Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 181-190).

No description available.

While rheological and microstructural complexities have posed tremendous challenges to researchers in developing first principles models and simulation techniques that can accurately and robustly predict the dynamical behaviour of polymeric flows, the past two decades have offered several significant advances towards accomplishing this goal. These accomplishments include: (1). Stable and accurate formulation of continuum-level viscoelastic constitutive models and their efficient implementation using operator splitting methods to explore steady and transient flows in complex geometries, (2). Prediction of rheology of polymer solutions and melts based on micromechanical models as well as highly parallel self-consistent multiscale simulations of non-homogeneous flows. The main objective of this study is to leverage and build upon the aforementioned advances to develop a quantitative understanding of the flow-micro-structure coupling mechanisms in viscoelastic polymeric fluids and in turn predict, consistent with experiments, their essential macroscopic flow properties e.g. frictional drag, interface shape, etc. To this end, we have performed extensive continuum and multiscale flow simulations in several industrially relevant bulk and free surface flows. The primary motivation for the selection of the specific flow problems is based on their ability to represent different deformation types, and the ability to experimentally verify the simulation results as well as their scientific and industrial significance.

No description available.

Many microorganisms have the ability to propel themselves through their fluid environments by periodically actuating their body. The biological fluid environments surrounding these microswimmers are typically complex fluids containing many high-molecular weight protein molecules, which give the fluid non-Newtonian rheological properties. In this thesis, we investigate the effect that one such rheological property, viscoelasticity, has on microswimming. We consider a classical model of a microswimmer, the so-called Taylor's waving sheet and generalise it to arbitrary shapes. We employ the Oldroyd-B model to study its swimming analytically and numerically. We attempt to develop a mechanistic understanding of the swimmer's behaviour in viscoelastic fluids. It has recently been suggested that continuum models of complex biological fluids might not be appropriate for studying the swimming of flagellated microorganisms as the size of biological macromolecules is comparable to the typical width of a microorganism's flagellum. A part of this thesis is devoted to exploring this scenario. We propose an alternative method for modelling complex fluids using a two-fluid depletion region model and we have developed a numerical solver to find the swimming speed and rate of work for the generalised Taylor's waving sheet model swimmer using this alternate depletion region model. This thesis is organised as follows. In the first chapter, we outline a physical mechanism for the slowing down of Taylor's sheet in an Oldroyd-B fluid as the Deborah number increases. We demonstrate how a microswimmer can be designed to avoid this. In the second chapter, we investigate swimming in an Oldroyd-B fluid near a solid boundary and show that, at large amplitudes and low polymer concentrations, the swimming speed of Taylor's sheet increases with De. In the third chapter, we show how the Oldroyd-B model can be adapted using depletion regions. In the final chapter, we investigate optimal swimming in a Newtonian fluid. We show that while the organism's energetics are important, the kinematics of planar-wave microswimmers do not optimise the hydrodynamic 'efficiency' typically used for mathematical optimisation in the literature.

The rheological and structural properties of polymeric liquids cannot be condensed within a single numerical model. They should be described within hierarchical, multi-level numerical models in which each sub-model is responsible for different time and length scales; atomistic, mesoscopic, and continuum. In this study, the rheological and structural properties of linear, short-chain polyethylene liquids were investigated from the classical atomistic level to the mesoscopic and continuum levels of description. At the atomistic level of description, nonequilibrium molecular dynamics (NEMD) simulations of linear, short-chain polyethylene liquids spanning from C16H24 to C128H256 were performed to advance our knowledge of fundamental characteristic of chain molecules under shear and planar elongational flow. Furthermore, entanglement characteristics, such as the shortest primitive path length, and the network configurations, were investigated as functions of strain rate in both vastly different flow fields using the topological Z-code. At the mesoscopic level of description, Brownian dynamics (BD) simulations of a freely-jointed chain with equivalent contour length to C78H158 were carried out to compare single-chain dynamics in dense liquids (NEMD) and dilute solutions (BD) under shear flow. In addition, the macromolecular configurational diversity of individual chains in dense liquids and dilute solutions was explored using a brightness distribution method inspired by the rheo-optical investigation of DNA solutions. Based on these observations, a simple coarse-grained mesoscopic model for unentangled polymeric liquids and semi-dilute solutions was proposed and compared with NEMD simulation data and experiments of semi-dilute DNA solutions under shear flow in terms of the rheological and structural properties, such as viscosity, normal stress coefficients, conformation tensor, and so on. Moreover, this model was further coarse-grained to the continuum level through pre-averaging and compared with NEMD simulation data to examine the relationships between different levels of description on the rheological and structural properties of unentangled polymeric materials under shear flow.

The accurate prediction of a complex fluid's equilibrium microstructure and corresponding thermodynamic properties relies on the capability to describe both the molecular level architecture and specific governing physics. This thesis makes key contributions to furthering the application and understanding of molecular models for complex bulk and inhomogeneous fluids with a specific interest in mixtures involving trace components. Such developments have potential for wide-ranging application to fields from consumer goods and medicine to energy and targeted specialized material design. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's first order thermodynamic perturbation theory (TPT1) is used to demonstrate the robustness and performance of intrinsic molecular parameters determined for a complex fluid (water) with a new fitting strategy. Experimental solubility data at ambient conditions was used to find the PC-SAFT parameters for water which where capable of reproducing water content for binary mixtures with liquid and vapor n -alkanes under a myriad of physical conditions. The model gave excellent qualitative and very good quantitative agreement without the need of a binary interaction parameter. For inhomogeneous fluids, the application of a density functional theory (DFT) also based on TPT1, is extended to model the self-assembly of amphiphilic molecules at a liquid-liquid interface. This DFT, interfacial SAFT ( i SAFT), is validated against molecular simulation results for the microstructure and interfacial tension of a simple diatomic surfactant based on the continuum oil-water-surfactant model of Telo da Gama and Gubbins. A comprehensive systematic study is conducted for characterizing the affects of part of the vast parameter space governing the fluid microstructure and observed interfacial tension. The role of surfactant structure, oil structure, surfactant concentration, nonionic cosurfactant mixtures, and temperature play in altering molecular level phenomena such as surfactant aggregation, solvent depletion, and surfactant chain conformation as a result of the balance between enthalpic and entropic driving forces are described.

This thesis is mainly concerned with some important properties of complex fluids, and how these properties are influenced by structures in the nano/mesoscopic scale. Short-range assembly of the constituent molecules results in an amazing variety of phase behavior in these systems. Liquid-liquid phase transitions, or transitions from a homogeneous(mixed) phase to an immiscible phase (two-phase coexistence), are the outcome of a competition between entropy and short-ranged attractive forces, and form an important part of this thesis. A rich phase behavior is uncovered by a detailed study of liquid-liquid phase transitions in a mixture of ethanol(E) and water(W), induced by the addition of ammonium sulfate(AS) ions (E and W are otherwise completely soluble in each other). This is the main motivation for choosing this system. Furthermore, experimental evidence of the presence of supramolecular association in alcohol-water mixtures [J.-H. Guo et al., Phys. Rev Lett, 91, 15401(2003)] enhances our interest to study the phase behavior in more detail. The presence of a critical point, at which there is a second order phase transition, is quite common in complex fluids. An issue which has been the subject of extensive scientific research in recent years is the influence of nano/mesoscopic structure on the critical behavior of these fluids corresponds to the Ising universality class. However, the approach to the asymptotic regime is governed by a competition between the correlation length of critical concentration fluctuations and the additional length scale arising due to structuring., which results in a crossover from the universal Ising behavior to the mean-field behavior, sometimes within the critical domain. This phenomenon of crossover criticality is presently explored in the E + W + AS system. A significant portion of the thesis presents explorations on the critical behavior in the vicinity of special critical points (SCP), which are formed by the coalescence of two or more critical points. Recentrant liquid-liquid phase transitions observed in the E + W + AS system, furnishes an unique opportunity for the realization of three SCPs – the double critical point(DCP) and the critical double point(CDP) formed by the merger of two critical points , and a critical inflection point(CIP), formed by the merger of three critical points. A CIP had not been experimentally realized prior to the studies presented in this thesis. Apart from the above studies investigations are also carried out on the conformational changes of a technologically important conducting polymer, polyethylene dioxythiophene doped with polystyrene suflonate (PEDOT-PSS), in various solvents. The electrical and optical properties of the polymer films get enhanced when solution processed with specific solvents. The experiments presented in this thesis are directed at unraveling the role of conformational modifications in the electrical and optical properties of these systems. The experimental techniques that were employed in the present studies are: Laser light scattering, small-angle X-ray scattering(SAXS) measurements and visual observations. The eoexistence surface of the system E + W + AS was determined by visual observations. Laser light scattering measurements were conducted to study the critical behavior of osmotic susceptibility (xr) of E + W + As, whereas SAXS studies were conducted to ascertain the existence, and quantify the spatial extent of the additional length scale in the two systems investigated. The main objectives of this research were: (i) to study the phase behavior of the ternary mixture E + W + AS at atmospheric pressure; (ii) to check the existence of crossover from 3-D Ising to mean-field critical behavior while moving away from Tc in this system; (iii) to determine the nature (monotonic or nonmonotonic) of crossover; (iv) to provide some insight into the origin of this crossover behavior in terms of an additional length scale characteristic of the system; (v) to understand the evolution of the critical behavior in the proximity of CDP, and DCP; (vi) to experimentally realize the CIP; and (vii) to investigate the presence of solvent-induced conformational changes in conducting polymer.

Thesis (Ph. D.)--Ohio State University, 2003. / Title from first page of PDF file. Document formatted into pages; contains xiv, 212 p.; also includes graphics. Includes bibliographical references (p. 195-202).

A new microrheology set-up is described, which allows us to quantitatively measure the transient rheological properties and microstructure of a variety of solvent-responsive complex fluids. The device was constructed by integrating particle tracking microrheology and microfluidics and offers unique experimental capabilities for performing solvent-response measurements on soft fragile materials without applying external shear forces. Transient analysis methods to quantitatively obtain rheological properties were also constructed, and guidelines for the trade-off between statistical validity and temporal resolution were developed to accurately capture physical transitions. With the new device and methodology, we successfully quantified the transient rheological and microstructural responses during gel formation and break-up, and viscosity changes of solvent-responsive complex fluids. The analysis method was expanded for heterogeneous samples, incorporating methods to quantify the microrheology of samples with broad distributions of individual particle dynamics. Transient microrheology measurements of fragile, heterogeneous, self-assembled block copolypeptide hydrogels revealed that solvent exchange via convective mixing and dialysis can lead to significantly different gel properties and that commonly applied sample preparation protocols for the characterization of soft biomaterials could lead to erroneous conclusions about microstructural dynamics. Systematic investigations by varying key parameters, like molecular structure, gel concentration, salt concentration, and tracer particle size for microrheology, revealed that subtle variations in molecular architecture can cause major structural and microrheological changes in response dynamics. Moreover, the results showed that the method can be applied for studying gel formation and breakup kinetics. The research in this thesis facilitates the design of solvent-responsive soft materials with appropriate microstructural dynamics for in vivo applications like tissue engineering and drug delivery, and can also be applied to study the effect of solvents on self-assembly mechanisms in other responsive soft materials, such as polymer solutions and colloidal dispersions.