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Description
Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) Å, b = 9.719(2) Å, and c = 4.4764(8) Å. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) Å. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) Å, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.
ContributorsPuhakainen, Kati (Author) / Häussermann, Ulrich (Thesis advisor) / Seo, Dong (Thesis advisor) / Kouvetakis, John (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Recently, the use of zinc oxide (ZnO) nanowires as an interphase in composite materials has been demonstrated to increase the interfacial shear strength between carbon fiber and an epoxy matrix. In this research work, the strong adhesion between ZnO and carbon fiber is investigated to elucidate the interactions at the interface that result in high interfacial strength. First, molecular dynamics (MD) simulations are performed to calculate the adhesive energy between bare carbon and ZnO. Since the carbon fiber surface has oxygen functional groups, these were modeled and MD simulations showed the preference of ketones to strongly interact with ZnO, however, this was not observed in the case of hydroxyls and carboxylic acid. It was also found that the ketone molecules ability to change orientation facilitated the interactions with the ZnO surface. Experimentally, the atomic force microscope (AFM) was used to measure the adhesive energy between ZnO and carbon through a liftoff test by employing highly oriented pyrolytic graphite (HOPG) substrate and a ZnO covered AFM tip. Oxygen functionalization of the HOPG surface shows the increase of adhesive energy. Additionally, the surface of ZnO was modified to hold a negative charge, which demonstrated an increase in the adhesive energy. This increase in adhesion resulted from increased induction forces given the relatively high polarizability of HOPG and the preservation of the charge on ZnO surface. It was found that the additional negative charge can be preserved on the ZnO surface because there is an energy barrier since carbon and ZnO form a Schottky contact. Other materials with the same ionic properties of ZnO but with higher polarizability also demonstrated good adhesion to carbon. This result substantiates that their induced interaction can be facilitated not only by the polarizability of carbon but by any of the materials at the interface. The versatility to modify the magnitude of the induced interaction between carbon and an ionic material provides a new route to create interfaces with controlled interfacial strength.
ContributorsGalan Vera, Magdian Ulises (Author) / Sodano, Henry A (Thesis advisor) / Jiang, Hanqing (Committee member) / Solanki, Kiran (Committee member) / Oswald, Jay (Committee member) / Speyer, Gil (Committee member) / Arizona State University (Publisher)
Created2013
Description
Wind measurements are fundamental inputs for the evaluation of potential energy yield and performance of wind farms. Three-dimensional scanning coherent Doppler lidar (CDL) may provide a new basis for wind farm site selection, design, and control. In this research, CDL measurements obtained from multiple wind energy developments are analyzed and a novel wind farm control approach has been modeled. The possibility of using lidar measurements to more fully characterize the wind field is discussed, specifically, terrain effects, spatial variation of winds, power density, and the effect of shear at different layers within the rotor swept area. Various vector retrieval methods have been applied to the lidar data, and results are presented on an elevated terrain-following surface at hub height. The vector retrieval estimates are compared with tower measurements, after interpolation to the appropriate level. CDL data is used to estimate the spatial power density at hub height. Since CDL can measure winds at different vertical levels, an approach for estimating wind power density over the wind turbine rotor-swept area is explored. Sample optimized layouts of wind farm using lidar data and global optimization algorithms, accounting for wake interaction effects, have been explored. An approach to evaluate spatial wind speed and direction estimates from a standard nested Coupled Ocean and Atmosphere Mesoscale Prediction System (COAMPS) model and CDL is presented. The magnitude of spatial difference between observations and simulation for wind energy assessment is researched. Diurnal effects and ramp events as estimated by CDL and COAMPS were inter-compared. Novel wind farm control based on incoming winds and direction input from CDL's is developed. Both yaw and pitch control using scanning CDL for efficient wind farm control is analyzed. The wind farm control optimizes power production and reduces loads on wind turbines for various lidar wind speed and direction inputs, accounting for wind farm wake losses and wind speed evolution. Several wind farm control configurations were developed, for enhanced integrability into the electrical grid. Finally, the value proposition of CDL for a wind farm development, based on uncertainty reduction and return of investment is analyzed.
ContributorsKrishnamurthy, Raghavendra (Author) / Calhoun, Ronald J (Thesis advisor) / Chen, Kangping (Committee member) / Huang, Huei-Ping (Committee member) / Fraser, Matthew (Committee member) / Phelan, Patrick (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation explores the use of bench-scale batch microcosms in remedial design of contaminated aquifers, presents an alternative methodology for conducting such treatability studies, and - from technical, economical, and social perspectives - examines real-world application of this new technology. In situ bioremediation (ISB) is an effective remedial approach for many contaminated groundwater sites. However, site-specific variability necessitates the performance of small-scale treatability studies prior to full-scale implementation. The most common methodology is the batch microcosm, whose potential limitations and suitable technical alternatives are explored in this thesis. In a critical literature review, I discuss how continuous-flow conditions stimulate microbial attachment and biofilm formation, and identify unique microbiological phenomena largely absent in batch bottles, yet potentially relevant to contaminant fate. Following up on this theoretical evaluation, I experimentally produce pyrosequencing data and perform beta diversity analysis to demonstrate that batch and continuous-flow (column) microcosms foster distinctly different microbial communities. Next, I introduce the In Situ Microcosm Array (ISMA), which took approximately two years to design, develop, build and iteratively improve. The ISMA can be deployed down-hole in groundwater monitoring wells of contaminated aquifers for the purpose of autonomously conducting multiple parallel continuous-flow treatability experiments. The ISMA stores all sample generated in the course of each experiment, thereby preventing the release of chemicals into the environment. Detailed results are presented from an ISMA demonstration evaluating ISB for the treatment of hexavalent chromium and trichloroethene. In a technical and economical comparison to batch microcosms, I demonstrate the ISMA is both effective in informing remedial design decisions and cost-competitive. Finally, I report on a participatory technology assessment (pTA) workshop attended by diverse stakeholders of the Phoenix 52nd Street Superfund Site evaluating the ISMA's ability for addressing a real-world problem. In addition to receiving valuable feedback on perceived ISMA limitations, I conclude from the workshop that pTA can facilitate mutual learning even among entrenched stakeholders. In summary, my doctoral research (i) pinpointed limitations of current remedial design approaches, (ii) produced a novel alternative approach, and (iii) demonstrated the technical, economical and social value of this novel remedial design tool, i.e., the In Situ Microcosm Array technology.
ContributorsKalinowski, Tomasz (Author) / Halden, Rolf U. (Thesis advisor) / Johnson, Paul C (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Bennett, Ira (Committee member) / Arizona State University (Publisher)
Created2013
Description
Production from a high pressure gas well at a high production-rate encounters the risk of operating near the choking condition for a compressible flow in porous media. The unbounded gas pressure gradient near the point of choking, which is located near the wellbore, generates an effective tensile stress on the porous rock frame. This tensile stress almost always exceeds the tensile strength of the rock and it causes a tensile failure of the rock, leading to wellbore instability. In a porous rock, not all pores are choked at the same flow rate, and when just one pore is choked, the flow through the entire porous medium should be considered choked as the gas pressure gradient at the point of choking becomes singular. This thesis investigates the choking condition for compressible gas flow in a single microscopic pore. Quasi-one-dimensional analysis and axisymmetric numerical simulations of compressible gas flow in a pore scale varicose tube with a number of bumps are carried out, and the local Mach number and pressure along the tube are computed for the flow near choking condition. The effects of tube length, inlet-to-outlet pressure ratio, the number of bumps and the amplitude of the bumps on the choking condition are obtained. These critical values provide guidance for avoiding the choking condition in practice.
ContributorsYuan, Jing (Author) / Chen, Kangping (Thesis advisor) / Wang, Liping (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2013
Description
ABSTRACT Peptide microarrays may prove to be a powerful tool for proteomics research and clinical diagnosis applications. Fodor et al. and Maurer et al. have shown proof-of-concept methods of light- and electrochemically-directed peptide microarray fabrication on glass and semiconductor microchips respectively. In this work, peptide microarray fabrication based on the abovementioned techniques were optimized. In addition, MALDI mass spectrometry based peptide synthesis characterization on semiconductor microchips was developed and novel applications of a CombiMatrix (CBMX) platform for electrochemically controlled synthesis were explored. We have investigated performance of 2-(2-nitrophenyl)propoxycarbonyl (NPPOC) derivatives as photo-labile protecting group. Specifically, influence of substituents on 4 and 5 positions of phenyl ring of NPPOC group on the rate of photolysis and the yield of the amine was investigated. The results indicated that substituents capable of forming a π-network with the nitro group enhanced the rate of photolysis and yield. Once such properly substituted NPPOC groups were used, the rate of photolysis/yield depended on the nature of protected amino group indicating that a different chemical step during the photo-cleavage process became the rate limiting step. We also focused on electrochemically-directed parallel synthesis of high-density peptide microarrays using the CBMX technology referred to above which uses electrochemically generated acids to perform patterned chemistry. Several issues related to peptide synthesis on the CBMX platform were studied and optimized, with emphasis placed on the reactions of electro-generated acids during the deprotection step of peptide synthesis. We have developed a MALDI mass spectrometry based method to determine the chemical composition of microarray synthesis, directly on the feature. This method utilizes non-diffusional chemical cleavage from the surface, thereby making the chemical characterization of high-density microarray features simple, accurate, and amenable to high-throughput. CBMX Corp. has developed a microarray reader which is based on electro-chemical detection of redox chemical species. Several parameters of the instrument were studied and optimized and novel redox applications of peptide microarrays on CBMX platform were also investigated using the instrument. These include (i) a search of metal binding catalytic peptides to reduce overpotential associated with water oxidation reaction and (ii) an immobilization of peptide microarrays using electro-polymerized polypyrrole.
ContributorsKumar, Pallav (Author) / Woodbury, Neal (Thesis advisor) / Allen, James (Committee member) / Johnston, Stephen (Committee member) / Arizona State University (Publisher)
Created2013
Description
Current policies subsidizing or accelerating deployment of photovoltaics (PV) are typically motivated by claims of environmental benefit, such as the reduction of CO2 emissions generated by the fossil-fuel fired power plants that PV is intended to displace. Existing practice is to assess these environmental benefits on a net life-cycle basis, where CO2 benefits occurring during use of the PV panels is found to exceed emissions generated during the PV manufacturing phase including materials extraction and manufacture of the PV panels prior to installation. However, this approach neglects to recognize that the environmental costs of CO2 release during manufacture are incurred early, while environmental benefits accrue later. Thus, where specific policy targets suggest meeting CO2 reduction targets established by a certain date, rapid PV deployment may have counter-intuitive, albeit temporary, undesired consequences. Thus, on a cumulative radiative forcing (CRF) basis, the environmental improvements attributable to PV might be realized much later than is currently understood. This phenomenon is particularly acute when PV manufacture occurs in areas using CO2 intensive energy sources (e.g., coal), but deployment occurs in areas with less CO2 intensive electricity sources (e.g., hydro). This thesis builds a dynamic Cumulative Radiative Forcing (CRF) model to examine the inter-temporal warming impacts of PV deployments in three locations: California, Wyoming and Arizona. The model includes the following factors that impact CRF: PV deployment rate, choice of PV technology, pace of PV technology improvements, and CO2 intensity in the electricity mix at manufacturing and deployment locations. Wyoming and California show the highest and lowest CRF benefits as they have the most and least CO2 intensive grids, respectively. CRF payback times are longer than CO2 payback times in all cases. Thin film, CdTe PV technologies have the lowest manufacturing CO2 emissions and therefore the shortest CRF payback times. This model can inform policies intended to fulfill time-sensitive CO2 mitigation goals while minimizing short term radiative forcing.
ContributorsTriplican Ravikumar, Dwarakanath (Author) / Seager, Thomas P (Thesis advisor) / Fraser, Matthew P (Thesis advisor) / Chester, Mikhail V (Committee member) / Sinha, Parikhit (Committee member) / Arizona State University (Publisher)
Created2013
Description
The objective of this thesis was to compare various approaches for classification of the `good' and `bad' parts via non-destructive resonance testing methods by collecting and analyzing experimental data in the frequency and time domains. A Laser Scanning Vibrometer was employed to measure vibrations samples in order to determine the spectral characteristics such as natural frequencies and amplitudes. Statistical pattern recognition tools such as Hilbert Huang, Fisher's Discriminant, and Neural Network were used to identify and classify the unknown samples whether they are defective or not. In this work, a Finite Element Analysis software packages (ANSYS 13.0 and NASTRAN NX8.0) was used to obtain estimates of resonance frequencies in `good' and `bad' samples. Furthermore, a system identification approach was used to generate Auto-Regressive-Moving Average with exogenous component, Box-Jenkins, and Output Error models from experimental data that can be used for classification
ContributorsJameel, Osama (Author) / Redkar, Sangram (Thesis advisor) / Arizona State University (Publisher)
Created2013
Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
Description
The ribosome is a ribozyme and central to the biosynthesis of proteins in all organisms. It has a strong bias against non-alpha-L-amino acids, such as alpha-D-amino acids and beta-amino acids. Additionally, the ribosome is only able to incorporate one amino acid in response to one codon. It has been demonstrated that reengineering of the peptidyltransferase center (PTC) of the ribosome enabled the incorporation of both alpha-D-amino acids and beta-amino acids into full length protein. Described in Chapter 2 are five modified ribosomes having modifications in the peptidyltrasnferase center in the 23S rRNA. These modified ribosomes successfully incorporated five different beta-amino acids (2.1 - 2.5) into E. coli dihydrofolate reductase (DHFR). The second project (Chapter 3) focused on the study of the modified ribosomes facilitating the incorporation of the dipeptide glycylphenylalanine (3.25) and fluorescent dipeptidomimetic 3.26 into DHFR. These ribosomes also had modifications in the peptidyltransferase center in the 23S rRNA of the 50S ribosomal subunit. The modified DHFRs having beta-amino acids 2.3 and 2.5, dipeptide glycylphenylalanine (3.25) and dipeptidomimetic 3.26 were successfully characterized by the MALDI-MS analysis of the peptide fragments produced by "in-gel" trypsin digestion of the modified proteins. The fluorescent spectra of the dipeptidomimetic 3.26 and modified DHFR having fluorescent dipeptidomimetic 3.26 were also measured. The type I and II DNA topoisomerases have been firmly established as effective molecular targets for many antitumor drugs. A "classical" topoisomerase I or II poison acts by misaligning the free hydroxyl group of the sugar moiety of DNA and preventing the reverse transesterfication reaction to religate DNA. There have been only two classes of compounds, saintopin and topopyrones, reported as dual topoisomerase I and II poisons. Chapter 4 describes the synthesis and biological evaluation of topopyrones. Compound 4.10, employed at 20 µM, was as efficient as 0.5 uM camptothecin, a potent topoisomerase I poison, in stabilizing the covalent binary complex (~30%). When compared with a known topoisomerase II poison, etoposide (at 0.5 uM), topopyorone 4.10 produced similar levels of stabilized DNA-enzyme binary complex (~34%) at 5 uM concentration.
ContributorsMaini, Rumit (Author) / Hecht, Sidney M. (Thesis advisor) / Gould, Ian (Committee member) / Yan, Hao (Committee member) / Arizona State University (Publisher)
Created2013