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- Genre: Doctoral Dissertation
Description
Fossil resources have enabled the development of the plastic industry in the last century. More recently biopolymers have been making gains in the global plastics market. Biopolymers are plastics derived from plants, primarily corn, which can function very similarly to fossil based plastics. One difference between some of the dominant biopolymers, namely polylactic acid and thermoplastic starch, and the most common fossil-based plastics is the feature of compostability. This means that biopolymers represent not only a shift from petroleum and natural gas to agricultural resources but also that these plastics have potentially different impacts resulting from alternative disposal routes. The current end of life material flows are not well understood since waste streams vary widely based on regional availability of end of life treatments and the role that decision making has on waste identification and disposal.
This dissertation is focused on highlighting the importance of end of life on the life-cycle of biopolymers, identifying how compostable biopolymer products are entering waste streams, improving collection and waste processing, and quantifying the impacts that result from the disposal of biopolymers. Biopolymers, while somewhat available to residential consumers, are primarily being used by various food service organizations trying to achieve a variety of goals such as zero waste, green advertising, and providing more consumer options. While compostable biopolymers may be able to help reduce wastes to landfill they do result in environmental tradeoffs associated with agriculture during the production phase. Biopolymers may improve the management for compostable waste streams by enabling streamlined services and reducing non-compostable fossil-based plastic contamination. The concerns about incomplete degradation of biopolymers in composting facilities may be ameliorated using alkaline amendments sourced from waste streams of other industries. While recycling still yields major benefits for traditional resins, bio-based equivalents may provide addition benefits and compostable biopolymers offer benefits with regards to global warming and fossil fuel depletion. The research presented here represents two published studies, two studies which have been accepted for publication, and a life-cycle assessment that will be submitted for publication.
This dissertation is focused on highlighting the importance of end of life on the life-cycle of biopolymers, identifying how compostable biopolymer products are entering waste streams, improving collection and waste processing, and quantifying the impacts that result from the disposal of biopolymers. Biopolymers, while somewhat available to residential consumers, are primarily being used by various food service organizations trying to achieve a variety of goals such as zero waste, green advertising, and providing more consumer options. While compostable biopolymers may be able to help reduce wastes to landfill they do result in environmental tradeoffs associated with agriculture during the production phase. Biopolymers may improve the management for compostable waste streams by enabling streamlined services and reducing non-compostable fossil-based plastic contamination. The concerns about incomplete degradation of biopolymers in composting facilities may be ameliorated using alkaline amendments sourced from waste streams of other industries. While recycling still yields major benefits for traditional resins, bio-based equivalents may provide addition benefits and compostable biopolymers offer benefits with regards to global warming and fossil fuel depletion. The research presented here represents two published studies, two studies which have been accepted for publication, and a life-cycle assessment that will be submitted for publication.
ContributorsHottle, Troy A (Author) / Landis, Amy E. (Thesis advisor) / Allenby, Braden R. (Thesis advisor) / Bilec, Melissa M (Committee member) / Arizona State University (Publisher)
Created2015
Description
Both molecular structure of macromolecular materials and subsequent processing of these materials dictate resulting material properties. In this work novel synthetic strategies combined with detailed analytical methodology reveal fundamental structure-processing-property relationships in thermoplastic polyesters, thermoplastic polyurethanes, covalently crosslinked acetal functionalized networks, and small molecule surfactants. 4,4’ dimethyloxybisbenzoate afforded a series of novel polyester structures, and the incorporation of this monomer both increased the Tg and decreased the crystallinity in cyclohexane dimethanol based polyesters. Solubility and dynamic light scattering experiments combined with oscillatory rheology techniques provided methodology to validate polyurethane extrusion in commercial polyurethanes. Acid catalyzed hydroxyl addition to vinyl ethers provided two families of acetal functionalized poly(ethylene glycol hydrogels). Stoichiometric control of binary thiol-acrylate polymerizations afforded hydrogels with both tunable mechanical properties and predictable degradation profiles. Following this work, a photoacid generator catalyzed cationic catalysis provided acetal functionalized organogels whose mechanical properties were predicted by excess vinyl ether monomers which underwent cationic polymerization under the same reaction conditions that yielded acetal functionalization. Time resolved FT-IR spectroscopy provided new understanding in hydroxyl vinyl ether reactions, where both hydroxyl addition to a vinyl ether and vinyl ether cationic polymerization occur concurrently. This work inspired research into new reactive systems for photobase generator applications. However, current photobase generator technologies proved incompatible for carbon-Michael reactions between acetoacetate and acrylate functionalities as a result of uncontrollable acrylate free radical polymerization. The fundamental knowledge and synthetic strategies afforded by these investigations were applied to small molecule surfactant systems for fire-fighting applications. Triethylsilyl-containing zwitterionic and cationic surfactants displayed surface tensions lower than hydrocarbon surfactants, but larger than siloxane-containing surfactants. For the first time, oscillatory rheology and polarized optical light imagine rheology highlighted shear-induced micelle alignment in triethylsilyl surfactants, which provided more stable foams than zwitterionic analogues. The knowledge gained from these investigations provided fundamental structure-processing-property relationships in small molecule surfactant solutions applied as fire-fighting foams. This discovery regarding the effect of self-assembled structures in foam solutions informs the design and analysis of next generation surfactants to replace fluorocarbon surfactants in fire-fighting foam applications.
ContributorsBrown, James Robert (Author) / Long, Timothy E (Thesis advisor) / Bortner, Michael J (Committee member) / Biegasiewicz, Kyle F (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2023
Description
Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this work, the solid oxide fuel cell (SOFC) nickel-yttria stabilized zirconia (Ni-YSZ) anode degradation due to poisoning by siloxane was investigated. For this purpose, experiments with different fuels, different deposition substrate materials, different structure of contamination siloxane (cyclic and linear) and entire failure process are conducted in this study. The electrochemical and material characterization methods, such as Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscope- Wavelength Dispersive Spectrometers (SEM-WDS), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Raman spectroscopy, were applied to investigate the anode degradation behavior. The electrochemical characterization results show that the SOFCs performance degradation caused by siloxane contamination is irreversible under bio-syngas condition. An equivalent circuit model (ECM) is developed based on electrochemical characterization results. Based on the Distribution of Relaxation Time (DRT) method, the detailed microstructure parameter changes are evaluated corresponding to the ECM results. The results contradict the previously proposed siloxane degradation mechanism as the experimental results show that water can inhibit anode deactivation. For anode materials, Ni is considered a major factor in siloxane deposition reactions in Ni-YSZ anode. Based on the results of XPS, XRD and WDS analysis, an initial layer of carbon deposition develops and is considered a critical process for the siloxane deposition reaction. Based on the experimental results in this study and previous studies about siloxane deposition on metal oxides, the proposed siloxane deposition process occurs in stages consisting of the siloxane adsorption, initial carbon deposition, siloxane polymerization and amorphous silicon dioxide deposition.
ContributorsTian, Jiashen (Author) / Milcarek, Ryan J. (Thesis advisor) / Muhich, Christopher (Committee member) / Wang, Liping (Committee member) / Phelan, Patrick (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2022