Inorganic-organic materials incorporating alumoxane nanoparticles
Vogelson, Cullen Taylor
Barron, Andrew R.
Doctor of Philosophy
Chemically functionalized alumina nanoparticles (carboxylate-alumoxanes) are used as the inorganic component of a new class of inorganic-organic material. Lysine- or para-hydroxybenzoic acid-derivatized alumoxanes are prepared from the reaction of boehmite, [Al(O)(OH)]n, with the appropriate carboxylic acid. The peripheral hydroxides and amines of these alumoxanes react directly with DER 332 epoxide to form a hybrid material, or in the presence of a resin and hardener system, to form a composite material. Solid state NMR spectroscopy demonstrates that the alumoxanes are chemically bound to the resin matrix. The properties and cure times of the alumoxane materials are distinct from both the pure resins and from a physical blend of the resins with traditional fillers. A significant increase in thermal stability and tensile strength is observed for the resin systems. In order to produce molecular coupling layers, epoxides cross-linked with self-assembled monolayers (SAMs) grown on the native oxide of aluminum thin films on silicon substrates have been investigated. Specifically, SAMs have been formed by the attachment of different carboxylic acids. In order to investigate the cross-linking reaction between carboxylate monolayers and an epoxide, grown monolayers were reacted with a mono-epoxy resin. In addition to these surface materials, aluminum oxide surfaces supporting carboxylate monolayers were reacted in pairs with DER 332 to form a structural adhesive. These materials have been characterized variously by SEM, AFM, XPS, EDX, and contact angle measurements. The particle size dependence on pH of a series of alumoxanes was investigated. For each of the alumoxanes, PCS particle size measurements were obtained as a function of pH. In all cases, particle size control was afforded by variations in pH. Finally, crystal structures of several model compounds were determined by X-ray crystallography, and shown to form either sheets of dimers or tetrameric units. Through a review of structures found in the Cambridge Crystallographic Database, compounds of the type X-CH(OH)CH 2NH-Y were investigated. The results of this study lead to a generalized approach for predicting the packing motifs of racemic mixtures in polar space groups.
Inorganic chemistry; Engineering; Materials science