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At least 1,261 records · Page 70

Improved adhesion of sputtered refractory carbides to metal substrates

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Wheeler, D. R.↗

Viking gas exchange reaction - Simulation on UV-irradiated manganese dioxide substrate

The exchange of O2 for H2O, analogous to that recorded on Mars by the Viking GEX experiment, has been observed on humidifying powdered beta-MnO2 (pyrolusite) which had been irradiated by UV in a humidified analog of the Martian atmosphere. Pyrolusite irradiated in a dry atmosphere did not release O2 on humidification. The XPS spectra of Mn and O of the reactive pyrolusite were shifted toward higher binding energies during UV irradiation. These shifts are consistent with the creation of a surface layer of a Mn(V) or Mn(VI) compound. The destruction of such a layer on humidification could account for the observed O2 release. Although manganese has not been identified in the Martian regolith, the upper limit of the Mn concentration is sufficiently high that O2 release from pyrolusite could have been responsible for the results of the Viking GEX experiment.

Blackburn, T. R.↗

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

Vander Wood, T. B.↗

Investigation of titanium-nitride layers for solar-cell contacts

Reactively sputtered titanium-nitride layers have been incorporated as diffusion barriers in a titanium-silver metallization scheme on silicon. Backscattering analysis (2-MeV He/+/, RBS) indicates that the integrity of the system is basically preserved during annealing at 600 C for 10 min. Electrical properties were determined for titanium-nitride layers prepared under different deposition conditions. Resistivity and Hall mobility appear to depend on the oxygen contamination of the deposited material. For the lowest oxygen concentration (less than 5 at %) a resistivity of 170 microohms/cm has been found.

Von Seefeld, H.↗

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

Clark, B. C.↗

The enhanced oxidation of SO2 by NO2 on carbon particulates

The oxidation of SO2 on carbon particles in dry air and in air at 65% relative humidity (RH) was found to be greatly enhanced by the presence of gaseous NO2. Exposures of 20-80ppm SO2 + 10ppm NO2 on 1-mg samples of commercial carbon black were found to produce both sorption and desorption coverages (weight retained after desorption into N2) of over one order of magnitude greater than for corresponding SO2 exposures. Significant agglomeration and wetting were observed to occur progressively during exposures at 65% RH, and samples, even after 150-h exposure, rarely reached steady-state weight gain. The wetting may have regenerated fresh reactive carbon surface. Sorptions conducted in nitrogen atmospheres, rather than in air, appeared to produce slightly higher sorptions and weight retentions for equivalent exposure concentrations and times, indicating that NO2 served as the oxidizer and that molecular oxygen, or some trace constitutents in air, may have weakly inhibited the oxidation by NO2. Wet chemical analysis of the desorbed phase indicated that sulfate, presumably H2SO4 accounted for over half of the retained weight. Measurements of pH from water-quenched samples indicated a highly acidic surface phase, and suggested the oxidation process could proceed in an acidic environment.

Cofer, W. R., III↗

The factors influencing the formation of Li2CO3 from LiOH and CO2

LiOH is used to remove CO2 from the atmosphere in three environmental control systems of the Shuttle program, and the investigation of the performance dependent parameters for the CO2 reaction with LiOH is reported. Emphasis is placed on LiOH quality acceptance criteria and on identifiying the relationships between the reaction rate and the following independent parameters: temperature, CO2 partial pressure (PP), H2O concentration in the solid, amount of remaining LiOH and the porosity of the LiOH pellets. Results showed that the reaction rate is proportional to the CO2 PP for PP at least as high as 40 mm Hg (5330 N/sq m). It is also noted that a significant difference in the reactivity of wet and dry LiOH was not detected.

Davis, S. H., Jr.↗

Silicon oxidation in fluoride solutions

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Sancier, K. M.↗

Template-directed synthesis and selective adsorption of oligoadenylates in hydroxyapatite

Polyuridylic acid is adsorbed completely from aqueous solution by hydroxyapatite under conditions that permit template-directed synthesis of oligoadenylates in free solution. The yield of oligoadenylates is enhanced to almost the same extent by poly(U) in the presence or the absence of hydroxyapatite. Under very similar conditions small quantities of hydroxyapatite adsorb higher-molecular-weight oligoadenylates selectively from a mixture of oligomers. On the basis of these results a mechanism for prebiotic oligonucleotide formation is proposed in which selective adsorption on hydroxyapatite or some other immobilized anion-exchanging material plays a major role. Monomers are released from the surface for reactivation, while oligomers are retained in a protected environment by adsorption to the apatite surface.

Gibbs, D.↗

A molecular beam investigation of the oxidation of CO on Pt/9/111/x/100//

The CO oxidation on Pt/9(111)x(100)/ was studied by molecular beam relaxation spectroscopy (MBRS). The reaction proceeded via the reaction of adsorbed CO and adsorbed oxygen. No evidence for direct reactive collisions between gaseous CO and adsorbed atomic oxygen was seen. The second order rate constant was measured by linearizing the reaction system to be 10 to the -7th exp/-(9700 kcal/mole)RT/ per sq cm s. The relatively low pre-exponential factor was explained by transition state theory on the basis of a high partition function for adsorbed carbon monoxide obtained previously from studies of CO desorption on this surface.

Fair, J. A.↗

Addition polyimide end cap study

The characterization of addition polyimides with various end caps for adhesive applications at 120-250 C environments is discussed. Oligometric polyimides were prepared from 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 3,3'-methylenedianiline which were end-capped with functionally reactive moities which cause crosslinking when the oligomers are heated to 200-400 C. The syntheses of the oligomers are outlined. The thermolysis of the oligomers was studied by differential scanning calorimetry and the resulting polymers were characterized by differential thermal analysis and adhesive performance. The adhesive data include lap shear strengths on titanium 6-4 adherends both before and after aging for 1000 hours at 121 C and/or 232 C.

St.clair, T. L.↗

Generation of boundary and boundary-layer fitting grids

The details of extended physical processes, such as the gas dynamic flow over an airfoil, the reactive flow through a combustor, or the electric field in a multi-contact transistor, are understood by solving the differential equations of a mathematical model of the process. The accuracy of finite difference methods for the numerical solution of the equations is increased if the underlying mesh fits the region boundaries and is closely spaced in regions where the solution is rapidly varying. Automatic methods for producing a satisfactorily adjusted mesh were developed for one dimensional problems. In one simple, effective scheme of this kind the unknown function and the distribution of mesh modes are found simultaneously, the nodes being placed so that they correspond to points uniformly spaced on the solution curve. In a two dimensional generalization, the nodes correspond to points equally spaced on the solution surface in two directions that are as nearly orthogonal as possible. Examples of such meshes are shown.

Ablow, C. M.↗

Photographic combustion characterization of LOX/Hydrocarbon type propellants

One hundred twenty-seven tests were conducted over a chamber pressure range of 125-1500 psia, a fuel temperature range of -245 F to 158 F, and a fuel velocity range of 48-707 ft/sec to demonstrate the advantages and limitations of using high speed photography to identify potential combustion anomalies such as pops, fuel freezing, reactive stream separation and carbon formations. Combustion evaluation criteria were developed to guide selection of the fuels, injector elements, and operating conditions for testing. Separate criteria were developed for fuel and injector element selection and evaluation. The photographic test results indicated conclusively that injector element type and design directly influence carbon formation. Unlike spray fan, impingement elements reduce carbon formation because they induce a relatively rapid near zone fuel vaporization rate. Coherent jet impingement elements, on the other hand, exhibit increased carbon formation.

Judd, D. C.↗

Photographic Combustion Characterization of LOX/Hydrocarbon Type Propellants

The advantages and limitations of using high speed photography to identify potential combustion anomalies (pops, fuel freezing, reactive stream separation (RSS), carbon formation) were demonstrated. Combustion evaluation criteria were developed for evaluating, characterizing, and screening promising low cost propellant combination(s) and injector element(s) for long life, reusable engine systems. Carbon formation and RSS mechanisms and trends were identified by using high speed color photography at speeds up to 6000 frames/sec. Single element injectors were tested with LOX/RP-1, LOX/Propane, LOX/Methane and LOX/Ammonia propellants. Tests were conducted using seven separate injector elements. Five different conventionally machined elements were tested: OFO Triplet; Rectangular Unlike Doublet (RUD); Unlike Doublet (UD); Like on Lke Doublet (LOL-EDM); and Slit Triplet.

Judd, D. C.↗

A numerical study of the NOL large-scale test

The large-scale gap test was modeled numerically using the reactive hydrodynamics code 2DE with forest fire burn rates. The model gives good agreement between calculated and experimental critical gap values. The calibration of peak pressure in the gap versus gap length is obtained from these calculations, and is in good agreement with the published experiment curve. The two dimensional nature of the gap test is evident from the curvature of the shock wave in the gap and test sample, and from the observed distance of run to detonation in the test samples.

Bowan, A. L.↗

Numerical calculation of shock-induced initiation of detonations

Results of numerical calculations of the impact of steel cylinders and spheres on the plastic bonded high explosive PBX 9501 are described. The calculations were carried out by a reactive, multicomponent, two dimensional, Eulerian hydrodynamic computer code, 2DE. The 2DE computer code is a finite difference code that uses the donor acceptor cell method to compute mixed cell fluxes. The parameters in the Forest Fire burn model are developed from experiments where the induced shock approximates a plane wave and are applied, in this case, to a situation where the induced shock is a divergent wave with curvature that depends on the size and shape of the projectile. The calculated results are compared with results from experiments involving instrumented mock and live high explosives, with projectiles of varying size, shapes, and velocities.

Cort, G. E.↗

Sympathetic reaction tests and analyses

The critical separation distances for explosive reactions of a solid rocket propellant were measured. Explosive reactions included low order explosion, low order detonation, and high order detonation. The effects of sample size, shape, damage and temperature on sympathetic reaction were determined experimentally. The sympathetic detonation of small cubes of solid rocket propellant was modelled numerically, using the Eulerian reactive hydrodynamic code 2DE with Forest Fire burn rates. The model was applied to cubes of 2.54 - 7.62 cm (1 - 3 in.), with agreement between calculated and experimental results.

Ricardson, D. E.↗