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Title: EFFECTIVENESS AND KINETICS OF FERRATE AS ADISINFECTANT FOR BALLAST WATER.
Creator: Jessen, Andrea, Randall, Andrew, University of Central Florida
Abstract / Description: The introduction of aquatic nuisance species (ANS) and bacterial pathogens from discharge of ballast water by sea-faring vessels is an ongoing problem that threatens ecosystems and human health. This study investigates the disinfecting capability of ferrate in a marine environment on several organisms listed in international standards for ballast water management. Organisms were grown in a saline solution and were treated with dosages of ferrate ranging from 0.25-5.0 mg/l. A ferrate dose of 5...
Show moreThe introduction of aquatic nuisance species (ANS) and bacterial pathogens from discharge of ballast water by sea-faring vessels is an ongoing problem that threatens ecosystems and human health. This study investigates the disinfecting capability of ferrate in a marine environment on several organisms listed in international standards for ballast water management. Organisms were grown in a saline solution and were treated with dosages of ferrate ranging from 0.25-5.0 mg/l. A ferrate dose of 5 mg/l resulted in almost complete kill for all organisms tested. Smaller dosages have also been very effective, particularly if all organic material from the nutrient broth used to cultivate them is removed by washing the cells with saline solution. Ferrate appears to act very quickly, with tailing occurring after about 5-15 minutes. Analyses of the data with the CT approach, the Chick-Watson and Hom's models, and an oxidant demand equation derived from equations recommended by the Water Environment Federation (WEF) are in good agreement that ferrate concentration is more important than contact time. The Hom's model appeared to most accurately represent the action of ferrate on these organisms. Salinity and pH did not adversely affect results, and regrowth was not a problem. Two measures to reduce clumping did not eliminate the observed tailing effect, suggesting a different mechanism for this phenomena. These preliminary tests indicate that ferrate could be a very effective disinfectant in the treatment of ballast water, and the short half-life of ferrate is an advantage, since the ballast water is subsequently released into the environment.
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Date Issued: 2006
Identifier: CFE0001287, ucf:46891
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001287

Title: Exploration of life and decay in technological civilization.
Creator: Wieser, Mauro, Kovach, Keith, Adams, JoAnne, Burrell, Jason, University of Central Florida
Abstract / Description: Reflecting upon humanity's obligatory use of technology and its place in our collective evolution has become my endeavor. These reflections happen in a studio and through a process that influences the fine art objects produced. In turn the objects both celebrate and warn us of the dynamic and immanent enhanced human. I balance the use of modern machining processes with dark humor to comment and raise questions about the coexistence of man and machine in an increasingly absurd environment.
Date Issued: 2019
Identifier: CFE0007555, ucf:52608
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007555

Title: CHARACTERIZATION OF A HYDROGEN-BASED SYNTHETIC FUEL IN A SHOCK TUBE.
Creator: Flaherty, Troy, Kassab, Alain, University of Central Florida
Abstract / Description: Shock-tube experiments were performed with syngas mixtures near atmospheric pressure with varying equivalence ratios behind reflected shock waves. Pressure and hydroxyl radical (OH*) emission traces were recorded and used to calculate ignition delay time for a single mixture at equivalence ratios of 0.4, 0.7, 1.0, and 2.0 over a range of temperatures from 913 – 1803 K. The syngas mixture was tested at full concentration as well as with 98% dilution in Argon. The full concentration...
Show moreShock-tube experiments were performed with syngas mixtures near atmospheric pressure with varying equivalence ratios behind reflected shock waves. Pressure and hydroxyl radical (OH*) emission traces were recorded and used to calculate ignition delay time for a single mixture at equivalence ratios of 0.4, 0.7, 1.0, and 2.0 over a range of temperatures from 913 – 1803 K. The syngas mixture was tested at full concentration as well as with 98% dilution in Argon. The full concentration mixtures were used to compare ignition delay time measurements with the theoretical calculations obtained through the use of chemical kinetics modeling using the Davis et al. mechanism. The dilute mixtures were used to study the OH* emission profiles compared to those of the kinetics model. The model was in poor agreement with the experimental data especially at lower temperatures with an ignition delay difference of more than an order of magnitude. These ignition delay time data supplement the few existing data and are in relative agreement. The species profile comparison of OH* compared to the model also showed poor agreement, with the worst agreement at the highest temperatures. While the disagreements with ignition delay time and profile comparisons cannot be explained at this time, the data presented support other findings. The data provide additional information towards understanding this disagreement relative to syngas mixtures despite the relatively well known kinetics of the primary constituents Hydrogen and Carbon Monoxide.
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Date Issued: 2009
Identifier: CFE0002552, ucf:47657
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002552

Title: AN OPTIMIZED KINETICS MODEL FOR OH CHEMILUMINESCENCE AT HIGH TEMPERATURES AND ATMOSPHERIC PRESSURES.
Creator: Hall, Joel, Petersen, Eric, University of Central Florida
Abstract / Description: Chemiluminescence from the OH(A-X) transition near 307 nm is a commonly used diagnostic in combustion applications such as flame chemistry, shock-tube experiments, and reacting-flow visualization. Measurements of the chemiluminescent intensity provide a simple, cost-effective, non-intrusive look at the combustion environment. The presence of the ultra-violet emission is often used as an indicator of the flame zone in practical combustion systems, and its intensity may be correlated to the...
Show moreChemiluminescence from the OH(A-X) transition near 307 nm is a commonly used diagnostic in combustion applications such as flame chemistry, shock-tube experiments, and reacting-flow visualization. Measurements of the chemiluminescent intensity provide a simple, cost-effective, non-intrusive look at the combustion environment. The presence of the ultra-violet emission is often used as an indicator of the flame zone in practical combustion systems, and its intensity may be correlated to the temperature distribution or other parameters of interest. While absolute measurements of the ground-state OH(X) concentrations are well-defined, there is no elementary relation between emission from the electronically excited state (OH*) and its absolute concentration. Thus, to enable quantitative emission measurements, a kinetics model has been assembled and optimized to predict OH* formation and quenching at combustion conditions. Shock-tube experiments were conducted in mixtures of H2/O2/Ar, CH4/O2/Ar and CH4/H2/O2/Ar with high levels of argon dilution (> 98%). Elementary reactions to model OH*, along with initial estimates of their rate coefficients, were taken from the literature. The important formation steps follow. CH + O2 = OH* + CO (R0) H + O + M = OH* + M (R1) H + OH + OH = OH* + H2O (R2) Sensitivity analyses were performed to design experiments at conditions most sensitive to the formation reactions. A fitting routine was developed to express the key rate parameters as a function of a single rate, k1 at the reference temperature (1490 K). With all rates so expressed, H2/CH4 mixtures were designed to uniquely determine the value of k1 at the reference temperature, from which the remaining rate parameters were calculated. Quenching rates were fixed at their literature values. Comparisons to predictions of previously available models show marked improvement relative to the new shock-tube data. An approach for using this work in the calibration of further measurements is outlined taking examples from a recent ethane oxidation study. The new model qualitatively matches the experimental data over the range of conditions studied and provides quantitative results applicable to real combustion environments, containing higher-order hydrocarbon fuels and lower levels of dilution in air.
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Date Issued: 2005
Identifier: CFE0000888, ucf:46642
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0000888

Title: STRUCTURE DIFFERENCE AND IMPLICATION TO ASSEMBLY MORPHOLOGY CONTROL OF ROUS SARCOMA VIRUS CAPSID PROTEIN.
Creator: Hastings, John, Chen, Bo, University of Central Florida
Abstract / Description: Rous Sarcoma Virus (RSV) is an avian retrovirus with an enclosing capsid protein (CA) shell. RSV CA is studied due to its similar molecular structure to other retrovirus capsid proteins such as Human Immunodeficiency Virus (HIV). In this project, turbidity assay is used to track the assembly process of RSV CA, while solid state nuclear magnetic resonance (ssNMR) is used to probe the CA structure at a site specific level and investigate the morphology of the spherical structure of the I190V...
Show moreRous Sarcoma Virus (RSV) is an avian retrovirus with an enclosing capsid protein (CA) shell. RSV CA is studied due to its similar molecular structure to other retrovirus capsid proteins such as Human Immunodeficiency Virus (HIV). In this project, turbidity assay is used to track the assembly process of RSV CA, while solid state nuclear magnetic resonance (ssNMR) is used to probe the CA structure at a site specific level and investigate the morphology of the spherical structure of the I190V mutated strain of RSV CA. The I190V mutant is a naturally occurring mutation and is able to form into roughly uniform spheres, where the wild type RSV CA cannot form as pure spheres as possible. Turbidity assay results of the mutated RSV CA revealed a lack of a noticeable lag time before assembly began, as well as, a prolonged time period to reach saturation when compared to the wild-type RSV CA. Using ssNMR, and the TALOS-N program the torsion angles of the protein backbone were found. Using Ramachandran plots, it was found that the mutation of the 190th residue from Isoleucine to Valine caused a changed in the secondary structure of residues, from ?-helix to ?-sheet and vice versa. These changes were concentrated at the loops between select interfaces of helices that make up the structure of RSV CA. In particular, between helices 4 (residues 65-85), 8 (residues 165-177), and 11 (residues 215-225). The differing secondary structure in the mutant RSV CA was supported by the overlaying of the NMR spectra of the wild-type RSV CA on to the spherically assembled mutant RSV CA. It can be concluded that the spherical assembly of the mutated RSV CA displays noticeable differences in assembly and overall structure when compared to the wild-type RSV CA.
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Date Issued: 2019
Identifier: CFH2000458, ucf:45705
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFH2000458

Title: CHARACTERIZING SPONTANEOUS FIRES IN LANDFILLS.
Creator: Moqbel, Shadi, Reinhart, Debra, University of Central Florida
Abstract / Description: Landfill fires are relatively common incidents that landfill operators encounter which have great impact on landfill structure and the environment. According to a U.S. Fire Administration report in 2001, an average of 8,300 landfill fires occurs each year in the United States, most of them in the spring and summer months. Subsurface spontaneous fires are considered the most dangerous and difficult to detect and extinguish among landfill fires. Few studies have been conducted on spontaneous...
Show moreLandfill fires are relatively common incidents that landfill operators encounter which have great impact on landfill structure and the environment. According to a U.S. Fire Administration report in 2001, an average of 8,300 landfill fires occurs each year in the United States, most of them in the spring and summer months. Subsurface spontaneous fires are considered the most dangerous and difficult to detect and extinguish among landfill fires. Few studies have been conducted on spontaneous fires in landfills. Information regarding the thermal behavior of solid waste is not available nor have measurements been made to evaluate spontaneous ignition of solid waste. The purpose of this research was to provide information concerning the initiation of spontaneous ignition incidents in landfills, and investigate the conditions favoring their occurrence. This study enabled better understanding of the self-heating process and spontaneous combustion in landfills. Effects of parameters critical to landfill operation on spontaneous combustion were determined. Spontaneous combustion occurs when materials are heated beyond the ignition temperature. Temperature rise occurs inside the landfill due to exothermic reactions which cause self-heating of the solid waste. Oxygen introduction leading to biological waste degradation and chemical oxidation is believed to be the main cause of rising solid waste temperatures to the point of ignition. A survey was distributed to landfill operators collecting information regarding spontaneous firs incidents in their landfills. Survey results raised new questions necessitating further study of subsurface fires incidents. Subsurface spontaneous fires were not restricted to any landfill geometry or type of waste (municipal, industrial, commercial, and construction and demolition). Results showed that landfill fires occur in landfills that do and do not recirculate leachate. Although new methods have been developed to detect subsurface fires, landfill operators depend primarily on visual observation of smoke or steam to detect the subsurface fires. Also, survey results indicated that excavating and covering with soil are the most widespread methods for extinguishing subsurface fires. Methane often has been suspected for initiating spontaneous subsurface firs in the landfill. However, combustible mixture of methane and oxygen requires very high temperature to ignite. In this study it was shown that spontaneous fires are initiated by solid materials with lower ignition points. Laboratory tests were conducted evaluating the effect of moisture content, oxygen concentration and leachate on spontaneous ignition of solid waste. A new procedure for testing spontaneous ignition is described based on the crossing-point method. The procedure was used to study the spontaneous combustion of solid waste and determine the auto-ignition temperature of the solid waste components and a synthesized solid waste. Correlations have been established between auto-ignition temperature, specific weight and energy content and between self-heating temperature and specific weight. Correlations indicated that compaction can help avoid spontaneous combustion in the landfill. Dense materials require higher energy to increase in temperature and limit the accessibility of oxygen. In the experimental work, moisture was found to promote both biological and chemical self-heating. Increasing moisture content lowers the solid waste permeability and absorbs more energy as it evaporates. Dissolved solids in leachate were found to promote self-heating and ignition more than distilled water. Varying oxygen concentrations indicated that heat generation occurs due to chemical oxidation even at oxygen concentration as low as 10% by volume. However, at 10% by volume oxygen, solid waste did not exhibit thermal runaway nor flammable combustion. At 0% by volume oxygen, tests results indicated occurrence of self-heating due to slow pyrolysis. A numerical one-dimensional energy model was created to simulate temperature rise in landfill for four different scenarios. Using the results from the laboratory experiment, the model estimated the heat generation in solid waste due to chemical reactions. Results from the scenario simulations indicated that moisture evaporation is the major heat sink in the landfill. The model showed that gas flow has a cooling effect due to increasing amount of evaporated water and can control the temperature inside the landfill. The model showed that a temperature higher than the biological limit can be maintained in the landfill without initiating spontaneous fire.
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Date Issued: 2009
Identifier: CFE0002589, ucf:48275
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002589

Title: Phase transformation and growth kinetics in reaction zone between uranium alloy and zirconium diffusion barrier.
Creator: Park, Young Joo, Sohn, Yongho, Coffey, Kevin, Fang, Jiyu, University of Central Florida
Abstract / Description: U-10wt.%Mo (U10Mo) alloy as a part of monolithic fuel system is being developed under Material Management and Minimization Reactor Conversion (MMMRC) program, tasked with replacing high-enriched uranium (HEU) fuel with low-enriched uranium (LEU) fuel in civilian research and test reactors. Use of U10Mo fuel alloy entails a Zr diffusion barrier to avoid the undesirable interdiffusion and reactions between the U10Mo and Al-alloy cladding. To better understand the interaction between these fuel...
Show moreU-10wt.%Mo (U10Mo) alloy as a part of monolithic fuel system is being developed under Material Management and Minimization Reactor Conversion (MMMRC) program, tasked with replacing high-enriched uranium (HEU) fuel with low-enriched uranium (LEU) fuel in civilian research and test reactors. Use of U10Mo fuel alloy entails a Zr diffusion barrier to avoid the undesirable interdiffusion and reactions between the U10Mo and Al-alloy cladding. To better understand the interaction between these fuel system constituents, microstructural development and diffusion kinetics in U-Mo-Zr, U-Zr and fuel plate assembly processed by co-rolling and hot isostatic pressing (HIP) were investigated using a variety of analytical techniques accompanying scanning electron microscopy and transmission electron microscopy.Phase constituents, microstructure and diffusion kinetics between U10Mo and Zr were examined using solid-to-solid diffusion couples annealed at 650 (&)deg;C for 240, 480 and 720 hours. Concentration profiles were mapped as diffusion paths on the isothermal ternary phase diagram. Within the diffusion zone, single-phase layers of (?U,?Zr) were observed along with a discontinuous layer of Mo2Zr between the ?Zr and ?U layers. In the vicinity of Mo2Zr phase, islands of ?Zr phase were also found. In addition, acicular ?Zr and U6Zr3Mo phases were observed within the ?U(Mo). Growth rate of the interdiffusion-reaction zone was determined to be 1.81 (&)#215; 10-15 m2/sec at 650 (&)deg;C, however with an assumption of a certain incubation period.Investigation for interdiffusion and reaction between U and Zr were carried out using solid-to-solid diffusion couples annealed at 580, 650, 680 and 710 (&)deg;C. The interdiffusion and reaction layer consisted of ?U containing Zr acicular precipitate, ?' (oC4-variant) and (?U,?Zr) solid solution at 650, 680 and 710 (&)deg;C. The ?-UZr2 phase, instead of (?U,?Zr) solid solution phase, was observed in the couple annealed at 580 (&)deg;C. The interdiffusion fluxes and coefficients were determined for the ?U, (?U,?Zr) and ?-UZr2 (580 ?C only) phases using both Sauer-Freise and Boltzmann-Matano analyses. For the ?'-phase with negligible concentration gradient, integrated interdiffusion coefficients were determined via Wagner method. Marker plane was found in (?U,?Zr) (cI2) solid solution from the couples annealed at 650, 680 and 710 (&)deg;C and ?-UZr2 from the couple at 580 (&)deg;C. Intrinsic diffusion coefficients at the compositions corresponding to the marker plane were determined based on Heumann analysis: U intrinsically diffused an order magnitude faster than Zr. Arrhenius temperature-dependence, Darken relation, and comparison to existing literature data demonstrated consistency in results.Monolithic fuel plate assembly was fabricated by sequential process of (1) co-rolling to laminate the Zr barrier onto the U10Mo fuel alloy and (2) HIP to encase the fuel laminated with Zr, within the Al-alloy 6061 (AA6061). In this study, HIP process was carried out as functions of temperature (520, 540, 560 and 580 (&)deg;C for 90 minutes), time (45, 60, 90, 180 and 345 minutes at 560 (&)deg;C) with ramp-cool rate (35, 70 and 280 (&)deg;C/hour). At the interface between the U10Mo and Zr, following the co-rolling, the UZr2 phase was observed to develop adjacent to Zr, and the ?U phase was found between the UZr2 and U10Mo. Mo2Zr was found as precipitates mostly within the ?U phase. Observable growth due to HIP was only observed for the (Al,Si)3Zr phase found at the Zr/AA6061 interface, however, with a large activation energy of 457 kJ/mol. Decomposition of ?U into ?U and ?' was observed in the U10Mo alloy. The volume fraction of ? and ?' increased as the HIP temperature and ramp-cool rate decreased. The UC-UO2 inclusions within the U10Mo fuel alloy were observed, but the volume percent of the UC-UO2 inclusions within the U10Mo alloy, ranging from approximately 0.5 to 1.8, did not change as functions of HIP temperature and holding time. However, the inclusions located near the surface of the U10Mo alloy, were frequently observed to interfere the uniformity of interdiffusion and reaction between the U10Mo alloy and Zr diffusion barrier. The regions of limited interaction between the U10Mo and Zr barrier associated with UC-UO2 inclusions decreased with an increase in HIP temperature, however no significant trend was observed with an increase in HIP duration at 560 (&)deg;C.
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Date Issued: 2016
Identifier: CFE0006371, ucf:51499
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006371

Title: From Excited Charge Dynamics to Cluster Diffusion: Development and Application of Techniques Beyond DFT and KMC.
Creator: Acharya, Shree Ram, Rahman, Talat, Chow, Lee, Stolbov, Sergey, Wu, Annie, University of Central Florida
Abstract / Description: This dissertation focuses on developing reliable and accurate computational techniques which enable the examination of static and dynamic properties of various activated phenomena using deterministic and stochastic approaches. To explore ultrafast electron dynamics in materials with strong electron-electron correlation, under the influence of a laser pulse, an ab initio electronic structure method based on time-dependent density functional theory (TDDFT) in combination with dynamical mean...
Show moreThis dissertation focuses on developing reliable and accurate computational techniques which enable the examination of static and dynamic properties of various activated phenomena using deterministic and stochastic approaches. To explore ultrafast electron dynamics in materials with strong electron-electron correlation, under the influence of a laser pulse, an ab initio electronic structure method based on time-dependent density functional theory (TDDFT) in combination with dynamical mean field theory (DMFT) is developed and applied to: 1) single-band Hubbard model; 2) multi-band metal Ni; and 3) multi-band insulator MnO. The ultrafast demagnetization in Ni reveal the importance of memory and correlation effects, leading to much better agreement with experimental data than previously obtained, while for MnO the main channels of charge response are identified. Furthermore, an analytical form of the exchange-correlation kernel is obtained for future applications, saving tremendous computational cost. In another project, size-dependent temporal and spatial evolution of homo- and hetero-epitaxial adatom islands on fcc(111) transition metals surfaces are investigated using the self-learning kinetic Monte Carlo (SLKMC) method that explores long-time dynamics unbiased by apriori selected diffusion processes. Novel multi-atom diffusion processes are revealed. Trends in the diffusion coefficients point to the relative role of adatom lateral interaction and island-substrate binding energy in determining island diffusivity. Moreover, analysis of the large data-base of the activation energy barriers generated for multitude of diffusion processes for variety of systems allows extraction of a set of descriptors that in turn generate predictive models for energy barrier evaluation. Finally, the kinetics of the industrially important methanol partial oxidation reaction on a model nanocatalyst is explored using KMC supplemented by DFT energetics. Calculated thermodynamics explores the active surface sites for reaction components including different intermediates and energetics of competing probable reaction pathways, while kinetic study attends to the selectivity of products and its variation with external factors.
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Date Issued: 2018
Identifier: CFE0006965, ucf:52910
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006965

Title: DRIVER-GAS TAILORING FOR TEST-TIME EXTENSION USING UNCONVENTIONAL DRIVER MIXTURES.
Creator: Amadio, Anthony, Petersen, Eric, University of Central Florida
Abstract / Description: To study combustion chemistry at low temperatures in a shock tube, it is of great importance to increase experimental test times, and this can be done by tailoring the interface between the driver and driven gases. Using unconventional driver-gas tailoring with the assistance of tailoring curves, shock-tube test times were increased from 1 to 15 ms for reflected-shock temperatures below 1000 K. Provided in this thesis is the introduction of tailoring curves, produced from a 1-D perfect gas...
Show moreTo study combustion chemistry at low temperatures in a shock tube, it is of great importance to increase experimental test times, and this can be done by tailoring the interface between the driver and driven gases. Using unconventional driver-gas tailoring with the assistance of tailoring curves, shock-tube test times were increased from 1 to 15 ms for reflected-shock temperatures below 1000 K. Provided in this thesis is the introduction of tailoring curves, produced from a 1-D perfect gas model for a wide range of driver gases and the production and demonstration of successful driver mixtures containing helium combined with either propane or carbon dioxide. The He/CO2 and He/C3H8 driver mixtures provide a unique way to produce a tailored interface and, hence, longer test times, when facility modification is not an option. The tailoring curves can be used to guide future applications of this technique to other configurations. Nonreacting validation experiments using driver mixtures identified from the tailoring curves were performed over a range of reflected-shock temperatures from approximately 800 to 1400 K, and some examples of ignition-time experiments that could not have otherwise been performed are presented.
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Date Issued: 2006
Identifier: CFE0001318, ucf:47027
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001318

Title: PHASE-FIELD SIMULATION OF MICROSTRUCTURALDEVELOPMENT INDUCED BY INTERDIFFUSIONFLUXES UNDER MULTIPLE GRADIENTS.
Creator: Mohanty, Rashmi, Sohn, Yongho, University of Central Florida
Abstract / Description: The diffuse-interface phase-field model is a powerful method to simulate and predict mesoscale microstructure evolution in materials using fundamental properties of thermodynamics and kinetics. The objective of this dissertation is to develop phase-field model for simulation and prediction of interdiffusion behavior and evolution of microstructure in multi-phase binary and ternary systems under composition and/or temperature gradients. Simulations were carried out with emphasis on...
Show moreThe diffuse-interface phase-field model is a powerful method to simulate and predict mesoscale microstructure evolution in materials using fundamental properties of thermodynamics and kinetics. The objective of this dissertation is to develop phase-field model for simulation and prediction of interdiffusion behavior and evolution of microstructure in multi-phase binary and ternary systems under composition and/or temperature gradients. Simulations were carried out with emphasis on multicomponent diffusional interactions in single-phase system, and microstructure evolution in multiphase systems using thermodynamics and kinetics of real systems such as Ni-Al and Ni-Cr-Al. In addition, selected experimental studies were carried out to examine interdiffusion and microstructure evolution in Ni-Cr-Al and Fe-Ni-Al alloys at 1000C. Based on Onsager's formalism, a phase-field model was developed for the first time to simulate the diffusion process under an applied temperature gradient (i.e., thermotransport) in single- and two-phase binary alloys. Development of concentration profiles with uphill diffusion and the occurrence of zero-flux planes were studied in single-phase diffusion couples using a regular solution model for a hypothetical ternary system. Zero-flux plane for a component was observed to develop for diffusion couples at the composition that corresponds to the activity of that component in one of the terminal alloys. Morphological evolution of interphase boundary in solid-to-solid two-phase diffusion couples (fcc- vs. B2-) was examined in Ni-Cr-Al system with actual thermodynamic data and concentration dependent chemical mobility. With the instability introduced as a small initial compositional fluctuation at the interphase boundary, the evolution of the interface morphology was found to vary largely as a function of terminal alloys and related composition-dependent chemical mobility. In a binary Ni-Al system, multiphase diffusion couples of fcc- vs. L12-,  vs. and  vs.  were simulated with alloys of varying compositions and volume fractions of second phase (i.e., ). Chemical mobility as a function of composition was employed in the study with constant gradient energy coefficient, and their effects on the final interdiffusion microstructure was examined. Interdiffusion microstructure was characterized by the type of boundaries formed, i.e. Type 0, Type I, and Type II boundaries, following various experimental observations in literature and thermodynamic considerations. Volume fraction profiles of alloy phases present in the diffusion couples were measured to quantitatively analyze the formation or dissolution of phases across the boundaries. Kinetics of dissolution of  phase was found to be a function of interdiffusion coefficients that can vary with composition and temperature. The evolution of interdiffusion microstructures in ternary Ni-Cr-Al solid-to-solid diffusion couples containing fcc- and + (fcc+B2) alloys was studied using a 2D phase-field model. Alloys of varying compositions and volume fractions of the second phase () were used to simulate the dissolution kinetics of the  phase. Semi-implicit Fourier-spectral method was used to solve the governing equations with chemical mobility as a function of compositions. The simulation results showed that the rate of dissolution of the  phase (i.e., recession of  two-phase region) was dependent on the composition of the single-phase  alloy and the volume fraction of the  phase in the two-phase alloy of the couple. Higher Cr and Al content in the  alloy and higher volume fraction of  in the  alloy lower the rate of dissolution. Simulated results were found to be in good agreement with the experimental observations in ternary Ni-Cr-Al solid-to-solid diffusion couples containing  and  alloys. For the first time, a phase-field model was developed to simulate the diffusion process under an applied temperature gradient (i.e., thermotransport) in multiphase binary alloys. Starting from the phenomenological description of Onsager's formalism, the field kinetic equations are derived and applied to single-phase and two-phase binary system. Simulation results show that a concentration gradient develops due to preferential movement of atoms towards the cold and hot end of an initially homogeneous single-phase binary alloy subjected to a temperature gradient. The temperature gradient causes the redistribution of both constituents and phases in the two-phase binary alloy. The direction of movement of elements depends on their atomic mobility and heat of transport values.
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Date Issued: 2009
Identifier: CFE0002515, ucf:47658
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002515

Title: AN INVESTIGATION OF THE AUTOIGNITION OF POWER GENERATION GAS TURBINE FUEL BLENDS USING A DESIGN OF EXPERIMENTS APPROACH.
Creator: de Vries, Jaap, Petersen, Eric, University of Central Florida
Abstract / Description: Natural gas has grown in popularity as a fuel for power generation gas turbines. However, changes in fuel composition are a topic of concern since fuel variability can have a great impact on the reliability and performance of the burner design. In particular, autoignition of the premixed fuel and air prior to entering the main burner is a potential concern when using exotic fuel blends. To obtain much-needed data in this area, autoignition experiments for a wide range of likely fuel blends...
Show moreNatural gas has grown in popularity as a fuel for power generation gas turbines. However, changes in fuel composition are a topic of concern since fuel variability can have a great impact on the reliability and performance of the burner design. In particular, autoignition of the premixed fuel and air prior to entering the main burner is a potential concern when using exotic fuel blends. To obtain much-needed data in this area, autoignition experiments for a wide range of likely fuel blends containing CH4 mixed with combinations of C2H6, C3H8, C4H10, C5H12, and H2 were performed in a high-pressure shock tube. However, testing every possible fuel blend combination and interaction was not feasible within a reasonable time and cost. Therefore, to predict the surface response over the complete mixture domain, a special experimental design was developed to significantly reduce the amount of 'trials' needed from 243 to only 41 using the Box-Behnkin factorial design methodology. Kinetics modeling was used to obtain numerical results for this matrix of fuel blends, setting the conditions at a temperature of 800 K and pressure of 17 atm. A further and successful attempt was made to reduce the 41-test matrix to a 21-test matrix. This was done using special mixture experimental techniques. The kinetics model was used to compare the smaller matrix to the expected results of the larger one. The new 21-test matrix produced a numerical correlation that agreed well with the results from the 41-test matrix, indicating that the smaller matrix would provide the same statistical information as the larger one with acceptable precision. iii After the experimental matrix was developed using the design of experiments approach, the physical experiments were performed in the shock tube. Long test times were created by "tailoring" the shock tube using a novel driver gas mixture, obtaining test times of 10 millisecond or more, which made experiments at low temperatures possible. Large discrepancies were found between the predicted results by numerical models and the actual experimental results. The main conclusion from the experiments is that the methane-based mixtures in this study enter a regime with a negative temperature coefficient when plotted in Arhennius form. This means that these mixtures are far more likely to ignite under conditions frequently encountered in a premixer, potentially creating hazardous situations. The experimental results were correlated as a function of the different species. It was found that the effect of higher-order hydrocarbon addition to methane is not as profound as seen at higher temperatures (>1100 K). However, the ignition delay time could still be reduced by a factor two or more. It is therefore evident that potential autoignition could occur within the premixer, given the conditions as stated in this study.
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Date Issued: 2005
Identifier: CFE0000817, ucf:46684
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0000817

Title: Nanoscale Characterization and Mechanism of Electroless Deposition of Silver Metal.
Creator: Grabill, Christopher, Kuebler, Stephen, Beazley, Melanie, Zou, Shengli, Frazer, Andrew, Bhattacharya, Aniket, University of Central Florida
Abstract / Description: This dissertation is an investigation of the nanoscale characteristics and mechanism of electrolessly deposited silver metal seeded by gold nanoparticles. The process of growing seed-nanoparticles on a polymer surface was studied. Several bifunctional amines and organic reducing agents were used to explore how these chemical factors affect the size and distribution of gold nanoparticles formed at the interface. The nanoparticles were characterized by transmission electron microscopy (TEM) and...
Show moreThis dissertation is an investigation of the nanoscale characteristics and mechanism of electrolessly deposited silver metal seeded by gold nanoparticles. The process of growing seed-nanoparticles on a polymer surface was studied. Several bifunctional amines and organic reducing agents were used to explore how these chemical factors affect the size and distribution of gold nanoparticles formed at the interface. The nanoparticles were characterized by transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). An electroless deposition (ED) bath developed by Danscher was selected to study electroless deposition of silver in detail. The chemical species in the bath were varied to determine how concentration, nature of the carboxylate buffering species, and the presence and absence of gum arabic affect the morphology of silver metal formed by ED and the overall rate of deposition at the surface. The kinetics of deposition using the Danscher bath was studied in detail to elucidate the mechanism of ED. Knowledge generated from this investigation can be used to expand applications of silver ED where strict control over the nanoscale morphology of the deposited metal is required to obtain specific chemical and physical properties.
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Date Issued: 2018
Identifier: CFE0007009, ucf:52051
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007009

Title: A study of organo-phosphorous simulants thermal destruction using shock tube/laser diagnostics techniques and chemical kinetics modeling.
Creator: Neupane, Sneha, Vasu Sumathi, Subith, Kassab, Alain, Chow, Louis, Peale, Robert, University of Central Florida
Abstract / Description: High-fidelity chemical kinetic models are critical in predictive modeling during design and optimization of next generation energy systems. Shock tube provides an ideal tool to investigate high-temperature chemical kinetics. Non-intrusive laser absorption diagnostics provide in-situ measurements of quantitative, time-resolved species concentration data in this complex chemically reacting system. In this work, shock tube and laser absorption spectroscopy were utilized to measure species...
Show moreHigh-fidelity chemical kinetic models are critical in predictive modeling during design and optimization of next generation energy systems. Shock tube provides an ideal tool to investigate high-temperature chemical kinetics. Non-intrusive laser absorption diagnostics provide in-situ measurements of quantitative, time-resolved species concentration data in this complex chemically reacting system. In this work, shock tube and laser absorption spectroscopy were utilized to measure species concentration time-histories during pyrolysis and oxidation of organo-phosphorous compounds (OPCs). The experiments data obtained were used as benchmark to develop an improved kinetic model of OPCs combustion. Interest in combustion chemistry of OPCs is associated to their use as fire suppressants and as chemical weapons. Pyrolysis and oxidation of OPCs were carried out behind reflected shock wave and laser absorption spectroscopy utilizing quantum cascade laser at mid-IR wavelength region was used to measure time resolved intermediate CO concentration produced during the process. Utilizing the experiments data, an improved chemical kinetic model for combustion of an OPC (-) Triethyl Phosphate (TEP) was developed. Various steps taken to develop the improved model include: calculation of thermochemical properties; updating hydrocarbon kinetics; calculation of reaction rates and addition of alternative TEP decomposition pathways. The prediction of TEP combustion, in terms intermediate CO concentration yield during its pyrolysis and oxidation, made by the improved model is in much better agreement with the experiments. Such an accurate kinetic model is critical in predicting the effectiveness of OPCs as flame retardants when used as dopants in hydrocarbon fuels; and in devising counter weapon of mass destruction strategies to destroy chemical weapons.
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Date Issued: 2019
Identifier: CFE0007691, ucf:52444
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007691

Title: COMPARATIVE STUDY OF ETHANOL AND METHANOL ELECTRO-OXIDATION ON A PLATINUM/CERIA COMPOSITE ELECTRODE IN ALKALINE AND ACID SOLUTIONS: ELECTRO-CATALYTIC PERFORMANCE AND REACTION KINETICS.
Creator: Hidalgo, Carlos, Diaz, Diego, University of Central Florida
Abstract / Description: A comparative study of the electro-oxidation of ethanol and methanol was carried out on a Pt/ceria composite electrode prepared by electro-deposition. Modification of the Pt electrode was realized by co-deposition from a 1.0 mM K2PtCl6 solution that also contained a 20 mM suspension of ceria. The electro-catalytic activities and stabilities of the Pt/ceria catalyst towards ethanol electro-oxidation reactions (EOR) and methanol electro-oxidation reactions (MOR) were investigated by...
Show moreA comparative study of the electro-oxidation of ethanol and methanol was carried out on a Pt/ceria composite electrode prepared by electro-deposition. Modification of the Pt electrode was realized by co-deposition from a 1.0 mM K2PtCl6 solution that also contained a 20 mM suspension of ceria. The electro-catalytic activities and stabilities of the Pt/ceria catalyst towards ethanol electro-oxidation reactions (EOR) and methanol electro-oxidation reactions (MOR) were investigated by potentiodynamic and potentiostatic methods in 0.5 M sulfuric acid and 1.0 M sodium hydroxide solutions at various concentrations of ethanol and methanol. The kinetics of ethanol and methanol on a Pt/ceria composite electrode were measured in 0.5 M sulfuric acid and 1.0 M sodium hydroxide solutions using a rotating disk electrode (RDE). Cyclic voltammetry was employed in temperatures ranging from 15 to 55°C to provide quantitative and qualitative information on the kinetics of alcohol oxidation. The temperature dependence of the electro-catalytic activities afforded the determination of apparent activation energies for ethanol and methanol oxidation.
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Date Issued: 2011
Identifier: CFE0003628, ucf:48853
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0003628

Title: Combustion kinetics of advanced biofuels.
Creator: Barari, Ghazal, Vasu Sumathi, Subith, Kapat, Jayanta, Kassab, Alain, Masunov, Artem, University of Central Florida
Abstract / Description: Use of biofuels, especially in automotive applications, is a growing trend due to their potential to lower greenhouse gas emissions from combustion. Ketones are a class of biofuel candidates which are produced from cellulose. However, ketones received rather scarce attention from the combustion community compared to other classes such as, alcohols, esters, and ethers. There is little knowledge on their combustion performance and pollutant generation. Hence their combustion chemistry needs to...
Show moreUse of biofuels, especially in automotive applications, is a growing trend due to their potential to lower greenhouse gas emissions from combustion. Ketones are a class of biofuel candidates which are produced from cellulose. However, ketones received rather scarce attention from the combustion community compared to other classes such as, alcohols, esters, and ethers. There is little knowledge on their combustion performance and pollutant generation. Hence their combustion chemistry needs to be investigated in detail. Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. A detailed understanding of the combustion kinetics of the oxidation of DIPK in advanced engines such as, the homogeneous charge compression ignition (HCCI) engine is warranted. This dissertation concentrates on the combustion kinetics of DIPK over a wide range of temperature and pressure with a focus on HCCI engine application.An existing DIPK kinetic mechanism has been reviewed and a single zone HCCI engine model has been modeled and validated against recent experimental data from Sandia National Lab. Therefore different HCCI modeling assumptions were tested and the DIPK reaction mechanism was modified with missing reactions and the required thermochemical data. As a result, the HCCI pressure trace, heat release rate and reactivity have been improved. In order to improve the ignition delay time simulation results, the low temperature oxidation of DIPK was studied as the fuel chemistry effects on the autoignition behavior becomes important in low temperature. Therefore DIPK low temperature oxidation experimental data was obtained from the synchrotron photoionization experiments conducted at the Advanced Light Source (ALS) so that the primary products as well as the dominant oxidation pathways are identified. Furthermore, the aldehydes oxidation, as a result of partial or incomplete combustion and as the primary stable intermediate products in oxidation and pyrolysis of biofuel were studied at low temperature in ALS. A high temperature reaction mechanism was created using the reaction class approach. The reaction mechanism for DIPK was improved using the experimental data along with quantum chemical calculation of activation energies and barriers as well as vibrational modes for the important reactions identified in ALS experiment. The rate constants for important reactions were calculated based on modified Arrhenius equation. DIPK oxidation and pyrolysis were studied at high temperature and pressure using UCF shock tube. The ignition delay times as well as the product (methane) time histories were investigated and used as validation targets for the new model.
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Date Issued: 2015
Identifier: CFE0005921, ucf:50847
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005921

Title: An Improved Biosolid Gasifier Model.
Creator: McLean, Hannah, Cooper, David, Randall, Andrew, Lee, Woo Hyoung, University of Central Florida
Abstract / Description: As populations increase and cities become denser, the production of waste, both sewage sludge and food biomass, increases exponentially while disposal options for these wastes are limited. Landfills have minimal space for biosolids; countries are now banning ocean disposal methods for fear of the negative environmental impacts. Agricultural application of biosolids cannot keep up with the production rates because of the accumulation of heavy metals in the soils. Gasification can convert...
Show moreAs populations increase and cities become denser, the production of waste, both sewage sludge and food biomass, increases exponentially while disposal options for these wastes are limited. Landfills have minimal space for biosolids; countries are now banning ocean disposal methods for fear of the negative environmental impacts. Agricultural application of biosolids cannot keep up with the production rates because of the accumulation of heavy metals in the soils. Gasification can convert biosolids into a renewable energy source that can reduce the amount of waste heading to the landfills and reduce our dependence on fossil fuels. A recently published chemical kinetic computer model for a fluidized-bed sewage sludge gasifier (Champion, Cooper, Mackie, (&) Cairney, 2014) was improved in this work based on limited experimental results obtained from a bubbling fluidized-bed sewage sludge gasifier at the MaxWest facility in Sanford, Florida and published information from the technical literature. The gasifier processed sewage sludge from the communities surrounding Sanford and was operated at various air equivalence ratios and biosolid feed rates. The temperature profile inside of the gasifier was recorded over the span of four months, and an average profile was used in the base case scenario. The improved model gave reasonable predictions of the axial bed temperature profile, syngas composition, heating value of the syngas, gas flow rate, and carbon conversion. The model was validated by comparing the simulation temperature profile data with the measured temperature profile data. An overall heat loss coefficient was calculated for the gasification unit to provide a more accurate energy balance. Once the model was equipped with a heat loss coefficient, the output syngas temperature closely matched the operational data from the MaxWest facility.The model was exercised at a constant equivalence ratio at varying temperatures, and again using a constant temperature with varying equivalence ratios. The resulting syngas compositions from these exercises were compared to various literature sources. It was decided that some of the reactions kinetics needed to be adjusted so that the change in syngas concentration versus change in bed temperature would more closely match the literature. The reaction kinetics for the Water-Gas Shift and Boudouard reactions were modified back to their original values previously obtained from the literature.
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Date Issued: 2015
Identifier: CFE0005663, ucf:50199
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005663

Title: A KINETICS STUDY OF SELECTED FILTRATION MEDIA FOR NUTRIENT REMOVAL AT VARIOUS TEMPERATURES.
Creator: Henderson, Elizabeth, Chang, Ni-Bin, University of Central Florida
Abstract / Description: In recent years the nutrient levels of the Upper Floridan aquifer have been increasing (USGS, 2008). An example of this is found in Ocala, Florida where Silver Springs nitrate concentrations have risen from 0.5 mg/L in the 1960's to approximately 1.0 mg/L in 2003 (Phelps, 2004). Because stormwater is a contributor to surficial and groundwater aquifer recharge, there is an increasing need for methods that decrease nitrogen and phosphorus levels. A laboratory column study was conducted to...
Show moreIn recent years the nutrient levels of the Upper Floridan aquifer have been increasing (USGS, 2008). An example of this is found in Ocala, Florida where Silver Springs nitrate concentrations have risen from 0.5 mg/L in the 1960's to approximately 1.0 mg/L in 2003 (Phelps, 2004). Because stormwater is a contributor to surficial and groundwater aquifer recharge, there is an increasing need for methods that decrease nitrogen and phosphorus levels. A laboratory column study was conducted to simulate a retention pond with saturated soil conditions. The objectives of the column studies reported in this thesis were to investigate the capabilities of a natural soil and soil augmentations to remove nitrogen and phosphorus for a range of concentrations at three different temperatures. An analytical attempt to model the columns through low order reaction kinetics and derive the corresponding temperature conversion constant to relate the rate constants is also presented. The Media Mixes were selected through a process of research, preliminary batch testing and then implemented in column studies. Three columns measuring three feet in length and 6 inches outer diameter were packed with a control and two media mixes. Media Mix 1 consisted of 50% fine sand, 30% tire crumb, 20% sawdust by weight and Media Mix 2 consisted of 50% fine sand, 25% sawdust, 15% tire crumb, 10% limestone by weight. The control column was packed with natural soil from Hunter's Trace retention pond located in Ocala, Florida. The reaction rates for nitrate are best modeled as first order for Media Mix 1, and zero order for the Control and Media Mix 2. The reaction rates for orthophosphate are best modeled as zero order, second order and first order for the Control, Media Mix 1, and Media Mix 2 respectively. The best overall media for both nitrate and orthophosphate removal from this study would be Media Mix 1. Media Mix 2 does have the highest average orthophosphate removal of all the mixes for all of the temperatures; however Media Mix 1 outperforms Mix 2 for the other two temperatures. The best column for Nitrate removal is the Media Mix 1 column. The temperature conversion factors for nitrate were found to be 1.11, 1.1, and 1.01 for Media Mix 1, the Control and Media Mix 2 respectively. The temperature conversion factors for orthophosphate were found to be 1.02, 0.99, and 0.95. As well as temperature conversion factors, the activation energies and frequency factors for the Arrhenius Equation were investigated. Average values corresponding to each column, species, and temperature would be inaccurate due to the large variation in calculated values.
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Date Issued: 2008
Identifier: CFE0002458, ucf:47727
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002458

Title: THE RISKS AND BENEFITS OF RUNNING BAREFOOT OR IN MINIMALIST SHOES: A SYSTEMATIC REVIEW.
Creator: Perkins, Kyle, Rothschild, Carey, University of Central Florida
Abstract / Description: The popularity of running barefoot or in minimalist shoes has notably increased in the last decade due to claims of injury prevention, enhanced running efficiency, and improved performance when compared to running in shoes (shod). A systematic review of the literature was performed using the Downs and Black checklist to assess the methodological quality of studies proposing risks or benefits between running barefoot, shod, or in minimalist shoes. The databases Ovid MEDLINE, SPORTDiscus, and...
Show moreThe popularity of running barefoot or in minimalist shoes has notably increased in the last decade due to claims of injury prevention, enhanced running efficiency, and improved performance when compared to running in shoes (shod). A systematic review of the literature was performed using the Downs and Black checklist to assess the methodological quality of studies proposing risks or benefits between running barefoot, shod, or in minimalist shoes. The databases Ovid MEDLINE, SPORTDiscus, and CINAHL were searched using keywords or "Booleans" including: "Barefoot", "Running" and "Minimalist," exclusively. All included articles were obtained from peer reviewed journals in the English language with a link to full text and no limit for year of publication. The final selection was made based on inclusion of at least one of the following outcome variables: pain, injury rate, running economy, joint forces, running velocity, electromyography, muscle performance, or edema. Significant results were gathered from identified articles and compared using "Levels of Evidence" by Furlan et al. Twenty-three publications were identified and rated for quality assessment in September 2013. Out of 27 possible points on the Downs and Black checklist, all articles scored between 13 and 19 points with a mean of 17.4. Evidence from the articles ranged from very limited to moderate. Moderate evidence suggested overall less maximum vertical ground reaction forces, less extension moment and power absorption at the knee, less foot and ankle dorsiflexion at ground contact, less ground contact time, shorter stride length, increased stride frequency (cadence), as well as increased knee flexion at ground contact in barefoot running compared to shod. The low scores from the quality assessment using the Downs and Black checklist indicates that improved methodological quality is necessary to provide strong evidence comparing the risks and benefits of running barefoot, shod, and in minimalist shoes. The literature between shod, minimalist, and barefoot running is inconclusive. There is limited evidence showing differences in kinematics, kinetics, electromyography, and economy results in minimalist shoes. Thus, an alternative and suitable method to effectively replicate barefoot running has not yet been determined.
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Date Issued: 2013
Identifier: CFH0004532, ucf:45194
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFH0004532

Title: Development of a chemical kinetic model for the combustion of a synthesis gas from a fluidized-bed sewage sludge gasifier in a thermal oxidizer.
Creator: Martinez, Luis, Cooper, David, Randall, Andrew, Vasu Sumathi, Subith, University of Central Florida
Abstract / Description: The need for sustainability has been on the rise. Municipalities are finding ways of reducing waste, but also finding ways to reduce energy costs. Waste-to-energy is a sustainable method that may reduce bio-solids volume while also producing energy. In this research study bio-solids enters a bubbling bed gasifier and within the gasifier a synthesis gas is produced. This synthesis gas exits through the top of the gasifier and enters a thermal oxidizer for combustion. The thermal oxidizer has...
Show moreThe need for sustainability has been on the rise. Municipalities are finding ways of reducing waste, but also finding ways to reduce energy costs. Waste-to-energy is a sustainable method that may reduce bio-solids volume while also producing energy. In this research study bio-solids enters a bubbling bed gasifier and within the gasifier a synthesis gas is produced. This synthesis gas exits through the top of the gasifier and enters a thermal oxidizer for combustion. The thermal oxidizer has an innovative method of oxidizing the synthesis gas. The thermal oxidizer has two air injection sites and the possibility for aqueous ammonia injection for further NOx reduction. Most thermal oxidizers already include an oxidizer such as air in the fuel before it enters the thermal oxidizer; thus making this research and operation different from many other thermal oxidizers and waste-to-energy plants.The reduction in waste means less volume loads to a landfill. This process significantly reduces the amount of bio-solids to a landfill. The energy produced from the synthesis is beneficial for any municipality, as it may be used to run the waste-to-energy facility. The purpose of this study is to determine methods in which operators may configure future plants to reduce NOx emissions. NOx mixed with volatile organic compounds (VOC) and sunlight, produce ozone (O3) a deadly gas at high concentrations.This study developed a model to determine the best methods to reduce NOx emissions. Results indicate that a fuel-rich then fuel-lean injection scheme results in lower NOx emissions. This is because at fuel-rich conditions not all of the ammonia in the first air ring is converted to NOx, but rather a partial of the ammonia is converted to NOx and N2 and then the second air ring operates at fuel-lean which further oxidizes the remaining ammonia which converts to NOx, but also a fraction to N2. If NOx standards reach more stringency then aqueous ammonia injection is a recommended method for NOx reduction; this method is also known as selective non-catalytic reduction (SNCR).The findings in this study will allow operators to make better judgment in the way that they operate a two air injection scheme thermal oxidizer. The goal of the operator and the organization is to meet air quality standards and this study aims at finding ways to reduce emissions, specifically NOx.
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Date Issued: 2014
Identifier: CFE0005528, ucf:50301
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005528

Title: Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid.
Creator: Franco, Carolina, Yestrebsky, Cherie, Clausen, Christian, Rex, Matthew, Harper, James, Duranceau, Steven, University of Central Florida
Abstract / Description: Alpha-ketoglutaric acid (AKGA) is an organic acid important for the metabolism of essential amino acids as well as for the transfer of cellular energy. It is a precursor of glutamic acid which is produced by the human body during the Krebs Cycle. AKGA has a specific industrial interest as it can be taken as a dietary supplement and is also widely used as a building block in chemical synthesis.Collectively termed as hydrazine (HZs), hydrazine (HZ) and monomethylhydrazine (MMH) are hypergolic...
Show moreAlpha-ketoglutaric acid (AKGA) is an organic acid important for the metabolism of essential amino acids as well as for the transfer of cellular energy. It is a precursor of glutamic acid which is produced by the human body during the Krebs Cycle. AKGA has a specific industrial interest as it can be taken as a dietary supplement and is also widely used as a building block in chemical synthesis.Collectively termed as hydrazine (HZs), hydrazine (HZ) and monomethylhydrazine (MMH) are hypergolic fuels that do not need an ignition source to burn. Because of the particular HZs' characteristics the National Aeronautics and Space Administration (NASA) at Kennedy Space Center (KSC) and the US Air Force at Cape Canaveral Air Force Station (CCAFS) consistently use HZ and MMH as hypergolic propellants. These propellants are highly reactive and toxic, and have carcinogenic properties. The handling, transport, and disposal of HZ waste are strictly regulated under the Resource Conservation and Recovery Act (RCRA) to protect human health and the environment. Significant quantities of wastewater containing residuals of HZ and MMH are generated at KSC and CCAFS that are subsequently disposed off-site as hazardous waste. This hazardous waste is shipped for disposal over public highways, which presents a potential threat to the public and the environment in the event of an accidental discharge in transit. NASA became aware of research done using AKGA to neutralize HZ waste. This research indicated that AKGA transformed HZ in an irreversible reaction potentially leading to the disposal of the hypergols via the wastewater treatment facility located at CCAFS eliminating the need to transport most of the HZ waste off-site.New Mexico Highlands University (NMHU) has researched this transformation of HZ by reaction with AKGA to form stabilized pyridazine derivatives. NMHU's research suggests that the treatment of HZ and MMH using AKGA is an irreversible reaction; once the reaction takes place, HZ and/or MMH cannot re-form from the byproducts obtained. However, further knowledge relating to the ultimate end products of the reaction, and their effects on human health and the environment, must still be addressed. The known byproduct of the AKGA/HZ neutralization reaction is 6-oxo-1,4,5,6-tetrahydro-pyridazine-3-carboxylic acid (PCA), and the byproduct of the AKGA/MMH reaction is 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA).This research addressed several primary areas of interest to further the potential use of AKGA for HZ and MMH neutralization: 1) isolation of the end-product of the MMH-AKGA degradation process, 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA), and determination of several physical properties of this substance, 2) evaluation of the kinetics of the reaction of AKGA with HZ or MMH, 3) verification of the chemical mechanism for the reaction of the individual hypergols with AKGA, 4) determination of whether the addition of a silicone-based antifoaming agent (AF), citric acid (CA) and/or isopropyl alcohol (IPA) to the AKGA and HZ or MMH solution interferes with the degradation reaction, 4) application of laboratory bench scale experiments in field samples, and 5) determination of the reaction enthalpy of these reactions.
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Date Issued: 2014
Identifier: CFE0005493, ucf:50334
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005493

kinetics (7)	+ -
chemical kinetics (5)	+ -
shock tube (4)	+ -
Combustion (2)	+ -
Fast/ Equilibrium Reactions (2)	+ -

Finite Element Method (2)	+ -
Fully-implicit (2)	+ -
Gasification (2)	+ -
Kinetic-Variable (2)	+ -
Lagrangian-Eulerian approach (2)	+ -
Modeling (2)	+ -
Operator-splitting (2)	+ -
Predictor-corrector (2)	+ -
Reactive Chemical Transport (2)	+ -
Slow/Kinetic Reactions (2)	+ -
combustion (2)	+ -
gasifier (2)	+ -
interdiffusion (2)	+ -
2D Materials (1)	+ -
Air Quality (1)	+ -
Art (1)	+ -
Assembly kinetics (1)	+ -
Bay/Estuary Model (1)	+ -
Biophysics (1)	+ -
Boudouard (1)	+ -
Catalysis (1)	+ -
Chemical Kinetic Modeling (1)	+ -
Chemical Kinetics (1)	+ -
Chemical Oxidation Kinetics (1)	+ -
Density functional theory (1)	+ -

ETD Collection (23)	+ -
Honors Collection (2)	+ -

University of Central Florida (25)	+ -
Randall, Andrew (4)	+ -
Vasu Sumathi, Subith (4)	+ -
Kassab, Alain (3)	+ -
Petersen, Eric (3)	+ -

Cooper, David (2)	+ -
Kapat, Jayanta (2)	+ -
Rahman, Talat (2)	+ -
Sohn, Yongho (2)	+ -
Yeh, Gour-Tsyh (2)	+ -
Zou, Shengli (2)	+ -
Acharya, Shree Ram (1)	+ -
Adams, JoAnne (1)	+ -
Ahmed, Kareem (1)	+ -
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