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- Genre: Doctoral Dissertation
Description
Water resource management is becoming increasingly burdened by uncertain and fluctuating conditions resulting from climate change and population growth which place increased demands on already strained resources. Innovative water management schemes are necessary to address the reality of available water supplies. One such approach is the substitution of trade in virtual water for the use of local water supplies. This study provides a review of existing work in the use of virtual water and water footprint methods. Virtual water trade has been shown to be a successful method for addressing water scarcity and decreasing overall water consumption by shifting high water consumptive processes to wetter regions. These results however assume that all water resource supplies are equivalent regardless of physical location and they do not tie directly to economic markets. In this study we introduce a new mathematical framework, Embedded Resource Accounting (ERA), which is a synthesis of several different analytical methods presently used to quantify and describe human interactions with the economy and the natural environment. We define the specifics of the ERA framework in a generic context for the analysis of embedded resource trade in a way that links directly with the economics of that trade. Acknowledging the cyclical nature of water and the abundance of actual water resources on Earth, this study addresses fresh water availability within a given region. That is to say, the quantities of fresh water supplies annually available at acceptable quality for anthropogenic uses. The results of this research provide useful tools for water resource managers and policy makers to inform decision making on, (1) reallocation of local available fresh water resources, and (2) strategic supplementation of those resources with outside fresh water resources via the import of virtual water.
ContributorsAdams, Elizabeth Anne (Author) / Ruddell, Benjamin L (Thesis advisor) / Allenby, Braden R. (Thesis advisor) / Seager, Thomas P (Committee member) / Arizona State University (Publisher)
Created2013
Description
After a decade of efforts, accurate and affordable DNA sequencing continues to remain an important goal in current research landscape. This thesis starts with a brief overview of the recent updates in the field of DNA sequencing technologies followed by description of the nanofluidics route to single molecule DNA detection. Chapter 2 presents discusses carbon nanotube(CNT) based nanofluidics. The fabrication and DNA sensing measurements of CNT forest membrane devices are presented. Chapter 3 gives the background for functionalization and recognition aspects of reader molecules. Chapter 4 marks the transition to solid state nanopore nanofluidics. The fabrication of Imidazole functionalized nanopores is discussed. The Single Molecule detection results of DNA from Palladium nanopore devices are presented next. Combining chemical recognition to nanopore technology, it has been possible to prolong the duration of single molecule events from the order of a few micro seconds to upto a few milliseconds. Overall, the work presented in this thesis promises longer single molecule detection time in a nanofludic set up and paves way for novel nanopore- tunnel junction devices that combine recognition chemistry, tunneling device and nanopore approach.
ContributorsKrishnakumar, Padmini (Author) / Lindsay, Stuart (Thesis advisor) / He, Jin (Committee member) / Vaiana, Sara (Committee member) / Schmidt, Kevin (Committee member) / Arizona State University (Publisher)
Created2013
Description
In a laboratory setting, the soil volume change behavior is best represented by using various testing standards on undisturbed or remolded samples. Whenever possible, it is most precise to use undisturbed samples to assess the volume change behavior but in the absence of undisturbed specimens, remodeled samples can be used. If that is the case, the soil is compacted to in-situ density and water content (or matric suction), which should best represent the expansive profile in question. It is standard practice to subject the specimen to a wetting process at a particular net normal stress. Even though currently accepted laboratory testing standard procedures provide insight on how the profile conditions changes with time, these procedures do not assess the long term effects on the soil due to climatic changes. In this experimental study, an assessment and quantification of the effect of multiple wetting/drying cycles on the volume change behavior of two different naturally occurring soils was performed. The changes in wetting and drying cycles were extreme when comparing the swings in matric suction. During the drying cycle, the expansive soil was subjected to extreme conditions, which decreased the moisture content less than the shrinkage limit. Nevertheless, both soils were remolded at five different compacted conditions and loaded to five different net normal stresses. Each sample was subjected to six wetting and drying cycles. During the assessment, it was evident from the results that the swell/collapse strain is highly non-linear at low stress levels. The strain-net normal stress relationship cannot be defined by one single function without transforming the data. Therefore, the dataset needs to be fitted to a bi-modal logarithmic function or to a logarithmic transformation of net normal stress in order to use a third order polynomial fit. It was also determined that the moisture content changes with time are best fit by non-linear functions. For the drying cycle, the radial strain was determined to have a constant rate of change with respect to the axial strain. However, for the wetting cycle, there was not enough radial strain data to develop correlations and therefore, an assumption was made based on 55 different test measurements/observations, for the wetting cycles. In general, it was observed that after each subsequent cycle, higher swelling was exhibited for lower net normal stress values; while higher collapse potential was observed for higher net normal stress values, once the net normal stress was less than/greater than a threshold net normal stress value. Furthermore, the swelling pressure underwent a reduction in all cases. Particularly, the Anthem soil exhibited a reduction in swelling pressure by at least 20 percent after the first wetting/drying cycle; while Colorado soil exhibited a reduction of 50 percent. After about the fourth cycle, the swelling pressure seemed to stabilized to an equilibrium value at which a reduction of 46 percent was observed for the Anthem soil and 68 percent reduction for the Colorado soil. The impact of the initial compacted conditions on heave characteristics was studied. Results indicated that materials compacted at higher densities exhibited greater swell potential. When comparing specimens compacted at the same density but at different moisture content (matric suction), it was observed that specimens compacted at higher suction would exhibit higher swelling potential, when subjected to the same net normal stress. The least amount of swelling strain was observed on specimens compacted at the lowest dry density and the lowest matric suction (higher water content). The results from the laboratory testing were used to develop ultimate heave profiles for both soils. This analysis showed that even though the swell pressure for each soil decreased with cycles, the amount of heave would increase or decrease depending upon the initial compaction condition. When the specimen was compacted at 110% of optimum moisture content and 90% of maximum dry density, it resulted in an ultimate heave reduction of 92 percent for Anthem and 685 percent for Colorado soil. On the other hand, when the soils were compacted at 90% optimum moisture content and 100% of the maximum dry density, Anthem specimens heave 78% more and Colorado specimens heave was reduced by 69%. Based on the results obtained, it is evident that the current methods to estimate heave and swelling pressure do not consider the effect of wetting/drying cycles; and seem to fail capturing the free swell potential of the soil. Recommendations for improvement current methods of practice are provided.
ContributorsRosenbalm, Daniel Curtis (Author) / Zapata, Claudia E (Thesis advisor) / Houston, Sandra L. (Committee member) / Kavazanjian, Edward (Committee member) / Witczak, Mathew W (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
The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states, exciton binding energies, and effects of electron irradiation on luminescence. Part of this work is focused on p-type Mg-doped GaN and InGaN. These materials are extremely important for the fabrication of visible light emitting diodes and diode lasers and their complex nature is currently not entirely understood. The luminescence of Mg-doped GaN films has been correlated with electrical and structural measurements in order to understand the behavior of hydrogen in the material. Deeply-bound excitons emitting near 3.37 and 3.42 eV are observed in films with a significant hydrogen concentration during cathodoluminescence at liquid helium temperatures. These radiative transitions are unstable during electron irradiation. Our observations suggest a hydrogen-related nature, as opposed to a previous assignment of stacking fault luminescence. The intensity of the 3.37 eV transition can be correlated with the electrical activation of the Mg acceptors. Next, the acceptor energy level of Mg in InGaN is shown to decrease significantly with an increase in the indium composition. This also corresponds to a decrease in the resistivity of these films. In addition, the hole concentration in multiple quantum well light emitting diode structures is much more uniform in the active region when Mg-doped InGaN (instead of Mg-doped GaN) is used. These results will help improve the efficiency of light emitting diodes, especially in the green/yellow color range. Also, the improved hole transport may prove to be important for the development of photovoltaic devices. Cathodoluminescence studies have also been performed on nanoindented ZnO crystals. Bulk, single crystal ZnO was indented using a sub-micron spherical diamond tip on various surface orientations. The resistance to deformation (the "hardness") of each surface orientation was measured, with the c-plane being the most resistive. This is due to the orientation of the easy glide planes, the c-planes, being positioned perpendicularly to the applied load. The a-plane oriented crystal is the least resistive to deformation. Cathodoluminescence imaging allows for the correlation of the luminescence with the regions located near the indentation. Sub-nanometer shifts in the band edge emission have been assigned to residual strain the crystals. The a- and m-plane oriented crystals show two-fold symmetry with regions of compressive and tensile strain located parallel and perpendicular to the ±c-directions, respectively. The c-plane oriented crystal shows six-fold symmetry with regions of tensile strain extending along the six equivalent a-directions.
ContributorsJuday, Reid (Author) / Ponce, Fernando A. (Thesis advisor) / Drucker, Jeff (Committee member) / Mccartney, Martha R (Committee member) / Menéndez, Jose (Committee member) / Shumway, John (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation is focused on material property exploration and analysis using computational quantum mechanics methods. Theoretical calculations were performed on the recently discovered hexahydride materials A2SiH6 (A=Rb, K) to calculate the lattice dynamics of the systems in order to check for structural stability, verify the experimental Raman and infrared spectrospcopy results, and obtain the theoretical free energies of formation. The electronic structure of the systems was calculated and the bonding and ionic properties of the systems were analyzed. The novel hexahydrides were compared to the important hydrogen storage material KSiH3. This showed that the hypervalent nature of the SiH62- ions reduced the Si-H bonding strength considerably. These hydrogen rich compounds could have promising energy applications as they link to alternative hydrogen fuel technology. The carbide systems Li-C (A=Li,Ca,Mg) were studied using \emph{ab initio} and evolutionary algorithms at high pressures. At ambient pressure Li2C2 and CaC2 are known to contain C22- dumbbell anions and CaC2 is polymorphic. At elevated pressure both CaC2 and Li2C2 display polymorphism. At ambient pressure the Mg-C system contains several experimentally known phases, however, all known phases are shown to be metastable with respect to the pure elements Mg and C. First principle investigation of the configurational space of these compounds via evolutionary algorithms results in a variety of metastable and unique structures. The binary compounds ZnSb and ZnAs are II-V electron-poor semiconductors with interesting thermoelectric properties. They contain rhomboid rings composed of Zn2Sb2 (Zn2As2) with multi-centered covalent bonds which are in turn covalently bonded to other rings via two-centered, two-electron bonds. Ionicity was explored via Bader charge analysis and it appears that the low ionicity that these materials display is a necessary condition of their multicentered bonding. Both compounds were found to have narrow, indirect band gaps with multi-valley valence and conduction bands; which are important characteristics for high thermopower in thermoelectric materials. Future work is needed to analyze the lattice properties of the II-V CdSb-type systems, especially in order to find the origin of the extremely low thermal conductivity that these systems display.
ContributorsBenson, Daryn Eugene (Author) / Häussermann, Ulrich (Thesis advisor) / Shumway, John (Thesis advisor) / Chamberlin, Ralph (Committee member) / Sankey, Otto (Committee member) / Treacy, Mike (Committee member) / Arizona State University (Publisher)
Created2013
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 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
Description
This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some fundamental issues regarding compositional fluctuations and microstructure in GaInNAs and InAlN alloys. In the first part, the microstructure of (001) InP scratched in an atomic force microscope with a small diamond tip has been studied as a function of applied normal force and crystalline direction in order to understand at the nanometer scale the deformation mechanisms in the zinc-blende structure. TEM images show deeper dislocation propagation for scratches along <110> compared to <100>. High strain fields were observed in <100> scratches, indicating hardening due to locking of dislocations gliding on different slip planes. Reverse plastic flow have been observed in <110> scratches in the form of pop-up events that result from recovery of stored elastic strain. In a separate study, nanoindentation-induced plastic deformation has been studied in c-, a-, and m-plane ZnO single crystals and c-plane GaN respectively, to study the deformation mechanism in wurtzite hexagonal structures. TEM results reveal that the prime deformation mechanism is slip on basal planes and in some cases, on pyramidal planes, and strain built up along particular directions. No evidence of phase transformation or cracking was observed in both materials. CL imaging reveals quenching of near band-edge emission by dislocations. In the second part, compositional inhomogeneity in quaternary GaInNAs and ternary InAlN alloys has been studied using TEM. It is shown that exposure to antimony during growth of GaInNAs results in uniform chemical composition in the epilayer, as antimony suppresses the surface mobility of adatoms that otherwise leads to two-dimensional growth and elemental segregation. In a separate study, compositional instability is observed in lattice-matched InAlN films grown on GaN, for growth beyond a certain thickness. Beyond 200 nm of thickness, two sub-layers with different indium content are observed, the top one with lower indium content.
ContributorsHuang, Jingyi (Author) / Ponce, Fernando A. (Thesis advisor) / Carpenter, Ray W (Committee member) / Smith, David J. (Committee member) / Yu, Hongbin (Committee member) / Treacy, Michael Mj (Committee member) / Arizona State University (Publisher)
Created2013
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 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
Description
One dimensional (1D) and quasi-one dimensional quantum wires have been a subject of both theoretical and experimental interest since 1990s and before. Phenomena such as the "0.7 structure" in the conductance leave many open questions. In this dissertation, I study the properties and the internal electron states of semiconductor quantum wires with the path integral Monte Carlo (PIMC) method. PIMC is a tool for simulating many-body quantum systems at finite temperature. Its ability to calculate thermodynamic properties and various correlation functions makes it an ideal tool in bridging experiments with theories. A general study of the features interpreted by the Luttinger liquid theory and observed in experiments is first presented, showing the need for new PIMC calculations in this field. I calculate the DC conductance at finite temperature for both noninteracting and interacting electrons. The quantized conductance is identified in PIMC simulations without making the same approximation in the Luttinger model. The low electron density regime is subject to strong interactions, since the kinetic energy decreases faster than the Coulomb interaction at low density. An electron state called the Wigner crystal has been proposed in this regime for quasi-1D wires. By using PIMC, I observe the zig-zag structure of the Wigner crystal. The quantum fluctuations suppress the long range correla- tions, making the order short-ranged. Spin correlations are calculated and used to evaluate the spin coupling strength in a zig-zag state. I also find that as the density increases, electrons undergo a structural phase transition to a dimer state, in which two electrons of opposite spins are coupled across the two rows of the zig-zag. A phase diagram is sketched for a range of densities and transverse confinements. The quantum point contact (QPC) is a typical realization of quantum wires. I study the QPC by explicitly simulating a system of electrons in and around a Timp potential (Timp, 1992). Localization of a single electron in the middle of the channel is observed at 5 K, as the split gate voltage increases. The DC conductance is calculated, which shows the effect of the Coulomb interaction. At 1 K and low electron density, a state similar to the Wigner crystal is found inside the channel.
ContributorsLiu, Jianheng, 1982- (Author) / Shumway, John B (Thesis advisor) / Schmidt, Kevin E (Committee member) / Chen, Tingyong (Committee member) / Yu, Hongbin (Committee member) / Ros, Robert (Committee member) / Arizona State University (Publisher)
Created2012