<p>  </p> <p>Plastics play crucial rules in almost every aspect of life. Unique properties of plastics like chemical and light resistant, strong, moldable, and low cost make plastic materials useful in many aspects of our global society. However, largely relying on feedstock resources like fossil fuels, plastics production is not sustainable. Thus, plastic recycling could be an efficient alternative to save feedstock resources as well as to reduce production cost.</p> <p>Recently, a series of polymer materials synthesized via topochemical polymerization are considered as strong candidates for next generation recyclable plastics. It is well-known that topochemical polymerization has high efficiency and environment-friendly features, such as solvent-free and catalyst-free reaction conditions, high reaction yield without side reactions, and atom economy. Yet, there exist few studies on depolymerizing and recycling those polymers. A unique topochemically polymerizable polyindenedione derivative [2,2'-Bi-1H-indene]-1,1'-dione-3,3'-diyl dialkylcarboxylate (polyBIT) with rapid and quantitative depolymerization was discovered via breakage of elongated carbon-carbon (C-C) bonds with bond length of 1.57∼1.63 Å. The elongated C-C bonds have been proven theoretically and experimentally to have significantly lower bond dissociation energies than normal C-C bonds, and it is the major driving force to depolymerize polyBIT polymer single crystals. </p> <p>Different from most traditional polymers that can be dissolved or melt processed, topochemical polymer single crystals are not soluble in most common solvents due to their highly crystalline and ordered nature. This unique feature inhibited topochemical polymer crystals from practical applications. To convert needle-like polyBIT crystals into useful forms, I developed an ultrasonication method to break large polymer crystals into small fibers that can be uniformly suspended in organic solvents. Followed by vacuum filtration and heat press, polyBIT crystals can be processed into robust and freestanding polymer thin films. The processed thin films presented reasonable mechanical properties with Young’s modulus of over 600MPa and are stable under harsh conditions.</p> <p>Topochemical polymerization reactions require specific monomer packings before applying external stimuli, and a small change in monomer structure may completely alter the reactivity. Therefore, functionalizing monomer structures for topochemical reactions is quite challenging. In the polyBIT system, we attempted to functionalize BIT monomer with several linear and branched side chains. After preparing monomer crystals, only needle-like 1D monomers can be photopolymerized, while plate-like 2D monomer crystals became photostable. Introducing heteroatoms (such as oxygen, sulfur, bromine, chlorine) can induce different non-bonding interactions and interactions, which combined can push monomers away from one another to make them unreactive. Introducing branched side chains will also change the distances between two BIT monomers and leads to unreactive crystals when the branched side chain is too bulky (such as when tertbutyl group is on the end of side chain). Functionalizing side chains for polyBIT crystals can further tune the mechanical properties of the crystals: swapping end methyl group with a simple bromine atom can induce multiple intermolecular and interchain interaction including weak hydrogen bonding and C−H···Br interactions. These interactions bind all the polymer chains together to provide a strong 1D polymer fiber with elastic modulus over 10.6 GPa. These results suggest that the crystalline polymers synthesized from simple photochemistry and without expensive catalysts are promising for practical applications with complete materials circularity and wide range of structural and mechanical turnabilities.</p>

<p>Superabsorbent polymer (SAP) hydrogel particles have been used as internal curing agents in concrete mixes as they are capable of absorbing and subsequently releasing large amounts of water. This reduces autogenous shrinkage during early stages of hydration. The size, shape, and composition of the hydrogel particles can be controlled during the synthesis, hence providing the opportunity to custom synthesize these internal curing agents to elicit desired structure-property relationships. Utilization of optimized dosage and formulation of SAP has the potential to improve the microstructure, durability, and strength of internally cured concrete. </p> <p>The first study focuses on the synthesis and application of novel composite hydrogel particles as internal curing agents in cementitious mixes. Composite polyacrylamide hydrogel particles containing two different amorphous silica–either nanosilica or silica fume–were used to investigate whether the internal curing performance of hydrogel particles could be enhanced. The dosage and type of silica, crosslinker amount were varied to identify the composite polyacrylamide hydrogel particle composition that provides optimum benefits to internally cured cementitious systems. The synthesized hydrogels were characterized by means of absorption capacity tests, compositional and size analysis. The beneficial impacts of the addition of composite hydrogels on cement paste microstructure are highlighted, including the preferential formation of cement hydration products (such as portlandite) within the hydrogel-induced voids that appeared to be influenced by the composition of the hydrogel particles. The interrelationship between extent of hydration, size of hydrogel voids, and void-filling with hydration products was found to strongly influence mechanical strength and is thus an important structure-property relationship to consider when selecting hydrogels for internal curing purposes. This study informs the design of composite hydrogel particles to optimize performance in cementitious mixes. Additionally, it provides a novel means of incorporating other commonly used admixtures in concrete without facing common challenges related to dispersion and health hazards.</p> <p>The second study focuses on the utilization of two retarding admixture-citric acid and sucrose-to custom synthesize composite polyacrylamides to investigate whether the composite hydrogels could delay hydration of cement paste. Isothermal calorimetry analysis results showed that composite sucrose-containing polyacrylamide hydrogel particles were successfully able to retard main hydration peak of cement paste, beyond the retardation capabilities of the pure polyacrylamide hydrogels. Thus, this study provides avenues of exploring the utilization of common admixtures to formulate novel composite hydrogels that imparts specific properties to cementitious systems.</p> <p>In another study, SAP formulated by admixture industries were used to investigate the feasibility of internal curing of bridge decks and pavement patches with SAP particles. The microstructure and early age hydration properties of SAP-cured cementitious systems were studied. Mitigation of microcracks in the matrix, along with portlandite growth in SAP voids, were observed in SAP-cured mortars. Presence of SAP also mitigated autogenous shrinkage and improved early age hydration as observed by isothermal calorimetry analysis. This thesis highlights some of the beneficial impacts of SAP-cured cementitious systems, and the potential to harness those benefits in large-scale applications of SAP-cured concrete.</p> <br>

<p dir="ltr">Water molecules present an obstacle between most synthetic adhesives and surfaces, limiting molecular contact between the glue and substrates. Water can also hydrolyze or swell bulk adhesives, weakening cohesive strength. Nature has solved these challenges for millennia. Marine mussels’ ability to adhere well to wet surfaces stems from an uncommon amino acid, 3,4-dihydroxyphenylalanine (Dopa). The amino acid Dopa contains a catechol moiety that contributes to adhesion and cohesion through hydrogen bonding, metal coordination, and oxidative cross-linking. Hence, biomimetic systems often incorporate catechol groups to provide strong adhesion in both dry and wet environments. In addition to Dopa, mussel adhesive proteins are rich in cationic amino acids lysine and arginine. Previous studies have suggested that cations could displace surface-bound ions, enhancing surface adhesion. However, adhesion performance varied between systems, with no agreement on whether cations are advantageous or disadvantageous. A clear picture of how cations influence underwater adhesion has yet to emerge; therefore, this thesis aims to systematically study these effects.</p><p dir="ltr">In Chapter 2, the synthesis of catechol-containing biomimetic polymers with varying amounts of quaternary ammoniums is presented. Quaternary ammoniums, unlike protonated primary amines, contain non-reactive cations and were used to isolate effects from only charges on adhesion. In Chapter 3, differences between reactive primary amines and quaternary ammoniums were investigated. Structure-function studies have shown how cations influence bulk cohesion versus surface adhesion in dry, under deionized water, and under salt water. The roles of cations in adhesion were complex, with both cohesive and surface bonding relevant in different ways, sometimes even working in opposite directions.</p><p dir="ltr">Furthermore, a styrene-based catechol-containing polymer with excellent underwater adhesion performance is ready to enter the market, but several barriers hinder its industrial implementation. In Chapter 4, new synthetic strategies were developed to scale up and reduce the cost of producing p[vinylcatechol-<i>co-</i>styrene], which are essential for commercialization. This was achieved by selecting cheaper starting materials, switching from anionic to suspension polymerization, and optimizing deprotection reaction conditions. This change also improved adhesion in both dry and underwater conditions. This work is presented as part of our effort to advance the design of adhesives that function in challenging environments.</p>

<p dir="ltr">Electronics have contributed to the advancement of healthcare, wellness, security, and mobility, resulting in a higher standard of living. However, these ever-accelerating advancements and widespread application come at the cost of a shortened product life cycle and increase in produced E-waste which poses a significant environmental challenge. Recycling E-waste is challenging due to the complexity of electronics and packaging, hindering component retrieval for reuse. While sustainable materials for electronics have been researched, sustainable integrated circuit (IC) packaging for conventional electronics remains unexplored. This study introduces a method involving dissolvable additively manufactured packaging materials to recover commercial-off-the-shelf (COTS) chips from used electronics, which would alleviate supply-chain stress, reduce the need for manufacturing similar chips, and minimize environmental impact. In this work, Polyvinyl alcohol (PVA) and Acrylonitrile butadiene styrene (ABS), are explored as potential dissolvable semiconductor packaging materials. Optimal dissolving conditions allow chip recovery in less than 11 minutes for PVA and 2 minutes for ABS. This approach offers a sustainable packaging method for commercial electronic chips that matches conventional packaging performance with the added functionality of recoverable and recyclable components, contributing to the gap in sustainability and recycling for conventional electronics.</p>

<p>High-performance fibers used for ballistic protection are characterized by having outstanding mechanical properties such high modulus and strength. These mechanical properties are granted by the fiber’s chemical and physical structure as well as their high degree of orientation. Twaron fibers are one of the most commonly used fibers on soft body armors such as bulletproof vests. They are made from poly (p-phenylene terephthalamide) (PPTA), a rigid-rod and highly crystalline polymer. Although these fibers are crystalline and have great mechanical properties, their performance can decrease when they are exposed to different degradation factors. Free volume is the unoccupied space between the polymer molecules. It is responsible for characteristics such as diffusion and viscosity. Hence, the free volume changes as the polymer degrades. This thesis focuses on the effects of sonication, pH changes, and sweat on the free volume of PPTA fibers. </p><p><br></p> <p>A non-destructive technique known as positron annihilation lifetime spectroscopy (PALS) was used to measure the free volume in PPTA. Changes in the free volume of fibers degraded under different conditions were compared to their mechanical performance. Degradation in DI water, pH 4 and pH 10 aqueous solutions was conducted for 10 weeks at 80^oC. Sweat degradation of PPTA fibers was also conducted for 10 weeks at 25^oC, 50^oC, and 100^oC. Fibers degraded in pH4 and sweat solutions had greater loss of mechanical performance and changes in the free volume. PALS was able to detect changes in the nanostructure of PPTA fibers at early stages of degradation. This data was supported by mechanical tests and is complementary to other characterization techniques such as small angle X-ray scattering (SAXS). Results of this research are a steppingstone for future studies on lifetime predictions of bulletproof vests and the development of the next generation of soft body armors. </p>

<div> <p><a>Polymer nanocomposites are envisioned for use in many advanced applications, such as structural industries, aerospace, automotive technology and electronic materials, due to the improved properties like mechanical strengthening, thermal and chemical stability, easy bulk processing, and/or light-weight instigated by the filler-matrix combination compared to the neat matrix. In recent years, due to increasing environmental concerns, many industries are inclining towards developing sustainable and renewable polymer nanocomposites. Cellulose nanomaterials (CNs), including cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs), have gained popularity due to their excellent mechanical properties and eco-friendliness (extracted from trees, algae, plants etc.). However, to develop CN-reinforced nanocomposites with industrial applications it is necessary to understand impact of hygroscopic swelling (which has very limited </a>quantitative study at present), aspect ratio, orientation, and content of CNs on the overall performance of nanocomposites; and overcome the low dispersibility of CNs and improve their compatibility with hydrophobic matrix. In this work, we attempt to understand the influence of single nanocrystals in the hygroscopic and optical response exhibited by nanostructured films; effect of CNCs on the properties of PVA/CNC fibers by experimental evidence with mathematical modeling predictions; and hydrophobized CNFs using a facile, aqueous surface modification to improve interfacial compatibility with epoxy. </p><p><br></p> <p>To evaluate the effect of CNC alignment in the bulk response to hygroscopic expansion, self-organized and shear-oriented CNC films were prepared under two different mechanisms. The coefficient of hygroscopic swelling (CHS) of these films was determined by using a new contact-free method of Contrast Enhanced Microscopy Digital Image Correlation (CEMDIC) that enabled the characterization of dimensional changes induced by hygroscopic swelling of the films. This method can be readily used for other soft materials to accurately measure hygroscopic strain in a non-destructive way. By calculating the CHS values of CNC films, it was determined that hygroscopic swelling is highly dependent on the alignment of nanocrystals within the films, with aligned CNC films showing dramatically reduced hygroscopic expansion than randomly oriented films. Finite element analysis was used to simulate moisture sorption and kinetics profile which further predicted moisture diffusion as the predominant mechanism for swelling of CNC films. </p> <p><br></p><p>To study the effects of different types and aspect ratios of CNCs on mechanical, thermal and morphological properties of polyvinyl alcohol (PVA) composite <a>fibers, CNCs extracted from wood pulp and cotton were reinforced into PVA to produce fibers by dry-jet-wet spinning. The fibers were collected as-spun and with first stage drawing up to draw ratio 2. </a>The elastic modulus and tensile strength of the fibers improved with increasing CNC content (5 – 15 wt. %) at the expense of their strain-to-failure. The mechanical properties of fibers with cotton CNC were higher than the fibers with wood CNC when the same amount of CNCs were added due to their higher aspect ratio. The degree of orientation along the spun fiber axis was quantified by 2D X-ray diffraction. As expected, the CNC orientation correlates to the mechanical properties of the composite fibers. Micromechanical models were used to predict the fiber performance and compare with experimental results. Finally, surface and cross-sectional morphologies of fibers were analyzed by scanning electron microscopy and optical microscopy.</p><p><br></p> <p>To improve the dispersibility and compatibility of CNFs with epoxy, CNFs were modified by using a two-step water-based method where tannic acid (TA) acts as a primer with CNF suspension and reacts with hexadecylamine (HDA), forming the modified product as CNF-TA-HDA. The modified (-m) and unmodified (-um) CNFs were filled into hydrophobic epoxy resin with a co-solvent (acetone), which was subsequently removed to form a solvent-free two component epoxy system, followed by addition of hardener to cure the resin. Better dispersion and stronger adhesion between fillers and epoxy were obtained for m-CNF than the um-CNF, resulting in better mechanical properties of nanocomposites at the same loading. Thermal stability and the degradation temperature of m-CNF/epoxy improved when compared to neat epoxy. </p> </div> <br>

<div> Design rules and application spaces for closed-shell conjugated polymers have been well established in the field of organic electronics, and this has allowed for significant breakthroughs to occur in myriad device platforms [e.g., organic field-effect transistors (OFETs) and organic light-emitting devices (OLEDs)]. Conversely, organic electronic materials that are based on the emerging design motif that includes open-shell stable radicals have not been evaluated in such detail, despite the promise these materials show for charge transfer, light-emission, and spin manipulation platforms. Moreover, recent results have demonstrated that the materials performance of hybrid systems will allow for future applications to harness both of these platform design archetypes to generate composites that combine the performance of current state-of-the-art conjugated polymer systems with the novel functions provided by open-shell species. Thus, establishing the underlying physical phenomena associated with the interactions between both classes of materials is imperative for the effective utilization of these soft materials.</div><div><br></div><div> In the first part of this work, Förster resonance energy transfer (FRET) is demonstrated to be the dominant mechanism by which energy transfer occurs from a common conjugated polymer to various radical species using a combination of experimental and computational approaches. Specifically, this is determined by monitoring the fluorescence quenching of poly(3hexylthiophene) (P3HT) in the presence of three radical species: (1) the galvinoxyl; (2) the 2phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO); and (3) the 4-hydroxy-2,2,6,6tetramethylpiperidine-1-oxyl (TEMPO) radicals. Both in solution and in the solid-state, the galvinoxyl and PTIO radicals show quenching on par with that of a common fullerene electronaccepting derivative. Conversely, the TEMPO radical shows minimal quenching at similar concentrations. Using both ultrafast transient absorption spectroscopy and computational studies, FRET is shown to occur at a significantly faster rate than other competing processes. These findings suggest that long-range energy transfer can be accomplished in applications when radicals that can act as FRET acceptors are utilized, forming a new design paradigm for future applications involving both closed- and open-shell soft materials.</div><div><br></div><div> Following this, addition of the galvinoxyl radical to P3HT is shown to alter the thin film transistor response from semiconducting to conducting. This is accompanied by a modest enhancement in electrical conductivity. This interaction is not seen with either the TEMPO or PTIO radicals. While an increase in charge carrier concentration is observed, the interaction is not otherwise consistent with a simple charge-transfer doping mechanism, due to the mismatched reduction and oxidation potentials of the two species. Additionally, no freeze-out of charge carriers is observed at reduced temperatures. It is also not due to parallel conduction through the radical fraction of the bulk composite, as the radical species is non-conductive. Hole mobility is enhanced at lower concentrations of the radical, but it decreases at higher concentrations due to the reduced fraction of conductive material in the polymer bulk. Despite the increase in mobility at lower concentrations, the activation energy for charge transport is increased by the presence of the radical. This suggests that the radical is not improving the charge transport through filling of deep trap states or by reducing the activation energy for the charge transport reaction; however, the galvinoxyl radical is likely filling shallow trap states within the P3HT for the composite thin film.</div><div><br></div><div> Finally, a novel analysis technique for polymer relaxation is investigated through dielectric spectroscopy of model polyalcohols. An understanding of relaxation phenomena and the physics of amorphous solids in general remains one of the grand open challenges in the field of condensed matter physics. This problem is particularly relevant to organic electronics as many organic electronic materials are found in the amorphous state, and their physical relaxation can lead to undesirable effects such as hysteresis and instability. Current procedures describe relaxation phenomena in terms of empirical functions, but the physical insights provided by this representation are limited. The new approach instead represents the dielectric response as a spectrum of Debye processes. Rather than varying the spectral strength at fixed time points as traditional spectral analysis implicitly does, this approach instead varies the characteristic time of each spectral element while the strength remains fixed. This allows the temperature dependence on relaxation time of each spectral element to be determined, and the <i>α</i>- and <i>β</i>-relaxation are interpreted in light of this analysis. </div><div> </div>

As an intrinsic requirement for digital image correlation (DIC)to be applicable, the images must exhibit a speckle pattern of sufficient unique features. Researchers have incorporated X-ray phase contrast imaging (PCI) and DIC (XDIC) and conducted studies on materials with natural internal features as speckles. This study is the first attempt to explore the applicability and standards of XDIC to be applied on materials that are transparent under X-ray PCI, mainly polymers, by deliberately embedding particles into the sample. The goal is to generate a high-quality speckle while maintaining the least influence on the material’s properties. Iron oxide (FeO), tungsten carbide (WC), and platinum (Pt) are embedded into Sylgard® epoxy at various weight ratios, and the Sylgard® samples are loaded with a Kolsky compression bar paired with high-speed X-ray PCI. The speckle quality of the PCI images is assessed using a mean intensity gradient based approach, as well as intensity distribution analysis. DIC is applied to the images to measure the displacement field in the loading direction, and the results are analyzed. The engineering stress-strain relationship is generated from the Kolsky bar apparatus, and the results are compared to find the influence of the added particles.<div><br></div><div>The results indicate thatthe addition of particles does not significantly alter the base polymer’s properties, and the theoretical deviation error can be as low as less than 0.01 pixels. Disregarding the limited applicability to embed into polymer samples, platinum produces the best speckle. WC particle is the superior choice of material to embed for its good speckle quality, ease of embedding, and good availability. Lower weight ratios are shown to be preferential. This study also emphasizes the importance of sample design when applying XDIC to materials with embedded particles. It is preferential for best accuracy to design the region of interest to be away from the surfaces of the samples and be located near the back of the sample with respect to the impact surface.<br></div>

<p>Concrete is in everyday life such as parking lots, buildings, bridges, and more. To keep concrete and its constituents together, binders such as cement are used. Cement’s production process is responsible for 8% of global carbon dioxide emissions as of 2018. With global warming being a severe global issue, the challenge of reducing cement carbon dioxide emissions can be greatly beneficial with even slight improvements. Various solutions to this challenge have developed over the years in the form of processing efficiency, material substitution, or material additives. Of the additives for cement and concrete that have been ventured, nanomaterials have had a strong development in recent years. Specifically, cellulose nanomaterials in the form of nanocrystals, nanofibrils, and more have demonstrated great improvement in cement’s performance resulting in a reduction in cement produced and reduction in emissions. This study expands on the knowledge of cellulose nanocrystals as an additive for cement using the formation factor methodology. Formation factor is a resistivity ratio of the specimen and pore solution that can be used in correlation to the diffusion of chloride ions through the use of the Nernst-Einstein equation. This study also investigates the effect that cellulose nanomaterials have on the mechanical properties and thermogravimetric analysis of gypsum, a material commonly used in cement production that delays the hardening of cement. </p>

<p>A variety of methods have been developed to enhance solid propellant burning rates, including adjusting oxidizer particle size, modifying metal additives, tailoring the propellant core geometry, and adding catalysts or wires. Fully consumable reactive wires embedded in propellant have been used to increase the burning rate by increasing the surface area; however, the manufacture of propellant grains and the observation of geometric effects with reactive components has been restricted by traditional manufacturing and viewing methods. In this work, a printable reactive filament was developed that is tailorable to a number of use cases spanning reactive fibers to photosensitive igniters. The filament employs aluminum fuel within a printable polyvinylidene fluoride matrix that can be tailored to a desired burning rate through stoichiometry or aluminum fuel configuration such as particle size and modified aluminum composites. The material is printable with fused filament fabrication, enabling access to more complex geometries such as spirals and branches that are inaccessible to traditionally cast reactive materials. However, additively manufacturing the reactive fluoropolymer and propellant together comes attendant with many challenges given the significantly different physical properties, particularly regarding adhesion. To circumvent the challenges posed by multiple printing techniques required for such dissimilar materials, the reactive fluoropolymer was included within a solid propellant carrier matrix as small fibers. The fibers were varied in aspect ratio (AR) and orientation, with aspect ratios greater than one exhibiting a self-alignment behavior in concordance with the prescribed extrusion direction. The effective burning rate of the propellant was improved nearly twofold with 10 wt.% reactive fibers with an AR of 7 and vertical orientation. </p> <p>The reactive wires and fibers in propellant proved difficult to image in realistic sample designs, given that traditional visible imaging techniques restrict the location and dimensions of the reactive wire due to the necessity of an intrusive window next to the wire, a single-view dynamic X-ray imaging technique was employed to analyze the evolution of the internal burning profile of propellant cast with embedded additively manufacture reactive components. To image complex branching geometries and propellant with multiple reactive components stacked within the same line of sight, the dynamic X-ray imaging technique was expanded to two views. Topographic reconstructions of propellants with multiple reactive fibers showed the evolution of the burning surface enhanced by the geometric effects caused by the faster burning fibers. These dual-view reconstructions provide a method for accurate quantitative analysis of volumetric burning rates that can improve the accessibility and viability of novel propellant grain designs.</p>