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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

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
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Description
At present, almost 70% of the electric energy in the United States is produced utilizing fossil fuels. Combustion of fossil fuels contributes CO2 to the atmosphere, potentially exacerbating the impact on global warming. To make the electric power system (EPS) more sustainable for the future, there has been an emphasis

At present, almost 70% of the electric energy in the United States is produced utilizing fossil fuels. Combustion of fossil fuels contributes CO2 to the atmosphere, potentially exacerbating the impact on global warming. To make the electric power system (EPS) more sustainable for the future, there has been an emphasis on scaling up generation of electric energy from wind and solar resources. These resources are renewable in nature and have pollution free operation. Various states in the US have set up different goals for achieving certain amount of electrical energy to be produced from renewable resources. The Southwestern region of the United States receives significant solar radiation throughout the year. High solar radiation makes concentrated solar power and solar PV the most suitable means of renewable energy production in this region. However, the majority of the projects that are presently being developed are either residential or utility owned solar PV plants. This research explores the impact of significant PV penetration on the steady state voltage profile of the electric power transmission system. This study also identifies the impact of PV penetration on the dynamic response of the transmission system such as rotor angle stability, frequency response and voltage response after a contingency. The light load case of spring 2010 and the peak load case of summer 2018 have been considered for analyzing the impact of PV. If the impact is found to be detrimental to the normal operation of the EPS, mitigation measures have been devised and presented in the thesis. Commercially available software tools/packages such as PSLF, PSS/E, DSA Tools have been used to analyze the power network and validate the results.
ContributorsPrakash, Nitin (Author) / Heydt, Gerald T. (Thesis advisor) / Vittal, Vijay (Thesis advisor) / Ayyanar, Raja (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The main objective of this research is to develop an integrated method to study emergent behavior and consequences of evolution and adaptation in engineered complex adaptive systems (ECASs). A multi-layer conceptual framework and modeling approach including behavioral and structural aspects is provided to describe the structure of a class of

The main objective of this research is to develop an integrated method to study emergent behavior and consequences of evolution and adaptation in engineered complex adaptive systems (ECASs). A multi-layer conceptual framework and modeling approach including behavioral and structural aspects is provided to describe the structure of a class of engineered complex systems and predict their future adaptive patterns. The approach allows the examination of complexity in the structure and the behavior of components as a result of their connections and in relation to their environment. This research describes and uses the major differences of natural complex adaptive systems (CASs) with artificial/engineered CASs to build a framework and platform for ECAS. While this framework focuses on the critical factors of an engineered system, it also enables one to synthetically employ engineering and mathematical models to analyze and measure complexity in such systems. In this way concepts of complex systems science are adapted to management science and system of systems engineering. In particular an integrated consumer-based optimization and agent-based modeling (ABM) platform is presented that enables managers to predict and partially control patterns of behaviors in ECASs. Demonstrated on the U.S. electricity markets, ABM is integrated with normative and subjective decision behavior recommended by the U.S. Department of Energy (DOE) and Federal Energy Regulatory Commission (FERC). The approach integrates social networks, social science, complexity theory, and diffusion theory. Furthermore, it has unique and significant contribution in exploring and representing concrete managerial insights for ECASs and offering new optimized actions and modeling paradigms in agent-based simulation.
ContributorsHaghnevis, Moeed (Author) / Askin, Ronald G. (Thesis advisor) / Armbruster, Dieter (Thesis advisor) / Mirchandani, Pitu (Committee member) / Wu, Tong (Committee member) / Hedman, Kory (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The ability to design high performance buildings has acquired great importance in recent years due to numerous federal, societal and environmental initiatives. However, this endeavor is much more demanding in terms of designer expertise and time. It requires a whole new level of synergy between automated performance prediction with the

The ability to design high performance buildings has acquired great importance in recent years due to numerous federal, societal and environmental initiatives. However, this endeavor is much more demanding in terms of designer expertise and time. It requires a whole new level of synergy between automated performance prediction with the human capabilities to perceive, evaluate and ultimately select a suitable solution. While performance prediction can be highly automated through the use of computers, performance evaluation cannot, unless it is with respect to a single criterion. The need to address multi-criteria requirements makes it more valuable for a designer to know the "latitude" or "degrees of freedom" he has in changing certain design variables while achieving preset criteria such as energy performance, life cycle cost, environmental impacts etc. This requirement can be met by a decision support framework based on near-optimal "satisficing" as opposed to purely optimal decision making techniques. Currently, such a comprehensive design framework is lacking, which is the basis for undertaking this research. The primary objective of this research is to facilitate a complementary relationship between designers and computers for Multi-Criterion Decision Making (MCDM) during high performance building design. It is based on the application of Monte Carlo approaches to create a database of solutions using deterministic whole building energy simulations, along with data mining methods to rank variable importance and reduce the multi-dimensionality of the problem. A novel interactive visualization approach is then proposed which uses regression based models to create dynamic interplays of how varying these important variables affect the multiple criteria, while providing a visual range or band of variation of the different design parameters. The MCDM process has been incorporated into an alternative methodology for high performance building design referred to as Visual Analytics based Decision Support Methodology [VADSM]. VADSM is envisioned to be most useful during the conceptual and early design performance modeling stages by providing a set of potential solutions that can be analyzed further for final design selection. The proposed methodology can be used for new building design synthesis as well as evaluation of retrofits and operational deficiencies in existing buildings.
ContributorsDutta, Ranojoy (Author) / Reddy, T Agami (Thesis advisor) / Runger, George C. (Committee member) / Addison, Marlin S. (Committee member) / Arizona State University (Publisher)
Created2013
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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

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
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Description
This thesis addresses the issue of making an economic case for energy storage in power systems. Bulk energy storage has often been suggested for large scale electric power systems in order to levelize load; store energy when it is inexpensive and discharge energy when it is expensive; potentially defer transmission

This thesis addresses the issue of making an economic case for energy storage in power systems. Bulk energy storage has often been suggested for large scale electric power systems in order to levelize load; store energy when it is inexpensive and discharge energy when it is expensive; potentially defer transmission and generation expansion; and provide for generation reserve margins. As renewable energy resource penetration increases, the uncertainty and variability of wind and solar may be alleviated by bulk energy storage technologies. The quadratic programming function in MATLAB is used to simulate an economic dispatch that includes energy storage. A program is created that utilizes quadratic programming to analyze various cases using a 2010 summer peak load from the Arizona transmission system, part of the Western Electricity Coordinating Council (WECC). The MATLAB program is used first to test the Arizona test bed with a low level of energy storage to study how the storage power limit effects several optimization out-puts such as the system wide operating costs. Very high levels of energy storage are then added to see how high level energy storage affects peak shaving, load factor, and other system applications. Finally, various constraint relaxations are made to analyze why the applications tested eventually approach a constant value. This research illustrates the use of energy storage which helps minimize the system wide generator operating cost by "shaving" energy off of the peak demand.
ContributorsRuggiero, John (Author) / Heydt, Gerald T (Thesis advisor) / Datta, Rajib (Committee member) / Karady, George G. (Committee member) / Arizona State University (Publisher)
Created2013
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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,

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
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Description
Recent trends in the electric power industry have led to more attention to optimal operation of power transformers. In a deregulated environment, optimal operation means minimizing the maintenance and extending the life of this critical and costly equipment for the purpose of maximizing profits. Optimal utilization of a transformer can

Recent trends in the electric power industry have led to more attention to optimal operation of power transformers. In a deregulated environment, optimal operation means minimizing the maintenance and extending the life of this critical and costly equipment for the purpose of maximizing profits. Optimal utilization of a transformer can be achieved through the use of dynamic loading. A benefit of dynamic loading is that it allows better utilization of the transformer capacity, thus increasing the flexibility and reliability of the power system. This document presents the progress on a software application which can estimate the maximum time-varying loading capability of transformers. This information can be used to load devices closer to their limits without exceeding the manufacturer specified operating limits. The maximally efficient dynamic loading of transformers requires a model that can accurately predict both top-oil temperatures (TOTs) and hottest-spot temperatures (HSTs). In the previous work, two kinds of thermal TOT and HST models have been studied and used in the application: the IEEE TOT/HST models and the ASU TOT/HST models. And, several metrics have been applied to evaluate the model acceptability and determine the most appropriate models for using in the dynamic loading calculations. In this work, an investigation to improve the existing transformer thermal models performance is presented. Some factors that may affect the model performance such as improper fan status and the error caused by the poor performance of IEEE models are discussed. Additional methods to determine the reliability of transformer thermal models using metrics such as time constant and the model parameters are also provided. A new production grade application for real-time dynamic loading operating purpose is introduced. This application is developed by using an existing planning application, TTeMP, as a start point, which is designed for the dispatchers and load specialists. To overcome the limitations of TTeMP, the new application can perform dynamic loading under emergency conditions, such as loss-of transformer loading. It also has the capability to determine the emergency rating of the transformers for a real-time estimation.
ContributorsZhang, Ming (Author) / Tylavsky, Daniel J (Thesis advisor) / Ayyanar, Raja (Committee member) / Holbert, Keith E. (Committee member) / Arizona State University (Publisher)
Created2013
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Description
According to the U.S. Energy Information Administration, commercial buildings represent about 40% of the United State's energy consumption of which office buildings consume a major portion. Gauging the extent to which an individual building consumes energy in excess of its peers is the first step in initiating energy efficiency improvement.

According to the U.S. Energy Information Administration, commercial buildings represent about 40% of the United State's energy consumption of which office buildings consume a major portion. Gauging the extent to which an individual building consumes energy in excess of its peers is the first step in initiating energy efficiency improvement. Energy Benchmarking offers initial building energy performance assessment without rigorous evaluation. Energy benchmarking tools based on the Commercial Buildings Energy Consumption Survey (CBECS) database are investigated in this thesis. This study proposes a new benchmarking methodology based on decision trees, where a relationship between the energy use intensities (EUI) and building parameters (continuous and categorical) is developed for different building types. This methodology was applied to medium office and school building types contained in the CBECS database. The Random Forest technique was used to find the most influential parameters that impact building energy use intensities. Subsequently, correlations which were significant were identified between EUIs and CBECS variables. Other than floor area, some of the important variables were number of workers, location, number of PCs and main cooling equipment. The coefficient of variation was used to evaluate the effectiveness of the new model. The customization technique proposed in this thesis was compared with another benchmarking model that is widely used by building owners and designers namely, the ENERGY STAR's Portfolio Manager. This tool relies on the standard Linear Regression methods which is only able to handle continuous variables. The model proposed uses data mining technique and was found to perform slightly better than the Portfolio Manager. The broader impacts of the new benchmarking methodology proposed is that it allows for identifying important categorical variables, and then incorporating them in a local, as against a global, model framework for EUI pertinent to the building type. The ability to identify and rank the important variables is of great importance in practical implementation of the benchmarking tools which rely on query-based building and HVAC variable filters specified by the user.
ContributorsKaskhedikar, Apoorva Prakash (Author) / Reddy, T. Agami (Thesis advisor) / Bryan, Harvey (Committee member) / Runger, George C. (Committee member) / Arizona State University (Publisher)
Created2013
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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

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