Pt-aluminide (PtAl) coatings form an integral part of thermal barrier coating (TBC) systems that are applied on Ni-based superalloy components operating in the hot sections of gas turbine engines. These coatings serve as a bond coat between the superalloy substrate and the ceramic yttrium stabilized zirconia (YSZ) coating in the TBC system and provide oxidation resistance to the superalloy component during service at high temperatures. The PtAl coatings are formed by the diffusion aluminizing process and form an integral part of the superalloy substrate. The microstructure of the PtAl coatings is heavily graded in composition as well as phase constitution. The matrix phase of the coating is constituted of the B2-NiAl phase. Pt, in the coating, is present as a separate PtAl2 phase as well as in solid solution in B2-NiAl. The oxidation resistance of the PtAl bond coat is derived from the B2-NiAl phase. At high temperatures, Al from the B2-NiAl phase forms a regenerative layer of alumina on the coating surface which, thereby, lowers the overall oxidation rate of the superalloy substrate. The presence of Pt is beneficial in improving the adherence of the alumina scale to the surface and thereby enhancing the oxidation resistance of the coating. However, despite its excellent oxidation resistance, the B2-NiAl being an intermetallic phase, renders the PtAl coating brittle and imparts it with a high brittle-to-ductile-transition-temperature (BDTT). The PtAl coating, therefore, remains prone to cracking during service. The penetration of these cracks into the substrate is known to degrade the strain tolerance of the components. Evaluation of the mechanical behavior of these coatings, therefore, becomes important from the point of views of scientific understanding as well as application of these coatings in gas turbine engine components. Studies on the mechanical behavior of coatings have been mostly carried on coated bulk superalloy specimens. However, since the coating is brittle and the superalloy substrate more ductile when compared to the coating, the results obtained from these studies may not be representative of the coating. Therefore, it is imperative that the mechanical behavior of the coating in stand-alone condition, i.e. the free-standing coating specimen without any substrate attached to it, be evaluated for ascertaining the true mechanical response of the coating. Study of stand-alone bond coats involves complex specimen preparation techniques and challenging testing procedures. Therefore, reports on the evaluation of mechanical properties of stand-alone coatings are limited in open literature. Further, no systematic effort has so far been made to examine important aspects such as the effect of temperature and strain rate on the tensile behavior of these coatings. The deformation mechanisms associated with these bond coats have also not been reported in the literature. In light of the above, the present research study aims at evaluating the tensile behavior of free-standing PtAl coatings by the micro-tensile testing technique. The micro-tensile testing method was chosen for property evaluation because of its inherent ability to generate uniform strain in the specimen while testing, which makes the results easy to interpret. Further, since the technique offers the feasibility to test the entire graded PtAl coating in-situ, the results remain representative of the coating. Using the above testing technique, the tensile behavior of the PtAl coating has been evaluated at various temperatures and strain rates. The effect of strain rate on the BDTT of the coating has been ascertained. Further, the effect of Pt content on the tensile behavior of these coatings has also been evaluated. Attempts have been made to identify the mechanisms associated with tensile deformation and fracture in these coatings. The thesis is divided into nine chapters. Chapter 1 presents a brief introduction on the operating environment in gas turbine engines and the materials that are used in the hot sections of gas turbine engines. The degradation mechanisms taking place in the superalloy in gas turbine environments and the need for application of coatings has also been highlighted. The basic architecture of a typical thermal barrier coating (TBC) system applied on gas turbine engine components has been presented. The constituents of the TBC system, i.e. the ceramic YSZ coating, MCrAlY overlay as well as diffusion aluminide bond coats and, the various techniques adopted for the deposition of these coatings have been described in brief. Chapter 2 presents an overview of the literature relevant to this study. This chapter is divided into four sub-chapters. The formation of diffusion aluminide coatings on Ni-based superalloys has been described in the first sub-chapter. Emphasis has been laid on pack cementation process for the formation of the coatings. The fundamentals of pack aluminizing process, including the thermodynamic and kinetic aspects, have been mentioned in brief. The microstructural aspects of high activity and low activity plain aluminide and Pt-aluminide coatings have also been illustrated. The techniques applied for the mechanical testing of bond coats have been discussed in the second sub-chapter. The macro-scale testing techniques have been mentioned in brief. The small scale testing methods such as indentation, bend tests and micro-tensile testing have also been discussed in the context of evaluation of mechanical properties of bond coats. Since the matrix in the aluminide bond coats is constituted of the B2-NiAl phase, a description of the crystal structure and deformation characteristics of this phase including the flow behavior, ductility and fracture behavior has been mentioned in the third sub-chapter. In the fourth sub-chapter, reported literature on the tensile behavior and brittle-to-ductile-transition-temperature (BDTT) of diffusion aluminide bond coats has been discussed. In Chapter 3, details on experiments carried out for the formation of various coatings used in the present study and, their microstructural characterization, are provided. The method for extraction of stand-alone coating specimens and their testing is discussed. The microstructure and composition of the various coatings used in the present study are discussed in detail in Chapter 4. Unlike in case of bulk tensile testing, for which standards on the design of specimens exist, there are no standards available for the design of micro-tensile specimens. Therefore, as part of the present research work, a finite element method (FEM)-based study was carried out for ascertaining the dimensions of the specimens. The simulation studies predicted that failure of the specimens within the gage length can be ensured only when certain correlations between the dimensional parameters are satisfied. Further, the predictions from the simulation study were validated experimentally by carrying out actual testing of specimens of various dimensions. Details on the above mentioned aspects of specimen design are provided in Chapter 5. The PtAl coatings undergo brittle fracture at lower temperatures while ductile fracture occurs at higher temperatures. Further, the coatings exhibit a scatter in the yielding behavior at temperatures in the vicinity of BDTT. Therefore, the BDTT, determined as the temperature at which yielding is first observed in the stress-strain curves, may not be representative of the PtAl coatings. In Chapter 6, a method for the precise determination of BDTT of aluminide bond coats, based on the variation in the plastic strain to fracture with temperature, has been demonstrated. The BDTT determined by the above method correlated well with the variation in fracture surface features of the coating and was found representative of these coatings. In Chapter 7, the effect of temperature and strain rate on the tensile properties of a PtAl bond coat has been evaluated. The temperature and strain rate was varied between room temperature (RT)-1100°C and 10-5 s-1-10-1 s-1, respectively. The effect of strain rate on the BDTT of the PtAl bond coat has been examined. Further, the variation in fracture surface features and mechanism of fracture with temperature and strain rate are illustrated. The micro-mechanisms of deformation and fracture in the coating at different temperature regimes have also been discussed. The coating exhibited brittle-to-ductile transition with increase in temperature at all strain rates. The BDTT was strain rate sensitive and increased significantly at higher strain rates. Above BDTT, YS and UTS of the coating decreased and its ductility increased with increase in the test temperature at all strain rates. Brittle behavior occurring in the coating at temperatures below the BDTT has been attributed to the lack of operative slip systems in the B2-NiAl phase of the coating. The onset of ductility in the coating in the vicinity of BDTT has been ascribed to generation of additional slip systems caused by climb of dislocations onto high index planes. The coating exhibited two distinct mechanisms for plastic deformation as the temperature was increased from BDTT to 1100°C. For temperatures in the range BDTT to about 100°C above it, deformation was controlled by dislocations overcoming the Peierls-Nabarro barrier. Above this temperature range, non-conservative motion of jogs by jog dragging mechanism controlled the deformation. The transition temperature for change of deformation mechanism also increased with increase in strain rate. For all strain rates, fracture in the coating at test temperatures below the BDTT, occurred by initiation of cracks in the intermediate single phase B2-NiAl layer of the coating and subsequent inside-out propagation of the cracks across the coating thickness. Ductile fracture in the coating above the BDTT was associated with micro-void formation throughout the coating. The effect of Pt content on the tensile behavior of PtAl coating, evaluated at various temperatures ranging from room temperature (RT) to 1100°C and at a nominal strain rate of 10-3 s-1, is presented in Chapter 8. Irrespective of Pt content in the coating, the variation in tensile behavior of the coating with temperature remained similar. At temperatures below BDTT, the coatings exhibited linear stress-strain response (brittle behavior) while yielding (ductile behavior) was observed at temperatures above BDTT. At any given temperature, the elastic modulus decreased while the strength increased with increase in Pt content in the coating. On the other hand, the ductility of the coating remained unaffected with Pt content. The BDTT of the coating also increased with increase in Pt content in the coating. Addition of Pt did not affect the fracture mechanism in the coating. Fracture at temperatures below BDTT was caused by nucleation of cracks at the intermediate layer and their subsequent inside-out propagation. At high temperatures, fracture occurred in a ductile manner comprising void formation, void linkage and subsequent joining with cracks. The deformation sub-structure of the coating did not get affected with Pt incorporation. Short straight dislocations were observed at temperatures below BDTT, while, curved dislocations marked by jog formation were observed at temperatures above BDTT. The factors controlling fracture stress and strength in the PtAl coatings at various temperatures have also been assessed. The overall summary of the present research study and recommendations for future studies are presented in the last chapter, i.e. Chapter 9.

Les systèmes intégrables quantiques ont des propriétés mathématiques qui permettent la détermination exacte de leur spectre énergétique. A partir des équations de Bethe, je présente la relation de Baxter «T-Q». Celle-ci est à l'origine des deux approches que j'ai prioritairement employé dans mes recherches, les deux basés sur des équations intégrales non linéaires, celui de l'ansatz de Bethe thermo- dynamique et celui des équations de Klümper-Batchelor-Pearce-Destri-de Vega. Je montre le chemin qui permet de dériver les équations à partir de certain modèles sur réseau. J'évalue les limites infrarouge et ultraviolet et je discute l'approche numérique. D'autres constantes de mouvement peuvent être établies, ce qui permet un certain contrôle sur les vecteurs propres. Enfin, le modèle d'Hubbard, qui décrit des électrons interagissants sur un réseau, est présenté en relation à la théorie de jauge supersymétrique N = 4. Dans la deuxième partie, je présente un modèle d'évolution darwinienne basé sur les machines de Turing. En faisant évoluer une population d'algorithmes, je peut décrire certains aspects de l'évolution biologique, notamment la transformation entre parties codantes et non-codantes dans un génome ou la présence d'un seuil d'erreur. L'assemblage des protéines oligomériques est un aspect important qui intéresse la majorité des protéines dans une cellule. Le projet «Gemini» que j'ai contribué à créer a pour finalité d'explorer les donnés structuraux des interfaces des dites protéines pour différentier le rôle des acides aminés et déterminer la présence de patterns typiques de certaines géométries.

<p>Uvod: Nespecifičnost kliničke slike sepse, velike individualne razlike u odgovoru organizma na infekciju kao i neophodnost adekvatne inicijalne procene težine kliničke slike, toka i ishoda bolesti, čine istraživanja biomarkera koji bi doprineli pravovremenom postavljanju dijagnoze i adekvatnoj prognozi bolesti izuzetno značajnim. Do sada je ispitivano preko 200 biomarkera od kojih ni jedan nije pokazao zadovoljavajuću senzitivnost i specifičnost. Uloga B limfocita u patogenezi sepse pri tome je nedovoljno istražena. Članovi superfamilije tumor-nekrozis faktora alfa: A proliferation inducing ligand (APRIL), Bcell activating factor (BAFF) i solubilni transmembrane activator and calcium modulator cyclophilin ligand interactor (sTACI) su citokini koji imaju ključnu ulogu u homeostazi B limfocita. Cilj istraživanja bio je da se ispita dijagnostički i prognostički značaj citokina članova superfamilije tumor nekrozis faktora alfa (APRIL, BAFF, sTACI) za procenu težine kliničke slike, razvoja multiorganske disfunkcije (MODS) u prvih 48h hospitalizacije i letalnog ishoda sepse. Ispitanici i metode: Istraživanjem je obuhvaćeno 150 obolelih od sepse lečenih na Klinici za infektivne bolesti i Odeljenju anestezije i reanimacije Kliničkog centra Vojvodine i 30 zdravih dobrovljnih davalaca krvi. Kod svih bolesnika evidentirani su demografski i ostali podaci iz istorije bolesti kao i laboratorijske analize u okviru rutinske dijagnostike sepse. Iz dodatnih 5ml venske krvi svim ispitanicima određene su koncentracije APRIL-a, BAFF-a, sTACI-ja ELISA metodom komercijalnim testovima proizvođača R&amp;D Systems. Rezultati pokazuju da su koncentracije sva tri citokina (APRIL, BAFF i sTACI) statistički značajno povi&scaron;ene kod obolelih od sepse u odnosu na zdravu populaciju (p&lt;0.001), pri čemu APRIL pokazuje najveću senzitinvost (99%) i specifičnost (97%). Najveći dijagnostički značaj BAFF-a ogleda se u sposobnosti distinkcije između sepsi uzrokovanih Gram pozitivnim i Gram negativnim bakterijama (p=0,03). U predikciji razvoja MODS-a i letalnog ishoda sepse multivarijantnom regresionom analizom kao nezavisni prediktori pokazali su se jedino antiinflamatorni biomarker sTACI receptor i klinička procena pacijenta iskazana kroz APACHE II i SOFA skor. Senzitivnost i specifilnost sTACI receptora u predikciji razvoja MODS-a i letalnog ishoda daleko nadma&scaron;uje do sada rutinski kori&scaron;ćen prokalcitonin. Zaključak: Dobijeni rezultati ukazuju na to da su citokini koji učestvuju u regulaciji funkcije B limfocita značajni dijagnostički i prognostički parametri u sepsi. Predominacija antiinflamatornog odgovora na koju ukazuju povi&scaron;ene koncentracije sTACI receptora pokazala se pored APACHE II i SOFA skora kao jedini nezavisni prediktor razvoja MODS-a i letalnog ishoda septičnih bolesnika. Neophodna su dalja istraživanja u pravcu određivanja momenta kada u imunskom odgovoru organizam prelazi iz stanja dominacije proniflamatornog u dominaciju antiinflamatornog odgovora radi pravovremenog reagovanja imunomodulatornom terapijom.</p> / <p>Introduction: The nonspecific clinical presentation of sepsis and great individual response variations, as well as huge significance of adequate early prognosis of its clinical course and outcome made sepsis biomarkers research extremely significant. The properties of more than 200 biomarkers have been evaluated for prognostic value, but none have adequate specificity and sensitivity. The role of the B cells in sepsis pathogenesis also remains unclear. Tumor necrosis factor alpha (TNF-&alpha;) superfamily members: A proliferation inducing ligand (APRIL), Bcell activating factor (BAFF) and soluble transmembrane activator and calcium modulator cyclophilin ligand interactor (sTACI) are key factors in B cell biology. The aim of the study was to evaluate the diagnostic and prognostic significance of determining the concentrations of tumor necrosis factor alpha superfamily members for the prediction of MODS development in the first 48h of hospitalization as well as outcome prediction.<br />Subjects and methods: The study included 150 patients suffering from sepsis treated at the Clinic for infectious diseases and Department for anesthesiology and reanimatology of the Clinical center of Vojvodina, and 30 healthy volunteer blood donors. The demographic and other data regarding routine blood analysis performed during sepsis treatment of the patients has been acquired from their hospitalization documentation. Additional 5 ml of venous blood was taken from the patients and the concentrations of APRIL, BAFF and sTACI have been determined using the ELISA method by using R&amp;D Systems commercial kit&rsquo;s. Results: There is a statistically significant difference in concentrations of APRIL, BAFF and sTACI between healthy blood donors and septic patients (p&lt;0.001). APRIL showed the highest sensitivity (99%) and specificity (97%) in distinguishing sepsis from healthy subjects. BAFF showed statistically significant higher concentrations in Gram positive than in Gram negative sepsis (p=0,03). In the multivariate logistic regression analysis, only anti-inflammatory cytokine sTACI and APACHE II or SOFA score remained significant predictors of MODS and lethal outcome. sTACI showed greater sensitivity and specificity for MODS and outcome prediction then the widely used procalcitonin.&nbsp; Conclusions: The concentrations of TNF superfamily members, the main regulators of B cell function, have a significant diagnostic and prognostic value in predicting sepsis course and outcome. The predomination of the anti-inflammatory response, as being pointed out by elevated concentrations of sTACI receptors, has proved to be the only independent predictor, besides APACHE II and SOFA score, in MODS and lethal outcome development in sepsis. Further research is needed in order to accurately determine the exact moment when the immunological response shifts from the predominance of the pro-inflammatory response to the predominance of the anti-inflammatory response, so as to ensure the timely application of therapy that modulates the immunological response.</p>

Le travail présenté dans ce manuscrit concerne la fabrication de biomatériaux poreux à base d’acide polylactique pour les tissus conjonctifs et calcifiés en utilisant des procédés de chimie verte. Le but de cette thèse est de corréler l’influence de certains paramètres de procédés à la structure morphologique et les propriétés des mousses générées. Nous avons étudié, d’un côté, les effets de mélange d’acide hyaluronique et d’acides polylactiques afin d’améliorer les propriétés d’adhésion de ces biomatériaux. Nos résultats montrent bien une augmentation de l’énergie d’adhésion mais aussi une diminution de la taille équivalente des pores et de la porosité des biomatériaux poreux après moussage par les fluides supercritiques. D’un autre côté, nous avons étudié les effets de mélanges des triphosphates de calcium et d’acides polylactiques en tant que substitut osseux. L’influence d’un ajout de cires en tant qu’agent porogène a été discutée et les méthodes de préparation des pastilles (voie sèche ou humide) ont été analysées. Dans cette optique la fabrication semi-industrielle de biomatériaux poreux a été testée en fixant les paramètres du procédé de moussage par le CO2 supercritique (pression, température et temps de saturation, vitesse de dépressurisation) et nous avons contrôlé les mousses de formulations optimisées en termes de porosité et de distribution des pores. En conclusion, ce travail rend possible d’adapter les paramètres des procédés de CO2 supercritique et de co-broyage aux propriétés des biomatériaux poreux. En perspective, cette ouvre la voie à de nouvelles recherches à la fois dans les domaines des modèles 3D tumoraux et d’ingénierie tissulaire. / The work presented in this manuscript concerns the production of scaffolds based polylactides for connective tissues and bone regeneration by adapting green technology. The aim of this thesis was to correlate the influence of different process parameters on the morphological structures and properties of the scaffold generated. On one hand, we studied effect of the blending of hyaluronic acid and polylactides to enhance the surface adhesion properties of scaffolds. Our results relate to an increase in surface properties but a decrease of equivalent pore size and porosity after foaming scaffolds by supercritical process. Calcium Tri-Phosphate On other hand, we studied the effect of the blending of calcium tri-phosphates and polylactides as bone substitute. Influence of adding wax as porogen agent has been discussed and a comparison between wet and dry methods to generate scaffolds has been analyzed. For this purpose, semi-industrial fabrication of porous biomaterials has been tested by blocking supercritical CO2 parameters (saturation pressure, temperature and time, depressurization rate) and you have control the optimized formulation composite scaffold, in term of porosity and distribution of pores. In conclusion, this work made it possible to adapt the process parameters of supercritical CO2 and co-grinding at the properties of scaffolds. In perspective, this research opens new development ways in scaffolds, in both domains of 3D tumoral model and tissue engineering.

No description available.

Neste trabalho apresentamos um estudo das reações de spallation a energias interme- diárias em núcleos actinídeos e pré-actinídeos. Para esta finalidade foi utilizado o modelo de Monte Carlo CRISP (Colaboração Rio-São Paulo), que neste estudo foi importante na reprodução da distribuição de massa de produtos residuais e as seções de choque de fissão e espalação. Estes observáveis são importantes para o estudo de Reatores Hibridos ADS considerado como dispositivos promissores para a transmutação de resíduos nucle- ares. Os modelos físicos necessários para uma correta simulação de dados experimentais foram já implementadas no CRISP, como o modelo de evaporação para emissão de par- tículas descrito por Weisskopf de 1937, e para fissão o clássico modelo de Bohr/Wheeler de 1939. Para a obtenção da distribuição dos fragmentos de massa de fissão o CRISP conta também com um modelo baseado na parametrização multimodal de fissão, que si- mula os processos de fissão simétrica e assimétrica predominantes em altas e baixas ener- gias, respectivamente. Os resultados obtidos do CRISP depois da aplicação dos modelos mencionados, foram os rendimentos de massa dos fragmentos residuais, os quais foram analisadas para o cálculo da seção de choque de fissão e espalação mediante uma fórmula implementada no modelo. Com o resultado se fez o gráfico da distribuição de massa para cada uma das reações analisadas. Uma das reações estudadas foi a reação induzida por fótons de Bremsstrahlung com energias máximas de 50 e 3500 MeV em um alvo de 181 Ta, calculando a distribuição de massa de fissão e espalação, mostrando bons resultados de acordo com os dados experimentais. Nas reações induzidas por prótons foram calcula- das as seções de choque de fissão e espalação assim como sua respectiva distribuição de massa dos produtos residuais. Neste caso estudamos duas reações, sendo: a reação p (1 GeV) + 208 Pb, e a reação de p (660 MeV) + 238 U. Para a primeira reação com chumbo os resultados do CRISP foram comparados com dados experimentais, e também com os resultados obtidos do modelo MCNPX-Bertini do trabalho de Baylac-Domengetroy de 2003, que simulou a mesma reação com chumbo. Obtendo-se melhores resultados com o CRISP mas com uma superestimação de dados no final da distribuição calculada. No caso do urânio, foi necessário usar a chamada fissão superassimétrica porque a distribuição de massa experimental é mais complexa e o modelo multimodal clássico não é suficiente para sua correta simulação. Foi também estudado as reações induzidas por dêuterons usando o modelo CRISP, mostrando os resultados da distribuição de massa para 197 Au e 208 Pb com algumas limitações do modelo para este tipo de reações. / In this work we present a study of the spallation reactions by intermediate energies in actinide and pre-actinide nuclei. For this purpose we used the Monte Carlo model CRISP (Rio-São Paulo Collaboration), for our study was important in the reproduction of the mass distribution of waste products and the total fission and spallation cross secti- ons. These observables are important for the study of Accelerator Driven System Reac- tors (ADS) considered as promising devices for the transmutation of nuclear waste. The physical models needed for a correct simulation of experimental data were already imple- mented in CRISP, such as the evaporation model for emission of particles described by Weisskopf in 1937, and the classical Bohr/Wheeler model in 1939, for fission. To obtain the fragment mass distribution for fission, CRISP has a model based on multimodal fis- sion parameter, which simulates the processes called symmetric and asymmetric fission that are predominant at high and low energies respectively. The CRISP results, obtai- ned after the application of the above mentioned models, were the mass yield of residual fragments, which were analyzed to calculate the fission and spallation cross section using a formula that was implemented in the CRISP model. With these result was obtained the mass distribution for each reaction analyzed. One of the reactions studied was a re- action induced by Bremsstrahlung photons with endpoint energies of 50 MeV and 3500 in a target 181 Ta, calculating the fission and spallation mass distribution, showing good results according the experimental data. In the reactions induced by protons were cal- culated fission and spallation cross sections as well as their respective mass distribution of the residual products. In this case we study two reactions, as follows: p (1 GeV) + 208 , and p (660 MeV) + 238 U. For the first reaction with lead, the results of CRISP were compared with experimental data and with results obtained of MCNPX-Bertini model of Baylac-Domengetroy work in 2003, simulated the same reaction with lead. Obtaining better results with CRISP, but with data-overestimated at the end of calculated distribu- tion. For uranium it was necessary to use the called superasymmetric fission, because the experimental mass distribution is more complicated and the classical model is not suffi- cient for a correct simulation. Has been also studied the reactions induced by deuterons using the CRISP model, showing the mass distribution

The goal of this project is to study novel nanoscale excitation volumes, sensitive enoughto study individual chromophores and go on to study new and exciting self assemblyapproaches to this problem. Small excitation volumes may be engineered using light con-finement inside apertures in metal films. These apertures enhance fluorescence emissionrates, quantum yields, decrease fluorescence quenching, enable higher signal-to-noiseratios and allow higher concentration single chromophore fluorescence, to be studied byrestricting this excitation volume. Excitation volumes are reported on using the chro-mophore's fluorescence by utilising fluorescence correlation spectroscopy, which monitorsfluctuations in fluorescence intensity. From the correlation in time, we can find the res-idence time, the number of chromophores, the volume in which they are diffusing andtherefore the fluorescence emission efficiency. Fluorescence properties are a probe ofthe local environment, a particularly powerful tool due to the high brightness (quantumyield) fluorescent dyes and sensitive photo-detection equipment both of which are readilyavailable, (such as avalanche photodiodes and photomultiplier tubes). Novel materialscombining the properties of conducting and non-conducting materials at scales muchsmaller than the incident wavelength are known as meta-materials. These allow combi-nations of properties not usually possible in natural materials at optical frequencies. Theproperties reported so far include; negative refraction, negative phase velocity, fluorescenceemission enhancement, lensing and therefore light confinement has also been proposed tobe possible. Instead of expensive and slow lithography methods many of these materialsmay be fabricated with self assembly techniques, which are truly nanoscopic and otherwiseinaccessible with even the most sophisticated equipment. It was found that nanoscaled volumes from ZMW and HMMs based on NW arrays wereall inefficient at enhancing fluorescence. The primary cause was the reduced fluorescencelifetime reducing the fluorescence efficiency, which runs contrary to some commentatorsin the literature. NW based lensing was found to possible in the blue region of the opticalspectrum in a HMM, without the background fluorescence normally associated with a PAAtemplate. This was achieved using a pseudo-ordered array of relatively large nanowireswith a period just smaller than lambda / 2 which minimised losses. Nanowires in the traditionalregime lambda / 10 produced significant scattering and lead to diffraction, such that they werewholly unsuitable for an optical lensing application.

Les travaux de cette thèse visent à apporter des éléments de solutions au problème de la durée de vie des systèmes pile à combustible (FCS – Fuel Cell System) de type à « membrane échangeuse de protons » (PEM – Proton Exchange Membrane) et se décline sur deux champs disciplinaires complémentaires :Une première approche vise à augmenter la durée de vie de celle-ci par la conception et la mise en œuvre d'une architecture de pronostic et de gestion de l'état de santé (PHM – Prognostics & Health Management). Les PEM-FCS, de par leur technologie, sont par essence des systèmes multi-physiques (électriques, fluidiques, électrochimiques, thermiques, mécaniques, etc.) et multi-échelles (de temps et d'espace) dont les comportements sont difficilement appréhendables. La nature non linéaire des phénomènes, le caractère réversible ou non des dégradations, et les interactions entre composants rendent effectivement difficile une étape de modélisation des défaillances. De plus, le manque d'homogénéité (actuel) dans le processus de fabrication rend difficile la caractérisation statistique de leur comportement. Le déploiement d'une solution PHM permettrait en effet d'anticiper et d'éviter les défaillances, d'évaluer l'état de santé, d'estimer le temps de vie résiduel du système, et finalement, d'envisager des actions de maîtrise (contrôle et/ou maintenance) pour assurer la continuité de fonctionnement. Une deuxième approche propose d'avoir recours à une hybridation passive de la PEMFC avec des super-condensateurs (UC – Ultra Capacitor) de façon à faire fonctionner la pile au plus proche de ses conditions opératoires optimales et ainsi, à minimiser l'impact du vieillissement. Les UCs apparaissent comme une source complémentaire à la PEMFC en raison de leur forte densité de puissance, de leur capacité de charge/décharge rapide, de leur réversibilité et de leur grande durée de vie. Si l'on prend l'exemple des véhicules à pile à combustible, l'association entre une PEMFC et des UCs peut être réalisée en utilisant un système hybride de type actif ou passif. Le comportement global du système dépend à la fois du choix de l'architecture et du positionnement de ces éléments en lien avec la charge électrique. Aujourd'hui, les recherches dans ce domaine se focalisent essentiellement sur la gestion d'énergie entre les sources et stockeurs embarqués ; et sur la définition et l'optimisation d'une interface électronique de puissance destinée à conditionner le flux d'énergie entre eux. Cependant, la présence de convertisseurs statiques augmente les sources de défaillances et pannes (défaillance des interrupteurs du convertisseur statique lui-même, impact des oscillations de courant haute fréquence sur le vieillissement de la pile), et augmente également les pertes énergétiques du système complet (même si le rendement du convertisseur statique est élevé, il dégrade néanmoins le bilan global). / This thesis work aims to provide solutions for the limited lifetime of Proton Exchange Membrane Fuel Cell Systems (PEM-FCS) based on two complementary disciplines:A first approach consists in increasing the lifetime of the PEM-FCS by designing and implementing a Prognostics & Health Management (PHM) architecture. The PEM-FCS are essentially multi-physical systems (electrical, fluid, electrochemical, thermal, mechanical, etc.) and multi-scale (time and space), thus its behaviors are hardly understandable. The nonlinear nature of phenomena, the reversibility or not of degradations and the interactions between components makes it quite difficult to have a failure modeling stage. Moreover, the lack of homogeneity (actual) in the manufacturing process makes it difficult for statistical characterization of their behavior. The deployment of a PHM solution would indeed anticipate and avoid failures, assess the state of health, estimate the Remaining Useful Lifetime (RUL) of the system and finally consider control actions (control and/or maintenance) to ensure operation continuity.A second approach proposes to use a passive hybridization of the PEMFC with Ultra Capacitors (UC) to operate the fuel cell closer to its optimum operating conditions and thereby minimize the impact of aging. The UC appear as an additional source to the PEMFC due to their high power density, their capacity to charge/discharge rapidly, their reversibility and their long life. If we take the example of fuel cell hybrid electrical vehicles, the association between a PEMFC and UC can be performed using a hybrid of active or passive type system. The overall behavior of the system depends on both, the choice of the architecture and the positioning of these elements in connection with the electric charge. Today, research in this area focuses mainly on energy management between the sources and embedded storage and the definition and optimization of a power electronic interface designated to adjust the flow of energy between them. However, the presence of power converters increases the source of faults and failures (failure of the switches of the power converter and the impact of high frequency current oscillations on the aging of the PEMFC), and also increases the energy losses of the entire system (even if the performance of the power converter is high, it nevertheless degrades the overall system).

La lecture automatique de plaques d’immatriculation de véhicule est considérée comme une approche de surveillance de masse. Elle permet, grâce à la détection /localisation ainsi que la reconnaissance optique, d’identifier un véhicule dans les images ou les séquences d’images. De nombreuses applications comme le suivi du trafic, la détection de véhicules volés, le télépéage ou la gestion d’entrée / sortie des parkings utilise ce procédé. Or malgré d’important progrès enregistré depuis l’apparition des premiers prototypes en 1979 accompagné d’un taux de reconnaissance parfois impressionnant, notamment grâce aux avancés en recherche scientifique et en technologie des capteurs, les contraintes imposés pour le bon fonctionnement de tels systèmes en limitent les portées. En effet, l’utilisation optimale des techniques de localisation et de reconnaissance de plaque d’immatriculation dans les scénarii opérationnels nécessite des conditions d’éclairage contrôlées ainsi qu’une limitation dans de la pose, de vitesse ou tout simplement de type de plaque. La lecture automatique de plaques d’immatriculation reste alors un problème de recherche ouvert. La contribution majeure de cette thèse est triple. D’abord une nouvelle approche robuste de localisation de plaque d’immatriculation dans des images ou des séquences d’images est proposée. Puis, l’amélioration de la qualité des plaques localisées est traitée par une adaptation de technique de super-résolution. Finalement, un modèle unifié de localisation et de super-résolution est proposé permettant de diminuer la complexité temporelle des deux approches combinées. / Automatic reading of vehicle license plates is considered an approach to mass surveillance. It allows, through the detection / localization and optical recognition to identify a vehicle in the images or video sequences. Many applications such as traffic monitoring, detection of stolen vehicles, the toll or the management of entrance/ exit parking uses this method. Yet in spite of important progress made since the appearance of the first prototype sin 1979, with a recognition rate sometimes impressive thanks to advanced science and sensor technology, the constraints imposed for the operation of such systems limit laid. Indeed, the optimal use of techniques for localizing and recognizing license plates in operational scenarios requiring controlled lighting conditions and a limitation of the pose, velocity, or simply type plate. Automatic reading of vehicle license plates then remains an open research problem. The major contribution of this thesis is threefold. First, a new approach to robust license plate localization in images or image sequences is proposed. Then, improving the quality of the plates is treated with a localized adaptation of super-resolution technique. Finally, a unified model of location and super-resolution is proposed to reduce the time complexity of both approaches combined.

Ce mémoire de thèse aborde la caractérisation expérimentale du transfert thermique à l’échelle nanométrique dans des matériaux compatibles avec les procédés de la micro-électronique. Pour cela deux techniques de caractérisation sont appliquées chacune à deux différents systèmes, le silicium mésoporeux irradié et les membranes de silicium suspendues. La première technique de caractérisation est la thermométrie micro-Raman. La puissance du laser chauffe l'échantillon exposé. La détermination de la conductivité thermique nécessite la modélisation de la source de chaleur par la méthode des éléments finis. Dans les cas considérés la modélisation de la source de chaleur repose sur différents paramètres qui doivent être soigneusement déterminés. La seconde technique de caractérisation est la microscopie à sonde locale (d’acronyme anglais SThM), basée sur le principe de la microscopie à force atomique (d’acronyme anglais AFM). Utilisée en mode actif, la sonde AFM est remplacée par une sonde résistive de type Wollaston qui est chauffée par effet Joule. Utilisée en mode AFM contact, cette technique permet une excitation thermique locale du matériau étudié. La détermination de la conductivité thermique nécessite l'analyse de la réponse thermique de la sonde au moyen d'échantillons d'étalonnage et également via la modélisation dans le cas des géométries complexes. L'effet de la position de la pointe sur le transfert de chaleur entre la pointe et l'échantillon est étudié. Une nouvelle méthode de découplage entre le transfert de chaleur entre la pointe et l'échantillon, respectivement à travers l'air et au contact, est proposée pour la détermination de la conductivité thermique des géométries complexes. Les résultats obtenus avec les deux techniques pour les échantillons de silicium mésoporeux irradiés à l’aide d’ions lourds dans le régime électronique sont en bon accord. Ils montrent la dégradation de la conductivité thermique du silicium mésoporeux suite à une augmentation dans la phase d’amorphe lorsque la dose d’irradiation croît. Les résultats obtenus sur les membranes de silicium suspendues montrent une réduction de la conductivité thermique de plus de 50 % par rapport au silicium massif. Lorsque la membrane est perforée périodiquement afin de réaliser une structure phononique de période inférieure à 100 nm, cette réduction est approximativement d’un ordre de grandeur. Un chapitre introduisant un matériau prometteur à base de silicium pour observer des effets de cohérence phononique conclut le manuscrit. / This PhD thesis deals with the experimental characterization of heat transfer at the nanoscale in materials compatible with microelectronic processes. Two characterization techniques are applied to two different systems, irradiated mesoporous silicon and suspended silicon membranes. The first characterization technique is micro-Raman thermometry. The laser power heats up the exposed sample. The determination of the thermal conductivity requires the modeling of the heat source using finite element simulations. The modeling of the heat source relies on different parameters that should be carefully determined. The second characterization technique is Scanning Thermal Microscopy (SThM), an Atomic Force Microscopy (AFM)-based technique. Operated in its active mode, the AFM probe is replaced by a resistive Wollaston probe that is heated by Joule heating. Used in AFM contact mode, this technique allows a local thermal excitation of the studied material. The determination of the thermal conductivity requires the analysis of the thermal response of the probe using calibration samples and modeling when dealing with complicated geometries. The effect of the tip position on heat transfer between the tip and the sample is studied. A new method decoupling the heat transfer between the tip and the sample, at the contact and through air, is proposed for determining the thermal conductivity of complicated geometries. The results obtained from the two techniques on irradiated mesoporous silicon samples using heavy ions in the electronic regime are in good agreement. They show a degradation of the thermal conductivity of mesoporous silicon due to the increase in the amorphous phase while increasing the ion fluence. The results obtained on suspended silicon membrane strips show a decrease in the thermal conductivity of more than 50 % in comparison to bulk silicon. When perforated into a phononic structure of sub-100 nm period, the membrane thermal conductivity is about one order of magnitude lower than the bulk. A chapter introducing a promising silicon-based material for the evidence of phonon coherence concludes the manuscript.