Neste trabalho usamos simulações computacionais para estudar inicialmente a estrutura das redes de ligação de hidrogênio (HB) formadas pelas misturas de metanol--água e 1-propanol--água e em seguida como essas misturas afetam as propriedades eletrônicas da sonda solvatocrômica 1-metilquinolin-8-olato (QB). Para a primeira parte fizemos uso do formalismo de redes complexas na análise das redes de HB formadas nas misturas. Com essa abordagem foi possível verificar o comportamento do sistema como um todo em diferentes concentrações de água nas misturas por meio do cálculo de diversas propriedades de rede. Da análise dessas propriedades pudemos, por exemplo, constatar bastante similaridade na conectividade dos dois tipos de misturas, entender melhor comportamentos anômalos, observar microssegregação, e verificar uma mudança na conectividade das moléculas de água em misturas com 1-propanol. Na parte seguinte, onde investigamos os efeitos das misturas nas propriedades eletrônicas da QB, foi necessário modelar uma parametrização adequada para o campo de força da sonda utilizado nas simulações. Essa parametrização incluiu adaptação de parâmetros geométricos da sonda e do conjunto de cargas atômicas polarizadas. Nessa último tópico, adaptamos o procedimento iterativo de polarização, dentro de uma abordagem sequencial de mecânica quântica e mecânica molecular. De posse desses parâmetros realizamos a simulação da QB em misturas de álcool--água em sete frações molares de água distintas. Analisamos a distribuição do solvente ao redor da QB e a solvatação preferencial. Em configurações amostradas nas simulações calculamos os efeitos das misturas no dipolo induzido, comprimento de onda de excitação eletrônica, índices globais de reatividade e blindagem magnética da QB. Fomos especialmente atentos em correlacionar esses efeitos com as propriedades estruturais do sistema, e percebemos quais das propriedades eletrônicas calculadas para a QB podem ser divididas nas duas classes: as que são mais susceptíveis às interações de curto alcance, como HB com o solvente e a solvatação preferencial; e as que são mais susceptíveis às interações de longo alcance. / In this work we use computer simulations to initially study the hydrogen bond (HB) networks formed in mixtures of methanol--water and 1-propanol--water and subsequently how these mixtures can affect the electronic properties of the solvatocromic probe 1-methylquinolin-8-olate (QB). For the first part, we use the complex networks formalism to analyse HB networks formed in mixtures. With this approach it was possible to verify the behavior of the system as a whole in different water concentrations by calculating several network properties. As a result we note, for example, the connectivities of the two types of mixtures are quite similar. We were also able to better understand the system anomalous behavior, observe microsegregation and verify a change in the connectivity of water molecules in mixtures with 1-propanol. In the following part, in which we investigated the effects of mixtures on the electronic properties of the QB, it was necessary to model an appropriate parameterization for the force field of the probe used in the simulations. This parameterization included adjustments for both the geometric parameters and the polarized atomic charges. In this last topic, we adapt the iterative polarization process within a sequential approach using quantum mechanics and molecular mechanics. With these parameters we performed the simulation of the QB in mixtures of alcohol--water in seven distinct water fractions. We analyzed the solvent distribution around the QB and the preferential solvation. Using configurations sampled in the simulations we calculate the mixtures effects on induced dipole, wavelength electronic excitation, global indices of reactivity and magnetic shielding of the QB. We were especially attentive to correlate these effects with the structural properties of the system, and realize that of the electronic properties calculated for the QB can be divided into two classes: those that are more susceptible to short-range interactions, such as solute-solvent HB and preferential solvation, and those which are more susceptible to long-range interactions.

La vidange d'un réservoir à travers un orifice a été décrite par Torricelli il y a presque 400 ans. Son modèle ne prévoit aucun effet du mouillage du fluide qui s’écoule sur la plaque percée. Cette thèse montre expérimentalement que pour un orifice de taille comparable à la longueur capillaire, pour des fluides newtoniens peu visqueux, l’effet du mouillage sur le débit est important. Un modèle calculant la variation d'énergie cinétique dans le ménisque à la sortie du trou rend compte des observations expérimentales. Une instabilité, inconnue, du jet en sortie du trou apparaît également ; l'oscillation de la ligne triple du ménisque en est la cause. Les relations de dispersion de la fréquence d’excitation et des fréquences secondaires apparaissant le long du jet ont été établies.Cette étude a été complétée par des écoulements de fluides visqueux et viscoélastiques. Pour les fluides visqueux, le modèle d’écoulement du fluide parfait est corrigé à partir de nos expériences. Pour les fluides viscoélastiques, les expériences montrent qu'il y a compétition entre les dissipations visqueuses et les effets élastiques tout le long de l'écoulement. La prédiction de ces deux effets n'est pas aisée. Nous montrons des situations où les effets élastiques prédominent, permettant à une solution de polymère de couler plus vite que de l'eau.Pour finir, un second système expérimental a été construit permettant l'écrasement de fluides complexes entre deux plaques de verre parallèles. La visualisation, la mesure de la position et de la force normale, permettent de mieux comprendre le comportement de systèmes tels que les mousses, les émulsions, les gels sous une contrainte normale. / The draining of a tank through an orifice was described by Torricelli almost 400 years ago. His model does not provide for any wetting effect of the flowing fluid on the drilled plate. This thesis shows experimentally that the effect of wetting on the flow rate is important for Newtonian fluids with low viscosity in the case of an orifice the size of which is comparable to the capillary length. A model calculating the kinetic energy variation within the meniscus at the outlet of the hole allows us to account for experimental observations. Unknown jet instability also appears at the outlet of the hole; this is the oscillation of the meniscus triple line that is causing it. The relations of dispersion of the excitation frequency as well as that of the secondary frequencies appearing along the jet have been established.This investigation was supplemented by flows of both viscous and viscoelastic fluids. For viscous fluids, the perfect fluid model is corrected based on our experiments. For viscoelastic fluids, experiments show that there is competition between viscous dissipations and elastic effects throughout the flow. The prediction of both effects is challenging. We show situations where elastic effects dominate, allowing a polymer solution to flow faster than water.Finally, a second experimental set-up was build for compressing complex fluids between two parallel glass plates. Visualization, both position and normal force measurements, allow a better understanding of the behavior under normal stress of systems such as foams, emulsions, gels.

L'avance technologique a encouragé, au cours de la dernière décennie, la fabrication et l'utilisation de nouveaux matériaux, ayant des propriétés innovantes et un comportement complexe. Leur développement a été conditionné par la nécessité d'augmenter l'efficacité de certains procédés technologiques, dans des domaines importants tels que la médecine, la fabrication de médicaments, de produits cosmétiques, de produits alimentaires, la production d'énergie, le recyclage des matériaux usagés, par exemple par l'industrie des transports dont la construction automobile. Dans le cadre de cette étude, nous nous sommes intéressés au comportement de fluides issus de ces matériaux complexes. En effet, leur développement, leur production et leur utilisation sont conditionnés par la compréhension et la modélisation de leur rhéologie, tant au niveau macroscopique que microscopique, voire même nanométrique. La rhéologie d'un fluide est implicitement déterminée par ses propriétés de viscosité, d'élasticité et de plasticité. Un grand intérêt a toujours été porté au comportement viscoélastique des matériaux, la viscoélasticité d'une matière étant la propriété à manifester simultanément un comportement rhéologique visqueux et élastique, quand elle est soumise à une déformation, en raison de l'application d'une tension. La caractérisation rhéologique d'un liquide suppose la détermination du tenseur de tension supplémentaire, présent dans l'équation de mouvement, provenant de mesures rhéométriques. L'expression de ce tenseur, qui dépend de la déformation et de la vitesse de déformation, s'appelle la relation ou loi constitutive. La détermination du comportement rhéologique des fluides, / This paper was dedicated exclusively to the rheological characterization of simple and complex fluids and a detailed analyze of available rheometric testing procedures. Throughout this thesis the rheological behavior of both simple and complex fluids has been studied and modeled in both shear and the complex motions (shear tests and squeezing tests). By linking conventional experimental test methods with numerical simulations of real flows, this thesis introduces a new concept in rheology: Computational Rheometry. All experimental investigations carried out in this study for the squeezing flows were accompanied by numerical simulations. For the oscillatory squeezing flow the influence of initial film thikness, oscillatory amplitude and frequency, computational time step was investigated by comparison with the theoretical predictions of squeeze force and a Genrealized Reynolds Equation inclued in a finite element code in Fortran. A validity domain was established for the analitical formulation of squeezing force. The constant velocity squeeze flow was investigated also using a quasi-steady approximation of the motion, which brings a significant reduction of the computational time, and a very good correlation with the transient (deformable mesh) approximation and the analytical predictions. The investigation of free surface influence on the distribution of normal force in both constant velocity and oscillatory squeeze flow was analyzed. In the case of constant velocity squeeze flow, the numerical simulations coupled with the free surface evolution and measured normal force during experimental investigations are suggesting the presence of a partial slip during the experimen

Optical Coherence Tomography Velocimetry (OCTV) is a technique based on principals developed for medical imaging and is used to measure the velocity as a function of sample depth for a range of complex fluid systems, revealing insight into rheological properties that are otherwise ignored by bulk rheometry methods. The technique fulfils the requirements needed to study a wide range of complex systems, being capable of measuring absolute velocity and velocity fluctuations with high spatial and temporal resolution, as well as in opaque materials. Improvements to the instrumentation behind OCTV are described in detail, with improvements to signal to noise being achieved through better detection and the use of modulation techniques. The technique is also demonstrated in a range of complex fluids including dense suspensions of hard spheres, DNA solutions, polyacrylamide solutions, bacteria and shampoo amongst others. Non-linear flow behaviour is revealed that includes shear banding, wall slip and elastic turbulence. X-ray scattering techniques are also discussed, with results from recent experiments at the Diamond synchrotron being presented. The commercial potential of OCTV is discussed in depth, with analysis of the market of scientific instruments for measuring flow, competitor analysis and a review of relevant intellectual property. Methods to commercialise OCTV are discussed, with licensing to an existing competitor being identified as the means with the least risk and greatest chance of success.

Dispersed multiphase flows occur in many biological, engineering and geophysical applications. Understanding the behavior of suspensions is a difficult task. In the present work, we numerically study the behavior of suspensions of finite-size rigid particles in different flows. Firstly, the sedimentation of spherical particles larger than the Taylor microscale in sustained homogeneous isotropic turbulence and quiescent fluid is investigated. The results show that the mean settling velocity is lower in an already turbulent flow than in a quiescent fluid. We also investigate the settling in quiescent fluid of oblate particles. We find that at low volume fractions the mean settling speed of the suspension is substantially larger than the terminal speed of an isolated oblate. Suspensions of finite-size spheres are also studied in turbulent channel flow. First, we change the solid volume and mass fractions, and the solid-to-fluid density ratio in an idealized scenario where gravity is neglected. Then we investigate the effects of polydispersity. It is found that the statistics are substantially altered by changes in volume fraction. We then consider suspensions of solid spheres in turbulent duct flows. We see that particles accumulate mostly at the corners or at the core depending on the volume fraction. Secondary motions are enhanced by increasing the volume fraction, until excluded volume effects are so strong that the turbulence activity is reduced. The inertial migration of spheres in laminar square duct flows is also investigated. We consider semi-dilute suspensions at different bulk Reynolds numbers and duct-to-particle size ratios. The highest particle concentration is found around the focusing points, except at very large volume fractions. Finally we study the rheology of confined dense suspensions of spheres in simple shear flow. We focus on the weakly inertial regime and show that the effective viscosity varies non-monotonically with increasing confinement. / <p>QC 20171117</p>

All biological cell membranes maintain an electric transmembrane potential of around 100 mV, due in part to an asymmetric distribution of charged phospholipids across the membrane. This asymmetry is crucial to cell health and physiological processes such as intracell signaling, receptor-mediated endocytosis, and membrane protein conformation and function as well as active processes involving flippase and floppase proteins. Despite the biological significance, there are limited studies linking the consequences of lipid asymmetry to critical membrane properties and processes involving ion channels. One reason for this is the scarcity of reliable methods to create artificial membrane systems that incorporate both transverse lipid asymmetry and ion channels. Experimental artificial membrane systems incorporate essential cell membrane structures, namely the phospholipid bilayer, in a controllable manner where specific properties and processes can be isolated and examined in an environment much simpler than living systems. It is of particular interest to study asymmetry in transverse lipid composition across the phospholipid bilayer on such a system to probe the effects of the lipid composition and asymmetric arrangement of these lipids on the physicochemical properties of the membrane. By doing so, an understanding of how membrane asymmetry dictates membrane properties and in turn impacts cellular processes will be achieved. The primary goal of this thesis is to develop a platform for fabricating and characterizing compositionally controlled planar, free-standing, asymmetric membranes. This asymmetry was qualitatively demonstrated using a fluorescence quenching assay, and it has been quantified using a combination of anionic and zwitterionic lipids in concert with a patch-clamp amplifier system. Initial measurements of a transmembrane potential on a partially asymmetric bilayer were found to be between 10 and 25 mV. Increasing membrane charge asymmetry increases the offset voltage, as expected, and also modifies the stiffness of the membrane. These initial successes demonstrate a viable pathway to fabricate and quantitatively characterize asymmetric bilayers that can be extended to accommodate more complex membrane processes in the future.

The expected outcome of this project is to develop a general strategy to functionalize dispersions, by noncovalent adsorption of HMW surfactants, ultimately for applications such as hydrophobic coatings with high hiding power and hardness, improved mechanical properties via pigment-latex interactions, improved substrate adhesion or improved freeze-thaw stability. So far, we have produced poly (methyl methacrylate-co-butyl acrylate) latexes in the presence of HMW surfactants via emulsion polymerization and demonstrated stronger adsorption of HMW surfactants on particle surface than sodium dodecyl sulfate (SDS). In addition, we have developed surfactant-free latexes, poly (methyl methacrylate-co-butyl acrylate-co-methacrylic acid), as models for post functionalization with high molecular weight surfactants. The successful transfer of surfactants onto particle surface from liquid crystals was indicated by the increase in zeta potential and confirmed via chemical shifts variation in 1H NMR spectra. Additionally, the HMW surfactants were used for dispersing hydrophobic inorganic particles, such as hydrophobic carbon black, in aqueous phase, providing an indication of the general applicability and versatility of our approach.

No description available.

In this study, instability and failure in complex fluids (Elastoviscoplastic fluids) is explored using the classic Considère (F˙ &lt; 0) and stress curvature (σ¨ &lt; 0) criteria. Employing the Saramito model, numerical simulation of the extensional protocol on non-Newtonian fluids is carried out. Validation is firstly performed (with a purely viscoelastic model) and in general found to be in agreement with previous works. Parameter variation of the Bingham number (Bi), capillary number (Ca) and extension rate (ε˙) is then undertaken. It is found out that for Oldroyd-B based fluids, the stress curvature condition almost always occurs from inception of the flow for all cases. Additionally, increasing surface tension has a stabilizing effect on the extending fluid when it is below a critical value, above which it aids breakup. Increasing the yield stress, though, delays the onset of instability, but reduces the final length of the extending filament. At mild to high extension rates, the Considère criterion and the extension at the maximum stress are suit-able indicators of the final extension at strain-to-break(εST B). Furthermore, the rate of the of necking instability till final breakup varies with the εST B at moderate to high ε˙. / I denna studie undersöks instabilitet och misslyckande i komplexa vätskor (Elastoviskoplas-tiska vätskor) med den klassiska Considère (F˙ &lt; 0) och stresskurvatur (σ¨ &lt; 0) kriterier. Genom att använda Saramito-modellen utförs numerisk simulering av det utökade protokol-let på icke-newtonska vätskor. Valideringen utförs först (med en rent viskoelastisk modell) och i allmänhet visar sig överensstämma med tidigare verk.Parametervariation av Bingham-numret (Bi), kapillärnummer (Ca) och förlängningshastighet (ε˙) genomförs sedan. Det har visat sig att för Oldroyd-B-baserade vätskor, uppträder stresskrökningstillståndet nästan alltid från början av flödet i alla fall. Dessutom har ökande ytspänningen stabiliserande effekt på den utsträckande vätskan när den är under ett kritiskt värde, över vilket den underlättar uppbrytning. En ökning av sträckgränsen fördröjer dock instabiliteten men minskar den slutliga längden på det utsträckta filamentet. Vid milda till höga utvidgningshastigheter är Considère-kriteriet och förlängningen vid maximal spänning lämpliga indikatorer för den slutliga förlängningen vid spänning till brott (εST B). Vidare varierar frekvensen av instabilitet i halsen till slutlig upplösning med εST B vid måttlig till hög ε˙.

This thesis focuses on two problems lying within the field of soft condensed matter: the viscous fingering or Saffman-Taylor instability and nematic liquid crystals in confinement. Whenever a low viscosity fluid displaces a high viscosity fluid in a porous medium, for example water pushing oil out of oil reservoirs, the interface between the two fluids is rendered unstable. Viscous fingers develop, grow and compete until a single finger spans all the way from inlet to outlet. Here, using a free energy lattice Boltzmann algorithm, we examine the Saffman-Taylor instability for two different wetting situations: (a) when neither of the two fluids wet the walls of the channel and (b) when the displacing fluids completely wets the walls. We demonstrate that curvature effects in the third dimension, which arise because of the wetting boundary conditions, can lead to a novel suppression of the instability. Recent experiments in microchannels using colloid-polymer mixtures support our findings. In the second part of the thesis we examine nematic liquid crystals confined in wedge-structured geometries. In these systems the final stable configuration of the liquid crystal system is controlled by the complex interplay between confinement, elasticity and surface anchoring. Varying the wedge opening angle this competition leads to a splay to bend transition mediated by a defect in the bulk of the wedge. Using a hybrid lattice Boltzmann algorithm we study the splay-bend transition and compare to recent experiments on {em fd} virus particles in microchannels. Our numerical results, in quantitative agreement with the experiments, enable us to predict the position of the defect as a function of opening angle, and elucidate its role in the change of director structure. This has relevance to novel energy saving, liquid crystal devices which rely on defect motion and pinning to create bistable director configurations.