The influence of surface curvature on polymer behavior at inorganic surfaces
Nunnery, Grady A.
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Nanoscale surfaces were examined in order to determine the influence of surface curvature on polymer behavior at polymer-ceramic interfaces, as well as the influence of nanoparticles in cellulosic media. Poly(methyl methacrylate) and block copolymers thereof were adsorbed onto porous alumina substrates of various pore sizes in order to determine how polymer and copolymer adsorption behavior at nanoscale surfaces differs from adsorption onto flat surfaces. It was determined that chain density on concave surfaces dramatically decreases as curvature increases in much the same way that it does on convex surfaces (e.g. on the surface of nanoparticles), and physical models are provided to explain this similarity. Diblock copolymer adsorption is observed to vary dramatically with solvent quality and block asymmetry and can be correlated with the surface curvature very similarly to the adsorptive behavior of homopolymers on those same surfaces. The addition of nanoparticles to cellulosic media was investigated as a means to significantly modify the properties of cellulosic composites with minimal additions of nanoparticles. Although cellulose is among the most abundant polymers on earth, its primary uses are limited to bulk commodity goods, such as paper and textiles. This work demonstrates a simple means to control cellulosic fluid viscosity, thereby increasing the versatility of these biopolymers in additional applications with higher value-added potential. The formation of iron-cellulosic nanocomposites by the in-situ thermolysis of metal carbonyls to form metallic nanoparticles was performed and was analyzed by viscometry among other techniques. It was determined that the nanocomposites that were formed exhibited significantly increased viscosity, up to the point of gelation. Additionally, an introduction to the expansive field of nanocomposites is provided, including how and why composite properties change abruptly as filler size approaches the nanoscale. An extensive background on this diverse field as it relates to the current work is provided with an emphasis on cellulosic nanocomposites and the dependence of curvature on polymer-surface interactions. A detailed account of the experimental work relevant to this work is provided, including materials and characterization methods. Future work is proposed for both cellulosic nanocomposites as well as for curvature-dependent polymer adsorption. Finally, conclusions are drawn from the entire work and its implications to the greater field of nanocomposites.