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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 55 records · Page 3

Stereomicrostructure-regulated biodegradable adhesives

Commercial adhesives are petroleum-based thermoset networks or nonbiodegradable thermoplastic hot melts, making them ideal targets for replacement by biodegradable alternatives. Poly(3-hydroxybutyrate) (P3HB) is a biorenewable and biodegradable alternative to conventional plastics, but microbial P3HB, which has a stereoperfect stereomicrostructure, exhibits no adhesion. Here, in this study, by elucidating the fundamental relationship between chemocatalytically engineered P3HB stereomicrostructures and adhesion properties, we found that biodegradable syndio-rich P3HB exhibits high adhesion strength and outperforms common commercial adhesives, whereas syndiotactic, isotactic, or iso-rich P3HB shows no measurable adhesion. The syndio-rich stereomicrostructure brings about desired thermomechanical and viscoelastic properties of P3HB that enable strong adhesion to a range of substrates tested, including aluminum, steel, glass, and wood, and its performance is insensitive to molar mass and reprocessing or reuse.

36 MATERIALS SCIENCE↗

Organic adhesives for hybrid microcircuits

Engineering design guidelines enumerate and briefly describe selected adhesive properties. General review of polymeric types of adhesives is included and major types of commercially available adhesives specifically designed for microelectronic use are identified.

Perkins, K. L.↗

Effect of Various Material Properties on the Adhesive Stage of Fretting

Various properties of metals and alloys were studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films were found to influence adhesion. High atomic density, low surface energy grain orientations exhibited lower adhesion than other orientations. Knowledge of interfacial surface binding energies assists in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents accomplishes both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Effect of various material properties on the adhesive stage of fretting

Various properties of metals and alloys have been studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films have all been found to influence adhesion. High atomic density, low surface energy grain orientations exhibit lower adhesion than other orientations. Hexagonal metals in general manifest less adhesive wear than cubic metal. Knowledge of interfacial surface binding energies can assist in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents can accomplish both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Effect of various material properties on the adhesive stage of fretting

Various properties of metals and alloys have been studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films have all been found to influence adhesion. High atomic density, low surface energy grain orientations exhibit lower adhesion than other orientations. Hexagonal metals in general manifest less adhesive wear than cubic metal. Knowledge of interfacial surface binding energies can assist in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents can accomplish both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Hydrocarboxylation of C=C Bonds in Polycyclooctene: Progress Toward Valorization of Waste Polyolefins

Upcycling of waste polyolefins into higher-value functional polymers through chemical functionalization is a promising strategy to recover value and minimize their environmental impact. We report the hydrocarboxylation of polycyclooctene as a model for accessing ethylene acrylic acid copolymers (EAA) from waste polyethylene. The effects of various process parameters on the hydrocarboxylation were investigated. The relationship between carboxylic acid concentration and material properties, including crystallinity, melting temperature, glass transition temperature, adhesive properties, and wettability, was studied in comparison to an unfunctionalized polyethylene. Among the catalysts evaluated, Co 2 (CO) 8 exhibited relatively slow kinetics toward the hydrocarboxylation and was not compatible with 2,6-di-tert-butyl hydroxytoluene, a common additive present in commercial polyolefins. PdCl 2 (PPh 3 ) 2 exhibited a higher reactivity toward the hydrocarboxylation, though polymer gelation was observed with extended reaction times or high catalyst loadings. Carboxylic acid incorporation into the polymer was readily controlled by varying the reaction time. Altogether, the resultant COOH-functionalized polyolefins possessed properties analogous to commercial EAA.

36 MATERIALS SCIENCE↗

LARC-TPI 1500 series controlled molecular weight polyimide

LARC-TPI, a linear high temperature thermoplastic polyimide, was developed several years ago at NASA Langley Research Center. This material has been commercialized by Mitsui Toatsu Chemicals, Inc., Tokyo, Japan, as a varnish and powder. More recently, a melt-extruded film of a controlled molecular weight of this same polymer has been supplied to NASA Langley Research Center for evaluation. This new form, called LARC-TPI 1500 series, has been prepared in three molecular weights - high, medium and low flow polymers. The subject of this investigation deals with the rheological properties of the high and medium flow powders and the adhesive properties of the medium flow melt-extruded film. Rheological studies indicate that the high and medium flow forms of the polymer fall in the flow range of injection moldable materials. Adhesive data generated on the medium flow extruded film shows this form to be well suited for structural adhesive bonding. The data are as good or better than that for LARC-TPI data of previous studies.

Progar, Donald↗

Evaluation of high-temperature structural adhesives for extended service

Candidate high-temperature stable resin formulations were evaluated for adhesive properties when bonded to titanium treated with various surface preparations. The adhesive formulations included LARC-13, NR150 A2, NR150 B2, NR056X, FM-34, HR-602, and polyphenylquinoxaline. Eight titanium surface preparations were compared for resulting bond strength with the candidate adhesives. After initial evaluation, three adhesive systems (comprised of adhesive, primer, and titanium surface preparation) were selected for further screening. The screening (still in progress) includes cure-cycle optimization and bond properties from 219 K (-65 F) to 505 K (450 F), after isothermal aging at 505 K (450 F) up to 15,000 hours, and after humidity aging at 322 K 9120 F)/ 95 percent R. H. for up to 2000 hours. Larger-area bond capability of the three adhesive system can be demonstrated by fabrication of 30.5 cm (12 in) square titanium honeycomb sandwich and metal-to-metal bonded panels.

Hendricks, C. L.↗

Should I stay or should I flow? An exploration of phase‐separated metallosupramolecular liquid crystal polymers

Abstract Dynamic liquid crystalline polymers (dLCPs) incorporate both liquid crystalline mesogens and dynamic bonds into a single polymeric material. These dual functionalities impart order‐dependent thermo‐responsive mechano‐optical properties and enhanced reprocessability/programmability enabling their use as soft actuators, adaptive adhesives, and damping materials. While many previous works studying dynamic LCPs utilize dynamic covalent bonds, metallosupramolecular bonds provide a modular platform where a series of materials can be accessed from a single polymeric feedstock through the variation of the metal ion used. A series of dLCPs were prepared by the addition of metal salts to a telechelic 2,6‐bisbenzimidazolylpyridine (Bip) ligand endcapped LCP to form metallosupramolecular liquid crystal polymers (MSLCPs). The resulting MSLCPs were found to phase separate into hard and soft phases which aids in their mechanical robustness. Variations of the metal salts used to access these materials allowed for control of the thermomechanical, viscoelastic, and adhesive properties with relaxations that can be tailored independently of the mesogenic transition. This work demonstrates that by accessing phase separation through the incorporation of metallosupramolecular moieties, highly processable yet robust MSLCP materials can be realized. This class of materials opens the door to LCPs with bulk flow behavior that can also be utilized as multi‐level adhesives.

Chemistry↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗

Method to Prepare Processable Polyimides with Non-Reactive Endgroups Using 1,3-bis(3-Aminophenoxy) Benzene

Polyimide copolymers were obtained containing 1,3-bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and terminating with the appropriate amount of a non-reactive endcapper, such as phthalic anhydride. Homopolymers containing only other diamines and dianhydrides which are not processable under conditions described previously can be made processable by incorporating various amounts of APB, depending on the chemical structures of the diamines and dianhydrides used. Polyimides that are more rigid in nature require more APB to impart processability than polyimides that are less rigid in nature. The copolymers that result from using APB to enhance processability have a unique combination of properties including excellent thin film properties, low pressure processing (200 psi and below), improved toughness, improved solvent resistance, improved adhesive properties, improved composite mechanical properties, long term melt stability (several hours at 390 C), and lower melt viscosities.

Jensen, Brian J.↗

Method to Prepare Processable Polymides with Reactive Endgroups using 1,3-Bis (3-Aminophenoxy) Benzene

Polyimide copolymers were obtained containing 1,3-bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and terminating with the appropriate amount of reactive endcapper. The reactive endcappers studied include but should not be limited to 4-phenylethynyl phthalic anhydride (PEPA ), 3-aminophenoxy- 4'-phenylethynylbenzophenone (3-APEB), maleic anhydride (MA) and nadic anhydride (5-norbomene-2,3-dicarboxylic anhydride, NA). Homopolymers containing only other diamines and dianhydrides which are not processable under conditions described previously can be made processable by incorporating various amounts of APB, depending on the chemical structures of the diamines and dianhydrides used. By simply changing the ratio of APB to the other diamine in the polyimide backbone, a material with a unique combination of solubility, Tg, Tm, melt viscosity, toughness and elevated temperature mechanical properties can be prepared. The copolymers that result from using APB to enhance processability have a unique combination of properties that include low pressure processing (200 psi and below), long term melt stability (several hours at 300 C. for the phenylethynyl terminated polymers), high toughness, improved solvent resistance, improved adhesive properties, and improved composite mechanical properties. These copolyimides are eminently suitable as adhesives, composite matrices, moldings, films and coatings.

Jensen, Brian J.↗

Method To Prepare Processable Polyimides With Reactive Endogroups Using 1,3-bis(3-aminophenoxy)benzene

Polyimide copolymers were obtained containing 1,3-bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and terminating with the appropriate amount of reactive endcapper. The reactive endcappers studied include but should not be limited to 4-phenylethynyl phthalic anhydride (PEPA), 3-aminophenoxy-4'phenylethynylbenzophenone (3-APEB), maleic anhydride (MA) and nadic anhydride (5-norbomene-2,3-dicarboxylic anhydride, NA). Homopolymers containing only other diamines and dianhydrides which are not processable under conditions described previously can be made processable by incorporating various amounts of APB, depending on the chemical structures of the diamines and dianhydrides used. By simply changing the ratio of APB to the other diamine in the polyimide backbone, a material with a unique combination of solubility, Tg, Tm, melt viscosity, toughness and elevated temperature mechanical properties can be prepared. The copolymers that result from using APB to enhance processability have a unique combination of properties that include low pressure processing (200 psi and below), long term melt stability (several hours at 300° C. for the phenylethynyl terminated polymers), high toughness, improved solvent resistance, improved adhesive properties, and improved composite mechanical properties. These copolyimides are eminently suitable as adhesives, composite matrices, moldings, films and coatings.

Brian J Jensen↗

Sustainable, degradable and malleable low-dielectric-constant thermosets derived from biomass for recyclable green electronics

In view of their excellent thermal and chemical resistance, favorable adhesion properties, high tensile strength, and other advantages, epoxy thermosets have numerous industrial applications such as coating, adhesive, and composite material production. However, bisphenol A (BPA)-based resins, which account for a significant fraction of the above thermosets, adversely affect human health by interfering with the normal functioning of the endocrine system and cannot be easily decomposed and recycled. Herein, degradable and sustainable bio-based epoxy thermosets with crosslinked network structures are prepared by the epoxidation of isosorbide with epichlorohydrin and the curing of the produced isosorbide diglycidyl ether (ISDGE) with cyclic lactones through a cationic ring-opening reaction. The ISDGE thermosets fully decompose into soluble and recyclable products under mildly basic conditions within three days, which is ascribed to the presence of ester moieties within the polymer network structure. Compared to a representative BPA-based epoxy, ISDGE-based thermosets exhibit lower dielectric constants and are more flexible. Moreover, the glass fibers in ISDGE-based prepregs can be fully recovered after on-demand degradation. Furthermore, our work provides promising eco-friendly alternatives to conventional epoxy thermosets and paves the way for the reduction of plastic waste generation and the development of recyclable green electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LARC-I-TPI: A New Thermoplastic Polyimide

"LARC-I-TPI" denotes improved version of LARC-TPI class of thermoplastic polyimides: high-performance polymers developed for manufacture of strong, lightweight aircraft structures. Melt-flow and adhesive properties of new polymers make them attractive for use as matrix resins for composites, molding powders, adhesives, and coating films. Less toxic, improved LARC-I-TPI polymers formulated without 3, 3'-diaminobenzophenone, which is mutagenic and commercially unavailable.

St. Clair, Terry L.↗

LARC-IA: A flexible backbone polyimide

A new linear, aromatic, thermoplastic polyimide, prepared from oxydiphthalic anhydride (ODPA) and 3,4'-oxydianiline (ODA) in diglyme and identified as LARC-IA, was synthesized and evaluated. The monomers are relatively inexpensive and physiologically safe. Molecular weight was controlled by use of a monofunctional anhydride, phthalic anhydride (PA), in order to promote controlled flow and wetting properties. The polymer is considered a safe alternative to commercially available LARC-TPI which is prepared with an expensive diamine of uncertain carcinogenicity. The evaluation was based primarily on the polymer's adhesive properties as determined by thermal and water boil exposure of lap shear specimens. Strengths were determined at room temperature, 177, 204 and 232 C before and after exposure to determine the adhesive system's durability to adverse environments over a period of time. Other properties (FWT, G(1c), film and composite properties) were examined which were determined to be typical of a high temperature polyimide. Results of the study show a favorable comparison to LARC-TPI, a commercially available polyimide.

Progar, Donald J.↗