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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

The lead ruthenate pyrochlore Pb2Ru2O6.5, in both high- and low-area forms, has been characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy, X-ray diffraction, cyclic voltammetry, and O2 reduction and generation kinetic-mechanistic studies. Mechanisms are proposed. Compounds in which part of the Ru is substituted with Ir have also been prepared. They exhibit somewhat better performance for O2 reduction in porous, gas-fed electrodes than the unsubstituted compound. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenate and plumbate out of the electrode. The O2 generation performance was improved with both types of electrodes. With a hydrogel overlayer, the O2 reduction performance was also improved.

Prakash, Jai↗

Modified Process For Formation Of Silicon Carbide Matrix Composites

Modified version of process for making SiC-fiber/SiC-matrix composite material reduces damage to SiC (SCS-6) fibers and to carbon-rich coatings on fibers. Modification consists of addition of second polymer-infiltration-and-pyrolysis step to increase carbon content of porous matrix before infiltration with liquid silicon or silicon alloy.

Behrendt, Donald R.↗

Molecular dynamics simulations of energy accommodation between gases and polymers for ultra-low thermal conductivity insulation

Determining the energy accommodation between gases and solids is essential to developing porous thermal insulation materials with ultra-low effective thermal conductivity that reduce energy use, greenhouse gas emissions, and fossil fuel consumption. The energy accommodation coefficients of most gases, however, have been rarely studied, especially with respect to solids that have relatively high thermal resistivity, e.g., polymers. Here, by using all-atom nonequilibrium molecular dynamics simulations, we reveal the accommodation coefficients of He, Ar, N 2 , and O 2 with polymers, mainly polystyrene. We find that their values are around 0.51, 0.72, 0.79, and 0.90, respectively, suggesting a critical reexamination of the commonly used theoretical maximum value of 1. We have also conducted experiments and validated the value for air, which is about 0.81. Such a change in accommodation coefficients can lead to a reduction of about 70%, 50%, 35%, and 20% in the thermal conductivity of He, Ar, N 2 , and O 2 gases in nano pores (below 100 nm) or at low pressures (below 1 millibar). With these new accommodation coefficients, we find that in a 10 nm pore with ambient pressure at 300 K, the gas thermal conductivity of He, Ar, N 2 , and O 2 in porous polystyrene can be as low as 9.7 × 10 –4 , 3.4 × 10 –4 , 7.3 × 10 –4 , and 8.5 × 10 –4 W·m –1 ·K –1 , respectively, which are two to three orders of magnitude lower than their bulk values, promising higher thermal resistivity of insulation materials. This work reveals the fundamental energy exchange between gases and polymers, providing important guidance for designing high-performance thermal insulation materials for various applications.

36 MATERIALS SCIENCE↗

Polymeric materials for unusual service conditions; Proceedings of the Conference, Moffett Field, Calif., November 29-December 1, 1972

Polymers for aircraft and spacecraft structures are considered, giving attention to novel foams and porous structures, aircraft nacelle composite structure technology, properties and processing of polyimidazoquinazoline composites, and the processing of organic matrices into structural composites. Other subjects discussed are related to high temperature resins and composites, elastomers for high temperature applications, fire retardant materials, polymers for critical pollution control, and polymers for critical medical use. Individual items are announced in this issue.

Golub, M. A.↗

Development of 3D Printing Techniques for Solid-State Lithium Batteries: Energy Storage Internship (Final Report)

The goal of this internship was to develop a solid polymer electrolyte with a suitable ionic conductivity and mechanical properties and integrate it with 3D printed cathode for solid state lithium batteries. While liquid electrolytes will have much higher conductivities and therefore higher power densities than solid electrolytes, batteries with such electrolytes suffer from extreme dendritic growth, short-circuiting, and general failure. Typically, batteries prevent this by including a solid yet porous separator somewhere between the anode and cathode to suppress dendritic growth. Solid polymer electrolyte acts as the conductive medium between electrodes as well as the separator that prevents failure from short-circuiting. The specific system explored is a vinyl ethylene carbonate (VEC) and polyethylene glycol diacrylate (PEGDA) mixed polymer solution using both 2,2’-azobis(2-methylpropionitrile) (AIBN) and Irgacure 819, respectively as thermal and photo- initiators. Electrochemical and rheological techniques were used to determine the optimal polymer solution and curing conditions. Through this research, multiple new pathways of exploration have been determined to create a usable solid polymer electrolyte through a combination of varying cure intensities and initiator concentrations.

25 ENERGY STORAGE↗

Manipulation of amorphous precursors to enhance zeolite nucleation

Crystallization in media comprised of amorphous precursors is becoming a more common phenomenon for numerous synthetic, biological, and natural materials that grow by a combination of classical and nonclassical pathways. Amorphous phases can exhibit a wide range of physicochemical properties that may evolve during the course of nucleation and crystal growth. This creates challenges for establishing causal relationships between amorphous precursor properties and their effect(s) on the selection of mechanistic pathways of crystallization and ultimately the properties of the crystalline product. In this study, we examine ways to manipulate the composition and colloidal stability of amorphous (alumino)silicate precursors that are prevalent in nanoporous zeolite syntheses. Changes in the amorphous precursor properties are evaluated on the basis of their ability to enhance rates of crystal formation. Here, we use fumed silica as the primary silicon source and examine the effects of infusing the source or growth medium with additional alkali metal, which serves as an inorganic structure-directing agent to facilitate the formation of porous crystal structures. We also assess the impact of adding a polymer additive, which reduces the colloidal stability of precursors, wherein we posit that the confined pockets of solution within the interstitial spaces of the precursor aggregates play an important role in regulating the rate of zeolite crystallization. Three commercially relevant zeolites (mordenite, SSZ-13, and ZSM-5) were selected for this study based on their diverse frameworks and methods of preparation. Here our findings reveal that alkali infusion significantly reduces the crystallization times for mordenite and SSZ-13, but has little impact on ZSM-5 synthesis. Conversely, we find that polymer addition markedly enhanced the rates of crystallization among all three zeolites, suggesting that this method may be a general approach to reduce zeolite synthesis times. Given the relatively high costs associated with commercial zeolite production, identifying new methods to improve the efficiency of hydrothermal syntheses can have significant practical implications beyond the fundamental benefits of developing new routes to tailor nonclassical crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-adsorbing porous thermo-responsive desiccants

Thermo-responsive hydrogel composite (TRHC) desiccants having high adsorption capacities, fast adsorption/desorption rates, and low regeneration temperatures (Treg) compared to traditional desiccants. TRHC desiccants may be synthesized by freeze drying. The porous structures resulting from freeze drying copolymers of thermo-responsive polymers and/or hygroscopic agents may be combined with hygroscopic inorganic salts, resulting in TRHC desiccants having superior performance properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fluid-like shock compression of dilute polymer nanocomposites

The shock Hugoniot of heterogenous mixtures of discrete particles has been experimentally investigated for porous agglomerates and fluids, while the study of full-density solids has been primarily limited to compressed powders and high-dimensional composites. By dispersing ceria nanoparticles in a polyethylene matrix, we are able to examine the hydrodynamic behavior of a nonporous, heterogenous solid in thermal equilibrium during weak shock compression. Phase-driven discontinuities in the Hugoniot particle velocity–shock velocity (u−D) relationship of pure polyethylene are replicated in the nanocomposites but are shifted to lower velocity and to higher pressure with higher particle concentration. The results are explained using an isothermal, two-velocity fluid model under the hydrodynamic approximation. The model, which assumes a theoretical equation-of-state for ceria and either a low-order or high-order fit to the measured polyethylene Hugoniot, reasonably predicts the Hugoniot for two different polyethylene/ceria nanocomposites. Using the model, the mixture Hugoniot is shown to be insensitive to the Hugoniot of the stiffer constituent when the moduli are sufficiently disparate, while dependence on particle density and volume fraction is preserved through fluid-like motion.

Moore, Nathan W. [Sandia National Laboratories (SN↗

Scalable method of fabricating structured polymers for passive daytime radiative cooling and other applications

A switchable light transmission module is disclosed that includes a substrate having a first surface defining at least part of an enclosed volume, a porous layer disposed on the first surface and in fluid communication with the enclosed volume, and a reservoir in fluid communication with the enclosed volume. The reservoir is configured to supply a fluid to the sealed volume such that the fluid contacts the porous layer. The fluid has a refractive index that is close to the refractive index of the porous layer, has a high wettability for the porous layer, and does not dissolve the porous layer. When in a dry state, voids in the porous layer are filled with air which has a much different refractive index than the porous layer itself, resulting in a surface that is reflective and not very transmissive. During wetting of the porous layer by the fluid, however, those voids are filled with the fluid, reducing the difference in refractive index across the polymer-fluid interfaces such that light scattering is negligible and the surface becomes light permeable.

Mandal, Jyotirmoy↗

Porous Polymeric Materials FY24 PDRD Final Report

Fillers and pore formers are used in many materials at Kansas City National Security Campus (KCNSC) to fine tune density and stiffness. Current off-the-shelf options such as urea and Expancel do not always provide the desired properties. This project investigated several methods for introducing porosity in rigid polymers such as epoxy and polyurethane. This work was done at partnering universities to identify a variety of methods to create porous polymeric materials. The University of Oklahoma (OU) investigated emulsion templating of epoxy, where the epoxy is mixed with a surfactant and water to form an emulsion. The emulsion is then molded and cured. During the cure process, water droplets evaporate to form porous structures. Total porosity can be tuned by changing the concentration of water added to the polymer. The University of Kansas (KU) investigated the synthesis of phenolic microballoons by spray drying, as well as methods of incorporating removable porogens into epoxy and polyurethane materials to create polymeric foams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub‐5 Ångstrom Porosity Tuning in Calixarene‐Derived Porous Liquids via Supramolecular Complexation Construction

Abstract Sub‐Ångstrom‐level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub‐5 Ångstrom scale is created via sophisticated porosity tuning in calixarene‐derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy‐, X‐ray‐, and neutron‐scattering techniques. The presence of permanent porosity in calixarene‐derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub‐5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. The approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

Li, Errui [Department of Chemistry University of T↗

Sub-5 Ångstrom Porosity Tuning in Calixarene-Derived Porous Liquids via Supramolecular Complexation Construction

Sub-Ångstrom-level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub-5 Ångstrom scale is created via sophisticated porosity tuning in calixarene-derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy-, X-ray-, and neutron-scattering techniques. The presence of permanent porosity in calixarene-derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub-5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. Further, the approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable synthesis of nanoporous atomically thin graphene membranes for dialysis and molecular separations via facile isopropanol-assisted hot lamination

Scalable graphene synthesis and facile large-area membrane fabrication are imperative to advance nanoporous atomically thin membranes (NATMs) for molecular separations. Although chemical vapor deposition (CVD) allows for roll-to-roll high-quality monolayer graphene synthesis, facile transfer with atomically clean interfaces to porous supports for large-area NATM fabrication remains extremely challenging. Sacrificial polymer scaffolds commonly used for graphene transfer typically leave polymer residues detrimental to membrane performance and transfers without polymer scaffolds suffer from low yield resulting in high non-selective leakage through NATMs. In this study, we systematically study the factors influencing graphene NATM fabrication and report on a novel roll-to-roll manufacturing compatible isopropanol-assisted hot lamination (IHL) process that enables scalable, facile and clean transfer of CVD graphene on to polycarbonate track etched (PCTE) supports with coverage ≥99.2%, while preserving support integrity/porosity. We demonstrate fully functional centimeter-scale graphene NATMs that show record high permeances (~2–3 orders of magnitude higher) and better selectivity than commercially available state-of-the-art polymeric dialysis membranes, specifically in the 0–1000 Da range. Our work highlights a scalable approach to fabricate graphene NATMs for practical applications and is fully compatible with roll-to-roll manufacturing processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Binder-Stabilized Carbon Fiber Hosts for High-Utilization Sodium–Polysulfide Flow Catholytes

Sodium-sulfur (Na-S) batteries hold promise as high-energy-density batteries for long-duration energy storage due to their high open circuit voltage and Earth-abundant active materials. However, low utilization of the sulfur active material limits the achievable specific capacity, especially when a liquid polysulfide catholyte is utilized. High-surface-area carbon materials demonstrate promise to increase sulfur utilization in a Na-S battery. To make the carbon host material applicable for a flow battery application, a binder is required to bind the carbon materials together and to a porous substrate. Here, we utilize a composite carbon paper electrode coated by polymer,carbon nanofibers (CNFs) and carbon black (CB). By varying the mass ratios of CNF to CB, we found that a 70/20/10 mass ratio of CNF/CB/binder provided the highest capacity (260 mAh g −1 compared to the baseline of 156 mAh g −1 ) and stable battery performance over 100 cycles. Analysis of the composite electrode and full cells reveals that the amount of CB in the composite electrode influences binder distribution, cell resistance, and full cell performance.

Lehmann, Michelle L. [Oak Ridge National Laborator↗

Development of a Self-calibrating Dissolved Oxygen Microsensor Array for the Monitoring and Control of Plant Growth in a Space Environment

Plant experiments in space will require active nutrient delivery concepts in which water and nutrients are replenished on a continuous basis for long-term growth. The goal of this study is to develop a novel microsensor array to provide information on the dissolved oxygen environment in the plant root zone for the optimum control of plant cultivation systems in the space environment. Control of water and oxygen is limited by the current state-of-the-art in sensor technology. Two capabilities of the new microsensor array were tested. First, a novel in situ self-diagnosis/self-calibration capability for the microsensor was explored by dynamically controlling the oxygen microenvironment in close proximity to an amperometric dissolved oxygen microsensors. A pair of integrated electrochemical actuator electrodes provided the microenvironments based on water electrolysis. Miniaturized thin film dissolved oxygen microsensors on a flexible polyimide (Kapton(Registered Trademark)? substrate were fabricated and their performances were tested. Secondly, measurements of dissolved oxygen in two representative plant growth systems were made, which had not been performed previously due to lack of proper sensing technology. The responses of the oxygen microsensor array on a flexible polymer substrate properly reflected the oxygen contents on the surface of a porous tube nutrient delivery system and within a particulate substrate system. Additionally, we demonstrated the feasibility of using a 4-point thin film microprobe for water contents measurements for both plant growth systems. mechanical flexibility, and self-diagnosis. The proposed technology is anticipated to provide a reliable sensor feedback plant growth nutrient delivery systems in both terrestrial environment and the microgravity environment during long term space missions. The unique features of the sensor include small size and volume, multiple-point sensing,

Kim, Chang-Soo↗

Amorphous fluorinated copolymer gas separation membranes

Membranes having a permselective active layer of a copolymerized perfluorinated monomer and an non-fluorinated alkylvinylester monomer demonstrate superior selective permeability performance for separating gas mixtures compared to membranes of exclusively perfluorinated polymers. Preferred active layer compositions are copolymers of perfluoro-2,2-dimethyl-1,3 dioxole (PDD) copolymerized with an alkylvinyl ester such as vinyl acetate, and vinyl pivalate, and with alkylvinyl esters that are substantially hydrolyzed to provide copolymerized vinyl alcohol functionality. The membranes can have a thin, high diffusion rate, “gutter layer” of a fluorinated polymer highly permeable to nitrogen positioned between the active layer and a porous support layer. A novel copolymer effective in selectively permeable membranes is a copolymer of PDD and an alkylvinyl ester compound having the formula H2C═CHOC(O)R1 in which R1 is a linear or branched alkyl group of from 2 to 5 carbon atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion power spectra as a window into dynamic materials architecture

Chemical recycling of commodity and specialty polymers presents a multifaceted challenge for industrial societies. On one hand, macromolecular architectures must be engineered to yield durable products that, on the other hand, rapidly deconstruct to recyclable monomers under pre-determined conditions. Polymer deconstruction is a chemical process that requires deep understanding of molecular reactivity in heterogeneous media, where porous material architectures evolve in both space and time. To build this understanding, we develop herein experimental and analytical methods describing sets of diffusive eigenmodes that exist within time-varying, non-Euclidean boundary conditions, a situation commonly encountered in the reactive deconstruction of polymers where chain fragments splay, alter their local dynamics, and evolve in their confinement of reacting media. Diffusion power spectra, discerned experimentally by NMR, yield polymer and solvent frequency-domain velocity autocorrelation functions that are analyzed in the context of physical models for chemical reactions parameterized with fractal mathematics. The results connect local motion in polymers to chemical reactivity during acidolysis of circular elastomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of Disordered Cocontinuous Phases by Randomly Linked Star Copolymers

Cocontinuous polymeric nanostructures have garnered significant interest due to their ability to combine different properties of two separate polymer domains. Randomly linked copolymer networks have proven to be especially robust for formation of disordered cocontinuous phases across wide composition ranges (≈30 wt % or more). While theoretical treatments of microphase-separated networks have focused primarily on the role of random elastic forces imposed on the self-assembled nanostructures by virtue of the network architecture, experimental studies seeking to disentangle these contributions from other potential effects, such as dispersity in preferred interfacial curvatures, have been scarce. To provide insight into this matter, we here study the self-assembly of randomly linked star copolymers (RSCs), constructed by linking premade polymer arms of polystyrene (PS) and poly(d,l-lactide) (PLA) using 3, 4, and 6-functional connectors. This architecture yields similar distributions of preferred curvature as networks made using corresponding difunctional strands, but lacks the elastic forces imposed by a network architecture. Gravimetry and small-angle X-ray scattering, coupled with scanning electron microscopy, were performed to identify the percolation of PS/PLA RSCs. Remarkably, the 4-arm RSC system exhibited a disordered cocontinuous window of ≈25 wt %, indicating that dispersity in preferred curvature can in some cases be sufficient to robustly drive formation of this morphology. However, the other RSC architectures showed smaller cocontinuous ranges, which we interpret in terms of the influence of homopolymer stars in the 3-arm case and the narrower distribution of preferred interfacial curvatures in the 6-arm case. Finally, thin layers of interconnected porous PS were achieved by solution-processing, suggesting that RSCs have the potential to serve as a robust and easily processable cocontinuous polymeric nanomaterials in both bulk and membrane geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗