The modification of materials and surfaces with fluorocarbons enables ultralow surface energies in the development of numerous applications of cutting-edge science and technology. The use of partially fluorinated materials offers advantages in terms of cost and synthetic flexibility, and in some cases, performance, when compared to allfluorocarbon materials. This research employs a surface-initiated polymerization (SIP), namely surface-initiated ring-opening metathesis polymerization (SI-ROMP), to grow partially fluorinated coatings with critical surface tensions as low as 9 mN/m that establish new standards in thickness with tremendous control over microscale surface texturing. SIP techniques provide robust chemisorption, diverse chemical functionality, control over film growth, and the ability to uniformly coat planar and non-planar surfaces. Although SIP methods have been previously used to deposit partially fluorinated films, the ability to grow such films with thicknesses above a few micrometers, with controlled textures, or within nanoporous materials has not been demonstrated prior to this work. Accordingly, this dissertation focuses on: (1) the fabrication and characterization of novel partially fluorinated/inorganic composites by employing SI-ROMP within nanoporous architectures to create membranes with tunable wettability and ion transport; (2) the amplification of the SIP of partially fluorinated polymer films to fabricate specialty coatings that yield thicknesses from 4 12 µm in as little as 15 min of polymerization. Remarkably, these films exhibit resistance against ion transport in excess of 10 GΩcm^2, which is the highest value ever reported for SIP films; and the development of a new SIP-based approach to (3) fabricate microscale surface features with height modulation and to (4) reproduce the complex surface topographies of superhydrophobic natural surfaces onto solid supports. This process enables the preparation of microtextured films and novel biomimetic coatings that reproduce superhydrophobic plant leaves, and could radically impact applications such as self-cleaning surfaces and chemical- and corrosion-resistant coatings.
| Identifer | oai:union.ndltd.org:VANDERBILT/oai:VANDERBILTETD:etd-01212014-134351 |
| Date | 23 January 2014 |
| Creators | Escobar, Carlos Andres |
| Contributors | Scott A. Guelcher, G. Kane Jennings, Paul E. Laibinis, Eva M. Harth |
| Publisher | VANDERBILT |
| Source Sets | Vanderbilt University Theses |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.library.vanderbilt.edu/available/etd-01212014-134351/ |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Vanderbilt University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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