Les composites C/C sont utilisés dans les domaines du spatial et de l'aéronautique pour leurs excellentes propriétés thermomécaniques depuis la température ambiante jusqu'aux très hautes températures (> 3000°C). Ces matériaux ont une architecture complexe constituée de nappes de fibres stratifiées et aiguilletées. Leur utilisation en zones fortement sollicitées et à haute température nécessite une maîtrise des propriétés thermiques et mécaniques. Actuellement, la conception du matériau se fait de manière empirique et itérative. Pour l'accélérer, le développement d'un modèle numérique multi-échelle prédictif du comportement du composite C/C est proposé. Ce matériau a tout d'abord été caractérisé morphologiquement à ses différentes échelles caractéristiques, les propriétés thermomécaniques de ses constituants élémentaires ont également été identifiées. A l'échelle microscopique, les fils sont représentés de façon homogène et thermoélastique à partir des taux de constituants qui leurs sont associés. A l'échelle mésoscopique, deux aspects morphologiques semblent prédominants : son architecture ainsi que ses porosités et endommagements. Leur effet sur le comportement effectif du composite C/C est étudié dans le but d'évaluer leur influence relative et d'aboutir à une description suffisamment fine de leurs morphologies dans la modélisation effectuée. Un modèle de matériau idéalisé ainsi qu'un modèle basé images ont été développés. La simulation d'essais macroscopiques a révélé que ces deux aspects avaient un effet non-négligeable sur le comportement effectif du composite C/C et ont permis le développement et la validation d'un modèle prédictif multi-échelle de ce matériau, prenant en compte les caractéristiques précédentes, et permettant le lien entre l'échelle de ses constituants élémentaires et celle macroscopique. / C/C composites are used in space and aeronautics for their excellent thermomechanical properties from room temperature to very high temperatures (> 3000°C). These materials have a complex architecture consisting of layers of laminated and needled fibers. Its use in highly stressed areas and at high temperature requires control of thermal and mechanical properties. Currently, the design of the material is done empirically and iteratively. To accelerate it, the development of a multi-scale digital model of the C/C composite is proposed. This material was first morphologically characterized at its different characteristic scales, the thermomechanical properties of its elementary constituents were also identified. At the microscopic scale, the wires are represented homogeneously and thermoelastically from the constituent levels associated with them. At the mesoscopic scale, two morphological aspects seem to predominate: its architecture as well as its porosities and damages. Their effect on the effective behavior of the C/C composite is studied in order to evaluate their relative influence and to arrive at a sufficiently fine description of their morphologies in the modeling carried out. An idealized material model as well as an image based model have been developed. The simulation of macroscopic tests revealed that both aspects had a non-negligible effect on the effective behavior of the C/C composite and allowed the development and validation of a multi-scale predictive model of this material, taking into account the preceding characteristics, and allowing the link between the scale of its elementary constituents and the macroscopic one.

La chimie des composés à base d'iode hypervalent (i.e., iodanes) connaît un fort intérêt depuis le début des années 1990 comme en témoigne le panel de composés iodés disponibles commercialement et le nombre de transformations chimiques que ces réactifs peuvent promouvoir. Au cours de la dernière décennie,les recherches se sont essentiellement concentrées sur le développement d’iodanes chiraux et leurs applications en synthèse asymétrique. La plupart de ces iodanes sont utilisés pour la création hautement sélective de liaison carbone-hétéroatome (C–O, C–N, C–F…). La création asymétrique de liaison carbone-carbone (C–C) médiée par des iodanes chiraux a cependant été très peu étudiée jusqu'à présent. Dans ce contexte, notre groupe de recherche a décrit la synthèse de nouveaux iodanes-λ5chiraux biaryliques et de type Salen ainsi que leurs applications à la désaromatisation oxygénante asymétrique de 2-alkyl phénols avec des excès énantiomériques (ee) supérieurs à 90%. Ces travaux de thèse sont consacrés au développement de nouveaux iodanes-λ3 chiraux porteurs de ligands carbonés transférables pour la création asymétrique sans métal de liaison C–C. Sont plus particulièrement décrits la synthèse de bis(alcynyl-iodanes-λ3) biphényliques atropopurs et leur utilisation dans l’alcynylation énantiosélective de β-cétoesters (jusqu’à 68% ee) et, pour la première fois, de naphtols (jusqu’à 84% ee). / The chemistry of hypervalent organoiodine compounds (i.e., iodanes) has unarguably experienced an impressive development since the early 1990s, as evidenced by both the diversity of iodane reagents that are commercially available today and the number of chemical transformations that those reagents can promote.Over the last decade, the elaboration of new chiral iodanes and their applications in asymmetric synthesis have attracted special interests and research efforts. Most ofthem are involved in highly selective carbon-heteroatom bond-forming reactions (C–O, C–N, C–F…). However, C–C bond-forming reactions in a stereoselective fashion with chiral iodane are yet underexploited. In this context, our research group reported the synthesis of new biarylic and Salen-type chiral λ5‐iodanes and their successful application to the asymmetric hydroxylative phenol dearomatization of 2alkylphenols, with enantiomeric excesses (ee) above 90%. This thesis work is dedicated to the development of new chiral λ3‐iodanes bearing transferable carbon-basedligands for metal‐free asymmetric C–C bond construction. In particular, the synthesis of chiral biphenylic bis(alkynyl-λ3-iodanes) and their successful application to the enantioselective alkynylation of β‐ketoesters (up to 68% ee) and 2‐substituted naphthols (up to 84% ee) are described.

L’utilisation d’un composite Carbone/Carbone 2D est envisagée pour des pièces de structure, travaillant entre 150 et 400°C, dans l’aéronautique civile. Dans ce domaine de température, la durabilité de ces matériaux n’est pas connue car ils n’ont jamais été développés pour de telles applications. Une première approche a permis de corréler la réactivité chimique des constituants élémentaires (fibres et matrices) à leur état d’organisation structurale. Les vieillissements réalisés sur matériau composite ont ensuite mis en évidence qu’un faible taux d’oxydation pouvait conduire à un abaissement significatif des propriétés mécaniques résiduelles. Les fissures et les décohésions consécutives au procédé d’élaboration conduisent à une oxydation préférentielle du composé le plus réactif et à la ruine prématurée du composite par délaminage. L'évolution des propriétés de ce matériau sur de longues durées est finalement discutée afin d’évaluer sa capacité à remplacer les matériaux métalliques dans des pièces aéronautiques. / A 2D Carbon/Carbon composite is envisaged for structural parts, operating between 150 and 400°C, in civil aircraft. In this temperature range, the durability of these materials remains unknown because they have never been developed for this kind of applications. A first approach allowed us to correlate the chemical reactivity of the elemental constituents (fiber and matrix) to their structural organization. Then, thermal ageing tests performed on the composite material have demonstrated that a low rate of oxidation could be responsible to a significant reduction of residual mechanical properties. Cracks and fiber/matrix debonding resulting to the elaboration process create an extended pathway to a preferential oxidation of the most reactive compound. This latter is followed by a premature failure by delamination. The reduction of the material properties over long periods is finally discussed in order to evaluate its ability to replace metallic materials in aircraft structural parts.

In recent times, composite materials have gained mainstay acceptance as a structural material of choice due to their tailorability and improved thermal, specific strength/stiffness and durability performance. Carbon-Carbon (C/C) composites are used for high temperature applications such as exit nozzles for rockets, leading edges for missiles, nose cones, brake pads etc. Mechanical property estimation of C/C composites is challenging due to their highly heterogeneous microstructure. Computed Tomography (CT) images (volumetric imaging) coupled with Scanning Electron Microscopy (SEM) reveal a highly heterogeneous microstructure comprised of woven C-fibers, amorphous C-matrix, irregularly shaped voids, cracks and other inclusions. The images also disclose structural hierarchy of the C/C composite at different length scales. Predicting the mechanical behavior of such complex hierarchical materials like C/C composites forms the motivation for the present work. A systematic study to predict the effective mechanical properties of C/C Composite using numerical homogenization has been undertaken in this work. The Micro-Meso-Macro (MMM) principle of ensemble averages for estimating the effective properties of the composite has been adopted. The hierarchical length scales in C/C composites has been identified as micro (single fiber with matrix), meso (fabric) and macro (laminate). Numerical homogenization along with periodic boundary conditions (PBCs) have been used to estimate the effective engineering properties of the material at different length scales. Concurrently, mechanical testing has also been carried out at macro (compression tests) and micro scale (using nano-indentation studies) to characterize the mechanical behavior of C/C composites.

Afin de comprendre les mécanismes d’usure et de frottement des composites carbone/carbone (C/C) utilisés en freinage aéronautique, un modèle numérique est utilisé pour dissocier les effets mécaniques des effets physico-chimiques et thermiques. Le modèle repose sur l’utilisation d’une approche par éléments finis et de techniques d’homogénéisation appliquées à un volume élémentaire représentatif (VER) du matériau à l’échelle mésoscopique frottant sur une surface rigide ou déformable. A cette échelle, le matériau est décrit par une matrice en carbone et des paquets de fibres de carbone appelés torons, perpendiculaires à la surface frottante. Pour assurer la représentativité de la structure du matériau, plusieurs modèles hétérogènes sont étudiés. Les résultats sont comparés à ceux obtenus avec le modèle homogène équivalent qui découle de l’homogénéisation. L’influence des conditions de contact (la rigidité), ainsi que l’influence de la distribution des torons proches de la surface frottante sur les régimes de vibrations des différents modèles sont mises en évidence. L’extension du modèle numérique à un contact entre deux composites a mis en évidence une forte augmentation des contraintes maximales localisées principales dans les torons présents à la surface frottante. Ces fortes localisations de contraintes peuvent avoir pour conséquence l’endommagement des torons ce qui induit la dégradation de la surface frottante jusqu’aux détachements de particules. / To understand the mechanisms of wear and friction of carbon 1 carbon composites (C/C} used in aeronautical braking, a numerical model is used to separate the mechanical effects of the physico-chemical and thermal effects. The model is based on the use of an approach by finite elements (FE} and techniques of homogenization applied to a representative elementary volume (RVE} of the material in the mesoscopic scale rubbing on a rigid or deformable surface. In this scale, the material is described by a matrix in carbon and packages of carbon fiber called strands, perpendicular on the contact surface. To insure the representativeness of the structure of the material, several heterogeneous models are studied. The results are compared with those obtained with the equivalent homogeneous model which ensues from the homogenization. The influence of the conditions of contact (the rigidity), as well as the influence of the distribution of strands at the contact surface on the regimes of vibrations of the various models are revealing. The extension of the numerical model in a contact between two composites underline a strong increase of maximal constraints mainly localized in the strands present on the contact surface. These strong localizations of constraints can have for consequence the damage of strands what leads the degradation of the contact surface until the detachments of particles.

Le matériau composite carbone/carbone ou C/C est utilisé en temps que matériau de friction en freinage aéronautique. Matériau complexe tant du point de vue de sa description microstructurale que de son comportement sous sollicitations tribologiques, il a été l’objet de nombreuses études visant à mieux comprendre les mécanismes régissant sa réponse (frottement, endommagement, usure) à ces sollicitations. Dans cette étude nous nous focalisons sur l’aspect mécanique de cette réponse. En particulier, nous nous intéressons aux endommagements présents dans le matériau : nous souhaitons étudier tant leurs origines que leur influence sur le comportement du matériau. Pour cela, nous choisissons une approche combinée numérique et expérimentale, nous permettant d’identifier de façon exhaustive ces endommagements puis de construire un modèle numérique tribologique permettant d’étudier les mécanismes d’usure du matériau. Nous montrons comment les mécanismes d’accommodation en volume du 1er corps influent sur les détachements de particules en surface, nous conduisant à parler de dialogue tribologique surface/volume. Le modèle numérique utilise la méthode des éléments discrets pour représenter 1er et 3ième corps simultanément. Un travail est réalisé autour de la représentativité du modèle vis-à-vis des caractéristiques mécaniques du composite C/C. Nous proposons également une démarche de recherche d’un Volume Elémentaire Représentatif sous condition de contact. Ce modèle ainsi que les observations du matériau nous permettent de proposer un scenario de comportement tribologique du composite C/C, en fonction des sollicitations thermomécaniques qui lui sont appliquées et correspondant aux différents types de freinages aéronautiques. Les endommagements identifiés dans le volume du matériau se révèlent être bénéfiques dans certains cas de figure au travers d’un mécanisme de rigidification du matériau intervenant à haute température, ce qui nous conduit à parler d’ « endommagement utile ». Le scenario intègre donc ce phénomène, ainsi que d’autres tant mécaniques que physicochimiques et identifiés par cette étude ou dans la littérature, et montre comment leur équilibre « dynamique » produit le comportement tribologique identifié du matériau pour les différentes gammes de sollicitations qui lui sont appliquées. / Carbon/Carbon (or C/C) composite is used as a friction material in aeronautical braking applications. This is a complex material from both microstructural and tribological behavior points of view. Thus, it has been studied through various works for several years, aiming at understanding what mechanisms guide this material response (friction, damage, wear) under tribological conditions. In this study, a focus is performed on mechanical aspects such as damages that occur in the numerical and experimental approach, in view to identify and classify the damages as well as to build a numerical model used to investigate wear mechanisms. It is underlined how first-body accommodation mechanisms have a great influence on particles detachment at the interface, as a surface/volume tribological dialogue take place. This model is based on the Discrete Elements method and represents simultaneously first- and third-body; such model is able to represent fist-body degradation as well as creation and flow of third-body particles. Its representativeness is ensured through experimental comparisons, particularly on mechanical aspects. A procedure is proposed for the research of a Representative Elementary Volume under contact conditions. Model results and material observations allow proposing a global scenario explaining C/C composite behavior under tribological conditions, which are representative of different aeronautical braking cases. Damages, identified in the volume of the first-body, reveal themselves to be sometimes beneficial, and could be characterized as “useful damages”. The scenario takes into account this phenomenon, as well as thermal, mechanical and physicochemical ones, identified from this work or literature. It explains the influences of these parameters on C/C tribology and show how the dynamic equilibrium between them results on the C/C response, particularly its wear mechanism.

De nouveaux matériaux hybrides « inorganique-organique » pour le captage de polluants organiques (pesticides, HAP) ont été préparés soit par greffage sur des oxydes métalliques, soit par procédé sol-gel. Pour préparer ces matériaux nous avons développé une méthodologie catalytique pour la synthèse des motifs organiques aromatiques. Cette méthodologie repose sur la réaction de couplage de Heck palladocatalysée entre le vinylphosphonate de diéthyle avec des différents halogénures d’aryles en utilisant des catalyseurs homogènes et hétérogènes. Des bons rendements isolés ont été obtenus. En complément, nous avons étudié l’arylation du diéthylacétale de l’acroléine en milieu aqueux qui donne principalement l’ester propanoïque et le cinnamaldéhyde. Nous avons mis en évidence l’influence de différents paramètres (catalyseurs, température, bases, additifs) et montré que l’ajout de cyclodextrines est bénéfique, en augmentant dans la plupart des cas la vitesse de la réaction. Dans le cadre de cette étude, nous avons montré que le remplacement de NaOAc par NH(i-Pr)2 conduisait à une inversion de la sélectivité du cinnamaldéhyde vers l’ester propanoïque. Les matériaux azotés (amine; guanidine; biguanide@oxyde métallique) ont été obtenus soit par greffage des composés bi fonctionnels [fonction azoté]/PO(OEt)2 sur les supports, soit par greffage d’un aminophosphonate suivi d’une condensation en phase solide avec le DIP.La capacités de piégeage de différents pesticides par extraction en phase solide a été évaluée et comparés à celle de deux matériaux courants (charbon actif et Si-C18) connus comme support solide universel dans ce domaine. Nous avons ainsi démontré la complémentarité des différents matériaux dans le piégeage des pesticides. / Development of new hybrid materials “inorganic-organics” for the collecting of the various organic pollutants (pesticides, PAH). These materials were prepared by two methods: grafting of metallic oxides and sol-gel method. A catalytic methodology of the aromatic organic matrix synthesis was considered. This methodology is based on the reaction of pallado-catalyzed Heck coupling between the diethyl vinylphosphonate with different aryl halogenurs by using homogeneous and heterogeneous catalysts. The good isolated yields for products were obtained. The complement, we study of the arylation reaction of the acrolein diethylacetal in aqueous medium, and the influence of various parameters (catalysts, bases, temperature, additifs) on this reaction. The addition of cyclodextrins in reaction medium is beneficial. Within the framework of this study, we showed that the replacement of NaOAc by NH (i-Pr)2 led to an inversion of the selectivity of cinnamaldéhyde towards propanoïque ester. Nitrogen material (amine, guanide, biguanide/PO-OEt)2 either by grafting of bifunctional compounds on the supports, and grafting of amiophosphonate flow condensation to DIP.The capacity of the trapping of pesticides by extraction in solid phase was evaluated and compared of two current materials (activated carbon and Si-C18) known as universal solid support. We thus showed the complementarity of various materials in the trapping of the pesticides

<p dir="ltr">Fretting wear occurs when two contacting bodies under load are subjected to small amplitude oscillatory motion. Depending on the applied normal load, displacement amplitude, coefficient of friction and resulting shear force, two types of fretting wear regimes exist – (i) partial slip and (ii) gross slip. At displacement amplitudes higher than gross slip condition, sliding wear regime prevails. Fretting wear becomes dominant in machine components subject to vibrations such as bearings, dovetail joints, etc. whereas sliding wear is observed in brakes, piston-ring applications, etc. The work in this dissertation primarily focuses on characterizing the material response of various machine components subjected to fretting and sliding wear regimes.</p><p dir="ltr">At first, the friction and fretting wear behavior of inlet ring and spring clip components used in land-based gas turbines was investigated at elevated (<a href="" target="_blank">500°C</a>) temperature. In order to achieve this objective, a novel high-temperature fretting wear apparatus was designed and developed to simulate the conditions existing in a gas turbine. The test apparatus was used to investigate fretting wear of atmospheric plasma sprayed (APS) Cr₃C₂-NiCr (25% wt.), high-velocity oxy-fuel (HVOF) sprayed Cr₃C₂-NiCr (25% wt.), HVOF sprayed T-800 and APS sprayed PS400 coated inlet rings against HVOF-sprayed Cr₃C₂-NiCr (25% wt.) coated spring clip. The PS400 coated inlet rings demonstrated a significant reduction in friction and wear. A finite element (FE) framework was also developed to simulate fretting wear in HVOF-sprayed Cr₃C₂-NiCr composite cermet coating. The material microstructure was modelled using Voronoi tessellations with a log-normal distribution of grain size. Moreover, the individual material phases in the coating were randomly assigned to resemble the microstructure from an actual SEM micrograph. A damage mechanics based cohesive zone model with grain deletion algorithm was used to simulate debonding of the ceramic carbide phase from the matrix and resulting degradation from repeated fretting cycles. The specific wear rate obtained from the model for the existing material microstructure was benchmarked against experiments. Novel material microstructures were also modeled and demonstrated to show less scatter in wear rate.</p><p dir="ltr">Following, a three-dimensional (3D) continuum damage mechanics (CDM) FE model was developed to investigate the effects of fretting wear on rolling contact fatigue (RCF) of bearing steels. In order to determine the fretting scar geometry, a 3D arbitrary Lagrangian-Eulerian (ALE) adaptive mesh (AM) FE model was developed to simulate fretting wear between two elastic bodies for different initially pristine fretting pressures (0.5, 0.75 and 1 GPa) and friction coefficients (0.15, 0.175 and 0.25) resulting in stick zone to contact width ratios, c/a = 0.35, 0.55 and 0.75. The resulting wear profiles were subjected to various initially pristine RCF pressures (1, 2.2 and 3.4 GPa). The pressure profiles for RCF were determined by moving the contact over the fretted wear profiles in 21 steps. These pressure profiles were then used in the CDM-FE model to predict the RCF life of fretted surfaces. The results indicate that increased fretting pressure leads to more wear on the surface, thereby reducing RCF life. As the RCF pressure increases (P_RCF ≥ 2.2 GPa), the effect of fretting on RCF life decreases for all fretting pressures and c/a values, indicating that life is primarily governed by the RCF pressure. The results from CDM-FE model were used to develop a life equation for evaluating the L₁₀ life of fretted M-50 bearing steel for the range of tested conditions.</p><p dir="ltr">Lastly, the sliding wear characteristics of pitch and poly-acrylonitrile based carbon-carbon (C/C) composites were investigated in air and nitrogen environment by designing and developing a disc brake test rig. It was found that the temperature of the disc, the surrounding environment, the supplied energy flux as well as the type of composite play a critical role in determining whether C/C composites operate in normal wear or dusting wear regime. Further analysis of wear mechanisms revealed interface and matrix cracking with fiber breakage from tests in air environment, whereas in nitrogen environment, particulate and layered debris played a prominent role.</p>

One approach to increasing the climate-regulating potential of the agricultural sector is carbon sequestration in agricultural soils. This involves storing atmospheric carbon dioxide in the soil in the form of soil organic carbon (SOC) through agricultural management practices (AMPs). Model simulations of area-specific current and future SOC stocks can be used to test appropriate AMPs. In this study, the CANDY Carbon Balance (CCB) model was used to determine how different AMPs could affect SOC stocks in a study area in northern Saxony, Germany. Specifically, we used scenarios with different intensities of sustainable AMPs to assess the potential effects of reduced tillage, crop cultivation, and fertilizer management, as well as the management of crop residues and by-products. The analysis was carried out for the simulation period 2020–2070, with and without consideration of climate change effects. The results showed an average carbon sequestration potential of 5.13–7.18 t C ha−1 for the whole study area, depending on the intensity of AMP implemented. While higher intensities of sustainable AMP implementation generally had a positive impact on carbon sequestration, the scenario with the highest implementation intensity only led to the second highest gains in SOC stocks. The most important factor in increasing SOC stocks was reduced tillage, which resulted in a carbon sequestration potential of 0.84 t C ha−1 by 2070. However, reduced application rates of fertilizers also proved to be critical, resulting in a reduction in carbon stocks of up to 2.2 t C ha−1 by 2070. Finally, the application of high-intensity sustainable AMPs was shown to be able to offset the negative impacts of an intermediate climate change scenario for most of the simulation period. Overall, the results not only confirmed existing knowledge on the effects of AMPs on carbon sequestration for a specific case study area, but also identified future management scenarios that stress the need for widespread adoption of sustainable management practices under changing climate conditions.

<p>The development of a novel charge inversion ion/ion reaction in conjunction with a mass spectrometry technique (collisional induced dissociation (CID)) to induce fragmentation of selected ions species in the gas-phase. The utility of this experiment allows identification of varying saturated and unsaturated classes of glycerophospholipids (GPLs) in a biological matrix. In this work, we are able to characterize GPLs species at the subclass, headgroup, fatty acyl sum compositional levels,  leaving the location(s) of carbon-carbon single bond (C-C), carbon-carbon double bond (C=C), cyclopropane moiety, branching site and differentiate isomeric species. </p> <p><br></p> <p>All data were collected on modified a Sciex QTRAP4000 hybrid triple quadrupole/linear ion trap mass spectrometer. Briefly, alternately, pulsed nano-electrospray ionization (nESI) was used for ion generation. Deprotonated lipid anions were generated via negative ion mode nESI, mass selected during transit through Q1, and transferred to q2 for storage. Next, the charge inversion (IIRXN) reagent doubly charged magnesium complex cations, were generated via positive ion mode nESI. To facilitate the ion/ion reaction, magnesium complex dictations and lipid anions were simultaneously stored in q2, resulting in the formation of charge-inverted lipid cations. Ion-trap CID of charge-inverted isomers resulted in distinctive fragmentation, facilitating differentiation of isomeric and localization of unsaturation sites in acyl chain constituents. </p>