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Doctor of Philosophy / Department of Chemistry / Viktor Chikan / Colloidal semiconductor nanoparticles will be important and practical next generation materials that can be cheaply manufactured. The objective of this project is to gain more inside into chemistry is used to control the formation and assembly of semiconductor nanoparticles (NPs). As a model system CdSe and CdTe nanoparticles are used in this work. The growth kinetics, aggregation dynamics, and heterogeneous growth of NPs by using novel tools such as; in-situ monitored fluorescence and absorption techniques, time-resolved and static fluorescence spectroscopy, TEM (transmission electron microscopy), and numerical simulations are studied. This study can be divided into the following four parts. The first part presents experimental observation of the quantized growth of CdTe quantum dots (QD). The high-temperature absorption spectra indicate the evolution of multiple peaks corresponding to various sizes of QDs. The observed aggregation is driven by dipole-dipole interaction of NPs. The second part is an investigation of the aggregation dynamics of magic-sized CdTe quantum dots and how this process can be controlled. It is shown that the growth kinetics of the QDs is very sensitive to the Cd/Te ratio. Cd-rich conditions form very different aggregation pattern due to the lack of formation of magic-sized nanoparticles. Simulations also suggest that the formation mechanism is mainly coalescence of the particles rather than the ‘neck formation’ within the CdTe aggregates. The next part investigates the growth of NPs in the presence of two distinctly sized NPs in the bimodal growth regime via numerical simulations. The bimodal distribution (or quantized Ostwald ripening) technique is found to be a slower process than the repeated injection technique to focus the size distribution of NPs. Slower growth will reduce inhomogeneity in a scaled-up production of NPs. The last part focuses on the effect of addition of doping on vii heterogeneous growth and the growth kinetics. The low temperature synthesis lacks the heterogeneous growth regime. However, as the temperature is increased to 120 0C, two different sizes emerge. Addition of In dopants seems to accelerate the growth kinetics and the magic sized NPs in the solution possess a negative anisotropy that is most likely due to supperlatice formation of magic-sized NPs.

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<p> The growth kinetics of a plates and rods in B-brass have been calculated using a local equilibrium model. These are in good agreement with published experimental data. Along with this, quantitative microanalysis of deep etched specimens ts cited in support of the proposed diffusional mechanism for their formation. </p> <p> The model was also employed to calculated the growth rates of upper bainitic rods in the Fe-C-Nisystem at 400° C. A "phase diagram" was constructed in order to supply the effective supersaturations required by the local equilibrium model$ Lengthening rates were also calculated using a paraequilibrtum Interface condition. The experimental data were correctly predicted assuming the former case but failed at the "phase" boundary. It seems that a solute drag might well operate in this system. These results have provided some further indication of the part alloying elements play in the formation of the microstructural constituents of steel. </p> / Thesis / Master of Engineering (MEngr)

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ABSTRACT Investigation of Microalgae Growth Kinetics using Coal-Fired Flue Gas as a Carbon Source Bryan Daniel Brooker Energy related carbon dioxide (CO2) emissions make up the majority of the United States’ greenhouse gas emissions. Emissions must be alleviated to reduce the effects of global climate change. Microalgae cultivation sequesters CO2 while producing biomass. Algal biomass can provide a renewable feedstock for biofuel and electricity production, and ingredients for pharmaceuticals, nutraceuticals, pigments and cosmetics. Utilizing microalgae to mitigate CO2 emissions encourages energy independence by providing a feedstock for biofuels and offers other potentially profitable avenues for the uses of biomass. This study focused on investigating the algal growth kinetics of microalgae cultivated with artificial coal-fired flue gas. Two algal strains, Chlorella vulgaris and Tetraselmis sp. were cultivated in lab scale photobioreactors to assess the feasibility of using flue gas as a carbon source for microalgae growth. The microalgae growth kinetics were compared between flue gas and pure CO2 treatments for each algal strain. Both microalgae species were able to grow under flue gas dosing. The differences in growth characteristics for Chlorella were statistically insignificant between the two gas dosing treatments. Tetraselmis yielded identical maximum specific growth rates among the two gas treatments, while the biomass production was greater using CO2. At a 95% confidence interval, the difference in biomass production between the gas treatments ranged from 45 to 225 mg/L. The decrease in biomass production for Tetraselmis was the only sign of growth inhibition from flue gas. Overall, Chlorella vulgaris and Tetraselmis sp. are capable of fixating CO2 from coal-fired flue gas.

This dissertation research aims to show that there are deterministic microbial distribution patterns based on quantifiable environmental thresholds by determining and rationalizing the relative abundances of hyperthermophilic methanogens, autotrophic iron(III) oxide reducers, and heterotrophic sulfur reducers within deep-sea hydrothermal vents. Organisms of these metabolisms are predicted to be relatively more abundant in different regions depending on environmental conditions such as reduction potential, organic carbon, and hydrogen availability. The relative abundances of these metabolic groups within samples from the Endeavour Segment and Axial Volcano in the northeastern Pacific Ocean were determined. Iron(III) oxide reducers were detected in nearly all samples while methanogens were generally not present or present in concentrations lower than those of the iron(III) reducers. To determine growth constraints and the effect of hydrogen concentration on hyperthermophilic methanogen growth kinetics, Methanocaldococcus jannaschii and two new Methanocaldococcus field isolates were grown at varying hydrogen concentrations. The hydrogen-dependent growth kinetics for all three strains were statistically indistinguishable, exhibiting longer doubling times and lower maximum cell concentrations with decreasing hydrogen concentrations until growth ceased below 17-23 μM. This minimum hydrogen concentration for hyperthermophilic methanogenesis was correlated with field microbiology and fluid geochemistry data from the Endeavour Segment and Axial Volcano. Anomalously high methane concentrations and thermophilic methanogens were only observed in fluid samples where hydrogen concentrations were above this predicted threshold. Aside from anomalous sites, methanogens are predicted to be hydrogen limited, and may rely on hydrogen produced by heterotrophs as suggested by in situ sampling and co-culture experiments. Models and kinetic experiments suggest that iron(III) oxide reducers are not hydrogen limited under the same conditions. A Methanocaldococcus strain that we isolated from Axial Volcano and used in our hydrogen threshold experiments was bioenergetically modeled over its range of growth temperatures, pH, NaCl concentrations, and NH4Cl concentrations. Its methane production rates and growth energies were largely constant but increased at superoptimal temperatures and when nitrogen was limiting. The results of this research demonstrate that the rates of and constraints on metabolic processes can be used to predict the distribution and biogeochemical impact of hyperthermophiles in deep-sea hydrothermal vent systems.

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There is potential for improving creep properties of stainless steels by reinforcing them with tungsten (W) wires. Past studies have shown that a detrimental factor that impairs the mechanical properties of tungsten wire reinforced superalloy composites is the formation of brittle intermetallic phases due to the interaction between W wire and constituents of the alloy matrices. Formation and growth of the intermetallic phases strongly depends on the matrix chemistry and for the retention of creep strength, matrix compositions that do not form intermetallic phases with tungsten are desirable for fabricating W wire reinforced composites for high temperature applications. This research investigated the formation and growth of reaction phases in W wire reinforced 316L (W/316L) stainless steel and HP alloy steel (W/HP) that were fabricated by casting method. Additionally, the effect of composition on the evolution and kinetics of reaction phases was studied in some W wire reinforced experimental alloys based on Fe-Ni-Cr only (W/Fe-Ni-Cr). The fabricated composites were diffusion annealed in the temperature range 1000-1200°C for 25-500 hours. Microstructure and chemistry of the reaction phases in the as-cast and diffusion annealed composites were studied using scanning electron microscopy, energy dispersive spectroscopy and electron backscattered diffraction techniques. Growth kinetics of the reaction layers and average effective interdiffusion coefficients in the layers were determined for the composites. Results showed that an intermetallic phase isostructural with µ-phase formed in the as-cast W/316L and W/Fe-Ni-Cr composites with 1 and 2 Fe:Ni matrix ratios. In W/HP a phase M12C with crystal structure similar to η-carbide was formed. These phases developed and formed brittle reaction layers around the W wires during diffusion annealing. A parabolic relationship between the µ-phase and η-carbide growth and diffusion annealing time indicated that the growth of reaction layers was diffusion controlled. In the W/Fe-Ni-Cr composites, formation of intermetallic phases did not occur in the matrices with 0.5Fe:Ni ratio, instead some isolated tungsten particles were observed in the matrix adjacent to the wires after diffusion annealing. In W/Fe-Ni-Cr composites with 1 and 2 Fe:Ni matrix ratio, the growth of µ-phase reaction layers during annealing was observed to be dependent on the matrix composition. It was found that with an increase in the Ni content in the matrix, growth of µ-phase reaction layer decreased. The study presented in this thesis gives first-hand information on phase formation and growth kinetics of the reaction layers in W/316L and W/HP composites. It revealed that the interaction of W with 316L and HP alloy matrices leads to formation of cracked intermetallic and carbide reaction layers which are not desirable in the composites designed for high temperature applications. It has also been shown in this study that in W/Fe-Ni-Cr composites, intermetallic phase formation can be suppressed by increasing Ni content in the matrix. In the composite with high Ni contents in the matrix (0.5Fe:Ni ratio) intermetallic phases do not form even after diffusion annealing at 1200°C. This intermetallic free W/Fe-Ni-Cr composite can further be studied for its creep strength.