Des catalyseurs à base de métaux nobles (Pt, Pd, Ir, Ru et Rh) supportés (TiO2, ZrO2, CeO2 et CeZrO2) ont dans un premier temps été préparés. L'Oxydation en Voie Humide Catalytique de l'ammoniaque en présence de ces catalyseurs a alors été réalisée. Le platine est le métal le plus actif. L'iridium et le palladium sont les plus sélectifs en diazote. Le catalyseur Pt/TiO2 est le plus performant car il combine une très forte activité et une sélectivité en diazote peu éloignée de celles de l'iridium et du palladium. Une étude approfondie sur ce catalyseur (méthode de préparation, nature du précurseur métallique,…) a montré que seule la basicité de surface du catalyseur a un impact négatif sur la sélectivité en diazote. Les autres paramètres étudiés sont non significatifs. Le travail réalisé sur les conditions opératoires (PO2, T, mcatalyseur, pH et concentration d'ammoniaque) toujours en présence de Pt/TiO2 ont montré qu'il est nécessaire de contrôler la fonction oxydante et notamment le rapport nO2/nNH3. En effet, si la valeur de ce rapport est trop élevée (nO2/nNH3 >> 0,75) alors la sélectivité en diazote se dégrade fortement. Pour terminer, des catalyseurs bimétalliques PtIr/TiO2 et PtPd/TiO2 ont été préparés afin d'allier l'activité du platine à la sélectivité en diazote du palladium ou iridium. L'utilisation de ces catalyseurs s'avère peu intéressante car leur comportement est similaire à celui des mélanges mécaniques. De plus, la sélectivité en diazote est également dégradée pour nO2/nNH3 >> 0,75 avec ces catalyseurs / TiO2, ZrO2, CeO2 and CeZrO2 supported noble metal catalysts (Pt, Pd, Ir, Ru and Rh) have been in a first time prepared to be used in the Catalytic Wet Air Oxidation of ammonia. The first results show that platinum is the most active metal. Palladium and iridium are the most selective toward nitrogen. Pt/TiO2 is the most interesting catalyst because it combines a very strong activity and a selectivity toward nitrogen close to iridium and palladium. An in-depth study on this catalyst (preparation method, nature of the metallic precursor…) shows that the single parameter which has a negative impact on the selectivity toward nitrogen is the basicity of the catalyst surface. The work realized on the operating conditions (PO2, catalyst weight, pH and ammonia concentration) in the presence of Pt/TiO2 shows the necessity to control the oxidizing function and particularly the nO2/nNH3 ratio. Indeed, if the value of this ratio is too high (nO2/nNH3 >> 0,75) then the selectivity toward nitrogen degrades strongly. To end, PtIr/TiO2 and PtPd/TiO2 bimetallic catalysts have been prepared to combine the activity of the platinum and the selectivity of palladium/iridium to nitrogen. These catalysts are not interesting because their behaviour is similar to the mechanical mixtures. Furthermore, the selectivity toward nitrogen is also degraded for nO2/nNH3 >> 0,75 with these catalysts

One of the key issues of our society is to decrease energy demand. About 40 % of energy consumption in Europe is related to building operation, mostly for heating. The required thermal comfort is related mainly to temperature of air and temperature of surrounding surfaces. Especially in older buildings with low level of thermal insulation the inner surface of perimeter wall can be several degrees colder than air. In such case the perception of thermal comfort will be lowered also depending on the layout of the room. Other issue can be related to thermal radiation asymmetry. The amount of energy that is eradiated from a surface is driven by material property called emissivity. A surface with sufficiently low emissivity will became “thermal mirror”. It is possible to elaborate about intelligent thermal management of the internal space with usage of low-emissive surfaces; where thermal radiation can be suppressed or can be enhanced. This depends on the surface emissivity and its real temperature. Recently, growing interest about the low-emissive surfaces can be seen. They can represent reasonable complement to conventional insulation, but they have certain limits. Potentially, even higher energy savings can be reached with so called retro reflection. If the thermal radiation of an object is reflected back, its thermal loss will be lower. In such case it can be expected that equivalent thermal comfort can be reached even with lower overall temperature of the room. The aim of the work is study of material combinations with potential for utilization as low-emissive interior surfaces. Research has been conducted on low-emissive paints and low-emissive foils. Another part of the work is related to retro reflection of thermal radiation as a potential way to influence thermal comfort. The work shows, that energy saving up to 20% can be obtained.

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En vue d’effectuer des préparations sélectives de composés hétérocycliques, une étude de la synthèse et de la réactivité de 7-oxanorborna-2,5-diènes portant des groupes électroattracteurs différents sur les positions 2 et 3 a été réalisée. Ces composés sont des formes masquées de composés acétyléniques dissymétriques.Dans un premier temps, nous avons optimisé une nouvelle méthode de synthèse sélective d’acétylènedicarboxylates dissymétriques par mono-transestérification d’acétylènedicarboxylates de dialkyle symétriques avec des alcools en présence de la lipase de Candida rugosa. Cette méthode nous a permis d’obtenir les diesters dissymétriques avec de bons rendements et une haute sélectivité a priori inattendue.Dans un second temps, nous avons développé des synthèses régiosélectives de dérivés de l’acide 7-oxanorborna-2,5-diène-2,3-dicarboxylique selon deux stratégies. Dans une première approche, une réaction de Diels-Alder intramoléculaire entre un furane et un composé acétylénique reliés par une agrafe siliciée a été réalisée, suivie d’une coupure des liaisons Si-C. Cette cycloaddition [4+2] s’effectue uniquement en présence de MeAlCl2 avec des rendements moyens. Dans certains cas, la coupure des liaisons Si-C conduit aux diesters désirés. Dans une deuxième approche, une mono-saponification d’oxanorbornadiène-2,3-dicarboxylates de dialkyle a permis d’accéder régiosélectivement à des monoacides et des réactions de couplage avec des amines ou des alcools ont conduit sélectivement à des dérivés présentant deux groupes électroattracteurs différents.Dans une dernière partie, nous avons effectué la préparation régiosélective de 3-pyrrolines par cycloaddition [2+3] d’un ylure d’azométhine suivie d’une réaction de rétro-Diels-Alder à partir des 7-oxanorbornadiènes comportant deux groupes électroattracteurs différents. La préparation aisée de 3-pyrrolines condensées non décrites dans la littérature a été obtenue par formation inattendue d’un motif succinimide dans le cas des amidoesters.En conclusion, il apparaît que la présence du groupe éthyle en tête de pont des 7-oxanorborna-2,5-diènes semble suffisante pour contrôler la régiosélectivité de ces cycloadditions. / In order to selectively prepare heterocyclic compounds, a study of the synthesis and reactivity of 7-oxanorborna-2,5-dienes with different electron-withdrawing groups on the 2 and 3 positions was performed. These compounds are masked forms of unsymmetrical acetylenic compounds. At first, we have optimized a new method for the selective synthesis of unsymmetrical diesters by transesterification of symmetrical dialkyl acetylenedicarboxylates in the presence of Candida rugosa lipase. This unexpectedly highly selective method allowed us to obtain unsymmetrical acetylenedicarboxylates in good yields.In a second part, we have developed a regioselective synthesis of 7-oxanorborna-2,5-diene-2,3-dicarboxylic acid derivatives according to two strategies. In one approach, an intramolecular Diels-Alder reaction between a furan and an acetylenic compound connected by silicon-containing tethers was performed, followed by a cleavage of the Si-C bonds. This [4+2] cycloaddition was carried in the presence of a Lewis acid, only MeAlCl2 gave the expected product and so in moderate yields. In most cases, the cleavage of Si-C bonds leads to the desired diesters. In a second approach, a mono-saponification of dialkyl oxanorbornadiene-2,3-dicarboxylates provided access regioselectively to mono-acids and coupling reactions with amines or alcohols selectively led to poly-functionalized products containing two different electron-withdrawing groups.In the last part, we have regioselectively prepared 3-pyrrolines by [2+3] cycloaddition of an azomethine ylide to 7-oxanorbornadienes bearing electroattracting groups followed by a retro-Diels-Alder reaction. An easy synthesis of previously unknown condensed 3-pyrrolines was obtained by formation of an unexpected succinimide pattern from amidoesters. In conclusion, it appears that the presence of an ethyl group on the bridgehead carbon atom of 7-oxanorborna-2,5-dienes seems sufficient to control the regioselectivity of these cycloadditions.

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.

Guidance is defined as the determination of a strategy for following a nominal path in the presence of o-nominal conditions, disturbances and uncertainties, and the strategy employed is called a guidance law. Variants of Proportional Navigation (PN), such as True Proportional Navigation (TPN) and Pure Proportional Navigation (PPN), have been studied extensively in the literature on tactical missile guidance. In the absence of target maneuvers, in a linear interceptor guidance problem, TPN was shown to be optimal. However, the standard PN class of guidance laws per se does not show good performance against maneuvering targets, and was found to be eective in intercepting a maneuvering target only from a restrictive set of initial geometries. Also, since these guidance laws were eectively designed for lower speed targets, they show a degraded performance when applied against higher speed targets. However, in the current defense scenario, two classes of agile targets, which are capable of continuous maneuver, and/or of much higher speed than the interceptor, are a reality. This thesis presents analysis of several variants of PN class of guidance laws against these two classes of agile targets. In the literature, an augmentation of the TPN guidance law, termed as Augmented Proportional Navigation (APN), was shown to be optimal in linearized engagement framework. The present work proposes an augmentation of the PPN guidance law, which is more realistic than TPN for an aerodynamically controlled interceptor, and an-alyzes its capturability in fully nonlinear framework, and develops sauciest conditions on speed ratio, navigation gain and augmentation parameter to ensure that all possible initial engagement geometries are included in the capture zone when applied against a target executing piecewise continuous maneuver. The thesis also obtains the capture zone in the relative velocity space for augmented PPN guidance law. In the literature, a novel guidance law was proposed for the interception of higher speed targets in planar engagement by using a negative navigation gain instead of the standard positive one, and was termed as Retro-PN. It was shown that even though the Retro-PN guided interceptor takes more time than PN guided one in achieving successful interception, Retro-PN performs significantly better than the classical PN law, in terms of capturability, lateral acceleration demand, and closing velocity, when used against higher speed targets. The thesis analyzes Retro-PN guidance law in 3-D engagement geometries to yield the complete capture zone of interceptors guided by Retro-PN guidance philosophy, and derives necessary and sucient conditions for the capture of higher speed non-maneuvering targets with and without a constraint on finiteness of lateral acceleration. Terminal impact angle control is crucial for enhancement of warhead eectiveness. In the literature, this problem has been addressed mostly in the context of targets with lower speeds than the interceptor. The thesis analyzes the performance of a composite PN guidance law, that uses standard PPN and the Retro-PN guidance laws based on initial engagement geometry and requirement of impact angle, against higher speed non-maneuvering targets. Then, to expand the set of achievable impact angles, it proposes a modified composite PN guidance scheme, and analyzes the same. For implementation of many modern guidance laws, a good estimate of time-to-go is essential. This requirement is especially severe in case of impact time constrained en-gagement scenarios. To this end, an ecient and fast time-to-go estimation algorithm for generic 3-D engagement is required. Two time-to-go estimation algorithms are presented and analyzed in this work for the engagement of a PPN or Retro-PN guided interceptor and a higher speed target. The first one is a closed form approximation of time-to-go in terms of range, nominal closing speed and an indicator of heading error, and the second one is a numerical recursive time-to-go estimation algorithm. To improve the odds of intercepting an intelligent target and destroying it, a salvo attack of two or more interceptors could be considered as a viable option. Moreover, this simultaneous salvo attack can also be further improved in eciency by incorporating the shoot-look-shoot approach in making a decision about launching interceptors. This can be considered as the first step towards a layered defense system, which has been described in the literature as a potentially eective strategy against short range or long range ballistic threat. To this end, the present work proposes two PPN and Retro-PN based guidance strategies for achieving simultaneous salvo attack on a higher speed non-maneuvering target. For the implementation of the same the numerical recursive time-to-go estimation technique proposed in this work is utilized

Pin-up images have played an important role in American culture, in both their illustrated and photographic configurations. The pin-up is viewed as a significant representational cultural artifact of idealistic and aspirational femininity and of consumerism and material wealth, especially reflective of the mid-twentieth century period in America spanning the 1930s to the 1960s. These images not only reflect great shifts in social mores and women’s social status, but also affected changes in both areas in turn. Furthermore, pin-up images internationally circulated in magazines, advertising and promotional material, contributed to the manner in which America was idealized in Europe and beyond. Crucially, they influenced how an eroticized and glamorous, yet unrealistic, example of femininity came to be generalized as a desirous model of femininity. In recent years there has been vital, though limited, scholarly research into the cultural and social impact of pin-up imagery, to which this thesis adds to. This thesis takes a genealogical approach, charting the development of popular female-centric “pin-up” imagery in America since the 1860s and up to the 1960s, and its resurgence since the 1980s onwards. In doing so this thesis aims to provide a social, political and cultural context to the emergence of a specific archetypal sexualized femininity, with the aim of challenging the tendency to dismiss sexualized imagery as “anti-feminist” or as trivial. Toward that end, I examine the complexity of intentions behind the production of “pin-up” images. In taking this revisionist approach I am better able to conclusively analyze the reasons for the resurgence and reappropriation of pin-up imagery in late-twentieth- and early-twenty-first-century popular culture, and consider what the gendered cultural implications may be.

Avec l’arrivée des dernières générations de téléphones chiffrés (BlackBerry PGP, iPhone), l’extraction des données par les experts est une tâche de plus en plus complexe et devient un véritable défi notamment après une catastrophe aérienne ou une attaque terroriste. Dans cette thèse, nous avons développé des attaques physiques sur systèmes cryptographiques à des fins d’expertises judiciaires. Une nouvelle technique de re-brasage à basse température des composants électroniques endommagés, utilisant un mélange eutectique 42Sn/58Bi, a été développée. Nous avons exploité les propriétés physico-chimiques de colles polymères et les avons utilisées dans l’extraction de données chiffrées. Une nouvelle technique a été développée pour faciliter l’injection et la modification à haute-fréquence des données. Le prototype permet des analyses en temps réel des échanges processeur-mémoire en attaque par le milieu. Ces deux techniques sont maintenant utilisées dans des dispositifs d’attaques plus complexes de systèmes cryptographiques. Nos travaux nous ont mené à sensibiliser les colles polymères aux attaques laser par pigmentation. Ce processus permet des réparations complexes avec une précision laser de l’ordre de 15 micromètres. Cette technique est utilisable en réparations judiciaires avancées des crypto-processeurs et des mémoires. Ainsi, les techniques développées, mises bout à bout et couplées avec des dispositifs physiques (tomographie 3D aux rayons X, MEB, laser, acide fumant) ont permis de réussir des transplantations judiciaires de systèmes chiffrés en conditions dégradées et appliquées pour la première fois avec succès sur les téléphones BlackBerry chiffrés à l’aide de PGP. / When considering the latest generation of encrypted mobile devices (BlackBerry’s PGP, Apple’s iPhone), data extraction by experts is an increasingly complex task. Forensic analyses even become a real challenge following an air crash or a terrorist attack. In this thesis, we have developed physical attacks on encrypted systems for the purpose of forensic analysis. A new low-temperature re-soldering technique of damaged electronic components, using a 42Sn/58Bi eutectic mixture, has been developed. Then we have exploited the physico-chemical properties of polymer adhesives and have used them for the extraction of encrypted data. A new technique has been developed to facilitate injection and high-frequency data modification. By a man-in-the-middle attack, the prototype allows analysing, in real-time, the data exchanges between the processor and the memory. Both techniques are now used in more complex attacks of cryptographic systems. Our research has led us to successfully sensitise polymer adhesives to laser attacks by pigmentation. This process allowed complex repairs with a laser with 15 micrometres precision and has been used in advanced forensic repair of crypto-processors and memory chips. Finally, the techniques developed in this thesis, put end-to-end and coupled with physical devices (X-ray 3D tomography, laser, SEM, fuming acids), have made it possible to have successful forensic transplants of encrypted systems in degraded conditions. We have successfully applied them, for the first time, on PGP-encrypted BlackBerry mobile phone.

Die Konversion konventioneller Kataloge ist - wie einst ihre Erstellung - eine Generationenaufgabe. Zu den Zielen der Abteilung Sammlungen zählt die vollständige Konversion des Autographenkataloges der Handschriftensammlung....

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