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Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts,

Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
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Description
As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of

As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of full-scale biological WWTPs for several weeks. NM loadings at the higher range of expected environmental concentrations were selected. To achieve the pseudo-equilibrium state concentration of NMs in biomass, SBR experiments needed to operate for more than three times the SRT value, approximately 18 days. Under the conditions tested, NMs had negligible effects on ability of the wastewater bacteria to biodegrade organic material, as measured by chemical oxygen demand (COD). NM mass balance closure was achieved by measuring NMs in liquid effluent and waste biosolids. All NMs were well removed at the typical biomass concentration (1~2 gSS/L). However, carboxy-terminated polymer coated silver nanoparticles (fn-Ag) were removed less effectively (88% removal) than hydroxylated fullerenes (fullerols; >90% removal), nano TiO2 (>95% removal) or aqueous fullerenes (nC60; >95% removal). Although most NMs did not settle out of the feed solution without bacteria present, approximately 65% of the titanium dioxide was removed even in the absence of biomass simply due to self-aggregation and settling. Experiments conducted over 4 months with daily loadings of nC60 showed that nC60 removal from solution depends on the biomass concentration. Under conditions representative of most suspended growth biological WWTPs (e.g., activated sludge), most of the NMs will accumulate in biosolids rather than in liquid effluent discharged to surface waters. Significant fractions of fn-Ag were associated with colloidal material which suggests that efficient particle separation processes (sedimentation or filtration) could further improve removal of NM from effluent. As most NMs appear to accumulate in biosolids, future research should examine the fate of NMs during disposal of WWTP biosolids, which may occur through composting or anaerobic digestion and/or land application, incineration, or landfill disposal.
ContributorsWang, Yifei (Author) / Westerhoff, Paul (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV

The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV modules lying in the landfills by 2050, that may not become a not-so-sustainable way of sourcing energy since all PV modules could contain certain amount of toxic substances. Currently in the United States, PV modules are categorized as general waste and can be disposed in landfills. However, potential leaching of toxic chemicals and materials, if any, from broken end-of-life modules may pose health or environmental risks. There is no standard procedure to remove samples from PV modules for chemical toxicity testing in the Toxicity Characteristic Leaching Procedure (TCLP) laboratories as per EPA 1311 standard. The main objective of this thesis is to develop an unbiased sampling approach for the TCLP testing of PV modules. The TCLP testing was concentrated only for the laminate part of the modules, as they are already existing recycling technologies for the frame and junction box components of PV modules. Four different sample removal methods have been applied to the laminates of five different module manufacturers: coring approach, cell-cut approach, strip-cut approach, and hybrid approach. These removed samples were sent to two different TCLP laboratories, and TCLP results were tested for repeatability within a lab and reproducibility between the labs. The pros and cons of each sample removal method have been explored and the influence of sample removal methods on the variability of TCLP results has been discussed. To reduce the variability of TCLP results to an acceptable level, additional improvements in the coring approach, the best of the four tested options, are still needed.
ContributorsLeslie, Joswin (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Kuitche, Joseph (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential

Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential health concerns in case of exposure to popular FRs. Carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) have been studied and applied to polymer composites and electronics extensively due to their remarkable properties. Hence CNMs are considered as potential alternative materials that present high flame retardancy. In this research, different kinds of CNMs coatings on polyester fabric are produced and evaluated for their use as flame retardants. To monitor the mass loading of CNMs coated on the fabric, a two-step analytical method for quantifying CNMs embedded in polymer composites was developed. This method consisted of polymer dissolution process using organic solvents followed by subsequent programmed thermal analysis (PTA). This quantification technique was applicable to CNTs with and without high metal impurities in a broad range of polymers. Various types of CNMs were coated on polyester fabric and the efficacy of coatings as flame retardant was evaluated. The oxygen content of CNMs emerged as a critical parameter impacting flame retardancy with higher oxygen content resulting in less FR efficacy. The most performant nanomaterials, multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nantoubes (NH2-MWCNT) showed similar FR properties to current flame retardants with low mass loading (0.18 g/m2) and hence are promising alternatives that warrant further investigation. Chemical/physical modification of MWCNTs was conducted to produce well-dispersed MWCNT solutions without involving oxygen for uniform FR coating. The MWCNTs coating was studied to evaluate the durability of the coating and the impact on the efficacy during use phase by conducting mechanical abrasion and washing test. Approximately 50% and 40% of MWCNTs were released from 1 set of mechanical abrasion and washing test respectively. The losses during simulated usage impacted the flame retardancy negatively.
ContributorsNosaka, Takayuki (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Semiconductor nanostructures are promising building blocks for light management in thin silicon solar cells and silicon-based tandems due their tunable optical properties. The present dissertation is organized along three main research areas: (1) characterization and modeling of III-V nanowires as active elements of solar cell tandems, (2) modeling of silicon

Semiconductor nanostructures are promising building blocks for light management in thin silicon solar cells and silicon-based tandems due their tunable optical properties. The present dissertation is organized along three main research areas: (1) characterization and modeling of III-V nanowires as active elements of solar cell tandems, (2) modeling of silicon nanopillars for reduced optical losses in ultra-thin silicon solar cells, and (3) characterization and modeling of nanoparticle-based optical coatings for light management.

First, the recombination mechanisms in polytype GaAs nanowires are studied through photoluminescence measurements coupled with rate equation analysis. When photons are absorbed in polytype nanowires, electrons and holes quickly thermalize to the band-edges of the zinc-blende and wurtzite phases, recombining indirectly in space across the type-II offset. Using a rate equation model, different configurations of polytype defects along the nanowire are investigated, which compare well with experiment considering spatially indirect recombination between different polytypes, and defect-related recombination due to twin planes and other defects. The presented analysis is a path towards predicting the performance of nanowire-based solar cells.

Following this topic, the optical mechanisms in silicon nanopillar arrays are investigated using full-wave optical simulations in comparison to measured reflectance data. The simulated electric field energy density profiles are used to elucidate the mechanisms contributing to the reduced front surface reflectance. Strong forward scattering and resonant absorption are observed for shorter- and longer- aspect ratio nanopillars, respectively, with the sub-wavelength periodicity causing additional diffraction. Their potential for light-trapping is investigated using full-wave optical simulation of an ultra-thin nanostructured substrate, where the conventional light-trapping limit is exceeded for near-bandgap wavelengths.

Finally, the correlation between the optical properties of silicon nanoparticle layers to their respective pore size distributions is investigated using optical and structural characterization coupled with full-wave optical simulation. The presence of

scattering is experimentally correlated to wider pore size distributions obtained from nitrogen adsorption measurements. The correlation is validated with optical simulation of random and clustered structures, with the latter approximating experimental. Reduced structural inhomogeneity in low-refractive-index nanoparticle inter-layers at the metal/semiconductor interface improves their performance as back reflectors, while reducing parasitic absorption in the metal.
ContributorsVulic, Natasa (Author) / Goodnick, Stephen M (Thesis advisor) / Honsberg, C. (Christiana B.) (Committee member) / Holman, Zachary C (Committee member) / Smith, David J. (Committee member) / Arizona State University (Publisher)
Created2019
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Description
In the nano-regime many materials exhibit properties that are quite different from their bulk counterparts. These nano-properties have been shown to be useful in a wide range of applications with nanomaterials being used for catalysts, in energy production, as protective coatings, and in medical treatment. While there is no shortage

In the nano-regime many materials exhibit properties that are quite different from their bulk counterparts. These nano-properties have been shown to be useful in a wide range of applications with nanomaterials being used for catalysts, in energy production, as protective coatings, and in medical treatment. While there is no shortage of exciting and novel applications, the world of nanomaterials suffers from a lack of large scale manufacturing techniques. The current methods and equipment used for manufacturing nanomaterials are generally slow, expensive, potentially dangerous, and material specific. The research and widespread use of nanomaterials has undoubtedly been hindered by this lack of appropriate tooling. This work details the effort to create a novel nanomaterial synthesis and deposition platform capable of operating at industrial level rates and reliability.

The tool, referred to as Deppy, deposits material via hypersonic impaction, a two chamber process that takes advantage of compressible fluids operating in the choked flow regime to accelerate particles to up several thousand meters per second before they impact and stick to the substrate. This allows for the energetic separation of the synthesis and deposition processes while still behaving as a continuous flow reactor giving Deppy the unique ability to independently control the particle properties and the deposited film properties. While the ultimate goal is to design a tool capable of producing a broad range of nanomaterial films, this work will showcase Deppy's ability to produce silicon nano-particle films as a proof of concept.

By adjusting parameters in the upstream chamber the particle composition was varied from completely amorphous to highly crystalline as confirmed by Raman spectroscopy. By adjusting parameters in the downstream chamber significant variation of the film's density was achieved. Further it was shown that the system is capable of making these adjustments in each chamber without affecting the operation of the other.
ContributorsFirth, Peter (Author) / Holman, Zachary C (Thesis advisor) / Kozicki, Michael (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic

Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic simultaneously from groundwater compared to existing sorbents?” Preliminary nano-composite sorbents outperformed existing sorbents in equilibrium tests, but struggled in packed bed applications and at low influent concentrations. The synthesis process was then tailored for weak base anion exchange (WBAX) while comparing titanium dioxide against iron hydroxide nanoparticles (Ti-WBAX and Fe-WBAX, respectively). Increasing metal precursor concentration increased the metal content of the created sorbents, but pollutant removal performance and usable surface area declined due to pore blockage and nanoparticle agglomeration. An acid-post rinse was required for Fe-WBAX to restore chromium removal capacity. Anticipatory life cycle assessment identified critical design constraints to improve environmental and human health performance like minimizing oven heating time, improving pollutant removal capacity, and efficiently reusing metal precursor solution. The life cycle environmental impact of Ti-WBAX was lower than Fe-WBAX as well as a mixed bed of WBAX and granular ferric hydroxide for all studied categories. A separate life cycle assessment found the total number of cancer and non-cancer cases prevented by drinking safer water outweighed those created by manufacture and use of water treatment materials and energy. However, treatment relocated who bore the health risk, concentrated it in a sub-population, and changed the primary manifestation from cancer to non-cancer disease. This tradeoff was partially mitigated by avoiding use of pH control chemicals. When properly synthesized, Fe-WBAX and Ti-WBAX sorbents maintained chromium removal capacity while significantly increasing arsenic removal capacity compared to the parent resin. The hybrid sorbent performance was demonstrated in packed beds using a challenging water matrix and low pollutant influent conditions. Breakthrough curves hint that the hexavalent chromium is removed by anion exchange and the arsenic is removed by metal oxide sorption. Overall, the hybrid nano-sorbent synthesis methods increased sustainability, improved sorbent characteristics, and increased simultaneous removal of chromium and arsenic for drinking water.
ContributorsGifford, James McKay (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Thesis advisor) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2016
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Description
High photoluminescence (PL) quantum yields reported from amorphous (a-Si) and crystalline (c-Si) nanoparticles have opened up lots of possibilities for use of silicon in optical applications such as light emitting diodes (LEDs), photonics and solar cells with added processing and cost benefits. However, the PL response and the mechanisms behind

High photoluminescence (PL) quantum yields reported from amorphous (a-Si) and crystalline (c-Si) nanoparticles have opened up lots of possibilities for use of silicon in optical applications such as light emitting diodes (LEDs), photonics and solar cells with added processing and cost benefits. However, the PL response and the mechanisms behind it are highly dependent on the matrix in which the nanoparticles are grown and on the growth method. While, the bottom-up approach for deposition of free standing nanoparticles seem to be perfectly suited for large area deposition for LED and solar cell applications, the dominant growth techniques (laser ablation and pyrolysis) have been shown to suffer from limitations in control over size distribution of nanoparticles and the requirement of equipment capable of withstanding high temperature. This led to the exploration of plasma based synthesis methods in this work.

Towards this effort, the development and automation of a novel tool “Anny” for synthesis of silicon nanoparticles using non-thermal plasma chamber is reported. These nanoparticles are then accelerated due to choked flow through a nozzle leading to substrate independent deposition. The nanoparticle properties are characterized against precursor gas flow rates and RF power to identify the optimum growth conditions for a stable, continuous deposition. It is found that amorphous nanoparticles offer a wide variety of chamber conditions for growth with a high throughput, stable plasma for continuous, long term operations.

The quantum confinement model for crystalline and spatial confinement models for amorphous nanoparticles in our size regime (6-8nm) are suggested for free standing nanoparticles and we report a high PL output from well passivated amorphous nanoparticles.

The PL output and its dependence on stability of surface hydrogen passivation is explored using Fourier Transform Infrared spectroscopy (FTIR). It is shown that the amorphous nanoparticles have a better and more stable passivation compared to crystalline nanoparticles grown under similar conditions. Hence, we show a-Si nanoparticles as exciting alternatives for optical applications to c-Si nanoparticles.
ContributorsGarg, Prateek (Author) / Holman, Zachary C (Thesis advisor) / Zhang, Yong H (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Nanomaterials exhibit unique properties that are substantially different from their bulk counterparts. These unique properties have gained recognition and application for various fields and products including sensors, displays, photovoltaics, and energy storage devices. Aerosol Deposition (AD) is a relatively new method for depositing nanomaterials. AD utilizes a nozzle to accelerate

Nanomaterials exhibit unique properties that are substantially different from their bulk counterparts. These unique properties have gained recognition and application for various fields and products including sensors, displays, photovoltaics, and energy storage devices. Aerosol Deposition (AD) is a relatively new method for depositing nanomaterials. AD utilizes a nozzle to accelerate the nanomaterial into a deposition chamber under near-vacuum conditions towards a substrate with which the nanomaterial collides and adheres. Traditional methods for designing nozzles at atmospheric conditions are not well suited for nozzle design for AD methods.

Computational Fluid Dynamics (CFD) software, ANSYS Fluent, is utilized to simulate two-phase flows consisting of a carrier gas (Helium) and silicon nanoparticles. The Cunningham Correction Factor is used to account for non-continuous effects at the relatively low pressures utilized in AD.

The nozzle, referred to herein as a boundary layer compensation (BLC) nozzle, comprises an area-ratio which is larger than traditionally designed nozzles to compensate for the thick boundary layer which forms within the viscosity-affected carrier gas flow. As a result, nanoparticles impact the substrate at velocities up to 300 times faster than the baseline nozzle.
ContributorsHoffman, Trent (Author) / Holman, Zachary C (Thesis advisor) / Herrmann, Marcus (Committee member) / Kozicki, Michael (Committee member) / Arizona State University (Publisher)
Created2017
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Description
With the application of reverse osmosis (RO) membranes in the wastewater treatment and seawater desalination, the limitation of flux and fouling problems of RO have gained more attention from researchers. Because of the tunable structure and physicochemical properties of nanomaterials, it is a suitable material that can be used to

With the application of reverse osmosis (RO) membranes in the wastewater treatment and seawater desalination, the limitation of flux and fouling problems of RO have gained more attention from researchers. Because of the tunable structure and physicochemical properties of nanomaterials, it is a suitable material that can be used to incorporate with RO to change the membrane performances. Silver is biocidal, which has been used in a variety of consumer products. Recent studies showed that fabricating silver nanoparticles (AgNPs) on membrane surfaces can mitigate the biofouling problem on the membrane. Studies have shown that Ag released from the membrane in the form of either Ag ions or AgNP will accelerate the antimicrobial activity of the membrane. However, the silver release from the membrane will lower the silver loading on the membrane, which will eventually shorten the antimicrobial activity lifetime of the membrane. Therefore, the silver leaching amount is a crucial parameter that needs to be determined for every type of Ag composite membrane.

This study is attempting to compare four different silver leaching test methods, to study the silver leaching potential of the silver impregnated membranes, conducting the advantages and disadvantages of the leaching methods. An In-situ reduction Ag loaded RO membrane was examined in this study. A custom waterjet test was established to create a high-velocity water flow to test the silver leaching from the nanocomposite membrane in a relative extreme environment. The batch leaching test was examined as the most common leaching test method for the silver composite membrane. The cross-flow filtration and dead-end test were also examined to compare the silver leaching amounts.

The silver coated membrane used in this experiment has an initial silver loading of 2.0± 0.51 ug/cm2. The mass balance was conducted for all of the leaching tests. For the batch test, water jet test, and dead-end filtration, the mass balances are all within 100±25%, which is acceptable in this experiment because of the variance of the initial silver loading on the membranes. A bad silver mass balance was observed at cross-flow filtration. Both of AgNP and Ag ions leached in the solution was examined in this experiment. The concentration of total silver leaching into solutions from the four leaching tests are all below the Secondary Drinking Water Standard for silver which is 100 ppb. The cross-flow test is the most aggressive leaching method, which has more than 80% of silver leached from the membrane after 50 hours of the test. The water jet (54 ± 6.9% of silver remaining) can cause higher silver leaching than batch test (85 ± 1.2% of silver remaining) in one-hour, and it can also cause both AgNP and Ag ions leaching from the membrane, which is closer to the leaching condition in the cross-flow test.
ContributorsHan, Bingru (Author) / Westerhoff, Paul (Thesis advisor) / Perreault, Francois (Committee member) / Sinha, Shahnawaz (Committee member) / Arizona State University (Publisher)
Created2017