Browsing by Author "Kennedy, Alan James"

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    Additive Manufacturing Filled Polymer Composites for Environmental Contaminants: Material Extrusion Processing, Structure and Performance
    Kennedy, Alan James (Virginia Tech, 2023-12-18)
    Research interest in Additive Manufacturing (AM) as an enabling technology for customizable parts is rapidly expanding. While much AM research focus is on high performance feedstocks and process optimization to obtain parts with improved mechanical properties, interest in the environmental applications of AM has recently increased. The lower cost and greater accessibility AM is leading to novel environmental research solutions in wastewater treatment and toxicity reduction by capitalizing on the increased affordability and accessibility of 3D printing (3DP) technologies for customizable, high surface area structures. The novelty and focus of this dissertation is exploration of Material Extrusion (MatEx) based Fused Filament Fabrication (FFF) of filled polymer composites as a disruptive technology enabler for deployable and retrievable structures in environmental media for adsorption, destruction and toxicity reduction of harmful chemicals. This dissertation addresses research questions that generally answer, "why AM for environmental applications?". The inherent layer-by-layer design provides larger surface area structures for interaction with contaminated media. Polylactic acid (PLA) was selected due to its green sources and biocompatibility relative to synthetic polymers and its wide processing window allowing shear thinning and "printability" despite the elevated viscosity and modulus of highly filled composites. The filler selected for contaminant adsorption was microporous zeolite, which has affinity for ammonia, radionuclides and Per- and Polyfluorinated Substances (PFAS). The filler selected for contaminant destruction was photocatalytic TiO2 nanoparticles which can degrade organic chemicals, harmful algal bloom toxins and PFAS. A preliminary research hurdle was overcome by demonstrating that immobilization of zeolite and TiO2 in a PLA binder matrix did not prevent adsorption or free radical release, respectively. The first major research objective involved investigation of high surface area printed PLA-zeolite geometries with different zeolite loadings and found that while ammonia was reduced, there were diminishing returns with increased loading in terms of mass standardized adsorptive performance due to insufficiently exposed zeolite. The research solution leveraged AM print process parameters to increase the macroporosity of the printed composite structure to create voids and channels allowing water infiltration and chemical adsorption to zeolite. Faster printing of larger roadways generated macrostructural voids that were maintained by extrusion at lower temperature for rapid solidification. The second research objective involved compounding different loadings and dispersion states of TiO2 in PLA to demonstrate immobilization of TiO2 closer to UV-light penetration water improves photocatalysis. Higher 32% w/w TiO2 loadings were heavily agglomerated and more difficult to print process due to high viscosity, rapid liquid-solid transition (G'>G") and particle network recovery during printer retractions, leading to nozzle clogging. Lower 20% w/w loading was more conducive to larger production printing due to lower viscosity, longer viscosity recovery times for retractions and thus generally a wider processing window. While altering twin screw processing parameters reduced TiO2 agglomerates in filaments, leading to increases in crystallinity (due to seeding effects and chain scission) and lower viscosity recovery, photocatalytic performance was not significantly improved. Evidence presented showed that larger particle agglomerates were more toward the inside of printed surfaces and thus less available to UV-light irradiation. This location of larger particles is supported by previous theoretical and empirical investigations showing larger particles migrate at a faster velocity away from the outer walls of confined extrudates within non-Newtonian flow fields due to normal forces, leaving more smaller particles toward outer surfaces. This research provided novel contributions to the environmental and AM research communities and pioneered a convergence of these fields into an interdisciplinary community of practice focused on better characterization and processing in environmental applications to improve structure-environmental property relationships. Future research should build on these findings to enhance performance through multi-functional materials that adsorb and destroy contaminants. The reactive surface area should be further increased through by high surface area designs and print parameter optimized porous structures providing a continuum of meso- to microporosity as confirmed by chemical flux and mass transfer studies for additional AM technologies (e.g., Direct Ink Write).
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    An Ecotoxicological Assessment of a Treated Coal-mining Effluent in the Leading Creek Watershed, Meigs County, Ohio
    Kennedy, Alan James (Virginia Tech, 2002-12-13)
    The majority of research studying the ecological impacts of the coal mining industry on freshwater systems has focused on abandoned-mined land, and the associated acid drainage and metals toxicity. Treated discharges from active mining and preparation facilities, however, can also impair lotic ecosystems through total dissolved solids (TDS) toxicity, caused primarily by the reagents used for pH modifications and the oxidation of reduced sulfur. Such impairment was best detected through application of (1) benthic macroinvertebrate surveys using metrics of biotic impairment such as relative Ephemeroptera abundance and Ephemeroptera-Plecoptera-Trichoptera (EPT) minus the tolerant caddisfly family Hydropsychidae (2) in situ growth of Corbicula fluminea during 96-d exposure and (3) laboratory testing using Ceriodaphnia dubia. Traditional metrics such as total taxa richness, EPT, diversity and biotic indices were not sensitive to elevated TDS levels. Further study using strength of evidence, regression analysis and manipulation of laboratory formulated media, indicated that the mine effluent was the primary causal agent of the observed biotic impairment, and its toxicity could be attributed to sodium/sulfate-dominated TDS, which is significantly ameliorated by water hardness. Finally, although testing with lentic cladocerans, such as Ceriodaphnia, is consistent, cost-effective and sensitive to TDS related toxicity, the ecological relevance and protective capability of such testing is questionable when assessing contaminant effects on sensitive macroinvertebrates indigenous to lotic systems. A more ecologically relevant laboratory bioassay using the mayfly, Isonychia bicolor, in simulated lotic microcosms provided more sensitive endpoints than Ceriodaphnia and Pimephales promelas. Although the heartiness of Isonychia in laboratory conditions is poorly understood relative to standardized test organisms, these results, along with potential toxic impacts from numerous sodium/sulfate-dominated wastewaters discharging into freshwater systems, may have important implications to future national pollution discharge and elimination system (NPDES) permit testing. Currently, however, strong recommendations can only be made using Ceriodaphnia endpoints. Potential acute toxicity to aquatic organisms in high hardness solution (~790 mg/L as CaCO₃) is possible where sodium/sulfate-dominated TDS levels exceed ~7000 uS/cm (5167 mg/L), with potential chronic toxicity occurring at ~3200 uS/cm (2342 mg/L). These endpoints were significantly reduced in solutions of lower hardness (88 mg/L as CaCO₃), with acute and chronic toxicity occurring at 5100 uS/cm (3754 mg/L) and ~2100 uS/cm (1523 mg/L), respectively. Point source discharges causing instream TDS concentrations to exceed these levels risk impairment to aquatic life.