abstract: Engineered nanomaterials (ENMs) are added to numerous consumer products to enhance their effectiveness, whether it be for environmental remediation, mechanical properties, or as dietary supplements. Uses of ENMs include adding to enhance products, carbon for strength or dielectric properties, silver for antimicrobial properties, zinc oxide for UV sun-blocking properties, titanium dioxide for photocatalysis, or silica for desiccant properties. However, concerns arise from ENM functional properties that can impact the environment and a lack of regulation regarding ENMs leads to potential public exposure to ENMs and results in ill-informed public or manufacturer perceptions of ENMs. My dissertation evaluates the environmental, human health, and societal impacts of using ENMs, with a focus on ionic silver and nanosilver, in consumer and industrial products. Reproducible experiments served as functional assays to assess ENM distributions among various environmental matrices. Functional assay results were visualized using radar plots and aid in a framework to estimate likely ENM disposition in the environment. To assess beneficial uses of ENMs, bromide ion removal from drinking waters to limit disinfection by-product formation was studied. Silver-enabled graphene oxide materials were capable of removing bromide from water, and exhibited less competition from background solutes (e.g. natural organic matter) when compared against solely ionic silver addition to water for bromide removal. To assess complex interactions of ENMs with the microbiome, batch experiments were performed using fecal samples spiked with ionic silver or commercial dietary silver nanoparticles. Dietary nanosilver and ionic silver exposures to the fecal microbiome for 24 hours reduce short chain fatty acid (SCFA) production and changes the relative abundance of the microbiota. To understand the social perceptions of ENMS, statistically rigorous surveys were conducted to assess related perceptions related to the use of ENMs in drinking water treatment devices the general public and, separately, industrial manufacturers. These stakeholders are influenced by costs and efficiency of the technologies, consumer concerns of the safety of technologies, and environmental health and safety of the technologies. This dissertation represents novel research that took an interdisciplinary approach, spanning from wet-lab engineering bench scale testing to social science survey assessments to better understand the environmental, human health, and societal impacts of using ENMs such as nanosilver and ionic silver in industrial processes and consumer products. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

Magnetic components such as inductors and transformers are generally the largest circuit elements in switch-mode power systems for controlling and processing electrical energy. To meet the demands of higher conversion efficiency and power density, there is a growing need to simplify the process of fabricating magnetics for better integration with other power electronics components. The potential benefits of additive manufacturing (AM), or more commonly known as three-dimensional (3D) printing technologies, include shorter lead times, mass customization, reduced parts count, more complex shapes, less material waste, and lower life-cycle energy usage—all of which are needed for manufacturing power magnetics. In this work, an AM technology for fabricating and integrating magnetic components, including the design of manufacturing methodology and the development of the feedstock material, was investigated. A process flow chart of additive manufacturing functional multi-material parts was developed and applied for the fabrication of magnetic components. One of the barriers preventing the application of 3D-printing in power magnetics manufacturing is the lack of compatible and efficient magnetic materials for the printer's feedstock. In this work, several magnetic-filled-benzocyclobutene (BCB) pastes curable below 250 degree C were formulated for a commercial multi-material extrusion-based 3D-printer to form the core part. Two magnetic fillers were used: round-shaped particles of permalloy, and flake-shaped particles of Metglas 2750M. To guide the formulation, 3D finite-element models of the composite, consisting of periodic unit cells of magnetic particles and flakes in the polymer-matrix, was constructed. Ansoft Maxwell was used to simulate magnetic properties of the composite. Based on the simulation results, the pastes consisted of 10 wt% of BCB and 90 wt% of magnetic fillers—the latter containing varying amounts of Metglas from 0 to 12.5 wt%. All the pastes displayed shear thinning behavior and were shown to be compatible with the AM platform. However, the viscoelastic behavior of the pastes did not exhibit solid-like behavior, instead requiring layer-by-layer drying to form a thick structure during printing. The key properties of the cured magnetic pastes were characterized. For example, bulk DC electrical resistivity approached 107 Ω⋅cm, and the relative permeability increased with Metglas addition, reaching a value of 26 at 12.5 wt%. However, the core loss data at 1 MHz and 5 MHz showed that the addition of Metglas flakes also increased core loss density. To demonstrate the feasibility of fabricating magnetic components via 3D-printing, several inductors of differing structural complexities (planar, toroid, and constant-flux inductors) were designed. An AM process for fabricating magnetic components by using as-prepared magnetic paste and a commercial nanosilver paste was developed and optimized. The properties of as-fabricated magnetic components, including inductance and DC winding resistance, were characterized to prove the feasibility of fabricating magnetic components via 3D-printing. The microstructures of the 3D-printed magnetic components were characterized by Scanning-electron-microscope (SEM). Results indicate that both the winding and core magnetic properties could be improved by adjusting the formulation and flow characteristics of the feed paste, by fine-tuning printer parameters (e.g., motor speed, extrusion rate, and nozzle size), and by updating the curing profile in the post-process. The main contributions of this study are listed below: 1. Developed a process flow chart for additive manufacturing of functional multi-material components. This methodology can be used as a general reference in any other research area targeting the utilization of AM technology. 2. Designed, formulated and characterized low-temperature curable magnetic pastes. The pastes are physically compatible with the additive manufacturing platform and have applications in the area of power electronics integration. 3. Provided an enhanced understanding of the core-loss mechanisms of soft magnetic materials and soft magnetic composites at high frequency applications. / Ph. D.

As the first level interconnection in electronic packages, chip attachment plays a key role in the total packaging process. Sintered nanosilver paste may be used as a lead-free alternative to solder for die-attachment at sintering temperature below 300 °C without applying any pressure. Typically, the substrate, such as direct bond copper (DBC) substrates, has surface metallization such as silver or gold to protect the copper surface from oxidation during the sintering process. This study focused on developing techniques for die-attachment on pure copper surface by low-temperature sintering of nanosilver paste. One of the difficulties lies in the need for oxygen to burn off the organics in the paste during sintering. However, the copper surface would oxidize, preventing the formation of a strong bond between sintered silver and copper substrate. Two approaches were investigated to develop a feasible technique for attachment. The first approach was to reduce air pressure as a means of varying the oxygen partial pressure and the second approach was to introduce inert gas to control the sintering atmosphere. For the first method, die-shear tests showed that increasing the oxygen partial pressure (PO₂ from 0.04 atm to 0.14 atm caused the bonding strength to increase but eventually decline at higher partial pressure. Scanning electron microscopy (SEM) imaging and energy dispersive spectroscopy (EDS) analysis showed that there was insufficient oxygen for complete organics burnout at low PO₂ condition, while the copper surface was heavily oxidized at high PO₂ levels, thus preventing strong bonding. A maximum bonding strength of about average 8 MPa was attained at about PO₂ = 0.08 atm. With the second method, the die-shear strength showed a significant increase to about 24 MPa by adjusting the oxygen exposure temperature and time during sintering. The processing conditions necessary for bonding large-area chips (6 mm à 6 mm) directly on pure copper surface by sintering nanosilver paste was also investigated. A double-print process with an applied sintering pressure of less than 5 MPa was developed. Die-shear test of the attached chips showed an average bonding strength of over 40 MPa at applied pressure of 3 MPa and over 77 MPa under 12 MPa sintering pressure. SEM imaging of the failure surface showed a much denser microstructure of sintered silver layer when pressure was applied. X-ray imaging showed a bond layer almost free of voids. Because the samples were sintered in air, the DBC surface showed some oxidation. Wirebondability test of the oxidized surface was performed with 250 μm-diameter aluminum wires wedge-bonded at different locations on the oxidized surface. Pull test results of the bonded wires showed a minimum pull-strength of 400 gram-force, exceeding the minimum of 100-gf required by the IPC-TM-650 test standard. / Master of Science

Bacterial resistance to antibiotics has become a worldwide health problem, resulting in untreatable infections and escalating healthcare costs. Wastewater treatment plants are a critical point of control between anthropogenic sources of pathogens, antibiotic resistant bacteria (ARBs), antibiotic resistance genes (ARGs), and the environment through discharge of treated effluent and land application of biosolids. Recent studies observing an apparent resuscitation of pathogens and pathogen indicators and the widening realization of the importance of addressing environmental reservoirs of ARGs all lead toward the need for improved understanding of ARG fate and pathogen inactivation kinetics and mechanisms in sludge stabilization technologies. This research has investigated the fate of two pathogens, methicillin-resistant Staphylococcus aureus (MRSA) and Escherichia coli, and various ARGs under pasteurization, anaerobic digestion, biosolids storage, and land application conditions. Pathogen die-off occurs at a rate specific to each pathogen and matrix in ambient and mesophilic temperature environments. Viable but nonculturable (VBNC) states are initiated by thermal treatments, such as thermophilic digestion and possibly pasteurization, and allow the persistence of pathogen cells and any ARGs contained therein through treatment and into the receiving environment where resuscitation or transformation could occur. Raw sludge ARG content does affect digester effluent quality, although the predominant mechanisms of ARG persistence may be different in mesophilic versus thermophilic digestion. In both thermophilic and mesophilic digestion, a correlation was observed between raw sludge and digester ARGs associated with Class 1 integrons, possibly as a result of horizontal gene transfer. ARB survival was shown to contribute to ARG content in mesophilic digestion, but not thermophilic digestion. Thermophilic digestion may achieve a higher ARG reduction because of reduced microbial diversity compared to mesophilic digestion. However, it is evident that horizontal gene transfer still does occur, particularly with highly mobile integrons, so that complete reduction of all ARGs would not be possible with thermophilic digestion alone. Surprisingly, the experiments that introduced various concentrations of antibiotic sulfamethoxazole and antimicrobial nanosilver did not induce enhanced rates of horizontal gene transfer. Finally, ARG concentrations in biosolids increased during cold temperature storage suggesting that there is a stress induction of horizontal gene transfer of integron-associated ARGs. / Ph. D.

No description available.

No description available.

In freshwater, there is more opportunity for silver (Ag) to interact with organic ligands than in seawater. Triclosan is an antibiotic agent which resembles thyroid hormone T3 and is finding its way into aquatic systems. Preliminary toxicology studies for the frogSCOPE program suggest that triclosan and nanosilver (nanoAg), also used as an antibiotic agent, may be chemically interacting, as they seem to synergistically increase the endocrine-disrupting abilities already observed independently in each chemical. Ag speciation methods can be used to determine if triclosan or thyroid hormone T3 are interacting with Ag ion (Ag+), which gets released over time by nanoAg. To fully utilize Ag speciation methods, however, total Ag in the sample must also be independently analyzed. Here we investigated a new total Ag analysis using cadmium sulfide quantum dots (CdS QDs) as fluorescence probes in solution. This method promises results in a fraction of the time of the established competitive ligand equilibration-solvent extraction (CLE-SE) technique utilizing PDC- and DDC- to bind Ag and bring it out of solution. Following this investigation were a series of experiments using CLE-SE for total Ag and Ag speciation in well water used to house bullfrog tadpoles in frogSCOPE Ag exposure studies. CLE-SE for Ag speciation was also applied to well water samples containing the two levels of nanoAg or Ag+ used in frogSCOPE Ag exposures, and used in ligand competition experiments to examine the potential of triclosan or T3 to act as strong Ag-binding ligands, as compared to glutathione and EDTA, two known Ag-binding ligands. The results of the latter experiments could be used to determine if either of these could be forming complexes with Ag which increase or decrease their delivery to amphibian cells. The fluorometric method using CdS QDs showed no ideal analytical response to nanomolar Ag+, even when commercial QDs were modified and used, so it could not be applied to our samples. Using CLE-SE for total Ag, the well water used as a base for toxicity studies in frogSCOPE contained Ag below the method detection limit of 5 pM. Using the speciation variation of the CLE-SE method, no evidence of naturally-occurring ligands which could produce extractable (hydrophobic) or non-extractable (hydrophilic) Ag complexes was found in this well water. EDTA and glutathione responded as model Ag-binding ligands to form non-extractable hydrophilic Ag complexes in fresh water. T3 behaved like these model ligands, while triclosan enhanced the extractability of Ag in the presence of certain concentrations of the added ligand, DDC-. In another set of experiments, coordination of Ag by triclosan or T3 was not detectable within that analytical window. These results suggest that ionic Ag released over time by nanoAg may be binding T3 and preventing it from reaching its receptor, but confirming the interaction of triclosan and Ag+ will require additional experiments using different analytical windows.