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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1973

Thermomechanical behavior of a polynorbornadiene

A high-temperature linear amorphous hydrocarbon polymer synthesized cationically from 2,5-norbornadiene was studied thermomechanically with respect to physical transitions and stability in nitrogen. The glass transition temperature was determined to be 320 C (at less than 1 cps), which is probably the highest known for a linear hydrocarbon addition polymer. The thermomechanical technique of torsional braid analysis, together with thermogravimetric analysis, differential thermal analysis, infrared analysis, and solubility studies, was used to investigate the sequential events of the glass transition and degradation. The polymer is of particular interest since it is a high-temperature plastic which in the bulk form would probably need to be processed at high speeds in the vicinity of the glass transition temperature in an inert atmosphere. The presence of tertiary hydrogen atoms should render it amenable to degradation by the earth's environment.

Roller, M. B.↗
NASA NTRS1992

The crystallization and crystalline properties of LARC-TPI

LARC-TPI, a thermoplastic polyimide, has been studied in order to develop an understanding of its crystalline phase transition. Our experiments suggest that samples synthesized in different laboratories apparently had different degrees of imidization and their thermal behaviors differed accordingly. When the most crystalline of these polyimides was studied in some detail, we found that it melted irreversibly in that once a sample was completely melted it would not recrystallize. A polymer that did not recrystallize displayed a glass transition, which increased in temperature upon subsequent cooling and reheating. Solubility experiments indicated that heating above the crystalline melting temperature led to network formation in the polymer, a conclusion that is consistent with other behavior just mentioned. Differential calorimetric studies revealed that annealing at slow heating rates or under isothermal conditions resulted in dual melting transitions. These studies, supported by X-ray diffraction results, strongly indicate that the annealing process involves a solid-liquid-solid transformation. From an existing phenomenological model for the kinetics of phase transitions, kinetic parameters for these crystallizations have been evaluated. The Avrami exponents n increased with the annealing temperature in the protocol used in this study. Their values were about 2 or lower, thus indicating that crystallization may have followed a mechanism that included heterogeneous nucleation of a low dimensional order in which all the embryonic crystallites formed at the beginning of the process. A positive temperature coefficient for these crystallizations indicated that diffusion may have had a rate controlling influence and affected the values of n.

Theil, Michael H.↗
NASA NTRS2003

Preparation and Characterization of Space Durable Polymer Nanocomposite Films from Functionalized Carbon Nanotubes

Low color, flexible, space durable polyimide films with inherent, robust electrical conductivity have been under investigation as part of a continuing materials development activity for future NASA space missions involving Gossamer structures. Electrical conductivity is needed in these films to dissipate electrostatic charge build-up that occurs due to the orbital environment. One method of imparting conductivity is through the use of single walled carbon nanotubes (SWNTs). However, the incompatibility and insolubility of the SWNTs severely hampers their dispersion in polymeric matrices. In an attempt to improve their dispersability, SWNTs were functionalized by the reaction with an alkyl hydrazone. After this functionalization, the SWNTs were soluble in select solvents and dispersed more readily in the polymer matrix. The functionalized SWNTs were characterized by Raman spectroscopy and thermogravimetric analysis (TGA). The functionalized nanotubes were dispersed in the bulk of the films using a solution technique. The functionalized nanotubes were also applied to the surface of polyimide films using a spray coating technique. The resultant polyimide nanocomposite films were evaluated for nanotube dispersion, electrical conductivity, mechanical, and optical properties and compared with previously prepared polyimide-SWNT samples to assess the effects of SWNT functionalization.

Delozier, D. M.↗
NASA NTRS1999

Thermal Protective Coating for High Temperature Polymer Composites

The central theme of this research is the application of carboxylate-alumoxane nanoparticles as precursors to thermally protective coatings for high temperature polymer composites. In addition, we will investigate the application of carboxylate-alumoxane nanoparticle as a component to polymer composites. The objective of this research was the high temperature protection of polymer composites via novel chemistry. The significance of this research is the development of a low cost and highly flexible synthetic methodology, with a compatible processing technique, for the fabrication of high temperature polymer composites. We proposed to accomplish this broad goal through the use of a class of ceramic precursor material, alumoxanes. Alumoxanes are nano-particles with a boehmite-like structure and an organic periphery. The technical goals of this program are to prepare and evaluate water soluble carboxylate-alumoxane for the preparation of ceramic coatings on polymer substrates. Our proposed approach is attractive since proof of concept has been demonstrated under the NRA 96-LeRC-1 Technology for Advanced High Temperature Gas Turbine Engines, HITEMP Program. For example, carbon and Kevlar(tm) fibers and matting have been successfully coated with ceramic thermally protective layers.

Barron, Andrew R.↗
NASA NTRS2011

Wholly aromatic liquid crystalline polyetherimide (LC-PEI) resins

The benefits of liquid crystal polymers and polyetherimides are combined in an all-aromatic thermoplastic liquid crystalline polyetherimide. Because of the unique molecular structure, all-aromatic thermotropic liquid crystal polymers exhibit outstanding processing properties, excellent barrier properties, low solubilities and low coefficients of thermal expansion in the processing direction. These characteristics are combined with the strength, thermal, and radiation stability of polyetherimides.

Weiser, Erik S.↗
NASA NTRS1997

The Wettability of LaRC Colorless Polyimide Resins on Casting Surfaces

Two colorless polyimides developed at NASA Langley Research Center, LaRC -CP1 and LaRC -CP2, are noted for being optically transparent, resistant to radiation, and soluble in the imide form. These materials may be used to make transparent, thin polymer films for building large space reflector/collector inflatable antennas, solar arrays, radiometers, etc. Structures such as these require large area, seamless films produced via spin casting or spray coating the soluble imide on a variety of substrates. The ability of the soluble imide to wet and spread over the mandrel or casting substrate is needed information for processing these structures with minimum waste and reprocessing, thereby, reducing the production costs. The wettability of a liquid is reported as the contact angle of the solid/liquid system. This fairly simple measurement is complicated by the porosity and the amount of contamination of the solid substrate. This work investigates the effect of inherent viscosity, concentration of polyimide solids, and solvent type on the wettability of various curing surfaces.

Miner, Gilda A.↗
NASA NTRS2003

Research to Significantly Enhance Composites Survivability at 550 F in Oxidative Environments

Methylene dianiline (MDA) and its derivatives have been used in the synthesis of polyimides to yield polymers with characteristic low-density, high tensile strength, improved solubility in organic solvents, low-melt viscosities and high thermal stability (greater than 550 F) in air. Polyimides with such properties are desirable for use in aerospace systems, e.g., jet engines, airframe, missiles, and rockets where weight is critical. Recent research at Prairie View A&M University is focused on developing monomers to generate polyimides with enhanced performance over that of NASA s PMR-15. The objective of this work is to synthesize three ring aromatic diamines which are non-toxic and when reacted with the appropriate dianhydrides will yield polyimides with lower viscosity, improve processability, good retention of mechanical properties, and oxidative stability at high environmental temperatures. Modifications of the three ring aromatic diamines include replacing the methylene linkages with aromatic ethers by nucleophilic aromatic substitution reactions and incorporating mono- and di-substituents to the center aromatic ring. An update of current reactions involved in synthesis efforts to generate three ring aromatic monomers for polyimides with methylene, carbonyl, and ether linkages separating the aromatic moieties will be displayed.

Meador, Michael A.↗
NASA NTRS1994

Photodeposition of Thin Polydiacetylene Films from Solution that Exhibit Large Third-Order Optical Nonlinearities

One promising class of organic compounds for applications in the field of nonlinear optics (NLO) are polydiacetylenes, which are of interest because they are highly conjugated polymers capable of exhibiting very large optical nonlinearities with fast response times. During the course of crystal growth studies in anticipation of a space experiment, we discovered a novel, simple method for the formation of polydiacetylene thin films by photodeposition from monomer solutions onto quartz or glass substrates. Characterization of these PDAMNA films is not trivial; they are not soluble in common organic solvents, which makes the standard solution-based methods of polymer analysis useless.

Paley, M. S.↗
NASA NTRS1989

Morphological control of inter-penetrating polymer networks

Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.

Hansen, Marion↗
NASA NTRS2018

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗
NASA NTRS1972

Quantitation of buried contamination by use of solvents. Part 1: Solvent degradation of amine cured epoxy resins

The solubility and/or swelling of cured epoxy resins was studied using the solubility parameter method. Determination of solubility parameters were found in order to select solvents for solvent-assisted degradation of cured epoxy polymers used in spacecraft. A method for improving recovery of seeded spores is suggested for assay of buried contaminants. Three commercial epoxy resins were cured using four different alkyl amines. For each resin-amine combination, three levels of amine were used, corresponding to 1/3, 2/3, and all of the amine required to react with the oxirane groups of the resin. The solubility parameters of the 36 resulting model compounds were determined in poorly and moderately hydrogen-bonded solvents. No strongly hydrogen-bonded solvents caused dissolution or swelling. The tolerance of cured resins is discussed in terms of polymer structure.

Rheineck, A. E.↗
NASA NTRS1986

Environmentally stable polymers and coatings for space application: CH-5, supplement 10

High molecular weight, randomly coupled poly(imide siloxane) soluble block copolymers were synthesized from bis(amino propyl) polydimethylsiloxane equilibrates of various molecular weights, aromatic metalinked diamines, and 3,3'-4,4'-benzophenone tetracarboxylic dianhydride (BTDA). Two synthetic procedures were successfully used to synthesize the poly(amic acid siloxane) intermediates. For both synthetic procedures, a cosolvent system was employed to achieve complete solvation of all components throughout the polymerization. Physical property characterization is continuing.

Sykes, G.↗
NASA NTRS1973

Method for estimating solubility parameter

Semiempirical correlations have been developed between solubility parameters and refractive indices for series of model hydrocarbon compounds and organic polymers. Measurement of intermolecular forces is useful for assessment of material compatibility, glass-transition temperature, and transport properties.

Lawson, D. D.↗
NASA NTRS2003

Metal chelate affinity precipitation of RNA and purification of plasmid DNA

The affinity of metal chelates for amino acids, such as histidine, is widely used in purifying proteins, most notably through six-histidine 'tails'. We have found that metal affinity interactions can also be applied to separation of single-stranded nucleic acids through interactions involving exposed purines. Here we describe a metal affinity precipitation method to resolve RNA from linear and plasmid DNA. A copper-charged copolymer of N-isopropyl acrylamide (NIPAM) and vinyl imidazole (VI) is used to purify plasmid from an alkaline lysate of E. coli. The NIPAM units confer reversible solubility on the copolymer while the imidazole chelates metal ions in a manner accessible to interaction with soluble ligands. RNA was separated from the plasmid by precipitation along with the polymer in the presence of 800 mM NaCl. Bound RNA could be recovered by elution with imidazole and separated from copolymer by a second precipitation step. RNA binding showed a strong dependence on temperature and on the type of buffer used.

Non-NASA Center↗
NASA NTRS2003

Functionalization of Carbon Nanotubes

These project will explore the functionalization of carbon nanotubes via the formation of molecular complexes with perylene diimide based systems. It is anticipated that these complexes would be soluble in organic solvent and enable the homogenous dispersion of carbon nanotubes in polymer films. Molecular complexes will be prepared and characterized using standard spectroscopic and thermal analytical techniques. Polymer films will be prepared with these complexes and their properties (electrical and thermal conductivity, mechanical properties, stability) evaluated.

Webber, Stephen E.↗
NASA NTRS2008

Photochemically Synthesized Polyimides

An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use of solvents is optional: The synthesis can be performed using the neat monomer or the monomer mixed with one or more solvent(s) in dilute or concentrated solution. The solubility of the monomer and the physical and chemical properties of the final polymer can be tailored through selection of the spacer group.

Meador, Michael A.↗
NASA NTRS1992

The Prebiotic Synthesis of Ethylenediamine Monoacetic Acid, The Repeating Unit of Peptide Nucleic Acids

The polymerization of ribonucleic acids or their precursors constitutes an important event in prebiotic chemistry. The various problems using ribonucleotides to make RNA suggest that there may have been a precursor. An attractive possibility are the peptide nucleic acids (PNA). PNAs are nucleotide analogs that make use of a polymer of ethylenediamine monoacetic acid (EDMA or 2-amninoethyl glycine) with the bases attached by an acetic acid. EDMA is an especially attractive alternative to the ribose phosphate or deoxyribose phosphate backbone because it contains no chiral centers and is potentially prebiotic, but there is no reported prebiotic synthesis. We have synthesized both EDMA and ethylenediamine diacetic acid (EDDA) from the prebiotic compounds ethylenediamine, formaldehyde, and hydrogen cyanide. The yields of EDMA range from 11 to 79% along with some sEDDA and uEDDA. These reactions work with concentrations of 10(exp -1)M and as low as 10(exp -4)M, and the reaction is likely to be effective at even lower concentrations. Ethylenediamine is a likely prebiotic compound, but it has not yet been demonstrated, although compounds such as ethanolamine and cysteamine have been proven to be prebiotic. Under neutral pH and heating at l00 C, EDMA is converted to the lactam, monoketopiperazine (MKP). The cyclization occurs and has an approximate ratio of MKP/EDMA = 3 at equilibrium. We have measured the solubilities of EDMA center dot H20 as 6.4 m, EDMA center dot HCl center dot H20 as 13.7 m, and EDMA center dot 2HCl center dot H20 as 3.4 m. These syntheses together with the high solubility of EDMA suggest that EDMA would concentrate in drying lagoons and might efficiently form polymers. Given the instability of ribose and the poor polymerizability of nucleotides, the prebiotic presence of EDMA and the possibility of its polymerization raises the possibility that PNAs are the progenitors of present day nucleic acids. A pre-RNA world may have existed in which PNAs or polymers with related peptide backbones were the dominant information macromolecules.

Nelson, Kevin E.↗