The relationships between molecular parameters and microdomain formation of a variety of block- and graft-copolymers were studied by Transmission Electron Microscopy (TEM). Molecular variables included chemical composition: dimethyl-, fluoropropyl and diphenyl-siloxane , sulfone styrene, paramethylstyrene, t-butylstyrene, arylester and methyl methacrylate, as well as molecular weight and distribution. Effects of the kinetics of phase-separation were also determined . Thick (approximately lmm) films cast from solvent showed more complete phase separation than either thin (about 10nm) cast films or compression-molded specimens.
Spherical domains formed in alternating poly(ester/siloxanes), and phase mixing seemed to correlate with the solubility parameters of the three siloxane types. Shear-stresses during molding changed domain shapes and eliminated short-range ordering. In the PMMA-graft-dimethyl siloxane system, SK, 10K and 20K <M<sub>n</sub>> siloxanes were incorporated at 16% and 45% by weight. At 16%, spherical siloxane domains formed in both thick- and thin-cast films. The domain sizes and interdomain distances scaled with siloxane molecular weight and total block molecular weight respectively to a 2/3 power law in excellent agreement with theoretical predictions for di- and triblock copolymers. Thin films cast from the 45% siloxane graft copolymers also showed spherical domains with sizes dependent on molecular weight. However, the thick films showed phase transitions from disordered bicontinuous (M<sub>n</sub> = 5K) to lamellar (M<sub>n</sub> = 10K) to cylindrical <M<sub>n</sub> = 20K). Qualitative TEM/EDX analysis of other systems was used to identify oligomers, homopolymers, and contaminants, thus monitoring the effects of novel reaction conditions and work-up procedures. / Master of Science
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/80085 |
| Date | January 1987 |
| Creators | York, Greg Allen |
| Contributors | Materials Engineering |
| Publisher | Virginia Polytechnic Institute and State University |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | en_US |
| Detected Language | English |
| Type | Thesis, Text |
| Format | xii, 181 leaves, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 16813119 |
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