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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

Scalable techniques for the formation of polymer-nanoplatelet hybrid membranes and characterization thereof

Johnson, Justin Ryan 04 November 2010 (has links)
Polymer-nanoplatelet hybrid membranes show promise as the next generation of membranes, but in order to make these realizable, methods to produce these materials on a large scale are necessary. Some authors have successfully produced these types of gas separation membranes. Typically these reports have utilized melt blending and in situ polymerization. Few, however, have utilized solution blending for creating membranes via phase inversion (asymmetric membranes). And to date, there have not been any reports regarding the fabrication of asymmetric membranes containing nanoplatelet filler materials. In this work we have developed a solution-based procedure for the formation of hybrid polymer-nanoplatelet dopes for dense film and asymmetric hollow fiber membrane formation. Dense film membrane studies were used to prove the effectiveness of our exfoliation and dispersion process developed for this work. Permeation measurements showed the hybrid membranes have desirable transport properties that are on par with mathematical model predictions. Additionally, TEM characterization provided strong evidence supporting the efficacy of our preparation procedures to produce an exfoliated system of nanoplatelets. We also showed that these procedures are applicable to different polymer systems (cellulose acetate and Torlon) of commercial relevance. Demonstrating the successful production of dense films set the stage for asymmetric hollow fiber membrane formation. We report the first production of asymmetric hollow fiber membranes containing nanoplatelet fillers; indicating that the process can be applied in a realistic membrane formation platform. These accomplishments serve as the groundwork for future nanocomposite formation.
2

Proton NMR relaxation investigations of particle exfoliation and distribution in polymer/clay nanocomposites

Xu, Bo 17 November 2010 (has links)
In the past two decades polymer/clay nanocomposites (PCNs) have emerged as promising materials that exhibit remarkably improved properties when compared to conventional composites and pristine polymers. Such improvements strongly depend on the dispersion of clay nanoparticles in the polymer matrix. In spite of great efforts expended in characterizing clay dispersion, effective, simple and quantitative techniques are still needed. This work addresses this challenge by presenting new aspects of 1H solid-state NMR for quantifying clay dispersion in PCNs filled with clay containing paramagnetic ions. Employing these 1H solid-state NMR methods, some structure-processing-deformation relationships of PCNs were derived, and basic insights into nuclear relaxation and spin diffusion in PCNs were gained as well. Detailed models and analyses were described for 1H spin-lattice relaxation in the presence of paramagnetic clays in PCNs. Relaxation recovery was analytically correlated to clay dispersion in two ways: one is the initial relaxation recovery which is related to clay surface area, and the other is the spin-lattice relaxation time which is related to interparticle spacing. These two NMR observables were employed to quantitatively observe the evolution of clay morphology in poly(propylene)/clay (PP/MMT) nanocomposites upon equibiaxial stretching, as well as upon in situ uniaxial deformation. The initial relaxation recovery was independently utilized to determine the polymer-clay interfacial surface area and the degree of clay exfoliation. We demonstrated the capabilities of our models in quantitatively characterizing several materials, including poly(vinyl alcohol), nylon 6, poly(å-caprolactone) (PCL), poly(lactic acid) (PLA) and PP nanocomposites. These results were used to examine the dependence of clay morphology upon processing (strain ratio, strain rate, temperature), deformation (extension), component characteristics (polymer molecular weight, clay surface modification) and clay content. Effects of paramagnetic Fe3+ concentration and external magnetic field strength on 1H spin-lattice relaxation in PCNs were also investigated and discussed. In particular, low field separates the initial relaxation recovery into two stages: one related to clay content and the other related to the polymer-clay interfacial surface area. The low field was observed to enhance the paramagnetic contribution to the spin-lattice relaxation rate, increasing its sensitivity to clay morphology. In addition, measurements of long-distance spin diffusion coefficients for a variety of polymers and paramagnetic characteristics of organically modified clay were explored. Overall, the utility of NMR relaxometry in characterizing PCNs has been significantly expanded and successfully demonstrated in this dissertation.

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