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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 307 records · Page 17

F + H2 collisions on two electronic potential energy surfaces - Quantum-mechanical study of the collinear reaction

Collinear quantum calculations are carried out for reactive F + H2 collisions on two electronic potential energy surfaces. The resulting transmission and reflection probabilities exhibit much greater variation with energy than single-surface studies would lead us to anticipate. Transmission to low-lying product channels is increased by orders of magnitude by the presence of the second surface; however, branching ratios among product states are found to be independent of the initial electronic state of the reactants. These apparently contradictory aspects of the calculation are discussed and a tentative explanation put forward to resolve them.

Zimmerman, I. H.↗

Detection of interstellar sodium hydroxide in self-absorption toward the galactic center

A weak self-absorbed emission line, which is identified as the J = 4-3 transition of sodium hydroxide, has been detected in the direction of Sgr B2(OH). The correspondingly weak Sgr B2(QH) emission line U75406, previously reported as an unidentified spectral feature by other investigators, is consistent with the J = 3-2 transition of sodium hydroxide. This detection may represent the first evidence of a grain reaction formation mechanism for simple metal hydroxides. The detection of H62 Delta toward Orion A is also reported.

Hollis, J. M.↗

Kinetics and mechanism of the IO + IO reaction

The flash photolysis-absorption technique has been used to measure the rate constant for the reaction IO + IO over the temperature range 250-373 K and pressure range 20-700 torr of N2. The rate constant for the overall reaction was found to be independent of pressure and equal to 1.73 x 10 to the -12th exp (1020 + or - 200)/T cu cm/molecule s. Branching ratios for the reaction channels forming 2I + O2, I2 + O2, and I2O2, were found to be pressure dependent, with the I2 channel accounting for less than 5 percent of the total reaction over the observed pressure range. A stable reaction product was observed between 230 and 300 nm which was formed on a long time scale compared to IO disappearance. The rate constant for the reaction I + O3 + yields to IO + O2 was measured at 298 K and found to be (9.5 + or - 1.5) x 10 to the -13th cu cm/molecule s.

Sander, S. P.↗

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗

Analysis of the NASA White Sands Test Facility (WSTF) Test System for Friction-Ignition of Metallic Materials

Friction is a known ignition source for metals in oxygen-enriched atmospheres. The test system developed by the NASA White Sands Test Facility in response to ASTM G-94 has been used successfully to determine the relative ignition from friction of numerous metallic materials and metallic materials pairs. These results have been ranked in terms of a pressure-velocity product (PV) as measured under the prescribed test conditions. A high value of 4.1(exp 8) watts per square meter for Inconel MA 754 is used to imply resistance to friction ignition, whereas a low value of 1.04(exp 8) watts per square meter for stainless steel 304 is taken as indicating material susceptible to friction ignition. No attempt has been made to relate PV values to other material properties. This work reports the analysis of the WSTF friction-ignition test system for producing fundamental properties of metallic materials relating to ignition through friction. Three materials, aluminum, titanium, and nickel were tested in the WSTF frictional ignition instrument system under atmospheres of oxygen or nitrogen. Test conditions were modified to reach a steady state of operation, that is applied, the force was reduced and the rotational speed was reduced. Additional temperature measurements were made on the stator sample. The aluminum immediately galled on contact (reproducible) and the test was stopped. Titanium immediately ignited as a result of non-uniform contact of the stator and rotor. This was reproducible. A portion of the stator sampled burned, but the test continued. Temperature measurements on the stator were used to validate the mathematical model used for estimating the interface (stator/rotor) temperature. These interface temperature measurements and the associate thermal flux into the stator were used to distinguish material-phase transitions, chemical reaction, and mechanical work. The mechanical work was used to analyze surface asperities in the materials and to estimate a coefficient of fiction. The coefficient of fiction was analyzed in terms of material properties that is, hardness, Young's modulus and elasticity/plasticity of the material.

Shoffstall, Michael S.↗

Minimizing Launch Mass for ISRU Processes

The University of Dayton and the Jet Propulsion Laboratory are developing a methodology for estimating the Earth launch mass (ELM) of processes for In-Situ Resource Utilization (ISRU) with a focus on lunar resource recovery. ISRU may be enabling for both an extended presence on the Moon, and for large sample return missions and for a human presence on Mars. To accomplish these exploration goals, the resources recovered by ISRU must offset the ELM for the recovery process. An appropriate figure of merit is the cost of the exploration mission, which is closely related to ELM. For a given production rate and resource concentration, the lowest ELM - and the best ISRU process - is achieved by minimizing capital equipment for both the ISRU process and energy production. ISRU processes incur Carnot limitations and second law losses (irreversibilities) that ultimately determine production rate, material utilization and energy efficiencies. Heat transfer, chemical reaction, and mechanical operations affect the ELM in ways that are best understood by examining the process's detailed energetics. Schemes for chemical and thermal processing that do not incorporate an understanding of second law losses will be incompletely understood. Our team is developing a methodology that will aid design and selection of ISRU processes by identifying the impact of thermodynamic losses on ELM. The methodology includes mechanical, thermal and chemical operations, and, when completed, will provide a procedure and rationale for optimizing their design and minimizing their cost. The technique for optimizing ISRU with respect to ELM draws from work of England and Funk that relates the cost of endothermic processes to their second law efficiencies. Our team joins their approach for recovering resources by chemical processing with analysis of thermal and mechanical operations in space. Commercial firms provide cost inputs for ELM and planetary landing. Additional information is included in the original extended abstract.

England, C.↗

High Temperature Degradation of Advanced Thermal and Environmental Barrier Coatings (TEBCs) by CaO-MgO-Al2O3-SiO2 (CMAS)

There is increasing interest in the degradation studies of thermal and environmental barrier coatings (TEBCs) of gas turbines by molten CaO-MgO-Al2O3-SiO2 (CMAS). CMAS minerals are usually referred as silica-containing sand dust and volcano ash materials that are carried by the intake air into gas turbines, e.g. aircraft engines. The low-melting deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated coating failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples (outer diameter 4.7 mm, wall thickness 0.76 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat- treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

Thermal and environmental barrier coatings↗

Oxidation effects on the mechanical properties of a SiC-fiber-reinforced reaction-bonded Si3N4 matrix composite

The room-temperature mechanical properties of SiC fiber reinforced reaction bonded silicon nitride composites were measured after 100 hrs exposure at temperatures to 1400 C in nitrogen and oxygen environments. The composites consisted of approx. 30 vol percent uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The results indicate that composites heat treated in a nitrogen environment at temperatures to 1400 C showed deformation and fracture behavior equivalent to that of the as-fabricated composites. Also, the composites heat treated in an oxidizing environment beyond 400 C yielded significantly lower tensile strength values. Specifically in the temperature range from 600 to 1000 C, composites retained approx. 40 percent of their as-fabricated strength, and those heat treated in the temperatures from 1200 to 1400 C retained 70 percent. Nonetheless, for all oxygen heat treatment conditions, composite specimens displayed strain capability beyond the matrix fracture stress; a typical behavior of a tough composite.

Bhatt, Ramakrishna T.↗

Can Chlorine Anion Catalyze the Reaction fo HOCl with HCl?

The reaction of HOCl + HCl -> Cl2 + H20 in the presence of Cl has been studied using ab initio methods. This reaction has been shown to have a high activation barrier of 46.5 kcal/mol. The chlorine anion, Cl- is found to catalyze the reaction, viz. two mechanisms. The first involves Cl- interacting through the concerted four-center transition state of the neutral reaction. The other mechanism involves the formation of a HCl-HOCl-Cl- intermediate which dissociates into Cl2 + Cl- + H20. The steps are found to have no barriers. The overall exothermicity is 15.5 kcal/mol.

Richardson, S. L.↗

Influence of interfacial shear strength on the mechanical properties of SiC fiber reinforced reaction-bonded silicon nitride matrix composites

The influence of fiber/matrix interface microstructure and interfacial shear strength on the mechanical properties of a fiber-reinforced ceramic composite was evaluated. The composite consisted of approximately 30 vol percent uniaxially aligned 142 microns diameter SiC fibers (Textron SCS-6) in a reaction-bonded Si3N4 matrix (SiC/RBSN). The interface microstructure was varied by controlling the composite fabrication conditions and by heat treating the composite in an oxidizing environment. Interfacial shear strength was determined by the matrix crack spacing method. The results of microstructural examination indicate that the carbon-rich coating provided with the as-produced SiC fibers was stable in composites fabricated at 1200 C in a nitrogen or in a nitrogen plus 4 percent hydrogen mixture for 40 hr. However this coating degraded in composites fabricated at 1350 C in N2 + 4 percent H2 for 40 and 72 hr and also in composites heat treated in an oxidizing environment at 600 C for 100 hr after fabrication at 1200 C in a nitrogen. It was determined that degradation occurred by carbon removal which in turn had a strong influence on interfacial shear strength and other mechanical properties. Specifically, as the carbon coating was removed, the composite interfacial shear strength, primary elastic modulus, first matrix cracking stress, and ultimate tensile strength decreased, but the first matrix cracking strain remained nearly the same.

Bhatt, Ramakrishna T.↗

Spectroscopy and reactions of molecules important in chemical evolution

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.↗

Supercritical water oxidation of products of human metabolism

Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

Tester, Jefferson W.↗