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At least 37 records · Page 2

Films, Preimpregnated Tapes and Composites Made from Polyimide "Salt-Like" Solutions

High quality films, preimpregnated tape (prepegs), and composites have been fabricated from polyimide precursor 'saltlike' solutions. These salt-like solutions have a low viscosity (5,000 to 10,000 cp) and a high solids content (50-65% by weight) and can be coated onto reinforcing fiber to produce prepegs with excellent tack and drape at 12-15% residual solvent (approximately 4-6% water from thermal imidization reaction). The processing of these types of prepegs significantly overcomes solvent removal problems and allows excellent fiber wet out. In addition, the physical characteristics of the polyimide precursor salt-like solutions permits processing into high-performance materials through the use of standard prepregging and composite fabrication equipment. The resultant composites are of high quality.

Cano, Roberto J.↗

An RNA motif that binds ATP

RNAs that contain specific high-affinity binding sites for small molecule ligands immobilized on a solid support are present at a frequency of roughly one in 10(10)-10(11) in pools of random sequence RNA molecules. Here we describe a new in vitro selection procedure designed to ensure the isolation of RNAs that bind the ligand of interest in solution as well as on a solid support. We have used this method to isolate a remarkably small RNA motif that binds ATP, a substrate in numerous biological reactions and the universal biological high-energy intermediate. The selected ATP-binding RNAs contain a consensus sequence, embedded in a common secondary structure. The binding properties of ATP analogues and modified RNAs show that the binding interaction is characterized by a large number of close contacts between the ATP and RNA, and by a change in the conformation of the RNA.

NASA Discipline Exobiology↗

Numerical Simulation of One- and Two-Phase Flows in Propulsion Systems

In this report, we present some results of problems investigated during joint research between the Hampton University Fluid Mechanics and Acoustics Laboratory (HU/FM&AL), NASA GRC, and the LaRC Hyper-X Program. This work is supported by joint research between the NASA GRC and the Institute of Mechanics at Moscow State University (IM/MSU) in Russia under a CRDF grant. The main areas of current scientific interest of the HU/FM&AL include an investigation of the proposed and patented advanced methods for aircraft engine thrust and noise benefits. These methods are based on nontraditional 3D corrugated and composite nozzle, inlet, propeller and screw designs such as a Bluebell and Telescope nozzle, Mobius-shaped screw, etc. This is the main subject of our other projects, of which one is presented at the current conference. Here we analyze additional methods for exhaust jet noise reduction without essential thrust loss and even with thrust augmentation. Such additional approaches are: (1) to add some solid, fluid, or gas mass at discrete locations to the main supersonic gas stream to minimize the negative influence of strong shock waves formed in propulsion systems. This mass addition may be accompanied by heat addition to the main stream as a result of the fuel combustion or by cooling of this stream as a result of the liquid mass evaporation and boiling; (2) Use of porous or permeable nozzles and additional shells at the nozzle exit for preliminary cooling of the hot jet exhaust and pressure compensation for off-design conditions (so-called continuous ejector with small mass flow rate); and (3) to propose and analyze new effective methods of fuel injection into the flow stream in air-breathing engines. The research is focused on a wide regime of problems in the propulsion field as well as in experimental testing and theoretical and numerical simulation analyses for advanced aircraft and rocket engines. The FM&AL Team uses analytical methods, numerical simulations, and experimental tests at the Hampton University campus, NASA, and IM/MSU. The main outcomes during this reporting period are: (1) Publications: The AIAA Paper #01-1893 has been accepted for the AIAA/NAL-NASDA-ISAS 10th International Space Planes and Hypersonic Systems and Technologies Conference, 24-27 April 2001, Kyoto, Japan. The AIAA Paper #01-3204 has been accepted for presentation at the 37th AIAA/ASME/SAE/ASEE Joint Propulsion Conference being held on 08-11 July, in Salt Lake City, UT; (2) Grants and proposals: The HU/FM&AL was awarded the NASA grant NAG3-2495 in October 2000 and the CRDF award was granted to the NASA GRC-HU FM&AL and IM/MSU (Russia) in July 2000. A solicited proposal was submitted for the NASA NRA-01GRC-02 competition and two unsolicited proposals to NASA are in preparation; (3) Theory and numerical simulations: Analytical theory, numerical simulation, comparison of theoretical with experimental results, and modification of theoretical approaches, models, grids, etc. Such investigations have been conducted for three main problems: (a) Combustion efficiency optimization in the half-duct combustor system; (b) Drag reduction effects for blunt bodies with solid needles; and (c) Solid particle injection from the butt-end against a supersonic flow. The NASA CFL3D, HU/FM&AL, and IM/MSU GODUNOV codes were used and modified for solution of these problems. The codes are based on full Euler and Navier-Stokes solvers with and without nonequilibrium oxygen-nitrogen and air-hydrogen chemical reactions in laminar and turbulent gas flow regimes; (4) Experimental tests: In the IM/MSU supersonic wind tunnel, experimental tests were conducted with different number, location, and geometric parameters of solid needles mounted at the front of the butt-end in supersonic flow. Optimal parameters were determined that provide minimal butt-end drag in the stationary flow regime. Experimental and numerical simulation results are in good agreement; (5) Student Research Activity: Involvement of one graduate and two undergraduate students as research assistants in the current project.

Gilinsky, Mikhail↗

Modeling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

The rates of hydrogen abstraction by peroxy radicals were proven to be too slow for significant oxidation of the alkane substrate to be important. The numerical procedure, independent of our particular data base was verified by reproducing concentration time profiles for a model reaction set describing the cesium flare system in the upper atmosphere. Simulation was identical to that given in the literature. Experimental verification of the data base is to be attempted by weatherometry studies in the coming year. Work on the new diagnostic techniques was completed. The adapted automated viscometer was demonstrated to be an efficient and reliable tool for routine measurements of viscosity (molecular weight) changes in solid samples after batch solutions have been made up. The laser photolysis GC method for monitoring extremely low levels of oxidation in polymers proved to be impractical because the yields of carbon monoxide were too low for quantification. Much progress was made with the computer model. The reaction matrix was completely revised, resulting in a new scheme of 31 reactions and time, lifetimes in excess of ten years. The results to date lead us to some tentative observations.

Somersall, A. C.↗

Free energies of formation of WC and WzC and the thermodynamic properties of carbon in solid tungsten

The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.

Gupta, D. K.↗

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

NASA Discipline Number 52-30↗

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Molina, M. J.↗

Chemistry of Ionic Silver and Implications for Design of Potable Water Systems

Ionic silver (Ag+) at approximately 400 µg/L is proposed as an ingestible biocide for potable water systems in future human spacecraft. This paper investigates the underlying chemistry of the silver ion at potable concentrations and its interactions with other solutes and surfaces. This chemistry evaluation will elucidate ionic silver behavior in potable water systems and enable design optimization to minimize ionic silver depletion during long duration crewed and uncrewed segments of missions. Ionic silver can be lost from the water phase to the water-solid interface via adsorption as the cation and oxidation-reduction reactions with passivation defects. The adsorption and oxidation-reduction reactions of heritage piping materials used on spacecraft – stainless steel 316L, titanium, Inconel 718, and Teflon flex hoses – are considered. Conceptual models of adsorption isotherms and pH adsorption edges are applied to understand the role of pH and the surface-to-volume ratio of pipes and tanks on the partitioning of ionic silver between the aqueous and the solid phase during aging. The effect of repeated exposure-aging to an Ag+ containing solution of two passivated alloys (316L and Inconel 718) is evaluated to determine if an equilibrium concentration of ionic silver in the potable range is attainable for a given alloy and surface-to-volume ratio. Aging unpassivated and passivated 316L reduced the ionic silver depletion rate relative to first time exposures, but the same beneficial effect was not observed for Inconel 718.

Water↗

Effects of Gas-Phase Radiation and Detailed Kinetics on the Burning and Extinction of a Solid Fuel

This is the first attempt to analyze both radiation and detailed kinetics on the burning and extinction of a solid fuel in a stagnation-point diffusion flame. We present a detailed and comparatively accurate computational model of a solid fuel flame along with a quantitative study of the kinetics mechanism, radiation interactions, and the extinction limits of the flame. A detailed kinetics model for the burning of solid trioxane (a trimer of formaldehyde) is coupled with a narrowband radiation model, with carbon dioxide, carbon monoxide, and water vapor as the gas-phase participating media. The solution of the solid trioxane diffusion flame over the flammable regime is presented in some detail, as this is the first solution of a heterogeneous trioxane flame. We identify high-temperature and low-temperature reaction paths for the heterogeneous trioxane flame. We then compare the adiabatic solution to solutions that include Surface radiation only and gas-phase and surface radiation using a black surface model. The analysis includes discussion of detailed flame chemistry over the flammable regime and, in particular, at the low stretch extinction limit. We emphasize the low stretch regime of the radiatively participating flame, since this is the region representative of microgravity flames. When only surface radiation is included, two extinction limits exist (the blow-off limit, and the low stretch radiative limit), and the burning rate and maximum flame temperatures are lower, as expected. With the inclusion of surface and gas-phase radiation, results show that, while flame temperatures are lower, the burning rate of the trioxane diffusion flame may actually increase at low stretch rate due to radiative feedback from the flame to the surface.

Rhatigan, Jennifer L.↗

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed.

Lee, K. N.↗

Thermodynamic Models for Aqueous Alteration Coupled with Volume and Pressure Changes in Asteroids

All major classes of chondrites show signs of alteration on their parent bodies (asteroids). The prevalence of oxidation and hydration in alteration pathways implies that water was the major reactant. Sublimation and melting of water ice, generation of gases, formation of aqueous solutions, alteration of primary minerals and glasses and formation of secondary solids in interior parts of asteroids was likely to be driven by heat from the radioactive decay of short-lived radionuclides. Progress of alteration reactions should have affected masses and volumes of solids, and aqueous and gas phases. In turn, pressure evolution should have been controlled by changes in volumes and temperatures, escape processes, and production/ consumption of gases.

Mironenko, M. V.↗

Making Single-Source Precursors of Ternary Semiconductors

A synthesis route has been developed for the commercial manufacture of single- source precursors of chalcopyrite semiconductor absorber layers of thin-film solar photovoltaic cells. A closely related class of single-source precursors of these semiconductors, and their synthesis routes, were reported in "Improved Single-Source Precursors for Solar-Cell Absorbers" (LEW-17445-1), NASA Tech Briefs, Vol. 31, No. 6 (June 2007), page 56. The present synthesis route is better suited to commercialization because it is simpler and involves the use of commercially available agents, yet offers the flexibility needed for synthesis of a variety of precursors. A single-source precursor of the type of interest here is denoted by the general formula L2M'(mu-ER)2M(ER)2, where L signifies a Lewis base; M signifies Al, In, or Ga; M' signifies Ag or Cu; R signifies an alkyl, aryl, silyl, or perfluorocarbon group; E signifies O, S, Se, or Te; and mu signifies a bridging ligand. This compound can be synthesized in a "one-pot" procedure from ingredients that are readily available from almost any chemical supplier. In a demonstration, the following synthesis was performed: Under anaerobic conditions, InCl3 was reacted with sodium ethanethiolate in methanol in a 1:4 molar ratio to afford the ionic stable intermediate compound Na+[In(SEt)4]- (where Et signifies ethyl group). After approximately 15 minutes, a heterogeneous solution of CuCl and the Lewis base PPh3 (where Ph signifies phenyl) in a 1:2 ratio in a mixture of CH3CN and CH2Cl2 was added directly to the freshly prepared Na+[In(SEt)4]-. After 24 hours, the reaction was essentially complete. The methanolic solution was concentrated, then the product was extracted with CH2Cl2, then the product was washed with dry ether and pentane. The product in its final form was a creamy white solid. Spectroscopic and elemental analysis confirmed that the product was (PPh3)2Cu(mu-SEt)2In(mu-SEt)2, which is known to be a precursor of the ternary semiconductor CuInS2.

Hepp, Aloysius↗

Reaction kinetics between fiber and matrix

Interdiffusion and interdiffusion controlled intermediate phase formation in metal matrix composites can be of interest for the prolonged application of these systems at high temperatures. Methods are discussed that address the kinetics of interdiffusion in systems that exhibit solid solution intermixing or the formation of a third intermediate phase at the fiber/matrix interface, or both. The tungsten fiber reinforced niobium and tungsten fiber reinforced superalloy systems are employed as model systems for experimentation and discussion. In an effort to impede interdiffusion, the concept of ion implanted diffusion barriers have been examined. Preliminary results on the feasibility and effectiveness of ion implanted diffusion barriers are presented.

Kopp, M. W.↗

The interaction of molten silicon with silicon aluminum oxynitrides

Silicon aluminum oxynitride solid solutions (sialons) based on beta-Si3N4 and Si2N2O behave differently in contact with molten silicon. The Si2N2O-based sialons convert to almost pure Si3N4, apparently through a two-step decomposition and solution-precipitation reaction, whereas the beta-Si3N4 sialons are preferentially attacked at the grain boundaries. The composition of the grain-boundary phase appears to control the rate of reaction.

Wills, R. R.↗

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Freund, F.↗

Physical phenomena and the microgravity response

The living biological cell is not a sack of Newtonian fluid containing systems of chemical reactions at equilibrium. It is a kinetically driven system, not a thermodynamically driven system. While the cell as a whole might be considered isothermal, at the scale of individual macromolecular events there is heat generated, and presumably sharp thermal gradients exist at the submicron level. Basic physical phenomena to be considered when exploring the cell's response to inertial acceleration include particle sedimentation, solutal convection, motility electrokinetics, cytoskeletal work, and hydrostatic pressure. Protein crystal growth experiments, for example, illustrate the profound effects of convection currents on macromolecular assembly. Reaction kinetics in the cell vary all the way from diffusion-limited to life-time limited. Transport processes vary from free diffusion, to facilitated and active transmembrane transport, to contractile-protein-driven motility, to crystalline immobilization. At least four physical states of matter exist in the cell: aqueous, non-aqueous, immiscible-aqueous, and solid. Levels of order vary from crystalline to free solution. The relative volumes of these states profoundly influence the cell's response to inertial acceleration. Such subcellular phenomena as stretch-receptor activation, microtubule re-assembly, synaptic junction formation, chemotactic receptor activation, and statolith sedimentation were studied recently with respect to both their basic mechanisms and their responsiveness to inertial acceleration. From such studies a widespread role of cytoskeletal organization is becoming apparent.

Todd, Paul↗

Effect of Si3N4 powder reactivity on the preparation of the Si2N2O-Al2O3 silicon aluminum oxynitride solid solution

Dense high-purity silicon aluminum oxynitride was prepared by reactive hot-pressing of an Si3N4-Al2O3-SiO2 mixture. The formation of a single-phase material was found to be critically dependent on the Si3N4 powder in the starting mixture. It is suggested that evolution of a chlorine- and nitrogen-containing species may enhance the reactivity of Si3N4 in this reaction. Densities of O prime sialons are very similar to that of Si2N2O, the widely quoted value in the ceramics literature of 3.1 g/cu cm for the density of Si2N2O being incorrect.

Sekercioglu, I.↗