Glass matrix composites containing a conducting filler such as antimony tin oxide (ATO) or silicon carbide whiskers (SiCw) have the potential for applications such as transparent electrodes, heating elements, and electromagnetic shielding. For these applications, the composite performance is highly dependent on the microstructure of the composite and the interactions the added filler has with one another. In this research, borosilicate glass-matrix composites were fabricated using a processing method that creates segregated percolated networks at low concentrations of conducting fillers. The conducting fillers were hot pressed with the glass microspheres at temperatures near the glass transition temperature (550°C) using various pressures. Upon hot-pressing at these low temperatures, the glass microspheres deformed into faceted polyhedra and the fillers were displaced to the edges of the glass particles, resulting in percolation. The processing method used in this study was able to bypass many of the current composition and densification issues associated with the creation of percolated networks in glass composites. In some cases, the formation of these percolated networks resulted in a 12-13 orders of magnitude decrease in the resistivity. Using a non-destructive electrical measurement technique, ac impedance spectroscopy (IS), the changes in the electrical properties were tracked as the conducting networks developed. Using IS in conjunction with other techniques, correlations were made between the electrical properties, the filler interfaces, and the influence the processing parameters had on the development of the percolation networks within these composites.

abstract: Redox reactions are crucial to energy transduction in biology. Protein film electrochemistry (PFE) is a technique for studying redox proteins in which the protein is immobilized at an electrode surface so as to allow direct exchange of electrons. Establishing a direct electronic connection eliminates the need for redox­active mediators, thus allowing for interrogation of the redox protein of interest. PFE has proven a versatile tool that has been used to elucidate the properties of many technologically relevant redox proteins including hydrogenases, laccases, and glucose oxidase. This dissertation is comprised of two parts: extension of PFE to a novel electrode material and application of PFE to the investigation of a new type of hydrogenase. In the first part, mesoporous antimony-doped tin oxide (ATO) is employed for the first time as an electrode material for protein film electrochemistry. Taking advantage of the excellent optical transparency of ATO, spectroelectrochemistry of cytochrome c is demonstrated. The electrochemical and spectroscopic properties of the protein are analogous to those measured for the native protein in solution, and the immobilized protein is stable for weeks at high loadings. In the second part, PFE is used to characterize the catalytic properties of the soluble hydrogenase I from <italic>Pyrococcus furiosus</italic> (<italic>Pf</italic>SHI). Since this protein is highly thermostable, the temperature dependence of catalytic properties was investigated. I show that the preference of the enzyme for reduction of protons (as opposed to oxidation of hydrogen) and the reactions with oxygen are highly dependent on temperature, and the enzyme is tolerant to oxygen during both oxidative and reductive catalysis. / Dissertation/Thesis / Doctoral Dissertation Biochemistry 2014