Due to their relative chemical stability and ubiquity in the environment, chlorinated organic contaminants such as polychlorinated biphenyls (PCBs) pose significant health risks and enduring remediation challenges. Engineered nanoparticles (NPs) provide a novel platform for sensing/remediation of these toxicants, in addition to the growing use of NPs in many industrial and biomedical applications, but there remains concern for their potential long-term health effects. Research highlighted herein also represents a transdisciplinary approach to address human health challenges associated with exposure to PCBs and NPs. The objectives of this dissertation research are two-fold, 1) to develop effective methods for capture/sensing and remediation of environmental toxicants, and 2) to better understand associated risks and to elucidate relevant protective mechanisms, such as lifestyle-related modulators of environmental disease. Prevalent engineered nanoparticles, including aluminum oxide and titanium dioxide, have been studied to better understand effective nanoparticle dispersion methods for in vitro nanotoxicology studies. This work has served both to effectively stabilize these nanoparticles under physiological conditions and to better understand the associated mechanisms of toxicity, which links these metal nanoparticles to endothelial oxidative stress and inflammation through phosphorylation of key cellular signaling molecules and increased DNA binding of pro-inflammatory NFκB. Surface functionalization, though, is being found to limit potential toxicity and has been utilized in subsequent research. A novel polyphenol-functionalized, NP-based system has been developed which combines the biomimetic binding capabilities of nutrient polyphenols with the separation and heating capabilities of superparamagnetic iron oxide NPs for the capture/sensing of organic contaminants in polluted water sources. Magnetic nanocomposite microparticles (MNMs) incorporating the fluorescent polyphenols quercetin and curcumin exhibit high affinity for model organic pollutants followed by rapid magnetic separation, addressing the need for sustainable pollutant remediation. Further work has been performed to both better understand health concerns associated with environmental toxicants such as PCBs and to determine effective methods for modulating their toxicity. This research has shown that PCB remediation through dechlorination is a viable technique for decreasing endothelial inflammation, although complete dechlorination to biphenyl is necessary to effectively eliminate superoxide production, NFκB activation, and induction of inflammatory markers. Additionally, the nutrient polyphenol EGCG, found in green tea, has been shown to serve as a biomedical modulator of in vivo PCB toxicity by up-regulating a battery of antioxidant enzymes transcriptionally controlled by AhR and Nrf2 proteins.

The objective of this research was to develop high performing polymer modified calcium sulfoaluminate (CSA) cement materials for use in applications requiring superior adhesion characteristics. Little information is available describing interactions of CSA cement containing minor phase tri-calcium aluminate (C3A) with commonly used admixtures. Given the scarcity of information, a basic approach for developing cementitious materials was followed. The basic approach consisted of four tasks: cement design, admixture design, polymer design and testing developed materials. The iterative, time consuming process is necessary for understanding the influence of specific constituent components on overall system behavior. Results from the cement design task suggest calcium sulfate type influences microstructural characteristics and strength development for materials based upon the experimental CSA cement. Results from the admixture design task suggest lithium carbonate and tartaric acid are effective accelerating and retarding admixtures for hydration reactions including reactants yeelimite, calcium sulfate and water. Results from the polymer design task suggest vinyl acetate / ethylene (VAE) dispersible polymer powders (DPP) are compatible with systems containing the experimental CSA cement and other commonly used admixtures. Additionally, results from the polymer design task highlight a method for specifying the ductile behavior of materials containing the experimental CSA cement as majority hydraulic binding agent. Finally, results from the testing of developed materials task suggests adhesion performance for materials containing the experimental CSA cement can be influenced by adjusting the ratio of polymer to hydraulic binding agent in material formulations. Polymer modified CSA cement mortars demonstrated bond strength resulting in substrate failure when cast over porous concrete substrates. Developed mortars demonstrated consistent bonding performance when applied to non-porous substrate materials, metal and glass. Select polymer modified mortars displayed adhesion bond performance such that the glass substrate materials fractured during pull off testing.

Advances in the biomedical field require functional materials and processes that can lead to devices that are biocompatible, and biodegradable while maintaining high performance and mechanical conformability. In this context, a current shift in focus is towards natural polymers as not only the structural but also functional components of such devices. This poses material-specific functionalization and fabrication related questions in the design and fabrication of such systems. Silk protein biopolymers from the silkworm show tremendous promise in this regard due to intrinsic properties: mechanical performance, optical transparency, biocompatibility, biodegradability, processability, and the ability to entrap and stabilize biomolecules. The unique ensemble of properties indicates opportunities to employ this material into numerous biomedical applications. However, specific processing, functionalization, and fabrication techniques are required to make a successful transition from the silk cocoon to silk-based devices. This research is focused on these challenges to form silk-based functional material and devices for application in areas of therapeutics, bio-optics, and bioelectronics. To make silk proteins mechanically conformable to biological tissues, the first exploration is directed towards the realization of precisely micro-patterned silk proteins in flexible formats. The optical properties of silk proteins are investigated by showing the angle-dependent iridescent behavior of micropatterned proteins, and developing soft micro-optical devices for light concentration and focusing. The optical characteristics and fabrication process reported in the work can lead to the future application of silk proteins in flexible optics and electronics. The microfabrication process of silk proteins is further extended to form shape-defined silk protein microparticles. Here, the specificity of shape and the ability to form monodisperse shapes can be used as shape encoded efficient cargo and contrast agents. Also, these particles can efficiently entrap and stabilize biomolecules for drug delivery and bioimaging applications. Next, a smart confluence of silk sericin and a synthetic functional polymer PEDOT:PSS is shown. The composite materials obtained have synergistic effects from both polymers. Silk proteins impart biodegradability and patternability, while the intrinsically conductive PEDOT:PSS imparts electrical conductivity and electrochemical activity. Conductive micro architectures on rigid as well as flexible formats are shown via a green, water-based fabrication process. The applications of the composite are successfully demonstrated by realizing biosensing and energy storage devices on rigid or flexible forms. The versatility of the approach will lead to the development of a variety of applications such as in bio-optics, bioelectronics, and in the fundamental study of cellular bio electrogenic environments. Finally, to expand the applicability of reported functional polymers and composites beyond the microscale, a method for silk nano-patterning via electron beam lithography is explored. The technique enables one-step fabrication of user defined structures at the submicron and nano-scales. By virtue of acrylate chemistry, a very low energetic beam and dosage are required to form silk nano-architectures. Also, the process can form both positive and negative features depending on the dosage. The fabrication platform can also form nano scale patterns of the conductive composite. The conductive measurements confirm the formation of conductive nanowires and the ability of silk sericin to entrap PEDOT:PSS particles in nanoscale features.

Articular cartilage injuries occur frequently in the knee joint. Several methods have been implemented clinically, to treat osteochondral defects but none have been able to produce a long term, durable solution. Photopolymerizable cartilage tissue engineering approaches appear promising; however, fundamentally, forming a stable interface between the tissue engineered cartilage and native tissue, mainly subchondral bone and native cartilage, remains a major challenge. The overall objective of this research is to find a solution for the current problem of dislodgment of tissue engineered cartilage at the defect site for the treatment of degraded cartilage that has been caused due to knee injuries or because of mild to moderate level of osteoarthritis. For this, an in-vitro model was created to analyze the integration of tissue engineered cartilage with the bone, healthy and diseased cartilage over time. We investigated the utility of hydroxyapatite (HA) nanoparticles to promote controlled bone-growth across the bone-cartilage interface in an in vitro engineered tissue model system using bone marrow derived stem cells. We also investigated the application of HA nanoparticles to promote enhance integration between tissue engineered cartilage and native cartilage both in healthy and diseased states. Samples incorporated with HA demonstrated significantly higher interfacial shear strength (at the junction between engineered cartilage and engineered bone and also with diseased cartilage) compared to the constructs without HA (p < 0.05), after 28 days of culture. These findings indicate that the incorporation of HA nanoparticles permits more stable anchorage of the injectable hydrogel-based engineered cartilage construct via augmented integration between bone and cartilage.

Three-dimensional graphene foam (3D GrF) is an interconnected, porous structure of graphene sheets with excellent mechanical, electrical and thermal properties, making it a candidate reinforcement for polymer matrices. GrF’s 3D structure eliminates nanoparticle agglomeration and provides seamless pathways for electron travel. The objective of this work is to fabricate low density GrF reinforced epoxy composites with superior mechanical and electrical properties and study the underlying deformation mechanisms. Dip coating and mold casting fabrication methods are employed in order to tailor the microstructure and properties. The composite’s microstructure revealed good interfacial interaction. By adding mere 0.63 wt.% GrF, flexural strength was improved by 56%. The addition of 2 wt.% GrF showed a surge in glass transition temperature (56oC), improvement in damping behavior (150%), and electrical conductivity 11 orders of magnitude higher than pure epoxy. Dip coated and mold casted composites showed a gauge factor of ~2.4 indicating electromechanically robust composite materials.

Traditional Lithium-Ion Batteries (LIBs) are a reliable and cost-efficient choice for energy storage. LIBs offer high energy density and low self-discharge. Recent developments in electric-based technologies push for replacing historically used Lead-Acid batteries with LIBs. However, LIBs do not yet meet the demands of modern technology. Silicon and graphene oxide (GO) have been identified as promising replacements to improve anode materials. Graphene oxide has a unique sheet-like structure that provides a mechanically stable, light weight material for LIB anodes. Due to its structure, reduced graphene oxide (rGO) is efficiently conductive and resistive to environmental changes. On the other hand, silicon-based anode materials offer the highest theoretical energy density and a high Li-ion loading capacity of various elements [20]. Silicon-based anodes that have previously been studied demonstrated extreme volumetric expansion over long cycles due to lithiation. Polysiloxane may be an interesting alternative as it is a Si-based material that can retain the high Li-ion loading capacity of Si while lacking the unattractive volumetric expansions of Si. Polymer derived ceramic-decorated graphene oxide anodes have been suggested to increase loading capacity, thermal resistance, power density, and mechanical stability of LIBs. Coupled with mechanically stable graphene oxide, polymer derived ceramic nanoparticle decorated graphene oxide anodes are studied to establish their efficiencies under operating conditions.

<p>Optical beams that travel through a material without undergoing divergence are known as self-trapped beams. Self-trapping occurs when a beam induces a suitable index gradient in the medium that is capable of guiding the original beam. An incoherent light consists of femtosecond scale speckles, due to random phase fluctuations and were not thought to self-trap until recently. In 1997, Mitchell et al., showed that white light can self-trap, provided the medium cannot respond fast enough to form index gradients to these speckles individually. However, detailed studies have been hampered by a lack of suitable materials and strategies for enabling such a response. In 2006, our group showed that a photopolymer is suitable for incoherent self-trapping, since the index change is governed by an inherently slow rate of polymerization (of the order of milliseconds). This has enabled further studies of various phenomena with white light self-trapping.</p> <p>The studies here show (i) the first direct experimental evidence of interactions of two incoherent white light self-trapped beams, as well as fission, fusion and repulsion. Existence of dark self-trapping beams with incoherent white light was also shown, counter intuitively in a positive nonlinear medium. (iii) Lattices were formed with multiple ordered bright as well as dark self-trapping filaments using optochemical self-organization. (iv) Woodpile-like 3D lattices with bright and dark beams were also demonstrated and simulations showed theoretical band gaps. (v) Self-trapping of a co-axial beam of incoherent white light was also shown experimentally and through simulations.</p> / Doctor of Philosophy (PhD)

<p>This thesis is concerned with a theoretical and experimental investigation of a duckbill valve (DBV). Duckbill valves are non-return valves made of a composite material, which deforms to open the valve as the upstream pressure increases. The head-discharge behavior is a fluid-structure interaction (FSI) problem since the discharge depends on the valve opening that in turn depends on the pressure distribution along the valve produced by the discharge. To design a duckbill valve, a theoretical model is required, which will predict the head-discharge characteristics as a function of the fluid flow through the valve and the valve material and geometry.</p> <p>The particular valves of concern in this study, which can be very large, are made from laminated, fiber-reinforced rubber. Thus, the structural problem has strong material as well as geometric nonlinearities due to large deflections. Clearly, a fully coupled FSI analysis using three-dimensional viscous flow would be very challenging and therefore, a simplified approach was sought that treats the essential aspects of the problem in a tractable way. For this purpose, the DBV was modeled using thick shell finite elements, which included the laminates of hyperelastic rubber and orthotropic fabric reinforcement. The finite element method (FEM) was simplified by assuming that the arch side edges of the valve were clamped. The unsteady 1D flow equation was used to model the ideal fluid dynamics that enabled a full FSI analysis. Moreover, verification for the ideal flow was carried out using a transient, Reynolds-averaged Navier-Stokes finite volume solver for the viscous flow corresponding to the deformed valve predicted by the simplified FSI model.</p> <p>In order to validate the predictions of the FSI simulations, an experimental study was performed at several mass flow rates. Pressure drops along the water tunnel, valve inlet and outlet velocity profiles were measured, as well as valve opening deformations as functions of upstream pressures.</p> <p>Additionally, the valve deformations under various back pressures were analyzed when the downstream pressure exceeded the upstream pressure using the layered shell model without coupling and with simplified boundary constraints to avoid solving the contact problem for the inward-deformed duckbill valve. Flow-induced vibration (FIV) of the valve at small openings was also examined to improve our understanding of the valve stability behaviour. Some interesting valve oscillation phenomena were observed.</p> <p>Conclusions are drawn regarding the FSI model on the predictions and comparisons with the experimental results. The transient 1D flow equation has been demonstrated to adequately model the fluid dynamics of a duckbill valve, largely due to the fact that viscous effects are negligible except when the valve is operating at very small openings. Fiber reinforcement of the layered composite rubber was found to play an important role in controlling duckbill valve material stretch, especially at large openings. The model predicts oscillations at small openings but more research is required to better understand this behaviour.</p> / Doctor of Philosophy (PhD)

Fatigue testing of stretch sensors often focuses on high amplitude, low-cycle fatigue (LCF) behavior; however, when used for orthopaedic, athletic, or ergonomic assessments, stretch sensors are subjected to low amplitude, high-cycle fatigue (HCF) conditions. As an added layer of complexity, the fatigue testing of stretch sensors is not only focused on the life of the material comprising the sensor, but also on the reliability of the signal produced during the extension and relaxation of the sensor. Research into the development of a smart sock that can be used to measure the range of motion (ROM) of the ankle joint during athletic practices and competitions using stretch sensors is ongoing at Mississippi State University. The current smart sock prototype utilizes StretchSense™ StretchFABRIC capacitive dielectric elastomer sensors. These sensors are no longer manufactured, and FlexSense stretch sensors are being investigated as a potential replacement. To assess the reliability of the signal of the StretchFABRIC sensors currently used in the prototype, two sensors were subjected to 25,000 cycles of fatigue, under with simultaneous capture of the capacitance. The capacitances of the fatigued sensors were then compared to the capacitance of an unfatigued StretchFABRIC sensor during participant trials. Participants completed four static movements and six dynamic gait trials using either the fatigued or unfatigued sensor. Following completion of the initial static and dynamic movements, the movements were repeated using the opposite sensor. Comparison of the fatigued sensor to the unfatigued sensor revealed an upward drift in the capacitance of the fatigued sensor for all trials. Two FlexSense sensors were then subjected to either 450,000 or 250,000 cycles of fatigue with simultaneous capture of the signal from the sensor. To assess the signal, the peak capacitance recorded during the fatigue test was compared to the peak stretch percentage produced by the sensor. The peak displacement remained tight about the mean, while the peak stretch percentage exhibited a high level of scatter. From a materials standpoint, the sensors conformed to the Rabinowitz-Beardmore model of polymer fatigue where an initial monotonic overload of the material is followed by a transition to cyclic stability of the material.

Claims of customization and control by socio-technical industries are altering the role of consumer and producer. These narratives are often misleading attempts to engage consumers with new forms of technology. By addressing capitalist intent, material, and the reproduction limits of 3-D printed objects’, I observe the aspirational promise of becoming a producer of my own belongings through new networks of production. I am interested in gaining a better understanding of the data consumed that perpetuates hyper-consumptive tendencies for new technological apparatuses. My role as a designer focuses on the resolution of not only the surface of the object through 3-D printing, but the social implications to acknowledge consequential conditions of new forms of consumer technology.