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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
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
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
Description
The distinguishing feature of the filamentous fungi is the hyphae - tube-like microscopic cells that exhibit polarized growth via apical extension and allow the fungus to interact with its environment. Fungi elongate at the hyphal apex, through the localized construction of new plasma membrane and cell wall through the exocytosis of secretory vesicles. One population of these vesicles have been identified as chitosomes, containing chitin synthase isoenzymes, which are responsible for the polymerization of N-acetylglucosamine from UDP N-acetylglucosamine into chitin, the primary fibrillar component of the fungal cell wall. The chitosomes, in addition to other vesicles, can be observed aggregating in the hyphal tip in most filamentous fungi. In the Ascomycota and Basidiomycota, this collection of vesicles exhibits discrete organization and has been termed a Spitzenkörper. Although accumulations of vesicles can be observed in the hyphal tip of many growing filamentous fungi, some debate continues as to what precisely defines a Spitzenkörper. This study reports the details of three separate projects: first, to document the effects of deleting a single chitin synthase, CHS-1 and CHS-6 in Neurospora crassa with regards to hyphal ultrastructure, cytoplasmic organization, and growth in comparison to the wild-type. Given the importance of chitin synthesis in fungal cell growth, deletion of a critical chitin synthase presumably impacts cell wall structure, fungal growth and cytoplasmic organization. Second, an examination of the ultrastructure of four zygomycetous fungi - Coemansia reversa, Mortierella verticillata, Mucor indicus, and Gilbertella persicaria has been conducted. Utilization of cryofixation and freeze-substitution techniques for electron microscopy has produced improved preservation of cytoplasmic ultrastructure, particularly at the hyphal apex, allowing detailed analysis of vesicle size, contents, and organization. Lastly, hyphal tip organization was reviewed in a broad range of fungi. Previous studies had either focused on a few select fungi or representative groups. Vesicle organization, composition and size do appear to vary among the classes of fungi, but some trends, like the vesicle crescent in the zygomycetous fungi have been documented.
ContributorsFisher, Karen Elizabeth (Author) / Roberson, Robert W. (Thesis advisor) / Chandler, Douglas (Committee member) / Riquelme, Meritxell (Committee member) / Stutz, Jeam (Committee member) / Wojciechowski, Martin (Committee member) / Arizona State University (Publisher)
Created2015
Description
This dissertation begins to lay out a small slice of the history of morphological research, and how it has changed, from the late 19th through the close of the 20th century. Investigators using different methods, addressing different questions, holding different assumptions, and coming from different research fields have pursued morphological research programs, i.e. research programs that explore the process of changing form. Subsequently, the way in which investigators have pursued and understood morphology has witnessed significant changes from the 19th century to modern day research. In order to trace this shifting history of morphology, I have selected a particular organ, teeth, and traced a tendril of research on the dentition beginning in the late 19th century and ending at the year 2000. But even focusing on teeth would be impossible; the scope of research on this organ is far too vast. Instead, I narrow this dissertation to investigation of research on a particular problem: explaining mammalian tooth morphology. How researchers have investigated mammalian tooth morphology and what counts as an explanation changed dramatically during this period.
ContributorsMacCord, Katherine (Author) / Maienschein, Jane (Thesis advisor) / Laubichler, Manfred (Thesis advisor) / Laplane, Lucie (Committee member) / Kimbel, William (Committee member) / Creath, Richard (Committee member) / Hurlbut, Benjamin (Committee member) / Arizona State University (Publisher)
Created2017
Description
Early hominins present an unusual pattern of sexual dimorphism. On one hand, the canine teeth of these species are weakly size-dimorphic, vertically short, and nonhoning, suggesting a social system characterized by infrequent, low-intensity intermale competition and monogamous pair-bonding. On the other hand, marked size variation in skeletal remains attributed to species of Australopithecus is thought to reflect strong body-mass dimorphism, which is more consistent with intense intermale competition. Reconciling these conflicting signals and understanding their adaptive significance is a major goal of paleoanthropology. This dissertation research contributes to this objective by investigating factors that may constrain or reduce canine height in extant anthropoid primates. Two hypotheses regarding the relationship between canine height and other elements of the masticatory system were tested using phylogenetic comparative methods. According to the first hypothesis, canine reduction is a pleiotropic by-product of changes in the sizes of other components of the dentition. With respect to canine height, the results of this study fail to support this idea. There is limited evidence for a relationship between basal canine crown dimensions and incisor and postcanine size, but significant interspecific correlations between these variables are not strong and are restricted primarily to the female maxillary dentition. These results indicate that if pleiotropy influences canine size, then its effects are weak. The second hypothesis proposes that canine reduction is a consequence of selection for increased jaw-muscle leverage. This hypothesis receives some support: there is a clear inverse relationship between canine height and the leverage of the masseter muscle in male anthropoids. Females do not exhibit this association due to the fact that dimorphism in muscle leverage is weak or absent in most anthropoid species; in other words, female muscle leverage tracks male muscle leverage, which is linked to canine height. Leverage of the temporalis muscle is not correlated with canine height in either sex. Two specimens of the 3.0-3.7-million-year-old hominin Australopithecus afarensis fall at or beyond the upper end of the great ape range of variation in masseter leverage, which is consistent with the idea that hominin canine evolution was influenced by selection for increased jaw-muscle leverage.
ContributorsScott, Jeremiah Ezekiel (Author) / Kimbel, William H. (Thesis advisor) / Schwartz, Gary T. (Committee member) / Spencer, Mark A. (Committee member) / Arizona State University (Publisher)
Created2010