The purpose of this study is to examine the burning behaviour of composite solid propellants (CSP) in the presence of nanoscale, heterogenous catalysts. The study targets the decomposition of ammonium perchlorate (AP) as a key component in the burning profile of these propellants, and seeks to identify parameters of AP decomposition reaction that can be affected by catalytic additives. The decomposition behavior of AP was studied in the presence of titanium dioxide nanoparticles in varying configurations, surface conditions, dopants, morphology, and synthesis parameters with the AP crystals. The catalytic nanoparticles were found to enhance the decomposition rate of the ammonium perchlorate, and promote an accelerated burning rate of CSP propellants containing the additives. Furthermore, different configurations were shown to have varying degrees of effectiveness in promoting the decomposition behaviour. To study the effect of the catalyst’s configuration in the bulk propellant, controlled dispersion conditions of the nanoparticle catalysts were created and studied using differential scanning calorimetry, as well as model propellant strand burning. The catalysts were shown to promote the greatest enthalpy of reaction, as well as the highest burn rate, when the AP crystals were recrystalized around the nanoparticle additives. This is in contrast to the lowest enthalpy condition, which corresponded to catalysts being dispersed upon the AP crystal surface using bio-molecule templates. Additionally, a method of facile, visible light nanoparticle tracking was developed to study the effect of mixing and settling parameters on the nano-catalysts. To accomplish this, the titania nanoparticles were doped with fluorescent europium molecules to track the dispersion of the catalysts in the propellant binder. This method was shown to succesfully allow for dispersion and agglomeration monitoring without affecting the catalytic effect of the TiO2 nanoparticles.

The Investigation of Nickel-Based Catalysts for the Oxidative Dehydrogenation of Ethane Justin Lane ParkDepartment of Chemistry & Biochemistry, BYU Doctor of Philosophy Chemistry The advancement of creating ethylene from ethane via oxidative dehydrogenation (ODH) rather than the traditional direct dehydrogenation is right on the cusp of commercialization. The oxidative pathway provides a novel route that reduces the operating temperature of this reaction by 400-500°C. A variety of metals including Mo, V, and Ni that have redox properties suitable for the partial oxidation of small chain alkanes have been investigated. Currently, a MoVNbTe oxide is the most promising catalyst but it suffers from a long and difficult preparation method and the combination of four expensive metals. Nickel based catalysts have also shown great promise but are limited by the reactivity of the oxygen species on the surface of the catalyst. In this manuscript, the details for improving the activity of the nickel and altering the activation mechanism are outlined.Bulk CeNiNb oxide catalysts were shown to almost double the rate of ethylene yields at temperatures as low as 300°C. This is partially related to the improved rate of oxygen adsorption and transfer to the active oxygens on the nickel oxide via the ceria additive. However, with further characterization of these materials, it was shown that there is likely an interaction between the Ce and Nb, forming a Ce-O- Nb linkage that is also selective towards ethylene. This facilitates a higher activity of the catalyst by creating two redox active sites. The improved rates of ethylene formation observed with these catalysts led to the initial development of a commercially viable nickel based catalyst. The support interactions of NiO with a novel silica doped alumina support show higher yields than previously reported studies of NiO on alumina for ODH. These initial metal support interactions show that the addition of the niobium and ceria to this catalyst should give ethylene yields that are satisfactory for the commercialization of this catalyst.

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Sol-gel titania particles were investigated, primarily by optical techniques, by systematically varying synthesis, sample handling, and annealing variables. The material phases investigated were amorphous titania, anatase TiO2, and rutile TiO2. Annealing-induced phase transformations from amorphous TiO2 to anatase to rutile were studied by Raman scattering, infrared reflectivity, infrared absorption, x-ray diffraction, and electron energy-loss spectroscopy (EELS). Detailed experiments were carried out on the effects of annealing on the Raman and infrared spectra of anatase nanocrystals. The frequencies of the zone-center transverse optical (TO) and longitudinal-optical (LO) phonons of anatase were determined and were used in analyzing the results obtained on composites consisting of annealed solgel particles. The TO and LO frequencies of anatase were obtained from polarization-dependent far-infrared reflectivity measurements on single crystals. These results, which determined the dielectric functions of anatase, were used to explain infrared (IR) reflectivity spectra of titania nanoparticles pressed into pellets, as well as the grazing-incidence IR reflectivity observed for titania thin films. Because of the polycrystalline character of the titania nanoparticles, the surface roughness of the pressed pellets, and the island-structure character of the thin films, effective-medium theories (appropriate for composites) were used, along with the anatase dielectric functions, to interpret the experimental results. The titania nanoparticles were prepared by the hydrolysis/condensation of Ti(OC2H5)4. A polymeric steric stabilizer was used in the sol-gel synthesis in order to prevent continued agglomeration during the condensation process. This yielded particles with a relatively narrow size distribution. The amount of water used in the reaction determines the final particle size. Particles as small as 80 nm and as large as 300 nm were used throughout this work. From the colloidal suspension, loose powders, pressed pellets, and thin films were formed. These samples were subjected to different annealing processes at temperatures ranging from room temperature up to 1000 C. Two different annealing atmospheres were used: air (oxygen-containing) and argon (no oxygen). The amorphous to anatase transformation was followed by in-situ IR transmission measurements carried out during annealing. The particles as prepared are amorphous and the anatase phase could be detected, using this sensitive IR technique, at temperatures as low as 150 C. This phase transition was shown to be particle size dependent. It was also shown that introducing the stabilizer by means of the alkoxide flask instead of the water flask (during the sol-gel synthesis) decreases the anatase to rutile transformation temperature. Loose powders were found to transform more readily than dense pellets, while island-structure films were found to be the hardest to transform. Even at 1000 C, most of these films did not transform to rutile. X-ray diffraction experiments were used to determine nanocrystal sizes in anatase samples obtained by air and argon anneals at temperatures from 300 to 800 C. A correlation was found between Raman band shape (peak position and linewidth) and crystallite size, but this correlation was different for air anneals and for argon anneals. These experiments called for an interpretation based on a stoichiometric effect rather than a finite size effect. Based on this interpretation, the as-prepared particles are slightly oxygen-deficient, with a stoichiometry corresponding to TiO1.98. In the electron energy-loss experiments, a special data-analysis technique was used to extract the EELS spectrum of the titania nanoparticles from the observed substrate-plus-particles signal. This technique successfully resolved the titania absorption-edge peak. Which was found to be momentum independent. For low electron momentum, the results were consistent with the reported optical absorption edge. / Ph. D.