Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-03-07T12:00:31Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Sandra Mara Wolff Campelo.pdf: 2947865 bytes, checksum: 60d712c905ba3cbd53cb55587b7d53bf (MD5) / Made available in DSpace on 2019-03-07T12:00:31Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Sandra Mara Wolff Campelo.pdf: 2947865 bytes, checksum: 60d712c905ba3cbd53cb55587b7d53bf (MD5) Previous issue date: 2018-11-19 / O amido pode ser obtido mais comumente a partir de milho, trigo, arroz e também de tubérculos e raízes. Mas outras fontes estão sendo estudadas, como amidos extraídos dos gêneros Dioscoreae spp., uma espécie deste gênero estudada com pouca frequência é a Dioscorea bulbifera Linn conhecida também como cará moela. Neste trabalho o amido nativo de D. bulbifera Linn foi obtido e modificados com extrato aquosos e hidroalcoólicos em três concentrações diferentes de erva-mate, Ilex paraguariensis, planta rica em compostos biotivos responsáveis por suas propriedades benéficas a saúde. Através das técnicas como Calorimetria Exploratória Diferencial (DSC), análises reológicas através da análise Viscoamilográfica (RVA), Termogravimetria acoplada ao sistema - Calorimetria Exploratória Diferencial - Espectrometria de Massas (TG-DSC-MS) e morfológicas como o Microscopia Eletrônica de Varredura (MEV), Difratometria de raios X método pó (DRX) e Colorimetria foi possível verificar a interação deste amido de D. bulbifera Linn com os compostos provenientes dos extratos obtidos das folhas de erva-mate. As temperaturas iniciais de gelatinização, dos amidos, com incorporação de 6% de extrato aquoso, e com 6% extrato hidroalcoólicos foram levemente superiores em relação ao amido nativo, quando estudados por DSC. A maior parte das amostras apresentaram valores de Tp e Tc e entalpia de gelatinização próximos ao nativo. Na análise de RVA observou que os picos de viscosidade foram maiores nos amidos modificados com extrato aquosos. A viscosidade final e a tendência a retrogradação aumentaram em relação ao nativo. As imagens MEV não se alteraram, a coloração do amido nativo teve maior tendência ao L* branco que os modificados. Os difratogramas de raios X apresentaram amido tipo “C. Na análise TG-DSC-MS os eventos principais no DSC foram mais intensos nas amostras tratada, assim como os sinais massa-carga detectados, medidos por espectrometria de massa, ocorreram com eventos mais intensos nas amostras tratadas com extratos hidroalcoólicos e no sinal m/z 58 foi detectado em todas as amostras exceto no amido nativo. Evidenciando que houve incorporação dos compostos fenólicos com modificação no perfil dos gases gerados durante a termo decomposição. / Starch can be obtained most commonly from corn, wheat, rice and also tubers and roots. But other sources are being studied, such as starches extracted from the genus Dioscoreae spp., A species of this genus studied infrequently is the Dioscorea bulbifera Linn also known as gizzard. In this work the native starch of D. bulbifera Linn was obtained and modified with aqueous and hydroalcoholic extract in three different concentrations of yerba mate, Ilex paraguariensis, a plant rich in bioactive compounds responsible for its beneficial health properties. Using the techniques such as Differential Scanning Calorimetry (DSC), rheological analysis through the Viscoamilographic (RVA) analysis. Thermogravimetry coupled to the system Differential Scanning Calorimetry - Mass Spectrometry (TG-DSC-MS) and morphological ones such as Scanning Electron Microscopy (SEM), X-ray diffraction method (XRD) and Colorimetry, it was possible to verify the interaction of this starch of D. bulbifera Linn with the extracts obtained from the leaves of yerba mate. Initial gelatinization temperatures of the starches with 6% aqueous extract incorporation and with 6% hydroalcoholic extract were slightly higher in relation to the native starch when studied by DSC. Most of the samples presented values of Tp and Tc and gelatinization enthalpy near to the native one. In the RVA analysis it was observed that the peaks of viscosity were higher in modified starches with extract aqueous. The final viscosity and tendency to retrograde increased relative to the native. SEM images did not change, native starch staining had a greater tendency to white L * than those modified. The X-ray diffractograms showed starch type "C. In the TG-DSC-MS analysis the main events in the DSC were more intense in the treated samples, as well as the mass-load signals detected, measured by mass spectrometry, occurred with more intense events in the samples treated with hydroalcoholic extracts and in the m / z 58 was detected in all samples except native starch. Evidence that there was incorporation of the phenolic compounds with modification in the profile of the gases generated during the decomposition.

Cette thèse présente la reconstruction de l’histoire tectono-thermique du massif varisque des Jebilet (Maroc) à fort potentiel minier, depuis son évolution pré-orogénique au Dévonien supérieur-Carbonifère inférieur jusqu’à sa structuration pendant l’orogénèse varisque-alléghanienne au Carbonifère supérieur-Permien inférieur. Pour répondre à cette problématique, ce travail s’organise autour de deux approches : (1) l’une métrologique appliquée à la géothermométrie Raman sur la matière carbonée (RSCM) et (2) l’autre intégrant une étude structurale, géochronologique et une analyse de la thermicité.L’approche métrologique a permis de valider l’applicabilité du géothermomètre RSCM (1) dans un contexte de métamorphisme polyphasé, (2) pour des roches carbonatées et des skarns des Jebilet et (3) de proposer un nouveau paramètre Raman RSA permettant de mieux préciser les températures supérieures à 500°C et d’étendre l’applicabilité de la méthode jusqu’à des températures maximales qui atteignent les 700°C.A partir de l’approche intégrée, trois épisodes tectono-thermiques ont été mis en évidence. Le premier épisode D₀ correspond à une tectonique extensive permettant l’ouverture du bassin des Jebilet au Dévonien supérieur-Carbonifère inférieur. Cette tectonique extensive est accompagnée par une anomalie thermique supérieure à 500°C déduites des mesures de géothermométrie RSCM (TRSCM) et par une importante activité magmatique bimodale et granodioritique datée dans ce travail entre 358 ± 7 et 336 ± 4 Ma. Au Carbonifère supérieur débute la phase compressive structurant le massif des Jebilet avec la mise en place de nappes superficielles au Namuro-Westphalien (D₁), suivie par la phase varisque majeure (D₂). L’analyse structurale a permis de montrer une évolution progressive du régime de déformation de D2 depuis une compression coaxiale à une transpression dextre compatible avec un raccourcissement horizontal WNW-ESE à NW-SE. D₂₁ est associée à deux événements thermiques, le premier syn-tectonique de moyenne température (300°<TRSCM<400°C), et le second syn- à post-tectonique de haute température (600°<TRSCM<660°C).Ce contexte tectono-thermique serait l’expression de processus géodynamiques impliquant à partir du Dévonien supérieur une délamination de la lithosphère rhéïque par « slab break-off » ou « slab roll-back » qui entrainerait (1) la remontée de courant asthénosphérique chaud, et (2) la rotation horaire de Gondwana et son amalgamation progressive avec Laurussia structurant au Carbonifère supérieur-Permien inférieur la chaine varisque-alléghanienne. / This thesis presents the reconstruction of the tectono-thermal history of the Paleozoic Jebilet massif (Morocco), from its pre-orogenic evolution at the Upper Devonian-Lower Carboniferous to its structuration during the variscan-alleghanian orogeny at the Upper Carboniferous-Lower Permian. To address this issue, this work is organized around two approaches: (1) one metrological applied to the Raman Spectroscopy of Carbonaceous Matterial (RSCM) and (2) the other integrating a structural and geochronological study and a thermicity analysis.The metrological approach allowed to validate the applicability of the RSCM geothermometer (1) in a context of polyphase metamorphism, (2) for carbonate rocks and skarns of Jebilet and (3) to propose a new parameter Raman RSA allowing to better specify temperatures above 500°C and extend the applicability of the method to maximum temperatures of up to 700°C.From the integrated approach, three tectono-thermal episodes were highlighted. The first episode D₀, corresponds to an extensive tectonic allowing the opening of the Jebilet basin at the Upper Devonian-Lower Carboniferous. This opening is accompanied by a HT thermal anomaly as shown by the important bimodal and granodioritic magmatic activity dated between 358 ± 7 Ma and 336 ± 4 Ma and the TRSCM higher than 500°C recorded by the rocks. During Upper Carboniferous, the compressive phase structuring the Jebilet massif begins with the emplacement of superficial nappes (D₁), followed by the variscan major phase (D2). Structural analysis showed a gradual evolution of D₂ deformation regime from coaxial compression to dextral transpression consistent with WNW-ESE to NW-SE horizontal shortening. D₂ is associated with two thermal events, the first is syn-tectonic with TRSCM between 300 and 400°C, and the second is syn- to post-tectonic with TRSCM between 600 and 660°C.This tectono-thermal context would be the expression of geodynamic processes involving from the Upper Devonian a delamination of the Rheic lithosphere by "slab break-off" or "slab roll-back" which would induce (1) the rise of hot asthenospheric current, and (2) the clockwise rotation of Gondwana and its gradual amalgamation with Laurussia structuring the variscan-alleghanian belt during the Upper Carboniferous-Lower Permian.

O estudo envolvendo a interação entre picratos de terras raras (III) hidratados e aminoácidos é reportado no presente trabalho. Este estudo consiste na preparação dos compostos de adição entre esses sais e os aminoácidos Larginina (Arg), L-lisina (Lys) e L-Ieucina (Leu), bem como a caracterização dos mesmos utilizando várias técnicas físico-químicas e analíticas. Os compostos foram preparados na relação molar 1:2 entre os respectivos sais hidratados e os ligantes (Arg, Lys e Leu) utilizando rotas de sínteses específicas para cada um desses aminoácidos. Os compostos obtidos são sólidos pouco cristalinos e higroscópicos. Os compostos com Arg e Lys são aparentemente, parcialmente solúveis em água e insolúveis em etanol, metanol, acetonitrila e nitrometano. Os compostos com Leu são aparentemente, solúveis em água, acetona, etanol, metanol, nitrometano, parcialmente solúveis em acetonitrila e comportam-se como não-eletrólitos em soluções de acetona e nitrometano. As fórmulas gerais dos compostos foram propostas tomando-se como base os teores de terras raras obtidos por análise complexométrica com EDTA e termogravimetria, dos teores de água também obtidos por termogravimetria, além dos teores de C, N e H obtidos por análise elementar. Através da combinação desses resultados foi possível sugerir as seguintes fórmulas gerais: TR(pic)32AA.2H2O e TR(pic)32Leu.5H2O (TR = La - Lu e Y, pic = picrato, AA = Arg e Lys). Em todos os compostos, os aminoácidos estão coordenados aos íons terras raras através do átomo de nitrogênio do grupo amino do carbono &#945; e os picratos, pelos menos em parte, estão coordenados de forma bidentada, através do átomo de oxigênio do grupo fenólico e um átomo de oxigênio de um dos grupos orto-nitro, conforme evidenciado por espectros de absorção no infravermelho. Todos os compostos de lisina são isomorfos entre si. Os compostos TR(pic)3.2Arg.2H2O (TR = La - Nd e Gd - Lu) formam uma série isomorfa, porém os compostos TR(pic)32Arg.2H2O (TR = Sm, Eu e Y) não pertencem a série citada e também não são isomorfos entre si. Os compostos de leucina formam três séries isomorfas. A primeira série corresponde aos compostos dos elementos La - Nd, a segunda Tb e Gd e a terceira Ho - Lu e Y. Os compostos de Sm, Eu e Dy não pertencem as séries citadas e também não são isomorfos entre si. Através dos parâmetros obtidos dos espectros de absorção na região do visível dos compostos de neodímio, foi verificado que as ligações metais-ligantes são de baixo caráter covalente. Os compostos de európio apresentam luminescência à temperatura ambiente e 77 K, já os compostos com térbio não mostram luminescência devido a seu estado emissor estar acima do estado tripleto do ligante, sendo este determinado utilizando o espectro de fosforescência do picrato, no complexo de gadolínio. As características espectrais e o comportamento biexponencial dos compostos de európio mostram que existe a presença de mais de um ambiente químico ao redor do íon Eu3+, ou seja, os compostos podem formar estruturas poliméricas. A estabilidade e o comportamento térmico dos compostos foram estudados por meio das técnicas de termogravimetrialtermogravimetria derivada (TG/DTG) e calorimetria exploratória diferencial (DSC). A estabilidade térmica dos compostos dentro de cada série é semelhante e comparando os compostos com os três aminoácidos, verifica-se que os compostos com o aminoácido Lys são os mais estáveis e os com Arg os menos estáveis. A decomposição térmica dos compostos com os três aminoácidos é distinta, porém dentro de cada série o processo ocorre de forma similar. Através das curvas termogravimétricas, além de informações quanto à estabilidade e os processos de decomposição térmica, foi possível também determinar a quantidade de moléculas de água, bem como as percentagens dos íons terras raras. / A study involving the interaction of rare-earth (III) hydrated picrates and amino acids is reported in this work. The addition compounds with L-arginine (Arg), L-Iysine (Lys) and L-Ieucine (Leu) were prepared and characterized by severaI common techniques. The compounds were prepared in the molar ratio 1:2 (hydrated salts: ligands, Arg, Lys and Leu) using specific synthetic routes for each amino acid. The Arg and Lys complexes are partially soluble in water and insoluble in ethanol, methanol,acetonitrile and nitromethane. The Leu complexes are soluble in water, acetone, ethanol, methanol and nitromethane; they are partially soluble in acetonitrile and they are non-electrolytes in acetone and nitromethane. The general formulae for the complexes, determined by EOTA titrations, elemental analyses and thermogravimetry, are RE(pic) 3.2AA.2H2O and RE(pic) 3.2Leu.5H2) (RE =La-Lu and Y, pic =picrate, AA =Arg and Lys). In all compounds, the amino acids are bonded to RE(III) ions through the &#945;aminogroup nitrogen atom and picrates, at least partially, are coordinated as bidentate ligands, through the phenoxy oxygen and one o-nitrogroup oxygen atom, as evidenced by IR absorption spectra. The Arg and Lys complexes display only one isomorphous series, but the Leu compounds present three isomorphous series. Parameters obtained from visible absorption spectra of the Nd complexes indicate that ligand-metal bonds are weakly covalent. Eu complexes are luminescent, both at room temperature and at 77K. Tb complexes are not luminescent, since their upper emitting state is above the Iigand\'s triplet state. The position of this state was determined by the picrate phosphorescence spectra of the Gd compound. Spectral characteristics, as well as the biexponential decay of Eu luminescence suggest that there is more than one coordination environment around the Eu(III) ion and that these complexes have polymeric structures. The stability and thermal behavior of these compounds were studied by thermogravimetry (TG), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC). In the three series of complexes thermal stability is similar, but the Lys complexes are the most stable and the Arg complexes the least stable ones. Thermal decompositions differ, but in each series the decomposition is similar. From TG curves it was possible also to determine water contents and the RE percent compositions.

No presente trabalho, foram desenvolvidos e avaliados comprimidos de liberação convencional de hidroclorotiazida 50mg: 6 por granulação úmida e 8 por compressão direta. Na etapa de pré-formulação, foram realizados estudos termoanalíticos (TG/DTG e DSC) para seleção de excipientes compatíveis com o fármaco e estudos micromeríticos para avaliação das propriedades de fluxo e compressibilidade das matérias-primas empregadas, dos granulados e das misturas para compressão direta obtidos. As formulações foram avaliadas quanto ao diâmetro, espessura, dureza, friabilidade, desintegração, dissolução, teor, uniformidade de conteúdo, perfil e eficiência de dissolução, empregando-se métodos analíticos devidamente validados. As melhores formulações obtidas por granulação úmida (formulação B1) e compressão direta (formulação J) foram comparadas com o produto referência para comprimidos de hidroclorotiazida, quanto à eficiência de dissolução e demonstraram ser estatisticamente semelhantes entre si e superiores ao produto referência, nas condições empregadas. / In this work, conventional liberation of hydrochlorothiazide 50 mg: 6 for wet granulation and 8 for direct compression - were developed and valuated. In the pre-formulation stage, thermoanalytical studies (TG/DTC and DSC) were realized to select compatible excipients with the drug; as well as micromeritical studies were realized to value the flow and compressibility properties of the used raw materials, granulates and obtained mixtures for direct compression. The prescriptions were valuated in relation to diameter, thickness, hardness, friability, disintegration, dissolution, assay, uniformity of contents, profile and efficiency of dissolution, using analytical methods property validated. The best formulations obtained by wet granulation (B1 formulation) and direct compression (J formulation) were compared with the reference product to tablet of hydrochlorothiazide, concerning to the efficiency of dissolution and they demonstrated to be statistically similar to each other and to be superior to the reference product, in the used conditions.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T19:45:04Z No. of bitstreams: 1 RicardoSousaFerreira.pdf: 2802747 bytes, checksum: 0d4bf284379fe32714f3b112e464cf64 (MD5) / Made available in DSpace on 2017-05-05T19:45:04Z (GMT). No. of bitstreams: 1 RicardoSousaFerreira.pdf: 2802747 bytes, checksum: 0d4bf284379fe32714f3b112e464cf64 (MD5) Previous issue date: 2016-03-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / Currently, the amino acid salt crystals are extensively studied, primarily because of their possible application in opto-electronic devices. Many amino acids complexed with chlorine crystals were synthesized and characterized, and suggested as promising materials in frequency conversion. However, the characterization of L-isoleucine hydrochloride monohydrate crystals (L-Ile.H2O.HCl) is poor because to date, one article has been published and only the authors determined the crystal structure of the synthesized material. Thus, the objective of this study was to synthesize crystals of L-Ile.HCl.H2O by the method of slow evaporation and characterize them by X-Ray Fluorescence (XRF), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TG), X-Ray diffraction (XRD) as a function of temperature and time, Raman scattering as a function of temperature and heat treating the material in a sealed glass tube with argon atmosphere for 24h at 170 °C. The XRF confirms the presence of chlorine. The XRD at 25 oC shows that the crystal belongs to orthorhombic system with lattice parameters a = 5.873 (3) Å, b = 24.814 (4) Å, c = 6.873 (5) Å. The TG, DTA and DSC indicated that the material loses water of solvation and crystallization at approximately 55 °C and 132 °C, respectively .The DRX a function of temperature, the material shows phase transformation starts at 60 oC and 155 oC extends to. The XRD at 140 oC shows that after 32h, the crystal loses water and chlorine. Raman spectra as a function of temperature, confirm the phase transformation at 60 °C and 100 °C. The material when subjected to 170 °C, for a period of 24 sealed in a glass tube with an inert atmosphere (Ar) and undergoes vaporization sublimate the same orthorhombic phase, when it has its temperature reduced to 25 °C. Therefore, the L-Ile.HCl.H2O crystal is not a material suitable for use in optical devices due to their low thermal stability. / Atualmente, os cristais de sais de aminoácidos são amplamente estudados, principalmente devido à sua possível aplicação em dispositivos opto eletrônicos. Muitos cristais de aminoácidos complexados com cloro foram sintetizados, caracterizados e sugeridos como materiais promissores na conversão de frequência. No entanto, a caracterização de cristais de L-isoleucina hidroclorídrica monohidratada (L-Ile.H2O.HCl) é deficiente, pois até o momento, um único artigo foi publicado e os autores apenas determinaram a estrutura cristalina do material sintetizado. Dessa forma, o objetivo do presente trabalho foi sintetizar cristais de L-Ile.HCl.H2O pelo método de evaporação lenta e caracterizá-los por Fluorescência de Raios-X (FRX), Análise Térmica Diferencial (DTA), Calorimetria Exploratória Diferencial (DSC), Análise Termogravimétrica (TG), Difração de Raios-X (DRX) em função da temperatura e do tempo, espalhamento Raman em função da temperatura e tratar termicamente o material em um tubo de vidro selado com atmosfera de argônio por 24h a 170 oC. A FRX confirmou a presença de cloro. O DRX a 25 oC mostrou que o cristal pertence ao sistema ortorrômbico, com parâmetros de rede a = 5,873(3) Å, b = 24,814(4) Å, c = 6,873(5) Å. O TG, DTA e DSC indicaram que o material perde água de solvatação e cristalização em aproximadamente 55 oC e 132 oC, respectivamente. O DRX em função da temperatura, revelou que o material inicia transformação de fase em 60 oC e se estende até 155 oC. O DRX a 140 oC mostrou que após 32h, o cristal perdeu água e cloro. Os espectros Raman em função da temperatura, confirmaram as transformações de fase em 60 oC e 100 oC. O material quando submetido a 170 oC, por um período de 24h selado em um tubo de vidro com atmosfera inerte (Ar), sofreu vaporização e ressublimou na mesma fase ortorrômbica, quando teve sua temperatura reduzida a 25 oC. Portanto, o cristal de L-Ile.HCl.H2O não é um material indicado para ser utilizado em dispositivos ópticos devido a sua baixa estabilidade térmica.

This thesis is focused on design of the turbine housing CAD model applicable for mixed flow turbine. It also deals with strength analysis of designed turbine housing. The aim of the thesis is to create a three-dimensional turbine housing model accompanied by drawings.

Nous avons étudié la chimie de surface de carbones poreux fonctionnalisés avec des oximes et amidoximes d’une part, et avec de la guanidine d’autre part. Nous avons axé ces travaux sur la compréhension et la quantification de ces fonctionnalisations par analyse thermique et plus particulièrement par thermo-désorption programmée en température couplée à la spectroscopie de masse (TPD-MS). Par la suite, nous avons évalué l’intérêt de la fonctionnalisation par la guanidine des carbones mésoporeux pour deux applications : le piégeage du CO2 et la capacité à synthétiser et stabiliser des nanoparticules métallique. Pour la première application, des tests d’adsorption du CO2 à 0°C et 20°C à 1 bar ont été réalisés sur un carbone mésoporeux oxydé sous air en présence ou non de guanidine. L’intensité des interactions (physisorption versus chimisorption) a été sondée par des calculs de chaleurs isostériques d’adsorption. Pour la seconde applications, nous avons utilisé des carbones mésoporeux oxydés en présence ou non de guanidine pour synthétiser des nanoparticules d’argent de taille inférieure à 2 nm et relativement monodisperses en taille. Des particules bimétalliques d’AgCu ont également été obtenues au sein de ces matrices carbonées mésoporeuses imprégnées par la guanidine. On a pu mettre ici en évidence un rôle bénéfique de la guanidine sur le taux de cuivre réduit. Des suivis thermiques par MET in situ ont également été réalisés afin d’évaluer la stabilité thermique de ces nanoparticules et de mieux appréhender l’intérêt de la fonctionnalisation sur les phénomènes de frittage de ces nanoparticules. Finalement, des tests catalytiques pour l’époxydation sélective du styrène ont aussi été effectués sur le matériau Ag/C. Les résultats préliminaires sont très prometteurs pour un procédé de préparation de catalyseur très simple à mettre en œuvre. / In this work, we studied the surface chemistry of porous carbons functionalized firstly with oximes and amidoximes and then with guanidine. We focused this work on the understanding and quantification of these functionalization with thermal analysis and more particularly by Temperature Programmed Desorption/Mass Spectrometry (TPD-MS). Subsequently, we evaluated the interest of guanidine functionalization of mesoporous carbons for two applications : the capture of CO2 and the ability to synthesize and stabilize metal nanoparticles. For the first application, CO2 adsorption tests at 0 ° C. and 20 ° C. at 1 bar were carried out on a mesoporous carbon oxidized under air in the presence or absence of guanidine. The intensity of interactions (physisorption versus chemisorption) was probed by isosteric adsorption heat calculations. For the second applications, we used oxidized mesoporous carbons with or without guanidine to synthesize silver nanoparticles less than 2 nm in size and relatively monodisperse in size. Bimetallic AgCu particles were also obtained from these mesoporous carbon matrices impregnated with guanidine. A beneficial role of guanidine on the reduced copper content has been shown here. In situ TEM has also been carried out in order to evaluate the thermal stability of these nanoparticles and to understand the interest of the functionalization on the sintering of these nanoparticles. Finally, catalytic tests for the selective epoxidation of styrene were also performed on these materials. The preliminary results are very promising for a catalyst preparation process and very simple to implement.

Pour mettre au point le système de contrôle thermique dun engin spatial (satellite, sonde ou véhicule habité), lingénieur thermicien utilise des logiciels adaptés, tels quESARAD et ESATAN, commercialisés par ALSTOM. Comme la composante radiative peut jouer un rôle prédominant, les logiciels utilisés contiennent fréquemment un algorithme de lancer de rayons pour calculer les facteurs de vue et facteurs déchange radiatif entre des surfaces de dimensions finies, supposées isothermes. Les flux externes (solaires, albédo et infrarouge terrestres) sont également calculés par lancer de rayons. Enfin, les couplages conductifs sont habituellement encodés manuellement par lutilisateur. Comme le lancer de rayons est basé sur un processus aléatoire, la précision atteinte est déterminée par le nombre de rayons lancés. En général, le choix de ce nombre de rayons est laissé à la discrétion de lingénieur, ce qui peut conduire à des erreurs. Un autre inconvénient du lancer de rayons est sa faible convergence. Une méthode daccélération du lancer de rayons est nécessaire. Dans le cadre de la thèse, nous avons développé une méthode de lancer de rayons plus performante, que nous avons appelée hémisphère stratifié, caractérisée par une meilleure convergence. Un contrôle statistique derreur a été développé : lutilisateur spécifie la précision souhaitée (définie par une erreur relative maximale et un intervalle de confiance) et lalgorithme adapte automatiquement le nombre de rayons en fonction de la configuration géométrique. Sur base de cette erreur géométrique, un système déquations adjointes est utilisé pour obtenir une erreur énergétique, caractérisant les transferts de chaleur entre les surfaces. Lhémisphère stratifié est étendu de manière à inclure des fonctions de réflexion plus complexes. Lapplication des relations de réciprocité et de fermeture est également considérée. La méthode matricielle de Gebhart, qui permet de dériver les facteurs déchange radiatifs des facteurs de vue, est étendue de manière à inclure des surfaces non-diffuses et non-isothermes. Pour accélérer le lancer de rayons, les intersections rayons-surfaces ont été soigneusement étudiées. Nous avons également développé une méthode qui combine les primitives géométriques avec des maillages éléments finis. La représentation tri-dimensionnelle du modèle géométrique est plus adaptée au calcul de la composante radiative du transfert thermique tandis que les maillages éléments finis sont plus adaptés au calcul de la conduction. Cette méthode fournit également une accélération du lancer de rayons. De plus, le lancer de rayons est effectué sur la géométrie exacte, ce qui est nécessaire si des réflexions spéculaires sont modélisées. Nous expliquons comment le lancer de rayons peut être effectué sur la géométrie exacte et comment les facteurs de vue résultants peuvent être projetés sur les éléments finis. Nous définissons la notion de facteur de vue élément fini en calculant les facteurs de vue aux noeuds et en les interpolant sur lélément fini au moyen des fonctions de forme. Ces facteurs de vue élément fini sont utilisés pour lier radiativement les noeuds du modèle. Comme le champ de température est projeté sur les fonctions de forme, nous obtenons des éléments non-isothermes, contrairement aux résultats de la méthode Thermal Lumped Parameter (différences finies) utilisée habituellement en thermique spatiale. Les liens conductifs sont calculés automatiquement sur base du maillage éléments finis. Toutes ces améliorations résultent dans un algorithme plus rapide que le programme de référence ESARAD (pour une précision équivalente) et qui fonctionne avec un petit nombre de paramètres définis par lutilisateur. Pour valider lalgorithme proposé, le modèle du vaisseau XEUS, de lESA, a été implémenté. Des comparaisons ont été effectuées avec ESARAD et le code éléments finis SAMCEF.

This thesis deals with peritectic reactions and transformations that occur during the solidification of many alloys. Peritectics are believed to be a major cause of crack-formation in many steels, thus, good knowledge of the mechanisms by which these phenomena occur is essential for preventing such defects. The thesis also handles the behaviour of metals, in particular cast structures, during hot forming. Grain size and microstructure are of most importance in determining the strength, toughness and performance of a steel. For achieving enhanced mechanical and microstructural properties, good understanding of the phenomena occurring during hot forming is required. Peritectic reactions and transformations were studied in Fe-base and steel alloys through differential thermal analysis (DTA) experiments and micrographic investigation of quenched DTA samples. The effect of the ferrite/austenite interface strain during the peritectic reaction on equilibrium conditions was thermodynamically analysed, and the results were related to temperature observations from DTA experiments conducted on Fe-base alloys and low-alloy steels. Massive transformations from ferrite to austenite were observed in the micrographs of a number of quenched low-alloy steel samples and it was proposed that these transformations are uncontrolled by diffusion, and occur in the solid state as a visco-plastic stress relief process. DTA study of an austenitic stainless steel indicated that the alloy can exhibit primary precipitations to either ferrite or austenite. A continuously-cast breakout shell of the steel was analyzed and it was suggested that the observed irregularities in growth were due to alternating precipitations of ferrite and austenite; parts of the shell with higher ratios of primary-precipitated ferrite shrink in volume at the peritectic temperature and experience reduced growths. An experimental method for studying the behaviour of metals during hot forming developed, and hot compression tests were conducted on cast copper and ball-bearing steel samples. Flow stress curves were obtained at varying temperatures and strain rates, and the results showed good agreement with earlier observations reported in literature. Micrographic analysis of quenched samples revealed variations in grain size and a model was fitted to describe the grain size as a function of deformation temperature and strain. Solidification growth during continuous casting of stainless steel and copper was numerically modelled. A varying heat transfer coefficient was proposed to approximate the experimentally measured growth irregularities in the continuously-cast stainless steel breakout shell. Solidification growth of pure copper was also modelled in the Southwire continuous casting process. Temperature measurements from the chill mould were used to approximate the temperature gradient and the heat extraction from the solidifying strand, and the results were used in a two-dimensional model of solidification. / QC 20100803

The scope of this thesis is the design and verification of an electronic packaging of a device which is a subunit of a network system that is designed for combat communication in sheltering ship. According to the project requirements this device is subjected to some environmental and electromagnetic interference tests. This thesis includes design and manufacturing steps as well as vibration, shock and thermal analyses. Electromagnetic interference is examined through the design procedure and total shielding effectiveness of the device is calculated after the applications of some electromagnetic interference precautions which are given in details.