Com o objetivo de estudar os efeitos provocados pela adição de um corante em um cristal líquido termotrópico (CL), pesquisamos neste trabalho a influência da temperatura na reorientação das moléculas deste composto, bem como o índice de refração e a absorção não-linear, devido à presença de um campo eletromagnético. O CL estudado apresenta a reorientação de suas moléculas na presença de luz polarizada. Esta reorientação se deve à polarização provocada pelo campo eletromagnético da luz incidente nas moléculas do CL. O torque, que ocasiona tal reorientação, é denominado torque óptico Gammaopt. Quando estes CLs são dopados com determinados corantes, o campo incidente também interage com o corante, induzindo assim dipolos elétricos. Estes dipolos, por sua vez, interagem com as moléculas do CL provocando nelas um torque adicional Gammadye. Este torque adicional é proporcional ao torque óptico Gammadye = eta Gammaopt, onde eta é uma característica do corante denominado de fator de amplificação do torque óptico e depende da temperatura em que a amostra se encontra. A principal ferramenta do nosso estudo é a técnica de varredura z e, é através dela, que observamos a influência da temperatura nos efeitos não-lineares, refrativo e absortivo, exibidos pelas amostras. Através de tal técnica, calculamos, em função da temperatura, o fator de amplificação do torque óptico (eta); os índices de refração não-lineares (n2) devido à reorientação molecular da amostra, com e sem corante; e os coeficientes de absorção não-lineares (Beta) da amostra dopada devido a efeitos térmicos, de reorientação (torque) e de todos os efeitos somados. / With the objective of studying the effects due to the addition of a dye in a thermotropic liquid crystal (LC), we investigated in this work the influence of the temperature in the reorientation of the molecules of this compound, as well as the refraction index and the non linear absorption, in the presence of a electromagnetic field. The studied LC presents the reorientation of its molecules in the presence of polarized light. This reorientation is due to the polarization induced by the electromagnetic field of the incident light in the molecules of LC. The torque, that causes such reorientation, is named Gammaopt. When these LCs are doped with certain dyes, the incident field also interact with the dye, inducing electric dipoles. These dipoles, interact with the molecules of the LC producing an additional torque Gammadye. This additional torque is proportional to the optical torque Gammadye = eta Gammaopt, where eta is a characteristic of the dye, a factor of amplification of the optical torque, that is temperature dependent. The main tool of our study is the z-scan technique and, it is through it, that we observed the influence of the temperature in the non linear, refractive and absorptive effects, exhibited by the samples. Through this technique, we calculated, as a function of the temperature, the amplification factor of the optical torque (eta); the non linear refractive index (n2) due to the molecular reorientation of the sample, with and without dye; and the non linear absorption coefficient (Beta) of the doped sample due to thermal effects, of reorientation (torque) and of all the effects together.

Com o objetivo de estudar os efeitos provocados pela adição de um corante em um cristal líquido termotrópico (CL), pesquisamos neste trabalho a influência da temperatura na reorientação das moléculas deste composto, bem como o índice de refração e a absorção não-linear, devido à presença de um campo eletromagnético. O CL estudado apresenta a reorientação de suas moléculas na presença de luz polarizada. Esta reorientação se deve à polarização provocada pelo campo eletromagnético da luz incidente nas moléculas do CL. O torque, que ocasiona tal reorientação, é denominado torque óptico Gammaopt. Quando estes CLs são dopados com determinados corantes, o campo incidente também interage com o corante, induzindo assim dipolos elétricos. Estes dipolos, por sua vez, interagem com as moléculas do CL provocando nelas um torque adicional Gammadye. Este torque adicional é proporcional ao torque óptico Gammadye = eta Gammaopt, onde eta é uma característica do corante denominado de fator de amplificação do torque óptico e depende da temperatura em que a amostra se encontra. A principal ferramenta do nosso estudo é a técnica de varredura z e, é através dela, que observamos a influência da temperatura nos efeitos não-lineares, refrativo e absortivo, exibidos pelas amostras. Através de tal técnica, calculamos, em função da temperatura, o fator de amplificação do torque óptico (eta); os índices de refração não-lineares (n2) devido à reorientação molecular da amostra, com e sem corante; e os coeficientes de absorção não-lineares (Beta) da amostra dopada devido a efeitos térmicos, de reorientação (torque) e de todos os efeitos somados. / With the objective of studying the effects due to the addition of a dye in a thermotropic liquid crystal (LC), we investigated in this work the influence of the temperature in the reorientation of the molecules of this compound, as well as the refraction index and the non linear absorption, in the presence of a electromagnetic field. The studied LC presents the reorientation of its molecules in the presence of polarized light. This reorientation is due to the polarization induced by the electromagnetic field of the incident light in the molecules of LC. The torque, that causes such reorientation, is named Gammaopt. When these LCs are doped with certain dyes, the incident field also interact with the dye, inducing electric dipoles. These dipoles, interact with the molecules of the LC producing an additional torque Gammadye. This additional torque is proportional to the optical torque Gammadye = eta Gammaopt, where eta is a characteristic of the dye, a factor of amplification of the optical torque, that is temperature dependent. The main tool of our study is the z-scan technique and, it is through it, that we observed the influence of the temperature in the non linear, refractive and absorptive effects, exhibited by the samples. Through this technique, we calculated, as a function of the temperature, the amplification factor of the optical torque (eta); the non linear refractive index (n2) due to the molecular reorientation of the sample, with and without dye; and the non linear absorption coefficient (Beta) of the doped sample due to thermal effects, of reorientation (torque) and of all the effects together.

Le rhéoépaississement est un phénomène spectaculaire apparaissant dans certaines suspensions concentrées en particules. Il se manifeste par l’augmentation brutale de la viscosité de la suspension au delà d’une contrainte critique. L’exemple emblématique de suspension présentant ce type de comportement est le mélange d’amidon de maïs et d’eau. Le rhéoépaississement est longtemps resté une énigme, jusqu’à des travaux théoriques et numériques récents proposant un modèle microscopique cohérent. Selon celui-ci, le rhéoépaississement provient d’une transition frictionnelle due à la présence d’une force répulsive entre les grains. Au cours de ma thèse, j’ai réalisé une des premières démonstrations expérimentales directe de ce mécanisme. En m'inspirant de travaux venant du domaine des milieux granulaires, j'ai montré qu'en accord avec le modèle de transition frictionnelle, une suspension rhéoépaississante possède à faible pression granulaire un état non frottant. J'ai ensuite mis en évidence la transition en elle-même dans des suspensions contrôlées de billes de silice dans des solutions salines. Pour cela, j'ai dû développer de nouvelles méthodes de rhéologie à pression imposée. En effet, les rhéomètres standard ne permettent pas d'accéder aux propriétés de frottement des suspensions. Le seul rhéomètre qui le permet n'est pas adapté aux suspensions étudiées ici, qui sont constituées de particules colloïdales. Ce travail ouvre donc la voie au développement d’une nouvelle génération de rhéomètres permettant de mesurer le frottement dans les suspensions colloïdales, un enjeu majeur pour la rhéologie des fluides complexes. / Shear thickening is a spectacular phenomenon which takes place in some dense suspensions. It manifests itself by a brutal increase of the suspension's viscosity above a certain critical stress. The most iconic example of shear-thickening suspensions is cornstarch and water mixes. Shear thickening long remained a mystery, until recent theoretical and numerical works which proposed a consistent microscopic model. This model explains the shear thickening transition as a frictional one due to the presence of a repulsive force between the grains.During my PhD, I provided one of the first direct experimental proofs of this mechanism. Inspired by granular physics, I showed that shear-thickening suspensions possess a frictionless flowing state at low granular pressure, which is consistent with the proposed model. I then evidenced the frictional transition with controlled experiments using suspensions of silica beads in ionic solutions. To do this, I developed new rheological techniques enabling pressure imposed measurements. Indeed, standard rheological tools do not allow access to the frictional properties of suspensions. The only rheometer that does that is not adapted to the suspensions we study here, which are colloidal. This work thus paves the way for the development of a new generation of pressure imposed rheometers, giving access to colloidal suspensions friction, which is a major challenge in complex fluids rheology.

The studies of the dynamics, phase behavior, interparticle interactions, and hydrodynamics of stimuli-responsive pNIPAm-co-AAc microgels were described in this thesis. Due to their responsiveness to external stimuli, these colloidal particles serve as excellent model systems to probe the relationship between colloidal interactions and phase behavior. As a first step, we established our core experimental methodology, by demonstrating that particle tracking video microscopy is an effective technique to quantify various parameters in colloidal systems. Then we used the technique in combination with a microfluidic device that provides in situ control over sample pH to probe the phase behavior of pNIPAm-co-AAc microgel suspensions. In essence, the experimental set-up enables changes in effective particle volume fractions by changing pH, which can be used to construct the phase diagram. In order to explain the unique features of the microgel phase diagram, we measured the underlying pairwise interparticle potential of pNIPAm-co-AAc microgels directly in quasi-2D suspension and proved that the interactions are pH dependent and can range from weakly attractive to soft repulsive. Finally, the hindered Brownian diffusion due of colloidal particles confined by hard walls was investigated systematically and striking differences between hard sphere and soft sphere were found, with soft pNIPAm-co-AAc microgels showing surprising mobility even under strong confinement.

In order to study suspensions of deformable particles, a hybrid numerical technique was developed that combined a lattice-Boltzmann (LB) fluid solver with a finite element (FE) solid-phase solver. The LB method accurately recovered Navier-Stokes hydrodynamics, while the linear FE method accurately modeled deformation of fluid-filled elastic capsules for moderate levels of deformation. The LB/FE technique was extended using the Message Passing Interface (MPI) to allow scalable simulations on leading-class distributed memory supercomputers. An extensive series of validations were conducted using model problems, and the LB/FE method was found to accurately capture proper capsule dynamics and fluid hydrodynamics. The dilute-limit rheology was studied, and the individual normal stresses were accurately measured. An extension to the analytical theory for viscoelastic spheres [R. Roscoe. J. Fluid Mech., 28(02):273-93, 1967] was proposed that included the isotropic pressure disturbance. Single-body deformation was found to have a small negative (tensile) effect on the particle pressure. Next, the rheology and microstructure of dense suspensions of elastic capsules were probed in detail. As elastic deformation was introduced to the capsules, the rheology exhibited rapid changes. Moderate amounts of shear thinning were observed, and the first normal stress difference showed a rapid increase from a negative value for the rigid case, to a positive value for moderate levels of deformation. The particle pressure also demonstrated a decrease in compressive stresses as deformation increased. The corresponding changes in microstructure were quantified. Changes in particle self-diffusivity were also noted.

Soft particle glasses like microgels and compressed emulsions are densely packed, disordered suspensions of deformable particles. Quantitative relationships among the constituent properties and the macroscopic properties of the suspension are determined for their customized design as rheological additives. The microscopic origin of their macroscopic properties is also determined. Advanced characterization techniques like Large Amplitude Oscillatory Shear (LAOS) and microrheology are studied to use them efficiently to characterize these materials. Their microstructure and rheology are investigated through theory, simulations and experiments. Soft particle glasses are used as rheological additives in many applications including coatings, solid inks and textured food and cosmetic products but their formulation is largely empirical. A quantitative connection between their formulation and rheology is critical to enable their rational design. Their microstructure will lead to the microscopic origin of some unique properties in common with other soft crowded materials like intracellular cytoplasm and clays. These are complex fluids and require novel techniques to characterize them. A study of these techniques is essential to efficiently interpret the observations in terms of their macroscopic properties and the microscopic dynamics involved. Particle scale simulations of steady and oscillatory shear flow are developed to predict the nonlinear rheology and microstructure of these glasses. The origin of yielding is determined as escape of particles from their cages giving rise to a shear induced diffusion. Microrheology is studied by developing simulations of a probe particle being pulled at a constant force and the rheological information from microrheology is quantitatively connected to that from bulk rheological measurements. Soft particle glasses develop internal stresses when quenched to a solid state by flow cessation during processing. Experiments are performed to characterize and a priori predict these stresses. Simulations are used to determine the particle scale mechanisms involved in the stress relaxation on flow cessation and the microstructural origin of internal stresses. A pairwise interaction theory is developed for quiescent glasses to quantitatively predict their microstructure and elastic properties. The theory is then extended to sheared glasses to quantitatively predict their nonlinear rheology. The implementation of the pairwise theories is computationally much faster than the full three-dimensional simulations. / text

This work addresses fundamental aspects of designing templates and curing conditions for the synthesis of mesoporous metal oxide thin films. The first section addresses selection of cationic-carbohydrate surfactant mixtures to synthesize templated silica thin films for selective adsorption of simple carbohydrates based on molecular imprinting. Nuclear magnetic resonance and fluorescence spectroscopy results suggest a novel structure for mixtures of alkyl glucopyranosides or xylopyranosides with cationic (trimethylammonium) surfactants. Despite thermodynamically favorable mixing, the carbohydrate headgroups in the mixed micelle adopt an inverted configuration with their headgroups in the micelle core, and therefore are inaccessible for molecular imprinting. This orientation occurs even when the alkyl tail length of the carbohydrate surfactant is greater than that of the cationic surfactant, but this limitation can be overcome by introducing a triazole linker to the carbohydrate surfactant. The next section addresses the effects of aging conditions on the structural and chemical evolution of surfactant templated silica thin films. The third section describes the synthesis of carbohydrate/cationic surfactant imprinted silica thin films with orthogonally oriented cylindrical pores by modifying the glass surface with a random copolymer. The last part of the dissertation addresses the effect of pore orientation on the transformation mechanism of block copolymer templated titania thin films during high temperature curing. Mesoporous titania thin films can be used for photochemical and solar cell applications, but doing so requires addressing the tradeoff between loss of mesostructural order and growth of crystallinity during thermal treatment. By using advanced x-ray scattering techniques it has been shown that the titania films with vertically oriented pores can better withstand the anisotropic stress that develops during thermal treatment compare to titania films with mixed pore orientation. For instance, films with parallel or mixed pores can only be heated at 400 °C for a brief time (~10 min) without loss of order, while orthogonally oriented films can be heated at 550 °C or greater for extended time periods (on the order of hours) without significant loss of long-range mesopore structure. Detailed kinetic modeling was applied to enable the comparison of activation energy for mesostructure loss in films as a function of pore orientation and thickness.

Thesis (Ph. D.)--University of Delaware, 2008. / Principal faculty advisor: Eric W. Kaler, College of Engineering. Includes bibliographical references.

OLIVEIRA, Jessé Pereira de. Transporte em um sistema binário de partículas autopropelidas. 2015. 55 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2015. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-10-28T17:59:25Z No. of bitstreams: 1 2015_dis_jpoliveira.pdf: 4553539 bytes, checksum: 34f5d2c643bcea3444dad8820e83f2a2 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-10-28T18:05:49Z (GMT) No. of bitstreams: 1 2015_dis_jpoliveira.pdf: 4553539 bytes, checksum: 34f5d2c643bcea3444dad8820e83f2a2 (MD5) / Made available in DSpace on 2015-10-28T18:05:49Z (GMT). No. of bitstreams: 1 2015_dis_jpoliveira.pdf: 4553539 bytes, checksum: 34f5d2c643bcea3444dad8820e83f2a2 (MD5) Previous issue date: 2015 / Originally introduced by T. Vicksek et al. [Phys. Rev. Lett. 75, 1226 (1995)], Self Propelled Particles (SPP) have an intrinsic constant speed which suffer variations ins its direction as results of external perturbations (another particles or system) and are used to model systems that shows agglomeration effects. The concept of SPP is applied to describe and understand dynamic effects of agglomeration in natural systems, such as living micro-organisms (bacteria, virus, etc.) and colonies of individuals which move in flocks (fishes, sheep, bees) or, artificially produced, as colloidal systems especially prepared in laboratory. The study of SPP has its relevance in several areas of knowledge, such as material engineering, medicine and sciences of nature (physics, chemistry and biology). In most of cases, the collective motion has an well-differentiated behaviour of the individual motion of the components of a given system. So, the movement of a certain individual is affected by the presence of the other elements of the system, changing its general behaviour, as direct consequences of the direct interaction between them. In this way, we see the importance of investigation and understanding of collective motion of the SPP. Especially in this dissertation, we study a binary two-dimensional system of SPP subject to the presence of rigid obstacles with anisotropic geometry (semi-circles) distributed neatly in form of a square web. Beyond the particle-particle and particleobstacle interaction, the individual movement of each SPP suffers influence of an white noise. The objective is characterize the transport of SPP trough the two-dimensional substratum in absence of an propeller external force. We present and systematic study of collective motion of SPP in function of the speed of the particles, of the noise intensity which defines the stochastic movement of SPP, of the size of the obstacles, of the SPP density e the separation between the obstacles. Due the anisotropy of the obstacles, arise an spontaneous and ordered collective motion in normal direction of the plane surface of the obstacles, characterized by an non-null mean speed for each type of SPP in absence of an external force which in affected by the system parameters. / Originalmente introduzidas por T. Vicksek et al. [Phys. Rev. Lett. 75, 1226 (1995)], part´ıculas auto-propelidas (PAP) possuem uma velocidade intr´ınseca constante que sofre varia¸c˜oes em sua dire¸c˜ao como resultados de perturba¸c˜oes externas (outras part´ıculas ou meio) e s˜ao usadas para modelar sistemas que apresentam efeitos de aglomera¸c˜ao. O conceito de PAP ´e aplicado para descrever e entender efeitos dinˆamicos de aglomera¸c˜ao em sistemas naturais, tais como microorganismos vivos (bact´erias, v´ırus, etc) e colˆonias de indiv´ıduos de que se movem em bandos (peixes, ovelhas, abelhas, etc) ou, produzidos artificialmente, como sistemas coloidais especialmente preparadas em laborat´orio. O estudo de PAP tem sua relevˆancia em diversas ´areas do conhecimento, tais como engenharia de materiais, medicina e ciˆencias da natureza (f´ısica, qu´ımica e biologia). Na maioria dos casos, o movimento coletivo tem um comportamento bastante diferenciado dos movimentos individuais dos componentes de um dado sistema. Assim, o movimento de um certo indiv´ıduo ´e influenciado pela presen¸ca dos outros constituintes do sistema, alterando o seu comportamento geral, como consequˆencia da intera¸c˜ao direta entre eles. Desta forma, vemos a importˆancia da investiga¸c˜ao e entendimento do comportamento coletivo das PAP. Nesta disserta¸c˜ao, estudamos um sistema bidimensional bin´ario de PAP na presen¸ca de obst´aculos r´ıgidos com geometria anisotr´opica (semi-c´ırculos) distribu´ıdos na forma de uma rede quadrada. Al´em das intera¸c˜oes part´ıcula-part´ıcula e part´ıcula-obst´aculo, o movimento individual de cada PAP sofre influˆencia de um ru´ıdo branco. O objetivo ´e caracterizar o transporte de PAP atrav´es do substrato bidimensional na ausˆencia de uma for¸ca externa propulsora. Apresentamos um estudo sistem´atico do movimento coletivo das PAP em fun¸c˜ao das velocidades das part´ıculas, da intensidade do ru´ıdo que define o movimento estoc´astico das PAP, do tamanho dos obst´aculos, da densidade de PAP e da separa¸c˜ao entre os obst´aculos. Devido a anisotropia dos obst´aculos, surge um movimento coletivo espontˆaneo e ordenado na dire¸c˜ao normal `a superf´ıcie plana dos obst´aculos, caracterizado por uma velocidade m´edia n˜ao-nula para cada tipo de PAP na ausˆencia de for¸ca externa e que ´e influenciado pelos parˆametros do sistema.

xii, 89 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Lipid membranes are a basic structural element of all cells. They provide a framework for the physical organization of the cell, act as a scaffold for numerous proteins, and serve as the host site for countless chemical reactions integral to cell function. Several key problems in membrane biophysics hinge on reliable methods for measuring membrane material properties. Properties such as rigidity, fluidity, charge density, etc., are important factors that govern membrane structure and function. As such, we need controllable, reliable, and quantitative methods of probing membrane material properties. In pursuit of such methods, we completed two related projects that, while distinct, aimed to create and apply quantitative measures of membrane material properties to current problems in biophysics. The first of these two lines of inquiry centered on the pervasive, pathogenic family of mycobacteria that is known to not only cause several diseases but also to survive prolonged periods of dehydration. We developed an experimental model system that mimics the structure of the mycobacterial envelope consisting of an immobile hydrophobic layer supporting a two-dimensionally fluid, glycolipid-rich outer monolayer. With this system, we show that glycolipid containing monolayers, in great contrast to phospholipid monolayers, survive desiccation with no loss of integrity, as assessed by both fluidity and protein binding, revealing a possible cause of mycobacterial persistence. In the second line of inquiry, we developed another general platform for probing membrane material properties that has produced the first reported observations of viscoelasticity in lipid membranes. We utilized recently developed microrheological techniques on freestanding lipid bilayer systems using high speed video particle tracking. The complex shear modulus of the bilayers was extracted at a variety of temperatures that span the liquid-ordered to disordered phase transition of the membranes. At many temperatures measured, the membranes displayed viscoelastic behavior reminiscent of a Maxwell material, namely elastic at high frequencies and viscous at low frequencies. Moreover, the viscoelastic behavior was suppressed at the critical phase transition temperature where the membranes behave as a purely viscous fluid. Surprisingly, the viscoelastic behavior was found in all of several distinct membrane compositions that were examined. / Committee in charge: Dr. Daniel Steck, Chair; Dr. Raghuveer Parthasarathy, Research Advisor; Dr. Darren Johnson; Dr. Heiner Linke; Dr. John Toner