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.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/51760 |
| Date | 06 March 2012 |
| Creators | Davis, Stanley Casey |
| Contributors | Sandhage, Kenneth |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation |
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