Matching Items (8)
Filtering by
- Creators: Barrett, The Honors College
- Status: Published
Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
Description
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Quercetin 2,3-dioxygenase from Bacillus subtilis has been identified and characterized as the first known prokaryotic quercetinase. This enzyme catalyzes the cleavage of the O-heteroaromatic ring of the flavonol quercetin to the corresponding depside and carbon monoxide. The first quercetinase was characterized from a species of Aspergillus genus, and was found to contain one Cu2+ per subunit. For many years, it was thought that the B. subtilis quercetinase contained two Fe2+ ions per subunit; however, it has since been discovered that Mn2+ is a much more likely cofactor. Studies of overexpressed bacterial enzyme in E. coli indicated that this enzyme may be active with other metal ions (e.g. Co2+); however, the production of enzyme with full metal incorporation has only been possible with Mn2+. This study explores the notion that metal manipulation after translation, by partially unfolding the enzyme, chelating the metal ions, and then refolding the protein in the presence of an excess of divalent metal ions, could generate enzyme with full metal occupancy. The protocols presented here included testing for activity after incubating purified quercetinase with EDTA, DDTC, imidazole and GndHCl. It was found that the metal chelators had little to no effect on quercetinase activity. Imidazole did appear to inhibit the enzyme at concentrations in the millimolar range. In addition, the quercetinase was denatured in GndHCl at concentrations above 1 M. Recovering an active enzyme after partial or complete unfolding proved difficult, if not impossible.
ContributorsKrojanker, Elan Daniel (Author) / Francisco, Wilson (Thesis director) / Allen, James P. (Committee member) / Barrett, The Honors College (Contributor) / Department of Chemistry and Biochemistry (Contributor)
Created2014-05
Description
Additive Manufacturing and 3D printing are becoming important technologies in the manufacturing sector. The benefits of this technology include complex part geometry, short lead-times, low waste, and simple user interface. However, the technology does not come without its drawbacks: mainly the removal of support structures from the component. Traditional techniques that involve sawing and cutting can be expensive and take a long time, increasing the overall price of 3D printed metal components. This paper discusses two approaches taken for dissolvable support structures in 3D printed stainless steel (17-4 PH). For the first time in powder bed fusion components, with the help of Christopher Lefky and Dr. Owen Hildreth, dissolvable support capabilities are achieved in metal prints. The first approach, direct dissolution, involves direct corrosion of the entire part, leading to support removal. This approach is not self-terminating, and leads to changes in final component geometry. The second approach involves a post-build sensitization step, which physically alters the microstructure and chemical stability of the first 100-200 microns of the metal. The component is then etched at an electric potential that will readily corrode this sensitized surface, but not the underlying base metal. An electrolytic solution of HNO3/KCl/HCl paired with an anodic bias was used for the direct dissolution approach, resulting in a loss of about 120 microns of material from the components surface. For the self-limiting approach, surface sensitization was achieve through a post build annealing step (800 C for 6 hours, air cooled) with exposure to a sodium hexacynoferrate slurry. When the slurry decomposes in the furnace, carbon atoms diffuse into the surface and precipitate a chromium-carbide, which reduces the chemical stability of the stainless steel. Etching is demonstrated in an anodic bias of HNO3/KCl. To determine proper etching potentials, open circuit potential and cyclic voltammetry experiments were run to create Potentiodynamic Polarization Curves. Further testing of the self-terminating approach was performed on a 316 stainless steel interlocking ring structure with a complex geometry. In this case, 32.5 hours of etching at anodic potentials replaced days of mechanical sawing and cutting.
ContributorsZucker, Brian Nicholas (Co-author) / Lefky, Christopher (Co-author) / Hildreth, Owen (Co-author, Thesis director) / Hsu, Keng (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
This project sought to analyze the effects of recycling Inconel 718 powder for Direct Metal Laser Sintering (DMSL) for additive manufacturing by testing low cycle fatigue tensile samples ranging from virgin to ten times recycled. Fracture generally occurs at the sample surface where persistent slip planes form and accumulate to cause a sudden fracture leading to signature markings for various phases of crack growth. Effects caused by contamination would be found in the first region of crack growth at the initiation site as the cause stress concentration. Tensile strength and fatigue life were compared to initiation site size found from fracture images obtained using scanning electron microscope imaging which found no significant deviations from the expected surface cracking and LCF region of slip plane buildups. Contamination was not found at any initiation site indicating that fracture life was not impacted by the amount of powder recycling. LCF life ranged from 60,000 to 250,000 which the majority experiencing fractures near 120,000 cyclic loadings. If defect effects were to be found than the low fatigue life sample would exhibit them however its fracture surface did not exhibit contamination but a slight increase in porosity found in the phase III cracking region. The In 718 powders were also analyzed to determine that the primary powder contaminates were brush fibers used to sweep away unused powders during processing however these were not seen in the final DMLS samples.
ContributorsLaws, Alec Ky (Author) / Tasooji, Amaneh (Thesis director) / Eylon, Daniel (Committee member) / Materials Science and Engineering Program (Contributor) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
This research aims to develop an understanding of how interventions designed to improve water quality in buildings can be used to mitigate Legionella pneumophila concentrations. Intervention methods can be described as any approach that can be used to improve microbial water quality. In order to provide a foundation of background knowledge, a literature review was conducted to identify similar studies and collect relevant and timely research similar to the subject. The information gathered from the literature review was used to structure the sampling process and parameters. Using the research collected from the literature review, a review table was created to summarize the differences in the studies conducted and to determine research gaps. To categorize the studies, intervention methods, contaminants addressed, and water quality meta-data were differentiated for each of the articles. For the purpose of the sampling process, the three interventions analyzed consist of flushing, water heater set point change, and both flushing and water heater set point change. The locations of the sampling consisted of the city drinking water inlet, the basement janitor's closet, basement shower, 2nd floor, 3rd floor, and 7th floor break rooms and restrooms of the Interdisciplinary Science and Technology Building IV at ASU. For the flushing intervention, the sampling results demonstrated an increase in free and total chlorine concentration post flushing which aligns with the research found in the literature review. In addition, it was observed that iron concentrations drastically increased for both the cold and hot water by flushing. There was a significant decrease detected for ATP concentrations post flush in the hot line. However through the sampling session, the flushing intervention did not yield statistically significant results for Legionella concentrations.
ContributorsKotta, Vishnu Vardhan Reddy (Author) / Cahill, Molly (Co-author) / Call, Kathryn (Thesis director) / Johnson, Elizabeth (Committee member) / Barrett, The Honors College (Contributor) / The Design School (Contributor) / School of Sustainable Engineering & Built Envirnmt (Contributor)
Created2023-05
Description
The purpose of this creative project is twofold: Firstly, to study various pattern-welding processes that have been used throughout history, and secondly, to attempt to create a piece or several pieces of art using the processes studied. Pattern-welding traditionally refers to the practice of creating forged laminates composed of alternating layers of two or more compositionally distinct metals. This term is typically used to specifically refer to these techniques when they are used for the creation of blades, with laminates made of high-phosphorus iron, low-phosphorus mild steel, and/or wrought iron, which was historically done to give the final weapon allegedly better mechanical properties (Thiele et al., 2015). This technique, while supposedly creating mechanically superior weapons in terms of durability and strength, also results in a unique, incredibly aesthetic visual effect. As the laminated billet of metals is twisted, deformed, etched, and polished, the different layers of metals become visible, resulting in a range of patterns depending on the deformation techniques used, and it was this aesthetic value that truly led to the widespread use of pattern-welding. Metals worked in this manner are colloquially known today as Damascus, although the process is technically distinct from true Damascus steel. For the purposes of this creative project, I will extend the concept of pattern-welding beyond strictly using iron and steel used to create swords, and include the similar artistic technique known as mokume-gane. Mokume-gane, which directly translates into English as “wood-grain metal” (Binnion, 2011), also involves forging alternating layers of different metals into a billet, but uses softer metals, historically silver, gold, copper, and alloys of the above. Mokume-gane, which has only relatively recently been used in the West, is the technique that I used to create my art pieces for this creative project.
ContributorsFox, Matthew Davis (Author) / Misquadace, Wanesia (Thesis director) / Burt, Donald (Committee member) / School of Earth and Space Exploration (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05