No description available.

No description available.

The main goal of this work is to determine values of elastic constants of orthotropic, transversely isotropic and cubic materials through indentation tests on thin layers bonded to rigid substrates. Accordingly, we first use the Stroh formalism to provide an analytical solution for generalized plane strain deformations of a linear elastic anisotropic layer bonded to a rigid substrate, and indented by a rigid cylindrical indenter. The mixed boundary-value problem is challenging since the deformed indented surface of the layer contacting the rigid cylinder is unknown a priori, and is to be determined as a part of the solution of the problem. For a rigid parabolic prismatic indenter contacting either an isotropic layer or an orthotropic layer, the computed solution is found to compare well with solutions available in the literature. Parametric studies have been conducted to delimit the length and the thickness of the layer for which the derived relation between the axial load and the indentation depth is valid. We then derive an expression relating the axial load, the indentation depth, and the elastic constants of an orthotropic material. This relation is specialized to a cubic material (e.g., an FCC single crystal). By using results of three virtual (i.e., numerical) indentation tests on the same specimen oriented differently, we compute values of the elastic moduli, and show that they agree well with their expected values. The technique can be extended to other anisotropic materials. We review the literature on relations between deformations at the atomic level and stresses and strains defined at the continuum level. These are then used to compare stress and strain distributions in mechanical tests performed on atomic systems and their equivalent continuum structures. Whereas averaged stresses and strains defined in terms of the overall deformations of the atomic system match well with those derived from the continuum description of the body, their local spatial distributions differ. / Ph. D.

La mousse métallique a des propriétés mécaniques et thermodynamiques uniques qui pourraient s'avérer utiles dans de nombreux domaines, tels que la construction légère et ingénierie automobile. Cependant, la mousse métallique n'est pas encore établie en génie.Une des raisons sont les difficultés et les prix élevés dans le processus de fabrication. Causée par drainage gravitaire en état liquide, peuvent se produire des distributions de matériel non homogènes. En outre, dépassant le drainage peut provoquer rupture de bulle et la génération de soufflures. Ces effets négatifs potentiellement peuvent être évités en ajoutant magnétique ou champs électromagnétiques au cours du processus de génération.Dans cette thèse, l'influence de ces champs est donc étudié en réalisant la phase de résolution des simulations. Ces simulations sont effectuées avec le code interne premier. Une modification de la modélisation de la collision était nécessaire pour enquêter sur l'agglomération de bulles dans le métal liquide.Calcul d'une configuration statique-drainage, les mécanismes de l'agglomération sont étudiés sans la présence de champs électriques ou magnétiques. Aux vitesses élevées de drainage, les bulles flottent. À des vitesses inférieures de drainage, les bulles s'agglomèrent dans la partie supérieure du domaine, formant des structures cristallines compacte.La préférence expérimentalement bien connue de commande cubes axés sur le visage, plus hexagonale compacte vous passez votre commande de volume égal bulles est reproduit numériquement. Appliquant davantage des simulations et expériences, un mécanisme de l'instabilité de la commande de façon hexagonale compacte est identifié, ayant pour résultat la préférence de commande de cubes axés sur le visage.Afin de déterminer les propriétés mécaniques de la mousse métallique solide avec la fraction de gaz faibles et aux fonctionnalités avantageuses et désavantageuses d'état d'arrangements de bulle, simulations par éléments finis de la mousse métallique solide avec cavités sphériques sont réalisées et comparées. Une influence significative de la quantité de cristaux de bulle sur la mécanique de la mousse se trouve. Le type de l'ordre cristallin est moins important.On étudie l'influence d'un champ magnétique horizontal sur l'agglomération de bulle. La résistance de drainage peut être augmentée sensiblement en ajoutant un champ magnétique. La structure résultante des bulles est moins sensible à un champ magnétique.Combinant un courant électrique horizontal et une perpendiculaire, champ magnétique horizontal se traduit par une force verticale de Lorentz. Cette force peut équilibrer la gravitation et donc, provoquer la rotation des bulles. Simuler cet État révèle une distribution homogène de bulle. Dans le même temps, friser les champs de force dans le voisinage de chaque bulle induire un mouvement continu en remuant. Petit champ électromagnétique forces n'empêchent pas les bulles d'agglomération, mais peuvent varier le montant de la commande cristallisé et par conséquent, les propriétés mécaniques de la mousse solide qui en résulte.En conclusion, un champ magnétique horizontal augmente la résistance de drainage, tandis que sa combinaison avec un courant électrique provoque des distributions de bulle homogène et peut modifier la structure de la mousse et la fraction de gaz. Les résultats de cette thèse pourraient aider à améliorer le processus de fabrication industrielle de mousse métallique ou même permettre la production de métal poreux avec la fraction de gaz définie par l'utilisateur. / Metal foam has unique mechanical and thermodynamic properties which could prove useful in many fields, such as light-weight construction and automotive engineering. However, metal foam is not yet established in engineering. One reason are the difficulties and high prices in the fabrication process. Caused by gravity-driven drainage in liquid state, inhomogeneous material distributions can occur. Also, exceeding drainage might cause bubble rupture and the generation of blow-holes. These negative effects potentially can be avoided by adding magnetic or electromagnetic fields during the generation process. In this thesis, the influence of these fields is therefore investigated by conducting phase resolving simulations. These simulations are carried out with the in-house code PRIME. A modification of the collision modelling was necessary in order to investigate the agglomeration of bubbles within liquid metal. Computing a static-drainage setup, the agglomeration mechanisms are investigated without the presence of electric or magnetic fields. At high drainage velocities the bubbles float. At lower drainage velocities the bubbles agglomerate in the upper part of the domain, forming close-packed crystalline structures. The experimentally well known preference of face-centred cubic ordering, over hexagonally close-packed ordering of equal-volume bubbles is reproduced numerically. Applying further simulations and experiments, an instability mechanism of hexagonally close-packed ordering is identified, resulting in the preference of face-centred cubic ordering. In order to determine the mechanical properties of solid metal foam with low gas fraction and to state advantageous and disadvantageous features of bubble arrangements, Finite-Element simulations of solid metal foam with spherical voids are carried out and compared. A significant influence of the amount of bubble crystals on the foam mechanics is found. The type of the crystalline ordering is less important. The influence of a horizontal magnetic field on the bubble agglomeration is investigated. The drainage resistance can be increased significantly by adding a magnetic field. The resulting structure of the bubbles is less sensitive to a magnetic field. Combining a horizontal electric current and a perpendicular, horizontal magnetic field results in a vertical Lorentz force. This force can balance gravitation and thus, cause rotation of the bubbles. Simulating this state reveals a homogeneous bubble distribution. At the same time, curling force fields in the vicinity of each bubble induce a continuous stirring motion. Small electromagnetic field strengths do not prevent the bubbles from agglomerating, but can vary the amount of crystallized ordering and therefore, the mechanical properties of the resulting solid foam. In conclusion, a horizontal magnetic field increases the drainage resistance, while its combination with an electric current causes homogeneous bubble distributions and can alter the foam structure and the gas fraction. The results of this thesis could help improve the industrial fabrication process of metal foam or even allow production of porous metal with user-defined gas fraction.

Esta tese descreve o desenvolvimento e implementação de um otimizador em tempo real da operação do conversor da unidade de craqueamento catalítico em leito fluidizado (FCC) da refinaria Henrique Lage localizada em São José dos Campos. É desenvolvida uma estratégia de otimização integrada ao controlador preditivo cuja função objetivo e restrições incorporam componentes dinâmicos e estáticos. Os problemas de controle multivariável e otimização econômica são resolvidos simultaneamente num mesmo algoritmo. É utilizado um modelo rigoroso do processo para determinar as condições econômicas ótimas do estado estacionário do conversor. Por intermédio do modelo dinâmico, obtido através de testes em degrau na planta, é determinada a melhor trajetória para conduzir o processo para o seu ponto de maior lucratividade, sem violar as suas restrições operacionais durante as transições. As variáveis controladas e manipuladas possuem restrições tanto no transiente como no estado estacionário. O problema de otimização não linear resultante é resolvido através de um algoritmo SQP. A nova estratégia de otimização forneceu excelentes resultados nas simulações com as condições normais de operação e as perturbações típicas da unidade. Na comparação desta estratégia com a convencional, cujas funções de controle e otimização estão separadas, a mesma mostrou um melhor desempenho por manter o processo mais estável. Na fase de implementação do otimizador, o controlador preditivo multivariável existente no conversor foi adaptado para a nova estrutura de otimização através da inclusão das funções de otimização que envolvem o modelo rigoroso do estado estacionário do processo. O controlador/otimizador foi inserido no software da Petrobras denominado SICON, o qual já era utilizado como plataforma de sintonia e manutenção do controlador multivariável linear do conversor. Esse software tem facilidades para desenvolvimento e implementação de estratégias de controle avançado. Neste trabalho são apresentados os aspectos mais importantes da integração do otimizador na estrutura de automação da refinaria e o seu comissionamento. Estão também relacionadas as principais dificuldades encontradas na implementação do otimizador e a forma que as mesmas foram solucionadas. Os resultados obtidos na planta mostram um bom desempenho do novo algoritmo tanto em relação aos benefícios econômicos como na estabilização da unidade. / This thesis describes the development and implementation of a real time optimizer of the operation of a fluid catalytic cracking (FCC) converter in the Henrique Lage refinery located in São José dos Campos. It is developed an optimization strategy integrated into the predictive controller whose objective function and constraints incorporate dynamic and static components. The multivariable control and the economic optimization problems are solved simultaneously by the same algorithm. A rigorous process model is used to determine the converter steady-state optimum economic operating conditions. By utilizing a dynamic model, obtained through step tests in the plant, calculations are carried out in order to determine the best path to drive the process to its more profitable operating point, without violating operational constraints during the transient modes. All controlled and manipulated variables are constrained, both in the steady-state and in the dynamic states. The resulting optimization problem is nonlinear and is solved by an SQP algorithm. The new optimization strategy has provided excellent results in the simulations performed at normal operating conditions and typical disturbances. Comparing to the conventional strategy, whose control and optimization functions are separated, the new one has shown a better performance by maintaining a smoother operation of the process. In the optimizer implementation phase, the existent predictive linear controller was adapted to the new optimization structure by including the optimization function that involves the rigorous steady-state model of the process. The optimizing controller was inserted in Petrobras SICON software, which was already being used as a tuning and maintenance platform of the linear multivariable controller of the converter. This software has nice features for the development and implementation of advanced process control strategies. In this work it is presented the more important aspects of the optimizer integration into the refinery automation structure and its commissioning. The main difficulties of the optimizer implementation and the way how they were solved are also related. Plant results show a good performance of the new algorithm in terms of economic benefits and unit stabilization.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Os óxidos de enxofre (SOx) são um dos maiores poluentes atmosféricos e um dos precursores da chuva ácida. Um levantamento feito na Petrobrás mostrou que cerca de 17% dos SOx emitidos numa refinaria são oriundos do processo de FCC. Com o avanço dos controles ambientais, traduzido numa legislação mais restritiva, a técnica de incorporação de aditivos para remoção de SOx em UFCCs apresenta-se como a alternativa de menor custo frente outras tecnologias de abate das emissões de SOx. No presente trabalho, foram estudados aditivos constituídos por compostos derivados de hidrotalcitas com a substituição parcial do magnésio e do alumínio por cobre e/ou manganês, sendo estes impregnados ou não por dióxido de cério. Estes aditivos foram submetidos a testes de desempenho em uma unidade multi-propósito acoplada a um micro-GC/TCD. Em todos os testes, a corrente gasosa para a etapa de adsorção oxidativa foi de 1700 ppm de SO2 e 1,5% O2 em He e, para a etapa de regeneração, 30% H2/He. No primeiro conjunto de testes, realizou-se uma adsorção a 720C de 10 min e regeneração com um patamar a 530C, seguido de um TPR até 800C. Observou-se que as amostras impregnadas com cério apresentaram o melhor desempenho na remoção de SO2, indicando que o cério pode ter um papel de promotor da oxidação de SO2 a SO3. Os resultados do TPR mostram que as amostras com cério e com manganês parecem apresentar menores temperaturas de redução dos sulfatos, apesar das maiores liberações de H2S serem identificadas nas amostras com cobre. No segundo conjunto de testes, a adsorção foi a 720C durante 35 min e a regeneração a 650C por 5 minutos em um patamar de 5 minutos, seguida de um TPR até 800C. Para os tempos de sulfatação curtos (5 e 10 min), os resultados confirmaram o efeito positivo que a incorporação de CeO2 apresenta sobre a adsorção oxidativa do SO2. Todavia, para tempos de reação maiores (35 min), não se observou uma correlação clara entre a composição química do catalisador e a quantidade total de SOx removida. Os aditivos foram ainda testados em ciclos de reação-regeneração em condições equivalentes ao segundo conjunto de testes descrito. De um modo geral, os aditivos que contêm cobre têm uma vida útil superior aos demais, possivelmente, pelo fato do cobre ter importante papel na regeneração do aditivo / The sulfur dioxide emissions are one of the most atmospheric pollutant and precursor of acid rain. A survey carried out by Petrobras shows that around 17% of the SOx emissions of its refineries derive from the FCC process. In recent years, the strengthening of environmental controls with more restrictive legislation turns the incorporation of additives for SOx removal into a low-cost alternative technique compared with other technologies of SOx abatement. The purpose of this work is to study additives composed by derivated hydrotalcite compounds with partial substitution of magnesium and aluminium for copper and/or manganese, and with or without dioxide cerium impregnation. The performance of these additives has been tested in a multi-proposal unit coupled with a micro-GC/TCD. In all the tests it was used a gas stream of 1700 ppm of SO2 and 1,5% O2 in He for the oxidative adsorption step and for the regeneration step a 30% H2 in He stream. In the first test, it was carried out an adsoprtion step at 720C for 10 minutes and a regeneration step at a 530C level, flollowed by an TPR until 800C. The cerium dioxide impregnated samples showed a better result for SO2 removal, which implies cerium may play a role as catalyst for SO2 to SO3 oxidation. The TPR results show cerium and manganese may diminish the temperature of sulfates reduction, besides copper samples releases more H2S gases. In the second test, the adsorption step was carry out at 720C for 35 minutes and the regeneration step at 650C for 5 minutes folloewd by a TPR until 800C. In short times reaction (5 or 10 min) the results confirm the positive effect of cerium in the SO2 oxidantion adsorption. However, for longer time reaction (35 min), it cant be observed a relationship between chemical composition of the aditive and the total amount of SOx removed. Additives were still tested in reaction-regeneration cycles in the same conditions of the second test described above. In general, the additives without copper in their composition has a life time minor than that with copper; possibly, because copper plays an important role in the additive regeneration

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Os óxidos de enxofre (SOx) são um dos maiores poluentes atmosféricos e um dos precursores da chuva ácida. Um levantamento feito na Petrobrás mostrou que cerca de 17% dos SOx emitidos numa refinaria são oriundos do processo de FCC. Com o avanço dos controles ambientais, traduzido numa legislação mais restritiva, a técnica de incorporação de aditivos para remoção de SOx em UFCCs apresenta-se como a alternativa de menor custo frente outras tecnologias de abate das emissões de SOx. No presente trabalho, foram estudados aditivos constituídos por compostos derivados de hidrotalcitas com a substituição parcial do magnésio e do alumínio por cobre e/ou manganês, sendo estes impregnados ou não por dióxido de cério. Estes aditivos foram submetidos a testes de desempenho em uma unidade multi-propósito acoplada a um micro-GC/TCD. Em todos os testes, a corrente gasosa para a etapa de adsorção oxidativa foi de 1700 ppm de SO2 e 1,5% O2 em He e, para a etapa de regeneração, 30% H2/He. No primeiro conjunto de testes, realizou-se uma adsorção a 720C de 10 min e regeneração com um patamar a 530C, seguido de um TPR até 800C. Observou-se que as amostras impregnadas com cério apresentaram o melhor desempenho na remoção de SO2, indicando que o cério pode ter um papel de promotor da oxidação de SO2 a SO3. Os resultados do TPR mostram que as amostras com cério e com manganês parecem apresentar menores temperaturas de redução dos sulfatos, apesar das maiores liberações de H2S serem identificadas nas amostras com cobre. No segundo conjunto de testes, a adsorção foi a 720C durante 35 min e a regeneração a 650C por 5 minutos em um patamar de 5 minutos, seguida de um TPR até 800C. Para os tempos de sulfatação curtos (5 e 10 min), os resultados confirmaram o efeito positivo que a incorporação de CeO2 apresenta sobre a adsorção oxidativa do SO2. Todavia, para tempos de reação maiores (35 min), não se observou uma correlação clara entre a composição química do catalisador e a quantidade total de SOx removida. Os aditivos foram ainda testados em ciclos de reação-regeneração em condições equivalentes ao segundo conjunto de testes descrito. De um modo geral, os aditivos que contêm cobre têm uma vida útil superior aos demais, possivelmente, pelo fato do cobre ter importante papel na regeneração do aditivo / The sulfur dioxide emissions are one of the most atmospheric pollutant and precursor of acid rain. A survey carried out by Petrobras shows that around 17% of the SOx emissions of its refineries derive from the FCC process. In recent years, the strengthening of environmental controls with more restrictive legislation turns the incorporation of additives for SOx removal into a low-cost alternative technique compared with other technologies of SOx abatement. The purpose of this work is to study additives composed by derivated hydrotalcite compounds with partial substitution of magnesium and aluminium for copper and/or manganese, and with or without dioxide cerium impregnation. The performance of these additives has been tested in a multi-proposal unit coupled with a micro-GC/TCD. In all the tests it was used a gas stream of 1700 ppm of SO2 and 1,5% O2 in He for the oxidative adsorption step and for the regeneration step a 30% H2 in He stream. In the first test, it was carried out an adsoprtion step at 720C for 10 minutes and a regeneration step at a 530C level, flollowed by an TPR until 800C. The cerium dioxide impregnated samples showed a better result for SO2 removal, which implies cerium may play a role as catalyst for SO2 to SO3 oxidation. The TPR results show cerium and manganese may diminish the temperature of sulfates reduction, besides copper samples releases more H2S gases. In the second test, the adsorption step was carry out at 720C for 35 minutes and the regeneration step at 650C for 5 minutes folloewd by a TPR until 800C. In short times reaction (5 or 10 min) the results confirm the positive effect of cerium in the SO2 oxidantion adsorption. However, for longer time reaction (35 min), it cant be observed a relationship between chemical composition of the aditive and the total amount of SOx removed. Additives were still tested in reaction-regeneration cycles in the same conditions of the second test described above. In general, the additives without copper in their composition has a life time minor than that with copper; possibly, because copper plays an important role in the additive regeneration

Esta tese descreve o desenvolvimento e implementação de um otimizador em tempo real da operação do conversor da unidade de craqueamento catalítico em leito fluidizado (FCC) da refinaria Henrique Lage localizada em São José dos Campos. É desenvolvida uma estratégia de otimização integrada ao controlador preditivo cuja função objetivo e restrições incorporam componentes dinâmicos e estáticos. Os problemas de controle multivariável e otimização econômica são resolvidos simultaneamente num mesmo algoritmo. É utilizado um modelo rigoroso do processo para determinar as condições econômicas ótimas do estado estacionário do conversor. Por intermédio do modelo dinâmico, obtido através de testes em degrau na planta, é determinada a melhor trajetória para conduzir o processo para o seu ponto de maior lucratividade, sem violar as suas restrições operacionais durante as transições. As variáveis controladas e manipuladas possuem restrições tanto no transiente como no estado estacionário. O problema de otimização não linear resultante é resolvido através de um algoritmo SQP. A nova estratégia de otimização forneceu excelentes resultados nas simulações com as condições normais de operação e as perturbações típicas da unidade. Na comparação desta estratégia com a convencional, cujas funções de controle e otimização estão separadas, a mesma mostrou um melhor desempenho por manter o processo mais estável. Na fase de implementação do otimizador, o controlador preditivo multivariável existente no conversor foi adaptado para a nova estrutura de otimização através da inclusão das funções de otimização que envolvem o modelo rigoroso do estado estacionário do processo. O controlador/otimizador foi inserido no software da Petrobras denominado SICON, o qual já era utilizado como plataforma de sintonia e manutenção do controlador multivariável linear do conversor. Esse software tem facilidades para desenvolvimento e implementação de estratégias de controle avançado. Neste trabalho são apresentados os aspectos mais importantes da integração do otimizador na estrutura de automação da refinaria e o seu comissionamento. Estão também relacionadas as principais dificuldades encontradas na implementação do otimizador e a forma que as mesmas foram solucionadas. Os resultados obtidos na planta mostram um bom desempenho do novo algoritmo tanto em relação aos benefícios econômicos como na estabilização da unidade. / This thesis describes the development and implementation of a real time optimizer of the operation of a fluid catalytic cracking (FCC) converter in the Henrique Lage refinery located in São José dos Campos. It is developed an optimization strategy integrated into the predictive controller whose objective function and constraints incorporate dynamic and static components. The multivariable control and the economic optimization problems are solved simultaneously by the same algorithm. A rigorous process model is used to determine the converter steady-state optimum economic operating conditions. By utilizing a dynamic model, obtained through step tests in the plant, calculations are carried out in order to determine the best path to drive the process to its more profitable operating point, without violating operational constraints during the transient modes. All controlled and manipulated variables are constrained, both in the steady-state and in the dynamic states. The resulting optimization problem is nonlinear and is solved by an SQP algorithm. The new optimization strategy has provided excellent results in the simulations performed at normal operating conditions and typical disturbances. Comparing to the conventional strategy, whose control and optimization functions are separated, the new one has shown a better performance by maintaining a smoother operation of the process. In the optimizer implementation phase, the existent predictive linear controller was adapted to the new optimization structure by including the optimization function that involves the rigorous steady-state model of the process. The optimizing controller was inserted in Petrobras SICON software, which was already being used as a tuning and maintenance platform of the linear multivariable controller of the converter. This software has nice features for the development and implementation of advanced process control strategies. In this work it is presented the more important aspects of the optimizer integration into the refinery automation structure and its commissioning. The main difficulties of the optimizer implementation and the way how they were solved are also related. Plant results show a good performance of the new algorithm in terms of economic benefits and unit stabilization.

No description available.

Inert gases in metals can occur due to ion implantation, from a plasma in a magnetron device or as a result of being by-products of nuclear reactions. Mainly because of the nuclear applications, the properties of the inert gases, helium, argon and xenon in the body centred cubic (bcc) iron crystal are examined theoretically using a combination of molecular dynamics, static energy minimisation and long time scale techniques using empirical potential functions. The same techniques are also used to investigate argon and xenon in aluminium. The primary interest of the work occurred because of He produced in nuclear fission and its effect on the structural materials of a fission reactor. This structure is modelled with perfectly crystalline bcc Fe. In bcc iron, helium is shown to diffuse rapidly forming small bubbles over picosecond time scales, which reach a certain optimum size. In the initial phase of He accumulation, Fe interstitials are ejected. This occurs instantaneously for bubbles containing 5 He atoms and as the more He accumulates, more Fe interstitials are ejected. The most energetically favourable He to vacancy ratios at 0 K, vary from 1 : 1 for 5 vacancies up to about 4 : 1 for larger numbers of vacancies. An existing He bubble can be enlarged by a nearby collision cascade through the ejection of Fe interstitials, allowing more He to be trapped. Ar and Xe in bcc Fe prefer to be substitutional rather than interstitial and there are large barriers to be overcome for the inert gas atoms to diffuse from a substitutional site. Bubbles that form can again be enlarged by the presence of a nearby collision cascade or at very high temperatures. In this case the most energetically favourable vacancy ratios in the bubbles is 1: 1 for Ar and from 0.6: 1 to 0.8: 1 for Xe. For Ar and Xe, bubble formation is more likely as a direct result of radiation or radiation enhanced diffusion rather than diffusion from a substitutional site. Ar in aluminium is also studied. Ar atoms in fcc Al prefer to be substitutional rather than interstitial and evolution into substitutional occurs over picosecond time scales at room temperature. Bubble formation can occur more easily than in bcc iron, mainly because the barriers for vacancy diffusion are much lower but the time scales for bubble accumulation are much longer than those for He. A vacancy assisted mechanism is found which allows Ar to diffuse through the lattice. Finally some preliminary results on the energetics of different geometrical structures of larger Xe bubbles in Al are investigated since experiment has indicated that these can become facetted.