Matching Items (66)
Description
As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium (Ti) in full-scale wastewater treatment plants, (2) quantify sorption of different ENMs to wastewater biomass in laboratory-scale batch reactors, (3) evaluate the use of a standard, soluble-pollutant sorption test method for quantifying ENM interaction with wastewater biomass, and (4) develop a mechanistic model of a biological wastewater treatment reactor to serve as the basis for modeling nanomaterial fate in WWTPs. Using titanium (Ti) as a model material for the fate of ENMs in WWTPs, Ti concentrations were measured in 10 municipal WWTPs. Ti concentrations in pant influent ranged from 181 to 3000 µg/L, and more than 96% of Ti was removed, with effluent Ti concentrations being less than 25 µg/L. Ti removed from wastewater accumulated in solids at concentrations ranging from 1 to 6 µg Ti/mg solids. Using transmission electron microscopy, spherical titanium oxide nanoparticles with diameters ranging from 4 to 30 nm were found in WWTP effluents, evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems. Batch experiments were conducted to quantify sorption of different ENM types to activated sludge. Percentages of sorption to 400 mg TSS/L biomass ranged from about 10 to 90%, depending on the ENM material and functionalization. Natural organic matter, surfactants, and proteins had a stabilizing effect on most of the ENMs tested. The United States Environmental Protection Agency's standard sorption testing method (OPPTS 835.1110) used for soluble compounds was found to be inapplicable to ENMs, as freeze-dried activated sludge transforms ENMs into stable particles in suspension. In conjunction with experiments, we created a mechanistic model of the microbiological processes in membrane bioreactors to predict MBR, extended and modified this model to predict the fate of soluble micropollutants, and then discussed how the micropollutant fate model could be used to predict the fate of nanomaterials in wastewater treatment plants.
ContributorsKiser, Mehlika Ayla (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Hristovski, Kiril D (Committee member) / Arizona State University (Publisher)
Created2011
Description
Titanium dioxide (TiO2) nanomaterial use is becoming more prevalent as is the likelihood of human exposure and environmental release. The goal of this thesis is to develop analytical techniques to quantify the level of TiO2 in complex matrices to support environmental, health, and safety research of TiO2 nanomaterials. A pharmacokinetic model showed that the inhalation of TiO2 nanomaterials caused the highest amount to be absorbed and distributed throughout the body. Smaller nanomaterials (< 5nm) accumulated in the kidneys before clearance. Nanoparticles of 25 nm diameter accumulated in the liver and spleen and were cleared from the body slower than smaller nanomaterials. A digestion method using nitric acid, hydrofluoric acid, and hydrogen peroxide was found to digest organic materials and TiO2 with a recovery of >80%. The samples were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the method detection limit was 600 ng of Ti. An intratracheal instillation study of TiO2 nanomaterials in rats found anatase TiO2 nanoparticles in the caudal lung lobe of rats 1 day post instillation at a concentration of 1.2 ug/mg dry tissue, the highest deposition rate of any TiO2 nanomaterial. For all TiO2 nanomaterial morphologies the concentrations in the caudal lobes were significantly higher than those in the cranial lobes. In a study of TiO2 concentration in food products, white colored foods or foods with a hard outer shell had higher concentrations of TiO2. Hostess Powdered Donettes were found to have the highest Ti mass per serving with 200 mg Ti. As much as 3.8% of the total TiO2 mass was able to pass through a 0.45 um indicating that some of the TiO2 is likely nanosized. In a study of TiO2 concentrations in personal care products and paints, the concentration of TiO2 was as high as 117 ug/mg in Benjamin Moore white paint and 70 ug/mg in a Neutrogena sunscreen. Greater than 6% of Ti in one sunscreen was able to pass through a 0.45 um filter. The nanosized TiO2 in food products and personal care products may release as much as 16 mg of nanosized TiO2 per individual per day to wastewater.
ContributorsWeir, Alex Alan (Author) / Westerhoff, Paul K (Thesis advisor) / Hristovski, Kiril (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2011
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