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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 55 records · Page 3

Nitrogen- and oxygen-rich organic material indicative of polymerization in pre-aqueous cryochemistry on Bennu’s parent body

Nitrogen-containing organic compounds play key biological roles, and their identification in primitive astromaterials such as meteorites can shed light on the origin of life. However, meteorites are typically contaminated by uncontrolled exposure to Earth. Here we show that pristine samples returned from asteroid Bennu contain polymeric organics exceptionally rich in nitrogen and oxygen. These polymers contain a variety of functional groups including amines, amides, N-heterocycles, and aliphatic and aromatic hydrocarbons, among others. They are seen in a carbonaceous vein with mineral inclusions and in multilayered organic sheets. Their morphology and composition indicate formation from pre-aqueous N-rich precursors and later modification during aqueous alteration. These findings demonstrate that asteroids like Bennu contain complex nitrogen-rich organic phases formed by pre-aqueous and aqueous processes, and they expand the known inventory of potential prebiotic extraterrestrial compounds.

Sandford, Scott A↗

Water-polyamide chemical interplay in desalination membranes explored by ambient pressure X-ray photoelectron spectroscopy

Reverse osmosis using aromatic polyamide membranes is currently the most important technology for seawater desalination. The performance of reverse osmosis membranes is highly dependent on the interplay of their surface chemical groups with water and water contaminants. In order to better understand the underlying mechanisms of these membranes, we study ultrathin polyamide films that chemically resemble reverse osmosis membranes, using ambient pressure X-ray photoelectron spectroscopy. This technique can identify the functional groups at the membrane–water interface and allows monitoring of small shifts in the electron binding energy that indicate interaction with water. We observe deprotonation of free acid groups and formation of a ‘water complex’ with nitrogen groups in the polymer upon exposure of the membrane to water vapour. The chemical changes are reversed when water is removed from the membrane. While the correlation between functional groups and water uptake is an established one, this experiment serves to understand the nature of their chemical interaction, and opens up possibilities for tailoring future materials to specific requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Structure–Property Relationships for Ammonium Transport through Charged Organogels

Ammonia is a promising carbon-free fuel, but current methods to produce ammonia are energy intensive. New methods are thereby needed, with one promising method being electrochemical nitrogen reduction cells. Efficient cell operation requires robust catalysts but also efficient membrane separators that permit the selective transport of ions while minimizing the transport of the products across the cell. Commercial membranes have an unknown morphology which makes designing improved cells challenging. To address this problem, we synthesized a series of membranes with controlled crosslinking density and chemical composition to understand their impact on ammonium transport. Higher crosslinking density led to lower ammonium permeability. At the highest crosslinking density, similar ammonium permeability was observed independent of the water volume fraction and hydrophobicity of the monomers. These results suggest new directions to develop membranes with reduced ammonium crossover to improve the efficiency of these electrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Gas chromatographic separation of nitrogen, oxygen, argon, and carbon monoxide using custom-made porous polymers from high purity divinylbenzene

Existing porous polymers were surveyed for their ability to separate the subject gases. Certain products that showed more promise than others were synthesized and the existing synthetic procedures studied and modified to produce new polymers with enhanced ability to separate the subject gases. Evaluation of the porous polymers was carried out practically by gas chromatography at ambient temperature. The modified synthetic procedures were somewhat simpler than the originals. The new porous polymers made with high purity divinylbenzene enabled use of shorter columns to obtain the separations desired.

Pollock, G. E.↗

The Effect of Polymer Char on Nitridation Kinetics of Silicon

Effects of polymer char on nitridation kinetics of attrition milled silicon powder have been investigated from 1200 to 1350 C. Results indicate that at and above 1250 C, the silicon compacts containing 3.5 wt percent polymer char were fully converted to Si3N4 after 24 hr exposure in nitrogen. In contrast, the silicon compacts without polymer char could not be fully converted to Si3N4 at 1350 C under similar exposure conditions. At 1250 and 1350 C, the silicon compacts with polymer char showed faster nitridation kinetics than those without the polymer char. As the polymer char content is increased, the amount of SiC in the nitrided material is also increased. By adding small amounts (approx. 2.5 wt percent) of NiO, the silicon compacts containing polymer char can be completely nitrided at 1200 C. The probable mechanism for the accelerated nitridation of silicon containing polymer char is discussed.

Chan, Rickmond C.↗

Preliminary Evaluation of Polyarylate Dielectric Films for Cryogenic Applications

Polymeric materials are used extensively on spacecraft and satellites in electrical power and distribution systems, as thermal blankets and optical surface coatings, as well as mechanical support structures. The reliability of these systems when exposed to the harsh environment of space is very critical to the success of the mission and the safety of the crew in manned-flight ventures. In this work, polyarylate films were evaluated for potential use as capacitor dielectrics and wiring insulation for cryogenic applications. Two grades of the film were characterized in terms of their electrical and mechanical properties before and after exposure to liquid nitrogen (-196 C). The electrical characterization consisted of capacitance and dielectric loss measure Cents in the frequency range of 50 Hz to 100 kHz, and volume and surface resistivities. The mechanical measurements performed included changes in tensile (Young's modulus, elongation-at-break, and tensile strength) and structural properties (dimensional change, weight, and surface morphology). The preliminary results, which indicate good stability of the polymer after exposure to liquid nitrogen, are presented and discussed.

Patterson, Richard L.↗

Leaching of nitroso rubber material removes uncured polymer

New leaching process removes uncured polymer from nitroso rubber, elastomer used in presence of nitrogen tetroxide. Uncured portion is removed by controlled soaking of polymer slab in Freon TF. Leaching with Freon TF prevents nitroso rubber from adhering to adjoining surfaces and limiting its usefulness in either static or dynamic applications.

Bratfisch, W. A.↗

Biological activity of ionene polymers

Ionene polymers are polyammonium salts with positive nitrogens in the backbone, resulting from the polycondensation of diamines with dihalides or from the polycondensation of halo amines. The mechanism of formation of ionene polymers of different structures and their biological activity is reviewed. The antimicrobial and antifungal properties are compared with low molecular weight ammonium salts. Ionenes were found to combine with DNA by means of ionic bonds to yield similar complexes to those obtained with polyamines (spermine and spermidine). They also combine with nerve cell receptors and exercise a more powerful and longer duration ganglionic blocking action than their monomeric analogs. The antiheparin activity of ionenes and the thromboresistance of elastomeric ionene heparin coatings is described. The enhanced biological activity of ionenes as compared with low molecular weight compounds is attributed to a cooperative effect of a large number of positive charges on the polymeric chains.

Rembaum, A.↗

The high explosives & affected targets (HEAT) dataset

Artificial Intelligence (AI) surrogate models offer a computationally efficient alternative to full-physics simulations, yet no existing datasets are publicly available for training, testing, and validation of machine learning models of the dynamics of high-explosive driven shocks through multiple materials. Shock propagation through materials is a computationally challenging problem because simulations must include material-specific equations of state (EOS) along with descriptions of other physical processes such as plastic deformation, phase change, damage processes, fluid instabilities, and multi-material interactions. Shocks are typically initiated by high-velocity impacts or explosive loading. The latter case necessitates the addition of models of reactive materials to represent high-explosive (HE) detonation. Here, to address the lack of an expansive dataset for multi-material shock propagation in the AI/ML community, we present the High-Explosives and Affected Targets (HEAT) Dataset. HEAT is a physics-rich collection of two-dimensional, cylindrically symmetric, simulations generated using an Eulerian, multi-material, shock-propagation code developed at Los Alamos National Laboratory. The dataset includes two partitions: (1) the expanding shock-cylinder (CYL) simulations, Figs. 1, and (2) the Perturbed Layered Interface (PLI) simulations, Fig. 2. Entries in both partitions consist of time series of arrays of thermodynamic fields (pressure, density, and temperature), kinematic fields (position and velocity), and additional fields that depend on thermodynamic and/or kinematic fields (e.g., material stress). Materials in the CYL partition include solids (aluminium, copper, depleted uranium, stainless steel, tantalum, and a generic polymer), a liquid (water), gases (air, nitrogen), and a generic detonating material (high explosive, HE). The PLI partition spans a highly varying geometry but consists of fixed materials across entries: Copper, aluminium, stainless steel, generic polymer, and generic HE. HEAT captures critical phenomena such as momentum transfer, shock propagation, plastic deformation, and thermal effects, making HEAT a valuable benchmark for development of AI/ML emulation of multi-material shock propagation.

36 MATERIALS SCIENCE↗

Reverse osmosis membrane of high urea rejection properties

Polymeric membranes suitable for use in reverse osmosis water purification because of their high urea and salt rejection properties are prepared by generating a plasma of an unsaturated hydrocarbon monomer and nitrogen gas from an electrical source. A polymeric membrane is formed by depositing a polymer of the unsaturated monomer from the plasma onto a substrate, so that nitrogen from the nitrogen gas is incorporated within the polymer in a chemically combined form.

Johnson, C. C.↗

Nitrogen-Doped PtNi Catalysts on Polybenzimidazole-Functionalized Carbon Support for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

PtM (M = 3d transition metals) alloys are known as the promising oxygen reduction reaction catalysts and have been considered as the replacement of pure Pt catalysts for the commercialization of proton exchange membrane fuel cells. Although great progress has been made in the past three decades, the performance and durability of PtM catalysts still face stringent challenges from practical applications. Functionalization of a catalyst carbon support with nitrogen-contained groups can add charges onto its surface, which can be utilized to build a more complete ionomer/catalyst interface, to reduce the catalyst particle size, and to improve particle size distribution. Nitriding of PtNi catalysts can effectively improve the catalyst activity and stability by the modification of lattice strain. Hereby, we propose a synergistic approach of combining polybenzimidazole-grafted Vulcan XC72 carbon as the catalyst carbon support and the nitriding of PtNi to develop PtNiN/XC72-polybenzimidazole catalysts. Such PtNiN/XC72-PBI catalysts exhibit the excellent performance of fuel cell membrane electrode assembly (i.e., mass activity, 440 mA mgPt –1 ; electrochemical surface area, 51 m 2 gPt –1 ; and rated power density, 836 mW cm –2 ) as well as promising catalyst stability. The developed PtNiN/XC72-PBI meets the US DOE 2020 targets of mass activity for the fuel cell catalysts. This work provides a novel approach and a promising pathway on the development of the catalyst using such a synergistic approach-modification of the catalyst structure by nitrogen doping and functionalization of carbon support by polybenzimidazole for both high performance and high durability.

25 ENERGY STORAGE↗

Diamond formation in double-shocked epoxy to 150 GPa

We present measurements of diamond formation in doubly shocked Stycast 1266 epoxy (comprising C, H, Cl, N, and O) using in situ x-ray diffraction. Epoxy samples were reshocked against a LiF window to pressures between 80 and 148 GPa in experiments at the Omega Laser Facility. Furthermore, the pressure and temperature conditions were diagnosed in situ using velocimetry and optical pyrometry, respectively. X-ray diffraction patterns of the compressed epoxy are consistent with cubic diamond (Fd3¯m), indicating that diamond can precipitate not only from twice-shocked CH polystyrene [Kraus et al. Nat. Astron. 1, 606 (2017)] at these conditions but also from twice-shocked CH polymers with the addition of oxygen, nitrogen, and chlorine. These results, in combination with previous works on CH, CH 2 , CH 4 , and methane hydrate, support that diamond often, but not always, forms from CH-based compounds at extreme pressures and temperatures, indicating that the chemical composition, thermodynamic compression path, and kinetics play an important role.

36 MATERIALS SCIENCE↗

Initial Testing of an In Situ Load Retention Aging Vessel

A thermal aging vessel instrumented with load cells was fabricated. The primary function of the vessel is to continuously monitor the in situ load retention of up to three compressed polymer coupons undergoing thermally accelerated aging under nitrogen. A secondary function is to enable gas sampling of the vessel headspace during thermal aging. Heating of the vessel is achieved using a custom heater jacket. To improve upon our conventional aging study methods which require periodic interruption of aging to perform load testing in an Instron machine at room temperature, this technology aims to automate/facilitate data acquisition/analysis, improve data quality, and enable uninterrupted compression of the polymer which represents the service condition. As an example case to assess functionality of the in situ vessel, the load retention of a siloxane elastomer material additively manufactured by direct-ink-writing (DIW) was measured at three different isothermal aging temperatures for ~1 month. Initial compression of the coupons while near the aging temperature was achieved by temporarily opening the heated vessel to access the interior chamber and manually tightening four nuts to drive the heated compression plate down onto the heated coupons. Initial testing demonstrated achievement of the primary load retention monitoring function. Unfortunately, the vessel leaked which prevented gas sampling; an active purge was used to maintain a nitrogen atmosphere. Welded or otherwise sealed joints, which could be implemented in a future design, would likely eliminate leak paths. To apply time-temperature superposition (TTS), a technique used to provide long-term prediction of the load retention from short-term isothermal data, the load retention needed to be calculated relative to the load at an estimated “equilibrium” time, after most of the transient viscoelastic physical relaxation occurred. The peak load immediately after compression could not be used as the load retention basis for two reasons: (1) age-related changes must be isolated from non-age-related physical relaxation before applying TTS and (2) the manual mechanism used to compress the specimens at the aging temperature was neither smooth nor repeatable which affected the peak load value. To better understand the effect of the mode of initial compression on the measured load, and possibly better estimate “equilibrium” physical relaxation times, systematic stress relaxation experiments were performed using an Instron machine with a thermal chamber. At a given temperature, the DIW polymer was compressed to a fixed strain in either a stepped or continuous manner at two different rates, then held at that strain for 24 hrs. The results indicated that, at a given temperature, the different stress relaxation curves appeared to converge to the same curve at some “equilibrium” time when the non-age-related physical relaxation was mostly complete. Though this observation suggests that the discontinuous manual compression employed by the vessel is feasible, a compression mechanism that is rapid, smooth, and repeatable would enhance its use.

36 MATERIALS SCIENCE↗

Plasma polymerization of an ethylene-nitrogen gas mixture

A procedure has been developed whereby nitrogen can be incorporated into an organic film from an ethylene-nitrogen gas mixture using an internal electrode capacitively coupled radio frequency reactor. The presence of nitrogen has been shown directly by infrared transmittance spectra and electron spectroscopic chemical analysis data, and further indirect evidence was provided by dielectric measurements and by the reverse osmosis properties of the film. Preparation of a nitrogen containing film did not require vapor from an organic nitrogen containing liquid monomer. Some control over the bonding and stoichiometry of the polymer film was provided by the added degree of freedom of the nitrogen partial pressure in the gas mixture. This new parameter strongly affected the dielectric properties of the plasma polymerized film and could affect the reverse osmosis behavior.

Hudis, M.↗

Investigation of porous polymer gas chromatographic packings for atmospheric analysis of extraterrestrial bodies

Measurement of the permanent gases in the atmospheres of mission targets is a major objective. A 16 meter long Porapak N column was used on the Venus probe and required a rather high carrier gas flow rate. The researchers have, therefore, surveyed commercial porous polymer types which had some ability to resolve nitrogen, oxygen, argon and carbon monoxide gases. Porapaks N and Q appeared superior to most. Batch to batch variation, however, was quite wide, so the researchers learned how to synthesize porous polymer and investigated some of the factors affecting the separations. A polymer was synthesized which was superior to all commercial products and allowed at least a 50% reduction in length and flow rate of carrier gas. Similar studies were made concerning the separation of hydrocarbons and new porous polymers have been synthesized which represent significant improvements in time of analysis, column, and carrier gas flow rate.

Pollock, G. E.↗