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Description
This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy.
Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC.
Battery testing based on [EMI+][FeCl4-] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4+][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements.
Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases producing water vapor. Principle advantage is high-energy efficiency of up to 70% in contrast to an internal combustion engine <40%. Nafion-based fuel cells are prone to carbon monoxide catalytic poisoning and polymer membrane degradation unless heavily hydrated under cell-pressurization. This novel "SiPOH" solid-electrolytic gel (originally liquid-state) operated in the fuel cell at 121oC yielding current and power densities high as 731mAcm-2 and 345mWcm-2, respectively. Enhanced proton conduction significantly increased H2 fuel efficiency to 89.7% utilizing only 3.1mlmin-1 under dry, unpressurized testing conditions. All these energy devices aforementioned evidently have future promise; therefore in early developmental stages.
Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC.
Battery testing based on [EMI+][FeCl4-] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4+][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements.
Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases producing water vapor. Principle advantage is high-energy efficiency of up to 70% in contrast to an internal combustion engine <40%. Nafion-based fuel cells are prone to carbon monoxide catalytic poisoning and polymer membrane degradation unless heavily hydrated under cell-pressurization. This novel "SiPOH" solid-electrolytic gel (originally liquid-state) operated in the fuel cell at 121oC yielding current and power densities high as 731mAcm-2 and 345mWcm-2, respectively. Enhanced proton conduction significantly increased H2 fuel efficiency to 89.7% utilizing only 3.1mlmin-1 under dry, unpressurized testing conditions. All these energy devices aforementioned evidently have future promise; therefore in early developmental stages.
ContributorsTucker, Telpriore G (Author) / Angell, Charles A. (Committee member) / Moore, Ana (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2014
Description
Structural details of phosphonic acid functionalized nanomaterials and protic ionic liquids (PILs) were characterized using nuclear magnetic resonance (NMR) spectroscopy. It is well known that ligands play a critical role in the synthesis and properties of nanomaterials. Therefore, elucidating the details of ligand-surface and ligand-ligand interactions is crucial to understanding nanomaterial systems more completely.
In an effort to further the understanding of ligand-surface interactions, a combination of multi-nuclear (1H, 29Si, 31P) and multi-dimensional solid-state NMR techniques were utilized to characterize the phosphonic acid functionalization of fumed silica nanoparticles using methyl phosphonic acid (MPA) and phenyl phosphonic acid (PPA). Quantitative 31P MAS solid-state NMR measurements indicate that ligands favor a monodentate binding mode. Furthermore, 1H-1H single quantum-double quantum (SQ-DQ) back-to-back (BABA) 2D NMR spectra of silica functionalized with MPA and PPA indicate that the MPA and PPA are within 4.2±0.2 Å on the surface of the nanomaterial.
The ligand capping of phosphonic acid (PA) functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of ligand exchange, solution and solid-state 31P NMR spectroscopy. In order to quantify the ligand populations on the surface of the QDs, ligand exchange facilitated by PPA resulted in the displacement of the PAs, and allowed for quantification of the free ligands using 31P liquid state NMR.
In addition to characterizing nanomaterials, the ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing NMR. Gas phase proton affinity was shown to be a better predictor for the extent of proton transfer, and in turn the ionicity of the PIL, than using ∆pKa. Furthermore, pulsed field gradient (PFG) NMR was used to determine that the exchangeable proton diffuses with the cation or the anion based on the strength of the acid used to generate the PILs.
In an effort to further the understanding of ligand-surface interactions, a combination of multi-nuclear (1H, 29Si, 31P) and multi-dimensional solid-state NMR techniques were utilized to characterize the phosphonic acid functionalization of fumed silica nanoparticles using methyl phosphonic acid (MPA) and phenyl phosphonic acid (PPA). Quantitative 31P MAS solid-state NMR measurements indicate that ligands favor a monodentate binding mode. Furthermore, 1H-1H single quantum-double quantum (SQ-DQ) back-to-back (BABA) 2D NMR spectra of silica functionalized with MPA and PPA indicate that the MPA and PPA are within 4.2±0.2 Å on the surface of the nanomaterial.
The ligand capping of phosphonic acid (PA) functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of ligand exchange, solution and solid-state 31P NMR spectroscopy. In order to quantify the ligand populations on the surface of the QDs, ligand exchange facilitated by PPA resulted in the displacement of the PAs, and allowed for quantification of the free ligands using 31P liquid state NMR.
In addition to characterizing nanomaterials, the ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing NMR. Gas phase proton affinity was shown to be a better predictor for the extent of proton transfer, and in turn the ionicity of the PIL, than using ∆pKa. Furthermore, pulsed field gradient (PFG) NMR was used to determine that the exchangeable proton diffuses with the cation or the anion based on the strength of the acid used to generate the PILs.
ContributorsDavidowski, Stephen (Author) / Yarger, Jeffery L. (Thesis advisor) / Holland, Gregory P (Thesis advisor) / Angell, Charles A. (Committee member) / Buttry, Daniel A. (Committee member) / Arizona State University (Publisher)
Created2015
Description
The US National Academy of Sciences and The Royal Society have recently released a detailed report on the causes and effects of global climate change.1 This report states that the Earth’s climate is rapidly changing due to human activity. Specifically, the burning of fossil fuels to satisfy the energy demands of rising global population has resulted in unprecedented levels of greenhouse gasses in the atmosphere. These high levels of greenhouse gasses are serving to warm the surface of the planet resulting in extreme weather events. Thus, controlling the atmospheric CO2 level is motivating a great deal of scientific research in the area of carbon capture and storage (CCS).
Despite the great strides being made in the areas of alternative energy and solar-energy conversion, consumption of fossil fuels for energy generation will likely continue into the foreseeable future. This is primarily motivated by economic factors inasmuch as fossil fuels are a proven resource base with robust harvesting and distribution infrastructure.2 Presently, there are more than 8,000 stationary CO2 emission sources with an annual output of 13,466 megatons of CO2 per year.2 In this context, development of systems that ameliorate the output of greenhouse gasses from stationary CO2 sources, such as coal and natural gas burning power plants, is urgently needed.
In this document the utility of sulfur nucleophiles for CCS schemes is explored. The main thrust of the research has been utilizing electrogenerated sulfur nucleophiles to capture CO2, which can be electrochemically recovered from the resulting thiocarbonates while concomitantly regenerating the masked capture agent. Further, a temperature swing CO2 capture scheme that employs benzylthiolate as the CO2 sorbent is proposed and methods of manipulating the release temperature and kinetics were investigated. These reports represent the first application of organosulfur compounds toward CCS technologies and there are a number of newly reported compounds. The appendix deviates from the theme of the first four chapters to describe the functionalization of poly(2,6-dimethyl-1,4-phenylene oxide) with ferrocene moieties by the copper catalyzed azide-alkyne coupling reaction. This material is discussed within the context of anion recognition and sensing applications.
Despite the great strides being made in the areas of alternative energy and solar-energy conversion, consumption of fossil fuels for energy generation will likely continue into the foreseeable future. This is primarily motivated by economic factors inasmuch as fossil fuels are a proven resource base with robust harvesting and distribution infrastructure.2 Presently, there are more than 8,000 stationary CO2 emission sources with an annual output of 13,466 megatons of CO2 per year.2 In this context, development of systems that ameliorate the output of greenhouse gasses from stationary CO2 sources, such as coal and natural gas burning power plants, is urgently needed.
In this document the utility of sulfur nucleophiles for CCS schemes is explored. The main thrust of the research has been utilizing electrogenerated sulfur nucleophiles to capture CO2, which can be electrochemically recovered from the resulting thiocarbonates while concomitantly regenerating the masked capture agent. Further, a temperature swing CO2 capture scheme that employs benzylthiolate as the CO2 sorbent is proposed and methods of manipulating the release temperature and kinetics were investigated. These reports represent the first application of organosulfur compounds toward CCS technologies and there are a number of newly reported compounds. The appendix deviates from the theme of the first four chapters to describe the functionalization of poly(2,6-dimethyl-1,4-phenylene oxide) with ferrocene moieties by the copper catalyzed azide-alkyne coupling reaction. This material is discussed within the context of anion recognition and sensing applications.
ContributorsRheinhardt, Joseph (Author) / Buttry, Daniel A. (Thesis advisor) / Angell, Charles A. (Committee member) / Chizmeshya, Andrew V. G. (Committee member) / Arizona State University (Publisher)
Created2018
Description
The current trend of interconnected devices, or the internet of things (IOT) has led to the popularization of single board computers (SBC). This is primarily due to their form-factor and low price. This has led to unique networks of devices that can have unstable network connections and minimal processing power. Many parallel program- ming libraries are intended for use in high performance computing (HPC) clusters. Unlike the IOT environment described, HPC clusters will in general look to obtain very consistent network speeds and topologies. There are a significant number of software choices that make up what is referred to as the HPC stack or parallel processing stack. My thesis focused on building an HPC stack that would run on the SCB computer name the Raspberry Pi. The intention in making this Raspberry Pi cluster is to research performance of MPI implementations in an IOT environment, which had an impact on the design choices of the cluster. This thesis is a compilation of my research efforts in creating this cluster as well as an evaluation of the software that was chosen to create the parallel processing stack.
ContributorsO'Meara, Braedon Richard (Author) / Meuth, Ryan (Thesis director) / Dasgupta, Partha (Committee member) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
This thesis discusses three recent optimization problems that seek to reduce disease spread on arbitrary graphs by deleting edges, and it discusses three approximation algorithms developed for these problems. Important definitions are presented including the Linear Threshold and Triggering Set models and the set function properties of submodularity and monotonicity. Also, important results regarding the Linear Threshold model and computation of the influence function are presented along with proof sketches. The three main problems are formally presented, and NP-hardness results along with proof sketches are presented where applicable. The first problem seeks to reduce spread of infection over the Linear Threshold process by making use of an efficient tree data structure. The second problem seeks to reduce the spread of infection over the Linear Threshold process while preserving the PageRank distribution of the input graph. The third problem seeks to minimize the spectral radius of the input graph. The algorithms designed for these problems are described in writing and with pseudocode, and their approximation bounds are stated along with time complexities. Discussion of these algorithms considers how these algorithms could see real-world use. Challenges and the ways in which these algorithms do or do not overcome them are noted. Two related works, one which presents an edge-deletion disease spread reduction problem over a deterministic threshold process and the other which considers a graph modification problem aimed at minimizing worst-case disease spread, are compared with the three main works to provide interesting perspectives. Furthermore, a new problem is proposed that could avoid some issues faced by the three main problems described, and directions for future work are suggested.
ContributorsStanton, Andrew Warren (Author) / Richa, Andrea (Thesis director) / Czygrinow, Andrzej (Committee member) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
In the last few years, billion-dollar companies like Yahoo and Equifax have had data breaches causing millions of people’s personal information to be leaked online. Other billion-dollar companies like Google and Facebook have gotten in trouble for abusing people’s personal information for financial gain as well. In this new age of technology where everything is being digitalized and stored online, people all over the world are concerned about what is happening to their personal information and how they can trust it is being kept safe. This paper describes, first, the importance of protecting user data, second, one easy tool that companies and developers can use to help ensure that their user’s information (credit card information specifically) is kept safe, how to implement that tool, and finally, future work and research that needs to be done. The solution I propose is a software tool that will keep credit card data secured. It is only a small step towards achieving a completely secure data anonymized system, but when implemented correctly, it can reduce the risk of credit card data from being exposed to the public. The software tool is a script that can scan every viable file in any given system, server, or other file-structured Linux system and detect if there any visible credit card numbers that should be hidden.
ContributorsPappas, Alexander (Author) / Zhao, Ming (Thesis director) / Kuznetsov, Eugene (Committee member) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
Political polarization is the coalescence of political parties -- and the individuals of which parties are composed -- around opposing ends of the ideological spectrum. Political parties in the United States have always been divided, however, in recent years this division has only intensified. Recently, polarization has also wound its way to the Supreme Court and the nomination processes of justices to the Court. This paper examines how prevalent polarization in the Supreme Court nomination process has become by looking specifically at the failed nomination of Judge Merrick Garland and the confirmations of now-Justices Neil Gorsuch and Brett Kavanaugh. This is accomplished by comparing the ideologies and qualifications of the three most recent nominees to those of previous nominees, as well as analysing the ideological composition of the Senate at the times of the individual nominations.
ContributorsJoss, Jacob (Author) / Hoekstra, Valerie (Thesis director) / Critchlow, Donald (Committee member) / Computer Science and Engineering Program (Contributor) / School of Politics and Global Studies (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
The original version of Helix, the one I pitched when first deciding to make a video game
for my thesis, is an action-platformer, with the intent of metroidvania-style progression
and an interconnected world map.
The current version of Helix is a turn based role-playing game, with the intent of roguelike
gameplay and a dark fantasy theme. We will first be exploring the challenges that came
with programming my own game - not quite from scratch, but also without a prebuilt
engine - then transition into game design and how Helix has evolved from its original form
to what we see today.
for my thesis, is an action-platformer, with the intent of metroidvania-style progression
and an interconnected world map.
The current version of Helix is a turn based role-playing game, with the intent of roguelike
gameplay and a dark fantasy theme. We will first be exploring the challenges that came
with programming my own game - not quite from scratch, but also without a prebuilt
engine - then transition into game design and how Helix has evolved from its original form
to what we see today.
ContributorsDiscipulo, Isaiah K (Author) / Meuth, Ryan (Thesis director) / Kobayashi, Yoshihiro (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
RecyclePlus is an iOS mobile application that allows users to be knowledgeable in the realms of sustainability. It gives encourages users to be environmental responsible by providing them access to recycling information. In particular, it allows users to search up certain materials and learn about its recyclability and how to properly dispose of the material. Some searches will show locations of facilities near users that collect certain materials and dispose of the materials properly. This is a full stack software project that explores open source software and APIs, UI/UX design, and iOS development.
ContributorsTran, Nikki (Author) / Ganesh, Tirupalavanam (Thesis director) / Meuth, Ryan (Committee member) / Watts College of Public Service & Community Solut (Contributor) / Department of Information Systems (Contributor) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
At present, the vast majority of human subjects with neurological disease are still diagnosed through in-person assessments and qualitative analysis of patient data. In this paper, we propose to use Topological Data Analysis (TDA) together with machine learning tools to automate the process of Parkinson’s disease classification and severity assessment. An automated, stable, and accurate method to evaluate Parkinson’s would be significant in streamlining diagnoses of patients and providing families more time for corrective measures. We propose a methodology which incorporates TDA into analyzing Parkinson’s disease postural shifts data through the representation of persistence images. Studying the topology of a system has proven to be invariant to small changes in data and has been shown to perform well in discrimination tasks. The contributions of the paper are twofold. We propose a method to 1) classify healthy patients from those afflicted by disease and 2) diagnose the severity of disease. We explore the use of the proposed method in an application involving a Parkinson’s disease dataset comprised of healthy-elderly, healthy-young and Parkinson’s disease patients.
ContributorsRahman, Farhan Nadir (Co-author) / Nawar, Afra (Co-author) / Turaga, Pavan (Thesis director) / Krishnamurthi, Narayanan (Committee member) / Electrical Engineering Program (Contributor) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05