Functional polymer foams are considered as a promising field which could potentially produce foams with added value. Specifically, functionally graded foams are materials which are expected to provide better mechanical properties while preserving low density in comparison with regular foams. In this thesis, a preparation process of such foams is designed, examination of prepared structure and comparison of mechanical properties with regular foams is performed. The obtained results are discussed and further research in this field is proposed.

<div> <div> <div> <p> </p><div> <div> <div> <div> <div> <div> <p> </p><div> <div> <div> <p>Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) and transition metal carbides/nitrides (MXenes), have been recently receiving attention for gas sensing applications due to their high specific area and rich surface functionalities. However, using pristine 2D materials for gas-sensing applications presents some drawbacks, including high operation temperatures, low gas response, and poor selectivity, limiting their practical sensing applications. Moreover, one of the long-standing challenges of MXenes is their poor stability against hydration and oxidation in a humid environment, which negatively influences their long- term storage and applications. Many studies have reported that the sensitivity and selectivity of 2D materials can be improved by surface functionalization and hybridization with other materials.</p><p>In this work, the effects of surface functionalization and/or hybridization of these two materials classes (TMDCs and MXenes) on their gas sensing performance have been investigated. In one of the lines of research, 2D MoS2 nanoflakes were functionalized with Au nanoparticles as a sensing material, providing a performance enhancement towards sensing of volatile organic compounds (VOCs) at room temperature. Next, a nanocomposite film composed of exfoliated MoS2, single-walled carbon nanotubes, and Cu(I)−tris(mercaptoimidazolyl)borate complexes was the sensing material used for the design of a chemiresistive sensor for the selective detection of ethylene (C2H4). Moreover, the hybridization of MXene (Ti3C2Tx) and TMDC (WSe2) as gas-sensing materials was also proposed. The Ti3C2Tx/WSe2 hybrid sensor reveals high sensitivity, good selectivity, low noise level, and ultrafast response/recovery times for the detection of various VOCs. Lastly, we demonstrated a surface functionalization strategy for Ti3C2Tx with fluoroalkylsilane (FOTS) molecules, providing a superhydrophobic surface, mechanical/environmental stability, and excellent sensing performance. The strategies presented here can be an effective solution for not only improving materials' stability, but also enhancing sensor performance, shedding light on the development of next-generation field-deployable sensors.</p> </div> </div> </div><div><div><div><div><div><div> </div> </div> </div> </div> </div> </div></div></div></div> </div> </div> </div></div></div></div><div><div><div> </div> </div> </div>

Microporous membranes act as selective barriers and play an important role in industrial gas separation and water purification. The permeability of such membranes is inversely proportional to their thickness. Synthetic two-dimensional materials (2DMs), with a thickness of one to a few atoms or monomer-units are ideal candidates for developing separation membranes. In this Progress Report, we present groundbreaking advances in the design, synthesis, processing, and application of 2DMs for gas and ion separations, as well as water desalination. After the introduction in Section 1, this report describes the syntheses, structures, and mechanical properties of 2DMs in Section 2. In Section 3, we will discuss the established methods for processing 2DMs into selective permeation membranes and address the separation mechanism and their performances. Finally, current challenges and emerging research directions, which need to be addressed for developing next generation separation membranes, are summarized in the Conclusion and Perspective.

<p>The potential use of enzymes in industrial synthesis of epoxidized soybean oil has been limited through the high cost of the enzyme catalyst, in this work we evaluate the effectiveness of chemo enzymatic epoxidation of high oleic soybean oil (HOSBO) using lipase B from <i>Candida antarctica </i>(CALB) on immobilization support Immobead 150 and H₂O₂in a solvent-free system. Additionally, we evaluated the production decay rates for hydrolytic activity and epoxide product formation over consecutive batches to determine half-life of the enzyme catalyst. </p> <p> Batch epoxidation of HOSBO using CALB on 4wt% loading shows yields higher than 90% after 12 hrs. of reaction, and with a correlation to the consumption of double bonds suggesting that the reaction is selective and limiting side product reactions. Non-selective hydrolysis of oil was not found beyond the initial hydrolysis degree of raw HOSBO. Evaluations of decay given by epoxide product formation and released free fatty acids shows a half-life of the enzyme catalyst on these activities is of 22 ad 25 hrs. respectively. Finally, we evaluated the physical parameters influencing this decay, and found that H₂O₂ presence is the most important parameter of enzyme inactivation with no significant effect from its slowed addition. We propose a new reactor configuration for the analysis of the specific steps on epoxide formation through peracid intermediates. </p>

Im Rahmen der vorliegenden Arbeit wurden neuartige keramik- und stahlreiche Verbundwerkstoffe, auf Basis von MgO-teilstabilisiertem Zirkoniumdioxid und hochlegiertem austenitischem TRIP Stahl entwickelt. Die keramikreiche Verbundwerkstoffe mit bis zu 30 Vol.% metallischer Partikelverstärkung wurden über die Schlickergusstechnologie bzw. die Druckschlickergusstechnologie hergestellt und können als thermo-mechanisch beanspruchte Bauteile zum Einsatz kommen. Es wurden weiterhin metallreiche Verbundwerkstoffe mit bis zu 10 Vol.% keramischer Partikelverstärkung erstmalig über die Papiertechnologie hergestellt. Dadurch ergeben sich vielfältige Möglichkeiten metallreiche Leichtbaustrukturen mit verbesserten Energieabsorptionsvermögen zu erzeugen. Im Mittelpunkt der vorliegenden Arbeit stand die Entwicklung der keramikreichen Schlicker, die Formgebungstechnologien, die Entwicklung geeigneter Entbinderungs- und Sinterregime sowie die Charakterisierung der Verbundwerkstoffe hinsichtlich ihrer Mikrostruktur sowie der mechanischen bzw. der thermo-mechanischen Eigenschaften.

<p>Impressive examples of the generation of hierarchically-patterned, three-dimensional (3-D) structures for the control of light can be found throughout nature. <i>Morpho rhetenor</i> butterflies, for example, possess scales with periodic parallel ridges, each of which consists of a stack of thin (nanoscale) layers (lamellae). The bright blue color of <i>Morpho</i> butterflies has been attributed to controlled scattering of the incident light by the lamellae of the wing scales. Another stunning example is the frustule (microshell) of the <i>Coscinodiscus wailesii</i> diatom, which is capable of focusing red light without possessing a traditional lens morphology. The photonic structures and the optical behaviors of <i>Morpho</i> butterflies and <i>Coscinodiscus wailesii</i> diatoms have been extensively studied. However, no work has been conducted to shift such light manipulation from the visible to the infrared (IR) range via shape-preserving conversion of such biogenic structures. Controlling IR radiation (i.e., heat) utilizing biogenic or biomimetic structures can be of significant utility for the development of energy-harvesting devices. In order to enhance the optical interaction in the IR range, inorganic replicas of biogenic structures comprised of high-refractive-index materials have been generated in this work. Such replicas of <i>Morpho</i> <i>rhetenor</i> scales were fabricated via a combination of sol-gel solution coating, organic pyrolysis, and gas/solid reaction methods. Diatomimetic structures have also been generated via sol-gel coating, gas/solid reaction, and then patterning of pore arrays using focused ion beam (FIB) milling.</p> Throughout the sol-gel solution coating and chemical conversion steps of the processes developed in this study, attention was paid to preserve the starting shapes of the nanopatterned, microscale biogenic or biomimetic structures. Factors affecting such shape preservation included the thicknesses and uniformities of coatings applied to the biogenic or biomimetic templates, nano/microstructural evolution during thermal treatment, and reaction-induced volume changes. A conformal surface sol-gel (SSG) coating process was developed in this work to generate oxide replicas of <i>Morpho rhetenor</i> butterfly scales with precisely-controlled coating thicknesses. The adsorption kinetics and relevant adsorption isotherm of the SSG process were investigated utilizing a quartz crystal microbalance. Analyses of thermodynamic driving forces, rate-limiting kinetic steps, and volume changes associated with various chemical reactions were used to tailor processing parameters for optimized shape preservation.

<div>Despite the abundant current applications for ionic hydrogels, much about the stimuli-responsive behavior of these materials remains poorly understood. Due to the soft nature of these materials, the number of traditional characterization methods which can be applied to these systems is limited. Many studies have been conducted to characterize bulk property responses of these materials, and experimental studies have been produced examining the distribution of free ions around single polyelectrolyte chains. However, little experimental work has been published in which molecular-scale interactions are elucidated in confined polyelectrolyte networks. Furthermore, the way in which responsive properties, other than bulk swelling capacity, scale with ionic fraction in mixed polyelectrolyte-non-polyelectrolyte hydrogel systems has not been thoroughly investigated.</div><div>The distribution and strength of polymer-counter-ion bonds has a remarkable effect on hydrogel properties such as absorption capacity, mechanical strength, and size and chemical selectivity. In order to tailor these properties for targeted applications in ionic environments, it is imperative that we thoroughly understand the character of these polymer-ion interactions and their arrangement within the bulk hydrogel. In order to do so, however, non-traditional methods of analysis must be employed.</div><div>This dissertation focuses on a model part-ionic hydrogel system, poly(sodium acrylate-co-acrylamide), in order to assess not only the polymer-counter-ion interactions but also the impact of gel ionic fraction on these interactions and the responses which they induce in gel performance properties. A model alkali (NaCl), alkaline earth (CaCl2), and transition (CuSO4) metal salt are employed to investigate changes in polymer properties from the macroscale to the nanoscale. The aim of this dissertation is to lay the foundation for the development of fundamental structure-property relationships by which we may fully understand the ionically-induced performance properties of polyelectrolyte networks.</div>

<div>Laser-to-composite interactions are becoming increasingly common in diverse applications such as diagnostics, fabrication and machining, and weapons systems. Lasers are capable of not only performing non-contact diagnostics, but also inducing seemingly imperceptible structural damage to materials. In safety-critical venues like aerospace, automotive, and civil infrastructure where composites are playing an increasingly prominent role, it is desirable to have means of sensing laser exposure on a composite material. Self-sensing materials may be a powerful method of addressing this need. Herein, we present an exploratory study on the potential of using changes in electrical measurements as a way of detecting laser exposure to a carbon nanofiber (CNF)-modified glass fiber/epoxy laminate. CNFs were dispersed in liquid epoxy resin prior to laminate fabrication via hand layup. The dispersed CNFs form a three-dimensional conductive network which allows for electrical measurements to be taken from the traditionally insulating glass fiber/epoxy material system. It is expected that damage to the network will disrupt the electrical pathways, thereby causing the material to exhibit slightly higher resistance. To test laser sensing capabilities, a resistance baseline of the CNF-modified glass fiber/epoxy specimens was first established before laser exposure. These specimens were then exposed to an infra-red laser operating at 1064 nm, 35 kHz, and pulse duration of 8 ns. The specimens were irradiated for a total of 20 seconds (4 exposures each at 5 seconds). The resistances of the specimens were then measured again post-ablation. In this study, it was found that for 1.0 wt.% CNF by weight the average resistance increased by about 18 percent. However, this values varied for specimens with different weight fractions. This established that the laser was indeed causing damage to the specimen sufficient to evoke a change in electrical properties. In order to expand on this result, electrical impedance tomography (EIT) was employed for localization of laser exposures of 1, 3, and 5 seconds on a larger specimen, a 3.25” square plate. EIT was used to measure the changes in conductivity after each exposure. EIT was not only successful in detecting damage that was virtually imperceptible to the human-eye, but it also accurately localized the exposure sites. The post-ablation conductivity of the exposure sites decreased in a manner that was comparable to the resistance increase obtained during prior testing. Based on this preliminary study, this research could lead to the development of a real-time exposure detection and tracking system for the measurement, fabrication, and defense industries.</div>

<p dir="ltr">Metamaterials are artificially engineered nanoscale systems with a three-dimensional repetitive arrangement of certain components, and present exceptional optical properties for applications in nanophotonics, solar cells, plasmonic devices, and more. Self-assembled oxide-metal vertically aligned nanocomposites (VANs), with metallic phase as nanopillars embedded in the matrix oxide, have been recently proposed as a promising candidate for metamaterial applications. However, precise microstructural control and the structure-property relationships in VANs are still in high demand. Thus, by employing multiple approaches for structural design, this dissertation attempts to investigate the mechanisms of nanostructure evolutions and the corresponding optical responses.</p><p dir="ltr">In this dissertation, the precise control over the nanostructures has been demonstrated through morphology tuning, nanopillar orderings, and strain engineering. Firstly, Au, a well-known plasmonic mediator, has been selected as the metallic phase that forms nanopillars. Based on the previously proposed strain compensation model which describes the basic formation mechanism of VAN morphology, two oxides were then considered: La_0.7Sr_0.3MnO₃(LSMO) and CeO₂. In the first two chapters of this dissertation, LSMO was considered due to its similar lattice (a_LSMO= 3.87 Å, a_Au= 4.08 Å) and its enormous potential in nanoelectronics and spintronics. Deposited on SrTiO₃ (001) substrate through pulsed laser deposition (PLD), LSMO-Au nanocomposites exhibit ideal VAN morphology as well as promising hyperbolic dispersions in response to the incident illuminations. By substrate surface treatment of annealing at 1000°C, and variation of STO substate orientations from (001), to (111) and (110), the improved and tunable in-plan orderings of Au nanopillars have been successfully achieved. In the third chapter, a new oxide-metal VAN system of <a href="" target="_blank">CeO₂</a>-Au (a_CeO2= 5.411 Å, and a_CeO2/= 3.83 Å) has been deposited. The intriguing 45° rotated in-plan epitaxy presents an unexpected update to the strain compensation model, and tuning of Au morphology from nanopillars, nanoantennas, to nanoparticles also shows an effective modulation of the LSPR responses. COMSOL simulations have been exploited to reveal the relationships between Au morphologies and optical responses. In the last chapter, the two VAN systems of LSMO-Au and CeO₂-Au have been combined to form a complex layered VAN thin film. Investigations into the strain states, the nature of complex interfaces, and the according hybrid properties, show dramatic possibilities for further strain engineering. In summary, this dissertation has provided multiple routes for highly tailorable oxide-metal nanocomposite designs. And the two proposed material systems present great potential in optical metamaterial applications including biosensors, photovoltaics, super lenses, and more.</p>

<p dir="ltr">The gastrointestinal (GI) tract and its diverse microbial community play a significant role in overall health, impacting various aspects such as metabolism, physiology, nutrition, and immune function. Disruptions in the gut microbiota have been associated with metabolic diseases, colorectal cancer, diabetes, obesity, inflammatory bowel disease, Alzheimer's disease, and depression. Despite recognizing the importance of the gut microbiota, the interrelationship between microbiota, diet, and disease prevention remains unclear. Current techniques for monitoring the microbiome often rely on fecal samples or invasive endoscopic procedures, limiting the understanding of spatial variations in the gut microbiota and posing invasiveness challenges. To address these limitations, this dissertation focuses on the design and development of an electronic-free smart capsule platform capable of targeted sampling of GI fluid within specific regions of the GI tract. The capsule can be retrieved for subsequent bacterial culture and sequencing analysis. The capsule design is based on stimuli-responsive polymers and superabsorbent hydrogels, chosen for their proven safety, compatibility, and scalability. By leveraging the pH variation across the GI tract, the pH-sensitive polymeric coatings dissolve at the desired region, activating the sampling process. The superabsorbent hydrogel inside the capsule collects the sampled GI fluid and facilitates capsule closure upon completion of sampling. Systematic studies were conducted to identify suitable pH-responsive polymer coatings, superabsorbent hydrogels, and processing conditions that effectively operated within the physiological conditions of the GI tract. The technology's effectiveness and safety were validated through rigorous <i>in vitro</i> and <i>in vivo</i> studies using pig models. These studies demonstrated the potential of the technology for targeted sampling of GI fluid in both small and large intestinal regions, enabling subsequent bacterial culture and gene sequencing analysis. Additionally, the capsule design was enhanced with the integration of a metal tracer, enabling traceability throughout the GI tract using X-ray imaging and portable metal detectors for ambulatory screening. This technology holds promise as a non-invasive tool for studying real-time metabolic and molecular interactions among the host, diet, and microbiota in challenging-to-access GI regions. Its application in clinical studies can provide new insights into diet-host-microbiome interactions and contribute to addressing the burden faced by patients and their families dealing with GI-related diseases.</p>