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- All Subjects: Materials Science
- All Subjects: Sustainability
- Creators: Sieradzki, Karl
Description
Phosphorus (P), an essential element for life, is becoming increasingly scarce, and its global management presents a serious challenge. As urban environments dominate the landscape, we need to elucidate how P cycles in urban ecosystems to better understand how cities contribute to — and provide opportunities to solve — problems of P management. The goal of my research was to increase our understanding of urban P cycling in the context of urban resource management through analysis of existing ecological and socio-economic data supplemented with expert interviews in order to facilitate a transition to sustainable P management. Study objectives were to: I) Quantify and map P stocks and flows in the Phoenix metropolitan area and analyze the drivers of spatial distribution and dynamics of P flows; II) examine changes in P-flow dynamics at the urban agricultural interface (UAI), and the drivers of those changes, between 1978 and 2008; III) compare the UAI's average annual P budget to the global agricultural P budget; and IV) explore opportunities for more sustainable P management in Phoenix. Results showed that Phoenix is a sink for P, and that agriculture played a primary role in the dynamics of P cycling. Internal P dynamics at the UAI shifted over the 30-year study period, with alfalfa replacing cotton as the main locus of agricultural P cycling. Results also suggest that the extent of P recycling in Phoenix is proportionally larger than comparable estimates available at the global scale due to the biophysical characteristics of the region and the proximity of various land uses. Uncertainty remains about the effectiveness of current recycling strategies and about best management strategies for the future because we do not have sufficient data to use as basis for evaluation and decision-making. By working in collaboration with practitioners, researchers can overcome some of these data limitations to develop a deeper understanding of the complexities of P dynamics and the range of options available to sustainably manage P. There is also a need to better connect P management with that of other resources, notably water and other nutrients, in order to sustainably manage cities.
ContributorsMetson, Genevieve (Author) / Childers, Daniel (Thesis advisor) / Aggarwal, Rimjhim (Thesis advisor) / Redman, Charles (Committee member) / Arizona State University (Publisher)
Created2011
Description
ABSTRACT Water resources in many parts of the world are subject to increasing stress because of (a) the growth in demand caused by population increase and economic development, (b) threats to supply caused by climate and land cover change, and (c) a heightened awareness of the importance of maintaining water supplies to other parts of the ecosystem. An additional factor is the quality of water management. The United States-Mexican border provides an example of poor water management combined with increasing demand for water resources that are both scarce and uncertain. This dissertation focuses on the problem of water management in the border city of Ciudad Juarez, Chihuahua. The city has attracted foreign investment during the last few decades, largely due to relatively low environmental and labor costs, and to a range of tax incentives and concessions. This has led to economic and population growth, but also to higher demand for public services such as water which leads to congestion and scarcity. In particular, as water resources have become scarce, the cost of water supply has increased. The dissertation analyzes the conditions that allow for the efficient use of water resources at sustainable levels of economic activity--i.e., employment and investment. In particular, it analyzes the water management strategies that lead to an efficient and sustainable use of water when the source of water is either an aquifer, or there is conjunctive use of ground and imported water. The first part of the dissertation constructs a model of the interactive effects of water supply, wage rates, inward migration of labor and inward investment of capital. It shows how growing water scarcity affects population growth through the impact it has on real wage rates, and how this erodes the comparative advantage of Ciudad Juarez--low wages--to the point where foreign investment stops. This reveals the very close connection between water management and the level of economic activity in Ciudad Juarez. The second part of the dissertation examines the effect of sustainable and efficient water management strategies on population and economic activity levels under two different settings. In the first Ciudad Juarez relies exclusively on ground water to meet demand--this reflects the current situation of Ciudad Juarez. In the second Ciudad Juarez is able both to import water and to draw on aquifers to meet demand. This situation is motivated by the fact that Ciudad Juarez is considering importing water from elsewhere to maintain its economic growth and mitigate the overdraft of the Bolson del Hueco aquifer. Both models were calibrated on data for Ciudad Juarez, and then used to run experiments with respect to different environmental and economic conditions, and different water management options. It is shown that for a given set of technological, institutional and environmental conditions, the way water is managed in a desert environment determines the long run equilibrium levels of employment, investment and output. It is also shown that the efficiency of water management is consistent with the sustainability of water use and economic activity. Importing water could allow the economy to operate at higher levels of activity than where it relies solely on local aquifers. However, at some scale, water availability will limit the level of economic activity, and the disposable income of the residents of Ciudad Juarez.
ContributorsGarduno Angeles, Gustavo Leopoldo (Author) / Perrings, Charles (Thesis advisor) / Holway, Jim (Thesis advisor) / Aggarwal, Rimjhim (Committee member) / Arizona State University (Publisher)
Created2011
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
ABSTRACT The behavior of the fission products, as they are released from fission events during nuclear reaction, plays an important role in nuclear fuel performance. Fission product release can occur through grain boundary (GB) at low burnups; therefore, this study simulates the mass transport of fission gases in a 2-D GB network to look into the effects of GB characteristics on this phenomenon, with emphasis on conditions that can lead to percolation. A finite element model was created based on the microstructure of a depleted UO2 sample characterized by Electron Backscattering Diffraction (EBSD). The GBs were categorized into high (D2), low (D1) and bulk diffusivity (Dbulk) based on their misorientation angles and Coincident Site Lattice (CSL) types. The simulation was run using different diffusivity ratios (D2/Dbulk) ranging from 1 to 10^8. The model was set up in three ways: constant temperature case, temperature gradient effects and window methods that mimic the environments in a Light Water Reactor (LWR). In general, the formation of percolation paths was observed at a ratio higher than 10^4 in the measured GB network, which had a 68% fraction of high diffusivity GBs. The presence of temperature gradient created an uneven concentration distribution and decreased the overall mass flux. Finally, radial temperature and fission gas concentration profiles were obtained for a fuel pellet in operation using an approximate 1-D model. The 100 µm long microstructurally explicit model was used to simulate, to the scale of a real UO2 pellet, the mass transport at different radial positions, with boundary conditions obtained from the profiles. Stronger percolation effects were observed at the intermediate and periphery position of the pellet. The results also showed that highest mass flux happens at the edge of a pellet at steady state to accommodate for the sharp concentration drop.
ContributorsLim, Harn Chyi (Author) / Peralta, Pedro (Thesis advisor) / Dey, Sandwip (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
Over the last decade copper electrodeposition has become the dominant process by which microelectronic interconnects are made. Replacing ultra-high vacuum evaporative film growth, the technology known as the Cu damascene process has been widely implemented in the microelectronics industry since the early 2000s. The transition from vacuum film growth to electrodeposition was enabled by solution chemistries that provide "bottom-up" or superfilling capability of vias and trenches. While the process has been and is used widely, the actual mechanisms responsible for superfilling remain relatively unknown. This dissertation presents and discusses the background and results of experimental investigations that have been done using in situ electrochemical surface stress monitoring techniques to study the evolution of stress on Cu{111} thin film electrodes. Because of its extreme sensitivity to the structure on both the electrode and solution sides of the interface, surface stress monitoring as analytical technique is well suited for the study of electrodeposition. These ultra-high resolution stress measurements reveal the dynamic response of copper electrodes to a number of electrochemical and chemical experimental variables. In the case of constant current pulsed deposition and stripping, the surface stress evolution depends not only on the magnitude of the current pulse, but also shows a marked response to plating bath composition. The plating bath chemistries used in this work include (1) additive free, (2) deposition suppressing solutions that include polyethylene glycol (PEG) and sodium chloride (NaCl) as well as (3) full additive solution combinations which contain PEG, NaCl, and a one of two deposition accelerating species (bis-(sodiumsulfopropyl)disulfide (SPS) or mercaptopropane sulfonic acid (MPS)). The development of thin film stress is further investigated through a series of solution exchange experiments that correlate the magnitude of electrode exchange current density and the stress state of the film. Remarkably, stress changes as large as ~8.5 N/m are observed during solution exchanges at the open circuit potential. Overall, this research demonstrates that solution chemistry can have a large impact on thin film stress evolution, even for very small deposition thicknesses (e.g. <10 ML) or in the absence of net addition or removal of material from the electrode.
ContributorsHeaton, Thomas Stanley (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa).
ContributorsMickelson, Lawrence (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Venables, John (Committee member) / Arizona State University (Publisher)
Created2011
Description
Haiti has witnessed high deforestation rates in recent decades, caused largely by the fuel needs of a growing population. The resulting soil loss is estimated to have contributed towards a decline in agricultural productivity of 0.5% -1.2% per year since 1997. Recent studies show the potential of biochar use through pyrolysis technology to increase crop yields and improve soil health. However, the appropriateness of this technology in the context of Haiti remains unexplored. The three objectives of this research were to identify agricultural- and fuel-use-related needs and gaps in rural Haitian communities; determine the appropriateness of biochar pyrolyzer technology, used to convert agricultural biomass into a carbon-rich charcoal; and develop an action-oriented plan for use by development organizations, communities, and governmental institutions to increase the likelihood of adoption. Data were collected using participatory rural appraisal techniques involving 30 individual interviews and three focus-group discussions in the villages of Cinquantin and La Boule in the La Coupe region of central Haiti. Topics discussed include agricultural practices and assets, fuel use and needs, technology use and adoption, and social management practices. The Sustainable Livelihoods framework was used to examine the assets of households and the livelihood strategies being employed. Individual and focus group interviews were analyzed to identify specific needs and gaps. E.M. Rogers' Diffusion of Innovations theory was used to develop potential strategies for the introduction of pyrolysis technology. Preliminary results indicate biochar pyrolysis has potential to address agricultural and fuel needs in rural Haiti. Probable early adopters of biochar technology include households that have adopted new agricultural techniques in the past, and those with livestock. Education about biochar, and a variety of pyrolysis technology options from which villagers may select, are important factors in successful adoption of biochar use. A grain mill as an example in one of the study villages provides a model of ownership and use of pyrolysis technology that may increase its likelihood of successful adoption. Additionally, women represent a group that may be well suited to control a new local biochar enterprise, potentially benefiting the community.
ContributorsDelaney, Michael Ryan (Author) / Aggarwal, Rimjhim (Thesis advisor) / Chhetri, Nalini (Committee member) / Henderson, Mark (Committee member) / Arizona State University (Publisher)
Created2011
Description
In-situ environmental transmission electron microscopy (ETEM) is a powerful tool for following the evolution of supported metal nanoparticles under different reacting gas conditions at elevated temperatures. The ability to observe the events in real time under reacting gas conditions can provide significant information on the fundamental processes taking place in catalytic materials, from which the performance of the catalyst can be understood. The first part of this dissertation presents the application of in-situ ETEM studies in developing structure-activity relationship in supported metal nanoparticles. In-situ ETEM studies on nanostructures in parallel with ex-situ reactor studies of conversions and selectivities were performed for partial oxidation of methane (POM) to syngas (CO+H2) on Ni/SiO2, Ru/SiO2 and NiRu/SiO2 catalysts. During POM, the gas composition varies along the catalyst bed with increasing temperature. It is important to consider these variations in gas composition in order to design experiments for in-situ ETEM. In-situ ETEM experiments were performed under three different reacting gas conditions. First in the presence of H2, this represents the state of the fresh catalyst for the catalytic reaction. Later in the presence of CH4 and O2 in 2:1 ratio, this is the composition of the reacting gases for the POM reaction and this composition acts as an oxidizing environment. Finally in the presence of CH4, this is the reducing gas. Oxidation and reduction behavior of Ni, Ru and NiRu nanoparticles were followed in an in-situ ETEM under reacting gas conditions and the observations were correlated with the performance of the catalyst for POM. The later part of the dissertation presents a technique for determining the gas compositional analysis inside the in-situ ETEM using electron energy-loss spectroscopy. Techniques were developed to identify the gas composition using both inner-shell and low-loss spectroscopy of EELS. Using EELS, an "operando TEM" technique was successfully developed for detecting the gas phase catalysis inside the ETEM. Overall this research demonstrates the importance of in-situ ETEM studies in understanding the structure-activity relationship in supported-metal catalysts for heterogeneous catalysis application.
ContributorsChenna, Santhosh (Author) / Crozier, Peter A. (Thesis advisor) / Carpenter, Ray (Committee member) / Sieradzki, Karl (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2011
Description
Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2*-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O}). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm+ cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.
ContributorsZeller, Robert August (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
Description
A full understanding of material behavior is important for the prediction of residual useful life of aerospace structures via computational modeling. In particular, the influence of rolling-induced anisotropy on fatigue properties has not been studied extensively and it is likely to have a meaningful effect. In this work, fatigue behavior of a wrought Al alloy (2024-T351) is studied using notched uniaxial samples with load axes along either the longitudinal or transverse direction, and center notched biaxial samples (cruciforms) with a uniaxial stress state of equivalent amplitude about the bore. Local composition and crystallography were quantified before testing using Energy Dispersive Spectroscopy and Electron Backscattering Diffraction. Interrupted fatigue testing at stresses close to yielding was performed on the samples to nucleate and propagate short cracks and nucleation sites were located and characterized using standard optical and Scanning Electron Microscopy. Results show that crack nucleation occurred due to fractured particles for longitudinal dogbone/cruciform samples; while transverse samples nucleated cracks by debonded and fractured particles. Change in crack nucleation mechanism is attributed to dimensional change of particles with respect to the material axes caused by global anisotropy. Crack nucleation from debonding reduced life till matrix fracture because debonded particles are sharper and generate matrix cracks sooner than their fractured counterparts. Longitudinal samples experienced multisite crack initiation because of reduced cross sectional areas of particles parallel to the loading direction. Conversely the favorable orientation of particles in transverse samples reduced instances of particle fracture eliminating multisite cracking and leading to increased fatigue life. Cyclic tests of cruciform samples showed that crack growth favors longitudinal and transverse directions with few instances of crack growth 45 degrees (diagonal) to the rolling direction. The diagonal crack growth is attributed to stronger influences of local anisotropy on crack nucleation. It was observed that majority of the time crack nucleation is governed by the mixed influences of global and local anisotropies. Measurements of crystal directions parallel to the load on main crack paths revealed directions clustered near the {110} planes and high index directions. This trend is attributed to environmental effects as a result of cyclic testing in air.
ContributorsMakaš, Admir (Author) / Peralta, Pedro D. (Thesis advisor) / Davidson, Joseph K. (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011