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- Genre: Doctoral Dissertation
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
Practical communication systems are subject to errors due to imperfect time alignment among the communicating nodes. Timing errors can occur in different forms depending on the underlying communication scenario. This doctoral study considers two different classes of asynchronous systems; point-to-point (P2P) communication systems with synchronization errors, and asynchronous cooperative systems. In particular, the focus is on an information theoretic analysis for P2P systems with synchronization errors and developing new signaling solutions for several asynchronous cooperative communication systems. The first part of the dissertation presents several bounds on the capacity of the P2P systems with synchronization errors. First, binary insertion and deletion channels are considered where lower bounds on the mutual information between the input and output sequences are computed for independent uniformly distributed (i.u.d.) inputs. Then, a channel suffering from both synchronization errors and additive noise is considered as a serial concatenation of a synchronization error-only channel and an additive noise channel. It is proved that the capacity of the original channel is lower bounded in terms of the synchronization error-only channel capacity and the parameters of both channels. On a different front, to better characterize the deletion channel capacity, the capacity of three independent deletion channels with different deletion probabilities are related through an inequality resulting in the tightest upper bound on the deletion channel capacity for deletion probabilities larger than 0.65. Furthermore, the first non-trivial upper bound on the 2K-ary input deletion channel capacity is provided by relating the 2K-ary input deletion channel capacity with the binary deletion channel capacity through an inequality. The second part of the dissertation develops two new relaying schemes to alleviate asynchronism issues in cooperative communications. The first one is a single carrier (SC)-based scheme providing a spectrally efficient Alamouti code structure at the receiver under flat fading channel conditions by reducing the overhead needed to overcome the asynchronism and obtain spatial diversity. The second one is an orthogonal frequency division multiplexing (OFDM)-based approach useful for asynchronous cooperative systems experiencing excessive relative delays among the relays under frequency-selective channel conditions to achieve a delay diversity structure at the receiver and extract spatial diversity.
ContributorsRahmati, Mojtaba (Author) / Duman, Tolga M. (Thesis advisor) / Zhang, Junshan (Committee member) / Tepedelenlioğlu, Cihan (Committee member) / Reisslein, Martin (Committee member) / Arizona State University (Publisher)
Created2013
Description
Digital sound synthesis allows the creation of a great variety of sounds. Focusing on interesting or ecologically valid sounds for music, simulation, aesthetics, or other purposes limits the otherwise vast digital audio palette. Tools for creating such sounds vary from arbitrary methods of altering recordings to precise simulations of vibrating objects. In this work, methods of sound synthesis by re-sonification are considered. Re-sonification, herein, refers to the general process of analyzing, possibly transforming, and resynthesizing or reusing recorded sounds in meaningful ways, to convey information. Applied to soundscapes, re-sonification is presented as a means of conveying activity within an environment. Applied to the sounds of objects, this work examines modeling the perception of objects as well as their physical properties and the ability to simulate interactive events with such objects. To create soundscapes to re-sonify geographic environments, a method of automated soundscape design is presented. Using recorded sounds that are classified based on acoustic, social, semantic, and geographic information, this method produces stochastically generated soundscapes to re-sonify selected geographic areas. Drawing on prior knowledge, local sounds and those deemed similar comprise a locale's soundscape. In the context of re-sonifying events, this work examines processes for modeling and estimating the excitations of sounding objects. These include plucking, striking, rubbing, and any interaction that imparts energy into a system, affecting the resultant sound. A method of estimating a linear system's input, constrained to a signal-subspace, is presented and applied toward improving the estimation of percussive excitations for re-sonification. To work toward robust recording-based modeling and re-sonification of objects, new implementations of banded waveguide (BWG) models are proposed for object modeling and sound synthesis. Previous implementations of BWGs use arbitrary model parameters and may produce a range of simulations that do not match digital waveguide or modal models of the same design. Subject to linear excitations, some models proposed here behave identically to other equivalently designed physical models. Under nonlinear interactions, such as bowing, many of the proposed implementations exhibit improvements in the attack characteristics of synthesized sounds.
ContributorsFink, Alex M (Author) / Spanias, Andreas S (Thesis advisor) / Cook, Perry R. (Committee member) / Turaga, Pavan (Committee member) / Tsakalis, Konstantinos (Committee member) / Arizona State University (Publisher)
Created2013
Description
Continuous monitoring in the adequate temporal and spatial scale is necessary for a better understanding of environmental variations. But field deployments of molecular biological analysis platforms in that scale are currently hindered because of issues with power, throughput and automation. Currently, such analysis is performed by the collection of large sample volumes from over a wide area and transporting them to laboratory testing facilities, which fail to provide any real-time information. This dissertation evaluates the systems currently utilized for in-situ field analyses and the issues hampering the successful deployment of such bioanalytial instruments for environmental applications. The design and development of high throughput, low power, and autonomous Polymerase Chain Reaction (PCR) instruments, amenable for portable field operations capable of providing quantitative results is presented here as part of this dissertation. A number of novel innovations have been reported here as part of this work in microfluidic design, PCR thermocycler design, optical design and systems integration. Emulsion microfluidics in conjunction with fluorinated oils and Teflon tubing have been used for the fluidic module that reduces cross-contamination eliminating the need for disposable components or constant cleaning. A cylindrical heater has been designed with the tubing wrapped around fixed temperature zones enabling continuous operation. Fluorescence excitation and detection have been achieved by using a light emitting diode (LED) as the excitation source and a photomultiplier tube (PMT) as the detector. Real-time quantitative PCR results were obtained by using multi-channel fluorescence excitation and detection using LED, optical fibers and a 64-channel multi-anode PMT for measuring continuous real-time fluorescence. The instrument was evaluated by comparing the results obtained with those obtained from a commercial instrument and found to be comparable. To further improve the design and enhance its field portability, this dissertation also presents a framework for the instrumentation necessary for a portable digital PCR platform to achieve higher throughputs with lower power. Both systems were designed such that it can easily couple with any upstream platform capable of providing nucleic acid for analysis using standard fluidic connections. Consequently, these instruments can be used not only in environmental applications, but portable diagnostics applications as well.
ContributorsRay, Tathagata (Author) / Youngbull, Cody (Thesis advisor) / Goryll, Michael (Thesis advisor) / Blain Christen, Jennifer (Committee member) / Yu, Hongyu (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
Global Positioning System (GPS) is a navigation system widely used in civilian and military application, but its accuracy is highly impacted with consequential fading, and possible loss of communication due to multipath propagation and high power interferences. This dissertation proposes alternatives to improve the performance of the GPS receivers to obtain a system that can be reliable in critical situations. The basic performance of the GPS receiver consists of receiving the signal with an antenna array, delaying the signal at each antenna element, weighting the delayed replicas, and finally, combining the weighted replicas to estimate the desired signal. Based on these, three modifications are proposed to improve the performance of the system. The first proposed modification is the use of the Least Mean Squares (LMS) algorithm with two variations to decrease the convergence time of the classic LMS while achieving good system stability. The results obtained by the proposed LMS demonstrate that the algorithm can achieve the same stability as the classic LMS using a small step size, and its convergence rate is better than the classic LMS using a large step size. The second proposed modification is to replace the uniform distribution of the time delays (or taps) by an exponential distribution that decreases the bit-error rate (BER) of the system without impacting the computational efficiency of the uniform taps. The results show that, for a BER of 0.001, the system can operate with a 1 to 2 dB lower signal-to-noise ratio (SNR) when an exponential distribution is used rather than a uniform distribution. Finally, the third modification is implemented in the design of the antenna array. In this case, the gain of each microstrip element is enhanced by embedding ferrite rings in the substrate, creating a hybrid substrate. The ferrite rings generates constructive interference between the incident and reflected fields; consequently, the gain of a single microstrip element is enhanced by up to 4 dB. When hybrid substrates are used in microstrip element arrays, a significant enhancement in angle range is achieved for a given reflection coefficient compared to using a conventional substrate.
ContributorsRivera-Albino, Alix (Author) / Balanis, Constantine A (Thesis advisor) / Tepedelenlioğlu, Cihan (Committee member) / Kiaei, Sayfe (Committee member) / Aberle, James T (Committee member) / Arizona State University (Publisher)
Created2013
Description
Distributed estimation uses many inexpensive sensors to compose an accurate estimate of a given parameter. It is frequently implemented using wireless sensor networks. There have been several studies on optimizing power allocation in wireless sensor networks used for distributed estimation, the vast majority of which assume linear radio-frequency amplifiers. Linear amplifiers are inherently inefficient, so in this dissertation nonlinear amplifiers are examined to gain efficiency while operating distributed sensor networks. This research presents a method to boost efficiency by operating the amplifiers in the nonlinear region of operation. Operating amplifiers nonlinearly presents new challenges. First, nonlinear amplifier characteristics change across manufacturing process variation, temperature, operating voltage, and aging. Secondly, the equations conventionally used for estimators and performance expectations in linear amplify-and-forward systems fail. To compensate for the first challenge, predistortion is utilized not to linearize amplifiers but rather to force them to fit a common nonlinear limiting amplifier model close to the inherent amplifier performance. This minimizes the power impact and the training requirements for predistortion. Second, new estimators are required that account for transmitter nonlinearity. This research derives analytically and confirms via simulation new estimators and performance expectation equations for use in nonlinear distributed estimation. An additional complication when operating nonlinear amplifiers in a wireless environment is the influence of varied and potentially unknown channel gains. The impact of these varied gains and both measurement and channel noise sources on estimation performance are analyzed in this paper. Techniques for minimizing the estimate variance are developed. It is shown that optimizing transmitter power allocation to minimize estimate variance for the most-compressed parameter measurement is equivalent to the problem for linear sensors. Finally, a method for operating distributed estimation in a multipath environment is presented that is capable of developing robust estimates for a wide range of Rician K-factors. This dissertation demonstrates that implementing distributed estimation using nonlinear sensors can boost system efficiency and is compatible with existing techniques from the literature for boosting efficiency at the system level via sensor power allocation. Nonlinear transmitters work best when channel gains are known and channel noise and receiver noise levels are low.
ContributorsSantucci, Robert (Author) / Spanias, Andreas (Thesis advisor) / Tepedelenlioðlu, Cihan (Committee member) / Bakkaloglu, Bertan (Committee member) / Tsakalis, Kostas (Committee member) / Arizona State University (Publisher)
Created2013
Description
Radio frequency (RF) transceivers require a disproportionately high effort in terms of test development time, test equipment cost, and test time. The relatively high test cost stems from two contributing factors. First, RF transceivers require the measurement of a diverse set of specifications, requiring multiple test set-ups and long test times, which complicates load-board design, debug, and diagnosis. Second, high frequency operation necessitates the use of expensive equipment, resulting in higher per second test time cost compared with mixed-signal or digital circuits. Moreover, in terms of the non-recurring engineering cost, the need to measure complex specfications complicates the test development process and necessitates a long learning process for test engineers. Test time is dominated by changing and settling time for each test set-up. Thus, single set-up test solutions are desirable. Loop-back configuration where the transmitter output is connected to the receiver input are used as the desirable test set- up for RF transceivers, since it eliminates the reliance on expensive instrumentation for RF signal analysis and enables measuring multiple parameters at once. In-phase and Quadrature (IQ) imbalance, non-linearity, DC offset and IQ time skews are some of the most detrimental imperfections in transceiver performance. Measurement of these parameters in the loop-back mode is challenging due to the coupling between the receiver (RX) and transmitter (TX) parameters. Loop-back based solutions are proposed in this work to resolve this issue. A calibration algorithm for a subset of the above mentioned impairments is also presented. Error Vector Magnitude (EVM) is a system-level parameter that is specified for most advanced communication standards. EVM measurement often takes extensive test development efforts, tester resources, and long test times. EVM is analytically related to system impairments, which are typically measured in a production test i environment. Thus, EVM test can be eliminated from the test list if the relations between EVM and system impairments are derived independent of the circuit implementation and manufacturing process. In this work, the focus is on the WLAN standard, and deriving the relations between EVM and three of the most detrimental impairments for QAM/OFDM based systems (IQ imbalance, non-linearity, and noise). Having low cost test techniques for measuring the RF transceivers imperfections and being able to analytically compute EVM from the measured parameters is a complete test solution for RF transceivers. These techniques along with the proposed calibration method can be used in improving the yield by widening the pass/fail boundaries for transceivers imperfections. For all of the proposed methods, simulation and hardware measurements prove that the proposed techniques provide accurate characterization of RF transceivers.
ContributorsNassery, Afsaneh (Author) / Ozev, Sule (Thesis advisor) / Bakkaloglu, Bertan (Committee member) / Kiaei, Sayfe (Committee member) / Kitchen, Jennifer (Committee member) / 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
Traditional approaches to modeling microgrids include the behavior of each inverter operating in a particular network configuration and at a particular operating point. Such models quickly become computationally intensive for large systems. Similarly, traditional approaches to control do not use advanced methodologies and suffer from poor performance and limited operating range. In this document a linear model is derived for an inverter connected to the Thevenin equivalent of a microgrid. This model is then compared to a nonlinear simulation model and analyzed using the open and closed loop systems in both the time and frequency domains. The modeling error is quantified with emphasis on its use for controller design purposes. Control design examples are given using a Glover McFarlane controller, gain sched- uled Glover McFarlane controller, and bumpless transfer controller which are compared to the standard droop control approach. These examples serve as a guide to illustrate the use of multi-variable modeling techniques in the context of robust controller design and show that gain scheduled MIMO control techniques can extend the operating range of a microgrid. A hardware implementation is used to compare constant gain droop controllers with Glover McFarlane controllers and shows a clear advantage of the Glover McFarlane approach.
ContributorsSteenis, Joel (Author) / Ayyanar, Raja (Thesis advisor) / Mittelmann, Hans (Committee member) / Tsakalis, Konstantinos (Committee member) / Tylavsky, Daniel (Committee member) / Arizona State University (Publisher)
Created2013