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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Rheo-NMR and synchrotron X-ray diffraction characterization of nanostructures of triglycerides crystallizing from solutions

20 April 2011 (has links)
The characteristics of crystallized fats depend on their solid fraction (SF) and fractal structures, which are affected by shear during crystallization. Binary mixtures of trilaurin (LLL) and trimyristin (MMM) diluted in triolein were used as samples. Pure diluted LLL and MMM were also studied. Samples were examined at different crystallization temperatures either statically or at shear rates of 800, 80, and 8 1/s. The sample cell combined a rheometer with a nuclear magnetic resonance (NMR) device to measure SF value and apparent viscosity. The measurements were compared to equations that describe the dependency of viscosity on solid volume fraction, to understand the effect of crystallites orientation at higher shear rates. Phase transitions during crystallization were observed by time-resolved synchrotron X-ray diffraction under similar conditions. Shear induced a strong reduction in phase onset and transition time and variations in phase distributions and the crystal size.
2

Nuclear magnetic resonance and rheo-NMR investigations of wormlike micelles, rheology modifiers, and ion-conducting polymers

Wilmsmeyer, Kyle Gregory 26 October 2012 (has links)
Investigation and characterization of polymeric materials are necessary to obtain in-depth understanding of their behavior and properties, which can fuel further development. To illuminate these molecular properties and their coupling to macroscopic behavior, we have performed nuclear magnetic resonance (NMR) studies on a variety of chemical systems. In addition to versatile "traditional" NMR measurements, we took advantage of specialized techniques, such as "rheo-NMR," 2H NMR, and NMR self-diffusion experiments to analyze alignment, orientational order, elaborate rheological behavior, and ion transport in polymer films and complex fluids. We employed self-diffusion and quadrupolar deuterium NMR methods to water-swollen channels in Nafion ionomer films commonly used in fuel cells and actuators. We also correlated water uptake and anisotropic diffusion with differing degrees and types of alignment in Nafion films based on membrane processing methods. Further, we made quantitative measurements of bulk channel alignment in Nafion membranes and determined anisotropic properties such as the biaxiality parameter using these methods. Additionally, our studies made the first direct comparison of directional transport (diffusion) with quantitative orientational order measurements for ionomer membranes. These results lend insight to the importance of water content in ionomer device performance, and showed that increased control over the direction and extent of orientational order of the hydrophilic channels could lead to improved materials design. We used the same techniques, with the addition of "rheo-NMR" and solution rheology measurements, to study the complex rheological behavior of cetyltrimethylammonium bromide wormlike micelle solutions, which behave as nematic liquid crystals at sufficiently high concentration. Amphiphilic solutions of this type are used in myriad applications, from fracturing fluids in oil fields to personal care products. We investigated the phase behavior and dynamics of shear and magnetic field alignment, and made the first observations of a novel bistable shear-activated phase in these solutions. Our first reports of the complex Leslie-Ericksen viscoelastic parameters in wormlike micelles and measurements of diffusion anisotropy show the potential for increased control and understanding of materials used in tissue engineering, oil extraction, personal care products, and advanced lubricants. / Ph. D.
3

Rheo-NMR studies of viscoelastic secondary flows in ducts of non-circular cross-section

Schroeder, Christian Berthold Karl 07 May 2012 (has links)
The existence of hydrodynamically developed, laminar Viscoelastic Secondary Flows (VSFs) of non-Newtonian fluids in straight ducts of non-circular cross-section was proposed in the 1950's. VSFs have since been observed sporadically, and only once with a velocimetric technique. Using axial and transverse full flow-field velocity-position raster maps made with Rheological Nuclear Magnetic Resonance (Rheo-NMR), Newtonian and non-Newtonian fluid flows were quantified in Hagen-Poiseuille and Power Law contexts, over more than two orders of magnitude of flow rate, in ducts of circle, square, triangle, and pentagon cross-section. VSF was reliably and repeatedly observed to occur at between one part in 130 and one part in 600 of the primary axial flow velocity. Velocity measurements ranged from <10 µm/s to approximately 30 cm/s, suggesting a velocity dynamic range >3E4 without optimization. To obtain VSF flow direction information, a novel flow directional phantom was developed and characterized. Aqueous solutions of Polyethylene Oxide (PEO), Viscarin GP-109NF, Viscarin GP-209NF (V209), Hyaluronan (HA) in a Phosphate-Buffered Saline-like solvent, and an aqueous Polyethylene Glycol/PEO-based Boger fluid were investigated. Axial data was corroborated with related data gathered by an independent method. Basic simulations corroborated the VSF observations. Duct hydraulic diameters (>= 1.6 mm) approached the micro-channel regime. VSF detections in HA --- synovial fluid's principal component --- and V209 were novel, as were observations of some artifacts which were subsequently characterized and corrected. The detection of VSF in HA represents the first experimental evidence suggesting that its second normal stress (N_2) is comparable to that of better-characterized fluids. In the first application of a new VSF-based method, a particular Boger fluid's constant viscosity and, in the square duct, its lack of VSF were used with established criteria to suggest that the fluid's N_2 approached zero. The development of a rudimentary, but versatile and inexpensive home-built velocimetric spectrometer is detailed, as are several new components. An exhaustive VSF literature review is included. The remarkable transverse velocimetric ability of Rheo-NMR in both optically opaque and transparent system is highlighted, suggesting that perhaps the technique might represent, in both micro-channels and conventional ducts, the gold-standard in flow velocimetry.

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