ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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Description
Electrospun fibrous membranes have gained increasing interest in membrane filtration applications due to their high surface area and porosity. To develop a high-performance water filtration membrane a novel zwitterionic functionalized zwitterionic Polysulfone was Electrospun to bead free fibers on Polysulfone membranes. The SBAES25 was successfully Electrospun on Polysulfone membrane and thermal pressed at above Tg to improve the properties of membrane. The aim of this work is to study Electrospun zwitterionic Polysulfone nanofiber membrane with different characterization methods. The electrospinning method was studied using different polymer concentrations and electrospinning conditions. Scanning Electron Microscopy was used to study the porosity and diameter size of the fiber. TGA-ASSAY method was used to study the difference in water uptake ratio of Polysulfone membrane with and without the Electrospun fiber. A goniometer was used to test the water contact angle of the membrane. Tensile tests were performed to study the improvements in mechanical properties.
ContributorsErravelly, Nitheesh Kumar (Author) / Green, Matthew (Thesis advisor) / Emady, Heather (Committee member) / Seo, Eileen S (Committee member) / Arizona State University (Publisher)
Created2023
Description
Polypropylene, a non-biodegradable plastic with a higher c-c bond disassociation energy than other conventional polymers like Polyethylene (PE), is used to manufacture these three-layered masks. The amount of plastic pollution in the environment has grown tremendously, nearing million tons in a short period of time. As a result, the purpose of this study is to reduce the environmental damage caused by facemasks. This M.S. thesis offers a concise overview of various thermochemical methods employed to depolymerize plastic waste materials. It emphasizes environmentally conscious and sustainable practices, specifically focusing on solvothermal processing. This innovative approach aims to convert discarded face masks into valuable resources, including hydrocarbons suitable for jet fuel and other useful products.
The thesis provides an in-depth exploration of experimental investigations into solvothermal liquefaction techniques. Operating under specific conditions, namely, a temperature of 350°C and a reaction duration of 90 minutes, the results were notably impressive. These results included an exceptional conversion rate of 99.8%, an oil yield of 39.3%, and higher heating values (HHV) of 46.81 MJ/kg for the generated oil samples. It's worth noting that the HHV of the oil samples obtained through the solvothermal liquefaction (STL) method, at 46.82 MJ/kg, surpasses the HHV of gasoline, which stands at 43.4 MJ/kg.
The significant role of the solvent in the depolymerization process involves the dissolution and dispersion of the feedstock through solvation. This reduces the required thermal cracking temperature by enhancing mass and thermal energy transfer. While solvolysis reactions between the solvent and feedstock are limited in thermal liquefaction, the primary depolymerization process follows thermal cracking. This involves the random scission of polypropylene (PP) molecules during heat treatment, with minimal polymerization, cyclization, and radical recombination reactions occurring through free radical mechanisms.
Overall, this work demonstrates the feasibility of a highly promising technique for the effective chemical upcycling of polypropylene-based plastics into valuable resources, particularly in the context of jet fuel hydrocarbons, showcasing the comprehensive analytical methods employed to characterize the products of this innovative process.
ContributorsAkula, kapil Chandra (Author) / Deng, Shuguang (Thesis advisor) / Fini, Elham (Committee member) / Salifu, Emmanuel (Committee member) / Arizona State University (Publisher)
Created2023
The Intercoupling of Thermal Transport and Mechanical Properties in Colloidal Nanocrystal Assemblies
Description
Colloidal nanocrystals (NCs) are promising candidates for a wide range of applications (electronics, optoelectronics, photovoltaics, thermoelectrics, etc.). Mechanical and thermal transport property play very important roles in all of these applications. On one hand, mechanical robustness and high thermal conductivity are desired in electronics, optoelectronics, and photovoltaics. This improves thermomechanical stability and minimizes the temperature rise during the device operation. On the other hand, low thermal conductivity is desired for higher thermoelectric figure of merit (ZT). This dissertation demonstrates that ligand structure and nanocrystal ordering are the primary determining factors for thermal transport and mechanical properties in colloidal nanocrystal assemblies. To eliminate the mechanics and thermal transport barrier, I first propose a ligand crosslinking method to improve the thermal transport across the ligand-ligand interface and thus increasing the overall thermal conductivity of NC assemblies. Young’s modulus of nanocrystal solids also increases simultaneously upon ligand crosslinking. My thermal transport measurements show that the thermal conductivity of the iron oxide NC solids increases by a factor of 2-3 upon ligand crosslinking. Further, I demonstrate that, though with same composition, long-range ordered nanocrystal superlattices possess higher mechanical and thermal transport properties than disordered nanocrystal thin films. Experimental measurements along with theoretical modeling indicate that stronger ligand-ligand interaction in NC superlattice accounts for the improved mechanics and thermal transport. This suggests that NC/ligand arranging order also plays important roles in determining mechanics and thermal transport properties of NC assemblies. Lastly, I show that inorganic ligand functionalization could lead to tremendous mechanical enhancement (a factor of ~60) in NC solids. After ligand exchange and drying, the short inorganic Sn2S64- ligands dissociate into a few atomic layers of amorphous SnS2 at room temperature and interconnects the neighboring NCs. I observe a reverse Hall-Petch relation as the size of NC decreases. Both atomistic simulations and analytical phase mixture modeling identify the grain boundaries and their activities as the mechanic bottleneck.
ContributorsWang, Zhongyong (Author) / Wang, Robert RW (Thesis advisor) / Wang, Liping LW (Committee member) / Newman, Nathan NN (Committee member) / Arizona State University (Publisher)
Created2021
Description
Cyanobacteria contribute to more than a quarter of the primary carbon fixation worldwide. They have evolved a CO2 concentrating mechanism (CCM) to enhance photosynthesis because inorganic carbon species are limited in the aqueous environment. Bicarbonate transporters SbtA and BicA are active components of CCM, and the determination of their structures is important to investigate the bicarbonate transport mechanisms. E. coli was selected as the expression host for these bicarbonate transporters, and optimization of expression and protein purification conditions was performed. Single particle electron cryomicroscopy (cryo-EM) or protein crystallography was carried out for each transporter. In this work, SbtA, BicA and SbtB, a regulator protein of SbtA, were heterologously expressed in E. coli and purified for structural studies. SbtB was highly expressed and two different crystal structures of SbtB were resolved at 2.01 Å and 1.8 Å, showing a trimer and dimer in the asymmetric unit, respectively. The yields of SbtA and BicA after purification reached 0.1 ± 0.04 and 6.5 ± 1.0 mg per liter culture, respectively. Single particle analysis showed a trimeric conformation of purified SbtA and promising interaction between SbtA and SbtB, where the bound SbtB was also possibly trimeric. For some crystallization experiments of these transporters, lipidic cubic phase (LCP) was used. In the case of LCP, often times the crystals grown are generally too tiny to withstand radiation damage from the X-ray beam during an X-ray diffraction experiment. As an alternative approach for this research, the microcrystal electron diffraction (MicroED) method was applied to the LCP-laden crystals because it is a powerful cryo-EM method for high-resolution structure determination from protein microcrystals. The new technique is termed as LCP-MicroED, however, prior to applying LCP-MicroED to the bicarbonate transporters, methods needed to be developed for LCP-MicroED. Therefore the model protein Proteinase K was used and its structure was determined to 2.0 Å by MicroED. Additionally, electron diffraction data from cholesterol and human A2A adenosine receptor crystals were collected at 1.0 Å and 4.5 Å using LCP-MicroED, respectively. Other applications of MicroED to different samples are also discussed.
ContributorsBu, Guanhong (Author) / Nannenga, Brent L (Thesis advisor) / Chiu, Po-Lin (Committee member) / Mills, Jeremy H (Committee member) / Nielsen, David R (Committee member) / Torres, César I (Committee member) / Arizona State University (Publisher)
Created2021
Description
The ironmaking process involves the removal of oxygen atoms from the iron oxides to produce iron. Currently, the coal/coke-based blast furnace process dominates the industry with a 71% share of global steel production, making it responsible for 25% of total global industrial CO2 emissions. Several processes have been commercialized to reduce these CO2 emissions such as the direct reduction process which utilizes natural gas for energy and reducing agent. In the last few decades, H2 has been identified as an alternative reducing agent in place of coal and reformed natural gas for decarbonizing the ironmaking process.To commercialize the H2 direct reduction (H2DR) process, it is necessary to study this process on a laboratory, pilot, and industrial scale to identify and address the roadblocks in the path of commercialization. Based on the literature review performed in this dissertation, four knowledge gaps were identified, and hypotheses were formulated to address the same.
First, a numerical model was developed for a single iron ore pellet reduction process with a dynamic porosity function, and it was validated using experiments.
Second, the equation of the radius of pellet was derived as a function of the degree of reduction using experimental data to account for the shrinking and swelling.
Third, a numerical model was developed for a pilot scale H2DR reactor and was validated for average metallization of the pellets at the reactor outlet and the internal temperature profile in the reduction zone.
Fourth, the numerical model for the pilot scale H2DR reactor showed a gradient of metallization at the outlet boundary which was validated by experimental metallization analysis of 31 randomly selected pellet samples one by one.
At the end of the dissertation, the pilot scale model of the H2DR reactor was scaled up to an industrial scale with a DRI production capacity of 2.38 million tons/year approximately. The mass balance obtained from the industrial scale model was used to perform the techno-economic analysis to determine the economic implications of shifting from a 100% natural gas operation to a 100% H2 operation on an industrial scale.
ContributorsMeshram, Amogh Prashant (Author) / Seetharaman, Sridhar (Thesis advisor) / O'Malley, Ronald J (Committee member) / Nannenga, Brent L (Committee member) / Green, Matthew (Committee member) / Korobeinikov, Yuri (Committee member) / Arizona State University (Publisher)
Created2024
Description
Separation of xylene isomers is one of the most energy-intensive processes in the petrochemical industry. MFI-type zeolite membranes offer an attractive alternative to the traditional energy-intensive xylene separation processes. However, current MFI-type zeolite membranes, including b-oriented ones, are prepared on non-scalable supports and only offer good xylene separation characteristics at low xylene vapor pressures (low activity). It is not clear how the microstructure of MFI zeolite membranes affects the xylene isomer separation characteristics, especially at high xylene activities. These unresolved matters hinder their potential industrial separation applications.The objectives of this dissertation are to understand the effects of MFI zeolite membrane microstructure on xylene isomer separation performance of these membranes and explore the synthesis of high-performance b-oriented MFI zeolite membranes on scalable stainless-steel supports. The work includes exploring the relationship between the synthesis, orientation, microstructure, quality, and separation efficiency of xylene isomers, investigating the dependence of xylene activity with distinct microstructures and orientations of zeolite membranes, developing high-quality b-oriented membranes with an uncomplicated synthesis method fabricated on expandable macroporous supports, which can be manufactured at a reduced cost, and investigating the effect of operating conditions such as temperature and xylene vapor pressure on the separation performance of random and b-oriented membranes synthesized with and without a template.
The research shows that the intercrystalline defects concentration and framework stability in randomly oriented MFI zeolite membranes at high p-xylene loading play a key role in separating xylene isomers via vapor permeation mode. The impact of structural distortion is particularly prominent in pervaporation separation under conditions corresponding to the highest loading of xylene in the zeolite framework. Randomly or b-oriented MFI membranes synthesized without a template offer a significant enhancement in xylene separation performance. Stainless-steel supports can be modified for use as supports for growing MFI zeolite membranes. High-performance b-oriented MFI zeolite membranes can be synthesized on such modified stainless-steel supports by scalable filtration seeding of MFI zeolite nanosheets followed by secondary growth. An improved understanding of the effects of membrane microstructure and synthesis of b-oriented MFI zeolite on stainless steel supports has further advanced zeolite membrane.
ContributorsBanihashemi, Seyede Fateme (Author) / Lin, Jerry JL (Thesis advisor, Committee member) / Treacy, Michael MT (Committee member) / Deng, Shuguang SD (Committee member) / Nannenga, Brent BN (Committee member) / Muhich, Christopher CM (Committee member) / Arizona State University (Publisher)
Created2024
Description
Cyclical chemical looping involves the thermal reduction of metal oxide to release O2 at high temperatures, followed by its oxidation using O-containing molecules like O2, H2O, or CO2. This process is a promising method for solar thermochemical water splitting (STCH), oxygen separation, and thermochemical energy storage (TCES). The efficiency and economic viability of this process hinge on the thermodynamics of metal oxide reduction. This dissertation presents innovative methods to enhance the performance of these processes, with a specific focus on STCH and TCES by advancing thermodynamic characterization and screening of potential metal oxides, thereby reducing H2 costs.A novel CALPHAD approach, the CrossFit Compound Energy Formalism (CEF), integrates theoretical (density functional theory) and experimental (thermogravimetric) data to develop thermodynamic models for desired materials. The CrossFit-CEF was applied to BaxSr1-xFeO3-δ identifying matching thermodynamics and off-stoichiometric values to literature (~100-180 kJ/mol O2 reduction enthalpies across the BaxSr1-xFeO3-δ compositional range). Comparisons with the traditional van ‘t Hoff thermodynamic extraction technique reveal that the CrossFit-CEF method significantly outperforms conventional methods. For instance, the CEF method was employed to extract thermodynamic data for CaFexMn1-xO3-δ and identify optimal TCES CaFexMn1-xO3-δ compositions. The CrossFit-CEF method found the same thermodynamic trends on less than half the data utilized in a van ‘t Hoff approach and determined that the optimal CaFexMn1-xO3-δ composition had the minimal Fe concentration synthesized (x=0.625), achieving ~60 kJ/mol TCES.
Bayesian Inference was employed was employed to expedite data collection. When combined with the CrossFit-CEF method, Bayesian Inference assesses the likelihood that the current model accurately describes the data, providing confidence intervals for the model. This approach reduces the amount of data needed for accurate thermodynamic modeling by 50%.
Finally, the CrossFit-CEF and Bayesian methods are integrated into a system-level STCH model to optimize and accelerate materials design for specific plant operating conditions. Overall, this dissertation introduces methods that yield more accurate thermodynamic models with reduced data requirements. The time saved in data collection enables screening of more materials, expediting material identification and optimization. The materials identified through these techniques are expected to enhance chemical looping cycles, leading to increased H2 production efficiency and reduced costs.
ContributorsWilson, Steven A (Author) / Muhich, Christopher L (Thesis advisor) / Rivera, Daniel E (Committee member) / Stechel, Ellen B (Committee member) / Lin, Jerry (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2024
Description
The properties of block polymers (BPs) are intricately coupled to the dynamic and rich nature of the nanostructured assemblies which result from the phase separation between blocks. The introduction of strong secondary forces, such as electrostatics and hydrogen bonding, into block polymers greatly influences their self-assembly behavior, and therefore affects their physical and electrochemical properties often in non-trivial ways. The recent surge of work expanding scientific understanding of complex spherical packing in block polymers (BPs) has unlocked new design space for the development of advanced soft materials. The continuous matrix phase which percolates throughout spherical morphologies is ideal for many applications involving transport of ions or other small molecules. Thus, determining the accessible parameter range of such morphologies is desirable. Bulk zwitterion-containing BPs hold great potential within the realm of electroactive materials while remaining relatively untapped. In this work, architecturally and compositionally asymmetric diblock polymers were prepared with the majority block having zwitterions tethered to side chain termini at different ratios. Thermally reversible Frank-Kasper phases are observed in multiple samples with significant signs of kinetic arrest and influence. The kinetic influences are validated and described by the temperature-dependent static permittivity. Polyzwitterions combine the attractive features of zwitterions with the mechanical support and processability of polymeric materials. Among these attractive features is a potential for superior permittivity which is limited by the propensity of zwitterions to pack into strongly associating structures. Block polymer self-assembly embodies a plethora of packing frustration opportunities for optimizing polyzwitterion permittivity. The capabilities of this novel approach are revealed here, where the permittivity of a polyzwitterionic block is enhanced to a level comparable to that of pure liquid zwitterions near room temperature (εs ~ 250), but with less than a third the zwitterion concentration. The mechanistic source of permittivity enhancement from a single zwitterion-tethered block polymer is realized deductively through a series of thermal pathways and control sample experiments. Tethered zwitterions within the mixed block interface are frustrated when subject to segmental segregation under sufficient interfacial tension and packing while non-interfacial zwitterions contribute very little to permittivity, highlighting the potential for improvement by several fold.
ContributorsGrim, Bradley James (Author) / Green, Matthew (Thesis advisor) / Long, Timothy (Committee member) / Richert, Ranko (Committee member) / Jin, Kailong (Committee member) / Seo, S. Eileen (Committee member) / Arizona State University (Publisher)
Created2024
Description
In order to develop a new approach to carbon capture using carbonate brines and solid acids, this research project begins the development of a theoretical basis for solid
acid based capture systems and experimental work to test the validity of the theory. It
appears that solid acids behave like weak acids and are able to increase the concentration
of carbon dioxide above a solution compared to what would be achievable without solid
acids. Experimental work aimed to show that solid acids behave as indicated by theory.
Experiments partially validated the theory through demonstrating desorption of carbon
dioxide from a carbonate brine. The regeneration of the solid acid with the help of a
strong acid was only partially successful due to instability of the solid acid in the
presence of a strong acid. The experimental work used activated.
ContributorsGrayson, Connor (Author) / Lackner, Klaus (Thesis advisor) / Fraser, Matthew (Thesis advisor) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2024
Description
Metabolic engineering has emerged as a highly effective approach to optimizing industrial fermentation processes by introducing purposeful genetic alterations using recombinant DNA technology. Successful metabolic engineering begins with a careful investigation of cellular function, and based on the outcomes of this analysis, an improved strain is created and then constructed using genetic engineering. By modifying the genetic makeup of cells, can increase the production of important chemicals, biofuels, medications, and agricultural products. The most often used genetic engineering tool is plasmid-based gene editing. In plasmid-based gene editing, the desired gene sequence is flanked by similar genome sequences, which encourages the foreign gene's integration into the genome. The main flaw of plasmid-based editing is the presence of selectable markers in the integrated DNA, which impacts cell stability as well as downstream applications that are critical to industries. Recently, with the growth of science, the new gene-editing technology CRISPR (clustered regularly interspaced short palindromic repeat) has revolutionized the field of gene editing. It has been used to incorporate the foreign genes into the genome of the microbial host without any mark and has more efficiency than the plasmid-based gene editing technique. CRISPR is utilized to achieve markerless integration of genes in genomes of microbes, which promotes cell stability and is also especially beneficial for applications in industries. In this experiment successfully integrated two genes into the genome of C.glutamicum employing markerless integration via homologous recombination, allowing cells to metabolize acetate into acetyl-CoA and improve the conversion of pyruvate into lactate. Further, this strain of C.glutamicum can be utilized as a platform for producing ethyl lactate, a green solvent using a microbial host
ContributorsBrahmankar, Sumant Milind (Author) / Varman, Arul M (Thesis advisor) / Nielsen, David R (Committee member) / Seto, Jong (Committee member) / Arizona State University (Publisher)
Created2024