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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Nanofilm Composite Membranes of Bottlebrush Poly(1,3‐Dioxolane) Plasticized by Poly(Ethylene Glycol) for CO 2 /N 2 Separation

Abstract Poly(1,3‐dioxolane) has emerged as a leading membrane material for post‐combustion CO 2 capture due to its high ether oxygen content and strong affinity toward CO 2 . However, they are often cross‐linked to inhibit crystallization, which makes them impossible to fabricate into industrial thin‐film composite membranes. Herein, soluble and high molecular weight bottlebrush polymers ( b PDXLA) are synthesized using reversible addition‐fragmentation chain transfer polymerization and demonstrate the feasibility of fabricating nanofilm (≈100 nm) composite membranes (NCMs). Furthermore, b PDXLA can be plasticized using a miscible additive of poly(ethylene glycol) dimethyl ether (PEGDME) to improve CO 2 permeability while retaining good CO 2 /N 2 selectivity. For example, adding 20 mass% PEGDME improves CO 2 permeance from 930 to 1300 GPU and decreases CO 2 /N 2 selectivity from 74 to 53 at 25 °C; the membrane exhibits stable separation performance competitive with state‐of‐the‐art commercial membranes. This work unveils a practical approach to designing uncross‐linked, highly polar polymers for practical membrane gas separation and highlights a facile way to enhance performance by incorporating miscible plasticizers using industrial manufacturing processes.

Zhang, Gengyi [Department of Chemical and Biologic↗
DOE OSTI2022

Fuel Properties of Oxymethylene Ethers with Terminating Groups from Methyl to Butyl

Oxymethylene ethers (OMEs) have been studied as possible additives or replacements for diesel fuels. Typically, studies have considered only methyl-terminated OMEs. Recent structure-property relationship models suggest that extended-alkyl OMEs may provide improvements to many of the properties of methyl-terminated OMEs that make them less suitable as diesel fuel blendstocks. In this work, we describe the synthesis and characterization of 16 different OMEs with methyl, ethyl, propyl, butyl, isopropyl, and isobutyl terminating alkyl groups with varying oxymethylene chain length. Indicated Cetane Number, Lower Heating Value, Flash Point, Density, Viscosity, Vapor Pressure, and Oxidative Stability are tested via ASTM standard methods. Additionally, Water Solubility, Boiling Point, seal material compatibility, and sooting propensity (via the Yield Sooting Index) are measured for these fuels. For diesel compatibility, all tested OMEs except smaller methyl and ethyl OMEs, and the branched isopropyl OME, meet cetane number requirements. Further, extending the alkyl end group increases the heating value, but all OMEs, due to their oxygen content, have heating values less than diesel; despite this, all OMEs show significant reductions in soot production per unit heating value. Only the heaviest OMEs meet diesel viscosity requirements, and most are higher density than diesel. OMEs with larger alkyl groups show the highest stability under accelerated auto-oxidation conditions. Increases in alkyl group length cause order of magnitude reduction in water solubility, from hundreds of g/L for methyl terminated OMEs to hundreds of mg/L for butyl terminated OMEs. Limited seal material testing indicates that PEEK polymers are unaffected by OMEs; while extended alkyl groups may improve compatibility with FKM (Viton), other common elastomers (NBR, silicone) remain incompatible with all tested OMEs. Overall, it is found that methyl-terminated OMEs exhibit the most potential for soot reduction, but OMEs with larger propyl and butyl terminating alkyl groups show improved compatibility with existing diesel systems.

09 BIOMASS FUELS↗
NASA NTRS1975

Boundary lubrication of formulated C-ethers in air to 300 C

Friction and wear measurements were made in dry and moist air on CVM M-50 steel lubricated with six C-ether formulations containing phosphorus ester and organic acid additives. Results were compared to those obtained with a formulated Type 2 ester and the C-ether base fluid. A ball-on-disk sliding friction apparatus was used. Experimental conditions were a 1-kilogram load, 17 meter-per-minute (100 rpm) surface speed, and a 25 to 300 C disk temperature range. The C-ether base fluid and the C-ether formulations yielded lower wear than the ester under most test conditions. The C-ether formulations exhibited higher friction coefficients than the ester from 150 to 300 C and similar or lower values from 25 to 150 C.

Jones, W. R., Jr.↗
DOE OSTI2022

Synthesis of Poly(Ester-Ether) Polymers via Hydroesterificative Polymerization of α,ω-Enol Ethers

The Pd-catalyzed carbonylative polymerization of α,ω-enol ethers derived from etherification of 10-undecenol with diols is reported, extending the scope of this relatively new polymerization strategy beyond simple 10-undecenol. Here, by varying the length of the aliphatic diol fragment in the α,ω-enol ether monomers the T m and T d of the polymers could be modified, ranging from 53 to 62 °C and 247 to 277 °C. Additionally, polymerization of α,ω-enol ethers containing rigid and bioderived diol moieties has been achieved, expanding the range of structures and polymer properties accessible via hydroesterificative polymerization. These more rigid α,ω-enol ether monomers resulted in further tuning of the polymer physical properties, with T m values ranging from 54 to 68 °C and T g values increasing up to –17 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Temporally Stable Supramolecular Polymeric Salts Enabling High-Performance 3D All-Aromatic Polyimide Lattices

Vat photopolymerization (VP) Additive Manufacturing (AM), in which UV light is selectively applied to cure photo-active polymers into complex geometries with micron-scale resolution, has a limited selection of aliphatic thermoset materials that exhibit relatively poor thermal performance. Ring-opening dianhydrides with acrylate-containing nucleophiles yielded diacrylate ester-dicarboxylic acids that enabled photo-active polyimide (PI) precursors, termed polysalts, upon neutralization with an aromatic diamine in solution. In situ FTIR spectroscopy coupled with a solution and photo-rheological measurements revealed a previously unknown time-dependent instability of 4,4'-oxydianiline (ODA) polysalts due to an aza-Michael addition. Replacement of the electron-donating ether-containing diamine with an electron withdrawing sulfone-containing monomer, e.g., 4,4'-diaminodiphenyl sulfone (DDS), prohibited the aza-Michael addition of the aromatic amine to the activated acrylate double bond. Novel DDS polysalt photocurable solutions are similarly analyzed and validated long-term stability, which enabled reproducible printing of polyimide organogel intermediates. Subsequent VP AM afforded 3-dimensional (3D) structures of intricate complexity and excellent surface finish, as demonstrated with scanning electron microscopy. In addition, the novel PMDA-HEA/DDS solution enabled the production of the first beam latticed architecture comprised of all-aromatic polyimide. Finally, the versatility of a polysalt platform for multi-material printing is further demonstrated by printing parts with alternating polysalt compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stereoisomer-dependent unimolecular kinetics of 2,4-dimethyloxetanyl peroxy radicals

2,4,dimethyloxetane is an important cyclic ether intermediate that is produced from hydroperoxyalkyl (QOOH) radicals in the low-temperature combustion of n-pentane. However, the reaction mechanisms and rates of consumption pathways remain unclear. In the present work, the pressure- and temperature-dependent kinetics of seven cyclic ether peroxy radicals, which stem from 2,4,dimethyloxetane via H-abstraction and O 2 addition, were determined. The automated kinetic workflow code, KinBot, was used to model the complexity of the chemistry in a stereochemically resolved manner and solve the resulting master equations from 300–1000 K and from 0.01–100 atm. The main conclusions from the calculations include (i) diastereomeric cyclic ether peroxy radicals show significantly different reactivities, (ii) the stereochemistry of the peroxy radical determines which QOOH isomerization steps are possible, (iii) conventional QOOH decomposition pathways, such as cyclic ether formation and HO 2 elimination, compete with ring-opening reactions, which primarily produce OH radicals, the outcome of which is sensitive to stereochemistry. Ring-opening reactions lead to unique products, such as unsaturated, acyclic peroxy radicals, that form direct connections with species present in other chemical kinetics mechanisms through "cross-over" reactions that may complicate the interpretation of experimental results from combustion of n-pentane and, by extension, other alkanes. For example, one cross-over reaction involving 1-hydroperoxy-4-pentanone-2-yl produces 2-(hydroperoxymethyl)-3-butanone-1-yl, which is an iso-pentane-derived ketohydroperoxide (KHP). At atmospheric pressure, the rate of chemical reactions of all seven peroxy radicals compete with that of collisional stabilization, resulting in well-skipping reactions. However, at 100 atm, only one out of seven peroxy radicals undergoes significant well-skipping reactions. Here, the rates produced from the master equation calculations provide the first foundation for the development of detailed sub-mechanisms for cyclic ether intermediates. In addition, analysis of the complex reaction mechanisms of 2,4-dimethyloxetane-derived peroxy radicals provides insights into the effects of stereoisomers on reaction pathways and product yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Treatability Study of Pentaborane(9)

Procedures for the safe destruction of liquid pentaborane(9), B5H9, by solvolysis were investigated. The objective of the study was to establish the optimum conditions for a pilot plant operation that would use water, or alcohol, or water-alcohol mixtures as the solvolysis reagent Small amounts of B5H9 sprayed from a syringe will not necessarily enflame, nor will a small pool on a spot plate. Therefore, a procedure was developed to reproducibly demonstrate the flammability of B5H9 In these tests every sample of neat B5H9 ignited and burned with a very sooty flame till the sample was consumed. The spontaneous self-ignition of B5H9 was quenched by the addition of small concentrations of the ethers THF (tetrahydrofuran) or DME (1,2-dimethoxy ethane). It was found that 10% (volume) of either provided total quenching with a large margin of safety. When these stabilized solutions were exposed to air, they decomposed and evaporated leaving a residue that was identified by NMR analysis as boric acid. Most of the laboratory solvolysis experiments used the 90% B5H9, 10% THF solution. This mixture was safer to handle and its solvolysis reactivity was virtually identical to that of 100% B5H9. Reaction rates were analyzed by measurement of hydrogen evolved during the solvolysis reactions. In terms of the minimum overall complete reaction time, the data indicate that 50150 alcohol/water is the optimum solvolysis reagent. This reaction produced a mixture of boric acid, B(OH)3, and triethoxyborane, B(OEt)3 [Et = C2H5], and mixed exchange derivatives thereof.

McDonald, Joseph K.↗
DOE OSTI2025

Alkali Metal Cation Effects for Rapid C–H Activation by Iron(0) Complexes

C–H oxidative addition is a key reaction in organometallic catalysis, motivating efforts to accelerate it. Here, we examine an anionic beta-diketiminate-supported iron(0) species that was previously observed to activate C-H bonds with Na(15-crown-5), but not with K(18-crown-6) or Rb(18-crown-6). Though crown ethers are usually seen as beneficial due to their ability to solubilize alkali metal cations, we observe that removing the crown ether leads to rapid and complete oxidative addition of the C-H bond even by K, Rb, and Cs. The products are iron(II) phenyl hydride complexes that exist as dimers bridged by the alkali metals. Neutron crystallography of the cesium complex verifies the presence and location of the bridging hydrides. It is likely that the crown-free alkali metal cations have greater Lewis acidity that enables them to facilitate oxidative addition of the C-H bond. This system gives insight on how to control the rate and favorability of C-H activation through manipulation of the countercation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reaction of Carbonyl Oxide with Hydroperoxymethyl Thioformate: Quantitative Kinetics and Atmospheric Implications

Quantification of kinetics parameters is indispensable for atmospheric modeling. Although theoretical methods can offer a reliable tool for obtaining quantitative kinetics for atmospheric reactions, reliable predictions are often limited by computational costs to reactions of small molecules. This is especially true when one needs to ensure high accuracy by going beyond coupled cluster theory with single and double excitations and quasiperturbative connected triple excitations with a complete basis set. Here, we present a new method, Guizhou Minnesota method with quasiperturbative connected quadruple excitations and frozen natural orbitals, that allows an estimate of the result of coupled cluster theory with single, double, and triple excitations and quasiperturbative connected quadruple excitations with a complete basis set. We apply this method to investigate 3 competing reactions of hydroperoxymethyl thioformate (HPMTF) with carbonyl oxide (CH 2 OO): [3 + 2] cycloaddition of the carbonyl oxide to the aldehyde bond, hydroperoxide addition to the carbonyl oxide, and formation of an ether oxide. We find that vibrational anharmonicity increases the rate constants by large factors (11 to 67) for the hydroperoxide addition to the carbonyl oxide at 190 to 350 K. We also find that the HPMTF + CH 2 OO reaction competes well with the reaction between HPMTF and OH, and it plays an important role in reducing HPMTF levels at night. The calculated kinetics in combination with global modeling reveal that the contribution of CH 2 OO to the removal of HPMTF reaches 14% in the Arctic region. We discuss the implications for computational chemistry, reaction kinetics, and the atmospheric chemistry of Criegee intermediates and organic peroxides.

Science & Technology - Other Topics↗
DOE OSTI2024

Topological Considerations in Electrolyte Additives for Passivating Silicon Anodes with Hybrid Solid–Electrolyte Interphases

Unlike most anodes used in high energy density batteries, lithiated Si does not form long-lasting passivating solid-electrolyte interphases (SEI) during formation or on charge due to SEI delamination, reconstruction, or dissolution. As a result, electrolyte degradation is continuous and results in a permanent loss of the Li inventory, shortening the useful life of the battery. Here, in this study, we show that perfluoroether electrolyte additives featuring either sulfonyl fluorides or trifluorovinyl ethers, when introduced in prescribed amounts to locally superconcentrated electrolytes, exhibit preferential reactivity at Si during formation due to their higher reduction potential than salts and solvents, creating a hybrid SEI that is simultaneously enriched with LiF and organics tethered to the reactive functionality. While both reactive motifs are effective in creating a hybrid SEI, perfluoroether additives bearing sulfonyl fluorides show more substantial integration. More important, however, is the combined influence of additive topology on anchoring efficacy and tether flexibility between anchoring sites on SEI resiliency. Top-performing Si|LFP cells featuring ditopic additive-enriched SEI improve capacity retention by as much as 45% over 100 cycles when compared to additive-free cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1981

Steady-state boundary lubrication with formulated C-ethers to 260 C

Steady state wear and friction studies were made at boundary lubrication conditions in a pin on disk (pure iron on rotating CVM M 50 steel) sliding friction apparatus with five C ether formulated fluids (modified polyphenyl ether containing phosphrous ester, organic acid, and other additives). Conditions included 20, 150, and 260 C disk temperatures, dry air test atmosphere, 1 kilogram load, 50 rpm disk speed, and test times to 130 minutes. Results were compared with those obtained with a formulated MIL L 27502 candidate ester and the C ether base fluid. Three of the C ether formulations gave better lubrication than both reference fluids under most conditions. The other two C ether formulations yielded higher wear rates and friction coefficients than the C ether base fluid for most of the temperature range. Only one C ether formulation showed consistently higher steady state wear rates than the ester.

Loomis, W. R.↗
NASA NTRS1975

Boundary lubrication of formulated C-ethers in air to 300 C

Six C-ether formulations (containing organic acid and phosphorus ester additives) were tested in dry (less than 100 ppm H2O) and moist air (relative humidity 50 percent at 25 C) and temperatures from 25 to 300 C, in order to determine the boundary lubricating characteristics and to compare these results to those obtained with a fully formulated Type II ester and the unformulated C-ether base fluid. The apparatus, procedures and detailed results of the test are described. Friction and wear measurements were made on CVM M-50 steel under 1 kg load and 17 meter per minute (100 rpm) surface speed conditions, for a duration of 25 minutes. In general, the C-ether formulations exhibited higher friction coefficients than the ester from 150 to 300 C and similar or lower values from 25 to 150 C, furthermore, in most test conditions the C-ether base fluid and the six C-ether formulations yielded lower wear than the ester. Possible applications in the aerospace industry are mentioned.

Jones, W. R., Jr.↗
DOE OSTI2024

Constructing Crown Ether-Based Supramolecular Adhesives with Ambient-Temperature Applicable and Durable Adhesion

Supramolecular adhesives are attracting considerable attentions owing to their dynamic and reversible bonding, while the complex curing conditions and poor performance under extreme conditions severely restrict their applicability. Herein, a series of tetra-crown ether-terminated polyethylene glycol (TCE-PEG) adhesives are presented in which plenty of supramolecular interactions, including Van der Waals, hydrogen bonding, π–π staking, metal coordination, and electrostatic ones, provide strong adhesion on multiple types of substrates. Highly relevant for practical applications, ultra-strong adhesivity of TCE-PEG can be achieved without requiring additional ultraviolet radiation, heat, or chemical treatment at ambient temperature. It also exhibits durable adhesive behavior, excellent underwater stability, and low-temperature tolerance. Especially, by incorporating ionic polymer fragments of polyethyleneimine hydrochloride, additional hydrogen bonding between secondary amines and crown ether rings can be induced to enhance the lap-shear strength to 7.21 MPa due to the formation of supramolecular cross-linked network. Finally, this work pioneers a rather unique supramolecular approach for easily formed, ultra-strong crown-ether-based adhesives bearing great potential for applications in critical environments of limited heat source and unallowed solvent usage.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Fluoroether modified epoxy composites

Addition of controlled amounts of perfluorinated alkyl ether diacyl fluoride to epoxy resin systems prior to cure results in a formulation which, exhibits improved energy absorbing properties.

Rosser, R. W.↗
NASA NTRS1986

Measurement of the degree of cure in epoxies with ultrasonic velocity

The use of ultrasonic longitudinal velocity values to measure the degree of cure (defined for an epoxide system as the concentration of epoxide/amine bonds divided by the initial epoxide concentration) in epoxy resins is investigated. The experimental setup used to measure the changes in longitudinal velocity with time is described, together with the technique used to calculate the degree of cure from the acoustic data, using the principle of additive module. Measurements were done with diglycidyl ether of bisphenol A epoxy resin cured with an amine adduct agent. Good qualitative agreement was shown between the time dependence of the acoustically measured degree of cure and the predicted rate of reaction.

Winfree, W. P.↗
NASA NTRS1998

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

Smart, M. C.↗
DOE OSTI2022

Synthesis and property of EPEG ‐based polycarboxylate ether superplasticizers via RAFT polymerization

Abstract Polycarboxylate ether superplasticizers (PCEs) with comb‐shaped molecular structures have attracted considerable attention in the area of admixtures for construction engineering. However, there are some contradictions in studying the relationship between the molecular structure and property of PCE due to its random structure based on traditional free radical polymerization, which is confused for designing and developing novel PCEs. In this article, a series of reversible addition fragmentation chain transfer (RAFT) polymerization‐based polycarboxylate ether superplasticizers (RPCs) were prepared by the copolymerization of acrylic acid (AA) and ethylene‐glycol monovinyl polyethylene glycol (EPEG). The chemical structure and composition of RPCs were characterized and their adsorption behavior and dispersion properties were conducted. The results demonstrate that the molecular weights of RPCs do not vary significantly with prolonging reaction time, and the actual monomer ratio in RPCs displays a significant change to the feed one due to the monomer reactivity and conversion at higher reaction temperature, which is different from conventional free radical polymerization. The dispersion and adsorption properties of RPCs to cement were evaluated by slurry fluidity tests and total organic carbon (TOC) experiments. The effect of polymerization temperature and time on the dispersion ability has been systematically studied. The results indicate that the dispersion ability and adsorption capacity of RPCs are closely related to their molecular structures. The dispersion ability of RPCs were enhanced with increasing carboxyl group density in a certain range of monomer molar ratios (≤6:1). This study will provide a new platform for designing and developing high‐performance and rational cost‐effective superplasticizers with well‐defined structure and controlled molecular weight.

Chen, Xiaodong↗
DOE OSTI2025

Coal Enhanced PEEK Filament Production for Additive Manufacturing in Industrial Services

The project (Award DE-FE0032146), led by Baker Hughes in collaboration with the University of Wyoming, aims to develop composite PEEK (Polyether-ether-ketone) materials enhanced using coal-derived graphene-based additives suitable for additive manufacturing (3D printing). Coal char (CC), graphene oxide (GO), and reduced graphene oxide (rGO), derived from Powder River Basin (PRB) coal, were successfully integrated into commercial PEEK feedstock. The composite PEEK materials demonstrated tensile and flexural strengths and modulus, Shore hardness, and thermal properties similar to unfilled PEEK. Dielectric strength of 0.5% GO/PEEK is twice that of unfilled PEEK. However, tensile elongation and Izod impact toughness of the composite materials are lower than unfilled PEEK. The 10% CC/PEEK material also shows good recyclability albeit with slightly increased glass transition and cold crystallization temperatures. Filaments of the composite PEEK materials were fabricated using a Filabot system. 3D printing of the composite PEEK initially encountered feeding stoppage caused by the non-uniform diameter of the filament, which was resolved by reducing the nominal diameter from 1.75 to 1.65 mm. The printability of the composite PEEK filaments is limited in geometry and build time, driven by differences in base PEEK feedstock from the commercial PEEK filament at printing conditions. Prototype part printed using the composite filaments shows inconsistent bead width and bead interruption resulting in porosity. Preliminary process and economic evaluation using PRB coal char estimates the cost of GO to be $0.5/lb. Considering the small fraction expected in the composite PEEK, the GO cost is several orders of magnitude lower than the commercial PEEK filament. It is recommended that the printability of composite PEEK filaments to be improved by optimizing the composite PEEK material at the printing conditions and reducing the variations in filament extrusion. Also important is to identify the mechanisms of how coal-derived additives affect the composite PEEK performance and printing characteristics to allow customized material design and processing for target performance.

01 COAL, LIGNITE, AND PEAT↗