Les systèmes d’imagerie infrarouge suivent depuis plusieurs années la même tendance de miniaturisation que les systèmes d’imagerie visible. Aujourd’hui cette miniaturisation se rapproche d’une limite physique qui amène la communauté à se tourner vers une nouvelle approche : la fonctionnalisation, c’est-à-dire l’apport de fonctions d’imagerie avancées aux systèmes telles que l’imagerie 3D.En infrarouge, la fonction d’imagerie 3D est très recherchée car elle pourrait apporter à un fantassin un outil de télémétrie passive fonctionnant de nuit comme de jour, ou encore permettre l’autonomie en environnements complexes à des systèmes tels que les drones. Cependant, le cout d’une caméra infrarouge hautes-performances est élevé. Multiplier le nombre de cameras n’est donc pas une solution acceptable pour répondre à ce besoin.C’est dans ce contexte que se situe ce travail qui consiste à apporter une fonction de vision 3D à des caméras infrarouges possédant un unique plan focal.Au cours de cette thèse, j’ai identifié la technologie d’imagerie 3D la plus adaptée à ce besoin : la camera plénoptique. J’ai montré que cette dernière permet de proposer, en intégrant une matrice de microlentilles dans le cryostat, un bloc de détection infrarouge avec une fonction d’imagerie 3D. L’environnement scellé du bloc de détection m’a amené à développer un modèle de dimensionnement rigoureux que j’ai appliqué pour concevoir et réaliser une camera plénoptique infrarouge refroidie. J’ai ensuite mis au point une méthode de caractérisation originale et intégré les mesures dans une série d’algorithmes de traitement d’image afin de remonter à la distance des objets observés. / For a few years now, infrared cameras have been following the same miniaturization trend introduced with visible cameras. Today, this miniaturization is nearing a physical limit, leading the community to take a different approach called functionalization: that is bringing an advanced imaging capability to the system.For infrared cameras, one of the most desired functions is 3D vision. This could be used to bring soldiers a passive telemetry tool or to help UAVs navigate a complex environment, even at night. However, high performance infrared cameras are expensive. Multiplying the number of cameras would thus not be an acceptable solution to bring 3D vision to these systems.That is why this work focuses on bringing 3D vision to cooled infrared cameras using only a single focal plane array.During this PhD, I have first identified the plenoptic technology as the most suitable for our need of 3D vision with a single cooled infrared sensor. I have shown that integrating a microlens array inside the dewar could bring this function to the infrared region. I have then developed a complete design model for such a camera and used it to design and build a cooled infrared plenoptic camera. I have created a method to characterize our camera and integrated this method into the image processing algorithms necessary to generate refocused images and derive the distance of objects in the scene.

The trend over the last 50 years of down-scaling the silicon transistor to achieve faster computations has led to doubling of the number of transistors and computation speed over about every two years. However, this trend cannot be maintained due to the fundamental limitations of silicon as the main material for the semiconducting industry. Therefore, there is an active search for exploration of alternate materials. Among the possible candidates that can may [sic] be able to replace silicon is graphene which has recently gained the most attention. Unique properties of graphene include exceedingly high carrier mobility, tunable band gap, huge optical density of a monolayer, anomalous quantum Hall effect, and many others. To be suitable for microelectronic applications the material should be semiconductive, i.e. have a non-zero band gap. Pristine graphene is a semimetal, but by the virtue of doping the graphene surface with different molecules and radicals a band gap can be opened. Because the electronic properties of all materials are intimately related to their atomic structure, characterization of molecular and electronic structure of functionalizing groups is of high interest. The ab-inito (from the first principles) calculations provide a unique opportunity to study the influence of the dopants and thus allow exploration of the physical phenomena in functionalized graphene structures. This ability paves the road to probe the properties based on the intuitive structural information only. A great advantage of this approach lies in the opportunity for quick screening of various atomic structures. We conducted a series of ab-inito investigations of graphene functionalized with covalently and hapticly bound groups, and demonstrated possible practical usage of functionalized graphene for microelectronic and optical applications. This investigation showed that it is possible [to] produce band gaps in graphene (i.e., produce semiconducting graphene) of about 1 eV, without degrading the carrier mobility. This was archived by considering the influence of those adducts on electronic band structure and conductivity properties.

The thesis deals with the surface modification of cotton fabric by low-pressure micro-wave plasma discharge. The main materials used for this experiment are cotton fabrics and hexamethyldisiloxane. The experiment itself is focused on the modification of cotton fabric to improve hydrophobic atributes. An argon process gas was used in the surface modification. The individual treated samples were operated with changes in process gas flow and the time during which the above-mentioned modifications was performed. Two methods were used to analyze the results of the experiment. The first one was aimed at determining changes in hydrophobic atributes in the form of wetta-bility in an unmodified sample compared to other modificated samples using the drop-let method. An electron microscope was used for the subsequent study of possible changes in surface topography. From the point of view of the examined results, the difference in hydrophobic properties was observed when using the droplet method to-gether with the change in the topography of the surface obtained on the electron mi-croscope in the cotton samples examined. The actual evaluation of individual methods points to the desirable changes in modified cotton compared to unmodified cotton. Further information regarding the results of the experiment, depending on the changes in individual parameters in the cotton treatment process using low pressure microwave plasma discharge, are presented in thesis.

The strength, thermal stability, pore structure and morphology are keys to success for wider deployment of aerogels. Furthermore, co or subsequent functionalization of the surfaces are equally, if not more important. This study addresses these issues through a new method. The path involves successful use of surfactant templating, supercritical extraction and drying, and supercritical fluid aided functionalization of the surface. Alumina support and alumina supported nickel catalyst particles are used to evaluate the approach. Initially thermally stable surfactant alumina was synthesized. The surfactant template was removed completely with the aid of a supercritical solvent mixture. Surfactant-templated alumina aerogel showed remarkable thermal stability and gave specific surface area above 500m2 /g both before and after calcination. The alumina support is subsequently impregnated with nickel. BET and BJH method (Nitrogen adsorption-desorption isotherms) were used to follow the removal of solvents and templates as well as tracking the textural properties for the synthesized gel. Meanwhile, co-precipitated nickel oxide/alumina system was also synthesized for comparison with the supercritical impregnation nickel oxide/alumina system. SEM-EDS and XPS were employed to study the distribution of the nickel on the alumina support and the percentage was compared with the initial mixture of the sol gels.

Avec le développement de nouveaux dispositifs apparait le besoin d’être capable de contrôler la chimique de surfaces de substrats multi-échelle et multi-matériaux. Plusieurs techniques font appel à de la chimie localisée via différentes technologies. Une approche consiste à exploiter les différences de réactivités chimiques entre les différents matériaux du substrat et différents groupements chimiques de manière à fonctionnaliser sélectivement chaque matériaux pour former des couches minces organiques de type « Self Assembled Monolayer »: Ce principe proposée par Pr. G. M. Whitesides est appelé chimie orthogonale. Dans le cadre de cette thèse, le but ultime était de réaliser la fonctionnalisation chimique orthogonale de substrats dont la surface était composée de SiO2/Au/TiW La première étape de ce travail a été de déterminer pour la première fois la fonction chimique la plus adaptée pour la fonctionnalisation de TiW. Pour se faire nous avons comparé la chimie des silanes, des acides phosphoniques et des catéchols. Après caractérisations (XPS, ToF-SIMS, IR) des différentes couches, la voie des acides phosphoniques semblait être celle donnant lieu à la couche la plus stable. Ensuite nous avons étudié l’orthogonalité sur de substrats bi-matériaux (SiO2/TiW ou Au/TiW), et enfin sur substrat dont la surface était constituée de Au/SiO2/TiW. / The development of nanotechnologies makes it possible to manufacture the micro or nanometric-sized patterns with various materials (dielectrics, metals, semiconductors). These heterogeneous surfaces are commonly used in the electronics industry for the production of nanoelectronic structures and components: transistors, memories or sensors. The concept of orthogonal chemical functionalization was first proposed by George M. Whitesides to modify the surfaces composed of different materials at the macroscopic scale. In this context, this PhD work aimed at exploring the orthogonal chemical functionalization approach on a predefined patterned titanium tungsten (TiW) surface by lithography producing. Pattern materials (Au, SiO2) are chosen to have different chemical properties, which can be functionalized with completely independent reactions. To achieve this aim, we have studied three different chemical groups for the formation of organolayers (silane, catechol, phosphonic acid) on TiW for the first time. The three layers were characterized (XPS, IR, ToF-SIMS) and the stability of the formed organolayers was also addressed. Then we developed and ascertained the orthogonal chemical functionalization of patterned Au/TiW and Au/SiO2/TiW surfaces. It proposes a novel strategy for the orthogonal functionalization on a triple-material patterned surface. In addition, the capture of nanoparticles by electrostatic interaction at specific location on Au/TiW patterned substrate was successfully implemented to prove the interest of such method for colloids trapping.

Since their first observation in 1991, carbon nanotubes (CNTs) have attracted a lot of attention owing to their exceptional properties. Their excellent electrical and thermal conducting performances combined with their high toughness and transverse flexibility allow their use in a large range of varied applications. Offering at the same time a high aspect ratio (length-to-diameter) and a low density, carbon nanotubes show strong application potential in reinforced composite materials. Unfortunately, CNTs have the strong tendency to form bundles very difficult to dissociate and disperse in a majority of polymer matrices. Without efficient CNTs dispersion, nanocomposites can not present optimal mechanical, thermal and electrical properties. To overcome this drawback, one solution consists to graft polymer chains on the carbon nanotubes surface in order to disaggregate bundles and, in few cases, to improve interaction between the polymer matrix and nanotubes. The thesis work can be divided into three parts. The first is the one-step amination of multi-walled carbon nanotubes (MWNTs) via an original microwave plasma process. The MWNTs, placed in the post-discharge chamber in presence of H2, are subjected to a reactive flow of atomic nitrogen produced by the plasma. The results give evidence for efficient covalent grafting of primary amine groups along the sidewalls of MWNTs, avoiding any structural damage and alteration of properties. The so-grafted amine groups have been further consider as initiation sites for promoting the ring opening polymerization of lactone monomers yielding polyester-grafted MWNT nanohybrids. Finally, these nanohybrids have been used as highly filled masterbatches to be dispersed in the molten state within several polymer matrices, such as polycaprolactone (PCL) and high density polyethylene (HDPE), to obtain nanocomposites with largely improved properties. For instance, electrical measurements and morphological characterizations showed that the polyester surface-grafting allows for improving the dispersion state of the nanotubes in the different polymer matrices leading to enhanced electrical properties as well as thermal and mechanical performances.

<p>South Africa s coal and platinum mineral resources are crucial resources towards creating an alternative and environmentally sustainable energy system. The beneficiation of these natural resources can help to enhance a sustainable and effective clean energy base infrastructure and further promote their exploration and exportation for economics gains. By diversification of these resources, coal and the platinum group metals (PGMs) especially palladium market can be further harnessed in the foreseeable future hence SA energy security can be guaranteed from the technological point of view. The South Africa power industry is a critical sector, and has served as a major platform in the South African socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. The South Africa power industry is a critical sector, and has served as a major platform in the SA&rsquo / s socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. Coal gasification is considered as a source of hydrogen gas and the effluent gases released during this process include hydrogen sulphide, oxides of carbon and nitrogen, hydrogen and other particulates. In developing an alternative hydrogen gas separating method, composite membrane based on organic-inorganic system is being considered since the other available methods of hydrogen separation are relatively expensive.<br /> &nbsp / </p>

This dissertation has been focused on the synthesis and characterization of novel functionalized silica mesoporous crystals by using cationic surfactant and co–structure directing agents (CSDA), the central concept of the synthesis method is to build proper organic/inorganic interactions by introducing CSDA into the synthesis system. By using cationic surfactant as template and anionic CSDA, carboxylic group functionalized mesoporous silicas were successfully synthesized. Well ordered 2D p6mm, cubic Fm-3m, mixture of CCP (Fm-3m) and HCP (P63/mmc), and cubic Fd-3m with uniform carboxylic group distribution have been obtained. Besides, we have investigated the Fm-3m/Fd-3m type intergrowth and new type defects observed in the Fd-3m structure using transmission electron microscopy (TEM) and proposed a “polyhedron packing” model. New amphoteric, inorganic amino acid with highly ordered mesopores were synthesized. Uniform distribution of acid and base organic groups on the mesopore surfaces were formed by interactions between the counter charged surfactant head groups and ionic parts of CSDAs. It has been demonstrated that organic (–NH2 and –COOH) pairs incorporated in the mesopore walls behave as natural amino acids, collectively exhibiting an isoelectric point of ~6.0. Moreover, we have demonstrated that the inorganic amino acid is an efficient catalyst for the reaction between aldehydes and carbon nucleophiles.

Graphene, a two dimensional single layer of graphite, attracts a lot of attention of researchers around the globe due to its remarkable physical properties and application potential. The origin can thereby be found in the peculiar electronic structure since graphene is a zero gap semi-conductor with a linear energy dispersion in the vicinity of the Fermi level. Consequently, the charge carriers in graphene mimic massless Dirac Fermions which brings principles of quantum electrodynamics and exotic effects like Klein tunneling into a bench-top experiment. Modifying the electronic and/or crystal structure structure by functionalization might therefore as well lead to new tantalizing physical properties, novel compound materials based on graphene like graphane (fully hydrogenated graphene) or flourographene (fluorinated graphene), and ultimately new applications. In this work, the influences on the electronic structure of graphene are investigated with photoemission spectroscopies after covalent functionalization by atomic hydrogen and ionic functionalization with potassium. Regarding hydrogenation, the formation of tunable bandgap is observed along with a full recovery of the electronic properties of graphene upon removing the hydrogen by thermal annealing. Using high resolution x-ray photoemission and molecular dynamics simulations, the formation of a C4H structure is predicted for substrate supported graphene at a saturation H-coverage of 25%, due to a preferential para- arrangement of hydrogen atoms. In fully electron doped, hydrogenated graphene the formation of dispersionless hydrogen impurity state is observed with angle-resolved photoemission spectroscopy. This flat state is extended over the whole Brillouin zone and according to calculations not localized. Potassium-doped graphene shows a similar doping level as its 3D parent component, the graphite intercalation compound KC8. Investigating the electron-phonon coupling in doped graphene, by direct derivation of the Eliashberg-function, shows an asymmetric coupling strength along the high-symmetry directions in the Brillouin Zone of graphene. In the K-M direction additional low energetic contributions could be identified which may originate from out-of-plane phonon modes. Regarding the electron-phonon-coupling strength of the high energy in-plane phonon modes a reasonable agreement with theoretical predictions is found.

Part 1: Transition-metal-catalyzed direct transformations of aromatic C-H bonds are emerging as valuable tools in organic synthesis. These reactions are attractive because of they allow for inherently efficient construction of organic building blocks by minimizing the pre-activation of substrates. Of these processes, direct arylation has recently received much attention due to the importance of the biaryl core in medicinal and materials chemistry. Also, alkyne hydroarylation has garnered interest because it allows for the atom-economical synthesis of functionalized alkenes directly from simple arenes and alkynes. Described in this thesis are number of advancements in these areas. First, palladium catalyzed direct arylation of azine N-oxides using synthetically important aryl triflates is described. Interesting reactivity of aryl triflates compared to aryl bromides was uncovered and exploited in the synthesis of a compound that exhibits antimalarial and antimicrobial activity. Also reported is the efficient, direct arylation enabled (formal) synthesis of six thiophene based organic electronic materials in high yields using simple starting materials. Additionally, the site-selective direct arylation of both sp2 and sp3 sites on azine N-oxide substrates is described. The arylation reactions are carried out in either a divergent manner or a sequential manner and is applied to the synthesis of the natural products, Papaverine and Crykonisine. Mechanistic investigations point towards the intimate involvement of the base in the mechanism of these reactions. Next, the rhodium(III)-catalyzed hydroarylation of internal alkynes is described. Good yields are obtained for a variety of alkynes and arenes with excellent regioselectivity for unsymmetrically substituted alkynes. Mechanistic investigations suggest that this reaction proceeds through arene metalation with the cationic rhodium catalyst, which enables challenging intermolecular reactivity. Part 2: Access to single enantiomer compounds is a fundamental goal in organic chemistry and despite remarkable advances in enantioselective synthesis, their preparation remains a challenge. Kinetic resolution of racemic products is an important method to access enantioenriched compounds, especially when alternative methods are scarce. Described in this thesis is the resolution of tertiary and secondary alcohols, which arise from ketone and aldehyde aldol additions. The method is technically simple, easily scalable, and provides tertiary and secondary alcohols in high enantiomeric ratios. A rationale for the unique reactivity/selectivity associated with (1S,2R)-N-methylephedrine in the resolution is proposed. Organocatalysis is a rapidly developing, powerful field for the construction of enantioenriched organic molecules. Described here is a complimentary class of organocatalysis using simple aldehydes as temporary tethers to perform challenging formally intermolecular reactions at room temperature. This strategy allows for the enantioselective, intermolecular cope-type hydroamination of allylic amines with hydroxyl amines. Also, interesting catalytic reactivity for dichloromethane is revealed.