La microscopie optique sur substrats antireflets est un outil de caractérisation simple et puissant qui a notamment permis l'isolation du graphène en 2004. Depuis, le domaine d'étude des matériaux bidimensionnels (2D) s'est rapidement développé, tant au niveau fondamental qu'appliqué. Ces matériaux ultraminces présentent des inhomogénéités (bords, joints de grains, multicouches, etc.) qui impactent fortement leurs propriétés physiques et chimiques. Ainsi leur caractérisation à l'échelle locale est primordiale. Cette thèse s'intéresse à une technique récente de microscopie optique à fort contraste, nommée BALM, basée sur l'utilisation originale de couches antireflets très minces (2-5 nm) et fortement absorbantes (métalliques). Elle a notamment pour but d'évaluer les mérites de cette technique pour l'étude des matériaux 2D et de leur réactivité chimique. Ainsi, les différents leviers permettant d'améliorer les conditions d'observation des matériaux 2D ont tout d'abord été étudiés et optimisés pour deux matériaux modèles : l'oxyde de graphène et les monocouches de MoS₂. L'étude de la dynamique de dépôt de couches moléculaires a notamment permis de montrer à la fois l'extrême sensibilité de BALM pour ce type de mesures et l'apport significatif des multicouches antireflets pour l'augmentation du contraste lors de l'observation des matériaux 2D. L'un des atouts principaux de BALM venant de sa combinaison à d'autres techniques, nous nous sommes particulièrement intéressés au couplage de mesures optiques et électrochimiques pour lesquelles le revêtement antireflet sert d'électrode de travail. Nous avons ainsi pu étudier optiquement la dynamique de réduction électrochimique de l'oxyde de graphène (GO), l'électro-greffage de couches minces organiques par réduction de sels de diazonium sur le GO et sa forme réduite (r-GO), ainsi que l'intercalation d'ions métalliques entre feuillets de GO. En combinant versatilité et fort-contraste, BALM est ainsi établi comme un outil prometteur pour l'étude des matériaux 2D et en particulier pour la caractérisation locale et in situ de leur réactivité chimique et électrochimique. / Optical microscopy based on anti-reflective coatings is a simple yet powerful characterization tool which notably allowed the first observation of graphene in 2004. Since then, the field of two-dimensional (2D) materials has developed rapidly both at the fundamental and applied levels. These ultrathin materials present inhomogeneities (edges, grain boundaries, multilayers, etc.) which strongly impact their physical and chemical properties. Thus their local characterization is essential. This thesis focuses on a recent enhanced-contrast optical microscopy technique, named BALM, based on ultrathin (2-5 nm) and strongly light-absorbing (metallic) anti-reflective layers. The goal is notably to evaluate the benefits of this technique for the study of 2D materials and their chemical reactivity. The various levers to improve 2D materials observation were investigated and optimized for two model materials: graphene oxide and MoS₂ monolayers. The investigation of molecular layer deposition dynamic notably showed the extreme sensitivity of BALM for such measurements and the significant contribution of multilayers anti-reflective coatings to enhance contrast during the observation of 2D materials. One of the main assets of BALM comes from its combination to other techniques. We particularly considered the coupling between optical measurements and electrochemistry for which the anti-reflective layer serves as working electrode. We investigated optically the dynamic of electrochemical reduction of Graphene Oxide (GO), the electrografting of organic layers by diazonium salts reduction on GO and its reduced form (rGO), as well as the intercalation of metallic ions within GO sheets. By combining versatility and high-contrast, BALM is established as a promising tool for the study of 2D materials, especially for the local and in situ characterization of their chemical and electrochemical reactivity.

Les tests de dispositifs de communication sans fil peuvent être réalisés en utilisant des simulations numériques ou des sondeurs de canaux. Bien que ne reflétant pas un environnement électromagnétique réaliste, une chambre réverbérante peut néanmoins émuler un canal de propagation comparable à un cas réel si l’on modifie convenablement ses propriétés. Les propriétés des signaux générés dans une chambre réverbérante sont fonction de différents paramètres. Au cours des trois années de thèse, nous avons analysé et mis en oeuvre plusieurs techniques pour mesurer et contrôler ces paramètres à l’intérieur d’une chambre réverbérante. D’abord, différents estimateurs du facteur K sont testés et leurs propriétés sont évaluées. Nous présentons les limites de fonctionnement utiles dans lesquelles différents estimateurspeuvent être utilisés. Ensuite, nous proposons deux nouveaux estimateurs qui utilisent comme données d’entrée seulement l’enveloppe du signal. Ils apportent en outre des améliorations sur la gamme des valeurs détectables du facteur K. Une des possibilités pour contrôler un canal de propagation à l’intérieur d’une chambre réverbérante est d’utiliser des matériaux absorbants. Nous présentons une méthode pour estimer la surface équivalente moyenne d’absorption en utilisant une seule antenne. Cette méthode exploite la mesure de la bande de cohérence du canal de propagation. Ensuite, nous étendons notre analyse à la prédiction de la surface équivalente moyenne d’absorption lorsqueles dimensions géométriques et les propriétés électromagnétiques des absorbants sont connues. On crée ensuite un modèle de canal de propagation en exploitant les régimes transitoire et permanent du signal. Avec ce modèle, selon les informations disponibles, on peut extraire le facteur K, la surface équivalente moyenne d’absorption et différents paramètres temporels (i.e., profil de l’étalement des retards). Nous poursuivons avec deux applications possibles des chambres réverbérantes. Tout d’abord, on évalue le gain d’une antenne à partir de mesures du coefficient de réflexion decette antenne. Nous étendons notre analyse à l’évaluation du diagramme de rayonnement de l’antenne et de son erreur d’estimation. Nous estimons aussi la désadaptation de l’antenne et son ouverture à 3 dB. La deuxième application porte sur l’évaluation du gain de diversité dans la chambre réverbérante. Nous isolons les influences des efficacités des antennes, des puissances des composantes brassées, et des facteurs K sur l’évaluation du gain de diversité.On obtient une relation simple de la corrélation de puissance en fonction de la corrélation complexe lorsque les facteurs K sur différents branches ne sont pas identiques. Nous montrons que lors d’un fort déséquilibre de facteur K il est impossible de conclure sur le gain de diversité à partir de la seule évaluation de la corrélation d’enveloppe ou de puissance. À l’aide de simulations statistiques on compare le gain de diversité mesuré avec les valeurs simulées. / The testing of wireless devices is generally done using numerical simulations or channel sounders. Though a reverberation chamber does not reflect a real transmission environment, its properties can also be appropriately modifiedto emulate one. This emulation may be achieved thanks to various parameters. Our PhD thesis has been devoted toanalyze and implement several techniques to measure and control these parameters inside reverberation chambers.First we evaluate different K-factor estimators and their capabilities. We present the useful limits in which severalcomplex, phase and envelope K-factor estimators can be used. Then, we propose two new envelope-based estimatorsimproving the useful range of detectable values of K-factor. One of the possibilities to control a propagation channel inside areverberation chamber is to use absorbing materials. We present a method to estimate the average absorbing crosssection by using only one antenna. This is done with measurements of coherence bandwidth of the channel. Then,we extend our analysis to predict the average absorbing cross section when we know the physical dimensions of aparallelepiped absorber as well its electromagnetic properties. Next, we create a model of the reverberation chamberpropagation channel using the transient regime and steady state of the signal. With this model, depending on the availableinformation, we can extract the K-factor, the average absorbing cross section and different time spreads parameters (i.e., mean delay spread and the root mean square delay spread). We continue with two possible applications of the reverberation chamber. First, we evaluate the gain of an antenna from only the measurement of reflection coefficient. We extend our analysis to the evaluation of antenna pattern and its estimation errors. We also estimate the antenna mismatch and half power beamwidth. The second application deals with the evaluation of the diversity gain in reverberation chamber. We isolate the effects on the diversity gain due to different antenna efficiencies, stirred powers and K-factors. Then, we estimate a simple relation of the power correlation as a function of the complex correlation when the K-factors on different branches are not identical. We show that using an envelope/power correlation as a criterion to characterize the diversity may bias the conclusions without taking into account other parameters. Using statistical simulations we compare the measured diversity gain with the simulated values.

Les polymères de phtalonitrile sont obtenus par des réactions d'addition des groupements cyano à haute température et pour un temps long à partir de dérivés de phtalonitrile. Ils trouvent de nombreuses applications dans les domaines de pointe comme l'aérospatiale et la marine. Cependant, leurs performances sont limitées par les inconvénients suivants : (1) fragilité liée intrinsèquement à leur réseau structural, (2) température de fusion élevée, fenêtre de conditions de mise en forme étroite, température de cuisson élevée, cinétique de cuisson faible, (3) Selon la litérature, le traitement du bisphthalonitrile pour obtenir la résine correspondante s'effectue souvent à des températures inférieures à 500°C. Il y a peu d'études sur les matériaux formés à des températures supérieures à celle-ci, (4) Il n'y a pas beaucoup d'études sur la fonctionnalisation de la résine bisphthalonitrile et son domaine d'application doit être élargis. Cette thèse porte sur le dévelopement de méthodes permettant la modification et la fonctionnalisation de la résine bisphthalonitrile conduisant à une amelioration des propriétés mécaniques de celle-ci. De plus, des nanotubes de carbone ayant une morphologie différente et des matériaux capables d'absorber les hyperfréquences ont été obtenus par pyrolyse de la résine bisphthalonitrile en présence de différents catalyseurs de fer et sur une plage de température allant de 600 a 900°C / Bisphthalonitrile polymers are obtained by addition curing reaction of cyano groups upon heating phthalonitrile derivatives at elevated temperature and for an extended period of time. They have found many applications in advanced technologies such as aerospace and marine. However, their performances are limited by the following disadvantages: (1) high brittleness of the inherent network structure; (2) high melting temperature, narrow processing window, high curing temperature, low curing rate and long curing time; (3) according to the literature, the processing temperature of bisphthalonitrile resin-based composites is controlled at 500°C or less, whereas there are few studies on materials formed above 500°C; (4) studies on the functionalization of bisphthalonitrile resins are not abundant and its application range needs to be expanded. Based on the above statement, this thesis is focused on the modification and functionalization of bisphthalonitrile resins. The latter were modified by a variety of methods, resulting in improved mechanical properties. Moreover, carbon nanotubes with different morphologies and microwave absorbing materials were obtained by pyrolysing bisphthalonitrile resins with different metal iron catalysts in the range of 600 to 900°C

Made available in DSpace on 2014-12-17T15:41:56Z (GMT). No. of bitstreams: 1 ManuellaKCR_DISSERT.pdf: 3952261 bytes, checksum: 56cf586893164ffedc3ec29beb8e775a (MD5) Previous issue date: 2010-08-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Were synthesized ferrites of NiZn on systems Ni0,5Zn0,5Fe2O4, the precursors citrate method. The decomposition of the precursors was studied by thermogravimetric analysis and spectroscopy in the infrared region, the temperature of 350?C/3h. The evolution of the phases formed after calcinations at 350?C/3h, 600, 1000 and 1100?C/2h was accompanied by X-ray diffraction using the Rietveld refinement method for better identification os structures formed. Was observed for samples calcined at different temperatures increased crystallinity with increasing calcination temperature, being observed for the samples calcined at 900 and 1100 ? C/2h was the precipitation of a secondary phase, the phase hematite. The ferrocarbonila of industrial origin was analyzed by X-ray diffraction and Rietveld for the identification of its structure. The carbonyl iron was added NiZn ferrite calcined at 350?C/3h, 600, 900, 1000 and 1100?C/2h to the formation of hybrid mixtures. They were then analyzed by Xray diffraction and Rietveld. The NiZn ferrite and ferrocarbonila as well as the hybrid mixtures were subjected to analysis of scanning electron microscopy, magnetic measurements and reflectivity. The magnetic measurements indicated that the ferrite, the ferrocarbonila, as well as hybrid mixtures showed characteristics of soft magnetic material. The addition of ferrocarbonila in all compositions showed an increase in the results of magnetic measurements and reflectivity. Best result was observed in the increase of the magnetization for the hybrid mixture of Ferrocarbonila / ferrite of NiZn calcined at 600?C/2h. The mixture Ferrocarbonila / ferrite calcined 1000?C/2h presented better absorption of electromagnetic radiation in the microwave / Foram sintetizadas ferritas de NiZn no sistema Ni0,5Zn0,5Fe2O4, pelo m?todo dos citratos precursores. A decomposi??o dos precursores foi estudada por an?lise termogravim?trica e espectroscopia na regi?o do infravermelho na temperatura de 350?C/3h. A evolu??o das fases formadas ap?s calcina??es a 350?C/3h, 600, 1000 e 1100?C/2h foi acompanhada por difra??o de raios X utilizando o refinamento de Rietveld para melhor identifica??o das estruturas formadas. Foi observado para as amostras calcinadas em diferentes temperaturas o aumento da cristalinidade com o aumento da temperatura de calcina??o, sendo verificado que para as amostras calcinadas a 900 e 1100?C/2h ocorreu a precipita??o de uma fase secund?ria, a fase hematita. A ferrocarbonila de proced?ncia industrial foi analisada por Difra??o de raios X e por Rietveld para a identifica??o de sua estrutura. A ferrocarbonila foi adicionada ? ferrita de NiZn calcinada a 350?C/3h, 600, 1000 e 1100?C/2h para a forma??o das misturas h?bridas. Em seguida foram analisadas por difra??o de raios X e por Rietveld. A ferrita de NiZn, a ferrocarbonila, assim como as misturas h?bridas foram submetidas ? an?lises de Microscopia Eletr?nica de Varredura, medidas magn?ticas e refletividade. As medidas magn?ticas indicaram que a ferrita, a ferrocarbonila, como tamb?m as misturas h?bridas apresentaram caracter?sticas de material magn?tico macios. A adi??o de ferrocarbonila em todas as composi??es indicou um aumento nos resultados de medidas magn?ticas e de refletividade. Foi verificado melhor resultado no aumento da magnetiza??o para a mistura h?brida de Ferrocarbonila/ferrita de NiZn calcinada 600?C/2h. A mistura Ferrocarbonila/ferrita calcinada 1000?C/2h apresentou melhor resultado absor??o da radia??o eletromagn?tica na faixa de microondas em rela??o ?s outras misturas

Atmospheric particulate matter (PM) is linked to various adverse environmental and health impacts. PM in the atmosphere reduces visibility, alters precipitation patterns by acting as cloud condensation nuclei (CCN), and changes the Earth’s radiative balance by absorbing or scattering solar radiation in the atmosphere. The long-range transport of pollutants leads to increase in PM concentrations even in remote locations such as polar regions and mountain ranges. One significant effect of PM on the earth’s climate occurs while light absorbing PM, such as Black Carbon (BC), deposits over snow. In the Arctic, BC deposition on highly reflective surfaces (e.g. glaciers and sea ices) has very intense effects, causing snow to melt more quickly. Thus, characterizing PM sources, identifying long-range transport pathways, and quantifying the climate impacts of PM are crucial in order to inform emission abatement policies for reducing both health and environmental impacts of PM. Chemical transport models provide mathematical tools for better understanding atmospheric system including chemical and particle transport, pollution diffusion, and deposition. The technological and computational advances in the past decades allow higher resolution air quality and weather forecast simulations with more accurate representations of physical and chemical mechanisms of the atmosphere. Due to the significant role of air pollutants on public health and environment, several countries and cities perform air quality forecasts for warning the population about the future air pollution events and taking local preventive measures such as traffic regulations to minimize the impacts of the forecasted episode. However, the costs associated with the complex air quality forecast models especially for simulations with higher resolution simulations make “forecasting” a challenge. This dissertation also focuses on applications, performance analysis, and optimization of meteorology and air quality modeling forecasting models. This dissertation presents several modeling studies with various scales to better understand transport of aerosols from different geographical sources and economic sectors (i.e. transportation, residential, industry, biomass burning, and power) and quantify their climate impacts. The simulations are evaluated using various observations including ground site measurements, field campaigns, and satellite data. The sector-based modeling studies elucidated the importance of various economical sector and geographical regions on global air quality and the climatic impacts associated with BC. This dissertation provides the policy makers with some implications to inform emission mitigation policies in order to target source sectors and regions with highest impacts. Furthermore, advances were made to better understand the impacts of light absorbing particles on climate and surface albedo. Finally, for improving the modeling speed, the performances of the models are analyzed, and optimizations were proposed for improving the computational efficiencies of the models. Theses optimizations show a significant improvement in the performance of Weather Research and Forecasting (WRF) and WRF-Chem models. The modified codes were validated and incorporated back into the WRF source code to benefit all WRF users. Although weather and air quality models are shown to be an excellent means for forecasting applications both for local and hemispheric scale, further studies are needed to optimize the models and improve the performance of the simulations.

Empirical models based on flow resistivity are commonly used to determine the bulk properties of porous sound absorbing materials. The bulk properties include the complex wavenumber and complex characteristic impedance which can be used directly in simulation models. Moreover, the bulk properties can also be utilized to determine the normal incidence sound absorption and specific acoustic impedance for sound absorbing materials of any thickness and for design of layered materials. The sound absorption coefficient of sound absorbing materials is measured in an impedance tube using wave decomposition and the measured data is used to determine the flow resistivity of the materials by least squares curve fitting to empirical equations. Results for several commonly used foams and fibers are tabulated to form a rudimentary materials database. The same approach is then used to determine the flow resistivity of compressed sound absorbing materials. The flow resistivities of the compressed materials are determined as a function of the compression ratio. Results are then used in conjunction with transfer matrix theory to predict the sound absorptive performance of layered compressed absorbers with good agreement to measurement.

The determination of the atmospheric aerosol size distribution is an inverse illposed problem. The shape and the material composition of the air-carried particles are two substantial model parameters. Present evaluation algorithms only used an approximation with spherical homogeneous particles. In this paper we propose a new numerically efficient recursive algorithm for inhomogeneous multilayered coated and absorbing particles. Numerical results of real existing particles show that the influence of the two parameters on the model is very important and therefore cannot be ignored.

M-type barium hexaferrite powders doped with titanium and/or cobalt have been synthesized according to the stochiometric formulations BaFe(12 &amp / #8211 / (4/3)x)TixO19, BaFe12-xCoxO19 , BaFe12-2xTixCoxO19 (x varying from 0 to 1.5 with an increment of 0.5) by the mixed oxide approach. The powders were used to manufacture small ceramic tiles by sintering each composition at 1250 &deg / C with soaking times ranging from 1 to 16 hours. XRD work revealed formation of the magnetoplumbite crystal structure in all ceramics. The variations in processing parameters led to differences in microstructure and various dielectric and magnetic properties of the ceramic tiles. The interaction of the ceramics with electromagnetic waves was characterized by using a vector network analyzer in the X and Ku bands. The results revealed that, undoped barium hexaferrite ceramics and those doped with low titanium exhibited good microwave absorption properties.

Electromagnetic wave absorbing properties of SiC-based and alumina ceramic woven fabrics have been investigated. Electrical conductivities of SiC-based ceramic woven fabrics were modified by heat treatment in air resulting in their oxidation. Surface properties of alumina woven fabrics were altered by gold-sputtering resulting in a high conductivity layer on the surface of the wovens. Electromagnetic wave interactions of single layer and double layered combinations of these ceramic woven fabrics were determined in 17-40 GHz frequency range using &ldquo / free-space&rdquo / method. Electromagnetic wave absorption potential of ceramic woven fabrics with different chemical compositions and woven types were correlated with their material properties by X-ray diffraction, scanning electron microscopy and electrical conductivity measurements. Effects of modifications and varying woven fabric arrangements in combinations on the electromagnetic wave absorption potential of the ceramic woven fabrics have been discussed. Various double layer combinations of SiC-based and alumina woven fabrics revealed a promising potential in terms of both reduced reflection and transmission resulting in more than ~95% absorption in millimeter wavelength range, which makes them powerful candidate materials for electromagnetic wave absorption applications.

A Markov chain is introduced to the major steps of the process of learning a subject matter by a group of students in the classroom, in order to obtain a mathematical representation of the above process. A classroom experiment for learning mathematics is also presented illustrating the applicability of our results in practice.