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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

The Oxidation of AlN in Dry and Wet Oxygen

The oxidation kinetics of AlN containing 3.5 wt% Y2O3 were studied by thermogravimetric analysis in dry oxygen and 10% H2O/balance oxygen at temperatures between 1000 and 1200 C for times between 48 and 100 h. The oxidation kinetics for AlN in dry oxygen were parabolic and of approximately the same magnitude and temperature dependence as other alumina forming materials. In this case, diffusion of oxygen and/or aluminum through the alumina scale is the rate limiting mechanism. The oxidation kinetics for AlN in wet oxygen were nearly linear and much more rapid than rates observed in dry oxygen. Numerous micropores were observed in the alumina formed on AIN in wet oxygen. These pores provide a fast path for oxygen transport. The linear kinetics observed in this case suggest that the interface reaction rate of AlN with wet oxygen is the oxidation rate limiting step.

Opila, Elizabeth↗
NASA NTRS1976

Absolute rate of the reaction of C l(2P) with methane from 200-500 K

Rate constants for the reaction of atomic chlorine with methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

Whytock, D. A.↗
NASA NTRS1978

Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.

Lee, J. H.↗
NASA NTRS1978

Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence (FP-RF) technique. The results can be expressed in Arrhenius form by k = (1.33 + or - 0.32) times (10 to the minus tenth power) exp(-449 + or - 58/T) cu cm/molecule per sec (two standard deviations). The present work is compared to two previous determinations and is theoretically discussed.

Lee, J. H.↗
NASA NTRS1985

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗
NASA NTRS1992

Kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8

The kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8 have been investigated. Phase pure hexacelsian was prepared by heat treatment of glass flakes at 990 C for 10 h. Bulk hexacelsian was isothermally heat treated at 1026, 1050, 1100, 1152, and 1200 C for various times. The amounts of monoclinic celsian formed were determined using quantitative X-ray diffraction. Values of reaction rate constant, k, at various temperatures were evaluated from the Avrami equation. The Avrami parameter was determined to be 1.1, suggesting a diffusionless, one-dimensional transformation mechanism. From the temperature dependence of k, the activation energy for this reaction was evaluated to be 527 plus or minus 50 kJ/mole (126 plus or minus 12 kcal/mole). This value is consistent with a mechanism involving the transformation of the layered hexacelsian structure to a three-dimensional network celsian structure which necessitates breaking of the strongest bonds, the Si-O bonds.

Bansal, Narottam P.↗
NASA NTRS1993

Kinetics of hexacelsian-to-celsian phase transformation in SrAl2Si2O8

The kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8 have been investigated. Phase pure hexacelsian was prepared by heat treatment of glass flakes at 990 C for 10 h. Bulk hexacelsian was isothermally heat treated at 1026, 1050, 1100, 1152, and 1200 C for various times. The amounts of monoclinic celsian formed were determined using quantitative X-ray diffraction. Values of reaction rate constant, k, at various temperatures were evaluated from the Avrami equation. The Avrami parameter was determined to be 1.1, suggesting a diffusionless, one-dimensional transformation mechanism. From the temperature dependence of k, the activation energy for this reaction was evaluated to be 527 plus or minus 50 kJ/mole (126 plus or minus 12 kcal/mole). This value is consistent with a mechanism involving the transformation of the layered hexacelsian structure to a three-dimensional network celsian structure which necessitates breaking of the strongest bonds, the Si-O bonds.

Bansal, Narottam P.↗
NASA NTRS1987

Kinetics of the reactions of SH radicals with NO2 and O2

The SH + NO2 reaction rate constant was measured by monitoring SH concentrations with long-path optical absorption at 324 nm in a laser photolysis system. At 298 K, the rate constant was found to be (4.8 + or - 1.0) x 10 to the -11th cu cm/molecule per sec. An upper limit of 4 x 10 to the -19th cu cm/molecule per sec was inferred for the SH + O2 reaction, indicating that the atmospheric oxidation of the SH radical may occur via reaction with species such as NO2 and O3.

Stachnik, R. A.↗
NASA NTRS1990

Enhanced thermochemical nonequilibrium computations of flow around the aeroassist flight experiment vehicle

A three-dimensional explicit, finite-rate, shock-capturing numerical algorithm is used to calculate thermochemical nonequilibrium flowfields about the Aeroassist Flight Experiment vehicle at one of its flight trajectory points. The full Navier-Stokes equations and an eleven species chemical model with the latest reaction rates are incorporated into the code. Results are compared against experimental data and other numerical solutions. The effects of changes to the physical model on the stagnation line and base region flow and surface quantities on the forebody are investigated.

Palmer, Grant↗
NASA NTRS1986

Channel specific rate constants for reactions of O(1D) with HCl and HBr

The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, in units of 10 to the -10th cu cm/molecule per sec, k(1) = 1.50 + or - 0.18 and k(2) 1.48 + or - 0.16; the absolute accuracy of these rate coefficients is estimated to be + or - 20 percent.

Wine, P. H.↗
NASA NTRS1971

Improved neutron activation prediction code system development

Two integrated neutron activation prediction code systems have been developed by modifying and integrating existing computer programs to perform the necessary computations to determine neutron induced activation gamma ray doses and dose rates in complex geometries. Each of the two systems is comprised of three computational modules. The first program module computes the spatial and energy distribution of the neutron flux from an input source and prepares input data for the second program which performs the reaction rate, decay chain and activation gamma source calculations. A third module then accepts input prepared by the second program to compute the cumulative gamma doses and/or dose rates at specified detector locations in complex, three-dimensional geometries.

Saqui, R. M.↗
NASA NTRS1972

Erosion of graphite surface exposed to hot supersonic hydrogen gas

A theoretical model based on laminar boundary layer flow equations was developed to predict the erosion rate of a graphite (AGCarb-101) surface exposed to a hot supersonic stream of hydrogen gas. The supersonic flow in the nozzle outside the boundary layer formed over the surface of the specimen was determined by assuming one-dimensional isentropic conditions. An overall surface reaction rate expression based on experimental studies was used to describe the interaction of hydrogen with graphite. A satisfactory agreement was found between the results of the computation, and the available experimental data. Some shortcomings of the model and further possible improvements are discussed.

Sharma, O. P.↗
NASA NTRS1972

Erosion of graphite surface exposed to hot supersonic hydrogen gas

A theoretical model based on laminar boundary layer flow equations is developed to predict the erosion rate of a graphite (AGCarb-101) surface exposed to a hot supersonic stream of hydrogen gas. The supersonic flow in the nozzle outside the boundary layer formed over the surface of the specimen is determined by assuming one-dimensional isentropic conditions. An overall surface reaction rate expression based on the experimental studies by Clarke and Fox is used to describe the interaction of hydrogen with graphite. A satisfactory agreement is found between the results of the computation, and the available experimental data. Some shortcomings of the model, and further possible improvements are discussed.

Sharma, O. P.↗
NASA NTRS1986

A kinetic model for the thermal nitridation of SiO2/Si

To explain the observed nitrogen distributions in thermally nitridated SiO2 films, a kinetic model is proposed in which the nitridation process is simulated, using the first-order chemical kinetics and Arrhenius dependence of the diffusion and reaction rates on temperature. The calculations show that initially, as the substrate reacts with diffusing nitrogen, a nitrogen-rich oxynitride forms at the SiO2-Si interface, while at nitridation temperatures above 1000 C, an oxygen-rich oxynitride subsequently forms at the interface, due to reaction of the substrate with an increasingly concentrated oxygen displaced by the slower nitridation of the SiO2. This sequence of events results in a nitrogen distribution in which the peak of the interfacial nitrogen concentration occurs away from the interface. The results are compared with the observed nitrogen distribution. The calculated results have correctly predicted the positions of the interfacial nitrogen peaks at the temperatures of 800, 1000, and 1150 C. To account for the observed width of the interfacial nitrogen distribution, it was found necessary to include in the simulations the effect of interfacial strain.

Vasquez, R. P.↗
NASA NTRS1992

Solar control of the upper atmosphere of Triton

If the upper atmosphere and ionosphere of Triton are controlled by precipitation of electrons from Neptune's magnetosphere as previously proposed, Triton could have the only ionosphere in the solar system not controlled by solar radiation. However, a new model of Triton's atmosphere, in which only solar radiation is present, predicts a large column of carbon atoms. With an assumed, but reasonable, rate of charge transfer between N2(+) and C, a peak C(+) abundance results that is close to the peak electron densities measured by Voyager in Triton's ionosphere. These results suggest that Triton's upper atmospheric chemistry may thus be solar-controlled. Measurement of key reaction rate constants, currently unknown or highly uncertain at Triton's low temperatures, would help to clarify the chemical and physical processes occurring in Triton's atmosphere.

Lyons, James R.↗
NASA NTRS1978

Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K

The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.

Michael, J. V.↗
NASA NTRS1990

Tropospheric OH in a three-dimensional chemical tracer model - An assessment based on observations of CH3CCl3

The paper introduces the representation of tropospheric chemistry allowing for calculation of chemical reaction rates within a chemical tracer model (CTM) simulation with the accuracy comparable to that of a detailed chemical model. The global distribution of tropospheric OH is calculated as a function of time, atmospheric composition, temperature, and solar irradiance. The globally integrated OH concentration weighted by frequency of reaction with CH3CCl3 is evaluated, along with the feasibility of using the observed latitudinal distribution of CH3CCl3 as a test for computed concentrations of OH. Seasonal variations of CH3CCl3 are also considered as a potential test for computed concentrations of OH. It is demonstrated that annual cycles of CH3CCl3 are controlled, or strongly influenced, by dynamical processes at latitudes northward of 25 deg South.

Spivakovsky, C. M.↗
NASA NTRS1990

In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

Self, Valerie A.↗