Graduate Theses & Dissertations

UV-Curable hybrid sol-gel materials
This thesis describes the synthesis, application and evaluation of a UV crosslinked 3-methacryloxypropyltrimethoxysilane-derived coating formulation. This is a two-component sol-gel system with 3-methacryloxypropyltrimethoxysilane (MaPTMS) and tetraethoxysilane (TEOS). Herein we show that if we change the co-solvent required for solubilizing MaPTMS from the more common methanol and ethanol to isopropanol we change the rate of hydrolysis from days or weeks to minutes. With the assistance of 2D 29Si-NMR we demonstrate that the system undergoes extensive condensation in twenty minutes. Using standard UV irradiation, the material can be extensively UV crosslinked with 70% of the methacryloxy functionality being consumed in 5 minutes upon irradiation in the presence of a photo-initiator. When this material is used to coat low carbon steel and immersed in an accelerated corrosion solution (dilute Harrison’s solution); this material affords low carbon steel 25 hours of protection when crosslinked and 17 hours of protection when uncrosslinked. The material was then used to encapsulate polyaniline (PANI), an intrinsic conductive polymer used in the corrosion protection of metal substrates. PANI has been encapsulated previously in sol-gel material, but due to the pH dependence of the solubility of PANI, it can not be encapsulated in more commonly chemically crosslinked sol-gel. As our system is UV crosslinked rather than chemically crosslinked, we were able to successfully demonstrate the inclusion of PANI into our coating system. Finally, this thesis includes a thorough computational investigation into the structure and band gap of PANI. Through the analysis of the band gap it was shown that the structure of the polymer commonly displayed in literature is not the correct structure of the polymer. Our results suggest that when PANI is made electrochemically, the oligomer contains two quinoid units next to one another instead of the more usually represented regularly alternating benzoid and quinoid units. The results also suggest that when PANI is made using the oxidant ammonium persulfate, the polymer most likely contains a Michael adduct structure somewhere in the polymer chain which dominates PANI’s electronic properties. Author Keywords: 3-Methacryloxypropyltrimethoxysilane, Computational Chemistry , Corrosion , Polyaniline, Tetraethoxysilane

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