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At least 55 records · Page 3

Preparation, characterization, physical testing and performance of flurocarbon membranes and separators

The direct fluorination method of converting carefully selected hydrocarbon substrates to fluorinated membranes was successfully applied to produce promising, novel membranes for electrochemical devices. A family of polymer blends was identified which permits wide latitude in the concentration of both crosslinks and carboxyl groups in hydrocarbon membranes. The membranes of paragraph two were successfully fluorinated.

Lagow, R. J.

Preparation, characterization, physical testing and performance of fluorocarbon membranes and separators

The direct fluorination method of converting carefully selected hydrocarbon substrates to fluorinated membranes was successfully applied to produce promising, novel membranes for electrochemical devices. A family of polymer blends was identified which permits wide latitude in the concentration of both crosslinks and carboxyl groups in hydrocarbon membranes. These membranes were successfully fluorinated and are potentially competitive with commercial membranes in performance, and potentially much cheaper in price.

Lagow, R. J.

Continuous inline blending of antimisting kerosene

A continuous inline blender was developed to blend polymer slurries with a stream of jet A fuel. The viscosity of the slurries ranged widely. The key element of the blender was a static mixer placed immediately downstream of the slurry injection point. A positive displacement gear pump for jet A was employed, and a progressive cavity rotary screw pump was used for slurry pumping. Turbine flow meters were employed for jet A metering while the slurry flow rate was calibrated against the pressure drop in the injection tube. While using one of the FM-9 variant slurries, a provision was made for a time delay between the addition of slurry and the addition of amine sequentially into the jet A stream.

Parikh, P.

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Sun, Sam-Shajing

J-OCTA Applications to in Space Manufacturing and Nanofluidic Technologies

We consider examples of J-OCTA software application to physics-based analysis of in-space manufacturing technologies. Firstly, we consider an atomistic model of thermal welding at the polymer-polymer interface for applications to 3D manufacturing by following diffusion of polymer chains. We show that each component of the polymer blend has its own characteristic time of diffusion and that both strain–stress and shear viscosity curves agree with experimental data. Next, nonlinear shrinkage of the metal part during manufacturing by bound metal deposition under microgravity, is considered using a multi-scale physics-based approach that spans from atomistic dynamics to full-part shrinkage. At the smallest scale we use atomistic dynamics to simulated sintering of a few Ti6Al4V nanoparticles, study sintering mechanisms and estimate important parameters including grain boundary width and diffusion rates of the atoms at the surface that are used at the other scales of modelling. Finally, we analyse selective ionic conduction through an artificial nanopore in a graphene sheet motivated by applications to desalination and energy harvesting. We build distributions of the number and orientation of water molecules in the ion’s hydration shells providing novel insight into the ion-water-carbon interaction at the nanopore.

molecular dynamics

Tuning Anion Composition and Mobility to Balance Ionic Conductivity and Cation Selectivity in Solid Polymer Electrolytes

Solid polymer electrolytes (SPEs) offer a promising route toward safe and high-performance electrochemical energy storage, yet a fundamental challenge in SPEs involves improving ionic conductivity while maintaining selective cation transport. The hurdle exists because ion transport is typically coupled closely to polymer segmental dynamics. Herein, a glassy single-ion-conducting polymer, poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] (PLiMTFSI), in which the anions were tethered to the polymer, was blended with a flexible polymer, poly(oligo-oxyethylene methyl ether methacrylate) (POEM), and a series of small-molecule lithium salts, in which the anions were untethered [lithium bis(trifluoromethane­sulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), or lithium perchlorate (LiClO 4 )]. The impact of salt anion volume and tethered-to-untethered anion ratio on the ion conduction behavior and thermal properties of blend electrolytes was investigated. In some cases, conductivity could be enhanced through this ternary blend approach. For example, a POEM-based polymer blend containing a bulky salt anion (TFSI⁻) and an equimolar mixture of PLiMTFSI and LiTFSI exhibited a Li + conductivity (4.8×10 -4 S/cm) an order of magnitude higher than that of a comparable POEM / LiTFSI system (6.3×10 -5 S/cm) at 100 °C. This enhancement was attributed to a more than ninefold increase in lithium transference number (0.66 in the ternary blend vs. 0.07 in POEM / LiTFSI). Overall, this study highlights the potential for tuning anion composition and mobility to achieve relatively high ionic conductivities and maintain selective cation transport in SPEs, offering a pathway to enable batteries that tolerate elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Analysis of Small-Angle Neutron Scattering from Blends of Charged and Neutral Polymers Based on Rod–Coil Random Phase Approximation

Blends of charged and neutral polymers are of interest due to potential applications in rechargeable batteries. In this study, concentration fluctuations in blends of charged poly[lithium 3-(methacryloyloxy)propylsulfonyl-1-(trifluoromethanesulfonyl)imide] (PLiMTFSI) and neutral poly(ethylene oxide) (PEO) were investigated by small-angle neutron scattering (SANS). The scattering data were analyzed in the framework of the random phase approximation (RPA). Since ion dissociation can lead to stiffening, the charged polymers were approximated as rods, while the neutral polymers were assumed to be random coils. This approach works reasonably well at low weight fractions of charged polymers. For blends with higher weight fractions of the charged polymer, concentration fluctuations were highly suppressed, resulting in q-independent coherent structure factors that are inconsistent with the rod-coil RPA.

Lee, Jaeyong

Chain rigidity controlled aggregation ability and solid-state microstructures for efficient stretchable conjugated polymer films

Stretchable conjugated polymer films with good electrical performance under mechanical deformation are highly desirable for soft electronics. However, the mechanical and electrical properties of these films, particularly in conjugated polymer:elastomer blends, are not fully understood at molecular level. Here, this study explores the relationships among molecular structure, aggregation ability, film microstructure, and the electrical/mechanical properties of three diketopyrrolopyrrole-based conjugated polymers (P1, P2, P3) with decreasing backbone rigidity and their corresponding polymer:elastomer blends. The most flexible polymer P3 shows strong aggregation, which forms highly crystalline fibers to produce fragile neat film and produces large isolated crystallites restricting charge transport in blend film. As chain rigidity increases, the P1 and P2 polymers show weaker aggregation, and produce smaller crystallites in neat films with enhanced ductility. P1 and P2 based blend films display nanocrystallites polymer networks with dispersed elastomer domains. As a result, we achieved near-constant charge mobility before and after stretching under 50 % strain for P2-based blend films with well-controlled pathways for both charge transport and energy dissipation. This study demonstrates the critical role of backbone rigidity in regulating the properties of stretchable conjugated polymer films, paving the way for more reliable and deformable materials in soft electronics.

36 MATERIALS SCIENCE

Emergent Nanostructure and Ion Transport in Polyzwitterion/Polyanion Blends

Solid polymer electrolytes (SPEs) hold great promise for the advancement of next-generation energy storage devices. However, the ion transport mechanism in SPEs remains poorly understood. In this study, we investigate blends of poly(1-(3-sulfonatopropyl)-2-vinylpyridinium) (P2VPPS) and poly(lithium (trifluoromethane)sulfonimide methacrylate) (P(MTFSI)Li) of varying molar ratios to develop a mechanistic understanding of ionic conductivity in a miscible polyzwitterion/polyanion system. Polyanions can act as single-ion conductors, but conductivity is often prohibitively low due to the decreased segmental mobility and ion aggregation. Here, it is hypothesized that the introduction of a polyzwitterion would competitively interact with the polyanion charge groups to realize improvements in the conductivity. Attractive interactions between the polyanions and polyzwitterions are confirmed by the blend’s increased glass transition temperature using the Gordon–Taylor equation. Notably, an ordered local nanostructure (∼24 Å) emerged in the P2VPPS/P(MTFSI)Li system at certain compositions, as characterized by small-angle X-ray and neutron scattering (SAXS/SANS). Concurrent with the emergence of this structure, broadband dielectric spectroscopy confirmed improvements in ionic conductivity. The highest conductivity is observed at a specific blend ratio P2VPPS:P(MTFSI)Li = 0.2:1 in the glassy state and 0.3:1 in the rubbery state, corresponding to the lowest effective activation energy (E*). Coarse-grained molecular dynamics simulations further emphasize the role of complexation between polyzwitterion and polyanion chains, correlating with the emergence of a new peak in SAXS and SANS for the blends. This work provides a fresh perspective on the role of local structural design in developing SPEs and offers insights into the morphological effects on ionic conductivity.

chemical structure

Production and Evaluation of Fluorophore-Doped Polymer Substrates to Screen for Plastic-Degrading Enzymes

Fast and sensitive analytical methods are the key to efficient screening of plastic-degrading enzymes. Here, we present a streamlined and affordable approach to assess the enzymatic deconstruction of insoluble synthetic polymers by blending them with a fluorescent dye, rhodamine 6G, and we evaluate this screening method using poly(ethylene terephthalate) (PET) as a model material. Our results indicate that enzymatic depolymerization of the rhodamine-doped PET can be observed in a high-throughput fashion by following release of the fluorophore. The fluorescence data obtained during the hydrolysis of rhodamine-doped PET by 14 PET hydrolases, produced with a robotic platform, correlated with the quantitative chromatographic analysis of PET degradation products. Remarkably, the use of the rhodamine-loaded PET substrate resulted in negligibly low background signals even when detecting PETase activity in crude cell lysates, suggesting suitability for screening of a wide variety of samples. Encouraged by these results, we next produced a selection of polyethylene- and nylon-based materials loaded with rhodamine 6G. While rapid leaching of fluorophore observed with nylon substrates limits the utility of the method for detecting nylonase activity, the rhodamine-loaded polyethylene showed promising performance in passive diffusion tests, indicating that this latter substrate may be used to screen for polyolefin-degrading enzymes.

09 BIOMASS FUELS

Processing of semicrystalline polymers

Our research group has been interested in the processing-structure-property relationships in semicrystalline polymers and blends for many years. In situ real time x ray scattering at elevated temperatures is being used to monitor the development of structure. An ongoing collaboration with Dr. Malcolm Capel at the Brookhaven National Synchrotron Light Source allows the performance of real time wide and small angle x ray scattering to study the phase transformations in semicrystalline polymers. The first part of my presentation will be about our recent use of x ray scattering to study blends of poly(ethylene terephthalate) with polyarylates. The purpose of the next portion of the presentation is to show how we may study effects of self-deformation of polymers during processing in the gravity environment, using real time x ray scattering. In this way, how processing stresses alter the microstructure of semicrystalline polymers was learned, and ultimately microgravity processing strategies that will result in more uniform morphology in these polymers is hoped to be developed.

Cebe, Peggy

Regulation of Side‐Chain Symmetry for Delaying Triplet Formation and Suppressing Non‐Radiative Loss in Organic Solar Cells

Abstract The structural revolutions of non‐fullerene acceptors (NFAs) have driven continuous efficiency breakthroughs in organic solar cells (OSCs). Rational regulation of NFA structures toward efficient exciton dissociation and mitigated non‐radiative recombination is pivotal for OSCs. The incorporation of asymmetric side chains on NFAs can often achieve these goals by inducing a desirable aggregate state. However, it lacks the studies to directly correlate the side‐chain symmetry of NFAs with the exciton delocalization and triplet dynamics in OSCs. Herein, The influence of structural symmetry on the aggregate properties is systematically investigated and exciton/charge dynamics based on two developed biaxial‐conjugated NFAs with varied side‐chain symmetry. The symmetric NFA having diverse molecular packing orientations can form multiple charge transfer channels in its blend with polymer donor, which cannot be found in that comprising the asymmetric ones. Moreover, a slower rate and lower ratio of the spin‐triplet state are formed in the blend of symmetric NFA, resulting in a much lower non‐radiative voltage loss in corresponding OSCs. This study reveals the distinct advantages of symmetric NFAs in both aggregate properties and exciton/charge dynamics over those of asymmetric ones, paving the way for developing high‐performance OSCs using easier‐to‐prepare, low‐cost symmetric materials.

Chemistry

Miscibility and Cocrystallization in Ethylene–Vinyl Alcohol Copolymer Blends

The compatibility among different ethylene−vinyl alcohol (EVOH) copolymer grades plays a crucial role in determining how easily they can be recycled when present together in a mixed waste stream. In this work, melt miscibility and cocrystallization in 50/50 wt/wt binary blends of EVOH copolymers with differing ethylene content were studied. Blends with up to a 21 mol % difference in composition were analyzed. Thin films of miscible blends appeared homogeneous in the melt as observed under an optical microscope, whereas AFM height images showed that immiscible blends underwent surface roughening due to phase separation. For copolymers with modest composition differences, the blend behaved as a single component, showing single, narrow melting and crystallization peaks in DSC thermograms, indicating cocrystallization at the level of crystal stems. Interestingly, even phase-separated blends demonstrated partial cocrystallization due to partial miscibility of the components in the molten phase-separated domains. The extent of cocrystallization is governed by the difference in freezing points of the components; rapid cooling increased cocrystallization in the blends. The maximum compositional difference allowed for miscibility is not constant but depends on the blend’s average comonomer content, in agreement with the “miscibility window” calculated from literature pressure−volume−temperature behavior for the individual EVOH copolymers and regular mixing theory. This study helps illuminate the effect of copolymer composition on miscibility, as well as cocrystallization behavior in blends of random copolymers with cocrystallizable units.

Cocrystallization

One-Step Radical-Induced Synthesis of Graft Copolymers for Effective Compatibilization of Polyethylene and Polypropylene

The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene (iPP) has gained increasing attention due to their ability to improve the recycling of incompatible mixed polyolefin waste feed streams. Herein, we report a new radical grafting process that yields HDPE-g-iPP copolymers from HDPE and iPP by using a commercially available peroxide. Tensile testing of brittle 70/30 HDPE/iPP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and iPP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE-g-iPP copolymers that compatibilize HDPE and iPP blends at loadings as low as 2.5 wt %. In conclusion, the versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated postconsumer waste plastics.

compatibilization