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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Photodeposition of Thin Polydiacetylene Films from Solution that Exhibit Large Third-Order Optical Nonlinearities

One promising class of organic compounds for applications in the field of nonlinear optics (NLO) are polydiacetylenes, which are of interest because they are highly conjugated polymers capable of exhibiting very large optical nonlinearities with fast response times. During the course of crystal growth studies in anticipation of a space experiment, we discovered a novel, simple method for the formation of polydiacetylene thin films by photodeposition from monomer solutions onto quartz or glass substrates. Characterization of these PDAMNA films is not trivial; they are not soluble in common organic solvents, which makes the standard solution-based methods of polymer analysis useless.

Paley, M. S.↗
DOE OSTI2024

Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures

Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. Here, in this study, we developed a series of non-fluorinated PEMs from poly(terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25% at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm 2 for PFLSH60 compared to 1.83 mA/cm 2 for Nafion 212) under testing conditions of 80 °C and 100% RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Morphological control of inter-penetrating polymer networks

Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.

Hansen, Marion↗
DOE OSTI2025

Understanding and tuning organocatalysts for versatile condensation polymer deconstruction

Plastics are widely used for their durability and versatility, but recycling remains a major challenge, especially for mixed or contaminated waste. Mechanical recycling works well for clean, single-polymer streams like PET but has limited efficiency for complex waste streams. Chemical recycling, particularly glycolysis, is often employed to selectively deconstruct condensation polymers under mild conditions. This study explores catalyst design for glycolysis using linear free energy (Hammett) analysis to evaluate how catalyst structure influences polymer deconstruction. Polycaprolactone (PCL) is used as a model polyester due to its solubility and low deconstruction temperature. Triazabicyclodecene (TBD) paired with benzoic acid derivatives depicts a clear linear trend in depolymerization rates with Hammett values. TBD with p-aminobenzoic acid (PABA) stands out for its catalytic efficiency, thermal stability, and scalability, along with PABA's commercial availability as vitamin B-10. The TBD : PABA catalyst not only effectively breaks down PCL but also enables sequential deconstruction of polycarbonate, PET, and Nylon in mixed waste streams. These results highlight the value of Hammett-guided catalyst design and establish TBD : PABA as a promising, scalable organocatalyst for mixed plastic recycling, enabling recovery of individual polymer building blocks from blended waste and offering a practical route toward circular plastics.

Zheng, Jackie [Univ. of Tennessee, Knoxville, TN (↗
DOE OSTI2022

A Nonaqueous Redox‐Matched Flow Battery with Charge Storage in Insoluble Polymer Beads**

Abstract We describe the nonaqueous redox‐matched flow battery (RMFB), where charge is stored on redox‐active moieties covalently tethered to non‐circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high‐solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox‐matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox‐active moieties via attachment to the versatile Merrifield resin.

25 ENERGY STORAGE↗
NASA NTRS2018

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗
NASA NTRS1972

Quantitation of buried contamination by use of solvents. Part 1: Solvent degradation of amine cured epoxy resins

The solubility and/or swelling of cured epoxy resins was studied using the solubility parameter method. Determination of solubility parameters were found in order to select solvents for solvent-assisted degradation of cured epoxy polymers used in spacecraft. A method for improving recovery of seeded spores is suggested for assay of buried contaminants. Three commercial epoxy resins were cured using four different alkyl amines. For each resin-amine combination, three levels of amine were used, corresponding to 1/3, 2/3, and all of the amine required to react with the oxirane groups of the resin. The solubility parameters of the 36 resulting model compounds were determined in poorly and moderately hydrogen-bonded solvents. No strongly hydrogen-bonded solvents caused dissolution or swelling. The tolerance of cured resins is discussed in terms of polymer structure.

Rheineck, A. E.↗
NASA NTRS1986

Environmentally stable polymers and coatings for space application: CH-5, supplement 10

High molecular weight, randomly coupled poly(imide siloxane) soluble block copolymers were synthesized from bis(amino propyl) polydimethylsiloxane equilibrates of various molecular weights, aromatic metalinked diamines, and 3,3'-4,4'-benzophenone tetracarboxylic dianhydride (BTDA). Two synthetic procedures were successfully used to synthesize the poly(amic acid siloxane) intermediates. For both synthetic procedures, a cosolvent system was employed to achieve complete solvation of all components throughout the polymerization. Physical property characterization is continuing.

Sykes, G.↗
DOE OSTI2021

Carbohydrate-Containing Conjugated Polymers: Solvent-Resistant Materials for Greener Organic Electronics

Organic semiconducting polymers are exciting materials for electronic applications because of their good mechanical and optoelectronic properties. A major advantage of organic semiconductors is their solution processability. This allows access to a variety of simple and cost-effective device fabrication methods compared to the expensive, high-temperature processing methods required for silicon-based electronics. However, these materials often have low solubility, which limits their processing to toxic halogenated solvents. Also, their limited solubility often leads to interfacial mixing during device fabrication. Herein, this work explores the incorporation of environmentally friendly carbohydrate side chains in conjugated polymers to enhance processability in eco-friendly solvents. Moreover, a mild postprocessing treatment was designed to enable solvent resistance. Isoindigo-based polymers with varied ratios of acetyl-protected galactose side chains were synthesized to improve solubility in o-anisole in the protected state, while inducing solvent resistance through intramolecular hydrogen bonding in the deprotected state. Solvent resistance was confirmed both visually upon submersion in various solvents and using UV–visible spectroscopy. Importantly, the mild basic treatment to achieve solvent resistance has no negative impact on the electronic performance of these materials in organic field-effect transistors, even after subsequent submersion in various solvents, making them a valuable platform for the production of green processable multilayer electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic Level Interactions and Suprastructural Configuration of Plant Cell Wall Polymers in Dialkylimidazolium Ionic Liquids

Ionic liquids (ILs) have been widely investigated for the pretreatment and deconstruction of lignocellulosic feedstocks. However, the modes of interaction between IL-anions and cations, and plant cell wall polymers, namely, cellulose, hemicellulose, and lignin, as well as the resulting ultrastructural changes are still unclear. In this study, we investigated the atomic level and suprastructural interactions of microcrystalline cellulose, birch wood xylan, and organosolv lignin with 1,3-dialkylimidazolium ILs having varying sizes of carboxylate anions. Analysis by 13 C NMR spectroscopy indicated that cellulose and lignin exhibited stronger hydrogen bonding with acetate ions than with formate ions, as evidenced by greater chemical shift changes. Small-angle X-ray scattering analysis showed that while both cellulose and xylan adopted a single-stranded conformation in acetate-ILs, twice as many acetate ions were bound to one anhydroglucose unit than to an anhydroxylose unit. Further, we also determined that a minimum of seven representative carbohydrate units must interact with an anion for that IL to effectively dissolve cellulose or xylan. Lignin is associated as groups of four polymer molecules in formate-ILs and dispersed as single molecules in acetate-ILs, which indicates that it is highly soluble in the latter. In summary, our study demonstrated that 1,3-dialkylimidazolium acetates displayed stronger binding interactions with cellulose and lignin, as compared to formates, and thus have superior potential to fractionate these polymers from lignocellulosic feedstocks.

13C NMR↗
NASA NTRS1973

Method for estimating solubility parameter

Semiempirical correlations have been developed between solubility parameters and refractive indices for series of model hydrocarbon compounds and organic polymers. Measurement of intermolecular forces is useful for assessment of material compatibility, glass-transition temperature, and transport properties.

Lawson, D. D.↗
NASA NTRS2003

Metal chelate affinity precipitation of RNA and purification of plasmid DNA

The affinity of metal chelates for amino acids, such as histidine, is widely used in purifying proteins, most notably through six-histidine 'tails'. We have found that metal affinity interactions can also be applied to separation of single-stranded nucleic acids through interactions involving exposed purines. Here we describe a metal affinity precipitation method to resolve RNA from linear and plasmid DNA. A copper-charged copolymer of N-isopropyl acrylamide (NIPAM) and vinyl imidazole (VI) is used to purify plasmid from an alkaline lysate of E. coli. The NIPAM units confer reversible solubility on the copolymer while the imidazole chelates metal ions in a manner accessible to interaction with soluble ligands. RNA was separated from the plasmid by precipitation along with the polymer in the presence of 800 mM NaCl. Bound RNA could be recovered by elution with imidazole and separated from copolymer by a second precipitation step. RNA binding showed a strong dependence on temperature and on the type of buffer used.

Non-NASA Center↗
NASA NTRS2003

Functionalization of Carbon Nanotubes

These project will explore the functionalization of carbon nanotubes via the formation of molecular complexes with perylene diimide based systems. It is anticipated that these complexes would be soluble in organic solvent and enable the homogenous dispersion of carbon nanotubes in polymer films. Molecular complexes will be prepared and characterized using standard spectroscopic and thermal analytical techniques. Polymer films will be prepared with these complexes and their properties (electrical and thermal conductivity, mechanical properties, stability) evaluated.

Webber, Stephen E.↗
NASA NTRS2008

Photochemically Synthesized Polyimides

An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use of solvents is optional: The synthesis can be performed using the neat monomer or the monomer mixed with one or more solvent(s) in dilute or concentrated solution. The solubility of the monomer and the physical and chemical properties of the final polymer can be tailored through selection of the spacer group.

Meador, Michael A.↗
DOE OSTI2020

Determination of effective attenuation length of slow electrons in polymer films

Slow electrons (with energy below 10 eV) play an important role in nature and technology. For instance, they are believed to initiate solubility change in extreme ultraviolet resists. Depending on their mobility, such secondary electrons can lead to image blur and degradation of patterning resolution. Hence, it is important to characterize the transport of slow electrons by measuring parameters such as the effective attenuation length (EAL). In this work, we present a technique that allows for prompt characterization of EAL in polymer films. In this experiment, slow electrons are generated in a substrate upon absorption of x-ray photons. The attenuation of electron flux by a polymer film is measured as a function of film thickness, allowing for the determination of EAL for slow electrons. We illustrate this method with poly(hydroxy styrene) and poly(methyl metacrylate) films. Furthermore, we propose an improvement for this technique that would enable the measurement of EAL as a function of electron kinetic energy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

The Anionic Polymerization of a tert-Butyl-Carboxylate-Activated Aziridine

N-Sulfonyl-activated aziridines are known to undergo anionic-ring-opening polymerizations (AROP) to form polysulfonyllaziridines. However, the post-polymerization deprotection of the sulfonyl groups from polysulfonyllaziridines remains challenging. In this report, the polymerization of tert-butyl aziridine-1-carboxylate (BocAz) is reported. BocAz has an electron-withdrawing tert-butyloxycarbonyl (BOC) group on the aziridine nitrogen. The BOC group activates the aziridine for AROP and allows the synthesis of low-molecular-weight poly(BocAz) chains. A 13C NMR spectroscopic analysis of poly(BocAz) suggested that the polymer is linear. The attainable molecular weight of poly(BocAz) is limited by the poor solubility of poly(BocAz) in AROP-compatible solvents. The deprotection of poly(BocAz) using trifluoroacetic acid (TFA) cleanly produces linear polyethyleneimine. Overall, these results suggest that carbonyl groups, such as BOC, can play a larger role in the in the activation of aziridines in anionic polymerization and in the synthesis of polyimines.

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

Catalytic, Spectroscopic, and Theoretical Studies of Fe 4 S 4 -Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Iron–sulfur clusters play essential roles in biological systems, and thus synthetic [Fe 4 S 4 ] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe 4 S 4 ] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO 2 reduction catalyst. Here, in this work, we demonstrate that incorporating these [Fe 4 S 4 ] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe 4 S 4 -based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO 2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn–H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe 4 S 4 ] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

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

Polymers depolymerizable by metathesis of a cleavable unit

Novel polymers are depolymerizable by metathesis of a cleavable unit. As an example, a series of linear and crosslinked polyurethanes were prepared that can be selectively depolymerized under mild conditions. Two unique polyols were synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis to five- and six-membered cycloalkenes. These polyols were co-polymerized with toluene diisocyanate to generate linear polyurethanes and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked polyurethanes. The polyol design is such that the ring-closing metathesis reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs' catalyst under ambient conditions, the polyurethanes were rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enabled further re-polymerization by traditional strategies for polymerization of double bonds. This general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.

Jones, Brad Howard↗