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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 811 records · Page 45

Protocols for isolating and characterizing polysaccharides from plant cell walls: a case study using rhamnogalacturonan-II

Abstract Background In plants, a large diversity of polysaccharides comprise the cell wall. Each major type of plant cell wall polysaccharide, including cellulose, hemicellulose, and pectin, has distinct structures and functions that contribute to wall mechanics and influence plant morphogenesis. In recent years, pectin valorization has attracted much attention due to its expanding roles in biomass deconstruction, food and material science, and environmental remediation. However, pectin utilization has been limited by our incomplete knowledge of its structure. Herein, we present a workflow of principles relevant for the characterization of polysaccharide primary structure using nature’s most complex polysaccharide, rhamnogalacturonan-II (RG-II), as a model. Results We outline how to isolate RG-II from celery and duckweed cell walls and from red wine using chemical or enzymatic treatments coupled with size-exclusion chromatography. From there, we applied mass spectrometry (MS)-based techniques to determine the glycosyl residue and linkage compositions of the intact RG-II and derived oligosaccharides including special considerations for labile monosaccharides. In doing so, we demonstrated that in the duckweed Wolffiella repanda the arabinopyranosyl (Ara p ) residue of side chain B is substituted at O- 2 with rhamnose. We used electrospray-MS techniques to identify non-glycosyl modifications including methyl-ethers, methyl-esters, and acetyl-esters on RG-II-derived oligosaccharides. We then showed the utility of proton nuclear magnetic resonance spectroscopy ( 1 H-NMR) to investigate the structure of intact RG-II and to complement the RG-II dimerization studies performed using size-exclusion chromatography. Conclusions The complexity of pectic polysaccharide structures has hampered efforts aimed at their valorization. In this work, we used RG-II as a model to demonstrate the steps necessary to isolate and characterize polysaccharides using chromatographic, MS, and NMR techniques. The principles can be applied to the characterization of other saccharide structures and will help inform researchers on how saccharide structure relates to functional properties in the future.

09 BIOMASS FUELS↗

Upcycling Linear Low-Density Polyethylene Waste into Graphene for High Mass Loading Supercapacitors

Upcycling plastic into advanced carbons, such as graphene and porous carbon, offers attractive options to manage waste streams by converting the plastic into carbon electrode materials for energy storage devices. Linear low density polyethylene (LLDPE) is firstly bulk-oxidized with a facile and scalable method and then carbonized and catalyticlly graphenized into porous graphene materials. The LLDPE derived graphene (LLDPE-G) has a BET specific surface area up to 1800 m2/g and Raman ID/IG ratio of 0.85. When used as electrode material for symmetric supercapacitor, LLDPE-G possesses outstanding specific capacitance and excellent areal capacitance. Moreover, LLDPE-G exhibits exceptional cycling stability with capacitance retention of 95.8% after 100,000 cycles. Last but not least, KCl is recycled and reused over 3 cycles with material quality and electrocapacitive performance of LLDPE-G retained and verified after each cycle.

Gao, Yuan↗

Transonic transport study: Economics

An economic analysis was performed to evaluate the impact of advanced materials, increased aerodynamic and structural efficiencies, and cruise speed on advanced transport aircraft designed for cruise Mach numbers of .90, .98, and 1.15. A detailed weight statement was generated by an aircraft synthesis computer program called TRANSYN-TST; these weights were used to estimate the cost to develop and manufacture a fleet of aircraft of each configuration. The direct and indirect operating costs were estimated for each aircraft, and an average return on investment was calculated for various operating conditions. There was very little difference between the operating economics of the aircraft designed for Mach numbers .90 and .98. The Mach number 1.15 aircraft was economically marginal in comparison but showed significant improvements with the application of carbon/epoxy structural material. However, the Mach .90 and Mach .98 aircraft are the most economically attractive vehicles in the study.

Smith, C. L.↗

Simulation of solidification in a Bridgman cell

Bridgman-type crystal growth techniques are attractive methods for producing homogeneous, high-quality infrared detector and junction device materials. However, crystal imperfections and interface shapes still must be controlled through modification of the temperature and concentration gradients created during solidification. The objective of this investigation was to study the temperature fields generated by various cell and heatpipe configurations and operating conditions. Continuum's numerical model of the temperature, species concentrations, and velocity fields was used to describe the thermal characteristics of Bridgman cell operation.

Dakhoul, Y. M.↗

Thermal aging effects in refractory metal alloys

The alloys of niobium and tantalum are attractive from a strength and compatibility viewpoint for high operating temperatures required in materials for fuel cladding, liquid metal transfer, and heat pipe applications in space power systems that will supply from 100 kWe to multi-megawatts for advanced space systems. To meet the system requirements, operating temperatures ranging from 1100 to 1600 K have been proposed. Expected lives of these space power systems are from 7 to 10 yr. A program is conducted at NASA Lewis to determine the effects of long-term, high-temperature exposure on the microstructural stability of several commercial tantalum and niobium alloys. Variables studied in the investigation include alloy composition, pre-age annealing temperature, aging time, temperature, and environment (lithium or vacuum), welding, and hydrogen doping. Alloys are investigated by means of cryogenic bend tests and tensile tests. Results show that the combination of tungsten and hafnium or zirconium found in commercial alloys such as T-111 and Cb-752 can lead to aging embrittlement and increased susceptibility to hydrogen embrittlement of ternary and more complex alloys. Modification of alloy composition helps to eliminate the embrittlement problem.

Stephens, J. R.↗

Thermal aging effects in refractory metal alloys

The alloys of niobium and tantalum are attractive from a strength and compatibility viewpoint for high operating temperatures required in materials for fuel cladding, liquid metal transfer, and heat pipe applications in space power systems that will supply from 100 kWe to multi-megawatts for advanced space systems. To meet the system requirements, operating temperatures ranging from 1100 to 1600 K have been proposed. Expected lives of these space power systems are from 7 to 10 yr. A program is conducted at NASA Lewis to determine the effects of long-term, high-temperature exposure on the microstructural stability of several commercial tantalum and niobium alloys. Variables studied in the investigation include alloy composition, pre-age annealing temperature, aging time, temperature, and environment (lithium or vacuum), welding, and hydrogen doping. Alloys are investigated by means of cryogenic bend tests and tensile tests. Results show that the combination of tungsten and hafnium or zirconium found in commercial alloys such as T-111 and Cb-752 can lead to aging embrittlement and increased susceptibility to hydrogen embrittlement of ternary and more complex alloys. Modification of alloy composition helps to eliminate the embrittlement problem.

Stephens, Joseph R.↗

Better PFAE's From Direct Fluorination

New low-molecular-weight perfluoroalkylethers (PFAE's) synthesized by direct fluorination in experimental study. Correlated viscosity and oxidation characteristics of PFAE's with structures to evaluate suitability as high-temperature lubricants and hydraulic fluids. Direct fluorination process attractive because it often involves single-step reaction and uses cheap starting materials. Versatile: produces highly branched ethers as well as polyethers containing more than two sequential carbon atoms in polymer chains. Such molecules cannot be made by conventional techniques.

Jones, W. R., Jr.↗

NASA Space applications of high-temperature superconductors

The application of superconducting technology in space has been limited by the requirement of cooling to near liquid helium temperatures. The only means of obtaining these temperatures has been with cryogenic fluids which severely limit mission lifetime. The development of materials with superconducting transition temperatures above 77 K has made superconducting technology more attractive and feasible for employment in aerospace systems. Here, potential applications of high temperature superconducting technology in cryocoolers, remote sensing, communications, and power systems are discussed.

Heinen, Vernon O.↗

Micro-opto-mechanical devices and systems using epitaxial lift off

The integration of high quality, single crystal thin film gallium arsenide (GaAs) and indium phosphide (InP) based photonic and electronic materials and devices with host microstructures fabricated from materials such as silicon (Si), glass, and polymers will enable the fabrication of the next generation of micro-opto-mechanical systems (MOMS) and optoelectronic integrated circuits. Thin film semiconductor devices deposited onto arbitrary host substrates and structures create hybrid (more than one material) near-monolithic integrated systems which can be interconnected electrically using standard inexpensive microfabrication techniques such as vacuum metallization and photolithography. These integrated systems take advantage of the optical and electronic properties of compound semiconductor devices while still using host substrate materials such as silicon, polysilicon, glass and polymers in the microstructures. This type of materials optimization for specific tasks creates higher performance systems than those systems which must use trade-offs in device performance to integrate all of the function in a single material system. The low weight of these thin film devices also makes them attractive for integration with micromechanical devices which may have difficulty supporting and translating the full weight of a standard device. These thin film devices and integrated systems will be attractive for applications, however, only when the development of low cost, high yield fabrication and integration techniques makes their use economically feasible. In this paper, we discuss methods for alignment, selective deposition, and interconnection of thin film epitaxial GaAs and InP based devices onto host substrates and host microstructures.

Camperi-Ginestet, C.↗

High Volume Fraction Carbon Nanotube Composites for Aerospace Applications

Reported nanoscale mechanical properties of carbon nanotubes (CNTs) suggest that their use may enable the fabrication of significantly lighter structures for use in space applications. To be useful in the fabrication of large structures, however, their attractive nanoscale properties must be retained as they are scaled up to bulk materials and converted into practically useful forms. Advances in CNT production have significantly increased the quantities available for use in manufacturing processes, but challenges remain with the retention of nanoscale properties in larger assemblies of CNTs. This work summarizes recent progress in producing carbon nanotube composites with tensile properties approaching those of carbon fiber reinforced polymer composites. These advances were achieved in nanocomposites with CNT content of ~70% by weight. The processing methods explored to yield these CNT composite properties will be discussed, as will the characterization and test methods that were developed to provide insight into the factors that contribute to the enhanced tensile properties. Technology maturation was guided by parallel advancements in computational modeling tools that aided in the interpretation of experimental data.

Siochi, Emilie J.↗

Effect of Urea Links in the Backbone of Polyimide Aerogels

Flexible, conformal polyimide aerogels with low density, good mechanical properties and high surface areas have attracted much attention for many potential applications such as lightweight antenna substrates, insulating materials for launch vehicles, inflatable structures, aircraft or space suits. Development and improvements to fabrication of polyimide aerogel thin films have been reported over the last decade to meet the needs of many of these applications. However, most starting materials are expensive. In this research, we utilized commercially available, low cost monomers including 4,4’-bis(4-aminophenoxy)propane (BAPP) and 3,3’,4,4’-benzophenone tetracarboxylic dianhydride (BTDA), and 4,4-methylene diphenyl di-isocyanate (MDI) in fabricating polyimide (PI) and polyimide-urea (PIU), which were then cross-linked with 1,3,5-tris(4-aminophenoxy)benzene (TAB). It was found that the addition of MDI into the PI chains not only maintained the flexibility of the aerogel films, but also enhanced the film casting, allowing the production on pilot scale. With the capability in producing robust films at affordable cost, application of the PIU aerogel films can be expanded to terrestrial goods such as winter clothing, or pipe wrapping, etc. In addition, the presence of only a small addition of the urea links in the polyimide chains in PIU aerogels led to lower shrinkage when compared to the corresponding PI aerogels, leading to lower density

Baochau N. Nguyen↗

Optical Sensors for Biomolecules Using Nanoporous Sol-Gel Materials

An important consideration for space missions to Mars is the ability to detect biosignatures. Solid-state sensing elements for optical detection of biological entities are possible using sol-gel based biologically active materials. We have used these materials as optical sensing elements in a variety of bioassays, including immunoassays and enzyme assays. By immobilizing an appropriate biomolecule in the sol-gel sensing element, we have successfully detected analytes such as amino acids and hormones. In the case of the amino acid glutamate, the enzyme glutamate dehydrogenase was the immobilized molecule, whereas in the case of the hormone cortisol, an anti-cortisol antibody was immobilized in the sensing element. In this previous work with immobilized enzymes and antibodies, excellent sensitivity and specificity were demonstrated in a variety of formats including bulk materials, thin films and fibers. We believe that the sol-gel approach is an attractive platform for bioastronautics sensing applications because of the ability to detect a wide range of entities such as amino acids, fatty acids, hopanes, porphyrins, etc. The sol-gel approach produces an optically transparent 3D silica matrix that forms around the biomolecule of interest, thus stabilizing its structure and functionality while allowing for optical detection. This encapsulation process protects the biomolecule and leads to a more "rugged" sensor. The nanoporous structure of the sol-gel matrix allows diffusion of small target molecules but keeps larger, biomolecules immobilized in the pores. We are currently developing these biologically active sol-gel materials into small portable devices for on-orbit cortisol detection

Fang, Jonathan↗

A thermochemical study of iron aluminate-based materials: a preferred class for isothermal water splitting

The use of hydrogen as a renewable fuel has been stymied by our inability to produce it cleanly and economically. The conventional solar thermochemical approach considers a two-step redox cycle with benchmark ceria or a perovskite in a temperature swing configuration, where reduction occurs at a temperature much higher than oxidation. Isothermal redox cycling is feasible and avoids the solid–solid heat recuperation and material stability challenges associated with temperature swing; yet, it has long been thought to be inefficient due to the thermodynamic unfavorability of operating the exothermic oxidation reaction at higher temperatures. Here, in this work, we show that this setback can be overcome with iron aluminate-based spinel solid solutions that preferentially exhibit large changes in oxygen content within the range of oxygen partial pressures expected in large-scale systems. We explain the experimental results with a defect model that assigns cation – not oxygen – vacancies as the predominant point defect responsible for their superior water-splitting ability. When operated isothermally at 1400 °C, the iron aluminate-based materials demonstrate a capacity for hydrogen production greater than 500 μmol g–1 and, as a result, remain viable even under high conversion conditions (i.e., pO 2 < 500 : 1 H 2 O : H 2 ), exceeding the hydrogen yields of ceria and two attractive perovskite candidates following a 400 °C (or less) temperature swing. Isothermal water splitting using iron aluminate-based materials opens the door for more simple, robust, and efficient production of renewable hydrogen.

36 MATERIALS SCIENCE↗

A hybrid optoelectronic Mott insulator

The coupling of electronic degrees of freedom in materials to create “hybridized functionalities” is a holy grail of modern condensed matter physics that may produce versatile mechanisms of control. Correlated electron systems often exhibit coupled degrees of freedom with a high degree of tunability which sometimes lead to hybridized functionalities based on external stimuli. However, the mechanisms of tunability and the sensitivity to external stimuli are determined by intrinsic material properties which are not always controllable. A Mott metal-insulator transition (MIT) is technologically attractive due to the large changes in resistance, tunable by doping, strain, electric fields, and orbital occupancy but not, in and of itself, controllable with light. Here, an alternate approach is presented to produce optical functionalities using a properly engineered photoconductor/strongly correlated hybrid heterostructure. This approach combines a photoconductor, which does not exhibit an MIT, with a strongly correlated oxide, which is not photoconducting. Due to the intimate proximity between the two materials, the heterostructure exhibits giant volatile and nonvolatile, photoinduced resistivity changes with substantial shifts in the MIT transition temperatures. This approach can be extended to other judicious combinations of strongly correlated materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Critical minerals lists for low-carbon transitions: Reviewing their structure, objectives, and limitations

Critical minerals lists have flourished in the past decade, in particular linked to the importance of critical minerals for low-carbon transitions. We identified 27 critical minerals or materials lists across 15 countries and the European Union (EU). These lists are designed to attract public and private attention and investments to secure both domestic and foreign supplies. This review article fills a gap in the existing literature by analyzing the ways in which these lists are defined and utilized by countries engaged in a mineral rush. We focus our attention on three categories of minerals – battery minerals, platinum-group metals (PGMs), and rare earth elements (REEs) that are particularly important to energy transitions. We situate this research in the broader legal and administrative developments that have driven critical minerals policies in the past decade. We provide an in-depth analysis of the commonalities and variations in the raw materials included in these lists, and identify six core limitations of critical minerals lists: (1) unclear links between criticality assessments and mineral prioritization (2) failure to account for the full mineral value-chain; (3) limited strategic alignment between allied nations; (4) limited flexibility in dynamic environments (5) limited consideration for recycling and by-product sourcing; and (6) reliance on incomplete reserve and resource data.

Battery minerals↗

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Banger, K. K.↗

Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

All-solid-state sodium-ion batteries have attracted increasing attention owing to the low cost of sodium and the enhanced safety compared to conventional Li-ion batteries. Recently, halides have been considered as promising solid electrolytes (SEs) due to their favorable combination of high ionic conductivity and chemical stability against high-voltage cathode materials. Although a wide variety of lithium chloride SEs, Li 3 MCl 6 , have been developed for high-voltage all-solid-state batteries, only a limited number of sodium chloride SEs have been reported. This study aims to offer a material design insight for the development of sodium chloride SEs through systematic assessment of the phase stability, electrochemical stability, and transport properties of novel Na 3 MCl 6 SEs. Structural calculations indicate that Na 3 MCl 6 exhibits trigonal $P\bar{3}$1c, monoclinic P2 1 /n, and trigonal $R\bar{3}$ phases, and the stable phase of Na 3 MCl 6 is dependent on the type and ionic radius of M. Na 3 MCl 6 typically exhibits a high oxidation potential, demonstrating good electrochemical stability against cathodes. The bond-valence site energy and ab initio molecular dynamics calculations revealed that Na 3 MCl 6 with P2 1 /n and $R\bar{3}$ phases showed low ionic conductivity, while the $P\bar{3}$1c phase slightly improved the ionic conductivity of Na 3 MCl 6 . The formation of Na vacancies by aliovalent substitution considerably increased the ionic conductivity up to four orders of magnitude for pristine Na 3 MCl 6 , exhibiting ~10 –5 S cm –1 for trigonal $P\bar{3}$1c and $R\bar{3}$ phases. The formation of defects could further enhance the ionic conductivity of Na 3 MCl 6 , and the optimization of defect type and ratio can be helpful in developing superionic Na chloride SEs. The material design of Na 3 MCl 6 in this study will provide fundamental guidelines for the development of novel sodium halide SEs for all-solid-state sodium-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural characterization of high temperature composites

Glass, ceramic, and carbon matrix composite materials have emerged in recent years with potential properties and temperature resistance which make them attractive for high temperature applications such as gas turbine engines. At the outset of this study, only flexural tests were available to evaluate brittle matrix composites at temperatures in the 600 to 1000 C range. The results are described of an ongoing effort to develop appropriate tensile, compression, and shear test methods for high temperature use. A tensile test for unidirectional composites was developed and used to evaluate the properties and behavior of ceramic fiber reinforced glass and glass-ceramic matrix composites in air at temperatures up to 1000 C. The results indicate generally efficient fiber reinforcement and tolerance to matrix cracking similar to polymer matrix composites. Limiting properties in these materials may be an inherently very low transverse strain to failure, and high temperature embrittlement due to fiber/matrix interface oxidation.

Mandell, J. F.↗