Matching Items (56)
Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
Hexavalant chromium (Cr(VI)) poses an emerging concern in drinking water treatment with stricter regulations on the horizon. Photocatalytic reduction of Cr(VI) was investigated as an engineering scale option to remove hexavalent chromium from drinking or industrial waters via a UV/titanium dioxide (TiO2) process. Using an integrated UV lamp/ceramic membrane system to recirculate TiO2, both hexavalent and total chromium levels were reduced through photocatalytic processes without additional chemicals. Cr(VI) removal increased as a function of higher energy input and TiO2 dosage, achieving above 90% removal for a 1g/L dose of TiO2. Surface analysis of effluent TiO2 confirmed the presence of chromium species.
ContributorsStancl, Heather O'Neal (Author) / Westerhoff, Paul K (Thesis advisor) / Chan, Candace (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
The purpose of this thesis was to investigate the properties of amorphous and crystalline NaTaO3 to determine what makes amorphous NaTaO3 a suitable photocatalyst for water splitting applications. Amorphous and nanocrystalline NaTaO3 were synthesized and characterized using X-Ray Diffraction (XRD), Raman Spectroscopy, and Fourier Transform Infrared Spectroscopy (FT-IR). The photocatalytic activity of the materials was analyzed using methylene blue degradation as an indicator of photocatalytic activity. The amorphous material showed significant photocatalytic activity in methylene blue degradation experiments, removing 100% of a 0.1 mmol methylene blue solution in 20 minutes, compared to the monoclinic crystalline NaTaO3, which showed negligible photocatalytic activity. Additional electrochemical characterization studies were carried out with methyl viologen (MV2+) to determine the band structure of the materials. Performing these synthesis and characterization has provided insight into further investigation of amorphous NaTaO3 and what makes the material an effective and inexpensive photocatalyst.
ContributorsRorrer, Julie Elaine (Author) / Chan, Candace (Thesis director) / Bertoni, Mariana (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
With the world's ever growing need for sustainable energy solutions, the field of thermoelectrics has seen rejuvenated interest. Specifically, modern advances in nanoscale technology have resulted in predictions that thermoelectric devices will soon become a viable waste heat recovery energy source, among other things. In order to achieve these predictions, however, key structure-property relationships must first be understood. Currently, the Thermal Energy and Nanomaterials Lab at Arizona State University is attempting to solve this problem. This project intends to aid the groups big picture goal by developing a robust and user friendly measurement platform which is capable of reporting charge carrier mobility, electrical conductivity, and Seebeck coefficient values. To date, the charge carrier mobility and electrical conductivity measurements have been successfully implemented and validated. First round analysis has been performed on β-In2Se3 thin film samples. Future work will feature a more comprehensive analysis of this material.
ContributorsNess, Kyle David (Author) / Wang, Robert (Thesis director) / Chan, Candace (Committee member) / Barrett, The Honors College (Contributor) / Mechanical and Aerospace Engineering Program (Contributor)
Created2014-05
Description
Lithium-ion batteries are one of the most widely used energy storage solutions today. As renewable energy sources proliferate to meet growth in worldwide energy consumption, it is important that lithium-ion batteries be improved to help capture this energy for use when the demand arises. One way to boost the performance of lithium-ion batteries is to replace the electrode active materials with materials of higher specific capacity. Silicon is one material that has been widely touted as a potential replacement for the graphite used in commercial anodes with a theoretical capacity of 3500 mAh/g as opposed to graphite's 372 mAh/g. However, bulk silicon is known to pulverize after experiencing large strains during lithiation. Here, silicon clathrates are investigated as a potential structure for accommodation of these strains. Silicon clathrates consist of covalently bonded silicon host cages surrounding a guest alkali or alkaline earth metal ion. Previous work has looked at silicon clathrates for their superconducting and thermoelectric properties. In this study, electrochemical properties of type I and II silicon clathrates with sodium guest ions (NaxSi46 and NaxSi136) and type I silicon clathrates with copper framework substitution and barium guest ions (Ba8CuxSi46-x) are examined. Sodium clathrates showed very high capacities during initial lithiation (>2500 mAh/g), but rapidly lost capacity thereafter. X-ray diffraction after lithiation showed conversion of the clathrate phase to lithium silicide and then to amorphous silicon after delithiation, indicating destruction of the clathrate structure as a possible explanation for the rapid capacity fade. Ba8CuxSi46-x clathrates were found to have their structures completely intact after 50 cycles. However, they had very low reversible capacities (<100 mAh/g) and potentially might not be electrochemically active. Further work is needed to better understand exactly how lithium is inserted into clathrates and if copper impurities detected during wavelength-dispersive X-ray spectroscopy could be inhibiting lithium transport into the clathrates.
ContributorsWagner, Nicholas Adam (Author) / Chan, Candace (Thesis director) / Sieradzki, Karl (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2014-05
Description
In the last several years, there has been interest in the development of flexible batteries as a substitute for traditional Li-ion batteries. Flexible batteries can fold, bend, and twist; studies have shown that mechanical stresses and fatigue may decrease battery performance and cause defects. In this paper, the viability of producing a mechanical fatigue-testing device from 3D printed and other off-the-shelf components was explored. The device was made using a servomotor and LCD screen controlled by a programmed Arduino board, and successfully met the expectations to be cheap, easily reproducible, versatile, and applicable to the testing of battery components. In a proof-of-concept test, the device was used to perform repeated folding tests on lithium cobalt oxide cathodes in different configurations, which were then characterized using a laser microscope. 3D topographical renderings suggested that bending at acute angles induces defects on the surface of the electrode where the electrode is creased. In future work, the device will be used to further explore the effect of mechanical fatigue on Li-ion battery components.
ContributorsBurchard, Joshua Thomas (Author) / Chan, Candace (Thesis director) / Anwar, Shahriar (Committee member) / Materials Science and Engineering Program (Contributor, Contributor) / Dean, W.P. Carey School of Business (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Recent studies indicate the presence of nano-scale titanium dioxide (TiO[subscript 2]) as an additive in human foodstuffs, but a practical protocol to isolate and separate nano-fractions from soluble foodstuffs as a source of material remains elusive. As such, we developed a method for separating the nano and submicron fractions found in commercial-grade TiO[subscript 2] (E171) and E171 extracted from soluble foodstuffs and pharmaceutical products (e.g., chewing gum, pain reliever, and allergy medicine). Primary particle analysis of commercial-grade E171 indicated that 54% of particles were nano-sized (i.e., < 100 nm). Isolation and primary particle analysis of five consumer goods intended to be ingested revealed differences in the percent of nano-sized particles from 32%‒58%. Separation and enrichment of nano- and submicron-sized particles from commercial-grade E171 and E171 isolated from foodstuffs and pharmaceuticals was accomplished using rate-zonal centrifugation. Commercial-grade E171 was separated into nano- and submicron-enriched fractions consisting of a nano:submicron fraction of approximately 0.45:1 and 3.2:1, respectively. E171 extracted from gum had nano:submicron fractions of 1.4:1 and 0.19:1 for nano- and submicron-enriched, respectively. We show a difference in particle adhesion to the cell surface, which was found to be dependent on particle size and epithelial orientation. Finally, we provide evidence that E171 particles are not immediately cytotoxic to the Caco-2 human intestinal epithelium model. These data suggest that this separation method is appropriate for studies interested in isolating the nano-sized particle fraction taken directly from consumer products, in order to study separately the effects of nano and submicron particles.
ContributorsFaust, James (Author) / Doudrick, Kyle (Author) / Yang, Yu (Author) / Capco, David (Author) / Westerhoff, Paul (Author) / College of Liberal Arts and Sciences (Contributor) / Molecular and Cellular Biology (Contributor) / School of Life Sciences (Contributor) / Ira A. Fulton Schools of Engineering (Contributor) / School of Sustainable Engineering and the Built Environment (Contributor)
Created2016-10-31
Description
GaN-based devices are currently limited by reliability issues such as gate leakage and current collapse, where the mechanisms responsible for degradation are closely related to the electronic surface state configuration. Therefore, understanding the electronic surface state configuration of GaN-based materials will help improve device performance. Since GaN has an inherent polarization, these materials are also subject to a bound polarization charge, which influences the electronic state configuration. In this study, the surface band bending of N-face GaN, Ga-face GaN, and Ga-face AlGaN was measured with x-ray photoemission spectroscopy after various cleaning steps to investigate the effects of the polarization. Despite the different surface bound charge on these materials, similar band bending was observed regardless of the magnitude or direction of the charge. Specifically, the band bending varied from −0.1 eV to 0.9 eV on these samples, which supported the models of a Fermi level pinning state at ∼0.4 eV to 0.8 eV below the conduction band. Based on available literature, we suggest this pinning state is indirectly evident of a nitrogen vacancy or gallium-dangling bond.
ContributorsEller, Brianna S. (Author) / Yang, Jialing (Author) / Nemanich, Robert (Author) / College of Liberal Arts and Sciences (Contributor) / Department of Physics (Contributor)
Created2014-12-01
Description
The effects of surface pretreatment, dielectric growth, and post deposition annealing on interface electronic structure and polarization charge compensation of Ga- and N-face bulk GaN were investigated. The cleaning process consisted of an ex-situ wet chemical NH[subscript 4]OH treatment and an in-situ elevated temperature NH[subscript 3] plasma process to remove carbon contamination, reduce oxygen coverage, and potentially passivate N-vacancy related defects. After the cleaning process, carbon contamination decreased below the x-ray photoemission spectroscopy detection limit, and the oxygen coverage stabilized at ∼1 monolayer on both Ga- and N-face GaN. In addition, Ga- and N-face GaN had an upward band bending of 0.8 ± 0.1 eV and 0.6 ± 0.1 eV, respectively, which suggested the net charge of the surface states and polarization bound charge was similar on Ga- and N-face GaN. Furthermore, three dielectrics (HfO[subscript 2], Al[subscript 2]O[subscript 3], and SiO[subscript 2]) were prepared by plasma-enhanced atomic layer deposition on Ga- or N-face GaN and annealed in N[subscript 2] ambient to investigate the effect of the polarization charge on the interface electronic structure and band offsets. The respective valence band offsets of HfO[subscript 2], Al[subscript 2]O[subscript 3], and SiO[subscript 2] with respect to Ga- and N-face GaN were 1.4 ± 0.1, 2.0 ± 0.1, and 3.2 ± 0.1 eV, regardless of dielectric thickness. The corresponding conduction band offsets were 1.0 ± 0.1, 1.3 ± 0.1, and 2.3 ± 0.1 eV, respectively. Experimental band offset results were consistent with theoretical calculations based on the charge neutrality level model. The trend of band offsets for dielectric/GaN interfaces was related to the band gap and/or the electronic part of the dielectric constant. The effect of polarization charge on band offset was apparently screened by the dielectric-GaN interface states.
ContributorsYang, Jialing (Author) / Eller, Brianna S. (Author) / Nemanich, Robert (Author) / College of Liberal Arts and Sciences (Contributor) / Department of Physics (Contributor)
Created2014-09-28
Description
Heavy metals such as selenium can be especially important to limit because they can cause serious health problems even at relatively low concentrations. In an effort to selectively remove selenium from solution, a PAABA (poly(aniline-co-p-aminobenzoic acid) conductive copolymer was synthesized in a selenic acid solution, and its ability to remove selenium was studied. Analysis of the Raman spectra confirmed the hypothesized formation of PAABA polymer. Constant voltage cycles showed success in precipitating the selenium out of solution via electroreduction, and ICP-MS confirmed the reduction of selenium concentrated in solution. These results indicate the PAABA synthesized in selenic acid shows promise for selective water treatment.
ContributorsSulzman, Serita Lynne (Author) / Wang, Qing Hua (Thesis director) / Chan, Candace (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05