Copolímeros de e-caprolactona e l,l-dilactídeo têm sido investigados com a finalidade de desenvolver materiais biodegradáveis para aplicações médicas. As sínteses dos homopolímeros e copolímeros de epsilon-caprolactona e l,l-dilactídeo por abertura de anel e polimerização em massa transcorreram a 120oC sob atmosfera de nitrogênio, usando o octanoato de estanho como iniciador. A composição dos copolímeros variou de 5,90% a 97,30% em massa de l,l-dilactídeo. As massas molares dos polímeros sintetizados foram determinadas por viscosimetria capilar e cromatografia de permeação em gel (GPC). A composição dos copolímeros foi determinada por RMN de 13C. As propriedades térmicas e mecânicas foram avaliadas por DSC e DMTA. O grau de cristalinidade e as fases cristalinas dos copolímeros foram determinados por difração de raios X (WAXS). Foram observadas altas taxas de conversão de monômeros para os homopolímeros e para os copolímeros Co60 ao Co90 (taxas de 70-80%). Os homopolímeros e copolímeros sintetizados apresentaram altas massas molares (M w até 106.500 g/mol para os copolímeros) e moderada polidispersidade (1,50). As análises de RMN de 13C demonstraram a predominância da formação de copolímeros estatísticos e a ausência da transesterificação durante a polimerização em massa. As propriedades dinâmico-mecânicas foram fortemente dependentes da estrutura cristalina e do grau de cristalinidade dos copolímeros. Os copolímeros sintetizados apresentaram propriedades mecânicas variando do flexível ao rígido termoplástico. Os copolímeros com composição próxima a equimolar (Co30 ao Co40) apresentaram os mais baixos graus de cristalinidade (13 a 15%) e, por conseqüência, apresentaram maior taxa de degradação (20% em 408 horas para o Co40), em comparação com os demais copolímeros. / Copolymers of epsilon-caprolactone with l,l-lactide have been investigated in order to develop biodegradable materials for medical applications. The synthesis of homopolymers and copolymers of e-caprolactone with l,l-lactide by ring-opening bulk polymerization was performed using stannous octoate as initiator at 120 ºC under nitrogen atmosphere. The copolymers composition was varied from 5.90 to 97.30 % in mass of l,l-lactide. The molecular weight of synthesized polymers were determined by viscometry and GPC. The copolymers composition was determined by 13C NMR. Thermal and mechanical properties have been evaluated by DSC and DMTA. The degree of crystallinity and the crystalline phase of copolymers were determined by WAXS. High conversion was observed for homopolymers and copolymers Co60 to Co90 of l,l-lactide (70-80%). The homopolymers and copolymers presented hight molecular weight (M w up to 106,500 g/mol for copolymers) and low polydispersivity (1,50). The analyses by 13C- NMR spectroscopy have shown the predominance of statistical copolymers formation and the transesterification reaction did not occur during the bulk polymerization. Thermal and mechanical properties were dependent on the crystalline phase and of the degree of crystallinity. The synthesized copolymers presented mechanical properties from rubbery to stiff thermoplastics. The copolymers with equimolar composition presented low degree of crystallinity (13 ? 15%) and higher degradation (20% during 408 hours for Co40).

This thesis is a representation of my contribution to the paper of the same name I co-author with Dr. Wasilkowski. It deals with linear problems defined on γ-weighted normed spaces of functions with infinitely many variables. In particular, I describe methods and discuss results for ε-truncation and ε-superposition methods. I show through these results that the ε-truncation and ε-superposition dimensions are small under modest error demand ε. These positive results are derived for product weights and the so-called anchored decomposition.

Les approximants de Padé et leurs généralisations sont depuis plusieurs années l'objet d'intenses recherches, et leurs applications sont nombreuses. Beaucoup de problèmes théoriques restent cependant en suspens: problèmes tout d'abord d'existence, d'unicité problèmes de convergence, d'accélération de convergence. L'objectif du travail présenté ici était justement d'apporter des réponses à de telles questions. Dans la première partie nous nous sommes intéressés aux approximants de Padé vectoriels de séries de matrices. Des conditions d'existence et d'unicité, des résultats de convergence sont donnés, ainsi que le lien avec la théorie de Lanczos pour la résolution de systèmes linéaires. Nous utilisons aussi les approximants de Padé vectoriels pour l'approximation simultanée d'une fonction et de sa dérivée. Dans la seconde partie une condition suffisante pour la convergence quadratique de l'epsilon algorithme topologique pour la résolution de systèmes non linéaires est donnée. Des résultats d'accélération de la convergence sont démontrés pour la deuxième colonne de l'epsilon algorithme/vectoriel et plus généralement pour des procédés quasi linéaires vectoriels. La troisième partie porte sur certains approximants de type Padé de fonctions entières. Des résultats sur l'accélération sont établis. La dernière partie fait le lien entre biorthogonalité, procédé de Gram-Schmidt, système linéaire et interpolation.

Copolímeros de e-caprolactona e l,l-dilactídeo têm sido investigados com a finalidade de desenvolver materiais biodegradáveis para aplicações médicas. As sínteses dos homopolímeros e copolímeros de epsilon-caprolactona e l,l-dilactídeo por abertura de anel e polimerização em massa transcorreram a 120oC sob atmosfera de nitrogênio, usando o octanoato de estanho como iniciador. A composição dos copolímeros variou de 5,90% a 97,30% em massa de l,l-dilactídeo. As massas molares dos polímeros sintetizados foram determinadas por viscosimetria capilar e cromatografia de permeação em gel (GPC). A composição dos copolímeros foi determinada por RMN de 13C. As propriedades térmicas e mecânicas foram avaliadas por DSC e DMTA. O grau de cristalinidade e as fases cristalinas dos copolímeros foram determinados por difração de raios X (WAXS). Foram observadas altas taxas de conversão de monômeros para os homopolímeros e para os copolímeros Co60 ao Co90 (taxas de 70-80%). Os homopolímeros e copolímeros sintetizados apresentaram altas massas molares (M w até 106.500 g/mol para os copolímeros) e moderada polidispersidade (1,50). As análises de RMN de 13C demonstraram a predominância da formação de copolímeros estatísticos e a ausência da transesterificação durante a polimerização em massa. As propriedades dinâmico-mecânicas foram fortemente dependentes da estrutura cristalina e do grau de cristalinidade dos copolímeros. Os copolímeros sintetizados apresentaram propriedades mecânicas variando do flexível ao rígido termoplástico. Os copolímeros com composição próxima a equimolar (Co30 ao Co40) apresentaram os mais baixos graus de cristalinidade (13 a 15%) e, por conseqüência, apresentaram maior taxa de degradação (20% em 408 horas para o Co40), em comparação com os demais copolímeros. / Copolymers of epsilon-caprolactone with l,l-lactide have been investigated in order to develop biodegradable materials for medical applications. The synthesis of homopolymers and copolymers of e-caprolactone with l,l-lactide by ring-opening bulk polymerization was performed using stannous octoate as initiator at 120 ºC under nitrogen atmosphere. The copolymers composition was varied from 5.90 to 97.30 % in mass of l,l-lactide. The molecular weight of synthesized polymers were determined by viscometry and GPC. The copolymers composition was determined by 13C NMR. Thermal and mechanical properties have been evaluated by DSC and DMTA. The degree of crystallinity and the crystalline phase of copolymers were determined by WAXS. High conversion was observed for homopolymers and copolymers Co60 to Co90 of l,l-lactide (70-80%). The homopolymers and copolymers presented hight molecular weight (M w up to 106,500 g/mol for copolymers) and low polydispersivity (1,50). The analyses by 13C- NMR spectroscopy have shown the predominance of statistical copolymers formation and the transesterification reaction did not occur during the bulk polymerization. Thermal and mechanical properties were dependent on the crystalline phase and of the degree of crystallinity. The synthesized copolymers presented mechanical properties from rubbery to stiff thermoplastics. The copolymers with equimolar composition presented low degree of crystallinity (13 ? 15%) and higher degradation (20% during 408 hours for Co40).

Neste trabalho estudamos problemas de evolução da forma \'d \' úpsilond\' SUP. \' úpsilon\' t\'\' + A (t,\'úpsilon\' )\' úpsilon\' = f(t,\'úpsilon\' ) \'úpsilon\'(0) = \' \' úpsilon\' IND. 0\' \', em um espaço de Banach X onde A(t, \'úpsilon\' ) : D \'está contido em\' X \'SETA \' X é um operador linear fechado e setorial para cada (t, \' úpsilon\' ). Quando o operador A(t, \' úpsilon\' ) é independente de \' úpsilon\' , isto é, A(t, \' úpsilon\') = A(t), mostramos um resultado de exitência, unicidade, continuidade relativamente a dados iniciais e continuação para o caso em que a não linearidade f tem crescimento crítico. Se A(t, \'úpsilon\' ) depende do tempo e do estado, então mostramos um resultado de existência, unicidade com f tendo crescimento sub-crítico semelhante aos resultados encontrados em [7, 33] / In this work we study initial value problems of the form \' d \'úpsilon\' SUP. dt + A (t, \'úpsilon\')\'úpsilon\' = f (t, \'úpsilon\' ) \' úpsilon\' (0) = \' úpsilon IND.0\', in a Banach space X where A(t,\' úpsilon\' ) : D \' this contained \' X \' ARROW\' X is an unbounded closed linear operator which is sectorial for each (t,\' úpsilon\' ). When the operator family A(t, \' úpsilon\' ) is independent of \' úpsilon\' , that is, A(t, \' úpsilon\' ) = A(t), we show a result on local well posedness and continuation with the nonlinearity f growing critically. If A(t,\' úpsilon\' ) depends on the time t and on the state \' úpsilon\' we show a local well posedness and continuation result that is similar to the result found in [7, 33]

Orientador: Patrícia de Oliveira Prada / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciências Médicas / Made available in DSpace on 2018-08-23T05:33:45Z (GMT). No. of bitstreams: 1 Weissmann_Lais_M.pdf: 2304567 bytes, checksum: b275887306c298a5ec1fd2910b146e00 (MD5) Previous issue date: 2013 / Resumo: Recentemente, demonstrou-se que IkB quinase e (IKK?) aumenta a resistência à insulina (RI) induzida por dieta hiperlipídica em tecido adiposo e hepático. Assim, os objetivos do presente estudo foram investigar: 1) a expressão e ativação de IKK? no hipotálamo de camundongos DIO e db/db; 2) o papel da IKK? hipotalâmica no metabolismo energético e da glicose, e na ação e sinalização da insulina e leptina. Observamos maior expressão e ativação de IKK? no hipotálamo de camundongos db/db e DIO quando comparados aos controles. Cinco dias de injeção intracerebroventricular (ICV) de CAY (inibidor farmacológico da IKK?) ou de IKK? siRNA, via mini-bomba ICV, reduziu 80% da atividade de IKK?, a fosforilação do IRS1Ser307 e não alterou a fosforilação de IKK?/? em hipotálamo. A inibição IKK? (ICV): reduziu a adiposidade e ingestão alimentar, aumentou o consumo de O2 e expressão de UCP-1 no adiposo marrom, melhorou os efeitos anorexigênicos da insulina e de leptina, aumentou a fosforilação do receptor de insulina, da AKT, JAK2 e STAT3 em hipotálamo de camundongos DIO e db/db. Esses resultados persistiram com pair-feeding e pair-weight. A inibição com CAY (ICV) reduziu: a glicemia de jejum, produção hepática de glicose e expressão da PEPCK em fígado de animais DIO e db/db. Em resumo, os dados sugerem que IKK? hipotalâmica está ativada em modelos de obesidade e participa no desenvolvimento da resistência à insulina e leptina. Sua inibição reduz a adiposidade, ingestão alimentar e aumenta o gasto energético. A IKK? além de influenciar o metabolismo energético, também tem um papel no metabolismo da glicose de animais obesos. Assim, pode-se sugerir que a IKK? representa uma ligação entre a obesidade e resistência à insulina e leptina no hipotálamo e pode ser um alvo terapêutico para a resistência à insulina, obesidade e diabetes / Abstract: It was demonstrated that IkB kinase epsilon (IKK?) increased insulin resistance (IR) in liver and adipose tissue of diet-induced obesity (DIO) mice. The aims of this study are to investigate: 1) the expression and activation of IKK? in the hypothalamus from DIO mice and db/db, 2) the role of hypothalamic IKK? in the energy and glucose metabolism, and in insulin and leptin action/signaling. We observed increased expression and activation of IKK? in the hypothalamus from db/db and DIO mice compared with controls. Five days of intracerebroventricular (ICV) injections of CAY (pharmacological inhibitor of IKK?) or siRNA, via ICV mini-pump, reduced 80% of IKK? activity as well asthe phosphorylation of IRS1Ser307 and did not alter the phosphorylation of IKK?/? in hypothalamus from obese mice. Inhibition of IKK? (ICV) reduced fat mass, food intake and increased O2 consumption and expression of UCP-1 in the brown adipose tissue, improved anorexigenic effects of leptin and insulin, increased insulin receptor, AKT, JAK2 and STAT3 phosphorylation in the hypothalamus of DIO and db/db mice. These results persisted even if in pair-fed and pair-weight mice. Inhibition of IKK? with ICV CAY reduced: fasting glycemia, hepatic glucose production and the expression of PEPCK in liver of DIO and db/db animals. In summary, the data suggest that hypothalamic IKK? is activated in models of obesity and participates in the development of insulin and leptin resistance. Its inhibition reduces adiposity, food intake and increases energy expenditure. Hypothalamic IKK? influences the energy and glucose metabolism in obese mice. Thus, it can be suggested that the IKK? represents a link between obesity and insulin resistance in the hypothalamus and may be a new therapeutic target to treat insulin resistance, obesity and diabetes / Mestrado / Clinica Medica / Mestra em Clínica Médica

Contrairement aux animaux, les plantes ont un développement largement post-embryonnaire et forment continuellement de nouveaux organes et tissus grâce à l’activité de leurs méristèmes. Ces massifs de cellules indifférenciées conservent la capacité à se diviser tout au long de la vie de la plante, et c’est également à partir du méristème caulinaire que se forment les gamètes. Chaque cycle de division peut être la source de mutations, suite par exemple à des erreurs de réplication. De plus, les méristèmes sont relativement exposés aux stress environnementaux qui peuvent également endommager l’ADN des cellules. Les mécanismes impliqués dans la détection des lésions de l’ADN ou des défauts de réplication et l’arrêt de la prolifération cellulaire en réponse à ces dommages jouent donc un rôle fondamental dans le maintien de la stabilité du génome, aussi bien au cours du développement végétatif que lors de la reproduction sexuée. Chez tous les eucaryotes, l’ADN Polymérase ε est un acteur central de ces mécanismes parce qu’elle assure non seulement la réplication fidèle de l’ADN au cours de la phase S du cycle cellulaire, mais est également directement impliquée dans la réparation de l’ADN, et dans la perception du stress réplicatif. L’étude détaillée de sa fonction est cependant rendue difficile chez beaucoup d’organismes par le fait que son inactivation est létale. Dans ce travail, nous avons utilisé des approches de génétique pour étudier le rôle de l’ADN Pol ε d’Arabidopsis au cours de la progression du cycle cellulaire et dans la réponse au stress réplicatif et aux lésions de l’ADN. Nous avons ainsi pu montrer que la sous-unité catalytique du complexe Pol ε ainsi que sa principale sous-unité accessoire DPB2 sont essentielles à la détection des défauts de réplication, et fonctionnent en amont de la kinase ATR pour induire l’arrêt du cycle cellulaire et activer les voies de réparation au cours du développement végétatif. En outre, nous avons découvert un nouveau point de contrôle activé lors de la phase de réplication pré-méiotique qui permet l’activation d’une mort cellulaire programmée en réponse à des défauts survenus pendant cette phase, grâce au facteur de transcription SOG1.Tous les stress biotiques ou abiotiques auxquels la plante est soumise pouvant conduire à la formation de lésions au niveau de l’ADN, nos résultats ouvrent des perspectives de recherche pour comprendre la réponse des plantes aux stress environnementaux. En outre, la disponibilité de mutants viables pour différents facteurs impliqués dans la réplication ou la réponse aux lésions de l’ADN nous a permis d’explorer chez un eucaryote pluricellulaire des mécanismes qui sont pour l’instant essentiellement décrits chez la levure, et ainsi d’acquérir des connaissances qui pourront être transférées aux systèmes animaux et notamment à l’Homme. / Plant development is a largely post-embryonic process that depends on the activity of meristems. These pools of undifferentiated cells retain the ability to proliferate throughout the lifespan of the plant, and are at the origin of gamete formation relatively late in its life cycle. Mutations can arise at each round of cell division, for example due to replication errors. In addition, meristems are relatively exposed to all kinds of environmental stresses that can also induce DNA damage. Detection of DNA lesions or replication defects and subsequent cell cycle arrest are thus instrumental to the maintenance of genome integrity, both during vegetative and reproductive growth. In all eukaryotes, DNA Pol ε is a key player of these mechanisms because it is not only responsible for the faithful reproduction of the genetic information during S-phase, but also directly involved in DNA repair and replicative stress perception. Detailed analysis of its function has however been complicated by the lethality of its inactivation in most organisms. In this work, we have used genetic approaches to investigate its role during cell cycle progression and replicative stress response. We have shown that both its catalytic sub-unit and its main accessory sub-unit DPB2 are involved in replicative stress sensing and that they function upstream of the ATR kinase to induce cell cycle arrest and DNA repair during vegetative growth. In addition, we have found that a specific checkpoint exists during pre-meiotic DNA replication that activates a cell death program via the SOG1 transcription factor upon replicative stress. Because all types of biotic and abiotic stresses can generate DNA damage, our work opens new research prospects to understand how plants cope with adverse conditions. Furthermore, the viability of Arabidopsis mutants deficient for various factors involved in DNA replication or DNA Damage Response allowed us to analyse into details in a multicellular eukaryote crucial cellular mechanisms that had until now been mainly investigated in yeast. This work thus allowed us to generate data that can be transferred to animal systems and notably to Human.

The new legal regulations derived from climate change dictate that hydraulic structures must be designed to handle flood events associated with return periods up to 10,000 years. This obviously involves adapting the existing infrastructure to meet such requirements. In order to avoid risks in the restitution of the flow discharged to rivers, such as bank overflows or streambed erosion and scour processes, hydraulic design must be supported by reliable tools capable of reproducing the behavior of hydraulic structures. In the work presented herein, a fully three-dimensional CFD model to reproduce the behavior of different types of air-water flow in hydraulic structures is presented. The flow is assumed to be turbulent, isotropic and incompressible. Several RANS turbulence models are tested and structured rectangular meshes are employed to discretize the analyzed domain. The presence of two fluids is modeled using different VOF approaches and simulations are run using the PIMPLE algorithm. The model is implemented using the open-source platform OpenFOAM and its performance is compared to the commercial code FLOW-3D. The analysis is conducted separately on two different parts of hydraulic structures, namely: the spillway and the stilling basin. Additionally, a case of practical application, where the model reproduces the flow of a real-life case, is also presented in order to prove the suitability of the model to actual design cases. Mesh independence and model validation using experimental data are checked in the results of all the case studies. The sensitivity of the presented model to certain parameters is extensively discussed using different indicator variables. Among these parameters are turbulence closure, discretization scheme, surface tracking approach, CFD code or boundary conditions. Pros and contras of each of them are addressed. The analyzed turbulence models are the Standard k ¿ ¿, the Realizable k ¿ ¿, the RNG k ¿ ¿, and the SST k ¿ ¿. The discretization schemes under study are: a first-order upwind method, the second-order limited Van Leer method, and a second-order limited central difference method. The VOF approaches analyzed are the Partial VOF, as implemented in OpenFOAM, and the TruVOF, as implemented in FLOW-3D. In most cases, the Standard k ¿ ¿ model provides the most accurate estimations of water free surface profiles, although the rest of variables, with few exceptions, are better predicted by the RNG k ¿ ¿. The latter model generally requires slightly longer computation times. The SST k ¿ ¿ reproduces correctly the phenomena under study, although it generally turned out to be less accurate than its k ¿ ¿ counterparts. As regards the comparison among VOF approaches and codes, it is impossible to determine which one performs best. E.g. OpenFOAM, using the Partial VOF, managed to reproduce the in- ternal hydraulic jump structure and all derived variables better than FLOW-3D, using the TruVOF, although the latter seems to capture better the momentum transfer and so all derived variables. In the case of flow in stepped spillways, OpenFOAM captures better the velocity profiles, although FLOW-3D is more accurate when estimating the water free surface profile. It is worth remark- ing that not even their response to certain model parameters is comparable. E.g. FLOW-3D is significantly less sensitive to mesh refinement than OpenFOAM. Given the result accuracy achieved in all cases, the proposed model is fully applicable to more complex design cases, where stilling basins, stepped spillways and hydraulic structures in general must be investigated. / Las nuevas disposiciones legales derivadas del cambio climático dictaminan que las estructuras hidráulicas sean capaces de funcionar correctamente con eventos de inundación asociados a periodos de retorno de hasta 10,000 años. Esto, obviamente, implica adaptar la infraestructura existente para satisfacer dichos requerimientos. A fin de evitar riesgos en la restitución de los caudales vertidos al río, como desbordamientos o procesos erosivos y de socavación, el diseño hidráulico ha de sustentarse en herramientas fiables capaces de reproducir el comportamiento de las estructuras hidráulicas. En este trabajo, se presenta un modelo numérico CFD completamente tridimensional para reproducir el comportamiento de diferentes tipos de flujo aire-agua en estructuras hidráulicas. Se asume que el flujo es turbulento, isotrópico e incompresible. Diversos modelos de turbulencia RANS son contrastados y se emplean mallas estructuradas rectanuglares para discretizar el dominio analizado. La presencia de dos fluidos es modelada utilizando diferentes enfoques VOF y las simulaciones son ejecutadas empleando el algoritmo PIMPLE. El modelo es implementado mediante la plataforma de código abierto OpenFOAM y su respuesta es comparada con la del modelo comercial FLOW-3D. El análisis se lleva a cabo sobre dos partes diferentes de una estructura hidráulica, a saber, el aliviadero y el cuenco amortiguador, de forma separada. Además, un caso de aplicación práctica, donde el modelo reproduce el flujo en una estructura real, es presentado también a fin de probar la adecuación del modelo a casos de diseño aplicado. Se comprueban la independencia de la malla y la validación con datos experimentales de los resultados de todos los casos de estudio. La sensibilidad del modelo presentado a ciertos parámetros es analizada de forma exhaustiva empleando diferentes variables indicadoras. Los pros y contras de cada uno de éstos son planteados. Los modelos de turbulencia analizados son el Standard k-epsilon, el Realizable k-epsilon, el RNG k-epsilon y el SST k-omega. Los esquemas de discretización estudiados son: un método de primer orden upwind, uno de Van Leer de segundo orden y un esquema de segundo orden limitado de diferencias centradas. Los enfoques VOF analizados son el Partial VOF, implementado en OpenFOAM, y el TruVOF, implementado en FLOW-3D. En la mayoría de casos, el modelo k-epsilon aporta las estimaciones más precisas de perfiles de lámina libre de agua, pese a que el resto de variables, con alguna excepción, son mejor predichas por el RNG k-epsilon. Este modelo generalmente requiere mayores tiempos de cálculo. El k-omega reproduce correctamente los fenómenos bajo estudio, pese a que su precisión es generalmente más baja que la de los modelos k-epsilon. En lo que respecta a la comparación entre enfoques VOF y códigos, es imposible determinar cuál es el mejor. Por ejemplo, OpenFOAM, empleando el Partial VOF, logra reproducir la estructura interna del resalto hidráulico y todas las variables derivadas mejor que FLOW-3D, empleando el TruVOF, a pesar de que este último parece capturar mejor la transferencia de cantidad de movimiento y, por tanto, todas las variables derivadas. En el caso del flujo en aliviaderos escalonados, OpenFOAM captura mejor los perfiles de velocidad, pese a que FLOW-3D es más preciso en la estimación de los perfiles de lámina libre de agua. Conviene recalcar que ni tan sólo su respuesta a ciertos parámetros del modelo es comparable. Por ejemplo, FLOW-3D es significativamente menos sensible al refinado de malla que OpenFOAM. A la luz de la precisión de los resultados obtenidos en todos los casos, el modelo propuesto es completamente aplicable a casos de diseño más complejos, donde cuencos amortiguadores, aliviaderos escalonados y estructuras hidráulicas en general han de ser investigadas. / Les noves disposicions legals derivades del canvi climàtic dictaminen que cal que les estructures hidràuliques siguen capaces de funcionar correctament amb esdeveniments d'inundació associats a períodes de retorn de fins a 10,000 anys. Això, òbviament, implica adaptar la infraestrctura existent per satisfer aquests requeriments. A fi d'evitar riscs en la restitució dels cabals vessats al riu, com desbordaments o processos erosius i de socavació, el disseny hidràulic ha de recolzar-se en ferramentes fiables capaces de reproduir el comportament de les estructures hidràuliques. En aquest treball, es prsenta un model numèric CFD completament tridimensional per a reproduir el comportament de diferents tipus de flux aire-aigua en estructures hidràuliques. S'assumeix que el flux és turbulent, isotròpic i incompressible. Diferents models de turbulència RANS són contrastats i s'empren malles estructurades rectangulars per discretitzar el domini analitzat. La presència de dos fluids és modelada utilitzant diferents enfocaments VOF i les simulacions són executades emprant l'algorisme PIMPLE. El model és implementat mitjançant la plataforma de codi obert OpenFOAM i la seua resposta és comparada amb la del codi comercial FLOW-3D. L'anàlisi es du a terme sobre les diferents parts d'una estructura hidràulica, a saber, sobreeixidors esgraonats i vas esmorteïdor, de forma separada. A més, un cas d'aplicació pràctica, on el model reprodueix el flux a una estructura real, és presentat també a fi de provar l'adequació del model a casos de disseny aplicat. Es comproven la independència de la malla i la validació amb dades experimentals dels resultats de tots els casos d'estudi. La sensibilitat del model presentat a certs paràmetres és analitzada de forma exhaustiva emprant diferents variables indicadores. Els pros i contres de cadascun d'aquests són plantejats. Els models de turbulència analitzats són l'Standard k-epsilon, el Realizable k-epsilon, el RNG k-epsilon i l'SST k-omega. Els esquemes de discretització estudiats són: un mètode de primer ordre upwind, un de Van Leer de segon ordre i un esquema de segon ordre limitat de diferències centrades. Els enfocaments VOF analitzats són el Partial VOF, implementat en OpenFOAM, i el TruVOF, implementat en FLOW-3D. En la majoria de casos, el model Standard k-epsilon aporta les estimacions més precises de perfils de làmina lliure d'aigua, tot i que la resta de variables, amb alguna excepció, són millor predites pel RNG k-epsilon. Aquest model generalment requereix majors temps de càlcul. El k-omega reprodueix correctament els fenòmens sota estudi, tot i que la seua precisió és generalment més baixa que la dels models k-epsilon. Pel que fa la comparació entre enfocaments VOF i codis, és impossible determinar quin és el millor. Per exemple, OpenFOAM, emprant el Partial VOF, aconsegueix reproduir l'estructura interna del ressalt hidràulic i totes les variables derivades millor que FLOW-3D, emprant el TruVOF, tot i que aquest últim pareix capturar millor la transferència de quantitat de moviment i, per tant, totes les variables derivades. En el cas del flux en sobreeixidors esgraonats, OpenFOAM captura millor els perfils de velocitat, tot i que FLOW-3D és més precís en estimar els perfils de làmina lliure d'aigua. Cal deixar palès que ni tan sols la seua resposta a certs paràmetres del model és comparable. Per exemple, FLOW-3D és significativament menys sensible al refinament de malla que OpenFOAM. En base a la precisió dels resultats obtinguts en tots els casos, el model proposat és completament aplicable a casos de disseny més complexos, on vassos esmorteïdors, sobreeixidors esgraonats i estructures hidràuliques en general han de ser investigades. / Bayón Barrachina, A. (2017). Numerical analysis of air-water flows in hydraulic structures using computational fluid dynamics (CFD) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90440 / TESIS

La relaxation des contraintes résiduelles de trempe au cours du revenu dépend fortement des évolutions des microstructures et du comportement thermomécanique. Ainsi, la prévision de l’évolution des contraintes résiduelles nécessite le couplage entre les calculs des champs de température, des transformations de phases, des contraintes et des déformations au cours du traitement. Dans ce travail, nous avons développé un modèle métallurgique pour décrire les cinétiques de précipitation au cour du revenu : la germination, la croissance et la coalescence (ou dissolution) du carbure epsilon et de la cémentite. Ce modèle permet de calculer les évolutions de la composition chimique de la matrice, du type, des distributions de taille des précipités lors du revenu de la martensite d’aciers faiblement alliés. Dans une deuxième étape, nous avons développé un modèle thermomécanique permettant de prédire l’évolution de la contrainte d’écoulement de la martensite revenue, basé sur les évolutions des paramètres microstructuraux obtenus par le modèle métallurgique. Le modèle thermomécanique prend en compte les différents mécanismes de durcissement (durcissement par solution solide, durcissement par les précipités et durcissement par dislocations), et l’effet de la température de déformation. Une validation expérimentale de ces modèles a été menée dans le cas de l’acier 80MnCr5 en s’appuyant sur des résultas obtenus par microscopie électronique à transmission et dilatométrie thermomécanique. Les modèles métallurgique et thermomécanique ont finalement été introduits dans le logiciel de calcul par éléments finis ZeBuLoN pour simuler l’évolution des contraintes internes lors de la trempe et du revenu. Une première analyse de la relaxation des contraintes au cours du revenu a été effectuée. / The relaxation of the residual stress during the tempering process is strongly related to the evolutions of the microstructure and thermomechanical properties. Thus, the simulation of the evolution of residual stresses requests the coupling of the temperature field, the phase transformations and the stress and strain evolutions all along the process. In this work, firstly, a metallurgical model has been developed to describe the tempering kinetics: nucleation, growth (or dissolution) and coarsening of the epsilon carbide and the cementite. This model allows to predict the evolutions of the matrix composition, the type, size and distribution of the precipitates during the tempering of martensite for low and middle alloyed steels. Secondly, based on the microstructure parameters calculated by the metallurgical model, a thermomechanical model has been also developed to predict the evolution of the flow stress of tempered martensite. The thermomechanical model not only takes into account the different hardening mechanisms (solution hardening, precipitate hardening and the dislocation hardening), but also the effect of deformation temperature. An experimental validation of the two models has been performed for a 80MnCr5 steel using the results obtained by electron transmission microscopy and thermomechanical dilatometry. Finally, the metallurgical model and the thermomechanical model have been implemented into the finite element calculation software ZeBuLoN to simulate the evolution of internal stress during the quenching and tempering process. A first analysis of the stress relaxation during tempering has been performed.

Os não-carbeno complexos pentacoordenados do tipo [RuCl2(PPh3)2(amina)], sendo as aminas pirrolidina, azocano e dietilamina, foram sintetizados e caracterizados por análise elementar, espectroscopia de absorção na região do infravermelho, espectroscopia de absorção na região do ultravioleta e visível, espectroscopia de ressonância magnética nuclear de fósforo-31 e espectroscopia de ressonância paramagnética eletrônica. Estudos da teoria do funcional da densidade dos complexos foram realizados para buscar melhor interpretação dos resultados experimentais obtidos. O complexo [RuCl2(PPh3)2(pirrolidina)] exibiu uma geometria do tipo pirâmide de base quadrada em solução, com a amina na posição apical e as trifenilfosfinasestão trans-posicionada. Os complexos [RuCl2(PPh3)2(azocano)] e [RuCl2(PPh3)2(dietilamina)] exibiram geometria do tipo bipirâmide trigonal na qual as duas trifenilfosfinas estão trans-posicionadas no eixo axial. O complexo [RuCl2(PPh3)2(pirrolidina)] exibiu boa atividade catalítica nas polimerizações de norborneno e norbornadieno, tanto em atmosfera de argônio quanto em ar a 25 °C, como observado com os complexos similares [RuCl2(PPh3)2(peridroazepina)] e [RuCl2(PPh3)2(piperidina)]. Os complexos [RuCl2(PPh3)2(azocano)] e [RuCl2(PPh3)2(dietilamina)] obtiveram baixo rendimento de polimerização mesmo a 40 °C. Acredita-se que a geometria do tipo pirâmide de base quadrada seja a ativa para formação da espécie metal-carbeno com o etil diazoacetato no período de indução e favorável para iniciar a reação de polimerização via metátese por abertura de anel. A geometria do tipo bipirâmide trigonal pode dificultar o período de indução. Os estudos teóricos corroboraram com essa discussão. Os polinorbornenos, polinorbornadienos e seus copolímeros obtidos com os três complexos ativos foram caracterizados por espectroscopia de ressonância magnética nuclear de carbono-13, calorimetria exploratória diferencial, análise dinâmico-mecânica, termogravimetria e microscopia eletrônica de varredura. O complexo [RuCl2(PPh3)2(peridroazepina)] foi eficiente na metátese cruzada entre lignina metacrilada e o 10-undecen-1-ol para modificar a lignina Protobind 2400, e a lignina modificada foi solúvel em diversos solventes. O complexo [RuCl2(PPh3)2(peridroazepina)] também foi utilizado na autometátese da olefina terminal do 10-undecen-1-ol para obtenção de um diol que foi usado como segmento flexível e extensor de cadeia em reações de poliuretanas com óleo de mamona ou poli(ε-caprolactona) diol. Esse diol, quando utilizado em pequenas quantidades (10% em massa) nas poliuretanas derivadas do óleo de mamona, foi capaz de prover características adesivas a um material inicialmente rígido. Os resultados das reações de poliuretanas derivadas da poli(ε-caprolactona) diol não apresentaram resultados satisfatórios. / Non-carbene five-coordinate [RuCl2(PPh3)2(amina)] complexes, with pyrrolidine, azocane and diethylamine, were synthesized and characterized by elemental analysis, infrared absorption spectroscopy, ultraviolet-visible absorption spectroscopy, phosphorus-31 nuclear magnetic resonance and electron paramagnetic resonance. Density functional theory studies of the complexes were performed to complete and improve the experimental studies. [RuCl2(PPh3)2(pyrrolidine)] presented a square pyramidal geometry in solution, with the amine in the apical position and trans-positioned phosphines. [RuCl2(PPh3)2(azocane)] and [RuCl2(PPh3)2(diethyl amine)] exhibited a trigonal bipyramidal geometry in solution, with two phosphine molecules trans-positioned in the axial axis. [RuCl2(PPh3)2(pyrrolidine)] presented activity for ring opening metathesis polymerization of norbornene and norbornadiene under either air or inert atmosphere of argon at 25 °C, as observed with the parent complexes with perhydroazepine and piperidine. The latter three complexes presented square pyramidal geometries and high yields of polynorbornene and polynorbornadiene, different from the trigonal bipyramidal geometry of the complexes with azocane and diethylamine, which showed lower yields for polymerization even at 40 °C. This suggests that the cyclic amines in the apical position of the square pyramidal geometry provoke less steric hindrance, which provides prompt reactivity for ring opening metathesis polymerization. The bipyramidal geometry can hinder the induction period. Theoretical studies corroborate this discussion. The polynorbornenes, polynorbornadienes, and their copolymers obtained with the three active complexes were characterized by carbon-13 nuclear magnetic resonance, differential scanning calorimetry, dynamic mechanical analysis, thermogravimetry analysis, and scanning electron microscopy. [RuCl2(PPh3)2(perhydroazepine)] was efficient to perform cross metathesis between the methacrylate lignin and 10-undecen-1-ol to modify the Protobind 2400 lignin, and the modified lignin was soluble in several solvents. Self-metathesis of the terminal olefin in 10-undecen-1-ol was conducted in the presence of [RuCl2(PPh3)2(perhydroazepine)] and ethyl diazoacetate to form a bioderived diol. The diol was utilized as soft segment and chain extender in polyurethane reactions with castor oil or poly(ε-caprolactone) diol. At only 10 wt% of the diol, an adhesive characteristic was observed in the castor oil-based polyurethane. The results from poly(ε-caprolactone) diol-based polyurethane were not satisfactory.