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At least 271 records · Page 15

Evaluation of Surlyn 8920 as PHE Visor Material and Evaluations of New Adhesives for Improving Bonding Between Teflon and Stainless Steel at Cryogenic Temperature

Two studies are presented, and in the first study, Surlyn 8920 (an ionic and amorphous low density polyethylene made by Dupont) was evaluated as a possible replacement of Plexyglass G as PHE visor material. Four formulations of the polymer were made by adding different amounts of UV stabilizer, energy quencher, and antioxident in a Brabender Plasticorder. The formulated polymers were molded in the form of sheets in a compression molder. Cut samples from the molded sheets were exposed in a weatherometer and tested on Instron Tensile Tester for strength and elongation. Specially molded samples of the formulated polymers were subjected to Charpy Impact Tests. In the second study, preliminary evaluations of adhesives for improvement of bonding between Teflon and stainless steel (SS) were performed. Kapton, a high temperature polyimide made by Dupont, and a rubber based adhesive made by Potter Paint Co., were evaluated against industrial quality epoxy, the current material used to bond Teflon and SS. The degreased surfaces of the SS discs were etched mechanically, with a few of these etched chemically. The surfaces of the SS discs were etched mechanically, with a few of these etched chemically. Bonding strengths were evaluated using lap shear tests on the Instron Tensile Tester for the samples bonded by Kapton and industrial quality epoxy. Bond strengths were also evaluated using a pull test on the Instron for the samples bonded by Potter adhesive (CWL-152) and industrial quality epoxy. Based on limited lap shear data, Kapton gave bond strength favorable compared to that of industrial epoxy. Based on limited pull test data, Kapton bonded and CWL-152 bonded samples showed poor strength compared to epoxy bonded sample.

Ray, Asit K.↗

Reducing dielectric loss and enhancing electrical insulation for multilayer polymer films by nanoconfined ion transport under high poling electric fields

High temperature polar polymers have demonstrated potential for good thermal stability and high dielectric constant at the same time. However, polarization of contaminated impurity ions in polar polymers, even at the ppm level, can significantly increase the dielectric loss at high temperature and low frequencies. One effective strategy to mitigate this problem is to multilayer them with a high temperature nonpolar dielectric polymer to confine impurity ion transport at the nanometer scale. In this study, confined ion transport in high temperature polycarbonate (HTPC)/poly(vinylidene fluoride) (PVDF) multilayer films under high AC electric fields was studied using a direct analytical simulation method. Different from the ion transport under low fields, the ion diffusion model failed to describe the ion transport under high electric fields. An exponential ion distribution profile, which was observed for the DC poling situation, was employed to implement the direct analytical simulation. Confined impurity ion transport under high AC fields was quantitatively understood. As the AC field increased, the mobile ion concentration decreased whereas the diffusion coefficient increased. The decrease of mobile ion concentration was explained by the blockage of impurity ions by the HTPC layers. This knowledge helped in the determination of optimal conditions to polarize impurity ions from the PVDF layers into the HTPC layers. After cooling below the glass transition temperature of HTPC, polarized impurity ions were locked inside the HTPC layers. As a result, increased discharge efficiency and enhanced electrical insulation (i.e., increased dielectric breakdown strength) were achieved for the polarized multilayer films.

36 MATERIALS SCIENCE↗

Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. In conclusion, this thorough study lays the groundwork for future development of PAN based electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Closed‐Loop Recycling of Poly(pentylene Adipate‐ co ‐Terephthalate) via Amine‐Catalyzed Methanolysis

Advancing circularity through effective chemical recycling strategies is essential for enabling the sustainable use of emerging biodegradable polyesters in film applications. In this context, poly(pentylene adipate-co-terephthalate) with a 40/60 adipate-to-terephthalate ratio (PPeAT60), a significantly stiffer and partially biobased copolyester recently reported by our team, offers improved mechanical performance and processability compared to commercial poly(butylene adipate-co-terephthalate), while providing a platform to evaluate advanced recycling approaches for film applications. Here, this study describes depolymerization of PPeAT60 through amine-catalyzed methanolysis, followed by the repolymerization of the recovered monomers. The resulting repolymerized material exhibited a molar mass distribution, chemical structure, and thermal stability comparable to the virgin polymer, confirming the technical feasibility of the methanolysis-based recycling route. Both polymers displayed nearly identical melting, glass transition, and decomposition temperatures, crystallinity, and modulus, demonstrating full structural and mechanical reproducibility after recycling. Variations in crystallization kinetics, elongation at break, and barrier properties likely arise from trace impurities (<1%) introduced during processing acting as nucleating and stress-inducing agents. Overall, these results demonstrate that PPeAT60 retains its key properties after chemical recycling, establishing methanolysis as a promising platform for recycling of this partially biobased polymer that may be able to replace both conventional polyolefins and PBAT in flexible packaging applications.

09 BIOMASS FUELS↗

Lead-free Cesium Europium Halide Perovskite Nanocrystals

Because of the toxicity of lead, searching for a lead-free halide perovskite semiconducting material with comparable optical and electronic properties is of great interest. Rare-earth-based halide perovskite represents a promising class of materials for this purpose. In this work, we demonstrate the solution-phase synthesis of single-crystalline CsEuCl 3 nanocrystals with a uniform size distribution centered around 15 nm. The CsEuCl 3 nanocrystals have photoluminescence emission centered at 435 nm, with a full width at half-maximum of 19 nm. Furthermore, CsEuCl 3 nanocrystals can be embedded in a polymer matrix that provides enhanced stability under continuous laser irradiation. Lead-free rare-earth cesium europium halide perovskite nanocrystals represent a promising candidate to replace lead halide perovskites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis, characterization, and polymerization of capped paddlewheel porous cages

Although paddlewheel-based structures are common among permanently porous metal–organic materials, suitable strategies for the isolation of metal node-terminated, capped paddlewheel-based cage structures remain limited. We explored the use of chelating dicarboxylate ligand derivates (esp) for the isolation of trimesate-linked cages, Mo 12 (btc) 4 (esp) 6 , that are structural analogs of the small octahedral pore of HKUST-1. The porosity of these novel cages is appreciably higher than that of previously reported structures of this type. We also demonstrate that pillaring the isolated cage with DABCO generated an amorphous polymer that featured exceptional thermal stability and enhanced porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fatty acid foams for nonselective physical removal of microplastics from aqueous solutions

Microplastics (MPs) are pervasive environmental contaminants whose removal from water remains a major challenge due to their small size, chemical diversity, and dynamic surface properties arising from environmental aging/weathering. Here, we present a concept of foam-based separation method that physically traps MPs in the foam phase using microtubular assemblies of 12-hydroxystearic acid. These foams are stabilized by anisotropic fatty acid microtubules formed in the presence of ethanolamine, which jam within the foam channels and suppress fluid drainage thereby enhancing MP retention and foam stability. MPs of different sizes, polymer compositions (including polystyrene, polypropylene, polyethylene terephthalate, and polytetrafluoroethylene), and weathered states were retained in the foam phase without requiring chemical modification or relying on chemical interactions between the fatty acid and MPs. Thermally induced transition of the fatty acid microtubules into nanomicelles above the characteristic phase transition temperature (∼35 °C) enables controlled foam collapse and recovery of trapped MPs. The cumulative removal efficiency can exceed 85% through multiple foaming cycles, matching predictions from a probabilistic retention model. This work shows that foams can provide a simple platform to trap MPs, thus providing a new physical-removal strategy that does not rely on the particles’ chemistry.

Guillot, Kennedy A. [Louisiana State Univ., Baton ↗

Structure-Property Study of Piezoelectricity in Polyimides

High performance piezoelectric polymers are of interest to NASA as they may be useful for a variety of sensor applications. Over the past few years research on piezoelectric polymers has led to the development of promising high temperature piezoelectric responses in some novel polyimides. In this study, a series of polyimides have been studied with systematic variations in the diamine monomers that comprise the polyimide while holding the dianhydride constant. The effect of structural changes, including variations in the nature and concentration of dipolar groups, on the remanent polarization and piezoelectric coefficient is examined. Fundamental structure-piezoelectric property insight will enable the molecular design of polymers possessing distinct improvements over state-of-the-art piezoelectric polymers including enhanced polarization, polarization stability at elevated temperatures, and improved processability.

Ounaies, Zoubeida↗

Dynamic Mechanical Characterization of Thin Film Polymer Nanocomposites

Many new materials are being produced for aerospace applications with the objective of maximizing certain ideal properties without sacrificing others. Polymer composites in various forms and configurations are being developed in an effort to provide lighter weight construction and better thermal and electrical properties and still maintain adequate strength and stability. To this end, thin film polymer nanocomposites, synthesized for the purpose of influencing electrical conductivity using metal oxide particles as filler without incurring losses in mechanical properties, were examined to determine elastic modulus and degree of dispersion of particles. The effects of various metal oxides on these properties will be discussed.

Herring, Helen M.↗

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗

Polymers in molten inorganic salt hydrate phase change materials: solubility and gelation

Inorganic salt hydrates are of interest as phase change materials (PCMs) for thermal energy storage because of their unique properties, such as high latent heats of fusion, moderate melting temperatures, high volumetric energy storage densities, and enhanced thermal conductivities compared to their organic counterparts. Because of the low viscosities of molten salt hydrates, the leakage and settling of solids can easily occur during their application. Polymers are promising candidates for preventing these issues. In addition, the non-flammability, non-volatility, and nontoxicity of many molten salt hydrates make them attractive options as “green” solvents for polymers. However, solutions of polymers in molten salt hydrates have rarely been studied and are poorly understood. The highly ionic environments in these materials created due to a scarcity of hydration water for ions leads to strong ionic interactions, with ramifications for polymer solubility and chain expansion. This Perspective article aims to focus on polymer solutions and gels in inorganic salt hydrates by comparing these systems with existing knowledge of polymers in traditional ionic liquids and aqueous salt solutions. To provide insight into the states of ions and water in molten salt hydrates and the degree of hydration of polymers in these solvents, infrared spectroscopy experiments have been performed, and the data are correlated with the temperature-responsive gelation of poly(vinyl alcohol), one candidate material currently used for the shape stabilization of inorganic PCMs. Finally, the thermal properties of inorganic salt hydrates and ionic liquids are compared and strategies for the shape stabilization of inorganic salt hydrates using polymers, through the formation of physical gels, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oligomers Terminated By Maleimide And Acetylene

Oligomeric molecules terminated with maleimide and acetylene groups synthesized and thermally treated to form cross-linked polymers exhibiting high or undetectable glass-transition temperatures and high thermo-oxidative stabilities. Compounds used to make thermally stable, glassy polymers.

St. Clair, Terry L.↗

Thermally stable and self-healable lignin-based polyester

The increased use of plastics and the associated environmental impact has catalyzed research on the development of bio-derived polymers. Bio-based polyesters have gained increased attention due to the abundance of their starting materials and ease of processing. Lignin is naturally occurring in biomass with rich carbon content, whose functionality and rigidity make it an ideal bio-derived candidate for bio-based polyesters. Herein, a lignin-based polyester with good thermal stability and self-repairability was synthesized from carboxylated lignin and epoxidized soybean oil. The synthesized lignin/epoxidized soybean oil (ESO) vitrimer was brittle such that its mechanical performance could not be recorded. However, when polyethylene glycol (PEG) was incorporated as a plasticizer, polymer samples exhibited acceptable ductility. From thermomechanical analysis of the synthesized polyesters, the plasticizer did not impair thermal stability of polymers, but greatly enhanced mechanical properties. Notably, all samples exhibited stability at high temperatures, and good glass transition temperatures (51.0 ± 0.9–78.0 ± 1.2 °C). The highest tensile strength (3.983 ± 0.1 MPa) and storage modulus (1463.67 ± 12.6 MPa) were recorded for the polyester containing 6 % w/w PEG. Moreover, the polymer samples exhibited self-healing capability at 180 °C. This work expands on valorization of lignin through the synthesis of bio-derived materials.

36 MATERIALS SCIENCE↗

Bead–Spring Simulation of Ionomer Melts—Studying the Effects of Chain-Length and Associating Group Fraction on Equilibrium Structure and Extensional Flow Behavior

Ionomers are associative polymers with diverse applications ranging from selective membranes and high-performance adhesives to abrasion- and chemical-resistant coatings, insulation layers, vacuum packaging, and foamed sheets. Within equilibrium melt, the ionic or associating groups are known to form thermally reversible, associative clusters whose presence can significantly affect the system’s mechanical, viscoelastic, and transport properties. It is, thus, of great interest to understand how to control such clusters’ size distribution, shape, and stability through the designed choice of polymer architecture and the ionic groups’ fraction, arrangement, and interaction strength. In this work, we represent linear associating polymers using a Kremer–Grest type bead–spring model and perform large-scale MD simulations to explore the effect of polymer chain-length (l) and fraction (f s ) of randomly placed associating groups on the size distribution and stability of formed clusters. We consider different chain-lengths (below and above entanglement), varying fractions of associating groups (represented by ‘sticky’ beads) between 5 and 20%, and a fixed sticky–sticky nonbond interaction strength of four times that between regular non-associating beads. For all melts containing associating groups the equilibrium structure factor S(q) displays a signature ionomer peak at low wave vector q whose intensity increases with increasing f s and l. The average cluster size Nc increases with f s . However, the effect of chain-length on Nc appears to be pronounced only at higher values of f s . Under extensional flows, the computed stress (and viscosity) is higher at higher f s and l regardless of strain rate. Beyond a critical strain rate, we observe fragmentation of the associative clusters, which has interesting effects on the stress/viscous response.

36 MATERIALS SCIENCE↗

Exceptional Electron-Rich Heteroaromatic Pentacycle for Ultralow Band Gap Conjugated Polymers and Photothermal Therapy

Stable redox-active conjugated molecules with exceptional electron-donating abilities are key components for the design and synthesis of ultralow band gap conjugated polymers. While hallmark electron-rich examples such as pentacene derivatives have been thoroughly explored, their poor air stability has hampered their broad incorporation into conjugated polymers for practical applications. Herein, we describe the synthesis of the electron-rich, fused pentacyclic pyrazino[2,3-b:5,6-b’]diindolizine (PDIz) motif and detail its optical and redox behavior. The PDIz ring system exhibits a lower oxidation potential and a reduced optical band gap than the isoelectronic pentacene while retaining greater air stability in both solution and the solid state. The enhanced stability and electron density, together with readily installed solubilizing groups and polymerization handles, allow for the use of the PDIz motif in the synthesis of a series of conjugated polymers with band gaps as small as 0.71 eV. Importantly; the tunable absorbance throughout the biologically relevant near-infrared I and II regions enables the use of these PDIz-based polymers as efficient photothermal therapeutic reagents for laser ablation of cancer cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of Arsenic Content in Water Using a Silver Coordination Polymer

In this report, we describe a practical method for the colorimetric determination of dissolved inorganic arsenic content in water samples, using a silver coordination polymer as the sensing material. We demonstrate that a crystalline polymer framework can be used to stabilize silver(I) ions, greatly reducing both photosensitivity and water solubility, while still affording sufficient reactivity to detect arsenic in water samples at low parts-per-billion (ppb) levels. Test strips fabricated with the silver-based polymer are shown to be effective for field tests of groundwater under real-world operating conditions and display performance that is competitive with commercially available mercury-based test strips. Spectroscopic methods are also used to probe the reaction products formed, in order to better understand the sensing mechanism. Thus, our work provides the foundation for an improved field test that could be deployed to help manage groundwater usage in regions where arsenic contamination is problematic but sophisticated lab testing is not readily available.

36 MATERIALS SCIENCE↗

Phenylated Polyimides With Greater Solubility

In experiments, 3,6-diphenylpyromellitic dianhydride monomer prepared and polymerized with several different diamines. Polyimides with pendent phenyl groups along polymer backbones considerably more soluble than PMDA-based materials. Increased solubility eases processing, providing increased potential use in variety of applications. Because most polymers soluble in organic solvents, usable in microelectronics applications. Excellent thermal stabilities and high transition temperatures make them ideally suited. Many polymers extremely rigid and useful as reinforcing polymers in molecular composites. More flexible compositions useful as matrix resins in carbon-reinforced composites.

Harris, Frank W.↗