Thesis (M.Sc.)--Memorial University of Newfoundland, 2002. / Bibliography: leaves 92-95.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 110-117).

Flame-based synthesis is an attractive industrial process for the large scale generation of nanoparticles. In this aerosol process, a gasifi ed precursor is injected into a high-temperature turbulent flame, where oxidation followed by particle nucleation and other solid phase dynamics create nanoparticles. Precursor oxidation, which ultimately leads to nucleation, is strongly influenced by the turbulent flame dynamics. Here, direct numerical simulation (DNS) of a canonical homogeneous flow is used to understand the interaction between a methane/air flame and titanium tetrachloride oxidation to titania. Detailed chemical kinetics is used to describe the combustion and precursor oxidation processes. Results show that the initial precursor decomposition is heavily influenced by the gas phase temperature field. However, temperature insensitivity of subsequent reactions in the precursor oxidation pathway slow down conversion to the titania. Consequently, titania formation occurs at much longer time scales compared to that of hydrocarbon oxidation. Further, only a fraction of the precursor is converted to titania, and a signi cant amount of partially-oxidized precursor species are formed. Introducing the precursor in the oxidizer stream as opposed to the fuel stream has only a minimal impact on the oxidation dynamics. In order to understand modeling issues, the DNS results are compared with the laminar flamelet model. It is shown that the flamelet assumption qualitatively reproduces the oxidation structure. Further, reduced oxygen concentration in the near-flame location critically a ffects titania formation. The DNS results also show that titania forms on the lean and rich sides of the flame. A reaction path analysis (RPA) is conducted. The results illustrate the di ffering reaction pathways of the detailed chemical mechanism depending on the composition of the mixture. The RPA results corroborate with the DNS results that titania formation is maximized at two mixture fraction values, one on the lean side of the flame, and one on the rich side. / text

M. Tech. Chemical Engineering. / Discusses the objectives of the research project are to: 1. Develop a cost effective technique for modifying the surface groups of ACs with a view to induce selectivity properties towards PGMs. 2. Characterize the chemically treated ACs. 3. Determine adsorption capacities and selectivity of Amine treated ACs by performing batch adsorption tests. 3. Investigate the adsorption of Pt (IV) in a Continuous stirred tank reactor. The data generated according to the project objectives will assist in obtaining the following informations. 1. Adsorption isotherms - Find the maximum adsorption capacity of ACs for different solution concentrations, and temperature. Determine the effect of base metals on adsorption and hence extend the adsorption isotherm equation from single component to a multi-component adsorption isotherm. 2. Kinetics data - Determine the rate of change of metals in solution with time at various initial concentration, temperature and acid strength. 3. Characterization of modified ACs - Determine surfaces morphology of ACs using SEM-EDS.

Stacking interactions, also known as π-π or face-to-face interactions, occur between molecules whose π bonds are in parallel planes. They are used to design self-assembling structures in nanotechnology, influence organic reactions and are ubiquitous in nature. The stacking interactions of substituted benzene heterodimers and substituted benzene-natural nucleobase heterodimers are examined. Both electron-donating and withdrawing groups are studied by varying their type, number and location around the benzene ring. The studies are done by carrying out systematic scans of the potential energy surface at the MP2/6-31G*(0.25) level of theory. Charge transfer interactions and extent of charge separation in the monomer are found to be dominant when the difference in ESP between the monomers is large and small, respectively. Dipole-dipole interactions are also found to affect stacking interactions. The results from MP2/6-31G*(0.25) are checked against those at the CCSD(T)/CBS limit for select cases and are found to be within 81- 110%. / xii, 166 leaves : ill. ; 29 cm

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The kinetics of incongruent reduction between sapphire and oxygen-controlled Mg-Al melts was studied by measuring spinel-layer thickness, sample-weight change and sample-thickness change as a function of time at various temperatures. To eliminate the crucible contamination caused by impurities in commercial MgO crucibles, self-made high-purity MgO crucibles were achieved by gelcasting method, which is an attractive ceramic-forming technique for making high-purity ceramic parts. The oxygen-controlled alloys were obtained by the three-phase-equilibrium experiments at various temperatures. To avoid MgO formation, the oxygen-controlled alloys prepared at relatively lower temperatures were used for incongruent reaction at relatively higher temperatures. That is to say, the oxygen-controlled alloys prepared at 900°C, 1000°C, and 1100°C were used for spinel formation at 1000°C, 1100°C, and 1200°C, respectively. The experiments were conducted in a vertical furnace, and sapphire wafers were hung vertically in high-purity MgO crucibles so that the natural convection induced by the density change in the melt could be investigated. Experimental results obtained at 1000°C, 1100°C, and 1200°C showed that the spinel layer thickness on two kinds of sapphire wafers, namely {0001} and , followed orientation-independent parabolic kinetics, indicating the diffusion in spinel was one of the rate-limiting steps. In addition, the spinel layer thickness was not a function of position. The results of sample-thickness- change measurements also indicated that the effect of natural convection could be neglected. XPS, XRD, and TEM were also employed to characterize some samples in this study. Based on a simple model where the diffusion in spinel was the only rate-limiting step, the governing partial differential equations for diffusion and fluid dynamics were solved by the finite element method. The calculated theoretical parabolic constants at various temperatures were compared with these experimental results, and a good agreement was obtained. Some preliminary studies were also made on the morphologies of spinel particles at the nucleation stage. It was found that the triangular {111} faces of spinel particles were parallel to the surface of {0001} sapphire substrate. The product shape was consistent with the tetrahedron composed of {111} faces. The morphology of spinel particles on a sapphire substrate was more complicated in that the triangular {111} faces of spinel had to be inclined at a certain angle to the substrate in order to maintain the orientation relationship.

Lignin, a byproduct of the chemical pulping can be gasified to produce fuel gas and value-added products. Two lignins, MeadWestvaco (MWV) lignin and Sigma Aldrich (SA) lignin, were studied using two different reactors. A laminar entrained flow reactor (LEFR) was used initially to determine the effect of lignin type, temperature and residence time on char yield and fixed carbon conversion during pyrolysis and gasification. During both pyrolysis and gasification, the maximum decrease in char yield took place in the initial stage of the reaction and there was little change at longer residence times. There was not much difference between pyrolysis and gasification in the residence times obtained in the LEFR. Furthermore, a thermogravimetric analyzer (TGA) was used to study the effect of lignin type on pyrolysis and gasification. The reaction rates and char yields were affected by the lignin composition. Lignin pyrolysis showed similar behavior until 600°C but only the high-ash SA lignin showed secondary pyrolysis reactions above 600°C. Carbon gasification reactions were delayed in SA lignin. Na2CO3 addition made the primary pyrolysis reaction occur at a lower rate and enhanced the rate for secondary pyrolysis reactions. Fourier Transform Infrared (FTIR) Spectroscopy results showed that the significant loss of spectral detail started at different temperatures for MWV lignin and SA lignin. Kinetic parameters obtained using differential and Coats - Redfern integral method were comparable at lower temperatures but varied at high temperatures. Na2CO3 addition decreased the activation energy of primary pyrolysis.