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Hybrid motors that employ non-toxic, non-explosive components with a liquid oxidizer and a solid hydrocarbon fuel grain have inherently safe operating characteristics. The inherent safety of hybrid rocket motors offers the potential to greatly reduce overall operating costs. Another key advantage of hybrid rocket motors is the potential for in-flight shutdown, restart, and throttle by controlling the pressure drop between the oxidizer tank and the injector. This research designed, developed, and ground tested a closed-loop throttle controller for a hybrid rocket motor using nitrous oxide and hydroxyl-terminated polybutadiene as propellants. The research simultaneously developed closed-loop throttle algorithms and lab scale motor hardware to evaluate the fidelity of the throttle simulations and algorithms. Initial open-loop motor tests were performed to better classify system parameters and to validate motor performance values. Deep-throttle open-loop tests evaluated limits of stable thrust that can be achieved on the test hardware. Open-loop tests demonstrated the ability to throttle the motor to less than 10% of maximum thrust with little reduction in effective specific impulse and acoustical stability. Following the open-loop development, closed-loop, hardware-in-the-loop tests were performed. The closed-loop controller successfully tracked prescribed step and ramp command profiles with a high degree of fidelity. Steady-state accuracy was greatly improved over uncontrolled thrust.

The effect of global warming on methane (CH₄) and nitrous oxide (N₂O) emissions from agriculture was investigated and simulated from a soil warming experiment. Experiments were designed and installed in a temperature controlled greenhouse. The relationships between elevated temperatures and CH₄ and N₂O emissions were determined and calculated as the Q₁₀s of production, emission and oxidation. A study of the populations of methanogens and methanotrophs at a range of soil temperatures was performed based on soil molecular DNA analysis. This study showed that global warming would increase CH₄ emissions from rice agriculture and that the resultant emissions will be potentially large enough to cause changes in the present atmospheric concentrations. This research also showed that this increase was most evident for soil temperatures below 30⁰C, above which emissions decreased with increasing temperature. The seasonal average Q₁₀s of CH₄ emission, production, oxidation, methanogen and methanotroph populations were found to be 1.7, 2.6 and 2.2, 2.6 and 3.8, respectively, over a temperature of 20-32⁰C. Considering that the processes of CH₄ production and emission are similar to those in natural wetlands, which is the largest source of atmospheric CH₄, the contribution of this feedback is likely to cause a significant increase to the present CH₄ atmospheric budget if the current global warming trend persists over the next century. The Q₁₀s of N₂O emissions and production were 0.5-3.3 and 0.4-2.9, respectively. The low Q₁₀ values found for N₂O suggest that although global warming will have a direct impact on the production and emission rates. Nevertheless, the magnitude of the impact of global on both CH₄ and N₂O emissions from agriculture is likely to vary from one region to another due to the spatial variations in agricultural soil temperatures and the likely changes in the global regional distribution of water resources (water tables, rainfall patterns), water management practices and the responses of terrestrial CH₄ and N₂O sources such as natural wetlands and plants.

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Corn (Zea mays L.) and soybean (Glycine max (L.) Merr.) production in Illinois has a significant impact on the economy and environmental footprint in the state and the Midwest region. Nutrient leaching from Midwestern agricultural fields is one of the major reasons for the hypoxic zone developed in the Gulf of Mexico. Winter-fallow and early spring (after fertilizer application) are the two most critical periods for nutrient leaching due to increased precipitation and availability of nutrients. Cover crops (CCs) in these seasons are a promising best management practice (BMP) to reduce nutrient leaching in the winter-fallow season. No-till (NT) and reduced tillage (RT) are some other BMPs that farmers in Illinois adopt to reduce erosion. The adoption of CCs is limited due to the lack of knowledge and data on the yield and environmental benefits of CCs in different climatic and soil regimes. Thereby, this doctoral dissertation addresses several critical questions about CC and tillage impacts in claypan soils of southern Illinois with four principal projects with multiple objectives. Research study 1 was a field experiment conducted from 2013-to 2021 to understand the effect of CCs (CCs vs. noCC) and two tillage (NT and RT) practices on soil nitrate-N leaching. The experimental design was a complete randomized design with CC treatments that had two levels (two crop rotations) corn-cereal rye (Secale cereale L.)-soybean-hairy vetch (Vicia villosa R.) [CcrShv] and corn-noCC-soybean-noCC [CncSnc] and tillage treatments with two levels (NT and RT) replicated three times in the field. Each plot had a pan lysimeter installed below the A horizon (22-30 cm depth) to collect water samples weekly or biweekly depending on the rainfall. The corn yield was significantly greater in RT rotations compared to NT rotations with a 36% increase in the yield in 2019 and 2021 corn rotations. The yield was significantly greater in CcrShv rotations compared to the CncSnc rotations. The greatest yield was observed in the interaction of CcrShv-RT in all years. This increase in yield is inversely correlated to the remaining soil N values when the N credit from CCs was not accounted for. Soil nitrate-N leaching was significantly greater in CcrShv rotations compared to the CncSnc rotation in 2021 indicating vetch CC biomass decomposition can lead to increased leaching losses if the window between CC termination and corn planting is not minimized. Precipitation during the early spring can play a vital role in flushing the newly applied fertilizer as well as the N released from decomposing CC residue. The excessively wet year of 2019 showed that N losses are dominated by both nitrate-N leaching and nitrous oxide emissions, but in a typical growing season N losses are dominated by leaching compared to emissions. Research study 2 was designed to better understand the N cycling and fate of applied N in a complete corn-soybean rotation in southern Illinois with CCs and tillage practices. The research was overlayed in the same field with the same crop rotation and tillage practices. In this study, 15N labeled urea fertilizer (9.2% atom) was applied before the corn and soybean seasons. Soil, water, and biomass samples were collected to understand N distribution in each pool. In the corn season in 2017 a significantly greater 15N recovery was observed in CC (CcrShv) plots compared to the noCC plots in the sample collected seven days after planting (DAP). In the CC and depth interaction, a significantly greater 15N recovery was observed in 15-30 cm depth showing that the increased macropores due to CCs can lead to subsurface movement of N through the topsoil. The 15N recovery in water samples was high in CncSnc rotations in the cereal rye season but was significantly greater in CcrShv rotations (8.95 kg ha-1) in hairy vetch seasons. In the two years of complete rotation, the cumulative 15N recovery (quantity derived from fertilizer in water) was significantly greater in CC rotation. In the corn plants, the 15N recovered from the soil was greater than the 15N recovered from fertilizer. This shows the importance of the residual N from prior fertilizer and organic matter input. In the cereal rye season, CCs recovered significantly greater 15N from fertilizer compared to noCC rotations, assuring that cereal rye is an effective nutrient scavenger. A similar pattern was observed in the hairy vetch season as well. However, the soybean 15N recovery was greater in noCC rotations compared to CC rotations. The third study was a field trial on CCs and tillage to understand their individual and combined impact on soil physical parameters. Soil physical parameters were first measured in 2014 and were repeated in 2021. Bulk density at the 0-5 cm depth was 5% lower in 2021 compared to 2014 with the lowest BD in CC rotations with RT practices. For the depth of 0-15 cm, the lowest BD was observed in CC rotation with RT but, the largest reduction was observed in the CC rotation with NT. The wet aggregate stability was improved from 15-28 % over the years in all rotations. The lowest percentage improvement was observed in noCC rotation with RT practice. Penetration resistance was significantly lower in CC plots for the depth of 0-2.5 cm. CCs further improved the time to runoff in plots even though the infiltration rates were not affected. Chemical soil health indices were not significant overtime for CCs or tillage practices. However, a large number of earthworm counts were observed in NT systems compared to RT systems. The final project was a field trial to identify the soil P response to the CC and tillage practices. For this study, three different CC rotations, [corn-cereal rye-soybean-hairy vetch / corn-cereal rye-soybean-oats+radish / corn-noCC-soybean-noCC] and two tillage practices (NT and RT) were used. Soil samples were collected after the corn harvest in 2015 and 2021 and were analyzed for soil Phosphorus (P), inorganic P fractions by Chan and Jackson method, and dissolved reactive phosphorus (DRP) in leachate. The soil Mehlich-3 and Bray-1 P values indicate a great concentration of P in 0-15 cm depth for both years. More refined sampling in 2021 showed that the majority of P in 0-15 cm depth concentrates at the near-surface soil, in 0-5 cm depth irrespective of the CC and tillage treatment. Inorganic soil P fractions were not significantly different between CCs or tillage practices over time. Yet, irrespective of the treatment the non- labile P forms increased in 2021in the soil compared to 2015. The average and cumulative DRP values were highly dependent on the precipitation amounts and timing. However, in general, NT systems had greater average and cumulative DRP leaching compared to RT in both years. In general, CCs in the winter-fallow season is a good recommendation for farms that seek to maximize their production with a minimal environmental footprint. In the long run, CCs can improve soil physical and chemical properties which ultimately can increase the yield potential for corn and soybean. The added benefit of N credit due to leguminous CCs can reduce the fertilizer inputs. The CC benefits including the reduction in nutrient leaching depend on the type of CCs used in the field. More importantly, the CC termination time will be critical to obtain the maximum benefit of CCs. Even though the NT practices improve soil physical properties, long-term NT can increase the risk of soil P stratification in near-surface soils and can ultimately lead to more P loss via erosion, runoff, and soil water leaching. However, the combined use of CC and NT practices can help minimize the potential for erosion and runoff.

<p dir="ltr">This work studies the kinetics of nitrous oxide decomposition over alumina-based catalysts, specifically at the high temperatures and high nitrous oxide (N2O) concentrations that would be experienced in catalyst beds for monopropellant rocket thruster applications. High- and low- order models are developed to understand the interaction between reaction kinetics and mass transfer in monolith catalyst tubes. However, nitrous oxide decomposition is not observed on monolith catalyst tubes on account of their lower geometric surface area leading to a majority of the gas not coming into contact with the catalyst surface. Pellet-bed catalysts are studied for the remainder of this work, starting from experiments with a constant-volume batch reactor. The batch experiments demonstrate N2O decomposition over catalyst pellets, and a one-dimensional, time-varying model is developed to quantify the reaction rate based on measured temperature and pressure rise from experimental data. The reaction rates predicted by the model are significantly lower than predicted in the literature for the same catalysts. The inaccuracy is attributed to the fact that the model cannot capture N2O decomposition occurring during the first few seconds of filling the batch tube. Additionally, the simplified temperature distribution applied in the model may not be accurate, and obtaining a higher fidelity temperature distribution experimentally would require more advanced diagnostics.</p><p dir="ltr">The final experiment is a conventional flow-through pellet bed reactor which uses infrared spectroscopy to measure the concentration of nitrous oxide in the decomposed gas mixture. The analysis method incorporates uncertainties from infrared measurements and other sources, and initial activity results of a cobalt oxide-on-alumina catalyst are consistent with the literature. Results from additional testing indicate that manganese oxide catalysts are more active than nickel oxide or cobalt oxide catalysts. At weight loadings of ~10%, results indicate that the Arrhenius pre-exponential constant is roughly an order or magnitude greater for manganese oxide catalysts than cobalt or nickel oxide catalysts. The results also indicate hysteresis in catalytic activity of all oxides. Surface area and x-ray diffraction measurements do not reveal any permanent change in the surface area or crystal structure of these catalysts. The findings lead to the conclusion that the temperature and surrounding environment of the catalyst (either nitrous oxide or nitrogen during system purges) cause short-lived changes to the crystal structure of the active phase, leading to the observed hysteresis.</p>

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