Modifications structurales à l échelle atomique dans les combustibles nucléaires irradiés

Cette thèse présente une analyse approfondie et comparative des résultats de mesures -XRD et -XAS sur des combustibles UO2 standard, dopé au sesquioxyde de chrome (Cr2O3) et MOX, irradiés ou non. Elle présente également l'interprétation des résultats en regard des effets induits par le chrome en tant que dopant ainsi que par la présence de plusieurs produits de fission. Les paramètres de maille de l UO2 et les paramètres de densité d'énergie de déformation élastique dans les matériaux irradiés ou non ont été mesurés et quantifiés. Les données de -XRD ont en outre permis l'évaluation de la taille des domaines cristallins, ainsi que l étude de la formation de sous-grains à différentes positions au sein des pastilles de combustibles irradiés. Le paramètre de maille et l'environnement atomique local du chrome dans des précipités d oxyde de chrome présents dans les pastilles de combustible non-irradié ont également été déterminés. La structure locale du Cr dans la matrice du combustible dopé et l'influence de l'irradiation sur l'état du chrome dans la matrice de combustible ont été étudiées. Enfin, pour une comparaison du comportement des gaz de fission et du phénomène de re-solution induite par l'irradiation dans l UO2 standard ou dopé, la dernière partie de ce travail propose une tentative d'analyse de l environnement atomique du Kr dans ces deux combustibles irradiés. Le travail effectué par micro-faisceau XAS sur ce gaz de fission a permis la détermination des distances du Kr avec ses proches voisins, une estimation des densités atomiques des gaz de fission dans les agrégats et des pressions internes apparentes dans ces nano-phases de gaz inertes.This thesis work reports in depth analyses of measured -XRD and -XAS data from standard UO2, chromia (Cr2O3) doped UO2 and MOX fuels, and interpretation of the results considering the role of chromium as a dopant as well as several fission product elements. The lattice parameters of UO2 in fresh and irradiated samples and elastic strain energy densities in the irradiated UO2 samples have been measured and quantified. The -XRD patterns have further allowed the evaluation of the crystalline domain size and sub-grain formation at different locations of the irradiated fuel pellets. Attempts have been made to determine lattice parameter and next neighbor atomic environment in chromia-precipitates found in fresh chromia-doped fuel pellets. The local structure around Cr in as-fabricated chromia-doped UO2 matrix and the influence of irradiation on the state of chromium in irradiated fuel matrix have been addressed. Finally, for a comparative understanding of fission gases behavior and irradiation induced re-solution phenomenon in standard and chromia-doped UO2, the last part of the present work tries to clarify the fission gas Kr atomic environment in these irradiated fuels. The work performed on Kr, by micro-beam XAS, comprises the determination of Kr next neighbor distances, an estimation of gas atom densities in the aggregates, and apparent internal pressures in the gas bubbles.PARIS11-SCD-Bib. électronique (914719901) / SudocSudocFranceF

Uranyl interaction with the hydrated (0001) basal face of gibbsite: A combined theoretical and spectroscopic study

International audienceThe sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory ͑DFT͒ computations. Both the calculated and experimental values of O–H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the-yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U – O surface bond lengths range between 2.1–2.2 and 2.6– 2.7 Å for the nonprotonated and protonated surface O atoms, respectively

Management of service composition based on self-controlled components

International audienceCloud computing and Future Internet promise a new ecosystem where everything is "as a service", reachable and connectable anywhere and anytime, everyone succeeding to get a service composition that meets his needs. But do we have the structure and the appropriate properties to design the service components and do we have the means to manage, at run-time, the personalised compositions corresponding to Service Level Agreement? In this article we introduce an entity of service composition called Self-Controlled Component (SCC), including, since the design step, functional and non-functional specifications. SCCs benefit both from the strong structure, explicit composition, and autonomic management of component-oriented programming, from the highly dynamic composition, and from the discovery capacities of service-oriented computing. Self-control mechanisms are then attached automatically to SCCs to enable autonomic application management during execution. The objective of this new concept is to provide strong Quality of Service (QoS) guarantees of composed applications. We illustrate the approach using an example called Springoo, to how in the context of a legacy application the contributions and benefits of our solution. For the management of the service composition we propose the concept of Virtual Private Service Network (VPSN) and Virtual Service Community (VSC) that allows us to model the personalised Service Level Agreement (SLA) where user requirements and provider offers converge on a QoS contract

Role of self-irradiation defects on the ageing of 239PuCoGa5

6 pages, 18 referencesInternational audienceLow-temperature accumulation and annealing experiments, in conjunction with electrical resistivity and critical current density measurements, were used to study the ageing of the actinide superconductor PuCoGa5. These measurements reveal that 2-nm sized non-superconducting point-like regions are the main damage formed during room temperature ageing; smaller point-like defect were irrelevant to transport properties. Defect sizes and densities deduced from experiment agree with Transmission Electron Micoscopy observations

Human Luteinizing Hormone and Chorionic Gonadotropin Display Biased Agonism at the LH and LH/CG Receptors.

Human luteinizing hormone (LH) and chorionic gonadotropin (hCG) have been considered biologically equivalent because of their structural similarities and their binding to the same receptor; the LH/CGR. However, accumulating evidence suggest that LH/CGR differentially responds to the two hormones triggering differential intracellular signaling and steroidogenesis. The mechanistic basis of such differential responses remains mostly unknown. Here, we compared the abilities of recombinant rhLH and rhCG to elicit cAMP, β-arrestin 2 activation, and steroidogenesis in HEK293 cells and mouse Leydig tumor cells (mLTC-1). For this, BRET and FRET technologies were used allowing quantitative analyses of hormone activities in real-time and in living cells. Our data indicate that rhLH and rhCG differentially promote cell responses mediated by LH/CGR revealing interesting divergences in their potencies, efficacies and kinetics: rhCG was more potent than rhLH in both HEK293 and mLTC-1 cells. Interestingly, partial effects of rhLH were found on β-arrestin recruitment and on progesterone production compared to rhCG. Such a link was further supported by knockdown experiments. These pharmacological differences demonstrate that rhLH and rhCG act as natural biased agonists. The discovery of novel mechanisms associated with gonadotropin-specific action may ultimately help improve and personalize assisted reproduction technologies

Genetic signature of differentiated thyroid carcinoma susceptibility: a machine learning approach

To identify a peculiar genetic combination predisposing to differentiated thyroid carcinoma (DTC), we selected a set of single-nucleotide polymorphisms (SNPs) associated with DTC risk, considering polygenic risk score (PRS), Bayesian statistics, and a machine learning (ML) classifier to describe cases and controls in 3 different datasets. Dataset 1 (649 DTC, 431 controls) has been previously genotyped in a genome-wide association study (GWAS) on Italian DTC. Dataset 2 (234 DTC, 101 controls) and dataset 3 (404 DTC, 392 controls) were genotyped. Associations of 171 SNPs reported to predispose to DTC in candidate studies were extracted from the GWAS of dataset 1, followed by replication of SNPs associated with DTC risk (P<0.05) in dataset 2. The reliability of the identified SNPs was confirmed by PRS and Bayesian statistics after merging the three datasets. SNPs were used to describe the case/control state of individuals by ML classifier. Starting from 171 SNPs associated with DTC, 15 were positive in both the datasets 1 and 2. Using these markers, PRS revealed that individuals in the fifth quintile had a 7-fold increased risk of DTC than those in the first. Bayesian inference confirmed that the selected 15 SNPs differentiate cases from controls. Results were corroborated by ML, finding a maximum AUC of about 0.7. A restricted selection of only 15 DTC-associated SNPs is able to describe the inner genetic structure of Italian individuals and ML allows a fair prediction of case or control status based solely on the individual genetic background

Sustainability of the global sand system in the Anthropocene

Sand, gravel, and crushed rock, together referred to as construction aggregates, are the most extracted solid materials. Growing demand is damaging ecosystems, triggering social conflicts, and fueling concerns over sand scarcity. Balancing protection efforts and extraction to meet society's needs requires designing sustainable pathways at a system level. Here, we present a perspective on global sand sustainability that shifts the focus from the mining site to the entire sand-supply network (SSN) of a region understood as a coupled human-natural system whose backbone is the physical system of construction aggregates. We introduce the idea of transitions in sand production from subsistence mining toward larger-scale regional supply systems that include mega-quarries for crushed rock, marine dredging, and recycled secondary materials. We discuss claims of an imminent global sand scarcity, evaluate whether new mining frontiers such as Greenland could alleviate it, and highlight three action fields to foster a sustainable global sand system