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- All Subjects: Materials Science
- Creators: Arizona State University
Description
ABSTRACTWith the National Aeronautics and Space Administration (NASA) Psyche Mission, humans will soon have the first opportunity to explore a new kind of planetary body: one composed mostly of metal as opposed to stony minerals or ices. Identifying the composition of asteroids from Earth-based observations has been an ongoing challenge. Although optical reflectance spectra, radar, and orbital dynamics can constrain an asteroid’s mineralogy and bulk density, in many cases there is not a clear or precise match with analogous materials such as meteorites. Additionally, the surfaces of asteroids and other small, airless planetary bodies can be heavily modified over geologic time by exposure to the space environment. To accurately interpret remote sensing observations of metal-rich asteroids, it is therefore necessary to understand how the processes active on asteroid surfaces affect metallic materials. This dissertation represents a first step toward that understanding. In collaboration with many colleagues, I have performed laboratory experiments on iron meteorites to simulate solar wind ion irradiation, surface heating, micrometeoroid bombardment, and high-velocity impacts. Characterizing the meteorite surface’s physical and chemical properties before and after each experiment can constrain the effects of each process on a metal-rich surface in space. While additional work will be needed for a complete understanding, it is nevertheless possible to make some early predictions of what (16) Psyche’s surface regolith might look like when humans observe it up close. Moreover, the results of these experiments will inform future exploration beyond asteroid Psyche as humans attempt to understand how Earth’s celestial neighborhood came to be.
ContributorsChristoph, John Morgan M. (Author) / Elkins-Tanton, Linda (Thesis advisor) / Williams, David (Committee member) / Dukes, Catherine (Committee member) / Sharp, Thomas (Committee member) / Bell III, James (Committee member) / Arizona State University (Publisher)
Created2023
Description
Electrochemical technologies emerge as a feasible solution to monitor and treat pollutants. Although electrochemical technologies have garnered widespread attention, their commercial applications are still constrained by the use of expensive electrocatalysts, and the bulky and rigid plate design of electrodes that restricts electrochemical reactor design to systems with poor electrode surface/ volume treated ratios. By making electrodes flexible, more compact designs that maximize electrode surface per volume treated might become a reality. This dissertation encompasses the successful fabrication of flexible nanocomposite electrodes for electrocatalysis and electroanalysis applications.First, nano boron-doped diamond electrodes (BDD) were prepared as an inexpensive alternative to commercial boron-doped diamond electrodes. Comparative detailed surface and electrochemical characterization was conducted. Empirical study showed that replacing commercial BDD electrodes with nano-BDD electrodes can result in a cost reduction of roughly 1000x while maintaining the same electrochemical performance.
Next, self-standing electrodes were fabricated through the electropolymerization of conducing polymer, polypyrrole. Surface characterizations, such as SEM, FTIR and XPS proved the successful fabrication of these self-standing electrodes. High mechanical stability and bending flexibility demonstrated the ability to use these electrodes in different designs, such as roll-to-roll membranes. Electrochemical nitrite reduction was employed to demonstrate the viability of using self-standing nanocomposite electrodes for electrocatalytic applications reducing hazardous nitrogen oxyanions (i.e., nitrite) towards innocuous species such as nitrogen gas. A high faradaic efficiency of 78% was achieved, with high selectivity of 91% towards nitrogen gas.
To further enhance the conductivity and charge transfer properties of self-standing polypyrrole electrodes, three different nanoparticles, including copper (Cu), gold (Au), and platinum (Pt), were incorporated in the polypyrrole matrix. Effect of nanoparticle wt% and interaction between metal nanoparticles and polypyrrole matrix was investigated for electroanalytical applications, specifically dopamine sensing. Flexible nanocomposite electrodes showed outstanding performance as electrochemical sensors with PPy-Cu 120s exhibiting a low limit of detection (LOD) of 1.19 µM and PPy-Au 120s exhibiting a high linear range of 5 µM - 300 µM.
This dissertation outlines a method of fabricating self-standing electrodes and provides a pathway of using self-standing electrodes based on polypyrrole and polypyrrole-metal nanocomposites for various applications in wastewater treatment and electroanalytical sensing.
ContributorsBansal, Rishabh (Author) / Garcia-Segura, Sergio (Thesis advisor) / Westerhoff, Paul (Committee member) / Perreault, Francois (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2023
Description
Perovskite solar cells are one of the rising stars in the solar cell industry. This thesis explores several approaches to enhance the properties of the perovskite layer and the solar cell devices in which they operate. They include studies of different antisolvent additives during spin coating of triple cation perovskites, the use of surfactants to improve the quality of perovskite film microstructures, the applicability of a new fabrication process, and the value of post-deposition thermal and chemical annealing processes.This thesis experimentally analyzes different antisolvents, viz., ethyl acetate, isopropyl alcohol, toluene, and chlorobenzene. It focuses on the antisolvent-assisted crystallization method to achieve homogenous nucleation of the perovskite film. Of all the antisolvents, ethyl acetate-treated films gave the best-performing device, achieving a power conversion efficiency of 15.5%.
This thesis also analyzes the effects of mixed antisolvents on the qualities of triple-cation perovskites. Different solution concentrations of chlorobenzene in ethyl acetate and isopropyl alcohol in ethyl acetate are optimized for optimal supersaturation to achieve enlarged perovskite grains. Evaluations are discussed in the context of solution polarity and boiling point of the antisolvents, where 25% chlorobenzene in ethyl acetate antisolvent mixture shows the best film properties.
Another study discusses a new fabrication process called electrical field-assisted direct ink deposition for large-scale printing of perovskite solar cells. This process involves the formation of nanodroplets under an electrical field deposited onto ITO/glass substrates. As a result, smooth Poly (3,4-ethylene dioxythiophene) polystyrene sulfonate layers are
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produced with an average effective electrical resistivity of 4.15104 0.26 -m compared to that of spin-coated films.
A successive chapter discusses the studies of the electrical field-assisted direct ink deposition of the photoactive CH3NH3PbI2 (MAPbI3) layer. Its focus is on the post-deposition chemical annealing of the MAPbI3 films in methylamine gas, termed as methylamine gas-assisted healing and growth of perovskite films. This treatment improved the smoothness, reduced porosity, increased density, and generated more uniform grain sizes. Moreover, it improved the inter-grain boundary contacts by eliminating secondary, fine-grained boundary structures. Mechanisms behind the initial liquefaction of the MAPbI3 film's subsequent re-solidification are discussed.
ContributorsGogoi, Banashree (Author) / Alford, Terry (Thesis advisor) / Petuskey, William (Thesis advisor) / Gould, Ian (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2023
Description
Both molecular structure of macromolecular materials and subsequent processing of these materials dictate resulting material properties. In this work novel synthetic strategies combined with detailed analytical methodology reveal fundamental structure-processing-property relationships in thermoplastic polyesters, thermoplastic polyurethanes, covalently crosslinked acetal functionalized networks, and small molecule surfactants. 4,4’ dimethyloxybisbenzoate afforded a series of novel polyester structures, and the incorporation of this monomer both increased the Tg and decreased the crystallinity in cyclohexane dimethanol based polyesters. Solubility and dynamic light scattering experiments combined with oscillatory rheology techniques provided methodology to validate polyurethane extrusion in commercial polyurethanes. Acid catalyzed hydroxyl addition to vinyl ethers provided two families of acetal functionalized poly(ethylene glycol hydrogels). Stoichiometric control of binary thiol-acrylate polymerizations afforded hydrogels with both tunable mechanical properties and predictable degradation profiles. Following this work, a photoacid generator catalyzed cationic catalysis provided acetal functionalized organogels whose mechanical properties were predicted by excess vinyl ether monomers which underwent cationic polymerization under the same reaction conditions that yielded acetal functionalization. Time resolved FT-IR spectroscopy provided new understanding in hydroxyl vinyl ether reactions, where both hydroxyl addition to a vinyl ether and vinyl ether cationic polymerization occur concurrently. This work inspired research into new reactive systems for photobase generator applications. However, current photobase generator technologies proved incompatible for carbon-Michael reactions between acetoacetate and acrylate functionalities as a result of uncontrollable acrylate free radical polymerization. The fundamental knowledge and synthetic strategies afforded by these investigations were applied to small molecule surfactant systems for fire-fighting applications. Triethylsilyl-containing zwitterionic and cationic surfactants displayed surface tensions lower than hydrocarbon surfactants, but larger than siloxane-containing surfactants. For the first time, oscillatory rheology and polarized optical light imagine rheology highlighted shear-induced micelle alignment in triethylsilyl surfactants, which provided more stable foams than zwitterionic analogues. The knowledge gained from these investigations provided fundamental structure-processing-property relationships in small molecule surfactant solutions applied as fire-fighting foams. This discovery regarding the effect of self-assembled structures in foam solutions informs the design and analysis of next generation surfactants to replace fluorocarbon surfactants in fire-fighting foam applications.
ContributorsBrown, James Robert (Author) / Long, Timothy E (Thesis advisor) / Bortner, Michael J (Committee member) / Biegasiewicz, Kyle F (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2023
Description
Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging. Moreover, there is no fixed framework to identify the doping concentration, which impedes their process integration for future commercialization. This work utilizes the Neutron Transmutation Doping technique to control the doping uniformly and precisely in TMDCs. Rhenium and Tin dopants are introduced in Tungsten- and Indium-based Chalcogenides, respectively. Fine-tuning over 0.001% doping level is achieved. Precise analytical techniques such as Gamma spectroscopy and Secondary Ion Mass Spectrometry are used to quantify ultra-low doping levels ranging from 0.005-0.01% with minimal error. Dopants in 2D TMDCs often exhibit a broad stokes-shifted emission, with high linewidths, due to extrinsic effects such as substrate disorder and surface adsorbates. A well-defined bound exciton emission induced by Rhenium dopants in monolayer WSe2 and WS2 at liquid nitrogen temperatures is reported along with specific annealing regimes to minimize the defects induced in the Neutron Transmutation process. This work demonstrates a framework for Neutron Doping in 2D materials, which can be a scalable process for controlling doping and doping-induced effects in 2D materials.
ContributorsLakhavade, Sushant Sambhaji (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2023
Description
Surface modification of (semi)conducting materials with polymers provides a strategy for interfacing electrodes with electrocatalysts for reactions of industrial importance. The resulting constructs create opportunities to capture, convert and store solar energy in the form of chemical bonds, generating solar fuels. This thesis describes III-V semiconductors, modified with molecular catalysts embedded in thin-film polymeric coatings. Overarching goals of this work include building protein-like, soft-material environments on solid-state electrode surfaces. This approach enables coordination of earth-abundant metal centers within the three-dimensional molecular coatings to modulate the electronic and catalytic properties of the overall assembly and provide assemblies for studying the effects of polymeric-encapsulation on electrocatalytic as well as photoelectrosynthetic performance. In summary, this work provides 1) new approaches to designing, interfacing, and characterizing (semi)conducting and catalytic materials to effectively power chemical transformations (including hydrogen evolution and carbon dioxide reduction), and 2) kinetic models for better understanding the structure-function relationships governing the performance of these assemblies.
ContributorsNguyen, Nghi Do Phuong (Author) / Moore, Gary F. (Thesis advisor) / Seo, Dong-Kyun (Committee member) / Sayres, Scott G. (Committee member) / Arizona State University (Publisher)
Created2023
Description
Lithium nickel manganese cobalt oxides (NMCs) are layered oxide cathode materials which are becoming increasingly popular as the demand for lithium-ion batteries increases. Lithium-ion batteries are used to power modern vehicles and for other battery applications. To better understand the structure and energetics of NMCs, various molar ratios of these compounds were synthesized via a sol-gel method and characterized with powder X-ray diffraction profile fitting. Lattice constants for the nickel, manganese, and cobalt solid solutions were determined. High temperature oxide melt solution calorimetry was used to determine the enthalpies of formation and mixing. All but Li2MnO3 had the same space group as LiCoO2 (R-3m). The lattice constants approximately followed a linear fit with cobalt mole fraction (R2average= 0.973) for the cobalt series. As the molar ratio of cobalt increased the lattice constants decreased. The nickel series was less linear (R2average=0.733) and had an opposite lattice constant trend to cobalt. The manganese series possessed a roughly linear trend when excluding the outlier Li2MnO3 (R2average=0.282). The formation enthalpy of the cobalt series becomes more negative as more cobalt is added. A second order polynomial fit could be used to model the enthalpies of mixing for the series. NMC2.5,2.5,5 exhibited the most stable energetics. A third order polynomial fit could be used to model the enthalpy of mixing for the nickel and manganese series with NMC811 and NMC181 exhibiting the most stable energetics.
ContributorsKanitz, William James (Author) / Navrotsky, Alexandra (Thesis advisor) / Chan, Candace (Committee member) / Xu, Hongwu (Committee member) / Arizona State University (Publisher)
Created2023
Description
Concrete develops strength rapidly after mixing and is highly influenced by temperature and curing process. The material characteristics and the rate of property development, along with the exposure conditions influences volume change mechanisms in concrete, and the cracking propensity of the mixtures. Furthermore, the structure geometry (due to restraint as well as the surface area-to-volume ratio) also influences shrinkage and cracking. Thus, goal of this research is to better understand and predict shrinkage cracking in concrete slab systems under different curing conditions. In this research, different concrete mixtures are evaluated on their propensity to shrink based on free shrinkage and restrained shrinkage tests.Furthermore, from the data obtained from restrained ring test, a casted slab is measured for shrinkage. Effects of different orientation of restraints are studied and compared to better understand the shrinking behavior of the concrete mixtures. The results show that the maximum shrinkage is near the edges of the slab and decreases towards the center. Shrinkage near the edges with no restraint is found out to be more than the shrinkage towards the edges with restraining effects.
ContributorsNimbalkar, Atharwa Samir (Author) / Neithalath, Narayanan (Thesis advisor) / Mobasher, Barzin (Thesis advisor) / Rajan, Subramaniam (Committee member) / Arizona State University (Publisher)
Created2023
Description
For the past two centuries, coal has played a vital role as the primary carbon source, fueling industries and enabling the production of essential carbon-rich materials, including carbon nanotubes, graphite, and diamond. However, the global transition towards sustainable energy production has resulted in a decline in coal usage for energy purposes, with the United States alone witnessing a substantial 50% reduction over the past decade. This shift aligns with the UN’s 2030 sustainability goals, which emphasize the reduction of greenhouse gas emissions and the promotion of cleaner energy sources. Despite the decreased use in energy production, the abundance of coal has sparked interest in exploring its potential for other sustainable and valuable applications.In this context, Direct Ink Writing (DIW) has emerged as a promising additive manufacturing technique that employs liquid or gel-like resins to construct three-dimensional structures. DIW offers a unique advantage by allowing the incorporation of particulate reinforcements, which enhance the properties and functionalities of the materials. This study focuses on evaluating the viability of coal as a sustainable and cost-effective substitute for other carbon-based reinforcements, such as graphite or carbon nanotubes. The research utilizes a thermosetting resin based on phenol-formaldehyde (commercially known as Bakelite) as the matrix, while pulverized coal (250 µm) and carbon black (CB) function as the reinforcements. The DIW ink is meticulously formulated to exhibit shear-thinning behavior, facilitating uniform and continuous printing of structures. Mechanical property testing of the printed structures was conducted following ASTM standards. Interestingly, the study reveals that incorporating a 2 wt% concentration of coal in the resin yields the most significant improvements in tensile modulus and flexural strength, with enhancements of 35% and 12.5% respectively. These findings underscore the promising potential of coal as a sustainable and environmentally friendly reinforcement material in additive manufacturing applications. By harnessing the unique properties of coal, this research opens new avenues for its utilization in the pursuit of greener and more efficient manufacturing processes.
ContributorsSundaravadivelan, Barath (Author) / Song, Kenan (Thesis advisor) / Marvi, Hamidreza (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2023
Description
High-entropy alloys (HEAs) is a new class of materials which have been studied heavily due to their special mechanical properties. HEAs refers to alloys with multiple equimolar or nearly equimolar elements. HEAs show exceptional and attractive properties currently absent from conventional alloys, which make them the center of intense investigation. HEAs obtain their properties from four core effects that they exhibit and most of the work on them have been dedicated to study their mechanical properties. In contrast, little or no research have gone into studying the functional or even thermal properties of HEAs. Some HEAs have also shown exceptional or very high melting points. According to the definition of HEAs, Si-Ge-Sn alloys with equal or comparable concentrations of the three group IV elements belong to the category of HEAs. Thus, the equimolar components of Si-Ge-Sn alloys probably allow their atomic structures to display the same fundamental effects of metallic HEAs. The experimental fabrication of such alloys has been proven to be very difficult, which is mainly due to differences between the properties of their constituent elements, as indicated from their binary phase diagrams. However, previous computational studies have shown that SiGeSn HEAs have some very interesting properties, such as high electrical conductivity, low thermal conductivity and semiconducting properties. In this work, going for a complete characterization of the SiGeSn HEA properties, the melting point of this alloy is studied using classical molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The aim is to investigate the effects of high Sn content in this alloy on the melting point compared with the traditional SiGe alloys. Classical MD simulations results strongly indicates that none of the available empirical potentials is able to predict accurate or reasonable melting points for SiGeSn HEAs and most of its subsystems. DFT calculations results show that SiGeSn HEA have a melting point which represent the mean value of its constituent elements and that no special deviations are found. This work contributes to the study of SiGeSn HEA properties, which can serve as guidance before the successful experimental fabrication of this alloy.
ContributorsAlqaisi, Ahmad Madhat Odeh (Author) / Hong, Qi-Jun (Thesis advisor) / Zhuang, Houlong (Thesis advisor) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2023