Matching Items (42)
155778-Thumbnail Image.png
Description
Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic

Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic oxidation of two model organic pollutants (methylene blue, (MB) and para-chlorobenzoic acid (pCBA)). By varying the photon fluence dose, two metrics (contaminant quantum yield (Φ), and electrical energy per order (EEO)) were used to assess photocatalytic reactor performance. A detailed literature review and experimental results demonstrated how different irradiance sources with variable intensity and emission spectra synergistically enhanced contaminant removal by a coupled photolytic/photocatalytic reaction mechanism. Cr(VI) was photocatalytically reduced on TiO2 and formed Cr(OH)3(s) in a large-scale slurry reactor, but Cr(III) was then photolyzed and reformed Cr(VI). UV light also led to photo-aggregation of TiO2 which improved its recovery by the ceramic membrane within the reactor. For nitrate reduction, light source emission spectra and fluence dose delineate the preferred pathways as intermediates were reduced via wavelength-dependent mechanisms. HONO was identified as a key nitrate reduction intermediate, which was reduced photocatalytically (UV wavelengths) and/or readily photolyzed at 365nm, to yield nitrogen gases. Photocatalytic nitrate reduction efficiency was higher for discrete wavelength irradiation than polychromatic irradiation. Light delivery through aqueous media to the catalyst surface limits efficiency of slurry-based photocatalysts because absorption and scattering of light in nanomaterial slurries decreases effective photon transmittance and minimizes photolytic reactions. The use of optical fibers coupled to light emitting diodes (OF-LED) with immobilized catalyst demonstrated higher performance compared to slurry systems. OF-LED increased Φ for MB degradation by increasing direct photon delivery to the photocatalyst. Design of OF-LED reactors using bundled optical fibers demonstrated photocatalytic pCBA removal with high Φ and reduced EEO due to increased surface area and catalytic sites compared to single OF/LED couples. This work advances light delivery as well as the suspension and attachment of nanoparticles in photocatalytic water treatment for selective transformation of oxo-anions and organic compounds to innocuous species.
ContributorsTugaoen, Heather O'Neal (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Thesis advisor) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2017
155664-Thumbnail Image.png
Description
Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are

Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are a lot more flexible in comparison. In this work, it was observed that not any α-alumina could be used by the blade coating process to get a good quality separator on Li4Ti5O12 (LTO) electrode. In this work specifically, the effect of particle size of α-alumina, on processability of slurry was investigated. The effect of the particle size variations on quality of separator formation was also studied. Most importantly, the effect of alumina particle size and its distribution on the performance of LTO/Li half cells is examined in detail. Large-sized particles were found to severely limit the ability to fabricate such separators. The α-alumina slurry was coated onto electrode substrate, leading to possible interaction between α-alumina and LTO substrate. The interaction between submicron sized particles of α-alumina with the substrate electrode pores, was found to affect the performance and the stability of the separator. Utilizing a bimodal distribution of submicron sized particles with micron sized particles of α-alumina to prepare the separator, improved cell performance was observed. Yet only a specific ratio of bimodal distribution achieved good results both in terms of separator formation and resulting cell performance. The interaction of α-alumina and binder in the separator, and its effect on the performance of substrate electrode was investigated, to understand the need for bimodal distribution of powder forming the separator.
ContributorsKanhere, Narayan Vishnu (Author) / Lin, Jerry Y. S. (Thesis advisor) / Kannan, Arunachala (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2017
155276-Thumbnail Image.png
Description
Dealloying, the selective electrochemical dissolution of an active component from an alloy, often results in nanoscale bi-continuous solid/void morphologies. These structures are attracting attention for a wide range of applications including catalysis, sensing and actuation. The evolution of these nanoporous structures has been widely studied for the case at low

Dealloying, the selective electrochemical dissolution of an active component from an alloy, often results in nanoscale bi-continuous solid/void morphologies. These structures are attracting attention for a wide range of applications including catalysis, sensing and actuation. The evolution of these nanoporous structures has been widely studied for the case at low homologous temperature, TH, such as in Ag-Au, Cu-Au, Cu-Pt, etc. Since at low TH the solid-state mobility of the components is of order 10-30 cm2s-1 or less, percolation dissolution is the only mechanism available to support dealloying over technologically relevant time scales. Without the necessity of solid-state mass transport, percolation dissolution involves sharp transitions based on two key features, the parting limit and critical potential.

Dealloying under conditions of high TH, (or high intrinsic diffusivity of the more electrochemically reactive component) is considerably more complicated than at low TH. Since solid-state mass transport is available to support this process, a rich set of morphologies, including negative or void dendrites, Kirkendall voids and bi-continuous porous structures, can evolve. In order to study dealloying at high TH we have examined the behavior of Li-Sn and Li-Pb alloys. The intrinsic diffusivities of Li were measured in these alloys using electrochemical titration and time of flight measurements. Morphology evolution was studied with varying alloy composition, host dimension and imposed electrochemical conditions. Owing to diffusive transport, there is no parting limit for dealloying, however, there is a compositional threshold (pPD) as well as a critical potential for the operation of percolation dissolution and the formation of bi-continuous structures. Negative or void dendrite morphologies evolve at compositions below pPD and at large values of the applied electrochemical potential when the rate of dealloying is limited by solid-state mass transport. This process is isomorphic to dendrite formation in electrodeposition. Kirkendall voiding morphologies evolve below the critical potential over the entire range of alloy compositions.

We summarize our results by introducing dealloying morphology diagrams that we use to graphically illustrate the electrochemical conditions resulting in various morphologies that can form under conditions of low and high TH.
ContributorsGeng, Ke (Author) / Sieradzki, Karl (Thesis advisor) / Crozier, Peter (Committee member) / Chan, Candace (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2017
135507-Thumbnail Image.png
Description
In 2015, the United States consumed about 140.43 billion gallons of gasoline, resulting in the emission of over 1 billion metric tons of carbon dioxide, according to the U.S. Energy Information Administration. Despite continued efforts to develop more efficient engines and cleaner fuels, a major barrier to reducing energy consumption

In 2015, the United States consumed about 140.43 billion gallons of gasoline, resulting in the emission of over 1 billion metric tons of carbon dioxide, according to the U.S. Energy Information Administration. Despite continued efforts to develop more efficient engines and cleaner fuels, a major barrier to reducing energy consumption and CO2 production is the mass of the vehicle. Replacing traditional automotive materials such as iron and steel with lighter-weight materials is a big step toward improving fuel economy. Magnesium has great potential for use in the automotive industry because of its low density, about 78% less than the density of steel, and high strength-to-weight ratio. Using cast magnesium instead of steel can reduce the overall weight of a vehicle, improving performance and increasing fuel efficiency. However, magnesium’s high susceptibility to corrosion limits its feasibility as a substitute for traditional materials.

This project aimed to understand the effects of composition and phase distribution on the corrosion behavior of magnesium-aluminum (Mg-Al) alloys in an ionic liquid electrolyte. The purpose of studying corrosion in nonaqueous ILs is to determine the anodic dissolution behaviors of the alloy phases without the interference of side reactions that occur in aqueous electrolytes, such as di-oxygen or water reduction. Three commercial Mg-Al alloys were studied: AZ91D (9% Al), AM60 (6% Al), and AZ31B (3% Al). An annealed alloy containing solid-solution α-phase Mg-Al with 5 at% aluminum content (Mg5Al) was also used. The ionic liquid chosen for this project was 1:2 molar ratio choline-chloride:urea (cc-urea), a deep eutectic solvent. After potentiostatic corrosion in cc-urea, the magnesium alloys were found to form a high surface area porous morphology as corrosion duration increased. This morphology consists of aluminum-rich ridges formed by Al nanowires surrounding an aluminum-poor base area, but with an overall increase in surface Al composition, indicating selective dealloying of the Mg in cc-urea and redistribution of the Al on the surface. Further work will focus on the development of hydrophobic coatings using ionic liquids.
ContributorsWeiss, Anna Caroline (Author) / Sieradzki, Karl (Thesis director) / Chan, Candace (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
147689-Thumbnail Image.png
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

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
168291-Thumbnail Image.png
Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and

Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021
168278-Thumbnail Image.png
Description
The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one

The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one of the most promising candidates to enable Li metal batteries due to its high ionic conductivity, chemical stability, and wide electrochemical stability window against Li metal. However, synthesis and processing of c-LLZO through conventional solid-sate reaction methods requires long periods of calcination (> 6 h) at high reaction temperatures (> 1000 °C). The need for high reaction temperature results to attain cubic-LLZO phase results in large aggerated LLZO particles and causes Li-loss from the garnet structure, making them unfavorable to process further as bulk pellets or thin films. To overcome processing challenges with solid-state reaction method, two novel facile synthesis approaches molten salt (flux growth method), and solution combustion are employed to produce submicron-sized LLZO powders at low reaction temperatures (< 1000 °C) in a short time. In the first case, molten salt synthesis method with LiCl-KCl eutectic mixture is employed to produce sub-micron sized Ta-doped LLZO (LLZTO) powders at low temperatures (900 °C, 4 h). In addition, a detailed investigation on effect of sintering medium and sintering additives on the structural, microstructural, chemical, and Li-ion transport behavior of the LLZTO pellets are investigated. Sintered LLZTO pellets prepared using molten salt synthesis route exhibited high Li-ion conductivity up to 0.6 mS cm-1 and high relative density (> 95 %) using Pt-crucible. In the second case, a facile solution-combustion technique using an amide-based fuel source CH6N4O is utilized to produce submicron-sized Al-doped LLZO (Al-LLZO) powders at low reaction temperatures 600-800 °C in a short duration of 4 h. In addition, effect of fuel to oxidizer ratio on phase purity, particle growth size, and formation mechanism of conductive Al-LLZO are reported and discussed. The Al-LLZO pellets sintered at 1100 °C/ 6 h exhibited high Li-ion conductivity up to 0.45 mS cm-1 with relative densities (> 90 %).
ContributorsBadami, Pavan Pramod (Author) / Kannan, Arunachalandar Mada (Thesis advisor) / Chan, Candace (Thesis advisor) / Song, Kenan (Committee member) / Arizona State University (Publisher)
Created2021
Description

The objective of this experiment was to use water contact angle (WCA) to measure the effectiveness of adhesion, Atomic Layer Deposition (ALD), and cleaning techniques within different operations at Intel Corporation. Using the Sessile Drop Method, goniometer instrument, and a Video Contact Angle system (VCA), the water contact angle across

The objective of this experiment was to use water contact angle (WCA) to measure the effectiveness of adhesion, Atomic Layer Deposition (ALD), and cleaning techniques within different operations at Intel Corporation. Using the Sessile Drop Method, goniometer instrument, and a Video Contact Angle system (VCA), the water contact angle across silicon wafers at various operations were determined. Based on the results, it was concluded that Operation 5 and Step 4.4 within Operation 5 were suspected to cause lack of uniformity across the wafers, which is detrimental to the durability of the wafer and the overall high performance of a microchip. Due to proprietary reasons, it could not be disclosed as to whether adhesion, ALD, or cleaning techniques were implemented and suspected to cause non-uniformity across the wafer, but despite any operation, the topography of the wafer should be leveled. The absolute slopes of Operation 5 and Step 4.4 were 2.445 and 3.189, respectively. These slopes represented the change in contact angles across different positions of the wafer. In comparison, these showed the greatest variation of contact angles across the wafers, meaning the surface topography was more concentrated in certain areas of the wafer than others. Given these characteristics, Operation 5 and Step 4.4 are not qualified to produce high performing microchips because their techniques and methods are prone to cause surface defects, wafer stress, and wafer breakage.

ContributorsMunoz, Camryn (Author) / Chan, Candace (Thesis director) / Frazier, Amy (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor)
Created2023-05
Description

This thesis focuses on exploring the reconditioning Ni-MH HEV batteries. The goal of this thesis is to demonstrate the viability of a method for reconditioning Ni-MH HEV batteries which involves charging battery modules in series. To do this, a set of 8 modules were reconditioned by charging them in series

This thesis focuses on exploring the reconditioning Ni-MH HEV batteries. The goal of this thesis is to demonstrate the viability of a method for reconditioning Ni-MH HEV batteries which involves charging battery modules in series. To do this, a set of 8 modules were reconditioned by charging them in series and another set of 8 modules were reconditioned by charging them individually. Both sets of modules were charged at a rate of around 0.05C. Additionally, the modules connected in series were charged using a controlled current for cell balancing. The effectiveness of each reconditioning method was evaluated through capacity estimation. The capacity estimation was done during a standard five-hour discharge using simple coulomb counting. This experiment showed that charging the set of 8 modules in series is an effective method to use for reconditioning. Furthermore, it can be reasonably assumed from these results that charging an entire Ni-MH HEV battery pack in series is an effective method for reconditioning.

ContributorsDobos, Michael (Author) / Chan, Candace (Thesis director) / Thomas, Marylaura (Committee member) / Barrett, The Honors College (Contributor) / Mechanical and Aerospace Engineering Program (Contributor)
Created2023-05
187724-Thumbnail Image.png
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

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