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This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The

This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Buildings consume a large portion of the world's energy, but with the integration of phase change materials (PCMs) in building elements this energy cost can be greatly reduced. The addition of PCMs into building elements, however, becomes a challenge to model and analyze how the material actually affects the energy

Buildings consume a large portion of the world's energy, but with the integration of phase change materials (PCMs) in building elements this energy cost can be greatly reduced. The addition of PCMs into building elements, however, becomes a challenge to model and analyze how the material actually affects the energy flow and temperatures in the system. This research work presents a comprehensive computer program used to model and analyze PCM embedded wall systems. The use of the finite element method (FEM) provides the tool to analyze the energy flow of these systems. Finite element analysis (FEA) can model the transient analysis of a typical climate cycle along with nonlinear problems, which the addition of PCM causes. The use of phase change materials is also a costly material expense. The initial expense of using PCMs can be compensated by the reduction in energy costs it can provide. Optimization is the tool used to determine the optimal point between adding PCM into a wall and the amount of energy savings that layer will provide. The integration of these two tools into a computer program allows for models to be efficiently created, analyzed and optimized. The program was then used to understand the benefits between two different wall models, a wall with a single layer of PCM or a wall with two different PCM layers. The effect of the PCMs on the inside wall temperature along with the energy flow across the wall are computed. The numerical results show that a multi-layer PCM wall was more energy efficient and cost effective than the single PCM layer wall. A structural analysis was then performed on the optimized designs using ABAQUS v. 6.10 to ensure the structural integrity of the wall was not affected by adding PCM layer(s).
ContributorsStockwell, Amie (Author) / Rajan, Subramaniam D. (Thesis advisor) / Neithalath, Narayanan (Thesis advisor) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Unsaturated soil mechanics is becoming a part of geotechnical engineering practice, particularly in applications to moisture sensitive soils such as expansive and collapsible soils and in geoenvironmental applications. The soil water characteristic curve, which describes the amount of water in a soil versus soil suction, is perhaps the most important

Unsaturated soil mechanics is becoming a part of geotechnical engineering practice, particularly in applications to moisture sensitive soils such as expansive and collapsible soils and in geoenvironmental applications. The soil water characteristic curve, which describes the amount of water in a soil versus soil suction, is perhaps the most important soil property function for application of unsaturated soil mechanics. The soil water characteristic curve has been used extensively for estimating unsaturated soil properties, and a number of fitting equations for development of soil water characteristic curves from laboratory data have been proposed by researchers. Although not always mentioned, the underlying assumption of soil water characteristic curve fitting equations is that the soil is sufficiently stiff so that there is no change in total volume of the soil while measuring the soil water characteristic curve in the laboratory, and researchers rarely take volume change of soils into account when generating or using the soil water characteristic curve. Further, there has been little attention to the applied net normal stress during laboratory soil water characteristic curve measurement, and often zero to only token net normal stress is applied. The applied net normal stress also affects the volume change of the specimen during soil suction change. When a soil changes volume in response to suction change, failure to consider the volume change of the soil leads to errors in the estimated air-entry value and the slope of the soil water characteristic curve between the air-entry value and the residual moisture state. Inaccuracies in the soil water characteristic curve may lead to inaccuracies in estimated soil property functions such as unsaturated hydraulic conductivity. A number of researchers have recently recognized the importance of considering soil volume change in soil water characteristic curves. The study of correct methods of soil water characteristic curve measurement and determination considering soil volume change, and impacts on the unsaturated hydraulic conductivity function was of the primary focus of this study. Emphasis was placed upon study of the effect of volume change consideration on soil water characteristic curves, for expansive clays and other high volume change soils. The research involved extensive literature review and laboratory soil water characteristic curve testing on expansive soils. The effect of the initial state of the specimen (i.e. slurry versus compacted) on soil water characteristic curves, with regard to volume change effects, and effect of net normal stress on volume change for determination of these curves, was studied for expansive clays. Hysteresis effects were included in laboratory measurements of soil water characteristic curves as both wetting and drying paths were used. Impacts of soil water characteristic curve volume change considerations on fluid flow computations and associated suction-change induced soil deformations were studied through numerical simulations. The study includes both coupled and uncoupled flow and stress-deformation analyses, demonstrating that the impact of volume change consideration on the soil water characteristic curve and the estimated unsaturated hydraulic conductivity function can be quite substantial for high volume change soils.
ContributorsBani Hashem, Elham (Author) / Houston, Sandra L. (Thesis advisor) / Kavazanjian, Edward (Committee member) / Zapata, Claudia (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Laboratory assessment of crack resistance and propagation in asphalt concrete is a difficult task that challenges researchers and engineers. Several fracture mechanics based laboratory tests currently exist; however, these tests and subsequent analysis methods rely on elastic behavior assumptions and do not consider the time-dependent nature of asphalt concrete. The

Laboratory assessment of crack resistance and propagation in asphalt concrete is a difficult task that challenges researchers and engineers. Several fracture mechanics based laboratory tests currently exist; however, these tests and subsequent analysis methods rely on elastic behavior assumptions and do not consider the time-dependent nature of asphalt concrete. The C* Line Integral test has shown promise to capture crack resistance and propagation within asphalt concrete. In addition, the fracture mechanics based C* parameter considers the time-dependent creep behavior of the materials. However, previous research was limited and lacked standardized test procedure and detailed data analysis methods were not fully presented. This dissertation describes the development and refinement of the C* Fracture Test (CFT) based on concepts of the C* line integral test. The CFT is a promising test to assess crack propagation and fracture resistance especially in modified mixtures. A detailed CFT test protocol was developed based on a laboratory study of different specimen sizes and test conditions. CFT numerical simulations agreed with laboratory results and indicated that the maximum horizontal tensile stress (Mode I) occurs at the crack tip but diminishes at longer crack lengths when shear stress (Mode II) becomes present. Using CFT test results and the principles of time-temperature superposition, a crack growth rate master curve was successfully developed to describe crack growth over a range of test temperatures. This master curve can be applied to pavement design and analysis to describe crack propagation as a function of traffic conditions and pavement temperatures. Several plant mixtures were subjected to the CFT and results showed differences in resistance to crack propagation, especially when comparing an asphalt rubber mixture to a conventional one. Results indicated that crack propagation is ideally captured within a given range of dynamic modulus values. Crack growth rates and C* prediction models were successfully developed for all unmodified mixtures in the CFT database. These models can be used to predict creep crack propagation and the C* parameter when laboratory testing is not feasible. Finally, a conceptual approach to incorporate crack growth rate and the C* parameter into pavement design and analysis was presented.
ContributorsStempihar, Jeffrey (Author) / Kaloush, Kamil (Thesis advisor) / Witczak, Matthew (Committee member) / Mamlouk, Michael (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Woven fabric composite materials are widely used in the construction of aircraft engine fan containment systems, mostly due to their high strength to weight ratios and ease of implementation. The development of a predictive model for fan blade containment would provide great benefit to engine manufactures in shortened development cycle

Woven fabric composite materials are widely used in the construction of aircraft engine fan containment systems, mostly due to their high strength to weight ratios and ease of implementation. The development of a predictive model for fan blade containment would provide great benefit to engine manufactures in shortened development cycle time, less risk in certification and fewer dollars lost to redesign/recertification cycles. A mechanistic user-defined material model subroutine has been developed at Arizona State University (ASU) that captures the behavioral response of these fabrics, namely Kevlar® 49, under ballistic loading. Previously developed finite element models used to validate the consistency of this material model neglected the effects of the physical constraints imposed on the test setup during ballistic testing performed at NASA Glenn Research Center (NASA GRC). Part of this research was to explore the effects of these boundary conditions on the results of the numerical simulations. These effects were found to be negligible in most instances. Other material models for woven fabrics are available in the LS-DYNA finite element code. One of these models, MAT234: MAT_VISCOELASTIC_LOOSE_FABRIC (Ivanov & Tabiei, 2004) was studied and implemented in the finite element simulations of ballistic testing associated with the FAA ASU research. The results from these models are compared to results obtained from the ASU UMAT as part of this research. The results indicate an underestimation in the energy absorption characteristics of the Kevlar 49 fabric containment systems. More investigation needs to be performed in the implementation of MAT234 for Kevlar 49 fabric. Static penetrator testing of Kevlar® 49 fabric was performed at ASU in conjunction with this research. These experiments are designed to mimic the type of loading experienced during fan blade out events. The resulting experimental strains were measured using a non-contact optical strain measurement system (ARAMIS).
ContributorsFein, Jonathan (Author) / Rajan, Subramaniam D. (Thesis advisor) / Mobasher, Barzin (Committee member) / Jiang, Hanqing (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of

Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of Ge-buffered Si(100) wafers as a low cost platform for epitaxy of In1-xGaxAs layers was explored. The results indicate that this approach has promise for transitioning from bulk Ge platforms to virtual substrates for a significant cost reduction. The electrical and optical properties of Ge and Ge1-ySny layers produced using several different techniques were explored via fabrication of high performance heterostructure photodiodes. First, a new CVD approach to Ge-like materials was developed in which germanium is alloyed with very small amounts of tin. These alloys exhibited no significant difference in their structural properties or band gap compared to pure Ge, however superior photo response and reduced dark currents were observed from fabricated devices relative to pure Ge on Si reference diodes. Additionally, pure Ge/Si(100) photodiodes were fabricated using layers grown via reactions of Ge4H10 on Si(100) and found to exhibit low dark current densities with high collection efficiencies. Ge1-x-ySixSny materials represent the newest member of group IV alloy family. The ability to decouple the lattice constant and the band gap in this system has led to strong interest both for strain/confinement layers in quantum well structures, and as the possible "missing" 1 eV junction in multijunction photovoltaics. Recent progress in this field has allowed for the first time growth, fabrication and measurement of novel photodiodes based on Ge1-x-ySixSny. This work presents the material, electrical and optical properties of Ge1-x-ySixSny layers and photodiodes grown directly on Ge and Si wafers using two different synthetic approaches. A series of photodiodes containing Sn concentrations from 1-5%, all lattice matched to Ge, was fabricated. The devices exhibited low dark current densities with high collection efficiencies as required for photovoltaics. By measuring the photoresponse, tunable band gaps ranging from 0.85 eV to 1.02 eV were observed.
ContributorsBeeler, Richard (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Urban water systems face sustainability challenges ranging from water quality, leaks, over-use, energy consumption, and long-term supply concerns. Resiliency challenges include the capacity to respond to drought, managing pipe deterioration, responding to natural disasters, and preventing terrorism. One strategy to enhance sustainability and resiliency is the development and adoption of

Urban water systems face sustainability challenges ranging from water quality, leaks, over-use, energy consumption, and long-term supply concerns. Resiliency challenges include the capacity to respond to drought, managing pipe deterioration, responding to natural disasters, and preventing terrorism. One strategy to enhance sustainability and resiliency is the development and adoption of smart water grids. A smart water grid incorporates networked monitoring and control devices into its structure, which provides diverse, real-time information about the system, as well as enhanced control. Data provide input for modeling and analysis, which informs control decisions, allowing for improvement in sustainability and resiliency. While smart water grids hold much potential, there are also potential tradeoffs and adoption challenges. More publicly available cost-benefit analyses are needed, as well as system-level research and application, rather than the current focus on individual technologies. This thesis seeks to fill one of these gaps by analyzing the cost and environmental benefits of smart irrigation controllers. Smart irrigation controllers can save water by adapting watering schedules to climate and soil conditions. The potential benefit of smart irrigation controllers is particularly high in southwestern U.S. states, where the arid climate makes water scarcer and increases watering needs of landscapes. To inform the technology development process, a design for environment (DfE) method was developed, which overlays economic and environmental performance parameters under different operating conditions. This method is applied to characterize design goals for controller price and water savings that smart irrigation controllers must meet to yield life cycle carbon dioxide reductions and economic savings in southwestern U.S. states, accounting for regional variability in electricity and water prices and carbon overhead. Results from applying the model to smart irrigation controllers in the Southwest suggest that some areas are significantly easier to design for.
ContributorsMutchek, Michele (Author) / Allenby, Braden (Thesis advisor) / Williams, Eric (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Mitochondria produce most of the ATP needed for the cell as an energy source. It is well known that cellular respiration results in oxidative damage to the cell due to the production of reactive oxygen species (ROS). Mitochondrial dysfunction is believed to contribute to a number of degenerative diseases; because

Mitochondria produce most of the ATP needed for the cell as an energy source. It is well known that cellular respiration results in oxidative damage to the cell due to the production of reactive oxygen species (ROS). Mitochondrial dysfunction is believed to contribute to a number of degenerative diseases; because of this the mitochondrial respiratory chain is considered as potential drug target. A few series of idebenone analogues with quinone, pyridinol and pyrimidinol redox cores have been synthesized and evaluated as antioxidants able to protect cellular integrity and, more specifically, mitochondrial function. The compounds exhibited a range of activities. The activities observed were used for the design of analogues with enhanced properties as antioxidants. Compounds were identified which provide better protection against oxidative stress than idebenone, and it is thought that they do so catalytically.
ContributorsArce Amezquita, Pablo M (Author) / Hecht, Sidney M. (Thesis advisor) / Moore, Ana (Committee member) / Rose, Seth (Committee member) / Arizona State University (Publisher)
Created2012
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Description
This study focuses on implementing probabilistic nature of material properties (Kevlar® 49) to the existing deterministic finite element analysis (FEA) of fabric based engine containment system through Monte Carlo simulations (MCS) and implementation of probabilistic analysis in engineering designs through Reliability Based Design Optimization (RBDO). First, the emphasis is on

This study focuses on implementing probabilistic nature of material properties (Kevlar® 49) to the existing deterministic finite element analysis (FEA) of fabric based engine containment system through Monte Carlo simulations (MCS) and implementation of probabilistic analysis in engineering designs through Reliability Based Design Optimization (RBDO). First, the emphasis is on experimental data analysis focusing on probabilistic distribution models which characterize the randomness associated with the experimental data. The material properties of Kevlar® 49 are modeled using experimental data analysis and implemented along with an existing spiral modeling scheme (SMS) and user defined constitutive model (UMAT) for fabric based engine containment simulations in LS-DYNA. MCS of the model are performed to observe the failure pattern and exit velocities of the models. Then the solutions are compared with NASA experimental tests and deterministic results. MCS with probabilistic material data give a good prospective on results rather than a single deterministic simulation results. The next part of research is to implement the probabilistic material properties in engineering designs. The main aim of structural design is to obtain optimal solutions. In any case, in a deterministic optimization problem even though the structures are cost effective, it becomes highly unreliable if the uncertainty that may be associated with the system (material properties, loading etc.) is not represented or considered in the solution process. Reliable and optimal solution can be obtained by performing reliability optimization along with the deterministic optimization, which is RBDO. In RBDO problem formulation, in addition to structural performance constraints, reliability constraints are also considered. This part of research starts with introduction to reliability analysis such as first order reliability analysis, second order reliability analysis followed by simulation technique that are performed to obtain probability of failure and reliability of structures. Next, decoupled RBDO procedure is proposed with a new reliability analysis formulation with sensitivity analysis, which is performed to remove the highly reliable constraints in the RBDO, thereby reducing the computational time and function evaluations. Followed by implementation of the reliability analysis concepts and RBDO in finite element 2D truss problems and a planar beam problem are presented and discussed.
ContributorsDeivanayagam, Arumugam (Author) / Rajan, Subramaniam D. (Thesis advisor) / Mobasher, Barzin (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2012
Description
As the genetic information storage vehicle, deoxyribonucleic acid (DNA) molecules are essential to all known living organisms and many viruses. It is amazing that such a large amount of information about how life develops can be stored in these tiny molecules. Countless scientists, especially some biologists, are trying to decipher

As the genetic information storage vehicle, deoxyribonucleic acid (DNA) molecules are essential to all known living organisms and many viruses. It is amazing that such a large amount of information about how life develops can be stored in these tiny molecules. Countless scientists, especially some biologists, are trying to decipher the genetic information stored in these captivating molecules. Meanwhile, another group of researchers, nanotechnologists in particular, have discovered that the unique and concise structural features of DNA together with its information coding ability can be utilized for nano-construction efforts. This idea culminated in the birth of the field of DNA nanotechnology which is the main topic of this dissertation. The ability of rationally designed DNA strands to self-assemble into arbitrary nanostructures without external direction is the basis of this field. A series of novel design principles for DNA nanotechnology are presented here, from topological DNA nanostructures to complex and curved DNA nanostructures, from pure DNA nanostructures to hybrid RNA/DNA nanostructures. As one of the most important and pioneering fields in controlling the assembly of materials (both DNA and other materials) at the nanoscale, DNA nanotechnology is developing at a dramatic speed and as more and more construction approaches are invented, exciting advances will emerge in ways that we may or may not predict.
ContributorsHan, Dongran (Author) / Yan, Hao (Thesis advisor) / Liu, Yan (Thesis advisor) / Ros, Anexandra (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2012