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At least 145 records · Page 8

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DOE OSTI2023

Synthesis and exceptional operational durability of polyaniline-inspired conductive ladder polymers

Ladder-type structures can impart exceptional stability to polymeric electronic materials. This article introduces a new class of conductive polymers featuring a fully ladder-type backbone. A judicious molecular design strategy enables the synthesis of a low-defect ladder polymer, which can be efficiently oxidized and acid-doped to achieve its conductive state. The structural elucidation of this polymer and the characterization of its open-shell nature are facilitated with the assistance of studies on small molecular models. An autonomous robotic system is used to optimize the conductivity of the polymer thin film, achieving over 7 mS cm −1 . Impressively, this polymer demonstrates unparalleled stability in strong acid and under harsh UV-irradiation, significantly surpassing commercial benchmarks like PEDOT:PSS and polyaniline. Moreover, it displays superior durability across numerous redox cycles as the active material in an electrochromic device and as the pseudocapacitive material in a supercapacitor device. This work provides structural design guidance for durable conductive polymers for long-term device operation.

36 MATERIALS SCIENCE↗

NASA NTRS1996

Polymer-Induced Depletion Interaction and Its Effect on Colloidal Sedimentation in Colloid-Polymer Mixtures

In this paper we focus on the polymer-induced depletion attraction and its effect on colloidal sedimentation in colloid-polymer mixtures. We first report a small angle neutron scattering (SANS) study of the depletion effect in a mixture of hard-sphere-like colloid and non-adsorbing polymer. Then we present results of our recent sedimentation measurements in the same colloid-polymer mixture. A key parameter in controlling the sedimentation of heavy colloidal particles is the interparticle potential U(tau), which is the work required to bring two colloidal particles from infinity to a distance tau under a give solvent condition. This potential is known to affect the average settling velocity of the particles and experimentally one needs to have a way to continuously vary U(tau) in order to test the theory. The interaction potential U(tau) can be altered by adding polymer molecules into the colloidal suspension. In a mixture of colloid and non-adsorbing polymer, the potential U(tau) can develop an attractive well because of the depletion effect, in that the polymer chains are expelled from the region between two colloidal particles when their surface separation becomes smaller than the size of the polymer chains. The exclusion of polymer molecules from the space between the colloidal particles leads to an unbalanced osmotic pressure difference pushing the colloidal particles together, which results in an effective attraction between the two colloidal particles. The polymer-induced depletion attraction controls the phase stability of many colloid-polymer mixtures, which are directly of interest to industry.

Tong, Penger↗

DOE OSTI2022

Polymers and methods for their manufacture

Embodiments of the invention relate to a novel class of polymers with superior mechanical properties and chemical stability, as compared to known polymers. These polymers are particularly well suited for use in anion exchange membranes (AEMs), including those employed in fuel cells. Novel methods for the manufacture of these polymers are also described.

Bae, Chulsung↗

DOE OSTI2022

Polymers and methods for their manufacture

Bae, Chulsung↗

DOE OSTI2023

Polymers and methods for their manufacture

Bae, Chulsung↗

NASA NTRS1993

Numerical simulation of non-Newtonian free shear flows

Free shear flows, like those of mixing layers, are encountered in aerodynamics, in the atmosphere, and in the ocean as well as in many industrial applications such as flow reactors or combustion chambers. It is, therefore, crucial to understand the mechanisms governing the process of transition to turbulence in order to predict and control the evolution of the flow. Delaying transition to turbulence as far downstream as possible allows a gain in energy expenditure while accelerating the transition can be of interest in processes where high mixing is desired. Various methods, including the use of polymer additives, can be effective in controlling fluid flows. The drag reduction obtained by the addition of small amounts of high polymers has been an active area of research for the last three decades. It is now widely believed that polymer additives can affect the stability of a large variety of flows and that dilute solutions of these polymers have been shown to produce drag reductions of over 80 percent in internal flows and over 60 percent in external flows under a wide range of conditions. The major thrust of this work is to study the effects of polymer additives on the stability of the incompressible mixing layer through large scale numerical simulations. In particular, we focus on the two dimensional flow and examine how the presence of viscoelasticity may affect the typical structures of the flow, namely roll-up and pairing of vortices.

Homsy, G. M.↗

NASA NTRS2003

Polymer/Silicate Nanocomposites Developed for Improved Strength and Thermal Stability

Over the past decade, polymer-silicate nanocomposites have been attracting considerable attention as a method of enhancing polymer properties. The nanometer dimensions of the dispersed silicate reinforcement can greatly improve the mechanical, thermal, and gas barrier properties of a polymer matrix. In a study at the NASA Glenn Research Center, the dispersion of small amounts (less than 5 wt%) of an organically modified layered silicate (OLS) into the polymer matrix of a carbon-fiber-reinforced composite has improved the thermal stability of the composite. The enhanced barrier properties of the polymer-clay hybrid are believed to slow the diffusion of oxygen into the bulk polymer, thereby slowing oxidative degradation of the polymer. Electron-backscattering images show cracking of a nanocomposite matrix composite in comparison to a neat resin matrix composite. The images show that dispersion of an OLS into the matrix resin reduces polymer oxidation during aging and reduces the amount of cracking in the matrix significantly. Improvements in composite flexural strength, flexural modulus, and interlaminar shear strength were also obtained with the addition of OLS. An increase of up to 15 percent in these mechanical properties was observed in composites tested at room temperature and 288 C. The best properties were seen with low silicate levels, 1 to 3 wt%, because of the better dispersion of the silicate in the polymer matrix.

Campbell, Sandi G.↗

NASA NTRS2021

Microstructural, Strength, and Creep Characterization of Sylramic™, Sylramic™-iBN and Super Sylramic™-iBN SiC Fibers

The chemical composition, microstructure, strength, and thermal stability of polymer-derived Sylramic™ SiC fibers fabricated by Dow Corning and COI Ceramics, Inc., and nitrogen-treated Sylramic™ SiC fibers, referred to as Sylramic™-iBN and Super Sylramic™-iBN SiC fibers, were investigated and compared. The baseline Sylramic™ SiC fibers fabricated by both vendors as well as the nitrogen-treated Sylramic™ SiC fibers are composed mostly of β-SiC (~97 wt%) with small amounts of TiB2 (~2 wt%), amorphous carbon (~1 wt%) and trace amounts of B4C. Most of the amorphous carbon is segregated at the core/interior of the fibers. Both baseline and nitrogen-treated Sylramic™ SiC fibers have similar grain size and pore size distribution, except for a thin layer of in-situ grown crystalline BN (30 to 70 nm) on the surface of Sylramic™-iBN and Super Sylramic™-iBN fibers. Wide variation in strength within a batch as well as between batches is observed in both baseline and nitrogen-treated Sylramic™ SiC fibers but both types of fibers are microstructurally stable at temperatures to 1800°C in argon and nitrogen environments compared to Nicalon™-S and Tyranno®-SA SiC fibers. Under the same creep condition, Super Sylramic™-iBN fibers show better creep resistance compared to Sylramic™, Sylramic™-iBN, Hi-Nicalon™-S, and Tyranno®-SA fibers. Possible reasons for strength variability and the mechanism of in-situ BN formation on Sylramic™ SiC fibers are discussed.

SiC fibers↗

DOE OSTI2020

Internal arcing and lightning strike damage in short carbon fiber reinforced thermoplastic composites

Short carbon fiber reinforced thermoplastic composites (S-CFRTP) are currently used in interior parts of aircraft such as electronic circuitry and assemblies, and their usage in aircraft's exterior is also being studied. In this paper, we present a lightning strike study on S-CFRTPs. High performance thermoplastics such as a polyphenylene sulfide (PPS) reinforced with 50% weight (wt.) short carbon fiber (CF), a polyphenyl sulfone (PPSU) reinforced with 25 % wt. Short CF and a acrylonitrile butadiene styrene (ABS) with 20 % wt. short CF were tested against artificial lightning strikes. All samples were prepared using an extrusion compression molding (ECM) technique. A modified component A (100 kA) of lightning waveform, as defined by SAE ARP 5412-B, was applied. High speed imaging, thermography, scanning electron microscopy (SEM) and ultrasonic non-destructive evaluation were performed to understand the effect of lightning strikes on the thermoplastic panels. The results show that electrical conductivity of the composite, thermal stability of the polymers, and CF orientation significantly affected the damage from artificial lightning strikes. PPS composite had the highest resilience against lightning strike damage, retaining 95% and 89% residual flexural strength and modulus, respectively. CF exfoliation due to internal arcing was observed in the carbon fiber-reinforced ABS polymer (CF-ABS) composite. CF exfoliation damage has been reported for the first time.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

Lignin is a major bioresource from 2nd generation biorefinery process streams and from pulp and paper production that is still severely underutilized nowadays. Its natural polymeric and aromatic structures make it suitable as a potential building block for biopolymer production. Due to the growing environmental and health concerns over conventional polyurethane (PU) manufacturing processes that utilize toxic isocyanates, there is a great interest to develop a non-isocyanate PU (NIPU) route. Herein, we demonstrate a novel strategy that uses highly pure lignin isolated from co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment of poplar wood to produce biobased NIPUs. In this strategy, hardwood poplar is firstly fractionated via a CELF pretreatment to produce a clean lignin stream that is rich in phenolics. The CELF lignin was then aminated by a Mannich reaction, and the aminated CELF lignin was finally reacted with bicyclic carbonates to yield an advanced NIPU. In this work, the structure, mechanical, and thermal properties of these novel NIPUs were elucidated by FTIR, NMR, tensile test, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The mechanical properties of these lignin based NIPUs could be tuned from highly rigid to elastic polymers by simply modifying the lignin constituents of the polymer. The thermal stabilities of NIPUs were improved because of the addition of aminated lignin, and NIPU containing 55 and 23 wt% lignin showed the highest tensile strength (~1.2 MPa) and elongation at break (~140%), respectively. The results obtained in this study demonstrate that the reaction of cyclic carbonate with aminated lignin represents an interesting pathway for the synthesizing of lignin based NIPU with a relative high lignin content.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Opinion to address the personal protective equipment shortage in the global community during the COVID-19 outbreak

The current COVID-19 pandemic is stretching both the global supply for face masks and personal protective equipment (PPE). Production capacity is severely limited in many countries. This is a call for the R&D community, particularly to those in the polymer degradation and stability field. We have not only an opportunity but an obligation to engage and collaborate with virology and bio-medical experts. We require comparative R&D for extended, reuse and recyclability options. Additionally, there is urgent need for large scale institutional approaches and methods that can be quickly applied locally by non-experts with limited resources.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Polydiallylammonium-Polysulfone Multiblock Copolymers for Moisture-Swing Direct Air Capture of Carbon Dioxide

Polysulfones are an important class of materials for a variety of applications due to their excellent strength and thermal stability. Quaternary ammonium polymers are also useful materials due to their ion exchange properties, and such materials with alkaline counterions have been used to capture carbon dioxide (CO 2 ) from ambient air through a moisture-driven mechanism. Herein, we design sulfone-based multiblock copolymers containing ammonium functionalities and demonstrate their potential for CO 2 capture. Specifically, a series of multiblock copolymers containing both polydiallyldimethylammonium (PDADMA) and polysulfone (PSf) blocks were synthesized. PSf blocks provide mechanical integrity, while the PDADMA blocks enable the direct air capture of CO 2 . Multiblock copolymers were synthesized at high yield, and PDADMA(OH)-PSf copolymer films with good flexibility and strength were formed with IECs of 424 μmol/g (17 mol % PDADMA(OH)), 1407 μmol/g (44 mol % PDADMA(OH)), and 1726 μmol/g (50 mol % PDADMA(OH)). Thermogravimetric analysis was used to determine that all films are thermally stable up to 345 °C. Differential scanning calorimetry revealed that the 17 and 44 mol % functionalized PDADMA(OH)-PSf multiblock copolymers showed one T g at 185 °C and 50 mol % PDADMA(OH)-PSf polymer showed a T g at 183 °C and a second T g at 16 °C. Atomic force microscopy showed that the multiblock polymers exhibit disordered phase separation. Furthermore, the copolymer materials displayed moisture-swing direct air capture of CO 2 , opening up pathways to utilize polymer architecture and chemistry to tailor the properties of promising sorbents.

42 ENGINEERING↗

DOE OSTI2023

Mechanical and Thermal Characterization of Phase-Change Material and High-Density Polyethylene Functional Composites for Thermal Energy Storage

Abstract Phase-change materials (PCMs) can be used to develop thermal energy storage systems as they absorb large amount of latent heat nearly at a constant temperature when changing phase from a solid to a liquid. To prevent leakage when in a liquid state, PCM is shape stabilized in a polymer matrix of high-density polyethylene (HDPE). The present research explores the injection-molded mechanical and thermal properties of different PCM/HDPE composite ratios. The tensile strength and modulus of elasticity at room temperature and with the PCM fully melted within the composite are measured. Additionally, the hardness, latent heat of fusion, phase-change temperature, and thermal conductivity are investigated. An analysis of microstructures of the composite is used to support the findings. The PCM within the PCM/HDPE composite gives it the benefit of thermal storage but causes a decrease in mechanical properties.

Energy & Fuels↗

NASA NTRS1975

Development of a special purpose spacecraft interior coating, phase 1

Coating formulations were developed consisting of latex blends of fluorocarbon polymers, acrylic resins, stabilizers, modifiers, other additives, and a variety of inorganic pigments. Suitable latex primers were also developed from an acrylic latex base. The formulations dried to touch in about one hour and were fully dry in about twenty-four hours under normal room temperature and humidity conditions. The resulting coatings displayed good optical and mechanical properties, including excellent bonding to (pre-treated) substrates. In addition, the preferred compositions were found to be self-extinguishing when applied to nonflammable substrates and could meet the offgassing requirements specified by NASA for the intended application. Improvements are needed in abrasion resistance and hardness.

Bartoszek, E. J.↗

NASA NTRS1979

Some final conclusions and supporting experiments related to the search for organic compounds on the surface of Mars

The Viking molecular analysis experiment has demonstrated the absence (within the detection limits which range from levels of parts per million to below parts per billion) of organic substances in the Martian surface soil at the two Viking landing sites. Laboratory experiments with sterile and nonsterile antarctic samples further demonstrate the capability and reliability of the instrument. The circumstances under which organic components could have escaped detection, such as inaccessibility or extreme thermal stability of organic polymers, are discussed but are found to be unlikely. The inability of the instrument to detect free oxygen evolved from soil samples is pointed out.

Biemann, K.↗

NASA NTRS1985

Nonyellowing Polycarbonate for Outdoor Use

Two-step photochemical process prevents yellowing of polycarbonate plastics. Use of polycarbonate plastics growing in windows, aircraft glazing, and streetlight globes. New photochemical process causes formation of stabilizers bound to polymer chains and therefore cannot be leached out.

Gupta, A.↗

NASA NTRS1984

Polymerizable ultraviolet stabilizers

Polymerizable ultraviolet stabilizers were examined. The objective was to synthesize polymerizable UV monomers, and to incorporate polymerizable UV stabilizers (benzotriazoles) into polymers.

Gomez, P.↗