Neste trabalho, foi estudado o comportamento reológico nos regimes de viscoelasticidade linear (VEL) e não linear (VENL) da mistura polimérica de polimetacrilato de metila/poliestireno (PMMA/PS), compatibilizada ou não com os copolímeros: estatístico P(S-co-MMA) (VEL e VENL) e bloco P(S-b-MMA) (VEL). No estudo do comportamento de VEL, ensaios de cisalhamento oscilatório de pequenas amplitudes (COPA) foram realizados utilizando-se um reômetro de tensão controlada. O comportamento de VEL das misturas poliméricas foi comparado com os modelos teóricos de Bousmina[1] e generalizado de Palierne[2]. Os tempos de relaxação das misturas poliméricas foram obtidos analisando o comportamento reológico no regime de VEL utilizando o software desenvolvido por Honerkamp e Weese[3]. Os tempos obtidos foram comparados com o modelo de Jacobs et al.[4]. O estudo do comportamento de VENL foi conduzido através de ensaios de relaxação de tensão utilizando-se um reômetro de deformação controlada. Os resultados do comportamento reológico no regime de VEL indicaram a presença de quatro tempos de relaxação, para as blendas compatibilizadas com P(S-co- MMA) (composições menores de 10% de fase dispersa e concentrações maiores de 4% de copolímero): dois picos relacionados às fases puras; F, relacionado com a relaxação das gotas da fase dispersa e o relacionado com a relaxação do compatibilizante na interface entre as fases matriz e dispersa. Os valores experimentais de F e foram utilizados para os cálculos de tensão interfacial () e do módulo complexo de interface () das blendas poliméricas compatibilizadas. Os resultados indicaram uma diminuição de com o aumento da concentração de copolímero. Os resultados do comportamento reológico no regime de VEL, para as blendas compatibilizadas com P(S-b-MMA), também apresentaram a presença de quatro tempos de relaxação. Observou-se que o aumento da adição de P(S-b-MMA) proporcionou uma redução no .. Os resultados de VENL de relaxação de tensão mostraram a presença de três fenômenos de relaxação, relacionados com: 1) as fases puras, 2) a relaxação das gotas da fase dispersa e um terceiro mais rápido. A adição de P(S-co-MMA) resultou numa diminuição do processo de relaxação das gotas da fase dispersa. / In this work, the dynamic behavior of polymethylmetacrylate/polystyrene (PMMA/PS) blends to which P(S-co-MMA) was added was studied. Several blend composition and copolymer concentrations were studied. The rheological behavior of blends was compared to Bousminas[1] and Paliernes generalized[2] models. The relaxation spectra of the blends were also inferred, and the results were analyzed in light of the analysis of Jacobs et al.[4]. The relaxation spectra of the blends with smaller dispersed phase (below 10 wt%) and larger copolymer concentrations (above 0.4 wt%) showed the presence of four relaxation times, two corresponding to the blend phases, F, corresponding to the relaxation of the shape of the dispersed phase of the blend, and , that can be attributed to the relaxation of Marangoni stresses tangential to the interface between the dispersed phase and matrix. The experimental values of F and were used to infer the interfacial tension () and the interfacial complex shear modulus () for the different blends, decreased with increasing copolymer concentration. decreased with increasing blend dispersed phase concentration and decreasing copolymer concentration. The predictions of Paliernes generalized model were found to corroborate the experimental data once the values of and found analyzing the relaxation spectra were used in the calculations. Bousminas model was found to corroborate the data only for larger dispersed phase concentration. The stress relaxation behavior of PMMA/PS blends with or without random copolymer addition, submitted to step shear strain experiments in the linear and nonlinear regime was studied. The effect of blend composition, viscosity ratio and random copolymer was evaluated. All blends presented three relaxation stages, a first relaxation which was attributed to the relaxation of the pure phases, a second one which was characterized by the presence of plateau and a third fast one.

A deposição eletroquímica, ou eletrodeposição, é uma técnica amplamente utilizada na obtenção de recobrimentos metálicos. A presença de certos compostos químicos (aditivos) nos banhos eletrolíticos pode influenciar o processo de eletrodeposição de maneira significativa. A glicina é um aminoácido presente em muitos banhos para a eletrodeposição de filmes finos de ligas de cobalto, que são interessantes devido às suas propriedades magnéticas. As propriedades de algumas ligas à base de cobalto obtidas a partir de banhos contendo glicina já foram bem descritas, mas há falta de estudos mais específicos sobre o papel do aminoácido no processo de eletrodeposição do cobalto. Esta Tese apresenta estudos realizados na tentativa de compreender a influência da glicina no mecanismo de eletrodeposição do cobalto. Técnicas de análise in situ, envolvendo espectroscopia no infravermelho por reflexão externa e medidas de pH na região próxima a interface via microeletrodo indicador foram acopladas aos estudos eletroquímicos. Depósitos de cobalto de boa qualidade foram obtidos a partir de banhos contendo glicina, e sob condições de sobrepotencial mais elevadas do que as possíveis para sistemas sem aditivos, onde ocorre precipitação de hidróxidos. Análises dos experimentos de voltametria cíclica indicaram a eletroatividade de complexos cobalto-glicina, e cinética de redução mais lenta foi observada, em relação a sistema sem glicina em valores de pH suficientemente elevados. Os estudos cinéticos foram dificultados pela reação de desprendimento de hidrogênio e a existência de diversos equilíbrios químicos em solução. Durante a eletrodeposição de cobalto em soluções contendo glicina, um aumento bastante significativo no pH próximo da interface foi observado. Os experimentos espectroeletroquímicos também demonstraram deslocamento dos equilíbrios químicos de complexação do cobalto em solução, devido ao aumento do pH interfacial. Todos os estudos mostraram que a presença de glicina favorece a reação de desprendimento de hidrogênio, diminuindo a eficiência de corrente do processo de eletrodeposição. Ainda assim, a glicina se mostrou eficaz na estabilização da solução eletrolítica. / The electrochemical deposition, or electrodeposition, is a widely used technique to obtain metallic coatings. The presence of certain chemical species (additives) in plating baths can significantly influence the metal electrodeposition process. Glycine is an aminoacid present in many electrolytic solutions for electrodeposition of cobalt thin films and alloys, which are interesting due to their magnetic properties. The properties of some Co-based alloys obtained from glycine-containing baths are well documented, but studies of the exact role of the aminoacid are lacking. This Thesis presents studies attempting to understand the influence of glycine on the mechanisms of cobalt electrodeposition. In situ analysis techniques - external reflection FTIR spectroscopy and pH measurement near the electrochemical interface using indicator microelectrodes - were coupled to the electrochemical studies. Good-quality cobalt deposits were obtained from glycine-containing baths, and under higher overpotentials than possible over systems with no additive (in which precipitation of hydroxides occurs). Analysis of the cyclic voltammetry experiments indicated the electroactivity of cobalt-glycine complexes, and the slower reduction kinetics in comparison with glycine-free solutions at sufficiently high pH values. The kinetic studies were hindered by the parallel hydrogen evolution reaction and the existence of several chemical equilibria in solution. During cobalt electrodeposition from glycine-containing solutions, an expressive elevation of the near interface pH was observed. The spectroelectrochemical experiments also showed the displacement of cobalt complexation equilibria in solution, caused by the increase in the interfacial pH. All the conducted studies showed that the presence of glycine favors the hydrogen evolution reaction, decreasing the current efficiency for the electrodeposition process. Nevertheless, glycine was able to stabilize the electrolyte solution.

A adequada quantificação do transporte interfacial de escalares em escoamentos turbulentos é de interesse prático para os processos industriais e para a gestão dos problemas ambientais. O fenômeno é matematicamente complexo devido ao uso de equações governantes estatísticas não lineares e não fechadas. Neste estudo, analisam-se detalhes do método de Ondas Quadradas Aleatórias (OQA), o qual fornece uma quantificação estatística que permite fechar as equações e obter um perfil normalizado da grandeza de interesse para a transferência unidimensional turbulenta de escalares, que, num caso idealizado, depende de apenas dois parâmetros adimensionais, A e k (neste caso, k representa um coeficiente de transferência e A depende da interação entre os fenômenos de transporte molecular e turbulento). Simulações numéricas foram realizadas no intuito de se verificar a influência das derivadas de ordem superior para a função normalizada de concentração. A sensibilidade do modelo e a análise de aspectos intrínsecos ao mesmo foram também realizadas. Importante análise das condições de contorno empregadas foi desenvolvida com a inserção de um contorno adicional, com base física, no seio líquido. Como os estudos iniciais tinham se concentrado em exemplos de transferência de massa, uma extensão para o caso de transporte de calor foi considerada. Os resultados obtidos reproduzem o comportamento dos dados experimentais observados na literatura. / The adequate quantification of interfacial scalar transport in turbulent flows is of practical interest for industrial processes and in environmental problems. The phenomenon is mathematically complex due to the use of unclosed nonlinear statistical equations. In this study, we analyze details of the method of Random Square Waves (RSW), which provides a statistical quantification that allows closing the set of equations and getting the normalized scalar profile of the one-dimensional turbulent scalar variable, which, in an idealized case, depends on only two nondimensional parameters, k and A (in this case, k represents a transfer coefficient and A depends on the interaction between the molecular and turbulent transports). Numerical simulations were performed in order to verify the influence of the higher order of derivatives over the normalized concentration function. The sensitivity of the model to the relevant parameters and the analysis of its intrinsic parameters were also performed. An important aspect is the analysis of the boundary conditions, for which an additional condition was proposed and employed in the bulk liquid (with based on physical grounds). Because the initial studies have focused on examples of mass transfer, an extension to the case of heat transport was here considered. The results reproduce the behavior of experimental data reported in the literature.

High-voltage (HV) outdoor composite insulators used in transmission lines are made of two polymers, comprising the core and housing, bonded together with metallic end-connections. The interface between these polymers is parallel to the electric field, which makes the insulators more prone to interfacial problems at these common points [1]. If interfacial ageing occurs, degradation and catastrophic breakdown can result [2]. Therefore, the design reliability of outdoor composite insulators depends on the high-strength bond between the core and the housing [3],[4]. Research findings by Kutil and Froshlic [5] indicate that delaminated areas, cavities and/or micro cracks in the medium are enough to initiate streamer discharges along the interface that are capable of degrading both insulating materials. The heat, UV radiation, and high-energy electrons produced from such discharge activity resulted in the growth of carbon paths along the interface, known as ‘tracking’, ultimately causing failure [6]. This investigation focuses on the development of tracking between silicone rubber and epoxy resin, with a view to replicating the tracking phenomena seen within composite insulators in service. A fine wire is placed between the dielectrics materials to enhance the local electric field magnitude and initiate discharge processes. The resulting partial discharge (PD) activity has been monitored. This Information has been used to understand the inception and propagation of the interfacial tracking. A strong relationship was found between maximum PD magnitude and track length. PD patterns and unique detailed images of the interfacial tracking development, allowed identification of the growth characteristics of interfacial channels and phases of tracking growth. Furthermore, a correlation in the mechanisms of interfacial degradation was found between the lab-fabricated samples and commercial composite rods. Finally, a growth model of interfacial ageing has been developed with the information from FEA models, PD patterns and the detailed images of tracking growth. The physical structure and chemical analysis of interfacial tracking is also disclosed to provide an insight into interfacial ageing mechanisms that occur in the composite insulators under electrical stress.

This dissertation considers the genesis and dynamics of interfacial instability in vertical laminar gas-liquid flows, using as a model the two-dimensional channel flow of a thin falling film sheared by counter-current gas. The methodology is linear stability theory by means of Orr-Sommerfeld analysis together with direct numerical simulation of the two-phase flow in the case of nonlinear disturbances. The influence of two main flow parameters on the interfacial dynamics, namely the film thickness and pressure drop applied to drive the gas stream, is investigated. To make contact with existing studies in the literature, the effect of various density and viscosity contrasts as well as surface tension is also examined. Energy budget analyses based on the Orr-Sommerfeld theory reveal various coexisting unstable modes (interfacial, shear, internal) in the case of high density contrasts, which results in mode coalescence and mode competition, but only one dynamically relevant unstable interfacial mode for low and intermediate density contrast. Furthermore, high viscosity contrast and increases in surface tension lead to some amount of mode competition for thin film. A study of absolute and convective instability for low density contrast shows that the system is absolutely unstable for all but two narrow regions of the investigated parameter space. These regions are extended at intermediate density contrast and exhibit only small changes with increased viscosity contrast or surface tension. Direct numerical simulations of the system with low density contrast show that linear theory holds up remarkably well upon the onset of large-amplitude waves as well as the existence of weakly nonlinear waves. For high density contrasts corresponding more closely to an air-water-type system, linear stability theory is also successful at determining the most-dominant features in the interfacial wave dynamics at early-to-intermediate times. Nevertheless, the short waves selected by the linear theory undergo secondary instability and the wave train is no longer regular but rather exhibits chaotic motion. Furthermore, linear stability theory also predicts when the direction of travel of the waves changes - from downwards to upwards. The practical implications of this change in terms of loading and flooding is discussed. The change in direction of the wave propagation is represented graphically for each investigated system in terms of a flow map based on the liquid and gas flow rates and the prediction carries over to the nonlinear regime with only a small deviation. Besides the semi-analytical and numerical analyses, experiments with an practically relevant setup and flow system have been carried out to benchmark and validate the models developed in this work.

This thesis uses neutron and x-ray reflectivity to measure the interfacial structures of three molecular components associated with bacteria. Firstly, the way in which the membrane targeting sequence of a cell division protein interacts with monolayer models for the inner leaflet of the inner membrane of bacteria was measured at the air-water interface. Secondly, the influence of lipopolysaccharide on a monolayer model for the outer leaflet of the outer membrane of Gram-negative bacteria was measured at the air-water interface, as well as how this lipopolysaccharide interacts with an antimicrobial peptide. Finally, the structure of a layer of protein found at the surface of a Gram-positive biofilm was measured at the air-water interface. Binding of the membrane targeting sequence of the MinD protein (MinD-mts) to the inner leaflet of the cytoplasmic membrane is thought to be key for bacterial cell division. Modelling this membrane as a monolayer at the air-water interface, it was found that the insertion of the MinD-mts increased with decreasing lateral pressure within the monolayer, as well as with increasing unsaturation of the lipid components, and the incorporation of cardiolipin into the monolayer. Lipopolysaccharide (LPS) is the major component of Gram-negative outer membranes, such as Escherichia coli, and can be considered as having three structural components: lipid A, a core oligosaccharide, and a variable polysaccharide chain. By incorporating LPS into a model membrane at the air-water interface, it was found that the polysaccharide chain undergoes conformational changes depending on the area per molecule. The effect of the antimicrobial peptide Pexiganan on the structure of this LPS layer was also determined, and was found to insert into the polysaccharide chain layer, but have no impact on the conformation of the chains. In nature, many bacteria live within a biofilm structure. A critical component of the Gram-positive Bacillus subtilis biofilm is a surface active amphipathic protein called BslA, which gives rise to the formation of the highly hydrophobic surface of the biofilm. The kinetics of this film formation, its thickness, and the lateral packing of the protein at the air-water interface, were measured using both neutron and x-ray reflectivity. It was found that a native BslA protein consistently formed the same structural film, whilst the structure of films formed by mutant proteins depended on the conditions under which the film was formed.

A adequada quantificação do transporte interfacial de escalares em escoamentos turbulentos é de interesse prático para os processos industriais e para a gestão dos problemas ambientais. O fenômeno é matematicamente complexo devido ao uso de equações governantes estatísticas não lineares e não fechadas. Neste estudo, analisam-se detalhes do método de Ondas Quadradas Aleatórias (OQA), o qual fornece uma quantificação estatística que permite fechar as equações e obter um perfil normalizado da grandeza de interesse para a transferência unidimensional turbulenta de escalares, que, num caso idealizado, depende de apenas dois parâmetros adimensionais, A e k (neste caso, k representa um coeficiente de transferência e A depende da interação entre os fenômenos de transporte molecular e turbulento). Simulações numéricas foram realizadas no intuito de se verificar a influência das derivadas de ordem superior para a função normalizada de concentração. A sensibilidade do modelo e a análise de aspectos intrínsecos ao mesmo foram também realizadas. Importante análise das condições de contorno empregadas foi desenvolvida com a inserção de um contorno adicional, com base física, no seio líquido. Como os estudos iniciais tinham se concentrado em exemplos de transferência de massa, uma extensão para o caso de transporte de calor foi considerada. Os resultados obtidos reproduzem o comportamento dos dados experimentais observados na literatura. / The adequate quantification of interfacial scalar transport in turbulent flows is of practical interest for industrial processes and in environmental problems. The phenomenon is mathematically complex due to the use of unclosed nonlinear statistical equations. In this study, we analyze details of the method of Random Square Waves (RSW), which provides a statistical quantification that allows closing the set of equations and getting the normalized scalar profile of the one-dimensional turbulent scalar variable, which, in an idealized case, depends on only two nondimensional parameters, k and A (in this case, k represents a transfer coefficient and A depends on the interaction between the molecular and turbulent transports). Numerical simulations were performed in order to verify the influence of the higher order of derivatives over the normalized concentration function. The sensitivity of the model to the relevant parameters and the analysis of its intrinsic parameters were also performed. An important aspect is the analysis of the boundary conditions, for which an additional condition was proposed and employed in the bulk liquid (with based on physical grounds). Because the initial studies have focused on examples of mass transfer, an extension to the case of heat transport was here considered. The results reproduce the behavior of experimental data reported in the literature.

Harnessing the Sun’s energy via the conversion of solar photons to electricity has emerged as a sustainable energy source to fulfill our future demands. In this regard, solution-processable, size-tunable PbS quantum dots (QDs) have been identified as a promising active materials for photovoltaics (PVs). Yet, there are still serious challenges that hinder the full exploitation of QD materials in PVs. This dissertation addresses two main challenges to aid these QDs in fulfilling their tremendous potential in PV applications. First, it is essential to establish a large-scale synthetic technique which maintains control over the reaction parameters to yield QDs with well-defined shape, size, and composition. Rigorous protocols for cost-effective production on a scale are still missing from literature. Particularly, previous reports of record-performance QD-PVs have been based on small-scale, manual, batch syntheses. One way to achieve a controlled large-scale synthesis is by reducing the reaction volume to ensure uniformity. Accordingly, we design a droplet-based continuous-flow synthesis of PbS QDs. Only upon separating the nucleation and growth phases, via a dual-temperature-stage reactor, it was possible to achieve high-quality QDs with high photoluminescence quantum yield (50%) in large-scale. The performance of these QDs in a PV device was comparable to batch-synthesized QDs, thus providing a promise in utilizing automated synthesis of QDs for PV applications. Second, it is crucial to study and control the charge transfer (CT) dynamics at QD interfaces in order to optimize their PV performance. Yet, the CT investigations based on PbS QDs are limited in literature. Here, we investigate the CT and charge separation (CS) at size-tunable PbS QDs and organic acceptor interfaces using a combination of femtosecond broadband transient spectroscopic techniques and steady-state measurements. The results reveal that the energy band alignment, tuned by the quantum confinement, is a key element for efficient CT and CS processes. Additionally, the presence of interfacial electrostatic interaction between the QDs and the acceptors facilitates CT from large PbS QD (bandgap < 1 eV); thus enabling light-harvesting from the broad near-infrared solar spectrum range. The advances in this work – from automated synthesis to charge transfer studies – pave new pathways towards energy harvesting from solution-processed nanomaterials.

The energy demand has increased dramatically in the last century, and so to have global CO2 emissions. Two critical challenges for the geo-energy sector are to develop different approaches for harvesting energy and to actively decrease atmospheric CO2 emissions. Addressing these challenges requires efficient, sustainable, and affordable technical solutions. Complex fluids are ubiquitous and offer great potential for geo-engineering applications such as the development of geo-energy, enhanced oil recovery and CO2 geological sequestration and utilization. This thesis will present new results on interfacial phenomena in CO2-fluid-mineral systems, including interfacial tension hysteresis, the effects of surface-active components on interfacial tension (surfactants, nanoparticles, organo-bentonites and asphaltenes), and the interfacial pinning of immiscible fluids on substrates. Pore-scale phenomena come together in the study of the physical properties of CO2 and its implication for both storage and assisted gravity oil drainage. Finally, we provide a better understanding of the interfacial phenomena of complex fluids and their interactions within porous media that can lead to efficient and sustainable geo-energy systems.

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