abstract: The hierarchical silica structure of the Coscinodiscus wailesii diatom was studied due to its intriguing optical properties. To bring the diatom into light harvesting applications, three crucial factors were investigated, including closely-packed diatom monolayer formation, bonding of the diatoms on a substrate, and conversion of silica diatom shells into silicon. The closely-packed monolayer formation of diatom valves on silicon substrates was accomplished using their hydrodynamic properties and the surface tension of water. Valves dispersed on a hydrophobic surface were able to float-up with a preferential orientation (convex side facing the water surface) when water was added. The floating diatom monolayer was subsequently transferred to a silicon substrate. A closely-packed diatom monolayer on the silicon substrate was obtained after the water evaporated at room temperature. The diatom monolayer was then directly bonded onto the substrate via a sintering process at high temperature in air. The percentage of bonded valves increased as the temperature increased. The valves started to sinter into the substrate at 1100°C. The sintering process caused shrinkage of the nanopores at temperatures above 1100°C. The more delicate structure was more sensitive to the elevated temperature. The cribellum, the most intricate nanostructure of the diatom (~50 nm), disappeared at 1125°C. The cribrum, consisting of approximated 100-300 nm diameter pores, disappeared at 1150°C. The areola, the micro-chamber-liked structure, can survive up to 1150°C. At 1200°C, the complete nanostructure was destroyed. In addition, cross-section images revealed that the valves fused into the thermally-grown oxide layer that was generated on the substrate at high temperatures. The silica-sintered diatom close-packed monolayer, processed at 1125°C, was magnesiothermically converted into porous silicon using magnesium silicide. X-ray diffraction, infrared absorption, energy dispersive X-say spectra and secondary electron images confirmed the formation of a Si layer with preserved diatom nano-microstructure. The conversion process and subsequent application of a PEDOT:PSS coating both decreased the light reflection from the sample. The photocurrent and reflectance spectra revealed that the Si-diatom dominantly enhanced light absorption between 414 to 586 nm and 730 to 800 nm. Though some of the structural features disappeared during the sintering process, the diatom is still able to improve light absorption. Therefore, the sintering process can be used for diatom direct bonding in light harvesting applications. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2018

The production of halloysite-derived silicon (HDS) is investigated as a potential anode material in lithium-ion batteries (LIBs). Other researchers have found HDS to be electrochemically active in small test cells. To test larger electrochemical cells, the production process needs to be scaled up and optimized. HDS is produced through magnesiothermic reduction of acid-etched halloysite. The reduction process is very exothermic and requires special consideration while being scaled up. A reactor and pressure release system were designed and fabricated to perform the reduction process in a safe manner. Various steps of the process were tested to determine their influence on the purity of the HDS and the stability of the reaction. The concentration of aluminum chloride was determined to be critical in preventing excessive thermal spikes during the reaction. We also found that there was no benefit to increasing the amount of the reducing agent, as it can lead to undesired side reactions. We also determined that proper mixing and sufficient temperature are some of the most important influences on the purity of HDS product. The HDS produced in our process performed well electrochemically. Si electrodes had up to 2284 mAh/g of discharge capacity after initial formation cycle. The Coulombic efficiency was as high as 95% for a given Si-G electrode. Detailed analyses using differential scanning calorimetry (DSC) revealed multiple side reactions involving magnesium, aluminum chloride, and silica. Magnesium reacts with aluminum chloride to produce magnesium chloride. This would mean that aluminum metal would react with silica, instead of magnesium. The combination of those two reactions releases 90% more heat than would magnesiothermic reduction of silica, increasing the possibility of unwanted thermal events. The newly formed magnesium chloride then reacts with the remaining aluminum chloride to form a hybrid salt, MgAl2Cl8.

Shape-preserving silica magnesiothermic reduction is a gas-solid reaction used to convert complex, 3-dimensional SiO₂ structures into replicas composed of a two-phase product of MgO and Si. The MgO/Si components of this reaction are found to form an interwoven aggregate product structure, which is suitably robust that the MgO phase can be selectively dissolved to yield porous Si. Here, the kinetics and mechanisms of growth of this robust product structure have been studied. The aggregate product structure was deduced to result because stacked layers of MgO/Si product phases with planar interfaces are geometrically unstable, owing to the growth kinetics of the products. The interwoven nature of the aggregate may be explained by the presence of an amorphous magnesium silicate phase ahead of the MgO/Si product during reaction. Complex composition gradients in the magnesium silicate can lead to tortuous and branching growth of MgO and Si phases as the magnesium silicate is consumed by reaction. In addition, a large residual stress (> 5 GPa) was measured in the MgO/Si product layer formed during reaction of planar quartz. Despite the presence of such a large stress, no distortion or cracking of reacted structures was found to occur after reaction in the temperature range 650-900 °C. XRD-based residual stress measurements and morphological observations of product films on reacted quartz substrates were used to evaluate possible mechanisms of stress relief in the structure. It was found that the migration of MgO to the external surface of the product layer could be correlated to the rate of stress relaxation that occurred in annealed product films. Finally, applications of silica magnesiothermic reduction and derivative processes were studied in the fields of chemical catalysis and optical chemical sensing.