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Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
Lunar Reconnaissance Orbiter (LRO) and MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft missions provide new data for investigating the youngest impact craters on Mercury and the Moon, along with lunar volcanic end-members: ancient silicic and young basaltic volcanism. The LRO Wide Angle Camera (WAC) and Narrow Angle Camera (NAC) in-flight absolute radiometric calibration used ground-based Robotic Lunar Observatory and Hubble Space Telescope data as standards. In-flight radiometric calibration is a small aspect of the entire calibration process but an important improvement upon the pre-flight measurements. Calibrated reflectance data are essential for comparing images from LRO to missions like MESSENGER, thus enabling science through engineering. Relative regolith optical maturation rates on Mercury and the Moon are estimated by comparing young impact crater densities and impact ejecta reflectance, thus empirically testing previous models of faster rates for Mercury relative to the Moon. Regolith maturation due to micrometeorite impacts and solar wind sputtering modies UV-VIS-NIR surface spectra, therefore understanding maturation rates is critical for interpreting remote sensing data from airless bodies. Results determined the regolith optical maturation rate on Mercury is 2 to 4 times faster than on the Moon. The Gruithuisen Domes, three lunar silicic volcanoes, represent relatively rare lunar lithologies possibly similar to rock fragments found in the Apollo sample collection. Lunar nonmare silicic volcanism has implications for lunar magmatic evolution. I estimated a rhyolitic composition using morphologic comparisons of the Gruithuisen Domes, measured from NAC 2-meter-per-pixel digital topographic models (DTMs), with terrestrial silicic dome morphologies and laboratory models of viscoplastic dome growth. Small, morphologically sharp irregular mare patches (IMPs) provide evidence for recent lunar volcanism widely distributed across the nearside lunar maria, which has implications for long-lived nearside magmatism. I identified 75 IMPs (100-5000 meters in dimension) in NAC images and DTMs, and determined stratigraphic relationships between units common to all IMPs. Crater counts give model ages from 18-58 Ma, and morphologic comparisons with young lunar features provided an additional age constraint of <100 Ma. The IMPs formed as low-volume basaltic eruptions significantly later than previous evidence of lunar mare basalt volcanism's end (1-1.2 Ga).
ContributorsBraden, Sarah E (Author) / Robinson, Mark S (Thesis advisor) / Bell, James F. (Committee member) / Christensen, Philip R. (Committee member) / Clarke, Amanda B (Committee member) / Lawrence, Samuel J (Committee member) / Arizona State University (Publisher)
Created2013
Description
Despite the wealth of folk music traditions in Portugal and the importance of the clarinet in the music of bandas filarmonicas, it is uncommon to find works featuring the clarinet using Portuguese folk music elements. In the interest of expanding this type of repertoire, three new works were commissioned from three different composers. The resulting works are Seres Imaginarios 3 by Luis Cardoso; Delirio Barroco by Tiago Derrica; and Memória by Pedro Faria Gomes. In an effort to submit these new works for inclusion into mainstream performance literature, the author has recorded these works on compact disc. This document includes interview transcripts with each composer, providing first-person discussion of each composition, as well as detailed biographical information on each composer. To provide context, the author has included a brief discussion on Portuguese folk music, and in particular, the role that the clarinet plays in Portuguese folk music culture.
ContributorsFerreira, Wesley (Contributor) / Spring, Robert S (Thesis advisor) / Bailey, Wayne (Committee member) / Gardner, Joshua (Committee member) / Hill, Gary (Committee member) / Schuring, Martin (Committee member) / Solis, Theodore (Committee member) / Arizona State University (Publisher)
Created2013
Description
There is an inexorable link between structure and stress, both of which require study in order to truly understand the physics of thin films. To further our knowledge of thin films, the relationship between structure and stress development was examined in three separate systems in vacuum. The first was continued copper thin film growth in ultra-high vacuum after adsorption of a sub-monolayer quantity of oxygen. Results showed an increase in compressive stress generation, and theory was proposed to explain the additional compressive stress within the films. The second system explored was the adsorption of carbon monoxide on the platinum {111} surface in vacuum. The experiments displayed a correlation between known structural developments in the adsorbed carbon monoxide adlayer and the surface stress state of the system. The third system consisted of the growth and annealing stresses of ice thin films at cryogenic temperatures in vacuum. It was shown that the growth stresses are clearly linked to known morphology development from literature, with crystalline ice developing compressive and amorphous ice developing tensile stresses respectively, and that amorphous ice films develop additional tensile stresses upon annealing.
ContributorsKennedy, Jordan (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2011
ContributorsBurton, Charlotte (Performer) / ASU Library. Music Library (Publisher)
Created2018-04-08
ContributorsDruesedow, Elizabeth (Performer) / ASU Library. Music Library (Publisher)
Created2018-04-07
Description
This work focuses on simulation of electrical resistivity and optical behaviors of thin films, where an Ag or Au thin layer is embedded in zinc oxide. Enhanced conductivity and transparency were earlier achieved with multilayer structured transparent conducting oxide (TCO) sandwich layer with metal (TCO/metal/TCO). Sputtering pattern of metal layer is simulated to obtain the morphology, covered area fraction, and the percolation strength. The resistivity as a function of the metal layer thickness fits the modeled trend of covered area fraction beyond the percolation threshold. This result not only presents the robustness of the simulation, but also demonstrates the influence of metal morphology in multilayer structure. Effective medium coefficients are defined from the coverage and percolation strength to obtain simulated optical transmittance which matches experimental observation. The coherence of resistivity and optical transmittance validates the simulation of the sputtered pattern and the incorporation of percolation theory in the model.
ContributorsFang, Chia-Ling (Author) / Alford, Terry L. (Thesis advisor) / Crozier, Peter (Committee member) / Theodore, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Extensive cross-linguistic data document a wide gamut of semantic and pragmatic uses of the diminutive that revolve around the fundamental concepts of `small' and `child'. As typical inventory of informal registers, diminutives are utilized as pragmatic markers of politeness in a wide range of contextual meanings. This dissertation is intended to fill some major gaps in the systematic and empirical research on the formation and pragmatic uses of the diminutives in Macedonian and to explore the role of diminutivization in a broader linguistic framework, by examining the consistency of the field of diminutives, the core and peripheral meanings of the diminutive, their typology, as well as their pragmatic potential. The morphology and pragmatics of the diminutive is examined by combining data from electronic and printed sources, video recordings of natural conversations, as well as from material collected from participant and non-participant observations. At the level of morphology, it is argued that three fundamental semantic constraints underlie the formation of diminutives: [-big], [+ emotional], and [+ informal]. Furthermore, it is shown how diminutive combinability is rule governed in Macedonian by proposing sets of formal constraints for all grades of diminutives. At the level of pragmatics, the pragmatic functions of the diminutives proper and the related periphrastic diminutive malku are investigated in a variety of contexts involving child-directed speech (CDS) and adult communication. By analyzing the pragmatic functions of the diminutive in a series of speech acts, and drawing upon cross-cultural interpretations suggested by Wierzbicka (1991), it is argued that, in Macedonian, social bonding, cordiality, intimacy or affection are pragmatically more salient than personal autonomy in the Anglo-Saxon societies, realized through non-imposition, tentativeness, or similar pragmatic strategies for saving face. Additionally, it is contended that there exist cultural differences in the assessment of the concept of imposition between these societies. The analyses of the pragmatic potential of the diminutive proper and the periphrastic diminutive 'malku' give rise to the claim that Macedonian culture is predominantly founded on the pragmatic principle of positive politeness.
ContributorsSpasovski, Lupco (Author) / Adams, Karen L (Thesis advisor) / Gelderen, Elly van (Committee member) / Sipka, Danko (Committee member) / Arizona State University (Publisher)
Created2012
Description
The exceptional mechanical properties of polymers with heterogeneous structure, such as the high toughness of polyethylene and the excellent blast-protection capability of polyurea, are strongly related to their morphology and nanoscale structure. Different polymer microstructures, such as semicrystalline morphology and segregated nanophases, lead to coordinated molecular motions during deformation in order to preserve compatibility between the different material phases. To study molecular relaxation in polyethylene, a coarse-grained model of polyethylene was calibrated to match the local structural variable distributions sampled from supercooled atomistic melts. The coarse-grained model accurately reproduces structural properties, e.g., the local structure of both the amorphous and crystalline phases, and thermal properties, e.g., glass transition and melt temperatures, and dynamic properties: including the vastly different relaxation time scales of the amorphous and crystalline phases. A hybrid Monte Carlo routine was developed to generate realistic semicrystalline configurations of polyethylene. The generated systems accurately predict the activation energy of the alpha relaxation process within the crystalline phase. Furthermore, the models show that connectivity to long chain segments in the amorphous phase increases the energy barrier for chain slip within crystalline phase. This prediction can guide the development of tougher semicrystalline polymers by providing a fundamental understanding of how nanoscale morphology contributes to chain mobility. In a different study, the macroscopic shock response of polyurea, a phase segregated copolymer, was analyzed using density functional theory (DFT) molecular dynamics (MD) simulations and classical MD simulations. The two models predict the shock response consistently up to shock pressures of 15 GPa, beyond which the DFT-based simulations predict a softer response. From the DFT simulations, an analysis of bond scission was performed as a first step in developing a more fundamental understanding of how shock induced material transformations effect the shock response and pressure dependent strength of polyurea subjected to extreme shocks.
ContributorsLi, Yiyang (Author) / Oswald, Jay (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Solanki, Kiran (Committee member) / Chamberlin, Ralph (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2017
Description
Mammals with a habitually orthograde trunk posture possess a more anterior foramen magnum than mammals with non-orthograde trunk postures. Russo & Kirk (2013) also found that bipedal orthograde mammals possess a more anteriorly placed foramen magnum than those that are just habitually orthograde. This finding has allowed us to use foramen magnum position as a predictor of trunk posture in early hominins. This prompts more research of how the other landmarks on the cranial base move in relation to this shift in foramen magnum positioning. I collected landmark data on images of 125 mammalian basicrania spanning 41 species that differed in trunk posture. Using Procrustes and Principal Components Analysis (PCA), I attempted to evaluate the effects of trunk posture on basicranial morphology, primarily focusing on the placement of the carotid and jugular foramina. The results supported Russo and Kirk's finding of a more anterior foramen magnum placement in orthograde mammals; in addition, the results displayed correlations between foramen magnum position and carotid foramen position among primates and diprotodonts.
ContributorsPena, Angela (Author) / Kimbel, William (Thesis director) / Schwartz, Gary T. (Committee member) / Barrett, The Honors College (Contributor) / School of Human Evolution and Social Change (Contributor)
Created2015-05