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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Preparation of large-particle-size monodisperse polystyrene latexes in microgravity

Three large-particle-size monodisperse latexes (3.44, 4.08, and 4.98 micron diameter) were prepared in an automated four-reactor apparatus on the third orbital mission of the 'Columbia' begun on March 22. Comparison with ground-based controls showed that the 4.98 micron-size flight sample was the more uniform; the uniformity at the other two sizes was about the same. The rates of polymerization in microgravity and on earth were the same within experimental error, demonstrating that radical-initiated vinyl addition polymerizations are unaffected by the weightless environment.

Vanderhoff, J. W.↗
NASA NTRS2010

Synergism of Saturn, Enceladus and Titan and Formation of HCNO Exobiological Molecules

Saturn as a system has two very exotic moons Titan and Enceladus. Titan with energy input from Saturn's magnetosphere, solar UV irradiation, and cosmic rays can make HCN based molecules as discussed in earlier paper by [1]. Space radiation effects at both moons, and as coupled by the Saturn magnetosphere could cause an unexpected series of events leading to the evolution of biological models at Titan composed of HCNO with oxygen as the new ingredient. The "Old Faithful" model by [2] suggests that Enceladus, highly irradiated by Saturn magnetospheric electrons, has episodic ejections of water vapor driven by radiolytic oxidation gas products into Saturn's magnetosphere. At Titan Cassini discovered 1) that keV oxygen ions, evidently from Enceladus, are bombarding Titan's upper atmosphere [3] and 2) the discovery of heavy positive and negative ions within Titan's upper atmosphere [4]. Initial models of heavy ion formation in Titan's upper atmosphere invoked polymerization of aromatics such as Benzenes and their radicals to make PAHs [5], while a more recent model by [6] has raised the possibility of carbon chains forming from the polymerization of acetylene and its radicals to eventually make fullerenes. Laboratory measurements indicate that fullerenes, which are hollow carbon shells, can trap the keV oxygen and with the clustering of fullerenes and possible mixture with PAHs, some with nitrogen molecules, can make the larger aerosols with oxygen within them. Then with further ionizing irradiation from cosmic rays deep in the atmosphere "tholin" molecules are produced with all the molecular components present from which organic molecules can form. Among the molecular components are amino acids, the fundamental building blocks of life as we know it. This process maybe a common chemical pathway, both at the system level and at the molecular level, to form prebiotic and perhaps even biotic molecules. Such processes can be occurring throughout our universe, such as molecular clouds in the ISM.

Sittler, Edward C., Jr.↗
NASA NTRS2011

Synergism of Saturn, Enceladus and Titan and Formation of HCNO Prebiotic Molecules

Saturn as a system has two very exotic moons Titan and Enceladus. Titan, taking in energy from Saturn's magnetosphere, solar UV irradiation, and cosmic rays, can make HCN based molecules as discussed in earlier paper by Raulin and Owen. Space radiation effects at both moons, and as coupled by the Saturn magnetosphere, could cause an unexpected series of events potentially leading to prebiotic chemical evolution at Titan with HCNO from magnetospheric oxygen as the new ingredient. The "Old Faithful" model suggests that Enceladus, highly irradiated by Saturn magnetospheric electrons and thus having a source of chemical energy from radiolytic gas production, has episodic ejections of water vapor, carbon dioxide, and various hydrocarbons into Saturn's magnetosphere. The hydrocarbons do not survive transport through the plasma environment, but oxygen ions from Enceladus water molecules become the dominant ion species in the outer magnetosphere. At Titan, Cassini discovered that 1) keV oxygen ions, evidently from Enceladus, are bombarding Titan's upper atmosphere and 2) heavy positive and negative ions exist in significant abundances within Titan's upper atmosphere. Initial models of heavy ion formation in Titan's upper atmosphere invoked polymerization of aromatics such as benzenes and their radicals to make polycyclic aromatic hydrocarbons (PAH) , while a more recent model by Sittler et al., has raised the possibility of carbon chains forming from the polymerization of acetylene and its radicals to make fullerenes. Laboratory measurements indicate that fullerenes, which are hollow carbon shells, can trap keV oxygen ions. Clustering of the fullerenes with aerosol mixtures from PAHs and the dominant nitrogen molecules could form larger aerosols enriched in trapped oxygen. Aerosol precipitation could then convey these chemically complex structures deeper into the atmosphere and to the moon surface. Ionizing solar UV, magnetospheric electron, and galactic cosmic ray irradiation would provide further energy for processing into more complex organic forms. Further ionizing irradiation from cosmic rays deep in the atmosphere "tho lin" molecules are produced with all the molecular components present from which prebiotic organic molecules can form. This synergy of Saturn system, exogenic irradiation, and molecular processes provides a potential pathway for accumulation of prebiotic chemistry on the surface of Titan. Since fullerenes are also thought to exist in interstellar space, similar processes may also occur there to seed molecular clouds with prebiotic chemical species. We will also discuss possible future laboratory experiments that could be done to investigate fullerene formation at Titan and the trapping of oxygen in fullerenes.

Sittler, Edward C.↗
NASA NTRS1986

Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

Frenklach, M.↗
NASA NTRS1983

Module degradation catalyzed by metal-encapsulation reactions

Four major properties are considered to be relevant in determining service life of a photovoltaic module: (1) Mechanical: creep resistance, modulus, tensile strength; (2) Optical: integrated transmission at 0.4 to 1.1 m wavelength; (3) Chemical: inertness with respect to metals and other components, retention of stabilizers, etc. and (4) Electrical; maintaining effective isolation of conductive components. These properties were measured after exposing polymer specimens to three types of accelerated stress: thermal, ultraviolet radiation and metal catalysts. These conditions give rise to a large number of complex interrelated free-radical reactions that result in the deterioration of polymeric materials.

Gallagher, B. D.↗
NASA NTRS1984

Homogeneous reactions of hydrocarbons, silane, and chlorosilanes in radiofrequency plasmas at low pressures

The ion-molecule and radical-molecule mechanisms are responsible for the dissociation of hydrocarbon, silane, and chlorosilane monomers and the formation of polymerized species, respectively, in an RF plasma discharge. In a plasma containing a mixture of monomer and argon the rate-determining step for both dissociation and polymerization is governed by an ion-molecule type of interaction. Adding hydrogen or ammonia to the monomer-argon mixture transforms the rate-determining step from an ion-molecule interaction to a radical-molecule interaction for both monomer dissociation and polymerization.

Avni, R.↗
NASA NTRS2001

Approaches for Exploring the Organic Evolution of Titan's Surface

Saturn's largest moon Titan has a cold, very dense nitrogen atmosphere rich in methane and the hydrocarbon and nitride products of methane photolysis. Sources of energy for atmospheric chemistry include solar ultraviolet radiation, Saturn magnetospheric particles, and galactic cosmic rays. The chemistry of Titan's atmosphere, while interesting from the point of view of planetary photochemistry, is largely free radical driven and therefore not particularly suited to the synthesis of polymeric biomolecules or even their precursors. However, the nature of Titan's atmosphere, in particular its redox state (hydrogen escapes rapidly and is under abundant compared to in the giant planets), and the presence of a variegated surface make consideration of surface chemistry on Titan interesting from an astrobiological viewpoint. Additional information is contained in the original extended abstract.

Beauchamp, P.↗
NASA NTRS1990

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Frenklach, Michael↗
NASA NTRS1985

Chemical control of rate and onset temperature of nadimide polymerization

The chemistry of norbornenyl capped imide compounds (nadimides) is briefly reviewed with emphasis on the contribution of Diels-Alder reversion in controlling the rate and onset of the thermal polymerization reaction. Control of onset temperature of the cure exotherm by adjusting the concentration of maleimide is demonstrated using selected model compounds. The effects of nitrophenyl compounds as free radical retarders on nadimide reactivity are discussed. A simple copolymerization model is proposed for the overall nadimide cure reaction. An approximate numerical analysis is carried out to demonstrate the ability of the model to simulate the trends observed for both maleimide and nitrophenyl additions.

Lauver, R. W.↗
NASA NTRS1983

Analytic modeling of soot nucleation under fuel rich conditions

The objective of the present research is to construct a soot nucleation model according to a proposed chemical kinetic scheme to delineate quantitatively the nucleation mechanism in the soot formation process. Instead of following the traditional views which generally associate sooting with the homogeneous nucleation process in phase transformation or polymerization, we choose a chemical kinetic approach. In our proposed scheme the number of carbon atoms in the intermediate species between the fuel molecule and soot nuclei is continuously increased by radical additions. The number of hydrogen atoms in the intermediate species on the other hand is steadily decreased by radical dehydrogenation. When the number of carbon atoms in each of the intermediate molecules has exceeded a certain limit and the number of hydrogen atoms has fallen below a certain level, they may coagulate with one and another to form a larger molecule which is regarded as the initial soot nuclei in the present theory. Further coagulation and surface growth of the nuclei will lead to observable soot particles.

Yang, C. H.↗
NASA NTRS2001

Polyimides and Process for Preparing Polyimides Having Thermal-Oxidative Stability

Polyimides and the process for preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of one or more of the polyamines such as the aromatic diamines, one or more of the tetracarboxylic dianhydrides and a novel dicarboxylic endcap having formula with an R1 group of either hydrogen or an alkyl radical of one to four carbons, an R2 group of either OH, NH2, F, or Cl radical, an R3 group of either H, OH, NH2, F, Cl or an alkylene radical, an R4 group of either an alkyl, aryl, aryloxy, nitro, F, or Cl radical, and/or an R5 group of either H, alkyl, aryl, alkoxy, aryloxy, nitro, F, or Cl radical. The polyimides are useful particularly in the preparation of prepegs and PMR composites.

Meador, Mary Ann B.↗
NASA NTRS2001

Polyimides And Process For Preparing Polyimides Having Improved Thermal-Oxidative Stability

Polyimides and the process for preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of one or more of the polyamines such as the aromatic diamines, one or more of the tetracarboxylic dianhydrides and a novel dicarboxylic endcap having formula with an R 1 group of either hydrogen or an alkyl radical of one to four carbons, an R 2 group of either OH, NH 2 , F, or Cl radical, an R 3 group of either H, OH, NH 2 , F, Cl or an alkylene radical, an R 4 group of either an alkyl, aryl, aryloxy, nitro, F, or Cl radical, and/or an R 5 group of either H, alkyl, aryl, alkoxy, aryloxy, nitro, F, or Cl radical. The polyimides are useful particularly in the preparation of prepegs and PMR composites.

Mary Ann B Meador↗
NASA NTRS2005

Protection of 2-(3-Thienyl)ethanol with 3-Thienylacetic Acid and Hard Cross- Linked Conducting Films by Electropolymerization of the Ester

The ester (compound 1) of 2-(3-thienyl)ethanol (T-etOH) with 3-thienylacetic acid was synthesized as a monomer whose two thiophene groups could be electropolymerized independently, becoming members of different polymer chains in a highly-crosslinked highly-insoluble polymer. Indeed, 1 was electropolymerized successfully alone and together with 3-methylthiophene (3MeT). Films of poly(1) are hard (3H, as opposed to less than 6B for poly(3MeT)), and the close proximity of the polymeric strands creates pi-stacking interactions. The behavior of 1 suggests that by: (a) limiting the potential used for the oxidation of monomeric esters of T-etOH at the foot of their oxidation waves (less than 1.8 V vs. Ag/AgCl); and, (b) compensating for the decrease in the electrogenerated radical concentration by increasing the monomer concentration, practically all esters of T-etOH should be electropolymerizable. This was confirmed by durable film formation from the archetypical ester of T-etOH, the 2-(3-thienyl)ethyl acetate (T-etOAc), whose homo-electropolymerization is reported for the first time.

Leventis, Nicholas↗
NASA NTRS2018

Topological Control of Polystyrene-Silica Core-Shell Microspheres

Controllable surface morphology is requisite across a gamut of processes, industries, and applications. The surface morphology of silica-coated polystyrene microspheres was controllably modified to enable generation of both smooth and bumpy, or raspberry-like, surfaces. Although smooth and raspberry-like silica shells on polystyrene templates have been demonstrated extensively, the method described here used readily available materials to produce radical changes in surface morphology from a single polystyrene template coated in silica through a facile sol-gel reaction processes. Silica shells were deposited via a sol-gel process (using tetraethyl orthosilicate as the silica precursor) onto 1 to 2 m diameter anionic polystyrene spheres, fabricated by emulsifier-free polymerization. By varying of the concentration of silica precursor and ammonium hydroxide catalyst and altering the electrostatic surface interactions via addition of a cationic polymeric brush, an array of surface topologies was generated. The resulting silica shells ranged from 100 to 200 nm in thickness, as measured by calcination of the polystyrene template. Empirical relations between reaction conditions and the resulting silica colloid diameter were utilized to understand the resultant silica shell topology. These results may serve as a guide to generate a versatile platform for research in the multitude of applications where polystyrene-silica core-shell particles are utilized.

Zane A. Grady↗
NASA NTRS2011

Fire-Retardant Polymeric Additives

Polyhydroxyamide (PHA) and polymethoxyamide (PMeOA) are fire-retardant (FR) thermoplastic polymers and have been found to be useful as an additive for imparting fire retardant properties to other compatible, thermoplastic polymers (including some elastomers). Examples of compatible flammable polymers include nylons, polyesters, and acrylics. Unlike most prior additives, PHA and PMeOA do not appreciably degrade the mechanical properties of the matrix polymer; indeed, in some cases, mechanical properties are enhanced. Also, unlike some prior additives, PHA and PMeOA do not decompose into large amounts of corrosive or toxic compounds during combustion and can be processed at elevated temperatures. PMeOA derivative formulations were synthesized and used as an FR additive in the fabrication of polyamide (PA) and polystyrene (PS) composites with notable reduction (>30 percent for PS) in peak heat release rates compared to the neat polymer as measured by a Cone Calorimeter (ASTM E1354). Synergistic effects were noted with nanosilica composites. These nanosilica composites had more than 50-percent reduction in peak heat release rates. In a typical application, a flammable thermoplastic, thermoplastic blend, or elastomer that one seeks to render flame-retardant is first dry-mixed with PHA or PMeOA or derivative thereof. The proportion of PHA or PMeOA or derivative in the mixture is typically chosen to lie between 1 and 20 weight percent. The dry blend can then be melt-extruded. The extruded polymer blend can further be extruded and/or molded into fibers, pipes, or any other of a variety of objects that may be required to be fire-retardant. The physical and chemical mechanisms which impart flame retardancy of the additive include inhibiting free-radical oxidation in the vapor phase, preventing vaporization of fuel (the polymer), and cooling through the formation of chemical bonds in either the vapor or the condensed phase. Under thermal stress, the cyclic hydroxyl/ methoxy component forms polybenzoxazole (PBO) in a reaction that absorbs heat from its surroundings. PBO under thermal stress cross-links, forming a protective char layer, which thermally insulates the polymer. Thus, the formation of the char layer further assists to extinguish the fire by preventing vaporization of the polymeric fuel.

Williams, Martha K.↗
NASA NTRS1997

Elucidation of the Cross-Link Structure of Nadic-End-Capped Polyimides Using NMR of C-13-Labeled Polymers

Solid NMR of C-13 isotope-labeled samples of PMR-15 was used to follow the cross-linking reaction of the nadic end cap. Some samples were labeled on one of the carbon atoms of the nadic end cap, and others on the methylene carbon atom of the methylenedianiline portion of the polymer. NMR spectra were run on these samples both before and after cross-linking. In this way, direct evidence of the major products of cross-linking under normal cure conditions is provided. The majority (approximately 85%) of the cross-linking derives from olefin polymerization through the double bond of the end cap. Approximately 15% of the products could come from a pathway involving a retro-Diels-Alder reaction. However, all of the products could be explained by a biradical intermediate without a retro-Diels-Alder reaction. Evidence is also presented that the methylene moiety in the methylenedianiline part of the polymer chain also participates in the cross-linking, albeit to a small extent, by a radical transfer reaction. Different cure conditions (higher temperatures, longer times) could change the relative distribution of the products.

Meador, Mary Ann B.↗