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New strategies for the rhodium-catalysed aqueous-biphasic hydroformylation of medium chain alkenesDesset, Simon L. January 2009 (has links)
Aqueous-biphasic organometallic catalysis is, as illustrated by the industrial hydroformylation of propene and butene, one of the most promising ways to overcome the intrinsic problem of catalyst separation in organometallic catalysis. However, for poorly water-soluble substrates, mass transfer limitations bring the reaction rate below any that could be economically viable, greatly limiting the scope of this elegant technology. We have studied three different strategies to overcome this limitation. We developed additives that speed up the reaction whilst retaining fast phase separation and good metal retention. Evidence suggests that those additives affect the reaction by forming emulsions with poor stability under the reaction conditions These emulsions increase the interfacial surface area but break after settling for a short time. We also developed ligands that allow the catalyst to be reversibly transported between an aqueous and an organic phase upon addition and removal of carbon dioxide. This allows the reaction to be carried out under homogeneous conditions, only limited by intrinsic kinetics, and the catalyst to be separated by aqueous extraction triggered by carbon dioxide. The catalyst can be returned to a fresh organic phase by flushing out the carbon dioxide. By applying this methodology for the hydroformylation of medium chain length alkenes, very high reaction rates were obtained and the catalyst could be recycle three times with excellent retention of activity and low metal leaching. This methodology could also be reversed with the reaction being carried out in an aqueous phase in the presence of carbon dioxide and extracting the catalyst into an organic solvent using nitrogen flushing. Finally, we briefly investigated the use of an oscillatory baffled reactor as a mean for mass transfer improvement for aqueous-biphasic hydroformylation. This new type reactor did not improve the performance of the system under the investigated conditions, but may require less energy input for equivalent agitation and mixing.
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Hétérogénéités compositionnelles dans les réservoirs de gaz acides : compréhension et modélisation du rôle d'un aquifère actif / Compositional heterogeneities in acid gas reservoirs : role of an active aquifer, mechanisms and simulationBonnaud, Estelle 29 June 2012 (has links)
La présence d'H2S dans un gisement est un important facteur de dévalorisation économique, c'est pourquoi connaitre sa concentration et sa distribution est capital pour optimiser toutes les étapes de l'exploration à la production d'un champ. Dans les conditions de pression et température des réservoirs, l'H2S est beaucoup plus soluble que les hydrocarbures et autres gaz. Le lessivage préférentiel de l'H2S par un aquifère actif pourrait ainsi entrainer la création d'hétérogénéités compositionnelles au cours du temps. L'objectif de la thèse est d'illustrer et quantifier ce processus à l'aide de simulations numériques réalisées avec Hytec, logiciel couplé géochimie-transport diphasique développé par MINES ParisTech. Le lessivage préférentiel de l'H2S est contrôlé par : la solubilité différentielle des gaz qui modifie les quantités relatives de chacun des gaz à proximité de l'aquifère ; le transport aqueux qui exporte les gaz dissous et améliore ainsi la dissolution des gaz sur le long terme ; le transport gazeux qui renouvelle les gaz dissous à l'interface et étend le lessivage du gaz à toute la structure ; les caractéristiques d'un réservoir (type d'aquifère, hétérogénéité des perméabilités). / The H2S occurrence in gas reservoirs is an important factor of economic depreciation. Thus, the knowledge of its content and distribution is a critical parameter when planning field development. Under typical reservoirs conditions of pressure and temperature, H2S is far more soluble than hydrocarbons and other gases. The preferential leaching of H2S by an active aquifer over time could explain the creation of compositional heterogeneities. The thesis aims at illustrating and quantifying this process based on numerical simulations performed with the two-phase transport and geochemical software Hytec, developed by Mines ParisTech (France). This mechanism may be controlled by: Differential solubility of gases, which changes the relative amounts of each gas near the gas-watercontact; Contact with an active aquifer, which can export the dissolved gases thus enhancing dissolution on the long-term; Diffusional transport in the gas phase, which transfers the compositional anomalies farther from the gas-water contact; Geological parameters (type of aquifer, permeability heterogeneities) which can modify the transport scenario.
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Étude de l'oxydation de différents composés phénoliques par la laccase de Myceliophtora thermophila : application à la fonctionnalisation du chitosane / Study of different phenolic compounds oxidaton by laccase from Myceliophtora thermophila : application in the fuctionalization of chitosaneIssa, Nizar 17 July 2009 (has links)
La laccase de Myceliophtora thermophila oxyde certains acides hydroxycinnamiques avec formation éphémère d’intermédiaires de différentes couleurs avant que ceux-ci n’évoluent ensuite spontanément en polymères brun noir. Quand cette oxydation est effectuée en milieu biphasique (tampon phosphate pH 7,5 / acétate d’éthyle), une partie de ces intermédiaires colorés peut être récupérée dans la phase organique et ainsi soustraite à la polycondensation ultérieure. Dans le cas de l’acide férulique, on peut ainsi isoler une fraction colorée en jaune orangé surtout composée de dimères résultant de la condensation des semiquinones initialement formées. La synthèse de ces colorants peut être favorisée et le rendement amélioré en contrôlant la réaction par un ajout minimum régulé d’oxygène. Ces colorants conservent le pouvoir antioxydant de l’acide férulique parent mais à concentration élevée (100 à 200 mg/ml), ils présentent une cytotoxicité plus élevée vis-à-vis de cellules humaines normales (HUVEC) et cancéreuses (Caco-2) ce qui limite éventuellement leur intérêt comme colorants naturels. Les semi quinones de l’acide férulique ne forment pas de dimères mixtes, quand on effectue l’oxydation laccasique de cet acide en présence d’autres acides phénoliques car la laccase de M. thermophila effectue une oxydation séquencée en fonction de sa plus ou moins grande affinité pour les différents substrats mis en jeu. En présence d’un polyoside aminé insoluble comme le chitosane, les intermédiaires d’oxydation laccasique de différents composés phénoliques (acides férulique, sinapique, syringique et catéchine) réagissent avec les groupements NH2 pour former des liaisons de covalence et conduire ainsi à des chitosanes colorés doués de nouvelles propriétés dues au greffage d’entités phénoliques. Ces chitosanes fonctionnalisés conservent les propriétés filmogènes du chitosane natif mais en plus, forment des solutions plus visqueuses et sont devenus solubles en milieux acide et basique. Ils permettent la croissance de cellules HUVEC. Ils ont surtout acquis des propriétés antioxydantes et forment des films imperméables à l’oxygène ce qui laisse entrevoir de multiples applications intéressantes / The laccase of Myceliophtora thermophila oxidizes some hydroxycinnamic acids with ephemeral formation of intermediates of different colors before these evolve spontaneously in dark brown polymers. When this oxidation is performed in biphasique medium (phosphate buffer pH 7.5 and ethyl acetate), a part of these colored intermediates can be recovered in the organic phase and it can be subtracted from an ulterior polycondensation. In the case of ferulic acid, we could isolate an orange yellow fraction, which is especially composed of dimers resulting from the condensation of the semiquinones initially formed. The synthesis of these colorants can be enhanced and their yield can be improved by controlling the reaction through a regulated minimum addition of oxygen. They keep the antioxidant power of related ferulic acid, but in high concentration (from 100 to 200 mg/ml), their cytotoxicity toward the human normal cells (HUVEC) and cancerous one (Caco-2) is important and consequently, their interest is limited as natural colorants. The semiquinone of ferulic acid doesn't form any mixed dimers, when the laccase-catalysed ferulic acid oxidation is performed in the presence of other phenolic acids. This can be explained by the fact that laccase from M. thermophila performes a multioxidation in the function of its high or little affinity for the involved substrates. In presence of an insoluble amino polyoside as chitosan, the intermediates of laccase-catalysed oxidation of different phenolic compounds (ferulic, sinapic, syringic acids and catechin) react with its NH2 groups forming covalent liaisons. Actually, this type of link leads to colored chitosans endowed of news properties due to the grafting of phenolic entities. These functionalized chitosans keep the filmogens properties of the native one. Moreover, also it can form more viscous solutions and become soluble in acidic and basic medium. It can permit the growth of HUVEC cells. They especially acquired some antioxidant properties and formed impermeable films to the oxygen which highlights multiple interesting applications
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Greffage de complexes organométalliques sur anions hydroxyborates : application à la transformation des oléfines / The use of hydroxyborate anions as anchors for organometallic complexes : application to olefin transformation reactionsKelsen, Vinciane 14 December 2010 (has links)
Cette thèse présente le greffage de complexes organométalliques sur des anions hydroxyborates. Ces ligands originaux sont susceptibles de conférer des propriétés particulières à la sphère de coordination du métal. Leur caractère anionique pourrait permettre l'immobilisation des catalyseurs dans une phase liquide ionique. La majeure partie des travaux a porté sur la réactivité des anions hydroxyborates avec les métaux du groupe IV de la classification périodique. Les complexes alkyles du zirconium et de l'hafnium réagissent avec la fonction hydroxyle de l'anion par protonolyse de la liaison métal-alkyle. La résolution par diffraction des rayons X de la structure des complexes métallocènes [Cp2MMe(OB(C6F5)3)]- [PPN]+ (M = Zr et Hf) a confirmé la nature covalente des liaisons M-O et B-O et donc l'intérêt des anions hydroxyborates comme ligands de complexes organométalliques. Cette réactivité a ensuite été déclinée sur différents précurseurs du zirconium et de l'hafnium. Le complexe ionique [Ti(OiPr)3(OB(C6F5)3]-[PPN]+ a été synthétisé à partir d'un complexe alkoxy du titane par une réaction d'échange de ligands. Ce complexe activé par le triéthylaluminium dimérise sélectivement l'éthylène en butène-1 en milieu liquide ionique. L'extension du concept à d'autres métaux de la classification périodique : aluminium, fer, molybdène, a été abordée. Deux complexes anioniques du molybdène ont notamment été isolés et sont des catalyseurs de métathèse des oléfines / This thesis presents the use of hydroxyborate anions as anchors for organometallic complexes. These original ligands might confer particular properties to the coordination sphere of the metal. Their anionic nature might also allow the immobilization of catalysts in ionic liquids. The main part of this work dealt with the reactivity of hydroxyborate anions with group IV metals. Zirconium and hafnium complexes reacted with the hydroxyl function of the anion by protonolysis of the metal-alkyl bond. Resolution of the structure of metallocene complexes [Cp2MMe(OB(C6F5)3)]-[PPN]+ (M = Zr and Hf) by X-Ray diffraction confirmed the covalent nature of M-O and B-O bonds and so the relevance of hydroxyborate anions as ligands for organometallic complexes. Then, this reactivity was extended to different zirconium and hafnium precursors. The ionic complex [Ti(OiPr)3(OB(C6F5)3)]- [PPN]+ was synthesized from an alkoxy titanium complex by a ligand exchange reaction. This complex activated by triethylaluminium selectively dimerized ethylene into 1-butene in ionic liquids. Extension of the concept to other metals such as aluminum, iron and molybdenum, was studied. Two anionic molybdenum complexes were isolated and are catalysts for olefin metathesis
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Compréhension des écoulements biphasiques stables et instables de fluides à seuil lors du forage d’un puits pétrolier / Stability of two-phase yield-stress fluid flow in borehole wellsMaimouni, Ilham 22 February 2017 (has links)
Cette thèse puise sa motivation dans l'industrie pétrolière, et plus particulièrement dans la phase de cimentation primaire des puits pétroliers. Le travail consiste en une étude expérimentale des écoulements biphasiques, stables et instables, des fluides utilisés durant cette opération. Dans les cas instables, l'instabilité de Rayleigh-Taylor, qui est susceptible de se développer quand un fluide lourd repose sur un fluide léger sous le champs gravitaire par exemple, est l'une des instabilités responsables des phénomènes de mélange observés entre les fluides déplacés, notamment la boue et le ciment. Elle est étudiée dans ce travail dans le cas de fluides modèles, à seuil, reprenant le même comportement rhéologique que les fluides pétroliers, à la fois d'un point de vue qualitatif et quantitatif. Dans les cas stables où les fluides pétroliers laissent des dépôt sur les parois du puits, une étude expérimentale, se basant sur des fluides à seuil modèles, permet de relier l'épaisseur du dépôt aux paramètres importants du problème, à savoir les paramètres rhéologiques du fluide à seuil et les propriétés de l'écoulement / This thesis draws its motivation from the petroleum industry, and more particularly from the phase of primary cementation of the oil wells. The work consists of an experimental study of the biphasic, stable and unstable flows, fluids were used during this operation. In the unstable cases, the instability of Rayleigh-Taylor, which may develop when a heavy fluid rests on a light fluid under fields’ gravitaire for example, is one of the instabilities responsible for phenomena of mixture observed between the uncalled-for fluids, in particular the mud and the cement. It is studied in this work in the case of model fluids, in threshold, resuming the same rheologic behavior as the oil fluids, at the same time from a qualitative and quantitative point of view
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Estimativa dos parâmetros acústicos em uma mistura de líquidos imiscíveis durante o processo de separação de fases / Acoustic parameters estimative for a mixture of inmiscible liquids during its dynamic phases separation processVillamarín Muñoz, Julián Antonio 14 November 2007 (has links)
Esta pesquisa estuda a evolução temporal dos parâmetros de propagação acústica de uma mistura de líquidos imiscíveis considerada como emulsão instável durante o processo de separação de suas fases. O principal objetivo neste trabalho é estudar o comportamento não linear de materiais que variam sua não homogeneidade quando são submetidos a um campo acústico. O estudo é baseado na teoria de análise espectral de ecos de ultra-som para entender o processo físico de interação da onda - emulsão. A emulsão bifásica que tem sido analisada neste estudo é composta principlamente por um óleo mineral A e um óleo vegetal B. A metodologia é baseada na análise tempo freqüência de ecos e sinais de backscattering de ultra-som com uma freqüência central de 5 MHz e uma largura de banda de 8 MHz @ - 3dB. A velocidade média de propagação acústica para a mistura liquida foi estimada em 1354 m/s. O coeficiente de atenuação foi calculado para cada fase separada e se obtiveram os seguintes resultados: 0.82 dB/cm - MHz para o óleo A e 0.59 dB/cm - MHz para o óleo B. O parâmetro B/A avaliado para cada fase separada foi de: 8.43 para óleo A e 10.74 para o óleo B. A variação dos parâmetros acústicos descreveram a evolução da emulsão no tempo mediante o decremento das curvas de atenuação, B/A e IBC. A velocidade de propagação não forneceu informações relevantes a respeito do processo de separação das fases, devido a sua variação mínima. A percentagem média de variação dos parâmetros acústicos durante o processo dinâmico de separação das fases da emulsão foi de 1.39% para a velocidade de propagação, 46.9 para B e 51% para B/A. Espera-se que o estudo possa ser extrapolado para o melhor entendimento da interação de ondas de ultra-som em meios não homogêneos e variantes no tempo. / This research studies the time evolution of acoustic propagation parameters of a mixture of inmiscible liquids considerated as unstable emulsion during the separation process into its original phases. The main aspect of this work is to deal with the behavior of nonlinear, nonhomogeneous and time-varying media when they are submitted in an acoustic field. The study is based on spectral analysis theory of ultrasound-backscattered echoes for understanding of physical process of the wave-emulsion interaction. The biphasic emulsion, which has been analyzed during this study, is composed by a mineral oil (phase A) and vegetable oil (phase B). The methodology was based on time-frequency analysis of backscattered broadband ultrasound echo at center frequency of 5 MHz and bandwidth of 8 MHz @ -3dB using an ultrasound system in pulse-echo mode. The mean acoustic propagation velocity for the mixture liquid was estimated in 1354 m/s. The attenuation coefficients were calculated for each separated phase resulting in 0.82 dB/cm-MHz to phase A and 0.59 dB/cm-MHz to phase B. The B/A parameter have been evaluated resulting in 8.43 (phase A) and 10.74 (phase B). The acoustic parameters variation allowed identified different emulsification state inside emulsion. The time evolution for the emulsion was described throught the decrease of attenuation, B/A and IBC. The acoustic propagation velocity don\'t provide relevant information about the phases separation process, because it showed a minimal variation. The mean percentage variation for the time evolution of the acoustic parameters was 1.39% to the acoustic propagation velocity, 46.9% to B and 51% to B/A. We hope that observations can be extrapolated aiming a better understanding of ultrasonic waves interaction in non-homogeneous time-varying medium.
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Adaptações no sistema de produção do fungo entomopotogênico Metarhizium anisopliae (Metch.) Sorokin (Ascomycota: Hypocreales) / Adaptations in the production system of the entomopathogenic fungus Metarhizium anisopliae (Metch.) Sorokin (Ascomycota: Hypocreales)Santos, Polyane de Sá 07 February 2017 (has links)
O método empregado na produção de fungos entomopatogênicos teve poucas alterações em mais de 40 anos de utilização no Brasil. A produção adotada nas biofábricas em larga escala é basicamente através da fermentação sólida em arroz com elevado uso de mão de obra e longo tempo de produção. Assim, o presente estudo consistiu em desenvolver estratégias que possam ser implementadas nas diferentes etapas do sistema de produção de Metarhizium anisopliae ESALQ1037, como adição ao arroz de materiais inertes (bagaço de cana-de-açúcar, maravalha, esponja vegetal e palha de arroz) e outros substratos (milheto, flocos de arroz e sagu) para separação dos grãos de arroz e aumento da aeração, uso de blastosporos como inóculo em sistemas bifásicos tendo como substrato sólido o arroz ou mistura de farelos (trigo, milho, aveia, arroz, soja e algodão) ou suportes de crescimento e esporulação (bagaço de cana-de-açúcar, vermiculita, tecido de lã, palha de arroz e maravalha). Foi testado o uso da esterilização por fervura em substituição à autoclavagem e recuperação de conídios por extração em água como substituto ao peneiramento, além de armazenamento em condições de alta e baixa temperatura e umidade: 97%UR e 22ºC; 97%UR e 4ºC; 0%UR e 22ºC; 0%UR e 4ºC. O meio líquido M11 (a base de 45g L-1 glicose e 36g L-1 extrato de levedura) foi o mais adequado para produção de blastosporos (3,0 x 108 blastosporos/mL) e biomassa. A inoculação de blastosporos em arroz resultou em produção maior e mais rápida de conídios (4,51 x 108 conídios/g) em 7 dias de crescimento fúngico. O farelo de trigo inoculado com blastosporos produzidos em meio M11 resultou em maior produção de conídios (1,2 x 109 conídios/g) quando comparado aos farelos e arroz inoculados com suspensão de conídios (máximo de 7,8 x 108 conídios/g). O bagaço de cana-de-açúcar autoclavado seco foi o suporte que resultou em maior produção do fungo quando associado ao meio líquido. A adição ao arroz de bagaço de cana-de-açúcar umedecido, maravalha e esponja vegetal não umedecidas promoveu incremento na produção de conídios (> 3,3 x 109 conídios/g) quando comparado ao arroz somente (1,00 x 109 conídios/g). A exposição do arroz à fervura por 10 e 15 minutos resultou em produção de conídios semelhante à produção em arroz autoclavado, sem a presença de contaminantes. Farelo de trigo foi o substrato mais promissor para produção do fungo especialmente quando misturado ao farelo de arroz (1,75 x 109 conídios/g) na fermentação sólida. Conídios extraídos do arroz por peneiramento ou lavagem em água e recuperados com ou sem a adição de argilas, terra de diatomácea e caulim apresentaram viabilidade superior a 92% após armazenamento por 60 dias a 22°C e 97% UR. A 22°C e 0% UR, somente os conídios extraídos do arroz por peneiramento e os extraídos em água e recuperados com a adição de argila preta e caulim apresentaram viabilidade superior a 92% após armazenamento por 60 dias. Estratégias testadas neste estudo para produção e extração de conídios de M. anisopliae são alternativas viáveis para serem incorporadas na produção em larga escala e reduzir o tempo de fermentação e mão de obra, aumentando a eficiência de conversão de substrato em conídios. / The method used in the production of entomopathogenic fungi had few changes in more than 40 years of use in Brasil. The production of large-scale biofactories is basically through solid fermentation in rice with high labor and long production time. Thus, the present study consisted in developing strategies that could be implemented in the different stages of the production system of Metarhizium anisopliae ESALQ1037, as addition to rice of inert materials (sugarcane bagasse, shavings, vegetable sponge, rice straw) and other substrates (millet, rice flakes and sago) for separation of rice grains and increased aeration, use of blastospores as inoculum in biphasic systems having as a solid substrate the rice or mixture of bran (wheat, corn, oats, rice, soybean and cotton) or growth and sporulation supports (sugarcane bagasse, vermiculite, wool, rice straw and shavings). The use of boiling sterilization to replace autoclaving and recovery of conidia by water extraction as a substitute for sieving was tested, as well as storage under high and low temperature and humidity conditions: 97% RH and 22 ºC; 97% RH and 4°C; 0% RH and 22°C; 0% RH and 4°C. The M11 liquid medium (the base of 45g L-1 glucose and 36g L-1 yeast extract) was the most suitable for the production of blastospores (3.0 x 108 blastospores / mL) and biomass. The inoculation of blastospores in rice resulted in larger and faster production of conidia (4.51 x 108 conidia / g) in 7 days of fungal growth. The wheat bran inoculated with blastospores produced in M11 medium resulted in higher conidia production (1.2 x 109 conidia / g) when compared to the bran and rice inoculated with conidial suspension (maximum of 7.8 x 108 conidia / g). The dried autoclaved sugarcane bagasse was the carrier that resulted in higher fungus production when associated with the liquid medium. The addition of moistened sugarcane bagasse and non-moistened shavings and vegetable sponges promoted increase in the production of conidia (> 3.3 x 109 conidia / g) when compared to rice only (1.0 x 109 conidia / g). Exposure of the boil rice for 10 and 15 minutes resulted in conidial production similar to the production in autoclaved rice without the presence of contaminants. Wheat bran was the most promising substrate for the fungus production especially when mixed with rice bran (1.75 x 109 conidia / g) in solid fermentation. Conidia extracted from rice by sieving or washing in water and recovered with or without the addition of clays, diatomaceous earth and kaolin showed viability higher than 92% after storage for 60 days at 22 °C and 97% RH. At 22 °C and 0% RH, only the conidia extracted from the rice by sieving and those extracted in water and recovered with the addition of black clays and kaolin had viability higher than 92% after storage for 60 days. Strategies tested in this study for the production and extraction of conidia of M. anisopliae are viable alternatives to be incorporated in the large scale production and to reduce the time of fermentation and manpower, to increasing the efficiency of conversion of substrate in conidia.
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Organometallic compounds and metal nanoparticles as catalysts in low environmental impact solventsEscárcega Bobadilla, Martha Verónica 17 January 2011 (has links)
Durant les darreres dècades, el disseny de processos en el marc de la química sostenible ha anat creixent de forma exponencial. La recerca constant de processos mes benignes amb el medi ambient ha implicat un gran esforç per obtenir millors rendiments mitjançant l'activació de llocs específics, i possant especial èmfasi amb el control de la quimio-, la regio- i la enantioselectivitat, punts crucials per a l'economia atómica. En aquest sentit, els dissolvents juguen un paper crític, i com podrà veure's al llarg d'aquesta memòria..Aquesta Tesi s'enfoca en l'ús de mitjans de reacció alternatius i sostenibles, com són els líquids iònics (ILs), el diòxid de carboni supercrític (scCO2) i la barreja de ambdós dissolvents, amb l'objectiu de disminuir l'ús de dissolvents orgànics convencionals i la seva aplicació en els següents processos catalítics: hidrogenació asimètrica, reacció de Suzuki d'acoblament creuat C-C, reacció d'alquilació al·lílica asimètrica i la hidrogenació de arens. / In the last decades, the design of processes in the framework of the sustainable chemistry has been exponentially growing. The constant searching of cleaner processes has led to a lot of effort to obtain higher yields by activation of specific sites, and improving chemo-, regio- and enantio-selectivities, which are crucial from a point of view of an atom economy strategy. In this sense, solvents play a critical role. This PhD thesis focuses on the use of alternative sustainable reaction media such as ionic liquids (ILs), supercritical carbon dioxide (scCO2) and mixtures of both solvents in different catalytic processes, with the aim of decreasing the use of conventional organic solvents applied in the following catalytic reactions: homogeneous and supported rhodium catalysed asymmetric hydrogenation, biphasic palladium catalysed Suzuki C-C cross-coupling, homogeneous palladium catalysed asymmetric allylic alkylation, and ruthenium and rhodium nanoparticles catalysed arene hydrogenation were tested.
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O Problema de Riemann para um escoamento bifásico em meios porosos com histerese nas duas fases. / The Riemann Problem for a two-phase flow in porous media with hysteresis in the two phases.ARAÚJO, Juliana Aragão de. 05 July 2018 (has links)
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Previous issue date: 2005-05 / Neste trabalho é apresentada a solução do problema de Riemann associado a um
sistema de leis de conservação. Este sistema é proveniente de um escoamento bifásico
unidimensional em meios porosos e considera os efeitos de histerese nas curvas de
permeabilidade das fases. A principal contribuição deste trabalho é que a solução do
problema de Riemann é obtida para um modelo que leva em conta a histerese nas duas
fases e que considera as curvas de embebição e de drenagem distintas sempre que haja
uma reversão de regime de drenagem para embebição e vice-versa. Os resultados obtidos aqui ampliam aqueles obtidos para um modelo mais simplificado em que a histerese era considerada apenas numa das fases e as curvas de permeabilidade eram tomadas coincidentes após urna segunda reversão. Uma vez obtida a solução do problema de Riemann, base para a construção de simuladores numéricos de alta precisão, é feita uma comparação entre esta solução e aquela obtida anteriormente, para os mesmo dados iniciais, mostrando que não só as velocidades de ondas podem ser distintas, mas também as próprias sequências de ondas que formam tais soluções. / In this work we prasent the Riemann solution for a system of conservation laws
associatcd to an unidimensional two-ph&sc fiow in a porous media taking into account
the hysteresis effects on the permeability curves. Our main contribution in this work
is that the solution of the Riemann problem is obtained for a model that takes into account
the hysteresis in both wetting and non-wetting phases and considers the scanning
curves of embebition and drainagc distincts whenever there is a reversion of regime.
The results obtained here improve those obtained for a simplified model where hysteresis
is considered only on the non-wetting phase and the scanning curves coincide aftcr
a second reversion of regime. Once obtained the solution of the Riemann problem,
which is basic for the construction of high aceurate numeric simulators, we compare
this solution and that one already obtained, for the same initial data. showing that
not only the speeds of waves can be distinct, but also the sequences of waves in such
Solutions.
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Avaliação de retorno elástico para processos de estampagem à frio dos aços bifásicos DP 600 e DP 800Zanluchi, Jeferson Jorge Dallagnol January 2014 (has links)
Este trabalho procura avaliar o retorno elástico em aços avançados de alta resistência utilizados em processo de dobramento. Para isso, foram usadas chapas de aço bifásico DP 600 e DP 800, ambas revestidas. Foram empregados dois métodos de medição a fim de abordar e avaliar o retorno elástico. O primeiro método abordado foi à conformação de tiras em U e o segundo método foi à realização do ensaio Dobramento Sob Tensão, aos quais possibilitaram a coleta de dados para aplicação em cálculo de coeficiente de atrito no processo de dobramento. Em ambas as avaliações foram utilizadas duas diferentes condições de lubrificação para o processo de dobramento, visando variar a condição de atrito no processo. A primeira foi à aplicação de um lubrificante em forma de pasta, de nome comercial Clarus Desmoldax DCP 35 e a segunda foi à aplicação em forma líquida, denominado Clarus Desmoldax DCP 35X. Para analisar o retorno elástico, foram utilizadas como critério de avaliação as medições de abertura da parede da tira conformada, permitindo desta forma considerar o atrito por intermédio da variação do tipo lubrificante. As análises realizadas nos corpos de prova conformados em formato U evidenciaram um retorno elástico menor para as amostras do aço DP 600, se comparadas com as amostras do aço DP 800. Não existiu relevância na variação dos lubrificantes quanto ao retorno elástico nas amostras de um mesmo tipo de aço. As análises realizadas nos corpos de prova submetidos ao ensaio de dobramento sob tensão, também evidenciaram um retorno elástico menor para as amostras do aço DP 600 se comparadas com as amostras do aço DP 800. Comparando as amostras com base nos dados coletados e aplicados ao cálculo de coeficiente de atrito, percebeu-se que as amostras que tiveram um retorno elástico menor, também possuíam coeficientes de atrito menor, constatando assim que quanto menor o coeficiente de atrito, menor é o retorno elástico. / This piece of work seeks to evaluate the springback effect on advanced high strength steel used in the bending process. For this, biphasic steel plates DP 600 and DP 800, both coated, were used. Two methods of measurement were used to approach and asses the springback effect. The first method approached was the conformation of strips in U and the second method was the preformance of the Bending Under Tension test, which enabled the data collect for the application in calculation of the friction coefficient in the bending process. In both assessments two different lubricant conditions for the bending process were used with the aim of varying the condition of friction in the process. The first one was the application of a paste lubricant, with the brand name Clarus Desmoldax DCP 35 and the second one was the application of a liquid lubricant, called Clarus Desmoldax DCP 35X. To analyze the springback effect the measurements of the opening of the wall of the conformed strip were used, thus allowing to consider the friction through the variation of the type of lubricant. The assessments carried out in the specimens in U shape showed a smaller springback effect for the steel samples DP 600 in comparison with the DP 800 ones. There was no relevance in the range of lubricants as the springback effect in the samples of the same type of steel. The analyzes carried out in the specimens subjected to bending under pressure test also showed a smaller springback effect for the steel samples DP 600 compared with the DP 800 ones. Comparing the samples based on the data collected and applied to the calculation of the friction coefficient, it was noticed that the samples that had a smaller springback effect also had lower friction coefficients, therefore verifying that the lower the friction coefficient is, the lower the springback effect.
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