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Description
Liquid-liquid interfaces serve as ideal 2-D templates on which solid particles can self-assemble into various structures. These self-assembly processes are important in fabrication of micron-sized devices and emulsion formulation. At oil/water interfaces, these structures can range from close-packed aggregates to ordered lattices. By incorporating an ionic liquid (IL) at the

Liquid-liquid interfaces serve as ideal 2-D templates on which solid particles can self-assemble into various structures. These self-assembly processes are important in fabrication of micron-sized devices and emulsion formulation. At oil/water interfaces, these structures can range from close-packed aggregates to ordered lattices. By incorporating an ionic liquid (IL) at the interface, new self-assembly phenomena emerge. ILs are ionic compounds that are liquid at room temperature (essentially molten salts at ambient conditions) that have remarkable properties such as negligible volatility and high chemical stability and can be optimized for nearly any application. The nature of IL-fluid interfaces has not yet been studied in depth. Consequently, the corresponding self-assembly phenomena have not yet been explored. We demonstrate how the unique molecular nature of ILs allows for new self-assembly phenomena to take place at their interfaces. These phenomena include droplet bridging (the self-assembly of both particles and emulsion droplets), spontaneous particle transport through the liquid-liquid interface, and various gelation behaviors. In droplet bridging, self-assembled monolayers of particles effectively "glue" emulsion droplets to one another, allowing the droplets to self-assembly into large networks. With particle transport, it is experimentally demonstrated the ILs overcome the strong adhesive nature of the liquid-liquid interface and extract solid particles from the bulk phase without the aid of external forces. These phenomena are quantified and corresponding mechanisms are proposed. The experimental investigations are supported by molecular dynamics (MD) simulations, which allow for a molecular view of the self-assembly process. In particular, we show that particle self-assembly depends primarily on the surface chemistry of the particles and the non-IL fluid at the interface. Free energy calculations show that the attractive forces between nanoparticles and the liquid-liquid interface are unusually long-ranged, due to capillary waves. Furthermore, IL cations can exhibit molecular ordering at the IL-oil interface, resulting in a slight residual charge at this interface. We also explore the transient IL-IL interface, revealing molecular interactions responsible for the unusually slow mixing dynamics between two ILs. This dissertation, therefore, contributes to both experimental and theoretical understanding of particle self-assembly at IL based interfaces.
ContributorsFrost, Denzil (Author) / Dai, Lenore L (Thesis advisor) / Torres, César I (Committee member) / Nielsen, David R (Committee member) / Squires, Kyle D (Committee member) / Rege, Kaushal (Committee member) / Arizona State University (Publisher)
Created2013
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Description
This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The

This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
ContributorsShi, Ge (Performer) / ASU Library. Music Library (Publisher)
Created2018-03-25
ContributorsShatuho, Kristina (Performer) / ASU Library. Music Library (Publisher)
Created2018-03-27
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Description
Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa

Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2*-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O}). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm+ cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.
ContributorsZeller, Robert August (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all

The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic liquids where it is found that surface adsorption of residual amine and chloride from the organic synthesis affect growth characteristics. The drivers of this work are to understand the processes occurring at the electrode-electrolyte interface and with that knowledge, engineer systems yielding optimal performance. With this in mind, the design of a bulk supercapacitor electrode architecture with excellent composite specific capacitances, as well as develop conditions producing ideal Zn deposition morphologies was completed.
ContributorsEngstrom, Erika (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
ContributorsCarlisi, Daniel (Performer) / ASU Library. Music Library (Publisher)
Created2018-04-07
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Description
Yannis Constantinidis was the last of the handful of composers referred to collectively as the Greek National School. The members of this group strove to create a distinctive national style for Greece, founded upon a synthesis of Western compositional idioms with melodic, rhyhmic, and modal features of their local folk

Yannis Constantinidis was the last of the handful of composers referred to collectively as the Greek National School. The members of this group strove to create a distinctive national style for Greece, founded upon a synthesis of Western compositional idioms with melodic, rhyhmic, and modal features of their local folk traditions. Constantinidis particularly looked to the folk melodies of his native Asia Minor and the nearby Dodecanese Islands. His musical output includes operettas, musical comedies, orchestral works, chamber and vocal music, and much piano music, all of which draws upon folk repertories for thematic material. The present essay examines how he incorporates this thematic material in his piano compositions, written between 1943 and 1971, with a special focus on the 22 Songs and Dances from the Dodecanese. In general, Constantinidis's pianistic style is expressed through miniature pieces in which the folk tunes are presented mostly intact, but embedded in accompaniment based in early twentieth-century modal harmony. Following the dictates of the founding members of the Greek National School, Manolis Kalomiris and Georgios Lambelet, the modal basis of his harmonic vocabulary is firmly rooted in the characteristics of the most common modes of Greek folk music. A close study of his 22 Songs and Dances from the Dodecanese not only offers a valuable insight into his harmonic imagination, but also demonstrates how he subtly adapts his source melodies. This work also reveals his care in creating a musical expression of the words of the original folk songs, even in purely instrumental compositon.
ContributorsSavvidou, Dina (Author) / Hamilton, Robert (Thesis advisor) / Little, Bliss (Committee member) / Meir, Baruch (Committee member) / Thompson, Janice M (Committee member) / Arizona State University (Publisher)
Created2011
Description
This paper describes six representative works by twentieth-century Chinese composers: Jian-Zhong Wang, Er-Yao Lin, Yi-Qiang Sun, Pei-Xun Chen, Ying-Hai Li, and Yi Chen, which are recorded by the author on the CD. The six pieces selected for the CD all exemplify traits of Nationalism, with or without Western influences. Of

This paper describes six representative works by twentieth-century Chinese composers: Jian-Zhong Wang, Er-Yao Lin, Yi-Qiang Sun, Pei-Xun Chen, Ying-Hai Li, and Yi Chen, which are recorded by the author on the CD. The six pieces selected for the CD all exemplify traits of Nationalism, with or without Western influences. Of the six works on the CD, two are transcriptions of the Han Chinese folk-like songs, one is a composition in the style of the Uyghur folk music, two are transcriptions of traditional Chinese instrumental music dating back to the eighteenth century, and one is an original composition in a contemporary style using folk materials. Two of the composers, who studied in the United States, were strongly influenced by Western compositional style. The other four, who did not study abroad, retained traditional Chinese style in their compositions. The pianistic level of difficulty in these six pieces varies from intermediate to advanced level. This paper includes biographical information for the six composers, background information on the compositions, and a brief analysis of each work. The author was exposed to these six pieces growing up, always believing that they are beautiful and deserve to be appreciated. When the author came to the United States for her studies, she realized that Chinese compositions, including these six pieces, were not sufficiently known to her peers. This recording and paper are offered in the hopes of promoting a wider familiarity with Chinese music and culture.
ContributorsLuo, Yali, D.M.A (Author) / Hamilton, Robert (Thesis advisor) / Campbell, Andrew (Committee member) / Pagano, Caio (Committee member) / Cosand, Walter (Committee member) / Rogers, Rodney (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The purpose of this project was to examine the lives and solo piano works of four members of the early generation of female composers in Taiwan. These four women were born between 1950 and 1960, began to appear on the Taiwanese musical scene after 1980, and were still active as

The purpose of this project was to examine the lives and solo piano works of four members of the early generation of female composers in Taiwan. These four women were born between 1950 and 1960, began to appear on the Taiwanese musical scene after 1980, and were still active as composers at the time of this study. They include Fan-Ling Su (b. 1955), Hwei-Lee Chang (b. 1956), Shyh-Ji Pan-Chew (b. 1957), and Kwang-I Ying (b. 1960). Detailed biographical information on the four composers is presented and discussed. In addition, the musical form and features of all solo piano works at all levels by the four composers are analyzed, and the musical characteristics of each composer's work are discussed. The biography of a fifth composer, Wei-Ho Dai (b. 1950), is also discussed but is placed in the Appendices because her piano music could not be located. This research paper is presented in six chapters: (1) Prologue; the life and music of (2) Fan-Ling Su, (3) Hwei-Lee Chang, (4) Shyh-Ji Pan-Chew, and (5) Kwang-I Ying; and (6) Conclusion. The Prologue provides an overview of the development of Western classical music in Taiwan, a review of extant literature on the selected composers and their music, and the development of piano music in Taiwan. The Conclusion is comprised of comparisons of the four composers' music, including their personal interests and preferences as exhibited in their music. For example, all of the composers have used atonality in their music. Two of the composers, Fan-Ling Su and Kwang-I Ying, openly apply Chinese elements in their piano works, while Hwei-Lee Chang tries to avoid direct use of the Chinese pentatonic scale. The piano works of Hwei-Lee Chang and Shyh-Ji Pan-Chew are chromatic and atonal, and show an economical usage of material. Biographical information on Wei-Ho Dai and an overview of Taiwanese history are presented in the Appendices.
ContributorsWang, Jinding (Author) / Pagano, Caio (Thesis advisor) / Campbell, Andrew (Committee member) / Humphreys, Jere T. (Committee member) / Meyer-Thompson, Janice (Committee member) / Norton, Kay (Committee member) / Arizona State University (Publisher)
Created2011