Le graphène, une monocouche de graphite, est composé d'atomes de carbone avec une structure en nid d'abeilles. Ses propriétés exceptionnelles ont attiré un intérêt mondial, dont le Prix Nobel de Physique en 2010. Le graphène épitaxié sur métal à rapidement été identifié comme un moyen de production de graphène de haute qualité de taille métrique, et est le sujet d'intenses activités de recherche en sciences de surface pour caractériser ses propriétés. En outre, ces études concernent aussi des systèmes plus complexes avec pour base le graphène, par exemple les réseaux ordonnés de nanoparticules à sa surface. Tout cela a mené à l'étude de la croissance, de la structure et des défauts du graphène épitaxié avec un grande variété de techniques expériementales, tel que la microscopie par effet tunnel, spectroscopie par photo-émission résolue en angle ou encore la microscopie électronique à basse énergie. Ce travail de recherche se concentre sur le graphène obtenu par croissance sur la surface (111) d'un monocristal d'iridium dans des conditions d'ultra vide et étudié avec plusieurs techniques de mesure par diffraction (diffraction de surface des rayons X, diffraction des rayons X en incidence rasante, réflectivité des rayons X et diffraction des électrons à haute énergie en réflexion). Ces expériences ont été faites au synchrotron européen ESRF à Grenoble, en France. La première partie de cette étude a été de déterminer la structure du graphène à l'échelle atomique. Le système montre une tendance à la commensurabilité, mais sa structure précise dépend fortement des conditions de préparation et de la température appliqué au système. En outre, en combinant des techniques de diffraction à haute résolution, une caractérisation précise de la structure, qui fait débat dans la littérature, est dévoilée. Le système étudié présente aussi une surperstructure, typique du graphène épitaxié, nommé moiré pour ses similarités avec l'effet optique du même nom. Celle-ci est utilisée comme gabarit pour faire croître des nanoparticules monodisperses à la surface en réseau auto-organisé. Durant cette étude, trois types de nanoparticules ont été examinés, des particules de platine de deux tailles différentes et des particules composées de platine et de cobalt. Ces systèmes hybrides présentent un fort degré d'organisation, partiellement hérité de la superstructure du moiré. Les nanoparticules forme une interaction forte avec leur support et elles subissent des contraintes de surface causées par leurs petites tailles. Par ailleurs, les nanoparticules de platine-cobalt, dont la croissance est en deux étapes, gardent une structure en couche et non une structure d'alliage métallique. / Graphene, a monolayer of graphite, is composed of carbon atoms arranged in a honeycomb lattice. Its exceptional properties have attracted a worldwide interest, including the Novel Prize in Physics in 2010. Epitaxial graphene on a metal was rapidly identified as an efficient method for large-area production of high quality graphene, and also was the matter of intense activities exploiting surface science approaches to address the various properties of graphene and of advanced systems based on graphene, for instance ordered lattice of metal nanoparticles on graphene. This resulted in the study of growth, structure and defects of epitaxial graphene on a wide variety of substrates with various techniques such as scanning tunneling microscopy, angle-resolved photoemission spectroscopy or low-energy electron microscopy. This work focuses on graphene grown on the (111) surface of iridium in ultra-high vacuum conditions and studied with several diffraction techniques (surface X-ray diffraction, grazing incidence X-ray diffraction, X-ray reflectivity, and reflection-high energy electron diffraction). These experiments were performed at the European Synchrotron Radiation Facility in Grenoble, France. The first step in our study was to determine the structure of graphene at the atomic scale. The system was found to have a tendency to commensurability, but that the precise structure depends on temperature and on preparation conditions. Moreover, with the combination of high resolution diffraction techniques, a precise characterization about the debated structure of graphene perpendicular to the surface was unveiled. The system, exhibits a superstructure, typical of epitaxial graphene, called a moiré, as an equivalent of the moiré effect in optics. This is used as a template to grown nanoparticles on top of the system to achieve the self-organisation of monodisperse nanoparticles. In this study, three type of nanoparticles were investigated, two different size of pure platinum ones and bimetallic ones, platinum and cobalt. These hybrid systems show very high degree of order, partly inherited by the superstructure lattice. The nanoparticles were found to strongly bond to their support, experience substantial surface strain related to their small size, and that bimetallic ones grown in a sequential manner retain a chemically layered structure.

L’entretien des voies navigables en France nécessité des opérations régulières de curage des sédiments. Ces boues de dragage ont parfois été déposées sur des sols nus, sans précaution préalable ou traitement. Cela peut poser des problèmes environnementaux (présence de polluants métalliques), surtout lorsque les sédiments proviennent de zones industrielles et minières comme c’est le cas pour le site étudié (Nord-Pas-de-Calais). L’un des risques principaux est le transfert d’éléments traces métalliques (ETM) dans le sol sous-jacent jusqu’à la nappe. L’objectif de cette étude est d’identifier et de caractériser les porteurs minéralogiques des ETM (limités ici à Zn et Pb) en combinant diverses techniques analytiques chimiques et spectroscopiques. Dans ce travail, nous montrons que dans le cas d’un matériau complexe comme l’anthroposol étudie, il est important d’avoir une approche méthodologique multi-échelle. Pour mener à bien cette étude, nous avons donc réalisé des analyses sur le terrain, des mesures en laboratoire (extractions chimiques séquentielles, DRX, MEB, MSE) et des expériences sur synchrotron (principalement XRF et XANES). Nous avons pu identifier différentes phases porteuses de Zn et Pb, mais nous n’avons pas observe d’évolution nette en fonction de la profondeur. Nous donnons pour finir, diverses pistes pour continuer ce travail. / Sediments originating from periodic dredging of waterways were traditionally deposited on soil without specific precaution or planed treatments. It may be of environmental concern especially when they came from areas historically contaminated with metallic pollutants like in the north French coal basin which is also well industrialised. The main risk is a migration Metallic Trace Elements (MTE) in the underlying soil and groundwater. This study aims to identify and characterise the mineralogical bearing phases of the MTE (limited here to Zn et Pb) by combining various techniques, analytical, chemical and spectroscopic. In this work, we show that in the case of a complex material as our studied anthroposol, it is important to have a multi-scale. Then, we have carried out field analyses, laboratory studies Sequential chemical extraction, XRD, SEM and EPMA) and synchrotron radiation experiment (mainly XRF and XANES). We have indentified various bearing phases of Zn and Pb, but we didn’t observe any clear evolution as a function of the depth. To conclude, we give several directions for completing this work.

Ce travail résume les résultats d'études de la croissance in situ de nanofils (NFs) SiGe par UHV-CVD à l'aide des techniques de diffusion et de diffraction des rayons X (RX) synchrotron sur la ligne de lumière BM32 à l'ESRF.Les conditions d'élaboration de NFs Si, Ge, SiGe dans notre bâti sont d'abord présentées. Les études in situ à l'aide de RX durant la croissance sont ensuite décrites. La longueur des NFs, leur taille, leur espacement, leur facetage ainsi que l'angle conique sont déterminés en temps réel. Des changements de forme de la goutte liquide aussi ont été clairement observés dans les premiers stades de la croissance. Une phase AuGe métastable à l'interface catalyseur-substrat a été identifiée. Sa formation pourrait être décisive pour la croissance sous-eutectique de NFs de Ge.La relaxation des contraintes dans des NFs coeur-coquille de Si-Ge est ensuite présentée. La composition et la déformation ont été déterminée in situ par diffusion anomale des RX, en fonction de la quantité de Ge deposé et de la durée du recuit. L'influence de la taille des NFs et de la température de croissance de la coquille ont aussi été étudiée.Enfin, des résultats sur la courbure in situ de NFs sont présentés. La courbure est induite par le dépôt d'un second matériau sur un côté des NFs. La déformation et la contrainte ont été déterminées par une combinaison de suivi de la position d'un pic de Bragg, de simulation et d'ajustement de l'intensité, et de calculs d'élasticité classiques. La courbure induite par le dépôt de Ge à 220°C est principalement déterminée par la contrainte de désaccord de maille, qui évolue presque linéairement avec l'épaisseur du film Ge. La courbure induite par le dépôt de Ge à la température ambiante (TA) se trouve principalement déterminée par la contrainte de surface, qui évolue progressivement de la tension à la compression pour une épaisseur de Ge plus grande. Pour le suivi de courbure en temps réel, nous avons mise au point une technique de mesures stationnaires avec un détecteur 2D. Elle a permis de mettre en évidence plusieurs changements de signe lors de dépôts d'Au et Ge à TA. / This work summarizes the progress made on the BM32 beamline at the ESRF over the past 4 years since the launch of the CVD project, which was aimed at studying the in situ growth of SiGe nanowires, using synchrotron X-ray scattering techniques.Results on the growth of Si and Ge NWs are first presented. The NWs length, size, spacing, facet morphology and their tapering angle are determined in real time with X-ray techniques. Special attention was paid to the very early stage of growth where changes in the shape of the AuSi liquid droplet were clearly observed. We also found clues indicating the presence of a metastable AuGe phase at the catalyst-substrate interface, the formation of which may be crucial to the sub-eutectic growth of Ge NWs.Strain relaxation in Si-Ge core-shell NWs is presented next. The composition and strain were determined in situ as a function of the Ge overgrowth amount and of the annealing time, using anomalous X-ray scattering techniques. Their dependence on the NW size and on the shell growth temperature was also studied.Finally, results on the in situ bending of as-grown NWs are shown. The bending was induced by depositing a second material on one side of the NWs. The strain and stress were determined by a combination of Bragg peak tracking, intensity simulation plus fitting and classic elasticity calculations. The bending induced by Ge deposition at 220°C is found to be mainly driven by the misfit stress, which scales almost linearly with Ge film thickness. On the other hand, the bending induced by Ge deposition at RT is found to be mainly driven by the surface stress, which evolves gradually from tensile to compressive for larger Ge thickness. A new technique was also devised which makes it possible to follow qualitatively the bending process. The NWs were seen dancing back and forth with increasing amount of deposition as revealed by real time stationary measurements with a 2D detector.

Les cristaux apériodiques possèdent la propriété d’avoir un ordre à grande distance mais sans la symétrie de translation. Ces cristaux se décrivent dans des superespaces cristallographiques de dimension supérieure à trois. Dans ce mémoire, nous nous intéressons plus particulièrement aux brisures de symétrie présentes dans de tels espaces cristallographiques en considérant la famille prototype de n-alcane/urée. Des études par diffraction de rayons X sur sources synchrotron révèlent de multiples solutions structurales impliquant des changements ou non de la dimension du groupe de superespace. Une fois la caractérisation du paramètre d’ordre et de la brisure de symétrie faite nous présentons les phénomènes prétransitionnels critiques associés à ces transitions de phase de type groupe/sous-groupe. La diffusion cohérente de neutrons et la diffusion de rayons X inélastiques permettent une analyse dynamique des différentes excitations dans ces matériaux (phonons, phasons). Les composés d’inclusion avec des molécules invitées courtes (alcane CnH2n+2 avec n variant de 7 à 13) révèlent à température ambiante des phases « quasi-liquides » uni-dimensionnelles. Ce désordre dynamique le long de la direction d'incommensurabilité de ces matériaux génère à basse température des solutions structurales nouvelles (composite monoclinique intermodulé, ancrages commensurables). / Aperiodic crystals have the property to possess long range order without translational symmetry. These crystals are described within the formalism of superspace crystallography. In this manuscript, we will focus on symmetry breakings which take place in such crystallographic superspace groups, considering the prototype family of n-alkane/urea. Studies performed by X-ray diffraction using synchrotron sources reveal multiple structural solutions implying or not changes of the dimension of the superspace. Once the characterization of the order parameter and of the symmetry breaking is done, we present the critical pretransitionnal phenomena associated to phase transitions of group/subgroup types. Coherent neutron scattering and X-ray scattering allow a dynamical analysis of different kind of excitations in these materials (phonons, phasons). The inclusion compounds with short guest molecules (alkane CnH2n+2, n varying from 7 to 13) show at room temperature unidimensional “liquid-like” phases. The dynamical disorder along the incommensurate direction of these materials generates new structural solutions at low temperature (intermodulated monoclinic composite, commensurate lock-in).

Au point de convergence entre les sciences fondamentales et les sciences appliquées, les nanosystèmes connaissent depuis une dizaine d'années un développement industriel à l'échelle planétaire. Parmi ces nanosystèmes, les agrégats, petites particules constituées de quelques atomes (ou molécules) à plusieurs milliers d'unités, constituent véritablement "le chaînon manquant" entre l'atome isolé et le solide massif. L'étude des interactions dans les agrégats permettrait de comprendre comment l'atome est influencé par son environnement lorsqu'il est inclus dans un système dense au sein d'autres atomes. La nanoparticule (NP) est constituée de plusieurs milliers à millions d'atomes, ses dimensions étant exprimées en nanomètres (nm, 1 nm = 10^{-9} m).L'engouement que suscitent les agrégats et les NPs est lié à leurs propriétés physiques particulières mais également à leur grande surface spécifique (rapport surface/volume). Il en résulte une grande réactivité liée à des sites réactionnels plus nombreux. Cette caractéristique est exploitée dans de très nombreux domaines d'applications (catalyse hétérogène, dépollution, photovoltaïque, nanomédecine).Cette expansion des activités "nanotechnologiques" implique le développement de méthodes de caractérisation de ces nouveaux types de matériaux, qui sont bel et bien présents dans notre vie.Parmi les méthodes de caractérisation de la matière, la spectroscopie de photoélectrons (XPS) générés par rayonnement synchrotron a, depuis longtemps, prouvé son efficacité pour l'étude des atomes, molécules et des matériaux, et s'est imposée en tant que technique de choix en science des surfaces. L'idée de ces travaux de thèse est de combiner la sélectivité atomique de la spectroscopie appliquée à la matière diluée, avec la sensibilité de surface de la spectroscopie X-mous sur les matériaux pour étudier des nanosystèmes (agrégats et NPs) en phase gazeuse par XPS dans le domaine d'énergie allant de 100 eV à 1000 eV.Nous présentons dans cette thèse les premiers résultats obtenus par cette approche sur la ligne de lumière PLEIADES du synchrotron SOLEIL, ligne à ultra-haute résolution dédiée à l'étude de la matière diluée. Les expériences ont porté sur des matériaux très utilisés dans les secteurs industriel et biomédical, en l'occurrence les NPs de TiO2, de Silicium et les NPs de polystyrène fonctionnalisées par des dérivés glucidiques}. Nous montrons comment l'XPS de NPs isolées nous permet de répondre à des questionnements concrets, comme la réactivité de surface des NPs, les processus et les dynamiques d'oxydation, l'inclusion d'hétéroatomes ainsi que l'interface ligand/NP. Les résultats présentés ici montrent non seulement la faisabilité de la méthode, mais plus encore, prouvent qu'il est possible d'adresser des problématiques appliquées ayant trait à des phénomènes réactionnels surfaciques, sur des NPs isolées, aléatoirement orientées. / During the past decade, a world-wide industrial expansion of nanosystems has been taking place at the junction between fundamental and applied sciences. Among these nanosystems, clusters, defined as small particles whose constitution ranges from few atoms (or molecules) to several thousand units, constitute "the missing link" between the isolated atom and the bulk solid. Studying the interactions in the aggregates would allow to understand how the atom is influenced by its neighborhood when it is included in a dense system within other atoms. "Nanoparticle" (NP) is usually defined as a system extanding from several thousands to millions of atoms, and its size is expressed in nanometer (nm, 1 nm = 10^{-9} m).This interest for nanosystems mainly results from their particular physical properties at the nanometer scale, but also from their large "surface to bulk" ratio. Hence, more active sites are available at the surface, enhancing their reactivity. This characteristic is used in numerous fields of applications (heterogeneous catalysis, cleanup, photovoltaics, nanomedicine).% and is also relevant in natural processes (atmospheric sprays, volcanic eruptions).This expansion of the "nanotechnological" activities involves the development of new methods for the characterization of these new kinds of materials, which take a considerable part in our daily life. Among the methods of matter characterization, synchrotron radiation based soft X-ray spectroscopy has shown to be a powerful technique for the study of atoms and molecules as well as materials, and appears today as an efficient technique of characterization in surface science.The idea of this thesis is to combine the atomic selectivity of the spectroscopy applied to dilute matter, with the surface sensitivity of soft X-ray spectroscopy, to study isolated nanosystems (clusters and NPs) in the gas phase, by XPS in the energy range of soft X-ray (typically 100 eV to 1000 eV). We present in this thesis the first results obtained by this approach at the PLEIADES beamline of SOLEIL synchrotron radiation facility. PLEIADES is a ultra-high resolution beamline dedicated to the study of dilute matter. The experiments carried out in this work relate to materials often used in the industrial and biomedical fields: TiO2 NPs, Silicon and glycosylated polystyrene NPs. We show how XPS on isolated NPs allows us to answer concrete questions, as the surface reactivity of the NPs, processes and oxidation dynamics, the doping efficiency or the interface ligand/NP. The results presented here not only show the feasibility of the method, but much more than that, prove that it is possible to give insight about surface chemical processes occuring on isolated, randomly oriented NPs.

Les lasers à électrons libres (LEL) X sont aujourd'hui des sources lumineuses cohérentes et intenses utilisées pour des investigations multidisciplinaires de la matière. Un nouveau schéma d'accélération, l'accélérateur laser plasma (LPA), est maintenant capable de produire une accélération de quelques GeV/cm, bien supérieure à celle des linacs radiofréquence. Ce travail de thèse a été mené dans le cadre des programmes de R&D du projet LUNEX5 (laser à électrons libres utilisant un nouvel accélérateur pour l’exploitation du rayonnement X de 5e génération) de démonstrateur LEL avancé et compact avec applications utilisatrices pilotes. Il comprend un linac supraconducteur de 400 MeV de haute cadence (10 kHz) pour l’étude de schémas LEL avancés, et LPA pour sa qualification par une application LEL. La ligne LEL utilise une configuration d’injection avancée dans la plage spectrale 40-4 nm par génération d’harmoniques à gain élevé (HGHG) et schéma d’écho (EEHG) avec des onduleurs compacts cryogéniques à champ élevé de courte période courte. L'étude de solutions adaptées aux applications LEL compactes et avancées est donc examinée. Un premier aspect concerne la réduction du milieu de gain du LEL (électrons dans l'onduleur), le raccourcissement de la période se faisant au détriment du champ magnétique. Les onduleurs cryogéniques compacts à base d'aimants permanents cryogéniques (CPMU), dans lesquels les performances de l'aimant sont améliorées à la température cryogénique sont étudiés. Une deuxième partie du travail développée dans le cadre l’expérience de R&D COXINEL visant à démontrer l’amplification LEL à l’aide d’un LPA. La ligne permet de manipuler les propriétés des faisceaux d’électrons produits (dispersion en énergie, divergence, variation de pointé) avant d’être utilisées pour des applications de sources lumineuses. Le faisceau d'électrons généré est très divergent et nécessite une bonne manipulation juste après la source avec des quadrupôles forts placés immédiatement après la génération d'électrons. Ainsi, des quadrupôles innovants à aimants permanents de gradient élevé réglable appelés «QUAPEVA», sont développés. Ils sont optimisés avec le code RADIA et caractérisées avec trois mesures magnétiques. Un gradient de 200 T/m avec une variabilité de 50 % est obtenu tout en maintenant une excursion du centre magnétique réduite à ± 10 µm, qui a permis un alignement par compensation de pointé du faisceau dans COXINEL grâce au centre magnétique variable des systèmes, avec un faisceau bien focalisé sans dispersion. Les QUAPEVA constituent des systèmes originaux dans le paysage des quadrupôles à de gradient élevé et variable développés jusqu'à présent. Une troisième partie des travaux concerne l’observation du rayonnement d’onduleur monochromatique ajustable sur la ligne COXINEL. Le faisceau d'électrons d'énergie de 170 MeV est transporté et focalisé dans un CPMU de 2 m et de période de 18 mm émettant à 200 nm. Le flux spectral est caractérisé à l'aide d'un spectromètre UV et le flux angulaire mesuré par une caméra CCD. La longueur d'onde est accordée avec l’entrefer. Les distributions spatio-spectrales mesurées en forme de lune du rayonnement de l'onduleur sont bien reproduites par les simulations de rayonnement utilisant les distributions d’électrons mesurées et transportées le long de la ligne. Elles permettent aussi de renseigner sur la qualité du faisceau d’électrons, de son transport et d'en estimer les paramètres tels que la dispersion en énergie et la divergence. Le dernier aspect du travail est lié à la comparaison entre la génération des harmoniques en gain élevé et le schéma d’écho, dans le cadre de ma participation à une expérience réalisée à FERMI @ ELETTRA. Nous avons pu démontrer un LEL de type écho à 5,9 nm, avec spectres plus étroits et une meilleure reproductibilité que le schéma HGHG à deux étages. Cette thèse constitue un pas en avant vers les lasers à électrons libres compacts et avancés. / X-ray Free Electron Lasers (FEL) are nowadays unique intense coherent fs light sources used for multi-disciplinary investigations of matter. A new acceleration scheme such as Laser Plasma Accelerator (LPA) is now capable of producing an accelerating gradient of few GeV/cm far superior to that of conventional RF linacs. This PhD work has been conducted in the framework of R&D programs of the LUNEX5 (free electron Laser Using a New accelerator for the Exploitation of X-ray radiation of 5th generation) project of advanced and compact Free Electron laser demonstrator with pilot user applications. It comprises a 400 MeV superconducting linac for studies of advanced FEL schemes, high repetition rate operation (10 kHz), multi-FEL lines, a Laser Wake Field Accelerator (LWFA) for its qualification by a FEL application. The FEL lines comports enables advanced seeding in the 40-4 nm spectral range using high gain harmonic generation (HGHG) and echo-enabled harmonic generation (EEHG) with compact short period high field cryogenic undulators. The study of compact devices suitable for compact FEL applications is thus examined. One first aspect concerns the reduction of the Free Electron Laser gain medium (electrons in undulator) where shortening of the period is on the expense of the magnetic field leading to an intensity reduction at high harmonics. Compact cryogenic permanent magnet based undulators (CPMUs), where the magnet performance is increased at cryogenic temperature making them suitable for compact applications, are studied. Three CPMUs of period 18 mm have been built: two are installed at SOLEIL storage ring and one at COXINEL experiment. A second part of the work is developed in the frame of the R&D programs is the COXINEL experiment with an aim at demonstrating FEL amplification using an LPA source. The line enables to manipulate the properties of the produced electron beams (as energy spread, divergence, induced dispersion due) before being used for light source applications. The electron beam generated is highly divergent and requires a good handling at an early stage with strong quadrupoles, to be installed immediately after the electron generation source. Hence, the development of the so-called QUAPEVAs, innovative permanent magnet quadrupoles with high tunable gradient, is presented. The QUAPEVAs are optimized with RADIA code and characterized with three magnetic measurements. High tunable gradient is achieved while maintaining a rather good magnetic center excursion that allowed for beam pointing alignment compensation at COXINEL, where the beam is well-focused with zero dispersion at any location along the line. The QUAPEVAs constitute original systems in the landscape of variable high gradient quadrupoles developed so far. A third part of the work concerns the observation of tunable monochromatic undulator radiation on the COXINEL line. The electron beam of energy of 170 MeV is transported and focused in a 2-m long CPMU with a period of 18 mm emitting radiation light at 200 nm. The spectral flux is characterized using a UV spectrometer and the angular flux is captured by a CCD camera. The wavelength is tuned with the undulator gap variation. The spatio-spectral moon shape type pattern of the undulator radiation provided an insight on the electron beam quality and its transport enabling the estimation of the electron beam parameters such as energy spread and divergence. The final aspect of the work is related to the comparison between the echo and high gain harmonic generation, in the frame of my participation to an experiment carried out at FERMI@ELETTRA. At FERMI, we have demonstrated a high gain lasing using EEHG at a wavelength of 5.9 nm where it showed a narrower spectra and better reproducibility compared to a two-stage HGHG. This PhD work constitutes a step forward towards advanced compact Free Electron Lasers.

Les neurones du cortex sont organisés en réseaux qui permettent de réaliser des fonctions complexes. Des anomalies des connexions neuronales qui forment ces réseaux peuvent altérer son fonctionnement et générer des activités pathologiques comme c’est le cas dans certaines formes d’épilepsie. L’épilepsie-absence est caractérisée par des crises généralisées non-convulsives présentant lors d’un enregistrement électroencéphalographique des décharges de pointes-ondes (DPO) bilatérales et synchrones qui s’accompagnent d’une altération de la conscience. Plusieurs équipes ont montré chez l’Homme et dans des modèles animaux que ces DPO sont initiées au niveau du cortex. Cependant, notre connaissance des altérations de connectivité neuronale qui sous-tendent ces activités reste encore très limitée. Nous avons émis l’hypothèse que les DPO sont favorisées par une connectivité neuronale exacerbée. Nous avons examiné cette hypothèse dans un modèle génétique d’épilepsie-absence, le rat GAERS. En étudiant la connectivité structurelle du cortex somatosensoriel primaire, aire d’initiation des DPO chez le GAERS, par traçage rétrograde monosynaptique ainsi que sa connectivité fonctionnelle par enregistrements électrophysiologiques extracellulaires multi-canaux in vivo, nous avons caractérisé le circuit de génération et de propagation des DPO entre les couches corticales. Ce circuit pathologique est différent du circuit canonique d’intégration de l’information sensorielle puisque les DPO sont initiées par les neurones des couches profondes. Ces neurones présentent une hyperconnectivité intralaminaire globale et translaminaire GABAergique et lorsque l’on altère ces connexions pathologiques par microtransection rayon-X synchrotron on réduit la puissance des DPO. Nous nous sommes ensuite intéressés à l’interférence que pouvait avoir le circuit pathologique sur l’intégration sensorielle. En utilisant un test de discrimination de texture nous avons monté que le traitement de l’information sensorielle liée aux vibrisses n’est pas altéré chez le GAERS. Grâce à des stimulations des vibrisses pendant des enregistrements électrophysiologiques extracellulaires multi-canaux in vivo, nous avons pu montrer que le circuit canonique est fonctionnel chez le GAERS. L’ensemble de nos données suggèrent que, chez le GAERS, les DPO sont sous-tendues par un réseau structurellement anormal au sein du cortex somatosensoriel mais que ce circuit pathologique n’empêche pas la fonction physiologique de cette région du cortex. / Cortical neurons are organized in networks which allow complex functions. Abnormalities of neuronal connections composing these networks can lead to functional alterations and pathological activities as in some forms of epilepsy. Absence-epilepsy is characterized by non-convulsive generalized seizures associated with synchronous and bilateral spike-and-wave discharges (SWD) on electroencephalographic recordings and impairment of consciousness. Many studies in patients and animal models have shown that SWD are initiated in the cortex but our understanding of underlying neuronal connection alterations remain limited. We hypothesized that SWD may result from an increased neuronal connectivity. To test this hypothesis, we used a genetic model of absence-epilepsy, the GAERS rat. By studying the structural connectivity of primary somatosensory cortex, the SWD-initiating area in GAERS, by retrograde monosynaptic tracers and the functional connectivity by in vivo multi-channel extracellular electrophysiology, we were able to describe the circuit of SWD generation and propagation across cortical layers. This pathological circuit is different from the canonical circuit of sensory information processing as SWD are initiated by deep layer neurons. These neurons present an intralaminar global and a translaminar GABAergic hyperconnectivity and by decreasing these connections by synchrotron-generated microtransections we were able to reduce the power of SWD. We next investigated if the pathological circuit would interfere with sensory integration. By using a texture discrimination task we showed that sensory information integration is unaltered in GAERS. By using vibrissae stimulations during in vivo multi-channel extracellular electrophysiology recordings we showed that the canonical circuit remain functional in GAERS. Altogether, our data suggest that SWD in GAERS are generated by an abnormal structural network in the somatosensory cortex but that this pathological circuit do not interfere with the physiological function of this brain area.

The relationship between microstructure and mechanical properties of semicrystalline polymer materials has been a hot topic since many years in materials science and engineering. Isotactic polypropylene (iPP) is frequently used as a model material, due to its good mechanical properties and wide applications. In the past few years, numerous studies have been performed in the field of structural evolution during deformation. Previous results revealed that phase transition from crystal to mesophase happens in the crystal scale, lamellae orientation and fragmentation occurs in the lamellae scale, and even cavitation behavior exists in the larger scale. Although abundant work has been done, some problems remain under debate, for instance the relationship between lamellae deformation and cavitation behavior, the role of phase transition on the void formation, et al. In this study, well defined microstructure of iPP is obtained by annealing or adding nucleating agent. Afterward, the structural evolution under three types of mechanical load modes (including uniaxial stretching, creep, and stress relaxation) is in-situ monitored by synchrotron X-ray scattering. During uniaxial stretching, we revealed, for the first time, how lamellae deformation occurs in the time scales of elastic deformation, intra-lamellar slip, and melting-recrystallization, separated by three critical strains which were only rarely found to be influenced by annealing. Strain I (a Hencky strain value of 0.1) marks the end of elastic deformation and the onset of intra-lamellar slip. Strain II (a Hencky strain value of 0.45) signifies the start of the recrystallization process, from where the long period in the stretching direction begins to decrease from its maximum and the polymer chains in the crystal start to orient along the stretching direction. The energy required by melting arises from the friction between the fragmented lamellae. Strain III (a Hencky strain value of 0.95) denotes the end of the recrystallization process. Beyond the strain of 0.95, the long period and the crystal size remain nearly unchanged. During further stretching, the extension of the polymer chains anchored by lamellae triggers the strain hardening behavior. On the other hand, annealing significantly decreases the critical strain for voids formation and increases the voids number, but restricts the void size. For those samples annealed at a temperature lower than 90 oC, voids are formed between strain II and strain III. The voids are oriented in the stretching direction once they are formed. For those samples annealed at a temperature higher than 105 oC, voids are formed between strain I and strain II. The voids are initially oriented with their longitudinal axis perpendicular to the stretching direction and then transferred along stretching direction via voids coalescence. Additionally, the formation of voids influences neither the critical strains for lamellae deformation, nor the final long period, the orientation of polymer chains or the crystal size. β-iPP is a kind of metastable phase which can be induced only under special condition. By adjusting the morphology of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide (NJS) through self-assembly, the relative content of β-iPP (Kβ) is successfully controlled, under the condition that the weight content of NJS in the composite keeps at 0.3 wt. %. The microstructural evolution of the iPP/NJS composites with different Kβ during uniaxial stretching is studied. The results show that a higher Kβ could increase the number of the voids. However, the size of the voids is similar regardless of the NJS morphology. The β-α phase transition takes place after voids formation. During intralamellar and inter-lamellar slip, no obvious polymer chains orientation can be found for α-iPP. In the strain range of 0.1~0.6, the c-axis of the β-iPP crystal tends to orient perpendicular to the stretching direction due to lamellae twisting, which is a unique deformation mode of β-iPP lamellae. And the lamellae twisting are proposed to be responsible for the intense voids formation of the composite with higher Kβ. During creep, the evolution of the long period can be divided into four stages (primary creep, transition stage, secondary creep, and tertiary creep). This fits quite well with the macroscopic displacement and strain evolution. In primary creep, the long period along loading direction (L_p^∥) increases with time due to the stretching of amorphous phase, whereas the long period perpendicular to loading direction (L_p^⊥) decreases slightly. In secondary creep, strain increases linearly with time. Both L_p^∥ and L_p^⊥ exhibit the same tendency with strain. The increase of the long period is caused by lamellae thickening, which is a kind of cooperative motion of molecular chains with their neighbors onto the lamellae surface. The increasing rate of L_p^∥ is larger than that of L_p^⊥, indicating that the orientation of molecular chains along loading direction decreases the energy barrier for the cooperative motion. In tertiary creep, strain grows dramatically within a limited time. The lamellae are tilted and rotated, and then disaggregated. In addition, fibrillary structure is formed during lamellae breaking. The length of the fibrillary structure increases from 364 nm to 497 nm but its width stays at 102 nm as creep time increases. During stress relaxation, the local deformation behavior of the long period is affine with the macroscopic stress relaxation. However, the evolution of the crystal orientation and the void size lag behind the macroscopic stress relaxation. The decrease of the long period is mainly caused by the relaxation of the strained polymer chains in the amorphous phase. The retardation of the evolution of the crystal orientation is probably caused by the phase transition from stable α-iPP to metastable mesomorphic-iPP. By phase transition, the highly oriented α-iPP is transferred to weakly oriented mesomorphic-iPP. Due to the fact that the void is confined by the network of the strained polymer chains where lamellae blocks serve as the physical anchoring points, the phase transition contributes greatly to the viscoplastic deformation of the network. Consequently, the evolution of the voids size shows a similar trend with that of the phase transition. With this thesis, we gained a deeper insight into the relationship between structure and properties of semicrystalline polymers. The current study will not only benefit the understanding of polymer materials science but also serve as guidance for the processing of semicrystalline polymers for engineering applications.:1 Introduction 1 1.1 Isotactic polypropylene (iPP) 1 1.1.1 Chain structure of PP 1 1.1.2 Crystal forms of iPP 2 1.1.3 Lamellae of iPP 4 1.1.4 The morphology of the supra-structure of iPP 4 1.2 Structural evolution during deformation 5 1.2.1 Deformation process of semicrystalline polymers 5 1.2.2 Cavitation behavior of semicrystalline polymers 7 1.3 Synchrotron X-ray scattering 9 1.3.1 X-ray and its sources 9 1.3.2 The interaction between X-rays and objects 11 1.3.3 Wide angle X-ray scattering 12 1.3.4 Small angle X-ray scattering 13 2 Motivation and objectives 15 3 Samples preparation and basic characterization 17 3.1 Materials and samples preparation 17 3.1.1 Preparation of iPP films with single layer of spherulites and transcrystalline regions 17 3.1.2 Preparation of iPP plates crystallized with different thermal histories 17 3.1.3 Preparation of iPP/NJS plates with different morphologies of NJS 18 3.1.4 Preparation of microinjection molded iPP/NJS sample 18 3.2 Characterization 18 3.2.1 Differential scanning calorimetry (DSC) 18 3.2.2 Dynamic mechanical analysis (DMA) 19 3.2.3 Scanning electron microscopy (SEM) 19 3.2.4 Polarized optical microscopy (POM) 20 3.2.5 Rheology test 20 3.2.6 Gel Permeation Chromatography (GPC) 21 3.2.7 In situ synchrotron X-ray scattering measurements 21 3.2.8 X-ray scattering pattern processing and calculation 24 4 Microstructure characterization in a single iPP spherulite by synchrotron microfocus wide angle X-ray scattering 29 4.1 Introduction 30 4.2 The nucleation efficiency of the carbon fiber on iPP 31 4.3 Morphology of iPP spherulites and transcrystalline region 32 4.4 Defining of the position of the carbon fiber 33 4.5 Microstructure studies of the spherulite 34 4.5.1 Crystallinity in the spherulite 35 4.5.2 The ratio between “daughter” lamellae and “mother” lamellae in the spherulite 36 4.5.3 The orientation of the crystal axis in the spherulite 37 4.6 Conclusion 39 5 Influence of annealing on the mechanical αc-relaxation of iPP: a study from the intermediate phase perspective 41 5.1 Introduction 42 5.2 Crystal form of water cooled and annealed iPP 44 5.3 Microstructure of iPP with different thermal history 45 5.4 Melting behavior of iPP with different thermal history 50 5.5 Mechanical relaxation behavior of iPP with different thermal history 52 5.6 Conclusion 57 6 Critical strains for lamellae deformation and cavitation during uniaxial stretching of annealed iPP 59 6.1 Introduction 60 6.2 The true stress-strain curves of iPP uniaxial stretched at 75 oC 61 6.3 In Situ SAXS and WAXS Results 63 6.3.1 Synchronize mechanical test and in-situ SAXS/WAXS measurement 66 6.4 Lamellae deformation 67 6.4.1 The evolution of the long period 67 6.4.2 The evolution of the crystal size 69 6.4.3 The orientation of the c-axis of the crystal 71 6.4.4 The evolution of the crystallinity 72 6.5 Cavitation behavior 74 6.5.1 The onset strain of the voids formation and the voids direction transition 74 6.5.2 The evolution of the voids size 75 6.5.3 The scattering invariant (Q) of the voids 76 6.5.4 The morphology of voids 77 6.6 Final discussion 79 6.7 Conclusion 82 7 Accelerating shear-induced crystallization and enhancing crystal orientation of iPP by controlling the morphology of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide 83 7.1 Introduction 84 7.2 The self-assembly process of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide 85 7.3 Rheological behavior 88 7.3.1 Frequency sweep test 88 7.3.2 Strain sweep test 88 7.3.3 Steady-state shear test 89 7.4 Shear-induced crystallization 91 7.4.1 Crystallization kinetics studied by rheological method 91 7.4.2 In-situ SAXS measurement 93 7.4.3 Microstructure of iPP after shear-induced crystallization 96 7.4.4 The morphology of the sample 98 7.4.5 The crystallization mechanism 99 7.5 Conclusion 100 8 Influence of nucleating agent self-assembly on structural evolution of iPP during uniaxial stretching 101 8.1 Introduction 102 8.2 The morphology of the NJS in the compression molded iPP 103 8.3 Microstructure of iPP with different NJS morphologies 104 8.4 In-situ SAXS results 105 8.4.1 Cavitation behavior 107 8.4.2 Evolution of the long period 110 8.5 In-situ WAXS results 111 8.5.1 The β-α phase transition behavior 112 8.5.2 The orientation of the crystal 115 8.6 Conclusion 117 9 Microstructural evolution of iPP during creep: an in-situ study by synchrotron SAXS 119 9.1 Introduction 120 9.2 The creep curve 121 9.3 In-situ SAXS results 123 9.3.1 Evolution of long period and domain thickness 125 9.3.2 Lamellae tilting and rotation 128 9.3.3 Lamellae orientation and fibrillary structure formation 129 9.4 Conclusions 132 10 Microstructural evolution of iPP during stress relaxation 133 10.1 Introduction 134 10.1.1 The structural evolution during stress relaxation at 60 oC 135 10.1.2 The structural evolution during stress relaxation at 90 oC 140 10.2 Conclusion 145 11 Conclusion and outlook 146 12 References 148 13 Appendix 158 13.1 List of symbols and abbreviations 158 13.2 List of figures and tables 163 13.3 List of publications 171 14 Acknowledgements 173 15 Eidesstattliche Erklärung 175

In this study polycrystalline NiAl has been subjected to torsion deformation. Torsion has been used because of its characteristics. By this deformation mode high shear strains (gamma = 18 in this study) can be imposed on the sample. The deformation conditions are well-defined because of the local deformation mode, which is simple shear. Due to the monoclinic sample symmetry one half of the pole figure is needed in order to obtain the complete texture information, which is more than is needed e.g. by extrusion or rolling. Therefore, texture analysis might be more sensitive with respect to texture components. Furthermore, torsion deformation is characterized by being inhomogeneous in terms of the amount of shear strain and shear strain rate along the sample radius. The shear strain gradient makes the analysis of different stages of deformation on the same sample (i.e. under the same deformation conditions) possible. Another characteristic being special for torsion is that samples change their length, although no axial stress is applied. This effect is known as Swift effect and will be analyzed in detail. The deformation, microstructure and texture development subject to the shear strain are studied by different techniques (Electron Back-Scatter and High Energy Synchrotron Radiation). Beside the development of microstructure and texture with shear strain, the effect of an initial texture as well as the deformation temperature on the development of texture and microstructure constitute an important part of this study. Therefore, samples with three different initial textures were deformed in the temperature range T = 700K – 1300K. The development of the microstructure is characterized by two different regimes depending on the deformation temperature T. For T up to 1000K, continuous dynamic recrystallization (CDRX) takes place. This mechanism leads to the deformation-induced dislocations forming low angle grain boundaries (LAGBs) or being incorporated into them and the successive transformation of these boundaries into high angle grain boundaries (HAGBs) by a further increase of their misorientation. The predictions of this model were compared with the experimental results. The shear stress – shear strain curves are characterized by a peak at low strains, which is followed by softening and a steady state at high strains. This condition is fulfilled for a number of samples, but especially <111> oriented samples do not show a softening stage at low temperatures. Grain refinement takes place for all samples and the average grain size decreases with temperature. The predicted LAGB decrease is in best agreement with the experiments at the lowest temperatures (T = 700K and 800K). Deviations from the model can be explained by the temperature dependence of the grain boundary mobility. For temperatures T > 1000K, discontinuous dynamic recrystallization (DDRX) occurs, by which new grains form by nucleation and subsequent growth. The texture is characterized by two components, {100}<100> (cube, C) and {110}<100> (Goss, G). The intensity of G increases with temperature, while that of C decreases independent of the initial orientation. Both components have their maximum deviated about the 1 axis. The deviation is larger for grains containing the C component and decreases with temperature. Grains containing the G component have the smaller deviation, which decreases with temperature and strain. Texture simulations based on the full constraint Taylor model under the assumption of {110}<100> and {110}<110> slip were done with the experimental <110> and <111> fibres as well as a theoretical <100> fibre and a {100}<100> single orientation (ideal as well as rotated about the torsion axis). The G component is predicted by the simulations and is therefore a deformation texture. However the C component does not appear in the simulation. It therefore must originate by different mechanisms. For the non-<100> oriented samples, possibly nucleation is responsible for the formation of C oriented nuclei. Simulations with single orientations lead to the conclusion, that the ideal C orientation rotates about the 1 axis, while other C orientations, which are rotated about the torsion axis, increasingly converge towards the G component with strain. A single G orientation on the other hand is stable against such a rotation and is therefore the most likely steady state texture. Based on these results it is proposed, that ideally C oriented nuclei rotate until an orientation is reached into which they grow. These new grains are further rotated up to a critical angle, at which a part of them disappears either by adjacent grains or new C oriented nuclei. The recrystallization texture for T > 1000K is most likely the C component as well. Torsional creep of NiAl is characterized by a stress exponent, which depends on temperature and an activation energy, which is stress dependent. A model incorporating both dependencies is proposed and applied to the creep data. It is shown that these equations are able to describe the experimental findings. Thus creep of NiAl based on this model is dominated by non-diffusional processes such as cross slip of <100> screw dislocations for T  1000K. For T > 1000K the stress exponent and the activation energy are in a region, which according to previous reports is rather dominated by dislocation-climb controlled creep. The Swift effect, due to which samples change their axial dimension during torsion without applied axial stress, is observed for NiAl. It is strongly related to the texture development and in the case of NiAl the C component is identified as being responsible for shortening, whereas the G component leads to lengthening as long as it is not aligned with the shear system. Both tendencies can be explained based on the active slip systems. Simulations fail to predict the experimental observation, because the C component is not present. HESR and EBSD were compared with respect to local texture measurements. It was concluded depending on the average grain size HESR has an advantage in terms of grain statistics. For DDRX samples however, both methods are limited. Local texture inhomogeneities can be better detected using EBSD, whereas for an overall local texture information HESR is better suited.

In this study polycrystalline NiAl has been subjected to torsion deformation. Torsion has been used because of its characteristics. By this deformation mode high shear strains (gamma = 18 in this study) can be imposed on the sample. The deformation conditions are well-defined because of the local deformation mode, which is simple shear. Due to the monoclinic sample symmetry one half of the pole figure is needed in order to obtain the complete texture information, which is more than is needed e.g. by extrusion or rolling. Therefore, texture analysis might be more sensitive with respect to texture components. Furthermore, torsion deformation is characterized by being inhomogeneous in terms of the amount of shear strain and shear strain rate along the sample radius. The shear strain gradient makes the analysis of different stages of deformation on the same sample (i.e. under the same deformation conditions) possible. Another characteristic being special for torsion is that samples change their length, although no axial stress is applied. This effect is known as Swift effect and will be analyzed in detail. The deformation, microstructure and texture development subject to the shear strain are studied by different techniques (Electron Back-Scatter and High Energy Synchrotron Radiation). Beside the development of microstructure and texture with shear strain, the effect of an initial texture as well as the deformation temperature on the development of texture and microstructure constitute an important part of this study. Therefore, samples with three different initial textures were deformed in the temperature range T = 700K – 1300K. The development of the microstructure is characterized by two different regimes depending on the deformation temperature T. For T up to 1000K, continuous dynamic recrystallization (CDRX) takes place. This mechanism leads to the deformation-induced dislocations forming low angle grain boundaries (LAGBs) or being incorporated into them and the successive transformation of these boundaries into high angle grain boundaries (HAGBs) by a further increase of their misorientation. The predictions of this model were compared with the experimental results. The shear stress – shear strain curves are characterized by a peak at low strains, which is followed by softening and a steady state at high strains. This condition is fulfilled for a number of samples, but especially <111> oriented samples do not show a softening stage at low temperatures. Grain refinement takes place for all samples and the average grain size decreases with temperature. The predicted LAGB decrease is in best agreement with the experiments at the lowest temperatures (T = 700K and 800K). Deviations from the model can be explained by the temperature dependence of the grain boundary mobility. For temperatures T > 1000K, discontinuous dynamic recrystallization (DDRX) occurs, by which new grains form by nucleation and subsequent growth. The texture is characterized by two components, {100}<100> (cube, C) and {110}<100> (Goss, G). The intensity of G increases with temperature, while that of C decreases independent of the initial orientation. Both components have their maximum deviated about the 1 axis. The deviation is larger for grains containing the C component and decreases with temperature. Grains containing the G component have the smaller deviation, which decreases with temperature and strain. Texture simulations based on the full constraint Taylor model under the assumption of {110}<100> and {110}<110> slip were done with the experimental <110> and <111> fibres as well as a theoretical <100> fibre and a {100}<100> single orientation (ideal as well as rotated about the torsion axis). The G component is predicted by the simulations and is therefore a deformation texture. However the C component does not appear in the simulation. It therefore must originate by different mechanisms. For the non-<100> oriented samples, possibly nucleation is responsible for the formation of C oriented nuclei. Simulations with single orientations lead to the conclusion, that the ideal C orientation rotates about the 1 axis, while other C orientations, which are rotated about the torsion axis, increasingly converge towards the G component with strain. A single G orientation on the other hand is stable against such a rotation and is therefore the most likely steady state texture. Based on these results it is proposed, that ideally C oriented nuclei rotate until an orientation is reached into which they grow. These new grains are further rotated up to a critical angle, at which a part of them disappears either by adjacent grains or new C oriented nuclei. The recrystallization texture for T > 1000K is most likely the C component as well. Torsional creep of NiAl is characterized by a stress exponent, which depends on temperature and an activation energy, which is stress dependent. A model incorporating both dependencies is proposed and applied to the creep data. It is shown that these equations are able to describe the experimental findings. Thus creep of NiAl based on this model is dominated by non-diffusional processes such as cross slip of <100> screw dislocations for T  1000K. For T > 1000K the stress exponent and the activation energy are in a region, which according to previous reports is rather dominated by dislocation-climb controlled creep. The Swift effect, due to which samples change their axial dimension during torsion without applied axial stress, is observed for NiAl. It is strongly related to the texture development and in the case of NiAl the C component is identified as being responsible for shortening, whereas the G component leads to lengthening as long as it is not aligned with the shear system. Both tendencies can be explained based on the active slip systems. Simulations fail to predict the experimental observation, because the C component is not present. HESR and EBSD were compared with respect to local texture measurements. It was concluded depending on the average grain size HESR has an advantage in terms of grain statistics. For DDRX samples however, both methods are limited. Local texture inhomogeneities can be better detected using EBSD, whereas for an overall local texture information HESR is better suited.