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At least 73 records · Page 4

Effects of multiquantum transitions on molecular populations in grain-forming circumstellar environments

Simplification of astrophysical calculations can be achieved by invoking the condition of local thermodynamic equilibrium; however, recent investigations suggest that this assumption may not be valid for certain astrophysical regions. To examine the effects of multiquantum translation to vibration transitions in expanding circumstellar envelopes, vibrational populations of the lowest 20 levels of CO have been calculated as a function of pressure and radiation density for H atom-CO collisions. Significant departure from local thermodynamic equilibrium is indicated, which implies lower dissociation rates for molecular components and a subsequent enhancement in the rate of grain formation by many orders of magnitude. Stabilization of intermediate species before they can dissociate may facilitate the formation of refractory grain cores in very hot, dilute outflows. As the present calculations indicate, laboratory measurements of state-to-state translation to vibration rates are needed for a more complete understanding of circumstellar chemistry.

Nuth, J. A.↗

Optical and other property changes of M-50 bearing steel surfaces for different lubricants and additive prior to scuffing

An ester lubricant base oil containing one or more standard additives to protect against wear, corrosion, and oxidation was used in an experimental ball/plate elastohydrodynamic contact under load and speed conditions such as to induce scuffing failure in short times. Both the ball and the plate were of identically treated M-50 steel. After various periods of operating time the wear track on the plate was examined with an interference microscope of plus or minus 30 A depth resolution and sometimes also with a scanning ellipsometer and an Auger spectrometer. The optically deduced surface profiles varied with wavelength, indicating the presence of surface coatings, which were confirmed by the other instruments. As scuffing was approached, a thin (approximately A) oxide layer and a carbide layer formed in the wear track in particular when tricresylphosphate antiwear additive was present in the lubricant. The rates of the formation of these layers and their reactivity toward dilute alcholic HCl depended strongly on the lubricant and additives. Based on these results suggestions for improved formulations and a test method for bearing reliability could be proposed.

Lauer, J. L.↗

Impurity effects in dendritic solidification

A quantitative calculation of growth rates and tip radii is presented for dendrites growing in undercooled dilute solutions. Included in the calculations are the capillary corrections to the steady-state Ivantsov needle-crystal solutions. The results show good agreement with available experimental data and support the validity of the marginal-stability theory of dendritic growth.

Karma, A.↗

Optical and other properties changes of M-50 bearing steel surfaces for different lubricants and additives prior to scuffing

An ester lubricant base oil containing one or more standard additives to protect against wear, corrosion, and oxidation was used in an experimental ball/plate elastohydrodynamic contact under load and speed conditions such as to induce scuffing failure in short times. Both the ball and the plate were of identically treated M-50 steel. After various periods of operating time the wear track on the plate was examined with an interference microscope of plus or minus 30 A depth resolution and sometimes also with a scanning ellipsometer and an Auger spectrometer. The optically deduced surface profiles varied with wavelength, indicating the presence of surface coatings, which were confirmed by the other instruments. As scuffing was approached, a thin (approximately A) oxide layer and a carbide layer formed in the wear track in particular when tricresylphosphate antiwear additive was present in the lubricant. The rates of the formation of these layers and their reactivity toward dilute alcoholic HCl depended strongly on the lubricant and additives. Based on these results suggestions for improved formulations and a test method for bearing reliability could be proposed.

Lauer, J. L.↗

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Dickerson, R. R.↗

Partial equilibrium model for predicting concentration of CO in combustion

A simple kinetic model, based upon the concept of partial equilibrium, is developed for predicting carbon monoxide concentrations in such steady-flow hydrocarbon-air combustion systems as gas-turbine combustors. The only two kinetic constraints used in the model are on the rate of change of the total number of gaseous particles in the system, and on the rate of change of the CO concentration. The accuracy of the model is verified by comparison with experimental results obtained by burning kerosene with air in a 130,000 Btu/hr atmospheric-pressure steady-flow burner. Burnt-gas cooling rates of 1,000,000 K/sec, about the magnitude encountered in the dilution zone of gas-turbine combustors, were obtained with a compact water-cooled heat exchanger. Good agreement between measured CO concentrations and the values predicted by the partial-equilibrium model was obtained.

Morr, A. R.↗

Characterization of the corrosion resistance of several alloys to dilute biologically active solutions

Sulfate reducing bacteria and acid producing bacteria/fungi detected in hygiene waters increased the corrosion rate in aluminum alloy. Biologically active media enhanced the formation of pits on metal coupons. Direct observation of gas evolved at the corrosion sample, coupled with scanning electron microscopy (SEM) and energy dispersive x-ray analysis of the corrosion products indicates that the corrosion rate is increased because the presence of bacteria favor the reduction of hydrogen as the cathodic reaction through the reaction of oxygen and water. SEM verifies the presence of microbes in a biofilm on the surface of corroding samples. The bacterial consortia are associated with anodic sites on the metal surface, aggressive pitting occurs adjacent to biofilms. Many pits are associated with triple points and inclusions in the aluminum alloy microstructure. Similar bacterial colonization was found on the stainless steel samples. Fourier transform Infrared Spectroscopy confirmed the presence of carbonyl groups in pitted areas of samples exposed to biologically active waters.

Walsh, Daniel W.↗

Acetylated Lysozyme as Impurity in Lysozyme Crystals: Constant Distribution Coefficient

Hen egg white lysozyme (HEWL) was acetylated to modify molecular charge keeping the molecular size and weight nearly constant. Two derivatives, A and B, more and less acetylated, respectively, were obtained, separated, purified and added to the solution from which crystals of tetragonal HEWL crystals were grown. Amounts of the A or B impurities added were 0.76, 0.38 and 0.1 milligram per millimeter while HEWL concentration were 20, 30 and 40 milligram per milliliter. The crystals grown in 18 experiments for each impurity were dissolved and quantities of A or B additives in these crystals were analyzed by cation exchange high performance liquid chromatography. All the data for each set of 18 samples with the different impurity and regular HEWL concentrations is well described by one distribution coefficient K = 2.15 plus or minus 0.13 for A and K = 3.42 plus or minus 0.25 for B. The observed independence of the distribution coefficient on both the impurity concentration and supersaturation is explained by the dilution model described in this paper. It shows that impurity adsorption and incorporation rate is proportional to the impurity concentration and that the growth rate is proportional to the crystallizing protein in solution. With the kinetic coefficient for crystallization, beta = 5.10(exp -7) centimeters per second, the frequency at which an impurity molecule near the growing interface irreversibly joins a molecular site on the crystal was found to be 3 1 per second, much higher than the average frequency for crystal molecules. For best quality protein crystals it is better to have low microheterogeneous protein impurity concentration and high supers aturation.

Thomas, B. R.↗

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

Stief, L. J.↗

Fatigue crack propagation of nickel-base superalloys at 650 deg C

The 650 C fatigue crack propagation behavior of two nickel-base superalloys, Rene 95 and Waspaloy, is studied with particular emphasis placed on understanding the roles of creep, environment, and two key grain boundary alloying additions, boron and zirconium. Comparison of air and vacuum data shows the air environment to be detrimental over a wide range of frequencies for both alloys. More in-depth analysis on Rene 95 shows at lower frequencies, such as 0.02 Hz, failure in air occurs by intergranular, environmentally-assisted creep crack growth, while at higher frequencies, up to 5.0 Hz, environmental interactions are still evident but creep effects are minimized. The effect of B and Zr in Waspaloy is found to be important where environmental and/or creep interactions are presented. In those instances, removal of B and Zr dramatically increases crack growth and it is therefore plausible that effective dilution of these elements may explain a previously observed trend in which crack growth rates increase with decreasing grain size.

Gayda, J.↗

Fatigue crack propagation of nickel-base superalloys at 650 deg C

The 650 C fatigue crack propagation behavior of two nickel-base superalloys, Rene 95 and Waspaloy, is studied with particular emphasis placed on understanding the roles of creep, environment, and two key grain boundary alloying additions, boron and zirconium. Comparison of air and vacuum data shows the air environment to be detrimental over a wide range of frequencies for both alloys. More in-depth analysis on Rene 95 shows at lower frequencies, such as 0.02 Hz, failure in air occurs by intergranular, environmentally-assisted creep crack growth, while at higher frequencies, up to 5.0 Hz, environmental interaction are still evident but creep effects are minimized. The effect of B and Zr in Waspaloy is found to be important where environmental and/or creep interactions are presented. In those instances, removal of B and Zr dramatically increases crack growth and it is therefore plausible that effective dilution of these elements may explain a previously observed trend in which crack growth rates increase with decreasing grain size.

Gayda, J.↗

Quantitative Aspects of Space Weathering: Implications for Regolith Breccia Meteorites and Asteroids

Space weathering is defined as the physical and optical changes incurred by material exposed to the space environment. Through studies of lunar soils, these changes are becoming well understood. However, the effects of space weathering are dependent on the physical environment to which the host materials are exposed, and thus, the effects will likely vary from body to body. The optical effects of space weathering result from nanophase iron (npFe(sup 0)) created during micrometeorite bombardment and solar wind sputtering. In the asteroid belt, bodies are farther from the sun than our Moon, and are widely known to incur less solar wind implantation and sputtering. The velocity of impacts is smaller resulting in less melting and vaporization, and therefore fewer space weathering products. The impact rate in the asteroid belt is greater, which will result in more comminution, further diluting any weathering products. Ergo, asteroidal regoliths should contain fewer space weathering products than lunar soils. However, even very small degrees of space weathering can have dramatic consequences for the optical properties of soils. A discussion on the optical effects of space weathering is presented.

Noble, S. K.↗

Sub-ppb Oxygen Contaminant Detection in Semi-Conductor Processing

Gaseous contaminants such as oxygen, water vapor, nitrogen and hydrocarbons are often present in the processing environment in semiconductor device fabrication and in containerless materials processing. The contaminants arise as a result of outgassing from hot surfaces or they may be part of the impurities in commercial ultra-high purity gases. Among these gaseous contaminants, oxygen is the most reactive and, therefore, has the most adverse effects on the end product. There has been an intense effort at the Jet Propulsion Laboratory to develop different types of oxygen sorbents to reduce oxygen concentration in a microgravity processing environment to sub-ppb (parts-per-billion) levels. Higher concentrations can lead to rapid surface oxide formation, hence reducing the quality of semiconductor devices. If the concentration of oxygen in a processing chamber at 1000oC is in the ppb level, it will only take approximately 10 seconds for an oxide layer to form on the surface of a sample. The interaction of oxygen with the water surface can lead to the formation of localized defects in semi-conductor devices, hence decreasing the manufacturing yield. For example, efficient production of 64 Mb RAM chips requires contaminations below ppb levels. This paper describes a technique for measuring trace quantities of oxygen contaminants by recording the monoatomic negative ions, O-, using mass spectrometry. The O- formation from the e--O2 interaction utilizes the electron dissociative attachment method that is greatly enhanced at the resonant energy (6.8 eV). The device combines a small gridded electron ionizer with a compact mass spectrometer. The concentrations of oxygen have been measured using the method of standard additions by diluting O2 in N2. The lowest detection limit obtained was 1.2 kHz (O- count rate) at a concentration of 10-10, corresponding to 0.1 ppb.

Sub-ppb Contaminant↗

Design and Analysis of an Isokinetic Sampling Probe for Submicron Particle Measurements at High Altitude

An isokinetic dilution probe has been designed with the aid of computational fluid dynamics to sample sub-micron particles emitted from aviation combustion sources. The intended operational range includes standard day atmospheric conditions up to 40,000-ft. With dry nitrogen as the diluent, the probe is intended to minimize losses from particle microphysics and transport while rapidly quenching chemical kinetics. Initial results indicate that the Mach number ratio of the aerosol sample and dilution streams in the mixing region is an important factor for successful operation. Flow rate through the probe tip was found to be highly sensitive to the static pressure at the probe exit. Particle losses through the system were estimated to be on the order of 50% with minimal change in the overall particle size distribution apparent. Following design refinement, experimental testing and validation will be conducted in the Particle Aerosol Laboratory, a research facility located at the NASA Glenn Research Center to study the evolution of aviation emissions at lower stratospheric conditions. Particle size distributions and number densities from various combustion sources will be used to better understand particle-phase microphysics, plume chemistry, evolution to cirrus, and environmental impacts of aviation.

Heath, Christopher M.↗

Reaction rates for O3 + HCl yielding O + O2 + HCl, Cl + O3 yielding ClO + O2, and HCl + O yielding OH + Cl at elevated temperatures

Ozone and a much greater quantity of hydrogen chloride, slightly diluted by oxygen and argon, were heated by a shock wave process to temperatures in the range 480-1300 K at pressures from four to eight atmospheres. From variations in ozone concentration, determined by the attentuation of 2537-A radiation, the rate coefficient for the reaction O3 + HCl yielding O + O2 + HCl was determined to be k1 = (4.0 plus or minus 1.5) x 10 to the minus 10 exp(-10,408/T)cm3/s for temperatures of 480-720 K. From the concentration of ClO remaining at the end of ozone decomposition the rate coefficients for the reactions Cl + O3 yielding ClO + O2 and HCl + O yielding OH + Cl were also deduced for a temperature of about 1100 K.

Park, C.↗

Rates of reactions ClO + ClO yields Cl2 + O2 and ClO + O yields Cl + O2 at elevated temperatures

Results are reported for an experiment in which a shock tube was employed to measure the reaction rates of chlorine-oxygen systems at high temperatures. In this experiment, a mixture of chlorine and ozone, diluted by oxygen and argon, was heated by two consecutive shock waves (primary and reflected) to produce a temperature in the range from 1000 to 1400 K and a pressure of between 3.5 and 9 atm. The reflected shock thermally decomposed the ozone; the resulting atomic oxygen reacted with molecular chlorine to produce ClO; and the variation in ClO concentration after passage of the reflected shock was observed by monitoring the intensity of 2537-A radiation passing through the test gas. The rates of the two cited reactions are deduced from the variation pattern. The rate coefficient values are found to be compatible with existing data obtained in lower pressure and temperature ranges.

Park, C.↗

Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

Brabbs, T. A.↗

Effects of Ambient Inert Gas Properties on Cool-Flame Combustion of Normal-Alkane Droplets in Microgravity

Cool-flame-supported quasi-steady droplet combustion was first observed during droplet combustion experiments conducted onboard the International Space Station (ISS) in the Combustion Integrated Rack (CIR) with n-alkane fuels. These cool flames, not visible to the naked eye, result from the existence of the negative-temperature-coefficient (NTC) region during the combustion n-alkane fuels when the chemical-kinetic pathways experience a transition from the low-temperature chemistry to the normal, high-temperature-controlled chemistry. In this study, we present results for the cool-flame-supported droplet burning rates and extinction diameters for n-alkane fuels (n-heptane, n-octane, n-decane, and n-dodecane) in inert-diluent-substituted ambient environments. In these ISS experiments, some of the nitrogen in the ambient gas mixture is replaced by an inert gas, namely, carbon dioxide, helium, or xenon. Different diluents were observed to exert remarkably different influences on the cool-flame combustion of fuel droplets. The results show that the cool-flame extinction diameter is drastically increased with helium dilution compared to N2, CO2 or Xe, and Xe dilution leads to longer burning with a smaller extinction diameter. Unlike hot flames, the cool-flame burning rates are controlled by the cool-flame temperature established in the NTC region by the chemical kinetics, rather than by equilibrium thermodynamics, and the thermo-physical properties of the ambient gases, which control the heat feed back to the liquid droplet. The cool-flame extinction is triggered by the instability that occurs at the low-temperature end of the NTC region, below which cool diffusion flames become statically unstable. A quasi-steady theoretical model, presented earlier, which involves a six-step reduced-chemistry mechanism, valid around the lower end of the NTC region, is shown to explain the observed experimental trends qualitatively.

microgravity↗