Thesis (Ph. D.)--University of Missouri-Columbia, 1998. / Typescript. Vita. Includes bibliographical references (leaves 179-185). Also available on the Internet.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 91-93).

Thesis (Ph.D.) - University of Queensland, 2006. / Includes bibliography.

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The motivation for the determination of the viscosity of polymer solutions in dense fluids at the critical polymer concentration stems from the need to understand the factors that influence the time scale of phase separation in systems that undergo spinodal decomposition upon a pressure quench. In a recent investigation of PDMS + CO₂ and PE + n-pentane where molecular weights of the polymers and the critical polymer concentrations were comparable, significant differences were observed in the time evolution of new phase growth. Among the reasons that contribute to the difference in phase separation kinetics is the viscosity of the solutions. This thesis has been carried out to experimentally demonstrate the differences in viscosities of solutions at their critical polymer concentration. Specifically, the thesis focused on the high-pressure density and viscosity of solutions of poly(dimethylsiloxane) (Mw = 93,700, Mw/Mn = 2.99) in supercritical carbon dioxide and of polyethylene (Mw = 121,000, Mw/Mn = 4.3) in near-critical n-pentane. The measurements have been carried out at the critical polymer concentrations, which is 5.5 wt % for solution of PDMS in CO2 and 5.75 wt % for solution of PE in n-pentane. For PDMS + CO₂ system, the measurements were conducted at 55, 70, 85 and 100 oC and pressures up to 50 MPa. For PE + n-pentane system, the measurements were conducted at 140 and 150 °C and again up to 50 MPa. All measurements were conducted in the one-phase homogenous regions. At these temperatures and pressures, the viscosities were observed to be in the range from 0.14 mPa.s to 0.22 mPa.s for PDMS + CO₂, and from 2.3 mPa.s to 4.6 mPa.s for PE + n-pentane systems. In both systems the viscosities increase with pressure and decrease with temperature. The temperature and pressure dependence could be described by Arrhenius type relationships in terms of flow activation energy (E#) and flow activation volume (V#) parameters. The flow activation energies in PDMS + CO₂ system were about 7 kJ/mol compared to about 18 kJ/mol for the PE + n-pentane system. The activation volumes were in the range 40-64 cm3/mol for PDMS + CO₂ system and 65-75 cm3/mol for the PE + n-pentane solution. The higher values of E# and V# represent the higher sensitivity of viscosity to temperature and pressure changes in the PE + n-pentane system. The viscosity data could also be correlated in terms of density using free-volume based Doolittle type equations. Density is shown to be an effective scaling parameter to describe T/P dependency of viscosity. The closed packed volumes suggested from density correlations were found to be around 0.33 cm³/g for the PDMS and 0.48 cm3/g for the PE systems. Comparison of the viscosity data in these systems with the data on the kinetics of pressure-induced phase separation confirms that the slower kinetics in the PE + n-pentane stems from the higher viscosity in this solution compared to the PDMS + CO₂ system, despite the similarity in the molecular weight of the polymer and the critical polymer concentrations. These viscosity and density measurements were conducted in a special falling-body type viscometer. In the course of this thesis a more reliable procedure for determining the terminal velocity of the falling sinker was implemented. This is based on the precise and more complete description of the position of the sinker with time with the aid of a set of linear variable differential transformers (LVDTs). The design of the new arrangement and procedure for terminal velocity determination and calibration procedures for the viscometer are also presented. The densities and viscosities are determined with an accuracy of ± 1 % and ± 5 % or better, respectively. / Master of Science

Chain conformations and the presence of chain overlaps and entanglements in dilute polymer solutions have been analyzed. The fundamental problem of existence of chain overlaps in dilute solutions is related to the drag reduction phenomenon (DR). Even though DR occurs in solutions with the concentration of only few parts per million (ppm), some theories suggest that entanglements may play an important role in DR mechanism. Brownian dynamics technique have been used to perform simulations of dilute polymer solutions at rest and under shear flow. A measure of interchain contacts and two different measures of entanglements have been devised to evaluate the structure of polymer chains in solution. Simulation results have shown that overlaps and entanglements do exist in static dilute solutions as well as in solutions under shear flow. The effect of solution concentration, shear rate and molecular mass have been examined. In agreement with the solvation theory of DR mechanism, simulation results have demonstrated the importance of polymer + polymer interactions in dilute solutions.

Thesis (MSc)--University of Stellenbosch, 2006. / ENGLISH ABSTRACT: static density and magnetic structure functions of a melt of flexible polymers whose monomers possess bond-directed dipoles which interact with each other. In order to observe the effect of screening of the dipolar interaction on the structure functions we obtain results for cases with and without steric interactions and also for cases with and without Debye-H¨uckel screening of the dipole moments. / AFRIKAANSE OPSOMMING: Approximation” RPA) om die statiese digtheids- en magnetiese struktuurfunksies te bereken vir ’n smelt van hoogsbuigsame polimere, waarvan die monomere dipole langs die verbindings besit wat met mekaar in wisselwerking tree. Om die effek van afskerming op die dipolare wisselwerking en die struktuurfunksies te kan waarneem, bepaal ons resultate vir die gevalle met en sonder steriese wisselwerkings en ook vir gevalle met en sonder die Debye-H¨uckel afskerming van die dipoolmomente.

In this thesis, we focus on the problem of interactions between solids and fluids. / The main part is the study of the motion of a rigid body immersed in an incompressible fluid. First, for the case of 2D ideal flow, a global weak solution is derived. Second, for the case of viscous flow in 3D, the problem is investigated in the Lp--framework. We get a decomposition of Lp-space associated with the problem. Then We prove that the corresponding semigroup is analytic in L65 R3∩L pR3 (p ≥ 2). Our result yields a local in time existence and uniqueness of strong solutions taking initial data in L65 R3∩L pR3 (p ≥ 3). / The other part is some research about micro-macro models of polymeric fluids. We provide a new proof for the global well-posedness of the coupling systems in 2D. / Wang, Yun. / Adviser: Zhouping Xin. / Source: Dissertation Abstracts International, Volume: 72-04, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 112-119). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

The research discussed in this dissertation was conducted to understand drop formation of inkjet printing with inks containing polymer. Solutions containing a water soluble polymer, poly ethylene oxide (PEO), with different molecular weights and polydispersities were used as inks. A flash photographic technique was used to visualize the whole process of DOD drop formation of dilute polymer solutions. The effects of driving signal, frequency and liquid properties on drop speed, drop size, breakup time and the formation of satellites were studied in detail. The addition of PEO increases the shear viscosity at all molecular weights, but the change is small for dilute solutions. However, the addition of a small amount of PEO can have a significant effect on the DOD drop formation process, increasing breakup time, decreasing primary drop speed and decreasing the number of satellites in some cases. The effects depend on both molecular weight and concentration. At lower molecular weights (14k and 35k g/mol), the effect of PEO was small when the drop formation process for the dilute solution was compared with that of a Newtonian liquid having similar shear viscosity, and the effect of PEO was small even at concentrations large enough that the solution does not fall in the dilute regime. As molecular weight is increased, the effects of PEO on DOD drop formation increase significantly, and the effects of concentration become important. These effects are explained by the fluid elasticity which increases with increasing in molecular weight and concentration. When the liquid jets out of the nozzle, the polymer chains are stretched, and thus depart from their ideal coiled state. As a result, an elastic stress develops in the liquid column and resists capillarity-driven pinch off from the nozzle and is responsible for the decrease in drop speed and longer breakup time. DOD drop formation data were shown to correlate closely with effective relaxation time, proposed by Tirtaatmadja based on Rouse-Zimm theory. When driving voltage amplitude is 44.2 V, two important parameters (breakup time and primary drop speed) in DOD drop formation for solutions containing monodispersed PEO and aqueous solutions containing mixtures of monodispersed PEO were closely predicted by correlation equations involving effective relaxation time . A mixture rule was developed to calculate the relaxation time for mixtures of monodispersed PEO. However, for polydispersed PEO, effective relaxation time was based on viscous molecular weight since the molecular weight distributions of the polydispersed PEO were unknown. When breakup time was plotted versus effective relaxation time for 1000k g/mol PEO, the data did not lie on the same line as that for the 100k and 300k g/mol PEO. This is believed to be due to the molecular weight distributions of the polydispersed PEO. When more than one species are present, viscous average molecular weight does not adequately account for the long chain species making up the polymer sample. DOD drop formation dynamics is highly affected by the actuating waveform, including the driving voltage, waveform shape, and frequency. The effects of parameters (jetting frequency, voltage amplitude and the shape of waveform) characterizing the signal were investigated. The open time and first drop problem were also studied. Research in this dissertation gives a better understanding of DOD drop formation process of polymer solutions, which may lead to improvement of inkjet printing quality for a variety of industry inks and polymer micro scale deposition and patterning in large areas.

The spinning process of hollow fiber membranes was investigated with regards to two fundamental phenomena: flow (shear and elongation) and phase separation. Quantitative analysis of phase separation kinetics of binary (polymer/solvent) and ternary (polymer/solvent/volatile co-solvent) polymer solution was carried out with a newly developed microfluidic device. The device enables visualization of in situ phase separation and structure formation in controlled vapor and liquid environments. Results from these studies indicated that there was a weak correlation between phase separation kinetics and macroscopic defect (macrovoid) formation. In addition, the effect of shear and elongation on membrane morphology was tested by performing fiber extrusion through microfluidic channels. It was found that the membrane morphology is dominated by different factors depending on the rate of deformation. At high shear rates typical of spinning processes, shear was found to induce macrovoid formation through normal stresses, while elongation suppressed macroscopic defect formation. Furthermore, draw resonance, one of the key instabilities that can occur during fiber spinning, was investigated. It was found that draw resonance occurs at aggressive elongation condition, and could be suppressed by enhanced phase separation kinetics. These results can be used as guidelines for predicting hollow fiber membrane spinnability.