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Analyse asymptotique, modélisation micromécanique et simulation numérique des interfaces courbées rugueuses dans des matériaux hétérogènes / Asymptotic analyse, micromechanic modelling and numerical simulation of rough curved interfaces in heterogeneous materialsNguyen, Dinh Hai 24 September 2014 (has links)
Dans ce travail de thèse, il s'agit essentiellement de déterminer les propriétés mécaniques et physiques linéaires effectives des composites dans lesquels l'interface entre deux phases n'est pas lisse mais très rugueuse. Une approche efficace pour surmonter les difficultés provenant de la présence de rugosités d'interface consiste d'abord à homogénéiser une zone d'interface rugueuse comme une interphase équivalente par une analyse asymptotique et ensuite à appliquer des schémas micromécaniques pour estimer les propriétés effectives en tenant en compte de la présence de l'interphase équivalente. L'objectif principal de ce travail est de développer cette approche dans un cadre général où la surface autour de laquelle l'interface oscille périodiquement et rapidement peut être courbée et les phénomènes physiques concernés peuvent être couplés. Pour atteindre cet objectif, la conduction thermique est premièrement étudiée comme un prototype des phénomènes de transport non couplés pour élaborer dans un cadre simple les éléments essentiels de notre approche. Cette étude, préliminaire mais très utile au vu de l'importance des phénomènes de transport, montre que des résultats généraux et compacts peuvent s'obtenir quand l'interface est ondulée dans une seule direction et que des méthodes numériques sont en général nécessaires dans le cas où l'interface oscille suivant deux directions. L'approche développée et les résultats obtenus pour la conduction thermique sont étendus d'abord à l'élasticité linéaire et ensuite aux phénomènes physiques linéaires couplés tels que la thermoélectricité et la piézoélectricité. Dans ces cas plus complexes, des résultats généraux sont obtenus pour les composites stratifiés avec les interfaces ondulées dans une seule direction et des méthodes numériques sont élaborées pour les composites dans lesquels les interfaces oscillent suivant deux directions / This work is essentially concerned with determining the effective linear mechanical and physical properties of composites in which the interface between two phases is not smooth but very rough. An efficient approach to overcome the difficulties arising from the presence of interfacial roughness is first to homogenize a rough interface zone as an equivalent interphase by an asymptotic analysis and then to apply micromechanical schemes to estimation of the effective properties while accounting for the equivalent interphase. The present work aims mainly to develop this approach in a general situation where the surface around which an interface oscillates periodically and quickly can be curved and the physical phenomena involved can be coupled. To achieve this goal, thermal conduction is first studied as a prototype of transport phenomena so as to elaborate key elements of our approach in a simple situation. This study,even preliminary but very useful in view of the importance of transport phenomena, shows that general and compact results can be obtained when the interface is corrugated in only one direction and that numerical methods are generally required when an interface is curved along two directions. The approach developed and the results obtained for thermal conduction are extended first to linear elasticity and then to linear coupled physical phenomena such as thermoelectricity and piezoelectricity. In these more complex cases, general results are obtained for composite laminates with interfaces oscillating in only one direction, and numerical methods are elaborated for composites in which the interfaces oscillate in two directions
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Hygorthermal performance assessment of damaged building materials / Evaluation des performances hygrothermiques des matériaux de construction endommagésRouchier, Simon 19 October 2012 (has links)
Les transferts d’humidité dans les matériaux de construction ont une influenceimportante sur leur durabilité et sur les performances hygriques et thermiques desbâtiments. De nombreux mécanismes d’endommagement chimiques et physiquesde ces matériaux sont en effet dus à l’infiltration d’eau. En conséquence, leur structureporeuse peut évoluer au cours du temps, et des fissures microscopiques commemacroscopiques peuvent s’y développer. La description des matériaux à l’échelle microscopiqueest cependant une source d’erreur importante dans les codes de simulationactuels des transferts d’humidité et de chaleur, notamment en raison du faitque lesmilieux sont considérés comme homogènes, et que les effets du vieillissementdes matériaux sont négligés. Il importe donc de trouver un moyen d’inclure les effetsde l’endommagement dans les simulations de transferts d’humidité et de chaleurà l’échelle du bâtiment. Des méthodes existent pour la prédiction du comportementde milieux soumis à des sollicitations hygriques et mécaniques, mais supposent quel’ensemble des facteurs extérieurs influant sur l’endommagement soient connus toutau long des simulations.Une nouvelleméthodologie est proposée ici pour compléter ces approches prédictives,en combinant des mesures expérimentales d’endommagement avec la simulationde transferts couplés d’humidité et de chaleur. Une étude préliminaire a d’abordété menée, consistant à mesurer la perméabilité vapeur équivalente d’éprouvettes demortier multi-fissurées. Cette démarche a permis d’identifier les besoins expérimentauxet numériques de la suite du travail, visant à modéliser les écoulements dans unréseau discret de fissures sur la base de leur caractérisation. Une méthodologie expérimentalecombinant corrélation d’images numériques et émissions acoustiques aensuite été développée, permettant de disposer de cartographies d’endommagementet de proposer une démarche pour lamesure de réseaux de fissures dans lesmatériauxde construction en place. La méthode optique, associée à une procédure de traitementd’images, a permis de disposer de données précises de la géométrie de réseauxde fissures. De plus, une méthode a été proposée pour permettre l’interprétation desmesures d’émissions acoustiques en termes de quantification, localisation et identificationdes phénomènes d’endommagement.Un code de simulation a ensuite été écrit, permettant d’intégrer ces mesures defissuration dans la modélisation des écoulements couplés d’humidité et de chaleuren milieu poreux. Ce modèle a été validé sur la base de mesures expérimentales : lacorrélation d’images numériques a été appliquée durant la fracturation d’éprouvettesde béton, dans lesquelles l’infiltration d’eau a ensuite été suivie par radiographie auxrayons X. Les résultats numériques obtenus sont en bonne conformité avec lesmesuresexpérimentales en termes de prédiction de la concentration d’eau en deux dimensions.Enfin, laméthodologie a été appliquée à une série de cas test, dans le but demodéliserles performances hygrothermiques de parois multi-couches, incluant des matériauxendommagés, soumises à des conditions climatiques réelles. On a ainsi pu estimer les conséquences potentielles de l’endommagement sur l’accumulation d’eau dans desparois, sur l’amplitude des cycles de sorption et de séchage, ainsi que sur les transfertsthermiques. / An importantmatter in the field of building physics is the questioning of how wellbuildings sustain ageing, and how their overall efficiency evolves over their lifetime.Many causes for degradation are carried by moisture transfer through these porousmaterials. Indeed, infiltratedwatermay transport chemicals, altermechanical properties,and cause freeze thaw damage or mould development. It may also affect thermalproperties and energetic efficiency, as well as the health and comfort of the occupants.The understanding of how moisture transfer properties evolve during the lifespan ofbuildingmaterials is however far fromcomplete. The pore structure of amaterial itselfmay change over time, or be altered by cracks and defects caused bymechanical loadingand aggravated bymoisture-induced degradation. All sizes of fracturesmay have astrong impact on heat and moisture flow in the building envelope, and their influenceis to be accounted for in any long-termperformance assessment, not only of buildingand building components,but of any built structure in general. A considerable amountof work has already been performed in order to allow predicting the hygrothermal behaviourof buildings over longer periods of time. However, an accurate prediction of allranges of damage in a building component, from microscopic to macroscopic cracks,supposes an extensive knowledge of all damage-inducing, time-varying boundary conditionsof the problem during the simulation time. This also implies high computationalcosts, as well as important needs formaterial characterisation.As a complement to these predictive methods, a new approach was undertaken,combining experimental characterisation of crack patterns and numerical simulationsof coupled heat and moisture transfer. First, a preliminary study was conducted, consistingof measurements of the water vapour permeability of diffusely damaged constructionmaterials.This allowed identifying the experimental and numerical requirementsof the remainder of the work, which aimed at providing measurements of fracturenetwork geometries for their explicitmodelling in heat andmoisture transfer simulations.Digital image correlation and acoustic emission monitoring were then performedduring the degradation of cementitiousmaterials, in order to obtain quantitativedata on crack pattern geometries, and to assess the possibilities for damagemonitoringat the building scale. The optical technique, along with an appropriate imageprocessing procedure, was found suitable for providing precisemeasurements of fracturenetworks. Amethodwas also proposed for the interpretation of acoustic emissionrecordings in terms of damage quantification, localisation and identification.Then, a newmodel for coupled heat andmoisturemodelling in cracked porousmediawas developed, that allows including such measurements of fracture patterns intoa finite element mesh, and simulating flow accordingly. This model was validated onthe basis of experimentalmeasurements: digital image correlationwas performed duringthe fracturing of concrete samples, in which moisture uptake was then monitoredusing X-ray radiography. A good accordance was found between experimental and numericalresults in terms of 2-dimensional moisture concentration distributions. The validated code was then used for the simulation of test cases, in order to assess the hygrothermalperformance of damagedmulti-layered building components subjected toreal climatic conditions. The consequences of fractures on themoisture accumulationin walls, on the amplitude of sorption/desorption cycles and on the thermal performance,were observed.
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Digital average-current control for the dual interleaved boost converterVillarruel-Parra, Alejandro January 2015 (has links)
This Thesis addressed the challenge of ensuring balanced currents in the phases of a multi-kW, interleaved dc-dc converter by means of closed-loop digital control. The Thesis examines uniformly-sampled, valley-current, peak-current and average-current control for a dual interleaved boost converter with inter-phase transformer which might form part of the power train of an electric vehicle. Also, an enhancement of the average-current control is investigated in which the transistor duty-ratio is updated more rapidly, which allows an improvement of approximately ten times in the response speed of the system. Based on the theoretical analysis, the average-current control methodology was determined to be the most suitable technique for this type of converter as it ensures well-balanced phase currents over a wide range. To provide a basis for control system analysis and design for interleaved converters, a modelling methodology is developed based on a combination of multi-rate data-sampled theory and a small-signal averaged converter model. The model is shown to represent accurately the interaction between the interleaved phases, revealing a reduced stability range compared with a non-interleaved converter. The modelling and control methods are validated using switched and average value simulations obtained with the SABER software and by experimental results from a 25 kW, 30 kHz converter prototype. The control techniques were implemented on a Texas Instruments TMS320F28335 digital signal controller.
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The role of human cytomegalovirus encoded viral G protein-coupled receptors in onco-modulatory signallingSubramoney, Preya 22 June 2011 (has links)
Human cytomegalovirus (HCMV) is a ubiquitous virus of the herpes type that infects a high percentage of some populations. One of the most researched genes expressed by HCMV with close homology to human chemokine receptors is the US28 G protein-coupled receptor. Study design: This study was initiated to elucidate the intracellular signalling pathways of an inflammatory factor (IL-6) and an angiogenic factor (STAT3) triggered by the viral US28 oncogene and the presence of US28 in the HCMV viral particle. These pathways were observed by introducing the US28 gene into two human cell lines by infection with a HCMV strain that expresses the US28 gene (wild type), and two HCMV strains where the US28 gene was deleted (ÄUS28 and ÄUS28/UL33). Special attention was directed at the expression of IL-6 after promotion of the US28 gene and subsequent phosphorolation of STAT3. A new US28 antibody was validated and a method developed in an attempt to determine US28 on the viral particle. The following techniques were applied: Cell culture work, two mammalian cell lines were used, HFF’s and U373 MG. Virus stock titre determination to determine the multiplicity of infection. Protein quantitation to determine very small quantities of protein for Western blot analysis. ELISA for the quantitative determination of IL-6. Western blotting for phospho- STAT3 determination and validation of the US28 antibody. Immunocytochemistry was used for back titrations of virally infected cells. Immunofluorescence assay and use of confocal microscopic techniques was used for the location of the US28 gene in the virion and for tSTAT3 translocation to the nucleus. Conclusion: A clear increase in IL-6 secretion (495% ± 1%) was seen, and this was after only an hour in HCMV WT infected cells. From the increase in IL-6 secretion a subsequent increase in STAT3 phosphorylation was detected in the same samples. A clear link has been established between IL-6 and STAT3. A method to determine whether US28 was present in the HCMV viral particle was designed and preliminary results obtained. The results were inclusive. / Dissertation (MSc)--University of Pretoria, 2011. / Pharmacology / unrestricted
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Determinação de hormônios em águas bruta e tratada via EFS-CL-EM/EM : eficiências de degradação com ozonização e cloroamoniação / Determination of hormones in raw water and treated via SPE-LC-MS/MS : degradation efficiencies with ozonation and chloroamoniationOliveira, André Felipe de, 1978- 27 August 2018 (has links)
Orientador: Maria Aparecida Carvalho de Medeiros / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-27T02:18:56Z (GMT). No. of bitstreams: 1
Oliveira_AndreFelipede_M.pdf: 2184303 bytes, checksum: b46c30ed510d7f32eb7aae82b851f80d (MD5)
Previous issue date: 2015 / Resumo: Há uma preocupação crescente na área de Saneamento Ambiental com relação a qualidade das águas dos corpos hídricos, tendo em vista que pesquisas têm revelado que os sistemas de tratamentos convencionais de esgotos e de água para abastecimento público não possuem eficiências adequadas para remoção de compostos orgânicos classificados como Desreguladores Endócrinos (DE). Nesta classe de compostos são destacados os estrógenos naturais 17 ß-estradiol (E2), estriol (E3), estrona (E1) e o sintético 17 ?-etinilestradiol (EE2). Os efeitos destes hormônios sexuais, que são compostos extremamente ativos biologicamente, têm sido citados como agentes etiológicos de feminilização em peixes e também de vários tipos de cânceres. Neste sentido, trabalhos aplicando tecnologias avançadas de tratamento destes DE estão sendo desenvolvidos por vários grupos de pesquisas. Apesar de que as Legislações ambientais relacionadas aos parâmetros de lançamento (RESOLUÇÃO CONAMA no. 430 de 2011) e de parâmetros de potabilidade (Portaria no. 2914 de 2011) não contemplarem estes compostos DE, sendo que diversos trabalhos têm sido publicados com quantificação destes compostos em água da ordem de ng L-1. Neste contexto, o presente trabalho teve como objetivos: (1) adaptação e validação de metodologia analítica para confirmar e quantificar simultaneamente os hormônios E1, E2, E3 e EE2, nas águas bruta e tratada do rio Atibaia, manancial que abastece o município de Campinas, utilizando a técnica de extração em fase sólida (EFS), juntamente com a técnica de Cromatografia Líquida acoplada à espectrometria de massas em tandem (CL-EM/EM), (2) aplicação de tecnologias de degradação destes compostos E1, E2, E3 e EE2 em escala piloto, pelos processos de ozonização e cloroamoniação, visando contribuir com as determinação das dosagens, do tempo de contato e da eficiências de remoção. Os resultados obtidos nas análises via EFS-LC-MS/MS mostraram a ocorrência do hormônio sexual natural E1, na água bruta do rio Atibaia com concentração de 17 ng L-1, sendo que para os demais E2 e E3 os valores obtidos foram inferiores ao limite de quantificação 2 ng L-1 e para o EE2 inferior a 5 ng L-1. As técnicas de oxidação ozonização e cloroamoniação utilizadas nos ensaios demonstraram eficiências de degradação em média, maiores do que 95% dos DE estudados, com exceção de E1, cuja eficiência de remoção ficou entre 87% a 93%, dependendo da faixa de fortificação / Abstract: There is growing concern in the field of Environmental Sanitation regarding the water quality of water bodies, given that research has shown that systems of conventional treatments of sewage and public water supply does not have adequate efficiencies to removal of some organic compounds Endocrine Disruptors (DE). In this class of compounds are included the natural estrogens 17 ß-estradiol (E2), estriol (E3), estrone (E1) and the synthetic 17 ?-ethinylestradiol (EE2). The effects of these sex hormones, which are highly biologically active compounds, have been cited as etiological agents of feminization in fish and various types of cancers. In this regard, several works by applying advanced technologies for treating these DE are being developed by many research groups. Although the environmental legislations related to the parameters of launch (CONAMA RESOLUTION. 430 of 2011) and potability parameters (Ordinance no. 2914 2011) does not address these DE compounds, several studies have been published with quantification of these compounds in the order of ng L-1. In this context, the aimsmof this paper were: (1) adaptation and validation of the analytical methodology to confirm and to quantify simultaneously the E1, E2, E3 and EE2 hormones, raw water and treated in the Atibaia River, a source that supplies the municipality Campinas, using the technique of solid phase extraction (EFS) with the technique of Liquid Chromatography coupled to mass spectrometry in tandem (LC-MS/MS), (2) applying degradation technologies of these compounds E1, E2, E3 and EE2 in pilot scale, by using the processes of ozonation and cloroamoniation, to contribute to the determination of dosage, contact time and degradation efficiencies. The results obtained in this study via EFS-LC-MS / MS showed the occurrence of natural sex hormone E1 in the Atibaia River raw water with a concentration of 17 ng L-1, and for the other E2 and E3 the values were lower the quantification limit of 2 ng L-1 and EE2 less than 5 ng L-1. The ozonation and chloroamoniation oxidation techniques used for the degradation tests were with efficiencies on average more than 95% of the studied DE, except E1, the removal efficiency was between 87% to 93% depending on the fortification range, by using ozonation in pre oxidation and cloroamoniation and the disinfection step / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia
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Rhenium and Osmium PNP Pincer Complexes for Nitrogen Fixation and Nitride TransferWätjen, Florian 27 September 2019 (has links)
No description available.
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Implementation of a Coupled Creep Damage Model in MOOSE Finite Element Framework: Application to Irradiated Concrete StructuresJanuary 2020 (has links)
abstract: There has been a renewed interest to understand the degradation mechanism of concrete under radiation as many nuclear reactors are reaching their expiration date. Much of the information on the degradation mechanism of concrete under radiation comes from the experiments, which are carried out on very small specimens. With the advent of finite element analysis, a numerical predictive tool is desired that can predict the extent of damage in the nuclear concrete structure.
A mesoscale micro-structural framework is proposed in Multiphysics Object-Oriented Simulation Environment (MOOSE) finite element framework which represents the first step in this direction. As part of the framework, a coupled creep damage algorithm was developed and implemented in MOOSE. The algorithm considers creep through rheological models, while damage evolves exponentially as a function of elastic strain and creep strain. A characteristic length is introduced in the formulation such that the energy release rate associated with each element remains the same to avoid vanishing energy dissipation with mesh refinement. A creep damage parameter quantifies the effect of creep strain on the damage that was calibrated using three-point bending experiments with varying rates of loading.
The creep damage model was also validated with restrained ring shrinkage tests on cementitious materials containing compliant/stiff inclusions subjected to variable drying conditions. The simulation approach explicitly considers: (i) moisture diffusion driven differential shrinkage along the depth of the specimen (ii) viscoelastic response of aging cementitious materials (iii) isotropic damage model with Rankine′s failure initiation criterion, and (iv) random distribution of tensile strengths of individual finite elements.
The model was finally validated with experimental results on neutron-irradiated concrete. The simulation approach considers: (i) coupled hygro-thermal model to predict the temperature and humidity profile inside the specimen (ii) radiation-induced volumetric expansion of aggregates (RIVE) (iii) thermal, shrinkage and creep effects based on the temperature and humidity profile and (iv) isotropic damage model with Rankine’s criterion to determine failure initiation. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020
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Inversion de valence induite par le Åh dans des complexes à deux fer / pH-induced valence inversion in bio-inspired diiron complexesBalasubramanian, Ramachandran 22 October 2013 (has links)
Le sujet de la thèse concerne l’étude de l’inversion de valence dans des complexes FeIIFeIII induite par la déprotonation d’un ligand de FeII. L’intérêt de cette étude vient de ce que le processus considéré peut être décrit comme un transfert d’électron induit par un transfert de proton. Les transferts de protons et d’électrons sont au cœur de nombreuses réactions catalytiques ou biologiques et la compréhension des mécanismes de leur mise œuvre, séquentielle ou couplée, est un enjeu très actuel. La première partie de la thèse est consacrée à la caractérisation du premier système présentant cette propriété originale. Il est fondé sur un complexe binucléaire FeIIFeIII dont les deux ions Fe sont pontés par un dicarboxylate et un phénolate. Le FeIII est lié par un groupe bis-2-picolylamine et le FeII par un groupe similaire dans lequel une pyridine a été remplacée par une aniline. C’est la déprotonation de ce groupe aniline lié au FeII qui provoque l’inversion de valence, l’anilinate formé étant lié au FeIII. Le complexe aniline est isolé avec le groupe aniline en position -trans par rapport au phénolate pontant mais il possède la particularité de ne pas être stable en solution et de s’isomériser, le groupe aniline passant en position -cis par échange avec une pyridine. Le même phénomène est observé pour le complexe anilinate formé par déprotonation. Ce phénomène a été étudié en combinant les spectroscopies UV-visible, RMN du proton et Mössbauer et les caractéristiques thermodynamiques et cinétiques de l’isomérisation ont été déterminées. La relation entre le transfert d’électron et le transfert de proton a été étudiée par des techniques électrochimiques. Des études approfondies par cyclovoltamétrie et marquage isotopique ont montré que dans ce système les transferts d’électron et de proton sont concertés. La deuxième partie de la thèse est consacrée à l’étude des facteurs qui sont susceptibles d’influencer le transfert d’électron, c’est-à-dire les potentiels rédox des deux sites à Fe, et le transfert de proton, c’est-à-dire le pKa du ligand protique. Pour ce faire, de nouveaux complexes ont été préparés en modifiant soit le ligand protique, l’aniline étant remplacée par un benzimidazole, soit le groupe complexant le Fe, remplacement de la bis-2-picolylamine par la bis-(2-méthyl-N-méthylbenzimidazole)amine. Des complexes présentant ces modifications mais dépourvus du ligand acide ont été synthétisés pour étudier les effets de ces modifications sur les propriétés rédox des ions Fe. L’étude de l’influence des propriétés rédox a été menée dans un premier temps. La substitution du groupe complexant le FeIII n’a pas de conséquence importante au plan structural pour le complexe protoné qui existe toujours sous la forme de deux isomères. Par contre, après déprotonation un seul isomère existe. Les propriétés spectroscopiques sont peu altérées ce qui montre que la structure électronique du système n’est pas bouleversée. L’étude de l’influence des propriétés acides a été menée ensuite. Deux complexes ont été étudiés qui diffèrent par la nature du groupe complexant le FeIII. La substitution de l’aniline par le benzimidazole ne change pas de façon notable les propriétés structurales du système mais on note cependant que les valences des deux ions sont moins localisées. La déprotonation du benzimidazole est observée et conduit à un chromophore sensiblement différent du précédent illustrant les différences de ligand. L’étude électrochimique préliminaire révèle un comportement similaire au premier complexe étudié. / The thesis matter concerns the valence inversion in FeIIFeIII induced by deprotonation of a FeII ligand. This study is of strong interest owing to the fact this process can be described as an electron transfer induced by a proton transfer. Protons and electrons transfers play essential roles in numerous catalytic or biologic reactions and therefore understanding whether they occur in a sequential or concerted manner is presently a major endeavor. The first part of the thesis is devoted to the characterization of the first system possessing this original property. It is based on binuclear complex FeIIFeIII where the two Fe ions are bridged by a dicarboxylate and a phenoxide. The ferric ion is bound by a bis-2-picolylamine group and the ferrous ion by a similar group where a pyridine has been replaced by aniline. Deprotonation of this FeII bound aniline induces the valence inversion, the resulting anilide being bound to the FeIII ion. The aniline complex was isolated with the aniline in trans position with respect to the bridging phenoxide, but it is not stable in solution and isomerizes, the aniline group moving to a cis position upon exchange with a pyridine. The same phenomenon was observed for the anilide complex obtained through deprotonation. This phenomenon was studied by combining UV-visible, 1H-RMN and Mössbauer spectroscopies, and the thermodynamic and kinetic characteristics of the isomerization were determined. The link between the electron transfer and the proton transfer were studied by electrochemical techniques. Thorough studies by cyclic voltammetry and isotopic labeling showed that in this system the electron and proton transfers are concerted. The second section of the thesis was aimed at studying the factors susceptible to influence the electron transfer, namely the redox potentials of the two Fe sites, and the proton transfer, namely the pKa of the protic ligand. To achieve it, new complexes were prepared by modifying either the protic ligand, the aniline being replaced by a benzimidazole, or the Fe binding group, substitution of bis-2-picolylamine by bis-(2-methyl-N-methylbenzimidazole)amine. Model complexes incorporating these changes but deprived of the protic ligand were also obtained to assess their influence on the redox properties of the Fe ions. The study of the influence of redox properties was considered first. The substitution of the group complexing FeIII has not a strong influence on the structure of the protonated complex which still exists as two isomers. By contrast, after deprotonation a single isomer exists. The spectroscopic properties are mostly unchanged which shows that the electronic structure of the system is not altered significantly. The study of the influence of the acidicity was then conducted. Two complexes differing by the nature of the FeIII bound group were considered. Replacing aniline by benzimidazole does not change significantly the structural properties of the system, but the valences of the Fe ions are less localized than in the original complex. The deprotonation of benzimidazole occurs and leads to a chromophore that differs from the preceding, revealing the difference in ligands. However, a preliminary electrochemical study reveals a behavior similar to that of the original complex.
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[pt] AVALIAÇÃO DE ESQUEMAS DE ACOPLAMENTO NA SIMULAÇÃO DE RESERVATÓRIOS DE PETRÓLEO / [en] EVALUATION OF COUPLING SCHEMES IN THE SIMULATION OF PETROLEUM RESERVOIRSNIURKA PATRICIA RODRIGUEZ YAQUETTO 04 July 2013 (has links)
[pt] Os estudos entre a interação do fluxo de fluido e a deformação do
meio poroso têm sido realizados com o objetivo de explicar alguns
fenômenos que ocorrem ao longo da produção/injeção de fluidos, e assim
obter uma simulação de reservatórios cada vez mais precisa. A solução
ideal para o problema é implementar um esquema, onde as leis que
governam o fluxo e analise de tensões sejam obedecidas
simultaneamente em cada intervalo de tempo. Este trabalho apresenta os
resultados de um código (programado em C positivo positivo) que permite acoplar um
simulador de fluxo convencional (ECLIPSE) e um programa que permite
analisar tensões e deslocamentos (Abaqus /CAE). O objetivo deste
trabalho é validar varias soluções para resolver um problema usando os
diferentes tipos de acoplamento, que juntamente com uma filosofia
empregada nas principais formulações permite dar respostas similares
aquelas do acoplamento total. São apresentadas as formas de
acoplamento e a formulação empregada em cada um dos esquemas
usados. Os resultados obtidos pelos esquemas são comparados em
termos de fluxo e tensões e deslocamentos a partir de modelos tridimensionais. / [en] Studies between the interaction of fluid flow and deformation of
porous media have been carried out with the aim of explaining some
phenomena that occur along the production/injection of fluids, thereby
obtaining a more accurate reservoir simulation. The ideal solution for this
problem is to implement a scheme where laws governing the flow and
stress analysis are met simultaneously at each time interval. This
dissertation presents the results of a computer code (programmed in C positive positive)
that allows the coupling of a conventional reservoir simulator (ECLIPSE)
and a stress-displacement finite element based program (Abaqus /CAE).
This work presents the use of various coupling schemes for the solution of
a synthetic case, in particular the use of a methodology that generates
results very close to the ones predicted from the use of fully coupled
methods. The results obtained by the different coupling schemes are
compared in terms of fluid pressure, stress and displacement responses
for synthetic three-dimensional models.
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Proton Coupled Electron Transfer at Heavy Metal SitesDelony, Daniel 10 December 2020 (has links)
No description available.
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