La synthèse de nouveaux composés d'intercalation du graphite a été réalisée en phase gazeuse et en solution dans HF anhydre. Les fluorures de chrome et de rhodium s'intercalent dans le graphite pour donner lieu à des composés de stades 1 à 3. Une étude structurale sur un monocristal a montré la commensurabilité entre le sous réseau du graphite et celui de l'intercalat. L'état d'oxydation des métaux de transition a été déterminé par RPE, XPS et par mesures magnétiques. Les mesures de la réflectivité optique ont permis une estimation du transfert de charge du graphite vers l'espèce insérée. L'étude de l'effet de la fluoration d'une série d'oxydes supraconducteurs a été réalisée. Un traitement sous fluor gazeux à basse température (20°C < F < 2100°C) a mis en évidence la formation d'une fine couche d'(oxy) fluorure à la surface des matériaux. Cette couche a été caractérisée par diffraction X, TEM et par spectroscopie Auger. Dans l'oxyde YBa2Cu3O7, un phénomène de passivation de surface vis-à-vis de la dégradation atmosphérique a été observé. L'influence de la fluoration sur les propriétés supraconductrices a été étudiée par RPE, mesures magnétiques et électriques. Une étude par XPS sur un monocristal de YBa2Cu3O7 a confirmé que la surface du matériau est complétement modifiée après traitement.

INTRODUCTION : L'apparition récente des premiers implants rachidiens, au milieu du vingtième siècle, marque non seulement une accélération du développement de la chirurgie rachidienne, mais également la naissance d'une technologie spécifique, qui n'en est encore qu'à ses débuts. Comment évaluer ces implants rachidiens, aussi bien lors de leur conception que lors de la planification de la chirurgie? C'est autour de cette problématique que nos travaux de recherche se sont articulés. MATERIELS & METHODES: Le premier de nos deux axes d'investigation concerne l'évaluation préclinique en fatigue des implants rachidiens, et plus particulièrement des implants d'ostéosynthèse. Nous avons ainsi animé un groupe de travail, composé d'industriels et de chercheurs du LBM, afin de proposer un projet de norme internationale définissant des méthodes d'évaluation fonctionnelle des implants rachidiens, prenant en compte les dernières connaissances scientifiques, notamment concernant les contraintes subies par les instrumentations rachidiennes in vivo. Notre second axe d'investigation concerne l'analyse biomécanique par méthode numérique de la chirurgie du rachis lombaire. Nous nous sommes appuyés pour cela sur un outil de modélisation, géométrique et mécanique, et de simulation par éléments finis personnalisées du rachis lombaire et de sa chirurgie. Nous avons, dans le cadre du projet européen Orthosim, contribué à faire évoluer cet outil. Ensuite, une évaluation extensive de l'outil, en tant qu'aide à la planification chirurgicale, a été réalisée. Nous avons enfin réalisé une évaluation préliminaire de l'influence de l'opérateur sur la réponse de l'outil et participé à son intégration dans le cadre d'un portail Internet. RESULTATS : Les essais réalisés suivant le protocole proposé ont permis de mettre en évidence des modes de rupture en fatigue des implants tels qu'observés in vivo, confirmant l'aspect fonctionnel de l'évaluation. Le contenu technique du projet de norme en découlant à fait l'objet d'un consensus des différents experts de l'ISO en septembre 2006. La publication définitive en tant que norme internationale a été acceptée en avril 2008. Ensuite, l'outil de simulation a été développé et amélioré, d'abord en fiabilisant le processus, puis en élargissant le panel des options de chirurgie proposées. L'évaluation rétrospective a confirmé le caractère prédictif des simulations proposées, quant à l'influence d'une stratégie chirurgicale donnée sur le résultat clinique. Enfin, la mise à disposition des cliniciens de l'outil de simulation a été engagée. CONCLUSION : Ce travail de doctorat, nous a permis de contribuer d'une part à l'évolution des normes d'évaluation auxquelles nous avons tenté de donner une dimension biomécanique, et d'autre part de participer à mise en place d'un outil innovant d'aide à la planification et à l'analyse biomécanique de la chirurgie rachidienne, basé sur les simulations numériques personnalisées.

La bactérie à Gram-negatif Pseudomonas aeruginosa est un pathogène opportuniste impliqué dans les infections nosocomiales et touchant essentiellement les individus immunodéprimés. Parmi les mécanismes de résistance aux antibiotiques, leur efflux actif par un système de transport transmembranaire appelé Mex (Multi-drug Efflux pump) a pris une grande importance clinique. Ces systèmes d'efflux sont constitués d'un assemblage de trois protéines différentes : une porine de la famille OMF (Outer Membrane Factor), un transporteur de la famille RND (Resistance Nodulation Division) localisé dans la membrane interne et un adaptateur périplasmique de la famille MFP (Membrane Fusion Protein) assurant la cohésion du système. Le sujet de thèse porte sur l'étude structurale, essentiellement par cristallographie RX, de la pompe d'efflux MexXY-OprM qui présente la particularité d'être spécifique aux antibiotiques de la famille des aminoglycosides.

It is relatively straightforward to establish equilibrium inmagnetically confined plasmas, but the plasma is frequentlysucceptible to a variety of instabilities that are driven bythe free energy in the magnetic field or in the pressuregradient. These unstable modes exhibit effects that affect theparticle, momentum and heat confinement properties of theconfiguration. Studies of the dynamics of several of the mostimportant modes are the subject of this thesis. The studies arecarried out on plasmas in the reversed field pinch (RFP)configuration. One phenomenon commonly observed in RFPs is mode walllocking. The localized nature of these phase- and wall lockedstructures results in localized power loads on the wall whichare detrimental for confinement. A detailed study of the walllocked mode phenomenon is performed based on magneticmeasurements from three RFP devices. The two possiblemechanisms for wall locking are investigated. Locking as aresult of tearing modes interacting with a static field errorand locking due to the presence of a non-ideal boundary. Thecharacteristics of the wall locked mode are qualitativelysimilar in a device with a conducting shell system (TPE-RX)compared to a device with a resistive shell (Extrap T2). Atheoretical model is used for evaluating the threshold valuesfor wall locking due to eddy currents in the vacuum vessel inthese devices. A good correlation with experiment is observedfor the conducting shell device. The possibility of succesfully sustaining discharges in aresistive shell RFP is introduced in the recently rebuiltdevice Extrap T2R. Fast spontaneous mode rotation is observed,resulting in low magnetic fluctuations, low loop voltage andimproved confinement. Wall locking is rarely observed. The lowtearingmode amplitudes allow for the theoretically predictedinternal nonresonant on-axis resistive wall modes to beobserved. These modes have not previously been distinguisheddue to the formation of wall locked modes. The internal andexternal nonresonant resistive wall modes grow on the timescale of the shell penetration time. These growth rates dependon the RFP equilibrium. The internal nonresonant resistive wallmodes dominate in Extrap T2R, especially for shallow reverseddischarges. The external nonresonant modes grow solely in deepreversal discharges. <b>Keywords</b>Nuclear fusion, reversed field pinch, resistiveinstabilities, wall locked modes, tearing modes, resistiveshell modes, field errors, EXTRAP-T2, EXTRAP-T2R, TPE-RX

With the explosive growth in wireless applications, the last decade witnessed an ever-increasing test challenge for radio frequency (RF) circuits. While the design community has pushed the envelope far into the future, by expanding CMOS process to be used with high-frequency wireless devices, test methodology has not advanced at the same pace. Consequently, testing such devices has become a major bottleneck in high-volume production, further driven by the growing need for tighter quality control. RF devices undergo testing during the prototype phase and during high-volume manufacturing (HVM). The benchtop test equipment used throughout prototyping is very precise yet specialized for a subset of functionalities. HVM calls for a different kind of test paradigm that emphasizes throughput and sufficiency, during which the projected performance parameters are measured one by one for each device by automated test equipment (ATE) and compared against defined limits called specifications. The set of tests required for each product differs greatly in terms of the equipment required and the time taken to test individual devices. Together with signal integrity, precision, and repeatability concerns, the initial cost of RF ATE is prohibitively high. As more functionality and protocols are integrated into a single RF device, the required number of specifications to be tested also increases, adding to the overall cost of testing, both in terms of the initial and recurring operating costs. In addition to the cost problem, RF testing proposes another challenge when these components are integrated into package-level system solutions. In systems-on-packages (SOP), the test problems resulting from signal integrity, input/output bandwidth (IO), and limited controllability and observability have initiated a paradigm shift in high-speed analog testing, favoring alternative approaches such as built-in tests (BIT) where the test functionality is brought into the package. This scheme can make use of a low-cost external tester connected through a low-bandwidth link in order to perform demanding response evaluations, as well as make use of the analog-to-digital converters and the digital signal processors available in the package to facilitate testing. Although research on analog built-in test has demonstrated hardware solutions for single specifications, the paradigm shift calls for a rather general approach in which a single methodology can be applied across different devices, and multiple specifications can be verified through a single test hardware unit, minimizing the area overhead. Specification-based alternate test methodology provides a suitable and flexible platform for handling the challenges addressed above. In this thesis, a framework that integrates ATE and system constraints into test stimulus generation and test response extraction is presented for the efficient production testing of high-performance RF devices using specification-based alternate tests. The main components of the presented framework are as follows: Constraint-driven RF alternate test stimulus generation: An automated test stimulus generation algorithm for RF devices that are evaluated by a specification-based alternate test solution is developed. The high-level models of the test signal path define constraints in the search space of the optimized test stimulus. These models are generated in enough detail such that they inherently define limitations of the low-cost ATE and the I/O restrictions of the device under test (DUT), yet they are simple enough that the non-linear optimization problem can be solved empirically in a reasonable amount of time. Feature extractors for BIT: A methodology for the built-in testing of RF devices integrated into SOPs is developed using additional hardware components. These hardware components correlate the high-bandwidth test response to low bandwidth signatures while extracting the test-critical features of the DUT. Supervised learning is used to map these extracted features, which otherwise are too complicated to decipher by plain mathematical analysis, into the specifications under test. Defect-based alternate testing of RF circuits: A methodology for the efficient testing of RF devices with low-cost defect-based alternate tests is developed. The signature of the DUT is probabilistically compared with a class of defect-free device signatures to explore possible corners under acceptable levels of process parameter variations. Such a defect filter applies discrimination rules generated by a supervised classifier and eliminates the need for a library of possible catastrophic defects.

<p>It is relatively straightforward to establish equilibrium inmagnetically confined plasmas, but the plasma is frequentlysucceptible to a variety of instabilities that are driven bythe free energy in the magnetic field or in the pressuregradient. These unstable modes exhibit effects that affect theparticle, momentum and heat confinement properties of theconfiguration. Studies of the dynamics of several of the mostimportant modes are the subject of this thesis. The studies arecarried out on plasmas in the reversed field pinch (RFP)configuration.</p><p>One phenomenon commonly observed in RFPs is mode walllocking. The localized nature of these phase- and wall lockedstructures results in localized power loads on the wall whichare detrimental for confinement. A detailed study of the walllocked mode phenomenon is performed based on magneticmeasurements from three RFP devices. The two possiblemechanisms for wall locking are investigated. Locking as aresult of tearing modes interacting with a static field errorand locking due to the presence of a non-ideal boundary. Thecharacteristics of the wall locked mode are qualitativelysimilar in a device with a conducting shell system (TPE-RX)compared to a device with a resistive shell (Extrap T2). Atheoretical model is used for evaluating the threshold valuesfor wall locking due to eddy currents in the vacuum vessel inthese devices. A good correlation with experiment is observedfor the conducting shell device.</p><p>The possibility of succesfully sustaining discharges in aresistive shell RFP is introduced in the recently rebuiltdevice Extrap T2R. Fast spontaneous mode rotation is observed,resulting in low magnetic fluctuations, low loop voltage andimproved confinement. Wall locking is rarely observed. The lowtearingmode amplitudes allow for the theoretically predictedinternal nonresonant on-axis resistive wall modes to beobserved. These modes have not previously been distinguisheddue to the formation of wall locked modes. The internal andexternal nonresonant resistive wall modes grow on the timescale of the shell penetration time. These growth rates dependon the RFP equilibrium. The internal nonresonant resistive wallmodes dominate in Extrap T2R, especially for shallow reverseddischarges. The external nonresonant modes grow solely in deepreversal discharges.</p><p><b>Keywords</b>Nuclear fusion, reversed field pinch, resistiveinstabilities, wall locked modes, tearing modes, resistiveshell modes, field errors, EXTRAP-T2, EXTRAP-T2R, TPE-RX</p>

La tres faible conductivite electronique de l' hydroxyde de nickel utilise a l' electrode positive de l' accumulateur nickel - cadmium rend necessaire l' ajout d' un conducteur electronique. Actuellement, les fabricants d' accumulateurs ont recours a l' addition de phases cobaltees pour ameliorer les performances de l' electrode de nickel. Ce travail est donc consacre a l' etude des differentes especes chimiques et des mecanismes impliques lors de l' utilisation d' un oxyde de cobalt du type CoO comme conducteur electronique ajoute a l' electrode positive d' une batterie nickel-cadmium. La premiere partie est relative a la caracterisation physico-chimique des phases responsables de la conduction electronique au sein de l' electrode de nickel (oxyhydroxydes de cobalt) : etude structurale par la methode de Rietveld, determination de la formulation chimique et analyse des proprietes de conduction electronique. Une etude electrochimique de ces materiaux a egalement ete effectuee a l' aide des techniques de cyclages voltamperotrique et galvanostatique. La seconde partie est relative a l' etude des mecanismes reactionnels conduisant du monoxyde de cobalt a l' oxyhydroxyde de cobalt.

No description available.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O clareamento dental se tornou um dos tratamentos estéticos mais realizados nos consultórios odontológicos, devido à simplicidade técnica e popularização através da mídia. Consiste na utilização de géis à base de peróxido de carbamida, peróxido de hidrogénio e, em uma menor escala, de perborato de sódio, com intuito de oxidar moléculas responsáveis pela pigmentação da estrutura dentária. Apesar da grande quantidade de estudos sobre o tema, não se sabe os efeitos do uso excessivo desses agentes sobre a estrutura dentária. O objetivo deste estudo foi avaliar os efeitos sobre a rugosidade superficial e conteúdo mineral do esmalte dental humano submetido a regimes de sobreclareamento associados ao uso de géis clareadores caseiros: peróxido de carbamida 10% (Opalescence PF Regular 10%, Ultradent do Brasil Produtos Odontológicos Ltda., Indaiatuba, São Paulo), peróxido de hidrogênio 9,5% (DayWhite 9,5%, Discus, LLC Culver City, EUA), bem como tiras clareadoras (Oral-B WhiteStrips, Anderson Packaging, Rockford, Estados Unidos). Quatro fragmentos de esmalte obtidos a partir de cinco dentes foram submetidos a um diferente tratamento: Grupo I - armazenamento em saliva artificial por oito semanas; Grupo 2 oito semanas de tratamento com gel de peróxido de carbamida 10% por 6 horas diárias; Grupo 3 oito semanas de tratamento com gel de peróxido de hidrogênio 9,5% com duas aplicações diárias de 30 minutos; Grupo 4 oito semanas de tratamento com tiras clareadoras duas aplicações diárias de 30 minutos. A alteração no conteúdo mineral foi avaliada semanalmente em seis pontos de cada fragmento devidamente identificados através de um sistema de coordenadas (X, Y e Z) utilizando-se a técnica de fluorescência de raios X (Artax 200). Alterações na rugosidade superficial das amostras também foram avaliadas através de um rugosímetro 3D (FormTalysurf 60, Taylor Leicester, Reino Unido). Apenas o grupo 3 apresentou diferenças estatísticas significativas com relação aos níveis de rugosidade (p<0,05), porém não consideradas como clinicamente significativos. Para os demais tratamentos e intervalos propostos, não foram encontradas diferenças estatisticamente significativas (p>0,05). Desse modo, não houve alterações compatíveis com um processo de desmineralização ou aumento real da rugosidade da superfície. Nas condições desse estudo in vitro os géis clareadores caseiros foram considerados seguros. São necessários novos estudos in situ e in vitro que analisem os efeitos de regimes de sobreclareamento quando em condições de somatório de desafios intra-orais. / Tooth bleaching has become one of the most performed cosmetic treatments in dental offices because of the technical simplicity and popularization through media. It is based in the use of gels containing carbamide peroxide, hydrogen peroxide, and sodium perborate to oxidize molecules responsible for pigmentation of the tooth structure. Despite the large amount of studies of the topic, the effects of overuse of these agents on tooth structure are not established. The aim of this study was to evaluate the effects on the surface roughness and mineral content of the enamel submitted to overbleaching protocols associated with the use of home bleaching gels: 10 % carbamide peroxide (Opalescence PF 10 % Regular, Ultradent Dental Products of Brazil Ltd., Indaiatuba, São Paulo), hydrogen peroxide 9.5% (DayWhite 9.5%, Discus, LLC Culver City, EUA), as well as bleaching strips (Oral- B Whitestrips, Anderson Packaging, Rockford, USA). Four enamel fragments obtained from five teeth were subjected to different treatments: Group I - storage in artificial saliva for eight weeks; Group 2 eight-week exposure to 10% carbamide peroxide gel for 6 hours daily; Group 3 eight-week exposure to 9,5% hydrogen peroxide gel - two 30-minute application, Group 4 eight-week exposure to bleaching strips - twice daily for 30 minutes. The change in mineral content was assessed weekly with the analysis of six points in each fragment properly identified by a coordinate system (X, Y and Z) using the technique of X-ray fluorescence (Artax 200). Changes in surface roughness of the samples were also evaluated using a 3D perfilometer (FormTalysurf 60, Taylor Leicester, UK). Only group 3 showed statistically significant differences for roughness (p <0.05), but this is not considered as clinically important. For other proposed treatments and intervals, there were no statistically significant differences for any of the treatments tested in any of the proposed ranges (p > 0,05). There was no sign of demineralization process. Under these in vitro conditions, home bleaching gels were considered safe. Further in situ and in vivo studies are necessary to examine the effects of overbleaching protocols with all other intra-oral challenges.

Cette thèse présente une étude expérimentale des mécanismes contrôlant la réponse macroscopique d’une interface sable-pieu sous sollicitations axiales monotones et cycliques. Une approche innovante associant la tomographie rayons X à des outils avancés d’analyses d’images en trois dimensions (3D) est utilisée dans le but d’extraire des informations à différentes échelles, notamment à l’échelle micro. L’analyse quantitative du comportement individuel des grains situés au voisinage du pieu fournit une collection de données 3D qui pourraient être utilisées pour la validation de modèles numériques ou théoriques.Une série de tests est réalisée sur un pieu instrumenté à pointe conique installé par vérinage monotone dans un échantillon dense de sable calcaire. Après l’installation, le pieu est soumis à un grand nombre de cycles axiaux contrôlés en déplacements (jusqu’à 2000 cycles), à contraintes constantes. Ces essais ont été conduits dans une mini chambre de calibration qui permet d’acquérir des tomographies rayons X à haute résolution après différentes étapes de chargement. Il est admis que le dispositif expérimental n’est pas représentatif des conditions d’essais sur pieux in-situ pour les raisons principales suivantes : le ratio entre le diamètre de la chambre le diamètre du pieu et le ratio entre le diamètre du pieu et la taille moyenne des grains sont bien inférieurs aux ratios recommandés dans la littérature afin de limiter les effets d’échelle. Par conséquent, les résultats obtenus dans ce travail ne peuvent et ne doivent pas être directement extrapolés pour le design de pieux réels. Cependant, un tel dispositif permet de reproduire qualitativement des tendances similaires à celles observées à l’échelle macro sur des essais à grande échelle et d’observer des mécanismes se déroulant à l’échelle micro.Les images 3D obtenues par reconstruction des tomographies rayons X sont utilisées afin d’identifier et de suivre l’évolution des grains individuels. Le champ cinématique complet en 3D est mesuré grâce à un code de corrélation d’images numériques 3D (DIC), « TomoWarp2 ». Des outils de traitement d’image sont également employés pour suivre les changements de porosité et la production de fines par broyage des grains à l’interface.Pendant la mise en place du pieu, plusieurs zones où les déplacements se concentrent sont identifiées. Une recirculation des grains le long du fût du pieu est mise en évidence. Globalement, le sable a un comportement dilatant à l’exception d’une fine couche (épaisseur d’environ 3 à 4·D50) autour du pieu où les fines sont produites. Pendant les cycles, la réponse macroscopique de l’interface montre une évolution en deux phases, avec une augmentation non négligeable de la résistance du fût dans la seconde phase. Pour ces deux phases, la mesure de la cinématique granulaire révèle un comportement du sol différent associé à une densification importante à l’interface. Dans la première phase, le sol se contracte radialement dans une zone de 4·D50 d’épaisseur. Ce phénomène est certainement dû au réarrangement granulaire mesuré par DIC. Dans la seconde phase, les grains de sables se déplacent difficilement et la densité à l’interface atteint un seuil pour lequel le frottement sur le pieu augmente de manière significative. / This doctoral work presents an experimental investigation into the mechanisms governing the macroscopic response of sand-pile interface during monotonic installation and subsequent axial cyclic loading. An innovative approach combining x-ray tomography and advanced image analysis tools is employed to extract information at different scales, including the micro-scale. A quantitative analysis of the behavior of individual sand grains in the vicinity of the pile offers valuable three-dimensional (3D) data set against which theoretical or numerical approaches could be tested.A series of tests is run on an instrumented close-ended conical model pile installed by monotonic jacking in a dense calcareous sand sample. Following the installation, the model pile is submitted to a large number of axial displacement-controlled loading cycles (a few thousands cycles) under constant normal stress. The tests are performed in a mini-calibration chamber that allows the acquisition of high resolution x-ray images at different stages of the loading. The chamber is admittedly not representative of field pile testing conditions for the main following reasons: the calibration chamber-to-pile diameter ratio and the sand particle-to-pile diameter ratio are far below the ratios recommended in the literature to limit scale effects on the interface response. Consequently, the results presented in this work can not, and should not, be directly extrapolated to field pile design. Yet, such a setup is able to reproduce qualitatively trends that are similar to those obtained at the macro-scale on large-scale experiments and allows the observation of full-field mechanisms taking place at the micro-scale.3D images resulting from the reconstruction of the x-ray scans are used to identify and follow the evolution of individual sand grains. Full-kinematics are measured thanks to a 3D Digital image Correlation (DIC) code, “TomoWarp2”. Image processing tools are also employed to measure local porosity changes and the production of fines by grain crushing at the interface.During pile installation, different zones where grains displacements concentrate are identified. A recirculation of the grains alongside the pile is also observed. Globally, the sand mass exhibits a dilative behavior except within a relatively thin layer (about 3 to 4·D50 thickness) around the model pile where grain crushing occurs. During subsequent loading cycles, the macroscopic response of sand-pile interface shows a two-phases evolution, with a non negligible increase of shaft resistance in the latter phase. For these two phases, the measurement of grain kinematics reveals a different behavior of the sand mass associated with a significant densification at the interface. In the first phase, the sand mass contracts radially within a region of thickness 4·D50. This mechanism is likely due to inter-granular rearrangement as measure by DIC. In the second phase, sand grains hardly move and the sand mass reaches a threshold density for which the friction on the shaft starts to increase substantially.