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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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10 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Quaternized Polynorbornene Random Copolymers for Fuel Cell Devices

Quaternized polymers are critical components for various energy devices. Vinyl-addition polynorbornenes provide high mechanical strength, high ion conductivity, and chemical stability in a wide range of pH environments due to the all-C–C bond backbone. In this paper, we present the synthesis of a series of quaternized polynorbornene random copolymers via vinyl addition polymerization and elucidate the impact of polymer composition on their properties. The quaternary ammonium alkyl tether length and the ratio of n-hexylnorbornene to unsubstituted norbornene are systemically tailored. A copolymer of 5-(3-bromopropyl)-2-norbornene and norbornene with pendant trimethylammonium groups achieved hydroxide conductivity of 109 mS/cm at 80 °C with a modest water uptake of 72%. The addition of n-hexylnorbornene to the copolymer, to make a terpolymer, allows for the polymer composition to be tailored for properties, including a decrease in water uptake and higher processability, despite a slightly decreased hydroxide conductivity. Moreover, the developed membranes are chemically robust and highly mechanically stable, enabling thin membranes to be easily fabricated. This study provides insight into important design parameters for quaternized polynorbornenes for a variety of energy storage and conversion devices, especially fuel cells.

25 ENERGY STORAGE↗
NASA NTRS1977

Insoluble polyelectrolyte and ion-exchange hollow fiber impregnated therewith

The number of quaternary sites and ion exchange capacity of a polyquaternary, cross linked, insoluble copolymer of a vinyl pyridine and a dihalo organic compound is increased by about 15-35% by reaction of the polymer with an amine followed by quaternization, if required. The polymer forms spontaneously in the presence of a substrate such as within the pores of a hollow fiber. The improved resin impregnated fiber may be utilized to remove ions from waste or process steams.

Rembaum, A.↗
NASA NTRS2007

Water-Free Proton-Conducting Membranes for Fuel Cells

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Narayanan, Sekharipuram↗
DOE OSTI2026

Molecular-Level Insights into the Influence of Ionic Liquids on the Structure and Dynamics of Neutral and Charged Polyimides

We use all-atom molecular dynamics simulations to investigate how increasing ionic functionalization influences polyimide (PI) behavior in ionic liquid (IL) solvation environments. Here, we examine three polymer systems with varying charge densities: a neutral polyimide [N−PI] containing imidazole rings and progressively introduce charge through quaternization to create singly [C−PI] + and doubly charged [C−2PI] 2+ variants across a wide range of IL concentration (0−90 wt %). Through comprehensive structural, mechanical, and electrostatic analyses, we reveal that polymer charge density plays a central role in shaping IL organization and interaction with the polymer matrix. At low IL content, charged systems exhibit strong electrostatic complexation, leading to chain compaction, localized ESP environments, and elevated dielectric constants. As IL concentration increases, the effect of the different polymer charge states becomes less significant. Notably, an intermediate composition regime at approximately 50 wt % IL is associated with changes in IL-rich domain connectivity and overall system behavior across all three PI systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Quaternized polyaromatics for use in electrochemical devices

Disclosed herein in various embodiments are aryl-ether free polyaromatic polymers based on random copolymer architecture with two, three, or more aromatic ring components and methods of preparing those polymers. The polymers of the present disclosure can be used as ion exchange membranes, e.g., as anion exchange membranes, and ionomer binders in alkaline electrochemical devices.

Bae, Chulsung↗
NASA NTRS1978

Novel polyelectrolytes

Cationic polyelectrolytes are formed by the polymerization in absence of oxygen of a monomer of the general formula: ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers. Segments of the linear polymer may be attached to or formed in the presence of polyfunctional reactive tertiary amines or halogen polymeric substrates or polyfunctional lower molecular reactive polyfunctional substrates to form branched or star polyelectrolytes by a quaternization polymerization reaction.

Rembaum, Alan↗
DOE OSTI2024

Aryl ether-free polymer electrolytes for electrochemical and energy devices

Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ethercontaining AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis via nucleophilic substitution, alkylation of polybenzimidazole, and Diels–Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure–property–performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO 2 electrolysers, along with the current status of scale-up synthesis and commercialization.

25 ENERGY STORAGE↗
NASA NTRS1978

Cationic vinyl pyridine copolymers and products thereof

Quaternized, cross-linked, insoluble copolymers of unsubstituted and substituted vinyl pyridines and a dihalo organic compound are spontaneously formed at ambient temperature on mixing the two monomers in bulk, in solution or in suspension. The amount of cross-linking may be varied according to the composition and reaction conditions. The polymer product exhibits ion exchange capacity and undergoes a reversible color change from black at a pH above 7 to yellow at a pH below 7. The polymer may be formed in the presence of preformed polymers, substrates such as porous or impervious particles or films to deposit an ion exchange film in situ or on the surface of the substrate. The coated or resin impregnated substrate may be utilized for separation of anionic species from aqueous solution.

Rembaum, Alan↗
DOE OSTI2023

Rapid Postgrafting Reaction to Prepare Quaternized Polycarbazoles

We report a rapid postgrafting reaction to prepare alkyl ammonium functionalized polycarbazoles from a commercially available monomer. This novel synthetic approach provides benefit to preparing the high molecular weight quaternized polycarbazoles within 1 h of Friedel–Crafts polycondensation, avoiding the synthesis and purification step to prepare a functionalized monomer. The postgrafting reaction produces hexyl alkyl ammonium functionalized polycarbazole with 100% grafting degree. However, the postgrafting reaction produced only 60% grafting with propyl alkyl ammonium due to the competitive elimination reaction because of the higher acidity of β-hydrogen in the propyl alkyl group resulting from the proximity of the bromide and ammonium groups. The hexyl alkyl ammonium functionalized polycarbazole has a high hydroxide conductivity of 103 mS cm –1 at 80 °C and showed excellent alkaline stability with less than 3% loss of ion group after 1 M NaOH treatment at 80 °C for 500 h. In conclusion, this study highlights that the postgrafting reaction provides a pathway for the scale-up synthesis of quaternized aryl ether-free polyaromatics.

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

Phase Behavior of Charged Star Block Copolymers at Fluids Interface

The phase behavior of block copolymers (BCPs) at the water-oil interface is influenced by the segmental interaction parameter (χ) and chain architecture. We synthesized a series of star block copolymers (s-BCPs) having polystyrene (PS) as core and poly(2-vinylpyridine) (P2VP) as corona. The interaction parameters of block-block (χ PS-P2VP ) and block-solvent (χ P2VP-solvent ) were varied by adjusting the pH of the aqueous solution. Lowering pH increased the fraction of quaternized-P2VP (Q-P2VP) with enhanced hydrophilicity. By transferring the equilibrated interfacial assemblies, morphologies ranging from bicontinuous films at pH of 7 and 3.1 to nanoporous and nanotubular structure at pH of 0.65 were observed. The nanoporous films formed hexagonally packed pores in s-BCP matrix, while nanotubes comprised Q-P2VP as corona and PS as core. Control over pore size, d-spacing between pores, and nanotube diameters was achieved by varying polymer concentration, molecular weight, volume fraction and arm number of s-BCPs. Large-scale nanoporous films were obtained by freeze-drying emulsions. Remarkably, the morphologies of linear BCPs were inverted, forming hexagonal-packed rigid spherical micelles with Q-P2VP as core and PS as corona in multilayer. Here, this work provides insights of phase behaviors of BCP at fluids interface and offer a facile approach to prepare nanoporous film with well-controlled pore structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗