This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane- materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si-1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation.

<p>This thesis deals with the engineering of novel nanomaterials, particularly nanocomposites and nanostructured surfaces with enhanced functionalities. The study includes two parts; in the first part, an in situ sol-gel polymerization approach is used for the synthesis of polymer-inorganic hybrid material and its exceptional transparent UV-shielding effect has been investigated. In the second part, electrodeposition process has been adapted to engineer surfaces and the boiling performance of the fabricated nanostructured surfaces is evaluated.</p><p>In the first part of the work, polymer-inorganic hybrid materials composed of poly(methylmethacrylate) (PMMA) and zinc compounds were prepared by in situ sol-gel transition polymerization of zinc complex in PMMA matrix. The immiscibility of heterophase of solid organic and inorganic constituents was significantly resolved by an in situ sol-gel transition polymerization of ZnO nanofillers within PMMA in the presence of dual functional agent, monoethanolamine, which provided strong secondary interfacial interactions for both complexing and crosslinking of constituents.</p><p>In the second part of the work, nanoengineering on the surface of copper plates has been performed in order to enhance the boiling heat transfer coefficient. Micro-porous surfaces with dendritic network of copper nanoparticles have been obtained by electrodeposition with dynamic templates. To further alter the grain size of the dendritic branches, the nanostructured surfaces underwent a high temperature annealing treatment.</p><p>Comprehensive characterization methods of the polymer-inorganic hybrid materials and nanoengineered surfaces have been undertaken. XRD, 1H NMR, FT-IR, TGA, DSC, UV-Vis, ED, SEM, TEM and HRTEM have been used for basic physical properties. Pool boiling tests were performed to evaluate the boiling performance of the electrodeposited nanostructured micro-porous structures.</p><p>The homogeneous PZHM exhibited enhanced UV-shielding effects in the entire UV range even at very low ZnO content of 0.02 wt%. Moreover, the relationship between band gap and particle size of incorporated ZnO by sol-gel process was in good agreement with the results calculated from the effective mass model between bandgap and particle size. The fabricated enhanced surface has shown an excellent performance in nucleate boiling. At heat flux of 1 W/cm2, the heat transfer coefficient is enhanced over 15 times compared to a plain reference surface. A model has been presented to explain the enhancement based on the structure characteristics.</p>

This thesis deals with the engineering of novel nanomaterials, particularly nanocomposites and nanostructured surfaces with enhanced functionalities. The study includes two parts; in the first part, an in situ sol-gel polymerization approach is used for the synthesis of polymer-inorganic hybrid material and its exceptional transparent UV-shielding effect has been investigated. In the second part, electrodeposition process has been adapted to engineer surfaces and the boiling performance of the fabricated nanostructured surfaces is evaluated. In the first part of the work, polymer-inorganic hybrid materials composed of poly(methylmethacrylate) (PMMA) and zinc compounds were prepared by in situ sol-gel transition polymerization of zinc complex in PMMA matrix. The immiscibility of heterophase of solid organic and inorganic constituents was significantly resolved by an in situ sol-gel transition polymerization of ZnO nanofillers within PMMA in the presence of dual functional agent, monoethanolamine, which provided strong secondary interfacial interactions for both complexing and crosslinking of constituents. In the second part of the work, nanoengineering on the surface of copper plates has been performed in order to enhance the boiling heat transfer coefficient. Micro-porous surfaces with dendritic network of copper nanoparticles have been obtained by electrodeposition with dynamic templates. To further alter the grain size of the dendritic branches, the nanostructured surfaces underwent a high temperature annealing treatment. Comprehensive characterization methods of the polymer-inorganic hybrid materials and nanoengineered surfaces have been undertaken. XRD, 1H NMR, FT-IR, TGA, DSC, UV-Vis, ED, SEM, TEM and HRTEM have been used for basic physical properties. Pool boiling tests were performed to evaluate the boiling performance of the electrodeposited nanostructured micro-porous structures. The homogeneous PZHM exhibited enhanced UV-shielding effects in the entire UV range even at very low ZnO content of 0.02 wt%. Moreover, the relationship between band gap and particle size of incorporated ZnO by sol-gel process was in good agreement with the results calculated from the effective mass model between bandgap and particle size. The fabricated enhanced surface has shown an excellent performance in nucleate boiling. At heat flux of 1 W/cm2, the heat transfer coefficient is enhanced over 15 times compared to a plain reference surface. A model has been presented to explain the enhancement based on the structure characteristics. / QC 20101118