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 Title: Morphology and crystal structure of random, main chain, semi-flexible, thermotropic liquid crystal polymers Author(s): Kent, Susan Louise Doctoral Committee Chair(s): Geil, Phillip H. Department / Program: Materials Science and Engineering Discipline: Materials Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Polymer Engineering, Materials Science Plastics Technology Abstract: The crystal structure and morphology of random, main chain, thermotropic liquid crystal polymers (LCP's) of equimolar amounts of the following structural units (with n equal to 4, 5, 6 and 7 in "A") have been examined by electron microscopy and diffraction:(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)When crystallized from the liquid crystal state in the form of thin films, the polymer forms a 50-70A lamellar texture. Electron diffraction reveals an orthorhombic unit cell (a = 8.34A and b = 5.10A). Similar results were obtained with the 4, 6 and 7 carbon spacer LCP's. The observations can only be interpreted in terms of chain folding, the flexibility of the "spacer" along the polymers backbone permitting folding to occur. High temperature electron diffraction shows little change in positional ordering above the crystal-liquid crystal transition temperature. Rapid quenching from the liquid crystal state produces a ribbon-like morphology with the molecules oriented perpendicular to the long direction of the ribbons.Shearing the 7 carbon spacer LCP in the liquid crystal state results in $\sim$150A lamellar crystals normal to the shear direction. The lamellae readily shear over one another, suggesting the presence of adjacent reentry chain folding.Single crystals of the 7 carbon flexible spacer LCP have been grown from dilute solution. This is the first report of solution grown single crystals of a liquid crystalline polymer. The crystals thicken (from $\sim$100A to 190A) upon annealing below their crystal-liquid crystal melting temperature. Annealing in the liquid crystalline state produces unusual and unique morphologies.Extruded pellets of the 7 carbon flexible spacer LCP resemble a composite material with 0.2 $-$ 1.8$\mu$m "fibers" oriented parallel to the extrusion direction. Etching revealed a lamellar morphology with the lamellae (50-1,800A) oriented perpendicular to the fiber extrusion direction. Thinner lamellae (50-130A) were observed on the surface of compression-molded articles with thicker, presumably extended chain lamellae, observed in the interior. Selected area electron diffraction confirms that the molecular axes are perpendicular to the lamellae.The results suggest significant degrees of chain folding in the liquid crystal state since it is unexpected that previously extended, nematically packed chains would fold during the liquid crystal-crystal transition. Issue Date: 1992 Type: Text Language: English URI: http://hdl.handle.net/2142/21202 Rights Information: Copyright 1992 Kent, Susan Louise Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9215837 OCLC Identifier: (UMI)AAI9215837
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