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A series of highly fluorinated acetylenes was prepared and their cyclization reactions were studied. A series of perfluoropolytriazines with -CF2I pendent groups were prepared. These materials can be cured thermally or photochemically to an elastomeric gum. Perfluoropolytriazines with -CN pendent groups were prepared. These materials can be crosslinked by reaction with terephthalonitrile oxide.
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A multiscale model was developed for predicting the thermoelastic behavior of semi-crystalline thermoplastic materials for composite aerospace applications. At the highest scale containing the semi-crystalline spherulite in an amorphous matrix, the generalized method of cells, or high fidelity method of cells, was used to perform the homogenization calculations to obtain the effective properties. Models were developed assuming a cubic, or spherical shape, for the spherulite to understand if the morphology of the spherulite affects the effective thermoelastic properties. The generalized method of cells was used to model at the repeating unit cells at the subscales of the microstructure including the lamellae stacks and granular crystal blocks. The scales are integrated using the multiscale micromechanics method in the NASA Multiscale Analysis Tool. Data from molecular dynamics simulations were used as inputs for the amorphous and crystalline constituents. Convergence studies were performed to determine the best level of discretization for the repeating unit cell at the highest scale. Effective Young’s modulus, shear modulus, Poisson’s ratio, coefficient of thermal expansion, and thermal conductivity were predicted for polyether ether ketone and polyether ketone ketone, and very good agreement between the model utilizing the cubic spherulite and the experimental data, where available, was observed for polyether ketone ketone. Normalization of the data for the bulk polyether ketone ketone, against amorphous data, improved the predictions as compared to experimental data. Overall, the high fidelity method of cells predicted a stiffer response then the generalized method of cells as the crystallinity was increased. The shape of the spherulite had a minimal effect on the predicted bulk properties of the polymers.
Concentration-response data are presented on the toxic effects of the pyrolysis gases from some natural and synthetic polymers, using the toxicity screening test method developed at the University of San Francisco. The pyrolysis gases from wool, red oak, Douglas fir, polycaprolactam, polyether sulfone, polyaryl sulfone, and polyphenylene sulfide appeared to exhibit the concentration-response relationships commonly encountered in toxicology. Carbon monoxide seemed to be an important toxicant in the pyrolysis gases from red oak, Douglas fir, and polycaprolactam, but did not appear to have been the principal toxicant in the pyrolysis gases from polyether sulfone and polyphenylene sulfide.
Epoxy resin networks cured with DDS were modified by incorporating tough ductile thermoplastics such as the amine terminated polyether sulfones and amine terminated polyether ketones. Both linear copolymers were able to significantly improve the fracture toughness values at the 15 and 30 weight percent concentrations examined. These improvements in fracture toughness were achieved without any significant change in the flexural modulus.
Recent cut damages to crewmember extravehicular mobility unit (EMU) gloves during extravehicular activity (EVA) onboard the International Space Station (ISS) has been found to result from contact with sharp edges or pinch points rather than general wear or abrasion. One possible source of cut-hazards are protruding sharp edged crater lips from impact of micrometeoroid and orbital debris (MMOD) particles on external metallic handrails along EVA translation paths. During impact of MMOD particles at hypervelocity an evacuation flow develops behind the shock wave, resulting in the formation of crater lips that can protrude above the target surface. In this study, two methods were evaluated to limit EMU glove cut-hazards due to MMOD impact craters. In the first phase, four flexible overwrap configurations are evaluated: a felt-reusable surface insulation (FRSI), polyurethane polyether foam with beta-cloth cover, double-layer polyurethane polyether foam with beta-cloth cover, and multi-layer beta-cloth with intermediate Dacron netting spacers. These overwraps are suitable for retrofitting ground equipment that has yet to be flown, and are not intended to protect the handrail from impact of MMOD particles, rather to act as a spacer between hazardous impact profiles and crewmember gloves. At the impact conditions considered, all four overwrap configurations evaluated were effective in limiting contact between EMU gloves and impact crater profiles. The multi-layer beta-cloth configuration was the most effective in reducing the height of potentially hazardous profiles in handrail-representative targets. In the second phase of the study, four material alternatives to current aluminum and stainless steel alloys were evaluated: a metal matrix composite, carbon fiber reinforced plastic (CFRP), fiberglass, and a fiber metal laminate. Alternative material handrails are intended to prevent the formation of hazardous damage profiles during MMOD impact and are suitable for flight hardware yet to be constructed. Of the four materials evaluated, only the fiberglass formed a less hazardous damage profile than the baseline metallic target. Although the CFRP laminate did not form any noticeable crater lip, brittle protruding fibers are considered a puncture risk. In parallel with EMU glove redesign efforts, modifications to metallic ISS handrails such as those evaluated in this study provide the means to significantly reduce cut-hazards from MMOD impact craters.
Water vapor permeability is shown to be useful in rejecting heat and managing moisture accumulation in launch-and-entry pressure suits. Currently this is accomplished through a porous Gortex layer in the Advanced Crew and Escape Suit (ACES) and in the baseline design of the Constellation Suit System Element (CSSE) Suit 1. Non-porous dense monolithic membranes (DMM) that are available offer potential improvements for water vapor permeability with reduced gas leak. Accordingly, three different pressure bladder materials were investigated for water vapor permeability and oxygen leak: ElasthaneTM 80A (thermoplastic polyether urethane) provided from stock polymer material and two custom thermoplastic polyether urethanes. Water vapor, carbon dioxide and oxygen permeability of the DMM's was measured in a 0.13 mm thick stand-alone layer, a 0.08 mm and 0.05 mm thick layer each bonded to two different nylon and polyester woven reinforcing materials. Additional water vapor permeability and mechanical compression measurements were made with the reinforced 0.05 mm thick layers, further bonded with a polyester wicking and overlaid with moistened polyester fleece thermal underwear .This simulated the pressure from a supine crew person. The 0.05 mm thick nylon reinforced sample with polyester wicking layer was further mechanically tested for wear and abrasion. Concepts for incorporating these materials in launch/entry and Extravehicular Activity pressure suits are presented.
Development of thermoplastic composites (TPCs) for aerospace structures is experiencing renewed enthusiasm attributed to the availability of rapid manufacturing technology, ease of joining through fusion welding processes, and the successful utilization of the material in flight critical structures. Semicrystalline thermoplastics such as polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyphenylene sulfide (PPS) have been successfully demonstrated as thermoplastic skins, keel beams, and angle brackets for commercial aircraft. Composite specimens were fabricated from the Toray TC1225 and TC1200 unidirectional prepreg systems and tested to gain confidence with NASA in-house TPC processing as part of the Thermoplastics Development for Exploration Application (TDEA) project. TC1225 is a relatively new material system that uses T700GC fibers and low-melt polyaryl ether ketone (LM-PAEK) resin. TC1200 is the latest version of a material system that has been available for several decades with AS4 fibers and PEEK resin. Results for ultrasonic inspection, optical microscopy, acid digestion, and differential scanning calorimetry establish the quality of the panels. Mechanical test data for unnotched and notched laminate tension and compression as well as compression after impact provide data for equivalency assessment and support material selection in TDEA. Satisfactory equivalence of the TC1225 results and the National Center for Advanced Materials Performance (NCAMP) database was found. The results indicate high-quality manufacturing was achieved, and the resulting mechanical test data are in agreement with that in the literature.
A multiscale repeating unit cell model of a single spherulite containing four disparate length scales was developed to predict the thermoelastic behavior of semicrystalline thermoplastic materials for composite aerospace applications. The continuum level scales were fully coupled and modeled using the generalized method of cells and the high fidelity generalized method of cells micromechanics theories. Data from molecular dynamics simulations were used as inputs for the amorphous and crystalline constituents in the multiscale continuum models. Effective Young’s modulus, shear modulus, Poisson’s ratio, coefficient of thermal expansion, and thermal conductivity were predicted for polyether ether ketone and polyether ketone ketone, showing good agreement with the available experimental data from the open literature. Moreover, it is shown that predicted properties are fairly insensitive to the fidelity of the micromechanics model used at the highest continuum scale or the assumed shape of the spherulite.
Adding trichlorofluoromethane to polyether resin accelerates the reaction between the resin and toluene diisocyanate. This accelerated reaction instantaneously produces a plastic foam of low density and uniform porosity needed to provide buoyancy for flotation recovery of instrument packages dropped into the sea from spacecraft.
Fluorinated polyethers are suitable lubricants for rolling-element bearings in cryogenic systems. Lubrication effectiveness is comparable to that of super-refined mineral oil lubricants operating at room temperature.
Series of highly fluorinated polyurethanes have been prepared as basis for development of nonflammable structural adhesives for use over wide temperature range. Backbone of polyurethanes is polyether of perfluoropropylene oxide. Adhesive system is developed that exhibits adequate strength properties and is self-extinguishing in oxygen-rich atmospheres.
Development of materials to improve flame resistance of elastic elastomeric fibers is discussed. Two approaches, synthesis of polyether based urethanes and modification of synthesized urethanes with flame ratardant additives, are described. Specific applications of both techniques are presented.
Existing material technology was applied to the development of a collapsible transparent window suitable for manned spacecraft structures. The effort reported encompasses the evaluation of flame retardants intended for use in the window matrix polymer, evaluation of reinforcement angle which would allow for a twisting pantographing motion as the cylindrical window is mechanically collapsed upon itself, and evaluation of several reinforcement embedment methods. A fabrication technique was developed to produce a reinforced cylindrical space window of 45.7 cm diameter and 61.0 cm length. The basic technique involved the application of a clear film on a male-section mold; winding axial and girth reinforcements and vacuum casting the outer layer. The high-strength transparent window composite consisted of a polyether urethane matrix reinforced with an orthogonal pattern of black-coated carbon steel wire cable. A thin film of RTV silicone rubber was applied to both surfaces of the urethane. The flexibility, retraction system, and installation system are described.
New polyurethanes containing a high degree of fluorine atoms are reported. The presence of the fluorine atoms in the polyurethane resins provides material having good thermal stability and chemical resistance. These polyurethanes are derived from a new hydroxy-terminated perfluoro polyether. The hydroxy terminated material is reacted with a diisocyanate to produce the polyurethanes. The polyurethanes can be used to form seals, coatings, potting material, hoses and the like.
Various flexible polyurethane structures containing halogen were synthesized from polyesters derived from aliphatic or aromatic polyols and dibasic acids. Aliphatic halide structures could not be used because they are unstable at the required reaction temperatures, giving of hydrogen halide which hydrolyzes the ester linkages. In contract, halogen-containing aromatic polyols were stable and satisfactory products were made. The most promising composition, a brominated neopentyl glycol capped with toluene disocyanate, was used as a conventional diisocyanate, in conjunction with hydroxy-terminated polyethers or polyesters to form elastomeric urethanes containing about 10% bromine with weight. Products made in this manner will not burn in air, have an oxygen index value of about 25, and have tensile strength values of about 5,000 psi at 450% elongation. The most efficient additives for imparting flame retardancy to Spandex urethanes are aromatic halides and the most effective of these are the bromide compounds. Various levels of flame retardancy have been achieved depending on the levels of additives used.
Fourier transforms of the noise-decoupled, natural abundance C-13 NMR free induction decays of the cyclic antibiotic valinomycin and its potassium-ion complex have been obtained at 25.2 MHz. Comparisons are made with C-13 NMR spectra taken at 22.6 MHz of the cyclic antibiotic nonactin and the synthetic polyether dicyclohexyl-18-crown-6 and their potassium complexes. The results obtained suggest that conformational rearrangements of the molecule as a whole can compete with direct interactions between carbons and the potassium ion in determining C-13 chemical shift differences between the free and complexed species.
A description is given of hydroxy containing polyethers which are prepared by the base polymerization of 2-hydro-perhaloisopropyl alcohols having the formula CF3 CH(OH)CH2X, where X is fluorine, chlorine, bromine or iodine.