrolysis is considered as one of the most promising technology for producing green hydrogen. The electrolysis reaction takes place in a Solid Oxide Cell (SOC) composed of an oxygen electrode (made of LSCF or PrOx) and a hydrogen electrode (made of Ni-YSZ) separated by an electrolyte (made of YSZ). To accompany industrialization f SOCs, the durability still needs to be improved. The main performance losses are due to the degradation of the two electrodes. In order to propose an improvement, it is essential to gain a precise understanding of electrode degradation mechanisms. In this thesis, we thus propose to apply high-resolution transmission electron microscopy and atom probe tomography (SAT) to study electrode degradation after aging under current. On the one hand, advanced electron microscopy techniques coupled with energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) will be applied. In addition, analyses carried out on a SAT will provide three-dimensional information particularly suited to the complex structure of the electrodes.
This work should provide a better understanding of the degradation mechanisms of high-temperature electrolysis cells. Recommendations for their manufacture can then be made to improve their lifespan.