The self-assembly behavior of arborescent polystyrene-<em>graft</em>-poly(ethylene oxide) copolymers (PS-<em>g</em>-PEO) at the air-water interface and the solubilization/release properties of arborescent polystyrene-<em>graft</em>-poly(2-vinylpyridine) (PS-<em>g</em>-P2VP) copolymers were investigated. These amphiphilic dendritic molecules are covalently bonded unimolecular micelles incorporating a highly branched hydrophobic polystyrene core surrounded by a hydrophilic poly(ethylene oxide) or poly(2-vinylpyridine) shell. Molecules of PS-<em>g</em>-PEO copolymers spontaneously formed supramolecular assemblies at the air-water interface. The type of superstructures formed was found to depend upon copolymer composition, while the level of association was more directly related to the branching density of the polymers. At low surface pressures the PEO segments apparently remained adsorbed on the water subphase, but desorbed into water at very high surface pressures, in the condensed monolayer state. Controlled degradation of the PEO chains with UV light greatly enhanced molecular association, resulting in the formation of either large clusters or long ribbon-like superstructures. The PS-<em>g</em>-P2VP copolymers were found to efficiently solubilize and release hydrophobic small molecules in aqueous media. The partition coefficient and solubilization capacity of the copolymers for hydrophobic polyaromatic hydrocarbons increased with the polystyrene content of the copolymers, while the rate of solubilization decreased with increasing branching functionality of the copolymers. The release profiles for two model drugs displayed an initial burst in release followed by gradual approach to equilibrium. The diffusion coefficients of the drugs in the micelles increased with the branching functionality and the generation number of the micelles, presumably due to increased electrostatic repulsions of the protonated vinylpyridine units.

The underlying idea of this thesis is that the surface chemical and morphological nature of bacterial strains uniquely differentiates one from another and hence can be used as the basis for their identification and control. It follows that their interactions with an artificial substratum uniquely characterize them. In principle, potentially it is easier and faster to evaluate the interfacial energy between a bacterium and a substratum than to characterize its genome or determine molecular biomarkers characteristic of the strain, hence validation of this thesis opens the way to rapid screening and diagnosis. Auxiliary to this main idea, an advanced metrology for evaluating the interfacial energies has been developed, exploiting the power of kinetic analysis.

Evaporation and wetting of droplets are a phenomena present in everyday life and in many industrial, biological or medical applications; thus controlling and understanding the underlying mechanisms governing this phenomena becomes of paramount importance. More recently, breakthroughs in the fabrication of new materials and nanomaterials have led to the synthesis of novel nanoscale particulates that dispersed into a base fluid modify the properties of this latter. Enhancement in heat transfer or the self-assembly of the particles in suspension during evaporation, are some of the areas in which nanofluids excel. Since it is a relatively new area of study, the interplay particle-particle, particle-fluid or particle-substrate at the macro-, micro-, and nanoscale is yet poorly understood. This work is an essay to elucidate the fundamental physics and mechanisms of these fluids during free evaporation, of great importance for the manipulation and precise control of the deposits. The evaporative behaviour of pure fluids on substrates varying in hydrophobicity has been studied and an unbalance Young’s force is proposed to explain the effect of substrate hydrophilicity on the pinning and the depinning forces involved during droplet evaporation. On other hand, the addition of nanoparticles to a base fluid modifies the evaporative behaviour of the latter and: a more marked “stick-slip” behaviour is observed when increasing concentration on hydrophobic substrates, besides the longer pinning of the contact line reported on hydrophilic ones when adding nanoparticles. A deposition theory to explain the final deposits observed, for the outermost ring, after the complete vanishing of a 0.1% TiO2-ethanol nanofluid droplet has also been developed. In addition, the evaporation of pinned nanofluid droplets on rough substrates at reduced pressures has been systematically studied. A revisited Young-Lippmann equation is proposed as one of the main findings to explain the enhancement on electrowetting performance of nanoparticle laden fluid droplets when compared to the pure fluid case. On the other hand, of relevant importance is the absence of “stick-slip” behaviour and the more homogeneous deposits found after the complete evaporation of a nanofluid droplet under an external electric field applied when compared to free evaporation of these fluids.

The broader technical objective of this work is to develop a strategy for using the biopolymer lignin in a wide variety of surfactant applications through polymer grafting. These applications include emulsion stabilizers, dispersants and foaming agents. The scientific objective of the research performed within this thesis is to understand the effect of molecular architecture and polymer grafting on the interfacial activity at the air-liquid, liquid-liquid and solid-liquid interface. Research has focused on designing of these lignopolymers with controlled architecture using polyethylene glycol, poly(acrylic acid) and polyacrylamide grafts. The interfacial activity for all polymer grafts has been tested at all three interfaces using a broad range of techniques specific to the interface. Results have shown that the hydrophobicity of the lignin core is responsible for enhanced interfacial activity at the air-liquid and liquid-liquid interface. Conversely, improved hydrophilicity and “electrosteric” interactions are required for higher interfacial activity of the lignin at the liquid-solid interface. The high interfacial activity of the polymer-grafted lignin observed in the air-liquid and liquid-liquid interfaces not only resulted in viscosity reduction but also strength enhancement at the liquid-solid interface. The broader implication of this study is to be able to predict what chemical functionalities need to be adjusted to get the desired viscosity reduction.

Made available in DSpace on 2018-08-01T23:29:04Z (GMT). No. of bitstreams: 1 tese_10249_Rômulo Fieni Fejoli.pdf: 7948045 bytes, checksum: 8967ae4538f0ddca168c3e5552421697 (MD5) Previous issue date: 2016-07-13 / Neste trabalho, é investigada a dinâmica interfacial de uma gota de óleo em água que flui através de um capilar reto e com garganta com geometria axial. O problema bidimensional, transiente, de fluidos newtonianos incompressíveis, bifásico, com forças de inércia pequenas, representa de forma simplificada, o que ocorre no reservatório de petróleo na escala microscópica durante a mobilização das gotas de óleo. A solução numérica do problema com interface é obtida pelo acoplamento dos métodos VOF (Volume of Fluid) e Level-set. Os resultados mostram que a dinâmica do processo do escoamento da gota de óleo, principalmente em capilares com garganta, provoca uma redução de mobilidade do escoamento, traduzido pelo parâmetro fator de bloqueio, o qual é influenciado pelos parâmetros adimensionais: número de capilaridade, razão de viscosidades e razões de diâmetros (da gota e do capilar). Obteve-se uma correlação destes parâmetros com o fator de bloqueio, em que seu valor decai para valores abaixo de um, com o aumento da razão de viscosidade e do tamanho da gota, e também uma pequena sensibilidade com a diminuição do número de capilaridade. De uma forma geral, a gota de óleo se deforma em maior ou menor grau em resposta aos parâmetros adimensionais, apresentando maior deformação com a diminuição da razão de viscosidades e do número de capilaridade. A presença da garganta aumenta significativamente a pressão assim como a velocidade de escoamento na garganta. Todas as simulações foram realizadas no software comercial ANSYS® Fluent® por meio de um longo processo de aprendizagem que permitiu adquirir conhecimentos importantes para este trabalho.

Cell surface properties are crucial to the mechanisms by which groups of cells organize themselves during embryogenesis, cancer metastases and tissue engineering. Measured surface tension values provide a quantitative basis for predicting a range of cell behaviors including sorting of embryonic cells, self-organization of pancreatic islet cells and invasive potential of tumor cells. Tissue surface tensions are a measurement of the tension that acts along the interface between a cell aggregate and its surrounding media and it is typically measured by compressing an aggregate of cells. In this study a novel apparatus is used to measure the surface tensions of aggregated embryonic chick cells from heart, liver, neural retina and mesencephalon tissues. These surface tension values are consistent with the known engulfment behavior of the cells involved and are in close agreement with measurements made previously by other means. It has been suggested that surface tensions and cell rearrangement patterns are a direct result of adhesion forces between cells arising from cadherins. However, cadherin binding alone is insufficient to account for observed engulfment phenomena and recent experimental evidence suggests that actin dynamics are involved. A cell surface property referred to as interfacial tension or cortical tension takes into account both adhesion forces and forces derived from actin microfilaments and could shed new light on the mechanisms involved in cell interactions. Computer simulations indicate that the interfacial tension between cells can be measured through a modified compression test experiment. In this cell aggregate compression study, cell shapes as well as the aggregate profile are measured in addition to the compression force in attempts to measure cell interfacial tensions.

Cell surface properties are crucial to the mechanisms by which groups of cells organize themselves during embryogenesis, cancer metastases and tissue engineering. Measured surface tension values provide a quantitative basis for predicting a range of cell behaviors including sorting of embryonic cells, self-organization of pancreatic islet cells and invasive potential of tumor cells. Tissue surface tensions are a measurement of the tension that acts along the interface between a cell aggregate and its surrounding media and it is typically measured by compressing an aggregate of cells. In this study a novel apparatus is used to measure the surface tensions of aggregated embryonic chick cells from heart, liver, neural retina and mesencephalon tissues. These surface tension values are consistent with the known engulfment behavior of the cells involved and are in close agreement with measurements made previously by other means. It has been suggested that surface tensions and cell rearrangement patterns are a direct result of adhesion forces between cells arising from cadherins. However, cadherin binding alone is insufficient to account for observed engulfment phenomena and recent experimental evidence suggests that actin dynamics are involved. A cell surface property referred to as interfacial tension or cortical tension takes into account both adhesion forces and forces derived from actin microfilaments and could shed new light on the mechanisms involved in cell interactions. Computer simulations indicate that the interfacial tension between cells can be measured through a modified compression test experiment. In this cell aggregate compression study, cell shapes as well as the aggregate profile are measured in addition to the compression force in attempts to measure cell interfacial tensions.

The behavior of dense colloidal fluids near surfaces can now be probed in great detail with experimental techniques like video and confocal microscopy. In fact we are approaching a point where quantitative comparisons of experiments with particle-level theory, such as classical density functional theory (DFT), are appropriate. In a forward sense, we may use a known surface potential to predict a particle density distribution function from DFT; in an inverse sense, we may use an experimentally measured particle density distribution function to predict the underlying surface potential from DFT. In this dissertation, we tested the ability of the closure-based DFT to perform forward and inverse calculations on potential models commonly employed for colloidal particles and surface under different surface topographies. To reduce sources of uncertainty in this initial study, Monte Carlo simulation results played the role of experimental data. The accuracy of the predictions depended on the bulk particle density, potential well depth and the choice of DFT closure relationships. For a reasonable range of choices of the density, temperature, potential parameters, and surface features, the inversion procedure yielded particle-surface potentials to an accuracy on the order of 0.1 kBT. Our results demonstrated that DFT is a valuable numerical tool for microcopy experiments to image three-dimensional surface energetic landscape accurately and rapidly. B

No description available.

The aim of this work was to develop an envelope function method to calculate the electronic states and optical properties of complex quantum well heterostructures, and to demonstrate its effectiveness by application to some device structures of topical interest. In particular, structures have been considered which might form the basis of intensity modulators and polarization insensitive amplifier devices for light at a wavelength of 1.55 µm. The modulator structures considered all have the general form of two coupled quantum wells of different widths as the active region. The application of an electric field in the growth direction is intended to result in a shift in the energy and spatial localisation of the confined states and produce an increase in the absorption coefficient at longer wavelengths than the zero field absorption edge. The effectiveness of certain structures is examined in terms of field induced absorption increase at 1.55 µm. A system which shows a significant increase in absorption coefficient at this wavelength on application of a practical electric field has been identified as a possible candidate for an intensity modulator. In the case of the amplifier, the active region of the most promising structure considered consists of a stepped well which comprises two layers, one with tensile and one with compressive strain. It is known that the presence of the two oppositely strained layers can result in the TE and TM gain peaks appearing at similar photon energies. Our calculations show that a suitable choice of strain and layer widths can result in a small or zero difference between the TE and TM gains at 1.55 µm, which can be important for the polarization insensitive operation of devices in optical communications applications. In order to predict the optical properties of quantum well devices it is necessary to calculate the electron and hole states for a range of in-plane wavevectors. The calculations developed and carried out in this work are based on a multi-layer (eight band) k.p model including strain effects. The interfacial boundary conditions which result from approximations to Burt's exact envelope function theory are included in the model. The effect of an electric field is modelled by including a potential energy term in each layer Hamiltonian which is equal to the average energy shift across the layer in question due to the presence of the field. The model has been developed with flexibility in mind and has applications beyond the specific devices considered in this thesis.