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
Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) Å, b = 9.719(2) Å, and c = 4.4764(8) Å. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) Å. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) Å, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.
ContributorsPuhakainen, Kati (Author) / Häussermann, Ulrich (Thesis advisor) / Seo, Dong (Thesis advisor) / Kouvetakis, John (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation investigates the long-term consequences of human land-use practices in general, and in early agricultural villages in specific. This pioneering case study investigates the "collapse" of the Early (Pre-Pottery) Neolithic lifeway, which was a major transformational event marked by significant changes in settlement patterns, material culture, and social markers. To move beyond traditional narratives of cultural collapse, I employ a Complex Adaptive Systems approach to this research, and combine agent-based computer simulations of Neolithic land-use with dynamic and spatially-explicit GIS-based environmental models to conduct experiments into long-term trajectories of different potential Neolithic socio-environmental systems. My analysis outlines how the Early Neolithic "collapse" was likely instigated by a non-linear sequence of events, and that it would have been impossible for Neolithic peoples to recognize the long-term outcome of their actions. The experiment-based simulation approach shows that, starting from the same initial conditions, complex combinations of feedback amplification, stochasticity, responses to internal and external stimuli, and the accumulation of incremental changes to the socio-natural landscape, can lead to widely divergent outcomes over time. Thus, rather than being an inevitable consequence of specific Neolithic land-use choices, the "catastrophic" transformation at the end of the Early Neolithic was an emergent property of the Early Neolithic socio-natural system itself, and thus likely not an easily predictable event. In this way, my work uses the technique of simulation modeling to connect CAS theory with the archaeological and geoarchaeological record to help better understand the causes and consequences of socio-ecological transformation at a regional scale. The research is broadly applicable to other archaeological cases of resilience and collapse, and is truly interdisciplinary in that it draws on fields such as geomorphology, computer science, and agronomy in addition to archaeology.
ContributorsUllah, Isaac (Author) / Barton, C. Michael (Thesis advisor) / Banning, Edward B. (Committee member) / Clark, Geoffrey (Committee member) / Arrowsmith, J. Ramon (Committee member) / Arizona State University (Publisher)
Created2013
Description
The causes and consequences of stylistic change have been a concern of archaeologists over the past several decades. The actual process of stylistic innovation, however, has received less attention. This project explores the relationship between the process of stylistic innovation on decorated pottery and the social context in which it occurred in the Hohokam area of south-central Arizona between A.D. 800 and 1300. This interval was punctuated by three episodes of reorganization, each of which was characterized to varying degrees by significant shifts in ideology, economics, and politics. Each reorganization episode was also accompanied by a rapid profusion of stylistic innovation on buff ware pottery. The goal of this study was to build a framework to understand the variation in the process of innovation as a response to different incentives and opportunities perceived in the changing social environment. By bringing stylistic analyses and provenance data together for the first time in Hohokam red-on-buff studies, I investigated how the process of innovation was variously influenced by social reorganizations at three different periods of time: the 9th, 11th, and 12th centuries A.D. Four variables were used to evaluate the process of innovation at each temporal period: 1) The origin of a stylistic invention, 2) the rate of its adoption, 3) the pattern of its adoption, and 4) the uniformity of its adoption among all buff ware potting communities. To accomplish the task, stylistic innovations and provenance were recorded on over 3,700 red-on-buff sherds were analyzed from 20 sites in the Phoenix Basin. The innovation process was found to vary with each reorganization episode, but often in different ways than expected. The results revealed the complexity and unpredictability of the process of stylistic innovation among the Hohokam. They also challenged some assumptions archaeologists have made regarding the scale and extent of the changes associated with some of the reorganization episodes. The variables utilized to measure the innovation process were found to be effective at providing a composite picture of that process, and thus warrant broader application to other archaeological contexts.
ContributorsLack, Andrew D (Author) / Abbott, David R. (Thesis advisor) / Hegmon, Michelle (Committee member) / Spielmann, Katherine A. (Committee member) / Nelson, Ben A. (Committee member) / Arizona State University (Publisher)
Created2013
Description
Topological insulators with conducting surface states yet insulating bulk states have generated a lot of interest amongst the physics community due to their varied characteristics and possible applications. Doped topological insulators have presented newer physical states of matter where topological order co&ndashexists; with other physical properties (like magnetic order). The electronic states of these materials are very intriguing and pose problems and the possible solutions to understanding their unique behaviors. In this work, we use Electron Energy Loss Spectroscopy (EELS) – an analytical TEM tool to study both core&ndashlevel; and valence&ndashlevel; excitations in Bi2Se3 and Cu(doped)Bi2Se3 topological insulators. We use this technique to retrieve information on the valence, bonding nature, co-ordination and lattice site occupancy of the undoped and the doped systems. Using the reference materials Cu(I)Se and Cu(II)Se we try to compare and understand the nature of doping that copper assumes in the lattice. And lastly we utilize the state of the art monochromated Nion UltraSTEM 100 to study electronic/vibrational excitations at a record energy resolution from sub-nm regions in the sample.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Jiang, Nan (Committee member) / Chen, Tingyong (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali-hydroxide concentration of the paste pore solution through the use of electrical conductivity measurements is also presented, with the results indicating the ion concentration of alkali is more prevalent in the pore solution of potassium-based systems. The use of advanced spectroscopic and thermal analysis techniques to distinguish the influence of studied parameters is also discussed.
ContributorsChowdhury, Ussala (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramanium D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
Description
Irrigation agriculture has been heralded as the solution to feeding the world's growing population. To this end, irrigation agriculture is both extensifying and intensifying in arid regions across the world in an effort to create highly productive agricultural systems. Over one third of modern irrigated fields, however, show signs of serious soil degradation, including salinization and waterlogging, which threaten the productivity of these fields and the world's food supply. Surprisingly, little ecological data on agricultural soils have been collected to understand and address these problems. How, then, can expanding and intensifying modern irrigation systems remain agriculturally productive for the long-term? Archaeological case studies can provide critical insight into how irrigated agricultural systems may be sustainable for hundreds, if not thousands, of years. Irrigation systems in Mesopotamia, for example, have been cited consistently as a cautionary tale of the relationship between mismanaged irrigation systems and the collapse of civilizations, but little data expressly link how and why irrigation failed in the past. This dissertation presents much needed ecological data from two different regions of the world - the Phoenix Basin in southern Arizona and the Pampa de Chaparrí on the north coast of Peru - to explore how agricultural soils were affected by long-term irrigation in a variety of social and economic contexts, including the longevity and intensification of irrigation agriculture. Data from soils in prehispanic and historic agricultural fields indicate that despite long-lived and intensive irrigation farming, farmers in both regions created strategies to sustain large populations with irrigation agriculture for hundreds of years. In the Phoenix Basin, Hohokam and O'odham farmers relied on sedimentation from irrigation water to add necessary fine sediments and nutrients to otherwise poor desert soils. Similarly, on the Pampa, farmers relied on sedimentation in localized contexts, but also constructed fields with ridges and furrows to draw detrimental salts away from planting surfaces in the furrows on onto the ridges. These case studies are then compared to failing modern and ancient irrigated systems across the world to understand how the centralization of management may affect the long-term sustainability of irrigation agriculture.
ContributorsStrawhacker, Colleen (Author) / Spielmann, Katherine A. (Thesis advisor) / Hall, Sharon J (Committee member) / Nelson, Margaret C. (Committee member) / Sandor, Jonathan A (Committee member) / Arizona State University (Publisher)
Created2013
Description
The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum of Ge-on-Si films, dominated by direct gap emission. It was found that the difference is due to the supression of self-absorption effects in Ge films, combined with a deviation from quasi-equilibrium conditions in the conduction band of undoped films. The latter is confirmed by a model suggesting that the deviation is caused by the shorter recombination lifetime in the films relative to bulk Ge. The knowledge acquired from this work was then utilized to study the PL properties of n-type Ge1-ySny/Si (y=0.004-0.04) samples grown via chemical vapor deposition of Ge2H6/SnD4/P(GeH3)3. It was found that the emission intensity (I) of these samples is at least 10x stronger than observed in un-doped counterparts and that the Idir/Iind ratio of direct over indirect gap emission increases for high-Sn contents due to the reduced gamma-L valley separation, as expected. Next the PL investigation was expanded to samples with y=0.05-0.09 grown via a new method using the more reactive Ge3H8 in place of Ge2H6. Optical quality, 1-um thick Ge1-ySny/Si(100) layers were produced using Ge3H10/SnD4 and found to exhibit strong, tunable PL near the threshold of the direct-indirect bandgap crossover. A byproduct of this study was the development of an enhanced process to produce Ge3H8, Ge4H10, and Ge5H12 analogs for application in ultra-low temperature deposition of Group-IV semiconductors. The thesis also studies synthesis routes of an entirely new class of semiconductor compounds and alloys described by Si5-2y(III-V)y (III=Al, V= As, P) comprising of specifically designed diamond-like structures based on a Si parent lattice incorporating isolated III-V units. The common theme of the two thesis topics is the development of new mono-crystalline materials on ubiquitous silicon platforms with the objective of enhancing the optoelectronic performance of Si and Ge semiconductors, potentially leading to the design of next generation optical devices including lasers, detectors and solar cells.
ContributorsGrzybowski, Gordon (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation research investigates both spatial and temporal aspects of Bronze Age land use and land cover in the Eastern Mediterranean using botanical macrofossils of charcoal and charred seeds as sources of proxy data. Comparisons through time and over space using seed and charcoal densities, seed to charcoal ratios, and seed and charcoal identifications provide a comprehensive view of island vs. mainland vegetative trajectories through the critical 1000 year time period from 2500 BC to 1500 BC of both climatic fluctuation and significant anthropogenic forces. This research focuses particularly on the Mediterranean island of Cyprus during this crucial interface of climatic and human impacts on the landscape. Macrobotanical data often are interpreted locally in reference to a specific site, whereas this research draws spatial comparisons between contemporaneous archaeological sites as well as temporal comparisons between non-contemporaneous sites. This larger perspective is particularly crucial on Cyprus, where field scientists commonly assume that botanical macrofossils are poorly preserved, thus unnecessarily limiting their use as an interpretive proxy. These data reveal very minor anthropogenic landscape changes on the island of Cyprus compared to those associated with contemporaneous mainland sites. These data also reveal that climatic forces influenced land use decisions on the mainland sites, and provides crucial evidence pertaining to the rise of early anthropogenic landscapes and urbanized civilization.
ContributorsKlinge, JoAnna M (Author) / Fall, Patricia L. (Thesis advisor) / Falconer, Steven E. (Committee member) / Brazel, Anthony J. (Committee member) / Pigg, Kathleen B (Committee member) / Arizona State University (Publisher)
Created2013
Description
This project examines the social and economic factors that contributed to the development of a specialist-based economy among the Phoenix Basin Hohokam. In the Hohokam case, widespread dependence on the products of a few concentrated pottery producers developed in the absence of political centralization or hierarchical social arrangements. The factors that promoted intensified pottery production, therefore, are the keys to addressing how economic systems can expand in small-scale and middle-range societies. This dissertation constructs a multi-factor model that explores changes to the organization of decorated pottery production during a substantial portion of the pre-Classic period (AD 700 - AD 1020). The analysis is designed to examine simultaneously several variables that may have encouraged demand for ceramic vessels made by specialists. This study evaluates the role of four factors in the development of supply and demand for specialist produced red-on-buff pottery in Hohokam settlements. The factors include 1) agricultural intensification in the form of irrigation agriculture, 2) increases in population density, 3) ritual or social obligations that require the production of particular craft items, and 4) reduced transport costs. Supply and demand for specialist-produced pottery is estimated through a sourcing analysis of non-local pottery at 13 Phoenix Basin settlements. Through a series of statistical analyses, the study measures changes in the influence of each factor on demand for specialist-produced pottery through four temporal phases of the Hohokam pre-Classic period. The analysis results indicate that specialized red-on-buff production was initially spurred by demand for light-colored, shiny, decorated pottery, but then by comparative advantages to specialized production in particular areas of the Phoenix Basin. Specialists concentrated on the Snaketown canal system were able to generate light-colored, mica-dense wares that Phoenix Basin consumers desired while lowering transport costs in the distribution of red-on-buff pottery. The circulation of decorated wares was accompanied by the production of plainware pottery in other areas of the Phoenix Basin. Economic growth in the region was based on complementary and coordinated economic activities between the Salt and the Gila River valleys.
ContributorsKelly, Sophia E (Author) / Abbott, David R. (Thesis advisor) / Darling, J. Andrew (Committee member) / Moore, Gordon (Committee member) / Spielmann, Katherine A. (Committee member) / Arizona State University (Publisher)
Created2013
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013