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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 217 records · Page 12
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NASA NTRS1997

Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

Nicovich, J. M.↗
NASA NTRS1997

Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Nicovich, J. M.↗
NASA NTRS1997

Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

Nicovich, J. M.↗
NASA NTRS1997

Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

Wine, P. H.↗
NASA NTRS1997

Temperature Dependence of the O + HO2 Rate Coefficient

A pulsed laser photolysis technique has been employed to investigate the kinetics of the radical-radical reaction O((sup 3)P) + HO2 OH + O2 over the temperature range 266-391 K in 80 Torr of N2 diluent gas. O((sup 3)P) was produced by 248.5-nm KrF laser photolysis of O3 followed by rapid quenching of O(1D) to O((sup 3)P) while HO2 was produced by simultaneous photolysis of H2O2 to create OH radicals which, in turn, reacted with H2O2 to yield HO2. The O((sup 3)P) temporal profile was monitored by using time-resolved resonance fluorescence spectroscopy. The HO2 concentration was calculated based on experimentally measured parameters. The following Arrhenius expression describes our experimental results: k(sub 1)(T) equals (2.91 +/- 0.70) x 10(exp -11) exp[(228 +/- 75)/T] where the errors are 2 sigma and represent precision only. The absolute uncertainty in k, at any temperature within the range 266-391 K is estimated to be +/- 22 percent. Our results are in excellent agreement with a discharge flow study of the temperature dependence of k(sub 1) in 1 Torr of He diluent reported by Keyser, and significantly reduce the uncertainty in the rate of this important stratospheric reaction at subambient temperatures.

Nicovich, J. M.↗
NASA NTRS1998

Check-Up of Planet Earth at the Turn of the Millennium: Anticipated New Phase in Earth Sciences

Langley's remarkable solar and lunar spectra collected from Mt. Whitney inspired Arrhenius to develop the first quantitative climate model in 1896. In 1999, NASA's Earth Observing AM Satellite (EOS-AM) will repeat Langley's experiment, but for the entire planet, thus pioneering calibrated spectral observations from space. Conceived in response to real environmental problems, EOS-AM, in conjunction with other international satellite efforts, will fill a major gap in current efforts by providing quantitative global data sets with a resolution of few kilometers on the physical, chemical and biological elements of the earth system. Thus, like Langley's data, EOS-AM can revolutionize climate research by inspiring a new generation of climate system models and enable us to assess the human impact on the environment.

Kaufman, Y. J.↗
NASA NTRS1999

Low-Temperature Oxidation Reactions and Cool Flames at Earth and Reduced Gravity

Non-isothermal studies of cool flames and low temperature oxidation reactions in unstirred closed vessels are complicated by the perturbing effects of natural convection at earth gravity. Buoyant convection due to self-heating during the course of slow reaction produces spatio-temporal variations in the thermal and thus specie concentration fields due to the Arrhenius temperature dependence of the reaction rates. Such complexities have never been quantitatively modeled and were the primary impetus for the development of CSTR's (continuously stirred tank reactors) 30 years ago. While CSTR's have been widely adopted since they offer the advantage of spatial uniformity in temperature and concentration, all gradients are necessarily destroyed along with any structure that may otherwise develop. Microgravity offers a unique environment where buoyant convection can be effectively minimized and the need for stirring eliminated. Moreover, eliminating buoyancy and the need for stirring eliminates complications associated with the induced hydrodynamic field whose influence on heat transport and hot spot formation, hence explosion limits, is not fully realized. The objective of this research is to quantitatively determine and understand the fundamental mechanisms that control the onset and evolution of low temperature reactions and cool flames in both static and flow reactors. Microgravity experiments will be conducted to obtain benchmark data on the structure (spatio-temporal temperature, concentration, flow fields), the dynamics of the chemical fronts, and the ignition diagrams (pressure vs. temperature). Ground-based experiments will be conducted to ascertain the role of buoyancy. Numerical simulations including detailed kinetics will be conducted and compared to experiment.

Pearlman, Howard↗
NASA NTRS1999

Check-Up of Planet Earth at the Turn of the Millennium Anticipated New Phase in Earth Sciences

Langley's remarkable solar and lunar spectra collected from mt. Whitney inspired Arrhenius to develop the first quantitative climate model in 1896. In 1999, NASA's Earth Observing AM Satellite named recently "Terra" (by Ms. Sasha Jones, a 17 year old student in St. Louis, MO) will repeat Langley's experiment, but for the entire planet, thus pioneering calibrated spectral observations from space. Conceived in response to real environmental problems, EOS-AM, in conjunction with other international satellite efforts, will fill a major gap in current efforts by providing quantitative global data sets with a resolution of few kilometers on the physical, chemical and biological elements of the earth system. Thus, like Langley's data, EOS-AM can revolutionize climate research by inspiring a new generation of climate system models and enable us to assess the human impact on the environment. In this talk I shall a give a historical perspective for the need for this expensive mission, give examples of the science that we anticipate to achieve using Terra measurements and describe this exciting mission.

Kaufman, Yoram↗
NASA NTRS1999

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Hwang, S. M.↗
NASA NTRS1999

Check-Up of Planet Earth at the Turn of the Millennium: Contribution of EOS-Terra to a New Phase in Earth Sciences

Langley's remarkable solar and lunar spectra collected from Mt. Whitney inspired Arrhenius to develop the first quantitative climate model in 1896. In 1999, NASA's Earth Observing AM Satellite (EOS-Terra) will repeat Langley's experiment, but for the entire planet, thus pioneering a wide array of calibrated spectral observations from space of the Earth System. Conceived in response to real environmental problems, EOS-Terra, in conjunction with other international satellite efforts, will fill a major gap in current efforts by providing quantitative global data sets with a resolution of few kilometers on the physical, chemical and biological elements of the earth system. Thus, like Langley's data, EOS-Terra can revolutionize climate research by inspiring a new generation of climate system models and enable us to assess the human impact on the environment. In the talk I shall review the historical developments that brought to the Terra mission, its objectives and example of application to biomass burning.

Kaufman, Yoram↗
NASA NTRS1999

Use of Several Thermal Analysis Techniques to Study the Cracking of a Nitrile Butadiene Rubber (NBR) Insulator on the Booster Separation Motor (BSM) of the Space Shuttle

Two different vendor rubber formulations have been used to produce the silica-filled NBR insulators for the BSM of each of the two Solid Rocket Boosters (SRBs) on the Space Shuttle. Each cured insulator is bonded to the BSM aluminum aft closure with an epoxy adhesive, and some of the curved areas in the rubber may have significant residual stresses. A number of recently bonded NBR insulators have shown fine surface cracks, and stressed insulator areas may be aging at a faster rate than unstressed areas, thus hastening the surface cracking. Thermal analysis data on both vendor insulators by Dynamic Mechanical Analysis (DMA) through a temperature/frequency sweep from 24 to 74 C have shown a higher flexural storage modulus and Arrhenius activation energy for the stressed area than for the unstressed area. Other thermal analysis techniques are being used to study the insulator surface vs. bulk interior for better understanding this anomaly.

Wingard, Charles D.↗
NASA NTRS1999

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Hwang, S. M.↗
NASA NTRS1999

Durability of Ceramic Matrix Composites in Combustion Environments

SiO2 scale volatility and the resulting recession of SiC has been previously identified for CVD, as well as sintered, SiC and Si3N4 materials. Linear weight loss and surface recession of SiC was observed as a result of SiO2 volatility for both fuel-lean and fuel-rich gas mixtures. A strong Arrhenius temperature dependence exist and parametric studies using multiple linear regression were used to develop recession relationships as a function of e(sup -Q/RT) central dot P(sup X)V(sup y) for both lean and rich combustion conditions. Recession of 0.2 - 2.0 micron/hr is predicted for typical combustion conditions at 1200 - 1400 C, with a somewhat higher absolute recession rate and activation energy for rich combustion versus lean.

Robinson, Raymond C.↗
NASA NTRS2000

Kinetics of the Cl(2)P(J)) + CH4 Reaction: Effects of Secondary Chemistry Below 300 K

Absolute rate data for the Cl(2)P(J) + CH4 yields HCl + CH3 reaction have been obtained from 218 to 298 K by using the discharge-flow resonance fluorescence technique at I Torr total pressure. The result at 298 K is (10.1 +/- 0.6) x 10(exp -14) cu cm/molecule/s. The temperature dependence in Arrhenius form is (6.5 +/- 0.9 ) x 10(exp -12) exp[(-1235 +/- 34 )/T]. The errors given are one standard deviation; overall experimental error is estimated at +/- 15%. Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals, and impurities in the CH4 source. There was no significant change in the observed rate constant when an efficient spin quencher, CF4, was added and estimates indicate that vibrational partitioning in CH4 should be at the ambient reactor temperature before the start of the reaction. The results were also independent of the source of Cl atoms (microwave discharge or thermal decomposition of Cl2) and whether CH4 was purified in-situ. However, the observed rate constant did depend on initial Cl atom concentrations and to a lesser extent on CH4 concentrations. Numerical simulations were used to assess the importance of secondary chemistry over a range of reactant concentrations

Wang, J. J.↗
NASA NTRS2000

The Earth Observing System Terra Mission

Langley's remarkable solar and lunar spectra collected from Mt. Whitney inspired Arrhenius to develop the first quantitative climate model in 1896. After the launch in Dec. 16 1999, NASA's Earth Observing AM Satellite (EOS-Terra) will repeat Langley's experiment, but for the entire planet, thus pioneering a wide array of calibrated spectral observations from space of the Earth System. Conceived in response to real environmental problems, EOS-Terra, in conjunction with other international satellite efforts, will fill a major gap in current efforts by providing quantitative global data sets with a resolution smaller than 1 km on the physical, chemical and biological elements of the earth system. Thus, like Langley's data, EOS-Terra can revolutionize climate research by inspiring a new generation of climate system models and enable us to assess the human impact on the environment. In the talk I shall review the historical perspective of the Terra mission and the key new elements of the mission. We expect to have some first images that demonstrate the most innovative capability from EOS Terra: MODIS - 1.37 microns cirrus channel; 250 m daily cover for clouds and vegetation change; 7 solar channels for land and aerosol; new fire channels; Chlorophyll fluorescence; MISR - 9 multi angle views of clouds and vegetation; MOPITT - Global CO maps and CH4 maps; ASTER - Thermal channels for geological studies with 15-90 m resolution.

Kaufman, Yoram J.↗
NASA NTRS2000

The Earth Observing System Terra Mission

Langley's remarkable solar and lunar spectra collected from Mt. Whitney inspired Arrhenius to develop the first quantitative climate model in 1896. After the launch in Dec. 16 1999, NASA's Earth Observing AM Satellite (EOS-Terra) will repeat Langley's experiment, but for the entire planet, thus pioneering a wide array of calibrated spectral observations from space of the Earth System. Conceived in response to real environmental problems, EOS-Terra, in conjunction with other international satellite efforts, will fill a major gap in current efforts by providing quantitative global data sets with a resolution better than 1 km on the physical, chemical and biological elements of the earth system. Thus, like Langley's data, EOS-Terra can revolutionize climate research by inspiring a new generation of climate system models and enable us to assess the human impact on the environment. In the talk I shall review the historical perspective of the Terra mission and the key new elements of the mission. We expect to have first images that demonstrate the most innovative capability from EOS Terra 5 instruments: MODIS - 1.37 micron cirrus cloud channel; 250m daily coverage for clouds and vegetation change; 7 solar channels for land and aerosol studies; new fire channels; Chlorophyll fluorescence; MISR - first 9 multi angle views of clouds and vegetation; MOPITT - first global CO maps and C114 maps; ASTER - Thermal channels for geological studies with 15-90 m resolution.

Kaufman, Yoram J.↗
NASA NTRS2000

Oxidation Behavior of GRCop-84 (Cu-8Cr-4Nb) at Intermediate and High Temperatures

The oxidation behavior of GRCop-84 (Cu-8 at %Cr-4 at %Nb) has been investigated in air and in oxygen, for durations of 0.5 to 50 hours and temperatures ranging from 500 to 900 C. For comparison, data was also obtained for the oxidation of Cu and NARloy-Z (Cu-3 wt% Ag-0.5 wt% Zr) under the same conditions. Arrhenius plots of those data showed that all three materials had similar oxidation rates at high temperatures (> 750 C). However, at intermediate temperatures (500 to 750 C) GRCop exhibited significantly higher oxidation resistance than Cu and NARloy-Z. The oxidation kinetics of GRCop-84 exhibited a sharp and discontinuous jump between the two regimes. Also, in the high temperature regime GRCop-84 oxidation rate was found to change from a high initial value to a significantly smaller terminal value at each temperature, with progress of oxidation; the two different oxidation rates were found to correlate with a porous intial oxide and a dense final oxide, respectively.

Thomas-Ogbuji, Linus U.↗
NASA NTRS2001

Long-Term Reliability of SiGe/Si HBTs From Accelerated Lifetime Testing

Accelerated lifetime tests were performed on double-mesa structure Si(0.7)Ge(0.3)/Si npn heterojunction bipolar transistors, grown by molecular beam epitaxy, in the temperature range of 175 C-275 C. The transistors (with 5x20 sq micron emitter area) have DC current gains approx. 40-50 and f(sub T) and f(sub max) of up to 22 GHz and 25 GHz, respectively. It is found that a gradual degradation in these devices is caused by the recombination enhanced impurity diffusion (REID) of boron atoms from the p-type base region and the associated formation of parasitic energy barriers to electron transport from the emitter to collector layers. This REED has been quantitatively modeled and explained, to the first order of approximation, and the agreement with the measured data is good. The mean time to failure (MTTF) of these devices at room temperature under 1.35 x 10(exp 4) A/sq cm current density operation is estimated from the extrapolation of the Arrhenius plots of device lifetime versus reciprocal temperature. The results of the reliability tests offer valuable feedback for SiGe heterostructure design in order to improve the long-term reliability of the devices and circuits made with them. Hot electron induced degradation of the base-emitter junction was also observed during the accelerated lifetime testing. In order to improve the HBT reliability endangered by the hot electrons, deuterium sintered techniques have been proposed. The preliminary results from this study show that a deuterium-sintered HBT is, indeed, more resistant to hot-electron induced base-emitter junction degradation.

Bhattacharya, Pallab↗