<p>Hydrogenated castor oil (HCO) crystals as a rheology modifier have been widely used in paints, cosmetics and household products. In this thesis, we are interested in the effect of crystal morphology on the suspension rheology of products. Three major types of micron-sized crystal morphologies have been observed: fiber, rosette and irregular crystal. Fibers show a high aspect ratio with the length ranging from 5 to 33 µm and width around 1~3 µm. The rosette (2~50 µm) is a three-dimensional spherulitic structure with nano-fibrous arms extruding from a heterogeneous central point. Irregular crystals with equivalent diameter ranging from 4 to 84 µm are hard solid and show irregular shapes. There is an additional fourth type of crystal morphology which is a nano-sized fibrous structure that is assumed to be broken down from arms of micron-sized rosettes and fibers. Due to the relatively small amount, the effects of nano-fibrous fragments on rheology were not considered separately in this work.</p> <p>The effect of temperature and shear history on the HCO crystal morphology has been studied. The energy barrier to nucleation for fibers is suggested to be higher than that of rosettes. Irregular crystals are thermodynamically less stable and tend to transform into stable polymorphs. A non-isothermal crystallization study showed that the formation of rosettes and fibers was favored by a slow cooling rate (1°C/min) while the formation of irregular crystals was favored by a fast cooling rate (5°C/min). Shear rates from zero to 100 s^-1 have been applied at cooling rates from 1°C/min to 5°C/min. Nucleation has been found to be promoted with the increase of shear rate. Morphological analysis indicated that the formation of fibers was favored by gentle shear (e.g., 1 s^-1), but fibers can be broken with the increase of shear time.</p> <p>Kinetics of isothermal crystallization of hydrogenated castor oil in water emulsions exhibiting multiple crystal morphologies has been studied in the temperature range of 55°C to 70°C. The induction time of nucleation increases with the increase of the isothermal temperature under which crystallization occurred. A linear increase in induction time with increased temperature was found for both fibers and rosettes. A modified Avrami model was developed by introducing the volume fraction of each type of morphology into three dimensional and one dimensional full Avrami models. It was found that the experimental trends for mixed crystal morphologies could be captured by the modified Avrami model.</p> <p>Due to the difficulty of obtaining samples with a single crystal morphology, rheological studies of suspensions containing mixtures of the three morphologies in a surfactant solution have been undertaken. The viscometry of dilute suspensions has shown that the magnitude of intrinsic viscosity is dominated by the fraction of a crystal morphology type, i.e. fiber > rosette > irregular crystal. A modified Farris model was fitted to the rheology data from mixtures of crystal morphology with interacting particles. A yield stress exists for concentrated suspensions followed by a shear thinning behavior with the increase of shear rate. A power-law relation has been found between yield stress and total particle volume fraction with a constant exponent of 1.5 regardless of crystal morphology.</p> / Doctor of Philosophy (PhD)

A common challenge in materials science is the "inverse design problem," wherein one seeks to use theoretical models to discover the microscopic characteristics (e.g., interparticle interactions) of a system which, if fabricated or synthesized, would yield a targeted material property. Inverse design problems are commonly addressed by stochastic optimization strategies like simulated annealing. Such approaches have the advantage of being general and easy to apply, and they can be effective as long as material properties required for evaluating the objective function of the optimization are feasible to accurately compute for thousands to millions of different trial interactions. This requirement typically means that "exact" yet computationally intensive methods for property predictions (e.g., molecular simulations) are impractical for use within such calculations. Approximate theories with analytical or simple numerical solutions are attractive alternatives, provided that they can make sufficiently accurate predictions for a wide range of microscopic interaction types. We propose a new approach, based on the fine discretization (i.e., terracing) of continuous pair interactions, that allows first-order mean-spherical approximation theory to predict the equilibrium structure and thermodynamics of a wide class of complex fluid pair interactions. We use this approach to predict the radial distribution functions and potential energies for systems with screened electrostatic repulsions, solute-mediated depletion interactions, and ramp-shaped repulsions. We create a web applet for introductory statistical mechanics courses using this approach to quickly estimate the equilibrium structure and thermodynamics of a fluid from its pair interaction. We use the applet to illustrate two fundamental fluid phenomena: the transition from ideal gas-like behavior to correlated-liquid behavior with increasing density in a system of hard spheres, and the water-like tradeoff between dominant length scales with changing temperature in a system with ramp-shaped repulsions. Finally, we test the accuracy of our approach and several other integral equation theories by comparing their predictions to simulated data for a series of different pair interactions. We introduce a simple cumulative structural error metric to quantify the comparison to simulation, and find that according to this metric, the reference hypernetted chain closure with a semi-empirical bridge function is the most accurate of the tested approximations. / text

Dans ce travail de thèse, nous avons développé deux méthodologies permettant d'acquérir rapidement et facilement des propriétés physico-chimiques, cinétiques et thermodynamiques de fluides complexes. Nous nous sommes focalisés sur le rôle de la concentration sur ces propriétés. Les deux méthodes développées sont basées sur la concentration en continu d'une solution aqueuse par évaporation contrôlée du solvant. Le premier outil est une goutte de quelques microlitres confinée entre deux plaques dont la hauteur est de 100µm. Dans cette géométrie à deux dimensions, l'évaporation est entièrement décrite par un modèle que nous avons développé. L'observation du séchage de la goutte couplée à des mesures locales de concentration par spectroscopie Raman, permet d'accéder quantitativement au diagramme de phase d'une solution de copolymères, et de mesurer l'activité ainsi que d'estimer le coefficient d'interdiffusion de la solution. Le second outil est une puce microfluidique permettant de concentrer des solutions aqueuses grâce à la pervaporation de l'eau à travers une membrane. Cet outil permet avec quelques microgrammes de soluté, de bâtir un gradient de concentration stationnaire le long d'un microcanal. Les techniques de spectroscopie Raman et de diffusion des rayons X aux petits angles permettent à nouveau de mesurer des propriétés physico-chimiques de la solution mais également de mettre en évidence le caractère discontinu du coefficient d'interdiffusion en fonction de la concentration, dépendant des mésophases présentes. / In this work, we developed two methods in order to access rapidly and easily physico-chemical, thermodynamic and kinetic properties of complex fluids. We focused on the role of the concentration on these properties. The two methods that we developed are based on the continuous concentration of an aqueous solution thanks to the evaporation of the solvent. The first tool is a microliter droplet confined between two circular plates with a cell height of about 100 µm. Within this two dimensional cylindrical geometry, the evaporation of the droplet is totally described by a model that we developed. The observation of the droplet evaporation combined to local Raman spectroscopy measurements permits us to build a quantitative phase diagram, to measure the activity of the solution and to estimate its mutual diffusion coefficient. The second tool is a microfluidic chip in which water is removed through a thin membrane. This device permits us to build with a few micrograms of solutes a stationary concentration gradient along a microchannel. Raman confocal spectroscopy and small angle X-ray scattering give access to the quantitative phase diagram and also permit to evidence that the mutual diffusion coefficient is discontinuous at some of the phase boundaries.

Thesis (Ph.D.)--Memorial University of Newfoundland, 2001. / Bibliography: leaves [143]-150.

Thesis (Ph.D.)--Brown University, 2008. / Vita. Advisor : Anubhav Tripathi. Includes bibliographical references.

A diffuse-interface finite-element method has been applied to simulate the flow of two-component rheologically complex fluids. It treats the interfaces as having a finite thickness with a phase-field parameter varying continuously from one phase to the other. Adaptive meshing is applied to produce fine grid near the interface and coarse mesh in the bulk. It leads to accurate resolution of the interface at modest computational costs. An advantage of this method is that topological changes such as interfacial rupture and coalescence happen naturally under a short-range force resembling the van der Waals force. There is no need for manual intervention as in sharp-interface model to effect such event. Moreover, this energy-based formulation easily incorporates complex rheology as long as the free energy of the microstructures is known. The complex fluids considered in this thesis include viscoelastic fluids and nematic liquid crystals. Viscoelasticity is represented by the Oldroyd-B model, derived for a dilute polymer solution as linear elastic dumbbells suspended in a Newtonian solvent. The Leslie-Ericksen model is used for nematic liquid crystals，which features distortional elasticity and viscous anisotropy. The interfacial dynamics of such complex fluids are of both scientific and practical significance. The thesis describes seven computational studies of physically interesting problems. The numerical simulations of monodisperse drop formation in microfluidic devices have reproduced scenarios of jet breakup and drop formation observed in experiments. Parametric studies have shown dripping and jetting regimes for increasing flow rates, and elucidated the effects of flow and rheological parameters on the drop formation process and the final drop size. A simple liquid drop model is used to study the neutrophil, the most common type of white blood cell, transit in pulmonary capillaries. The cell size, viscosity and rheological properties are found to determine the transit time. A compound drop model is also employed to account for the cell nucleus. The other four cases concern drop and bubble dynamics in nematic liquid crystals, as determined by the coupling among interfacial anchoring, bulk elasticity and anisotropic viscosity. In particular, the simulations reproduce unusual bubble shapes seen in experiments, and predict self-assembly of microdroplets in nematic media.

No description available.

A diffuse-interface finite-element method has been applied to simulate the flow of two-component rheologically complex fluids. It treats the interfaces as having a finite thickness with a phase-field parameter varying continuously from one phase to the other. Adaptive meshing is applied to produce fine grid near the interface and coarse mesh in the bulk. It leads to accurate resolution of the interface at modest computational costs. An advantage of this method is that topological changes such as interfacial rupture and coalescence happen naturally under a short-range force resembling the van der Waals force. There is no need for manual intervention as in sharp-interface model to effect such event. Moreover, this energy-based formulation easily incorporates complex rheology as long as the free energy of the microstructures is known. The complex fluids considered in this thesis include viscoelastic fluids and nematic liquid crystals. Viscoelasticity is represented by the Oldroyd-B model, derived for a dilute polymer solution as linear elastic dumbbells suspended in a Newtonian solvent. The Leslie-Ericksen model is used for nematic liquid crystals，which features distortional elasticity and viscous anisotropy. The interfacial dynamics of such complex fluids are of both scientific and practical significance. The thesis describes seven computational studies of physically interesting problems. The numerical simulations of monodisperse drop formation in microfluidic devices have reproduced scenarios of jet breakup and drop formation observed in experiments. Parametric studies have shown dripping and jetting regimes for increasing flow rates, and elucidated the effects of flow and rheological parameters on the drop formation process and the final drop size. A simple liquid drop model is used to study the neutrophil, the most common type of white blood cell, transit in pulmonary capillaries. The cell size, viscosity and rheological properties are found to determine the transit time. A compound drop model is also employed to account for the cell nucleus. The other four cases concern drop and bubble dynamics in nematic liquid crystals, as determined by the coupling among interfacial anchoring, bulk elasticity and anisotropic viscosity. In particular, the simulations reproduce unusual bubble shapes seen in experiments, and predict self-assembly of microdroplets in nematic media.

Thesis (Ph. D.)--University of Oregon, 2006. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 104-111). Also available for download via the World Wide Web; free to University of Oregon users.

Thesis (Ph. D.)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2007. / Andreas S. Bommarius, Committee Member ; L. Andrew Lyon, Committee Member ; J. Carson Meredith, Committee Member ; William J. Koros, Committee Member ; Victor Breedveld, Committee Chair.