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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Flower-shaped 2D crystals grown in curved fluid vesicle membranes

Abstract The morphologies of two-dimensional (2D) crystals, nucleated, grown, and integrated within 2D elastic fluids, for instance in giant vesicle membranes, are dictated by an interplay of mechanics, permeability, and thermal contraction. Mitigation of solid strain drives the formation of crystals with vanishing Gaussian curvature (i.e., developable domain shapes) and, correspondingly, enhanced Gaussian curvature in the surrounding 2D fluid. However, upon cooling to grow the crystals, large vesicles sustain greater inflation and tension because their small area-to-volume ratio slows water permeation. As a result, more elaborate shapes, for instance, flowers with bendable but inextensible petals, form on large vesicles despite their more gradual curvature, while small vesicles harbor compact planar crystals. This size dependence runs counter to the known cumulative growth of strain energy of 2D colloidal crystals on rigid spherical templates. This interplay of intra-membrane mechanics and processing points to the scalable production of flexible molecular crystals of controllable complex shape.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Water as a gas separation membrane

Efficient gas separation membranes are essential for carbon capture, biogas upgrading, and hydrogen purification. Inspired by how plants absorb CO 2 through water, we present a membrane platform that uses liquid water as the selective layer. Hydrophilic sub-100-nm pores stabilize water through strong capillary forces, enabling operation at feed pressures above 72 bar under dry and humid conditions. Selectivity is governed by gas solubility in water, while permeance is tuned by adjusting the water layer thickness. Reducing this thickness below 200 nm yields CO 2 permeances up to 11,600 gas permeation units with CO 2 :N 2 , CO 2 :CH 4 , and CO 2 :H 2 selectivities of 40, 26, and 31, respectively, surpassing the performance of state-of-the-art membranes. Operation is sustained for over a week without water loss, and performance scales using commercially available porous polymer supports under mixed-gas crossflow conditions. Water’s dissolution-based transport avoids saturation and reaction-rate limits, enabling a robust, high-performance, and environmentally benign gas separation platform.

08 HYDROGEN↗
DOE OSTI2023

Tailoring planar slip to achieve pure metal-like ductility in body-centred-cubic multi-principal element alloys

Uniform tensile ductility (UTD) is crucial for the forming/machining capabilities of structural materials. Normally, planar-slip induced narrow deformation bands localize the plastic strains and hence hamper UTD, particularly in body-centred-cubic (bcc) multi-principal element high-entropy alloys (HEAs), which generally exhibit early necking (UTD < 5%). Here we demonstrate a strategy to tailor the planar-slip bands in a Ti-Zr-V-Nb-Al bcc HEA, achieving a 25% UTD together with nearly 50% elongation-to-failure (approaching a ductile elemental metal), while offering gigapascal yield strength. The HEA composition is designed not only to enhance the B2-like local chemical order (LCO), seeding sites to disperse planar slip, but also to generate excess lattice distortion upon deformation-induced LCO destruction, which promotes elastic strains and dislocation debris to cause dynamic hardening. Further, this encourages second-generation planar-slip bands to branch out from first-generation bands, effectively spreading the plastic flow to permeate the sample volume. Moreover, the profuse bands frequently intersect to sustain adequate work-hardening rate (WHR) to large strains. Our strategy showcases the tuning of plastic flow dynamics that turns an otherwise-undesirable deformation mode to our advantage, enabling an unusual synergy of yield strength and UTD for bcc HEAs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Lignin deconstruction by anaerobic fungi

Abstract Lignocellulose forms plant cell walls, and its three constituent polymers, cellulose, hemicellulose and lignin, represent the largest renewable organic carbon pool in the terrestrial biosphere. Insights into biological lignocellulose deconstruction inform understandings of global carbon sequestration dynamics and provide inspiration for biotechnologies seeking to address the current climate crisis by producing renewable chemicals from plant biomass. Organisms in diverse environments disassemble lignocellulose, and carbohydrate degradation processes are well defined, but biological lignin deconstruction is described only in aerobic systems. It is currently unclear whether anaerobic lignin deconstruction is impossible because of biochemical constraints or, alternatively, has not yet been measured. We applied whole cell-wall nuclear magnetic resonance, gel-permeation chromatography and transcriptome sequencing to interrogate the apparent paradox that anaerobic fungi (Neocallimastigomycetes), well-documented lignocellulose degradation specialists, are unable to modify lignin. We find that Neocallimastigomycetes anaerobically break chemical bonds in grass and hardwood lignins, and we further associate upregulated gene products with the observed lignocellulose deconstruction. These findings alter perceptions of lignin deconstruction by anaerobes and provide opportunities to advance decarbonization biotechnologies that depend on depolymerizing lignocellulose.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Furthermore, corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells, and batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li + ). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li + partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium-metal batteries for electric mobility.

42 ENGINEERING↗
DOE OSTI2022

A detailed map of Higgs boson interactions by the ATLAS experiment ten years after the discovery

The standard model of particle physics describes the known fundamental particles and forces that make up our Universe, with the exception of gravity. One of the central features of the standard model is a field that permeates all of space and interacts with fundamental particles. The quantum excitation of this field, known as the Higgs field, manifests itself as the Higgs boson, the only fundamental particle with no spin. In 2012, a particle with properties consistent with the Higgs boson of the standard model was observed by the ATLAS and CMS experiments at the Large Hadron Collider at CERN. Since then, more than 30 times as many Higgs bosons have been recorded by the ATLAS experiment, enabling much more precise measurements and new tests of the theory. Here, on the basis of this larger dataset, we combine an unprecedented number of production and decay processes of the Higgs boson to scrutinize its interactions with elementary particles. Interactions with gluons, photons, and W and Z bosons—the carriers of the strong, electromagnetic and weak forces—are studied in detail. Interactions with three third-generation matter particles (bottom (b) and top (t) quarks, and tau leptons (τ)) are well measured and indications of interactions with a second-generation particle (muons, μ) are emerging. These tests reveal that the Higgs boson discovered ten years ago is remarkably consistent with the predictions of the theory and provide stringent constraints on many models of new phenomena beyond the standard model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗
DOE OSTI2022

Altering the localization and toxicity of arsenic in rice grain

Previous work has shown that inorganic As localizes in rice bran whereas DMA localizes in the endosperm, but less is known about co-localization of As and S species and how they are affected by growing conditions. We used high-resolution synchrotron X-ray fluorescence imaging to image As and S species in rice grain from plants grown to maturity in soil (field and pot) and hydroponically (DMA or arsenite dosed) at field-relevant As concentrations. In hydroponics, arsenite was localized in the ovular vascular trace (OVT) and the bran while DMA permeated the endosperm and was absent from the OVT in all grains analyzed, and As species had no affect on S species. In pot studies, soil amended with Si-rich rice husk with higher DMA shifted grain As into the endosperm for both japonica and indica ecotypes. In field-grown rice from low-As soil, As localized in the OVT as arsenite glutathione, arsenite, and DMA. Results support a circumferential model of grain filling for arsenite and DMA and show Si-rich soil amendments alter grain As localization, potentially lessening risk to rice consumers.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Slippery liquid infused porous surface (SLIPS) condensers for high efficiency air gap membrane distillation

Abstract To address growing water scarcity, we must improve the energy efficiency of thermal desalination technologies such as air gap membrane distillation. However, promising functional materials such as slippery liquid infused porous surfaces have not yet implemented for any desalination technology. Here, we fabricate and test slippery liquid infused porous surfaces (using Krytox 16,256 lubricant and CuO nanostructures) in an air gap membrane distillation apparatus. System-level transport models, validated by experimental data, establish a framework for improving performance through enhanced condensation surfaces. Results are obtained across a range of temperatures (50–80 °C), salinities (5–105 g/kg), and module lengths. We find that small air gap thickness and efficient droplet shedding significantly improves performance. The CuO Krytox process achieves these with a conductive-self-limiting coating, high nanostructure rugosity, strong covalent and metallic bonding, high hydrophobicity, minimal droplet pinning sites, and ultra-low contact angle hysteresis. The greatest efficiency enhancement from SLIPS is derived from the improved droplet shedding, which allows for reduced gap sizes without flooding, and is further augmented by the increased permeate flux.

Yogi, Yashwant S.↗
DOE OSTI2024

Pushing the limits of size selectivity in nanoscale solute separations

Transport of a spherical solute through a cylindrical pore has been modelled for decades using well-established hindered transport theory, predicting solutes with a size smaller than the pore to be rejected nonetheless because of convective and diffusive hindrance; this rejection mechanism prevents extremely sharp solute separations by a membrane. Whereas the model has been historically verified, solute transport through near-perfect isoporous membranes may finally overcome this limitation. Here, in this study, encouraging solute rejections are achieved using nanofabricated, defect-free silicon nitride isoporous membranes. The membrane is challenged by a recirculated feed to increase the opportunity for interactions between solutes and the pore array. Results show the membrane completely reject solutes with greater size than the pore size while effectively allowing smaller solutes to permeate through. With effectively increasing the number of interactions, we propose that a steeper size-selective rejection curve may be achieved. With this traditional hurdle overcome, there is new promise for unprecedented membrane separations through judicious process design and extremely tight pore-size distributions.

Gao, Feng↗
DOE OSTI2020

Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass

Several deep eutectic solvents (DESs) have been demonstrated to be highly effective for lignocellulosic biomass pretreatment, combining the advantages of simple synthesis, relatively low chemical cost and better biocompatibility. However, low biomass loading that is usually involved with DES pretreatment hinders its practical use. Here, a twin-screw extruder was used for pretreating biomass sorghum bagasse at solid loadings up to 50%, mediated by a neutral-pH DES, choline chloride : glycerol (ChCl : Gly). This continuous extrusion process led to high glucose and xylose yields of >85% from enzymatic saccharification of the pretreated sorghum. A combination of microscopic, spectroscopic, and X-ray diffraction analyses demonstrate a high degree of defibration and disruption of the biomass cell wall structures; however, little or no change in chemical compositions. Further results from gel permeation chromatographic (GPC) and nuclear magnetic resonance (NMR) spectroscopic analyses indicate that ChCl : Gly-mediated extrusion preserved the basic lignin structural characteristics with no significant differences between extruded biomass at a solid loading of 30% and 50%. This study demonstrates the potential of DES-mediated extrusion as a highly effective continuous high-solid biomass pretreatment technology for industrially relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A 3D nm-thin biomimetic membrane for ultimate molecular separation

Multi-functional membranes with high permeance and selectivity that can mimic nature's designs have tremendous industrial and bio-medical applications. In this paper, we report a novel concept of a 3D nanometer (nm)-thin membrane that can overcome the shortcomings of conventional membrane structures. Our 3D membrane is composed of two three-dimensionally interwoven channels that are separated by a continuous nm-thin amorphous TiO 2 layer. This 3D architecture dramatically increases the surface area by 6000 times, coupled with an ultra-short diffusion distance through the 2–4 nm-thin selective layer that allows for ultrafast gas and water transport, ~900 l m –2 h –1 bar –1 . The 3D membrane also exhibits a very high ion rejection (R ~ 100% for potassium ferricyanide) due to the combined size- and charge-based exclusion mechanisms. The combination of high ion rejection and ultrafast permeation makes our 3DM superior to the state-of-the-art high-flux membranes whose performances are limited by the flux-rejection tradeoff. Furthermore, its ultimate Li+ selectivity over polysulfide or gas can potentially solve major technical challenges in energy storage applications, such as lithium–sulfur or lithium–O 2 batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mesoscopic analyses of the impact of morphology and operating conditions on the transport resistances in a proton-exchange-membrane fuel-cell catalyst layer

Exploring the origins of local transport resistance and characterizing the oxygen transport resistances in the catalyst layer (RCL) are critical for cost reduction. In this paper, a comprehensive mesoscopic model for simulating coupled transport processes of oxygen and water vapor for different structural parameters under different operating conditions in reconstructed microstructures is proposed. The local transport resistance is calculated after achieving the limiting current density and the effective diffusivity of oxygen. The results demonstrate that RCL increases greatly with decreasing platinum loading (LPt) and the transport resistances in other components of the cell dominate for high-loadings. Both the reduced oxygen permeation coefficient in the ionomer thin-film and the adsorption resistance account for the origins of local transport resistance. The local transport resistance increases with the bare carbon ratio for a constant LPt and Pt/C ratio due to the decreased effective ionomer surface, and increases with the I/C ratio due to the increased ionomer thickness and decreased Knudsen diffusivity. Due to the presence of liquid water, a slight decrease followed by an increase of the local transport resistance versus relative humidity is obtained. The contribution of ionomer thin-films to RCL is more sensitive to liquid saturation compared with that of pores. This journal is

Mu, YT↗
DOE OSTI2021

Elucidating the mechanisms of enhanced lignin bioconversion by an alkali sterilization strategy

Biological lignin valorization represents an emerging green approach to upgrade lignin for sustainable and economic biorefineries. However, lignin generally exhibits poor water solubility and inhomogeneous distribution in an aqueous medium, significantly limiting its bioconversion efficiency. Herein, we develop a novel alkali sterilization strategy to effectively enhance the dispersion and fermentation performance of lignin substrates. The colloidal particle size and molecular structure variations of lignin during the sterilization were thoroughly investigated to reveal the mechanisms of enhanced fermentation performance. Results showed that alkali sterilization achieved a completely aseptic effect when mixing lignin medium at an initial pH of 12.7 for 24 h. Dynamic light scattering (DLS) analysis demonstrated that the hydrodynamic volume of colloidal lignin particles decreased by 96.3% by alkali sterilization compared with the conventional thermal sterilization. Moreover, lignin characterizations by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) suggested that alkali sterilization modified the lignin molecular structure by generating 50% more hydrophilic carboxyl groups, reducing the weight-average molecular weight (M w ) by 23.0%, and narrowing the molar-mass dispersity (D M ) by 23.8%. The generation of lignin substrates with more uniform distribution and lower molecular weight improved Rhodococcus opacus PD630 cell growth and metabolism. Microbial cell amount, lignin degradation, and lipid production in alkali sterilized medium increased by 309%, 30.3%, and 48.3%, respectively, compared to those in thermally sterilized medium. These results clearly demonstrated that alkali sterilization dramatically improved the lignin bioconversion performance. Furthermore, this work presents a facile and effective sterilization strategy to overcome inhomogeneous lignin distribution in aqueous fermentation media, showing great potentials as a platform technique for promoting biological lignin valorization.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Strikingly high amount of tricin-lignin observed from vanilla (Vanilla planifolia) aerial roots

Lignin has attracted tremendous interest as a renewable resource for biofuels, biomaterials, and chemicals especially in the era of bio-based refineries. The structural studies of lignin play an essential role in both understanding the nature and biosynthesis of these polymers and optimizing their valorization values. In this study, we have investigated the structures of lignin from different tissues—aerial roots, nodes, internodes, and seeds, from vanilla (Vanilla planifolia) by using gel permeation chromatography (GPC), heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance (NMR), and 31P NMR. An unusual tricin-lignin was observed in the aerial roots of vanilla with an strikingly high level of tricin unit, whereas the lignin from the nodes and internodes displayed traditional S/G type lignin with only 4–10% tricin abundance. The aerial roots lignin is primarily composed of β-O-4' alkyl-aryl ether substructures (96% of linkages) in comparison to 65 and 73% in the nodes and internodes lignin, respectively. Additionally, thioacidolysis quantification results showed that lignin from aerial roots has 29.1 mg g -1 tricin, about 3- to 5-fold higher than the lignins isolated from nodes (10.1 mg g -1 ) and internodes (6.9 mg g -1 ). This communication of a particularly high level of tricin-lignin in vanilla plant has important impacts including: (1) the presence of the high amount of tricin as part of lignin from aerial roots could play a vital role for the valorization of lignin, even tricin itself, as a feedstock for value-added chemicals and commodities; and (2) it could open new ways to scientists to design and engineer the structure of tricin-lignin, or lignin in general, to confer plants with new or improved properties due to the plasticity of lignification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Design, synthesis, and characterization of vinyl-addition polynorbornenes with tunable thermal properties

Unfunctionalized vinyl-addition polynorbornene (VAPNB) possesses many outstanding properties such as high thermal, chemical, and oxidative stability. These features make VAPNB a promising candidate for many engineering applications. However, VAPNB has a small service window between its glass transition temperature (T g ) and decomposition temperature (T d ), and it cannot be readily processed in a melt state. In this work, we demonstrate that the service window of VAPNBs can be tailored through the use of norbornene monomers bearing alkyl, aryl, and aryl ether substituents. The vinyl addition homopolymerization and copolymerization of these functionalized norbornyl-based monomers yielded VAPNBs with high T' g s (>150 °C) and large service windows (T d –T g > 100 °C), which are comparable to other commercial engineering thermoplastics. To further establish the feasibility of melt processing, a functionalized VAPNB material with T g = 209 °C and a service window of 170 °C was successfully extruded and molded into bars. Subsequent characterization of the bars by dynamic mechanical analysis (DMA), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography (GPC) revealed only minor signs of polymer degradation. Furthermore, these studies suggest that substituted VAPNBs could be developed into a new class of engineering thermoplastics that is compatible with workhorse melt processing techniques such as extrusion and injection molding, as well as emerging techniques such as extrusion-based 3D printing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗