No description available.

No description available.

The focus of this research was to improve the sustainability of various processes by employing tunable solvents, switchable solvents, and catalysis. In Chapter 2, we report applications of tunable solvents to metal and enzyme catalyzed reactions of hydrophobic substrates. Tunable solvents are defined as solvent that change properties rapidly but continuously upon the application of an external physical stimulus and we utilize these solvents to couple homogeneous reactions with heterogeneous separations. We developed organic-aqueous tunable solvents that utilize propane for efficient phase separation at moderate pressures around 1 MPa; for example the water contents in the propane-expanded THF is 3 wt% at 0.8MPa at 30°C. Also, we extended the use of CO2-organic-aqueous tunable solvents to a pharmaceutically-relevant reaction--the hydroformylation of p-methylstyrene. The homogeneous reactions provide fast rates with excellent yields. At 60°C, the reaction reaches completion after 180 minutes with 95% branched aldehyde yield. The CO2-induced heterogeneous separation of the product from the catalyst provides an efficient and simple way to remove 99% of the product, to retain 99.9% of catalyst, and to recycle the Rh-TPPMS catalyst for five consecutive reactions. In chapter 3, we investigated the use of reversible ionic liquids (RevILs) for synthesis of nanoparticles. RevILs are formed by the reversible reaction of compounds with basic nitrogen functionalities (molecular liquid) with CO2 at ambient pressure to form a liquid salt (ionic liquid). We demonstrated that RevILs form microemulsions that can be switched-on by bubbling CO2 and switched-off by heating. These microemulsions solubilize ionic compounds such as chloroauric acid. We utilized these microemulsions as a template for controlled synthesis of gold nanoparticles. With 2-component RevILs, [TMBGH]+[O2COCH3]-/N-propyl-octylsulfonamide/hexane were used to form particles in the size range of 6-20 nm with an average particles size of 11.4±3.3. With 1-component RevILs, (3-aminopropyl)-tripropylsilane was used to prepare semi-spherical gold particles with an average size of about 20nm. The 1-component RevILs systems provide a simpler method to form microemulsions when compared to the 2-componenet RevILs systems since they eliminate the need for alcohols and surfactants. In chapter 4, we developed a catalyst that efficiently decomposes hydrazine to selectively produce ammonia. This enables the use of the chemical propulsion hydrazine for electric propulsion as well. We prepared nickel, copper, cobalt, ruthenium, rhodium, and iridium nanoparticles that were supported on silica and we tested these silica-supported metals for the decomposition of hydrazine. To study the catalytic activity, we designed and constructed a continuous flow reactor. The results show that nano-nickel supported on silica is the most active and selective catalyst with 100% conversion of hydrazine and 94±3% yield of ammonia.

Current hydro-turbines aim to capture the immense energy available in tidal movements, however commonly applied technologies rely on principles more applicable in hydroelectric dams. Tidal stream currents, such as in Coastal Georgia, are not strong enough to make such turbines both efficient and economically viable. This research proposes a novel low-energy vortex shedding vertical axis turbine (VOSTURB) to combat the inefficiencies and challenges of hydro-turbines in low velocity free tidal streams. Some of the energy in tidal streams is extracted naturally from vortex shedding; as water streams past a bluff body, such as pier, low pressure vortices form alternatively on each side, inducing a rhythm of pressure differentials on the bluff body and anything in its wake. VOSTURB aims to capture this energy of the vortices by installing a hydrofoil subsequent to the bluff body. This foil, free to oscillate, translates the vortex energy into oscillatory motion, which can be converted into a form of potential energy. The presented research will act as a 'proof of concept.' It aims to assess such foil motion, or the ability of VOSTURB to capture vortex energy, and begin to assess the amount of tidal energy that can be theoretically harnessed. In this study a small scale model of VOSTURB, a cylindrical bluff body with a hammer shaped hydrofoil, was tested in a hydraulic flume for various mean flow speeds. Tangential accelerations of the foil's center of gravity were obtained through the use of an accelerometer. The acceleration data was analyzed utilizing Fourier analysis to determine the fundamental frequency of the wing oscillations. The available power to be harnessed from the oscillatory motion was then estimated utilizing this fundamental frequency. Ultimately it was found that the frequency of the VOSTURB foil oscillations corresponded highly with the theoretical frequency of vortex shedding for all moderate to high flow speeds. Low speeds were found to produce inconsistent and intermittent small oscillations. This signifies at moderate to high flow speeds, VOSTURB was able to transform some vortical energy into kinetic. The maximum average power obtained 8.4 mW corresponded to the highest flow velocity 0.27 m/s. Scaled to Rose Dhu prototype conditions this represented 50 W at a flow velocity of 0.95m/s, the maximum available at Rose Dhu. Although it was ascertained that VOSTURB could consistently capture some of the vortical energy; the percentage of which could not be calculated with certainty. Thus, the average kinetic power assessments of the foil were compared to the available power of the mean flow for each flow speed calculated by two methods: (1) over the foil's swept area; (2) the area of fluid displaced by the bluff body immediately in front of the foil. The maximum efficiency of the foil, found for the fastest flow speed was at 18% and 45% respectively. It was found that both average foil power, available flow power, and efficiency all decreased with a decrease in flow velocity. This study can serve as only a preliminary study for the effectiveness of VOSTURB as a hydro-turbine for tidal power. In the experiments, the foil was allowed to oscillate freely with little resistance. Future testing of VOSTURB needs to observe whether the vortex energy can overcome the resistive torque introduced by a generator to induce oscillatory motion as well as further optimize the foil design. While the testing in this project assesses the kinetic energy or power of the vortex shedding, this future testing will provide insight into the actual work that can actually be converted into potential energy or power. Complementing this research, both a Harmonic Analysis of Least Squares (HAMELS) and a Complex Empirical Orthogonal Function (CEOF) Analysis was conducted on available surface height and current velocity data separately from an available Regional Ocean Modeling System (ROMS) model of Coastal Georgia. Such analysis were conducted to observe spatial and temporal tidal patterns advantageous to a possible prototype installation of a tidal turbine such as VOSTURB. The more conventional HAMELS analysis, which isolates components of a signal with a certain frequency, identified temporal and spatial patterns attributed to tidal constituents. CEOF analysis, where major patterns of variance are identified not according to prescribed frequencies, was employed to identify any patterns possible not attributed to the tidal constituents. This study was also in part to observe whether the CEOF analysis could identify any patterns of tidal propagation that could not be resolved by the HAMELS analysis. The CEOF and HAMELS analysis of the surface height output produced very similar results: major modes of surface height variation due to the diurnal and semidiurnal tidal constituents propagating up the estuary. The CEOF results did not produce any additional information that could not be found through the HAMELS analysis of the constituents and presented such results in an arguably more convoluted manner. In addition, the surface height analysis provided no direct insight into areas more advantageous to tidal power. The CEOF analysis of the vector current velocity data however did provide some insight. The CEOF of the current data was able to isolate patterns of variance corresponding to the tidal constituents. However, the CEOF was also able to identify local 'hotspots' of high current magnitudes not resolved by HAMELS. These local areas of high current magnitudes, most likely due to changes in hydrodynamic conditions such as channel constrictions, are advantageous for tidal power applications. These general areas could serve as a starting point for the location selection process for a possible prototype installation of VOSTURB if the area was refined more. Ultimately for a prototype installation of VOSTURB, further experimentation and analysis is required for both the turbine design and placement, such as a power conversion methodology for the turbine and a more spatially resolute set of data to perform a CEOF analysis on. With these tasks completed, the prototype installation will be part of a larger effort between the Georgia Institute of Technology and the Girl Scouts of America to create completely sustainable "Eco-Village" on Rose Dhu Island, GA. With an extensive community outreach planned to educate the public, Rose Dhu, along with championing hydrokinetic energy, will serve as a paradigm for sustainable design and energy.

Due to increasing interest in sustainable development, today s engineer is often tasked with designing systems that are environmentally benign over their entire life cycles. Unfortunately, environmental assessments commonly suffer from significant uncertainty due to lack of information, particularly for time-distant life cycle aspects. Under severe uncertainty, traditional uncertainty formalisms require more information than is available. However, a recently devised formalism, information-gap decision theory (IGDT), requires no more information than a nominal estimate; error bounds on that estimate are unknown. The IGDT decision strategy, accordingly, favors the design that is robust to the most estimation error while still guaranteeing no worse than some good enough critical level of performance. In some cases, one can use IGDT to identify a preferable design option without needing more information or more complex uncertainty analysis. In this dissertation, IGDT is investigated and shown to enhance decision support for environmentally benign design and manufacturing (EBDM) problems. First, the applicability of the theory to EBDM problems is characterized. Conditions that warrant an info-gap analysis are reviewed, the insight it can reveal about design robustness is demonstrated, and practical limitations to its use are revealed. Second, a new mathematical technique is presented that expands capabilities for analyzing robustness to multiple info-gap uncertainties simultaneously. The technique elicits scaling factors more rigorously than before and allows one to imprecisely express their beliefs about info-gap scaling. Two examples problems affected by info-gaps are investigated: oil filter selection and remanufacturing process selection. It is shown that limited information about uncertainty can, in some cases, indeed enable one to identify a most preferable design without requiring more information.

Laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2), a multi-copper-containing oxidoreductase enzyme, is able to catalyze the oxidation of various low-molecular weight compounds, specifically, phenols and anilines. Due to their high stability, selectivity for phenolic substructures, and mild reaction conditions, laccases are attractive for fine chemical synthesis. In this study, new green domino syntheses were developed by conducting the reaction in an aqueous medium, an environmentally-friendly solvent, and using laccase as a biocatalyst. The first study presents a work on the synthesis of naphthoquinones in the aqueous medium. Herein, laccase was used to oxidize o- and p-benzenediols to generate o- and p-benzoquinones in situ. These quinones then underwent Diels-Alder and oxidation reactions to finally generate napthoquinone products. This reaction system can yield naphthoquinones in up to 80% yield. The next part of this thesis reports the cascade synthesis of benzofuran derivatives from the reaction of catechols and 1,3-dicarbonyl compounds via oxidation-Michael addition in the presence of laccase and Sc(OTf)3/SDS in an aqueous medium. Depending on the substrates, one-pot yields of benzofurans averaged 50-79%. From an environmental concern, this system still produced a hazardous waste from the transition metal catalyst. Therefore, the development of alternative methodologies to replace the lanthanide metal catalyst in this synthesis is a high priority to enhance the overall green chemistry aspect. As a consequence, lipase was used as a catalyst to replace Sc(OTf)3 for the synthesis of benzofuran derivatives. In addition, this catalytic system was also used to catalyze the reaction of anilines and catechol. In the last part of this thesis, laccase was applied to the modification of high-lignin softwood kraft pulp. This modification demonstrates the potential of laccase-facilitated grafting of amino acids to high lignin content pulps to improve their physical properties in paper products which resulted from the increase of carboxylic acid group of the fibers. In this study, a variety of amino acids were examined. Laccase-histidine treatment provided the best yield of acid groups on pulp fiber and was used in the preparation of handsheets for physical strength testing. Laccase-histidine-treated pulp showed an increase in the strength properties of the resulting paper.

No description available.

<p>    </p> <p>Electronic waste is one of the fastest growing waste streams, spurred by their rising market and demand. However, these devices contain an array of metals that is recyclable for economic and environmental benefit through secondary manufacturing. As the turnaround rate for newer models quickens, consumers are motivated to purchase novel devices, leaving their current ones behind. Focusing on how United States (U.S.) households manage their electronics, a top-down approach stock and flow STELLA model was created to model the lifecycle of eight common electronics. Input data for the model came from a public online survey directed to U.S. household owning adults. From the model, a metallic stock and flow analysis was conducted to quantify the trends, environmental footprint, and economic value of stored devices in U.S. households and how it compares to devices being used, disposed, and recycled. The number of stored devices in the U.S. was found to be increasing annually with a stored amount of over 757 million stored individual electronic devices, nearly half of which originate from cell phones, carrying an economic value of 32.6 billion US dollars (USD) and carbon emissions of 7.6 billion kilograms (kg) from their metallic components alone for the year 2020. Most of the pollution and economic value stems from precious metals (PMs) and in a circular economy, these stored metals can have a significant impact to the environment and economy through recycled. Also, with advancing capabilities of smartphones, the metallic composition for device components of Samsung galaxy smartphones was quantified to assess their evolving metallic content. With the growing market of electronic devices, knowing the value and importance of devices currently in U.S. households is critical. This underlies the influence of sustainable design through a circular economy to push initiatives to manufacture recyclable friendly devices, expand the metal recycling industry, and motivate citizens to properly handle their stored devices. </p>

<p>To accurately estimate the potential recovery of metals from electronic devices, various tools such as mass flow analysis, dynamic models, and forecasting models have been employed. However, the reliability of the model-generated outputs hinges on the accuracy of the input data. To ensure accurate data collection, it is imperative to examine and compare different methodologies. Although surveys have conventionally been used in information and telecommunications technologies to gather consumer information, their validity is seldom contrasted with alternative methods due to the lack thereof. In response, a new mixed methodology has been developed to obtain primary consumer data through tangible information, offering new avenues for data acquisition. The methodology involves quantitative and qualitative approaches taking direct physical measurements (dimensions, weight, and quantity) of devices and including a ten question semi-structured interview to discussed consumer devices use, stock and transfer patterns, composition changes of the electronic devices, and disposal behavior. As a result, it was found new methodology measured 79% of the devices directly at laboratories and 21% of the remaining devices were self-reported by the participant. The devices on consumer stage frequently have the same type and number of components as fabric and a positive difference of about 17.99 g compared with the mass reported by fabricants or literature. The sequential steps undertaken by participants in the new methodology to acquire consumer-stage data offer distinct advantages over surveys, particularly in capturing a more comprehensive inventory of devices in storage.</p><p>Additional results indicate that the proposed methodology can provide valuable insights into the stock of electronic devices. Nevertheless, further research is required to understand the implications of surveys versus direct measurements in accurately representing mass flows during the user stage. Additionally, the relevance of external power supply or charging systems on storage will be explored as part of the supplementary findings. By improving the accuracy of metal recovery estimation and exploring more effective data collection methods, we can optimize closed-loop projects and contribute to sustainable resource management.</p>

<p>  </p> <p>Plastics are the most common polymers used in various industries. However, million tons of plastics are produced and disposed every year around the world, and part of them end up entering the environment and agricultural ecosystems in the form of microplastics. Microplastics have become an environmental and health threat to aquatic species and humans because they are small and can easily reach water bodies for municipal and agricultural uses. Microplastics have been traced in food commodities and products derived from animals and even found in bottles of drinking water. As an approach to permanently remediating microplastics, current microplastic degradation techniques, however, require high energy inputs and thus are generally not cost-efficient. High-voltage atmospheric cold plasma (HVACP) is a low-cost energy-efficient technology to produce highly reactive species that can induce physicochemical changes in polymers. This study, for the first time, used HVACP as a novel remediation strategy for microplastics. HVACP was generated by dielectric barrier discharge at 50 kV using oxygen, nitrogen, or their mixture as working gas. Two types of microplastics, polypropylene (PP) and low-density polyethylene (LDPE), were treated for 30 min, and the effect of 24-h post-treatment was also studied. The properties of HVACP-treated microplastics, including weight, particle size, crystallinity, melting point, carbonyl index (CI), and surface morphology, were comprehensively analyzed. HVACP treatments were found effective in degrading both PP and LDPE microplastics. A larger extent of degradation was observed with PP microplastics treated by O/N mixture plasma, but the nitrogen plasma-treated sample showed a higher degree of oxidation according to its CI. For PE microplastics, oxygen plasma caused more degradation, but post-treatment did not promote further oxidation. The results indicated two potential mechanisms for microplastic degradation by HVACP. LDPE microplastics were degraded by oxidative reactions caused by highly reactive oxygen species, and PP microplastics followed a hydrolytic pathway of degradation as they became more hydrophilic after HVACP treatment. This study proved that HVACP is a promising method for microplastic degradation, and thus has great potential for addressing the severe challenges of microplastics that the food and agriculture sectors are currently facing.</p>