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
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
Description
Solid-state lithium-ion batteries are a major area of research due to their increased safety characteristics over conventional liquid electrolyte batteries. Lithium lanthanum zirconate (LLZO) is a promising garnet-type ceramic for use as a solid-state electrolyte due to its high ionic conductivity. The material exists in two dierent phases, one that is cubic in structure and one that is tetragonal. One potential synthesis method that results in LLZO in the more useful, cubic phase, is electrospinning, where a mat of nanowires is spun and then calcined into LLZO. A phase containing lanthanum zirconate (LZO) and amorphous lithium occursas an intermediate during the calcination process. LZO has been shown to be a sintering aid for LLZO, allowing for lower sintering temperatures. Here it is shown the eects of internal LZO on the sintered pellets. This is done by varying the 700C calcination time to transform diering amounts of LZO and LLZO in electrospun nanowires, and then using the same sintering parameters for each sample. X-ray diraction was used to get structural and compositional analysis of both the calcined powders and sintered pellets. Pellets formed from wires calcined at 1 hour or longer contained only LLZO even if the calcined powder had only undergone the rst phase transformation. The relative density of the pellet with no initial LLZO of 61.0% was higher than that of the pellet with no LZO, which had a relative density of 57.7%. This allows for the same, or slightly higher, quality material to be synthesized with a shorter amount of processing time.
ContributorsLondon, Nathan Harry (Author) / Chan, Candace (Thesis director) / Tongay, Sefaattin (Committee member) / Department of Physics (Contributor) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
Topological insulators with conducting surface states yet insulating bulk states have generated a lot of interest amongst the physics community due to their varied characteristics and possible applications. Doped topological insulators have presented newer physical states of matter where topological order co&ndashexists; with other physical properties (like magnetic order). The electronic states of these materials are very intriguing and pose problems and the possible solutions to understanding their unique behaviors. In this work, we use Electron Energy Loss Spectroscopy (EELS) – an analytical TEM tool to study both core&ndashlevel; and valence&ndashlevel; excitations in Bi2Se3 and Cu(doped)Bi2Se3 topological insulators. We use this technique to retrieve information on the valence, bonding nature, co-ordination and lattice site occupancy of the undoped and the doped systems. Using the reference materials Cu(I)Se and Cu(II)Se we try to compare and understand the nature of doping that copper assumes in the lattice. And lastly we utilize the state of the art monochromated Nion UltraSTEM 100 to study electronic/vibrational excitations at a record energy resolution from sub-nm regions in the sample.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Jiang, Nan (Committee member) / Chen, Tingyong (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
Cubic boron nitride (c-BN), hexagonal boron nitride (h-BN), and semiconducting diamond all have physical properties that make them ideal materials for applications in high power and high frequency electronics, as well as radiation detectors. However, there is limited research on the unique properties and growth of c-BN or h-BN thin films. This dissertation addresses the deposition of c-BN via plasma enhanced chemical vapor deposition (PECVD) on boron doped diamond substrates. In-Situ X-ray photoelectron spectroscopy (XPS) is used to characterize the thickness and hexagonal to cubic ratio of boron nitride thin films. The effects of hydrogen concentration during the deposition of boron nitride are investigated. The boron nitride deposition rate is found to be dependent on the hydrogen gas flow. The sp2 to sp3 bonding is also found to be dependent on the hydrogen gas flow. Preferential growth of h-BN is observed when an excess of hydrogen is supplied to the reaction, while h-BN growth is suppressed when hydrogen flow is reduced to be the limiting reactant. Reduced hydrogen flow is also observed to promote preferential growth of c-BN.
The hydrogen limited reaction is used to deposit c-BN on single crystal (100) boron-doped diamond substrates. In-situ ultra-violet photoelectron spectroscopy (UPS) and XPS are used to deduce the valence band offset of the diamond/c-BN interface. A valence band offset of -0.3 eV is measured with the diamond VBM above the VBM of c-BN. This value is then discussed in context of previous experimental results and theoretical calculations.
Finally, UPS and XPS are used to characterize the surface states of phosphorus-doped diamond. Variations within the processing parameters for surface preparation and the effects on the electronic surface states are presented and discussed.
ContributorsBrown, Jesse (Author) / Nemanich, Robert J (Thesis advisor) / Alarcon, Ricardo (Committee member) / Lindsay, Stuart (Committee member) / Zaniewski, Anna (Committee member) / Arizona State University (Publisher)
Created2021