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Results for “Ring polymers”

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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

Organic materials able to detect analytes

The present invention generally relates to polymers with lasing characteristics that allow the polymers to be useful in detecting analytes. In one aspect, the polymer, upon an interaction with an analyte, may exhibit a change in a lasing characteristic that can be determined in some fashion. For example, interaction of an analyte with the polymer may affect the ability of the polymer to reach an excited state that allows stimulated emission of photons to occur, which may be determined, thereby determining the analyte. In another aspect, the polymer, upon interaction with an analyte, may exhibit a change in stimulated emission that is at least 10 times greater with respect to a change in the spontaneous emission of the polymer upon interaction with the analyte. The polymer may be a conjugated polymer in some cases. In one set of embodiments, the polymer includes one or more hydrocarbon side chains, which may be parallel to the polymer backbone in some instances. In another set of embodiments, the polymer may include one or more pendant aromatic rings. In yet another set of embodiments, the polymer may be substantially encapsulated in a hydrocarbon. In still another set of embodiments, the polymer may be substantially resistant to photobleaching. In certain aspects, the polymer may be useful in the detection of explosive agents, such as 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT).

Rose, Aimee↗
DOE OSTI2021

Compositions and methods for depolymerizing lignin using a chelator-mediated Fenton reaction

The present invention provides for a method to depolymerize a lignin comprising: (a) mixing a lignin, a chelator, and FeCl3 to produce a first solution, (b) optionally incubating the solution for a first suitable period of time, (c) introducing an oxidizing agent to the first solution to produce a second solution, and (d) optionally incubating the solution for a second suitable period of time; such that at least one aromatic ring of one lignin polymer is opened.

Kent, Michael S.↗
DOE OSTI2021

A DNA packaging motor inchworms along one strand allowing it to adapt to alternative double-helical structures

Abstract Ring ATPases that translocate disordered polymers possess lock-washer architectures that they impose on their substrates during transport via a hand-over-hand mechanism. Here, we investigate the operation of ring motors that transport ordered, helical substrates, such as the bacteriophage ϕ29 dsDNA packaging motor. This pentameric motor alternates between an ATP loading dwell and a hydrolysis burst wherein it packages one turn of DNA in four steps. When challenged with DNA-RNA hybrids and dsRNA, the motor matches its burst to the shorter helical pitches, keeping three power strokes invariant while shortening the fourth. Intermittently, the motor loses grip on the RNA-containing substrates, indicating that it makes optimal load-bearing contacts with dsDNA. To rationalize these observations, we propose a helical inchworm translocation mechanism in which, during each cycle, the motor increasingly adopts a lock-washer structure during the ATP loading dwell and successively regains its planar form with each power stroke during the burst.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Pentiptycene-based ladder polymers with configurational free volume for enhanced gas separation performance and physical aging resistance

Significance Gas separation membranes are an emerging energy-efficient alternative toward conventional, energy-intensive separation technologies such as cryogenic distillation. Ladder polymers with intrinsic microporosity show exceptional promise toward redefining state-of-the-art gas separation membranes due to their high permeability (throughput) and selectivity (separation efficiency). However, they are typically inhibited by major reductions in permeability over time due to collapsing membrane free volume (open space between polymer chains), forfeiting their greatest asset. This work explores a route toward enhanced aging resistance and overall separation performance by incorporating pentiptycene (an H-shaped scaffold containing five fused arene rings) into ladder-like polymers to incorporate natural, more permanent “micropores” that aren’t susceptible to densification of polymer chains that occurs over time in traditional microporous polymers.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Ultrahigh Molecular Weight Aromatic Siloxane Polymers

Silphenylene-siloxane polymers can be prepared by a condensation reaction of a diol 1,4-bis(hydroxydimethylsilyl)benzene and a silane bis(dimethylamino)dimethylsilane. Using a stepwise condensation technique, a polymer (R=CH3) with a molecular weight in excess of 1.0 x 1 million has been produced. The polymer exhibits increased thermal stability, compared to a methyl siloxane polymer without the aromatic phenyl ring in the backbone. The use of bis(dimethylamino)methylvinylsilane should allow for ready crosslinking at the vinyl sites (R=-CH=CH2) introduced into the backbone. However, under the conditions of the reaction system a high molecular weight polymer was not obtained or the polymer underwent a crosslinking process during the synthesis.

Ludwick, L. M.↗
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↗
DOE OSTI2022

Poly(ionic liquid)s with Dicationic Pendants as Gas Separation Membranes

Poly(norbornene)s and poly(ionic liquid)s are two different classes of attractive materials, which are known for their structural tunability and thermal stabilities, and have been extensively studied as gas separation membranes. The incorporation of ionic liquids (ILs) into the poly(norbornene) through post-polymerization has resulted in unique materials with synergistic properties. However, direct polymerization of norbornene-containing IL monomers as gas separation membranes are limited. To this end, a series of norbornene-containing imidazolium-based mono- and di-cationic ILs (NBM-mIm and NBM-DILs) with different connectivity and spacer lengths were synthesized and characterized spectroscopically. Subsequently, the poly(NBM-mIm) with bistriflimide [Tf2N−] and poly([NBM-DILs][Tf2N]2) comprising homo-, random-, and block- (co)polymers were synthesized via ring-opening metathesis polymerization using the air-stable Grubbs second-generation catalyst. Block copolymers (BCPs), specifically, [NBM-mIM][Tf2N] and [NBM-ImCnmIm] [Tf2N]2 (n = 4 and 6) were synthesized at two different compositions, which generated high molecular weight polymers with decent solubility relative to homo- and random (co)polymers of [NBM-DILs] [Tf2N]2. The prepared BCPs were efficiently analyzed by a host of analytical tools, including 1H-NMR, GPC, and WAXD. The successfully BCPs were cast into thin membranes ranging from 47 to 125 μm and their gas (CO2, N2, CH4, and H2) permeations were measured at 20 °C using a time-lag apparatus. These membranes displayed modest CO2 permeability in a non-linear fashion with respect to composition and a reverse trend in CO2/N2 permselectivity was observed, as a usual trade-off behavior between permeability and permselectivity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Polyhalohydrins: Investigating Vicinal Functionalities by Ring-Opening of Epoxides on Polyolefins

Halohydrins are functional groups that are underexplored in polymer science. This study synthesized and examined structure–property relationships of halohydrin-functionalized polymers derived from polycyclooctene (PCOE), which was obtained via ring-opening metathesis polymerization (ROMP). The polyhalohydrins, including polychlorohydrin, polybromohydrin, and polyiodohydrin, were produced through a two-step process involving epoxidation of PCOE followed by epoxide ring-opening using hydrochloric, hydrobromic, or hydroiodic acid. These stereoirregular and regioirregular polymers are amorphous as measured by differential scanning calorimetry and X-ray scattering. Lap joint shear testing revealed an enhanced adhesive performance in polychlorohydrin and polybromohydrin, with the former demonstrating nearly three times the ultimate shear stress compared to a model polyethylene, hydrogenated PCOE. Additionally, contact angle measurements and surface free energy analysis showed an increase in hydrophilicity and polarity from iodine- to bromine- to chlorine-functionalized polyhalohydrins, aligning with trends in adhesion strength. Furthermore, these results underscore the potential of halohydrin functionalization as a versatile approach for tuning surface properties, offering new opportunities for polymer-to-polymer transformations.

Functional groups↗
DOE OSTI2020

Electron‐Deficient and Quinoid Central Unit Engineering for Unfused Ring‐Based A 1 –D–A 2 –D–A 1 ‐Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High V oc and PCE Simultaneously

Abstract Here, a pair of A 1 –D–A 2 –D–A 1 unfused ring core‐based nonfullerene small molecule acceptors (NF‐SMAs), BO2FIDT‐4Cl and BT2FIDT‐4Cl is synthesized, which possess the same terminals (A 1 ) and indacenodithiophene unit (D), coupling with different fluorinated electron‐deficient central unit (difluorobenzoxadiazole or difluorobenzothiadiazole) (A 2 ). BT2FIDT‐4Cl exhibits a slightly smaller optical bandgap of 1.56 eV, upshifted highest occupied molecular orbital energy levels, much higher electron mobility, and slightly enhanced molecular packing order in neat thin films than that of BO2FIDT‐4Cl . The polymer solar cells (PSCs) based on BT2FIDT‐4Cl:PM7 yield the best power conversion efficiency (PCE) of 12.5% with a V oc of 0.97 V, which is higher than that of BO2FIDT‐4Cl ‐based devices (PCE of 10.4%). The results demonstrate that the subtle modification of A 2 unit would result in lower trap‐assisted recombination, more favorable morphology features, and more balanced electron and hole mobility in the PM7:BT2FIDT‐4Cl blend films. It is worth mentioning that the PCE of 12.5% is the highest value in nonfused ring NF‐SMA‐based binary PSCs with high V oc over 0.90 V. These results suggest that appropriate modulation of the quinoid electron‐deficient central unit is an effective approach to construct highly efficient unfused ring NF‐SMAs to boost PCE and V oc simultaneously.

Zhang, Chao↗
NASA NTRS2003

Molecular modeling of polymer composite-analyte interactions in electronic nose sensors

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites. c2003 Elsevier Science B.V. All rights reserved.

NASA Center JPL↗
NASA NTRS2002

Molecular modeling of polymer composite interactions with analytes in electronic nose sensors for environmental monitoring in International Space Station

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL Electronic Nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings (with no hydrogens). The Dreiding 2.21 force field is used for the polymer and solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4- vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic (ammonia) and organic (methanol, toluene, hydrazine) compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites.

electronic noise environmental monitoring polymer ↗
DOE OSTI2022

Miktoarm Star Polymers: Synthesis and Applications

Polymers with precisely controlled structure and function are in high demand across a diverse array of applications spanning the life sciences and nanotechnology. One prototypical example is a class of branched block copolymers known as miktoarm stars (μ-stars), which contain two or more arm compositions connected at a common junction. Miktoarm stars have attracted considerable attention since their physical properties can be different from conventional linear block copolymers. This perspective highlights the latest developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools used to avoid common preparation pitfalls and tailor properties for emerging applications. Furthermore, our contemporary perspective on μ-star polymers is a resource for inspiring future research into this exciting class of materials at the intersection of chemistry, physics, and advanced technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

Hot piston ring/cylinder liner materials: Selection and evaluation

In current designs of the automotive (kinematic) Stirling engine, the piston rings are made of a reinforced polymer and are located below the pistons because they cannot withstand the high temperatures in the upper cylinder area. Theoretically, efficiency could be improved if hot piston rings were located near the top of the pistons. Described is a program to select piston ring and cylinder coating materials to test this theory. Candidate materials were screened, then subjected to a pin or disk friction and wear test machine. Tests were performed in hydrogen at specimen temperatures up to 760 C to simulate environmental conditions in the region of the hot piston ring reversal. Based on the results of these tests, a cobalt based alloy, Stellite 6B, was chosen for the piston rings and PS200, which consists of a metal-bonded chromium carbide matrix with dispersed solid lubricants, was chosen as the cylinder coating. Tests of a modified engine and a baseline engine showed that the hot ring reduced specific fuel consumption by up to 7 percent for some operating conditions and averaged about 3 percent for all conditions evaluated. Related applications of high-temperature coatings for shaft seals and as back-up lubricants are also described.

Sliney, Harold E.↗
NASA NTRS2001

Phenylethynyl Terminated Arylene Ether Oxadiazole and Triazole Oligomers and Their Cured Polymers

Several novel phenylethynyl terminated arylene ether oligomers containing oxadiazole and triazole rings were prepared as part of an effort to develop high performance polymers with an attractive combination of properties (e.g. processability and mechanical performance) for future NASA applications. The oligomers displayed low melt viscosities and good solubilities. Thin films cast from solutions of the oligomers and cured for one hour at 350 C in air gave good tensile properties. Titanium to titanium (6Al-4V) tensile shear specimens were readily fabricated and provided moderate strengths. The chemistry and properties of these new materials are discussed.

Thompson, C. M.↗
DOE OSTI2025

Toward Efficient Entropic Recycling by Mastering Ring–Chain Kinetics

Traditional chemical recycling approaches for condensation polymers suffer compounding energy losses and CO 2 emissions across multiple polymerization and depolymerization cycles. Entropic recycling can address these energy losses by entrapping free energy within the deconstruction products. Entropic recycling involves depolymerization to macrocyclic monomers, but such processes have not been feasible due to the high dilutions typically required to generate macrocyclic compounds. Here, we leverage selective catalysis to allow entropic recycling at concentrations 20–2000× higher than typical for macrocyclization reactions. We find that Ru-based olefin metathesis catalysts containing bulky iodine ligands significantly bias the ring–chain kinetic product distribution during ring-closing metathesis (RCM) toward the formation of oligomeric cycloalkenes. Further improvements in reaction concentration and macrocycle yield are obtained by using high catalyst loadings and by predisposing the alkene substrates to undergo favorable macrocyclization. These RCM optimizations translate effectively to cyclodepolymerization (CDP) of an olefin-containing polymer, with RCM and CDP affording similar macrocycle product distributions under identical reaction conditions. Macrocycle polymerization by entropy-driven ring-opening metathesis provides much higher molecular weight polymers than condensation polymerization of linear analogues, reducing the time to achieve high molecular weight from hours to minutes and enabling polymerization at room temperature. Finally, our findings re-emphasize the importance of energy consumption during a polymer’s lifecycle and provide a framework for the design of efficient entropic recycling systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Synthesis and thermal stability of carborane-containing phosphazenes

Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034

Fewell, L. L.↗
NASA NTRS1990

Squeezing Salvages Oversize Seals

Thermal and mechanical properties of seal material used to advantage. Simple sizing tool compresses polychlorotrifluoroethylene seal to smaller diameter. Polymer seal held by aluminum rings, then compressed by differential thermal expansion between seal and rings. Inner diameter of seal reduced by small amount sufficient to enable remachining to specified size.

Stewart, Gerald M.↗
DOE OSTI2023

Chemically recyclable polyolefin-like multiblock polymers

Polyolefins are the most important and largest volume plastics produced. Unfortunately, the enormous use of plastics and lack of effective disposal or recycling options have created a plastic waste catastrophe. Here in this work, we report an approach to create chemically recyclable polyolefin-like materials with diverse mechanical properties through the construction of multiblock polymers from hard and soft oligomeric building blocks synthesized with ruthenium-mediated ring-opening metathesis polymerization of cyclooctenes. The multiblock polymers exhibit broad mechanical properties, spanning elastomers to plastomers to thermoplastics, while integrating a high melting transition temperature (T m ) and low glass transition temperature (T g ), making them suitable for use across diverse applications (T m as high as 128°C and T g as low as –60°C). After use, the different plastics can be combined and efficiently deconstructed back to the fundamental hard and soft building blocks for separation and repolymerization to realize a closed-loop recycling process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗