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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- Creators: Green, Matthew
- Creators: Chawla, Nikhilesh
Description
Membrane based technology is one of the principal methods currently in widespread use to address the global water shortage. Pervaporation desalination is a membrane technology for water purification currently under investigation as a method for processing reverse osmosis concentrates or for stand-alone applications. Concentration polarization is a potential problem in any membrane separation. In desalination concentration polarization can lead to reduced water flux, increased propensity for membrane scaling, and decreased quality of the product water. Quantifying concentration polarization is important because reducing concentration polarization requires increased capital and operating costs in the form of feed spacers and high feed flow velocities. The prevalent methods for quantifying concentration polarization are based on the steady state thin film boundary layer theory. Baker’s method, previously used for pervaporation volatile organic compound separations but not desalination, was successfully applied to data from five previously published pervaporation desalination studies. Further investigation suggests that Baker’s method may not have wide applicability in desalination. Instead, the limitations of the steady state assumption were exposed. Additionally, preliminary results of nanophotonic enhancement of pervaporation membranes were found to produce significant flux enhancement. A novel theory on the mitigation of concentration polarization by the photothermal effect was discussed.
ContributorsMann, Stewart, Ph.D (Author) / Lind, Mary Laura (Thesis advisor) / Walker, Shane (Committee member) / Green, Matthew (Committee member) / Forzani, Erica (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2019
Description
Various research papers and literature were reviewed and consulted for the depolymerization of polyethylene terephthalate (PET) using long chain alkyl amines and ethylene glycol (EG) as catalyst in the aminolysis process. The main hypothesis of this thesis is to use EG as a catalyst in the aminolysis of PET using octylamine, dodecylamine and hexadecylamine. Initial reactions with the three amines were performed with and without EG to observe and compare the terephthalamides obtained from these reactions to test this hypothesis. Various reaction conditions like concentration of reactants, temperature and time of reaction were later considered and employed to find the optimal conditions for the depolymerization of PET before confirming the catalytic properties of EG in the aminolysis reaction. The depolymerized products were subjected to attenuated total reflectance-infrared spectroscopy (ATR-IR Spectroscopy) to check for presence of important amide and ester peaks through their infrared absorption peaks, thermogravimetric analysis (TGA) to find their Td5 temperatures and differential scanning calorimetry (DSC) to check for endothermic melting temperature of the obtained products. These characterization techniques were used to understand, examine, and compare the different properties of the products obtained from different reaction mixtures. The three distinct amines considered for this reaction also showed differences in the conversion rate of PET under similar reaction conditions thus signifying the importance of selecting an appropriate amine reactant for the aminolysis process. Finally, the in-situ IR probe was used to determine the reaction kinetics of the aminolysis reaction and the formation and loss of products and reactants with time.
ContributorsBakkireddy, Adarsh (Author) / Green, Matthew (Thesis advisor) / Emady, Heather (Committee member) / Seo, Eileen S. (Committee member) / Arizona State University (Publisher)
Created2023
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
A comprehensive and systematic investigation on the diffusion and phase behaviors of nanoparticles and macromolecules in two component liquid-liquid systems via Molecule Dynamic (MD) simulations is presented in this dissertation.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
ContributorsGao, Wei (Author) / Dai, Lenore (Thesis advisor) / Jiao, Yang (Committee member) / Liu, Yongming (Committee member) / Green, Matthew (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2017
Description
Energy return in footwear is associated with the damping behavior of midsole foams, which stems from the combination of cellular structure and polymeric material behavior. Recently, traditional ethyl vinyl acetate (EVA) foams have been replaced by BOOST(TM) foams, thereby reducing the energetic cost of running. These are bead foams made from expanded thermoplastic polyurethane (eTPU), which have a multi-scale structure consisting of fused porous beads, at the meso-scale, and thousands of small closed cells within the beads at the micro-scale. Existing predictive models coarsely describe the macroscopic behavior but do not take into account strain localizations and microstructural heterogeneities. Thus, enhancement in material performance and optimization requires a comprehensive understanding of the foam’s cellular structure at all length scales and its influence on mechanical response.
This dissertation focused on characterization and deformation behavior of eTPU bead foams with a unique graded cell structure at the micro and meso-scale. The evolution of the foam structure during compression was studied using a combination of in situ lab scale and synchrotron x-ray tomography using a four-dimensional (4D, deformation + time) approach. A digital volume correlation (DVC) method was developed to elucidate the role of cell structure on local deformation mechanisms. The overall mechanical response was also studied ex situ to probe the effect of cell size distribution on the force-deflection behavior. The radial variation in porosity and ligament thickness profoundly influenced the global mechanical behavior. The correlation of changes in void size and shape helped in identifying potentially weak regions in the microstructure. Strain maps showed the initiation of failure in cell structure and it was found to be influenced by the heterogeneities around the immediate neighbors in a cluster of voids. Poisson’s ratio evaluated from DVC was related to the microstructure of the bead foams. The 4D approach taken here provided an in depth and mechanistic understanding of the material behavior, both at the bead and plate levels, that will be invaluable in designing the next generation of high-performance footwear.
This dissertation focused on characterization and deformation behavior of eTPU bead foams with a unique graded cell structure at the micro and meso-scale. The evolution of the foam structure during compression was studied using a combination of in situ lab scale and synchrotron x-ray tomography using a four-dimensional (4D, deformation + time) approach. A digital volume correlation (DVC) method was developed to elucidate the role of cell structure on local deformation mechanisms. The overall mechanical response was also studied ex situ to probe the effect of cell size distribution on the force-deflection behavior. The radial variation in porosity and ligament thickness profoundly influenced the global mechanical behavior. The correlation of changes in void size and shape helped in identifying potentially weak regions in the microstructure. Strain maps showed the initiation of failure in cell structure and it was found to be influenced by the heterogeneities around the immediate neighbors in a cluster of voids. Poisson’s ratio evaluated from DVC was related to the microstructure of the bead foams. The 4D approach taken here provided an in depth and mechanistic understanding of the material behavior, both at the bead and plate levels, that will be invaluable in designing the next generation of high-performance footwear.
ContributorsSundaram Singaravelu, Arun Sundar (Author) / Chawla, Nikhilesh (Thesis advisor) / Emady, Heather (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020
Description
As experiencing hot months and thermal stresses is becoming more common, chemically protective fabrics must adapt and provide protections while reducing the heat stress to the body. These concerns affect first responders, warfighters, and workers regularly surrounded by hazardous chemical agents. While adapting traditional garments with cooling devices provides one route to mitigate this issue, these cooling methods add bulk, are time limited, and may not be applicable in locations without logistical support. Here I take inspiration from nature to guide the development of smart fabrics that have high breathability, but self-seal on exposure to target chemical(s), providing a better balance between cooling and protection.
Natural barrier materials were explored as a guide, focusing specifically on prickly pear cacti. These cacti have a natural waxy barrier that provides protection from dehydration and physically changes shape to modify surface wettability and water vapor transport. The results of this study provided a basis for a shape changing polymer to be used to respond directly to hazardous chemicals, swelling to contain the agent.
To create a stimuli responsive material, a novel superabsorbent polymer was synthesized, based on acrylamide chemistry. The polymer was tested for swelling properties in a wide range of organic liquids and found to highly swell in moderately polar organic liquids. To help predict swelling in untested liquids, the swelling of multiple test liquids were compared with their thermodynamic properties to observe trends. As the smart fabric needs to remain breathable to allow evaporative cooling, while retaining functionality when soaked with sweat, absorption of water, as well as that of an absorbing liquid in the presence of water were tested.
Micron sized particles of the developed polymer were deposited on a plastic mesh with pore size and open area similar to common clothing fabric to establish the proof of concept of using a breathable barrier to provide chemical protection. The polymer coated mesh showed minimal additional resistance to water vapor transport, relative to the mesh alone, but blocked more than 99% of a xylene aerosol from penetrating the barrier.
Natural barrier materials were explored as a guide, focusing specifically on prickly pear cacti. These cacti have a natural waxy barrier that provides protection from dehydration and physically changes shape to modify surface wettability and water vapor transport. The results of this study provided a basis for a shape changing polymer to be used to respond directly to hazardous chemicals, swelling to contain the agent.
To create a stimuli responsive material, a novel superabsorbent polymer was synthesized, based on acrylamide chemistry. The polymer was tested for swelling properties in a wide range of organic liquids and found to highly swell in moderately polar organic liquids. To help predict swelling in untested liquids, the swelling of multiple test liquids were compared with their thermodynamic properties to observe trends. As the smart fabric needs to remain breathable to allow evaporative cooling, while retaining functionality when soaked with sweat, absorption of water, as well as that of an absorbing liquid in the presence of water were tested.
Micron sized particles of the developed polymer were deposited on a plastic mesh with pore size and open area similar to common clothing fabric to establish the proof of concept of using a breathable barrier to provide chemical protection. The polymer coated mesh showed minimal additional resistance to water vapor transport, relative to the mesh alone, but blocked more than 99% of a xylene aerosol from penetrating the barrier.
ContributorsManning, Kenneth (Author) / Rykaczewski, Konrad (Thesis advisor) / Burgin, Timothy (Committee member) / Emady, Heather (Committee member) / Green, Matthew (Committee member) / Thomas, Marylaura (Committee member) / Arizona State University (Publisher)
Created2020