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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Development of Hydroxyl Tagging Velocimetry for Low Velocity Flows

Hydroxyl tagging velocimetry (HTV) is a molecular tagging technique that relies on the photo-dissociation of water vapor into OH radicals and their subsequent tracking using laser induced fluorescence. Velocities are then obtained from time-of-flight calculations. At ambient temperature in air, the OH species lifetime is relatively short (<50 μs), making it suited for high speed flows. Lifetime and radicals formation increases with temperature, which allows HTV to also probe low-velocity, high-temperature flows or reacting flows such as flames. The present work aims at extending the domain of applicability of HTV, particularly towards low-speed (<10 m/s) and moderate (<500 K) temperature flows. Results are compared to particle image velocimetry (PIV) measurements recorded in identical conditions. Single shot and averaged velocity profiles are obtained in an air jet at room temperature. By modestly raising the temperature (100-200 degC) the OH production increases, resulting in an improvement of the signal-to-noise ratio (SNR). Use of nitrogen - a non-reactive gas with minimal collisional quenching - extends the OH species lifetime (to over 500 μs), which allows probing of slower flows or, alternately, increases the measurement precision at the expense of spatial resolution. Instantaneous velocity profiles are resolved in a 100degC nitrogen jet (maximum jet-center velocity of 6.5 m/s) with an uncertainty down to 0.10 m/s (1.5%) at 68% confidence level. MTV measurements are compared with particle image velocimetry and show agreement within 2%.

Andre, Matthieu A.↗
NASA NTRS1993

On reaction kinetics and atmospheric lifetimes of CF3CFHCF3 and CF3CH2Br

The rate constants for the reaction of the OH radical with CF3CFHCF3 and with CF3CH2Br have been measured as a function of temperature using the discharge flow technique with laser induced fluorescence detection of the OH radicals. The temperature dependent rate coefficients are well described by a simple Arrhenius expression, k(T) = A exp(E/(RT)). For the reaction of OH with CF3CFHCF3 we find A = 3.7 x 10 exp -13 cu cm/molecules/s and E/R = 1615 K; for the reaction of OH with CF3CH2Br we report A = 1.4 x 10 exp -12 cu cm/molecule/s and E/R = 1350 K. These Arrhenius parameters imply rate coefficients at 277 K of 1.09 x 10 exp -15 cu cm/molecule/s for CF3CFHCF3 and 1.06 x 10 exp -14 cu cm/molecule/s for CF3CH2Br. We find atmospheric lifetimes for CF3CFHCH3 and CF3CH2Br of 42 years and 4.1 years, respectively. We also estimate the steady state ozone depletion potential (ODP) of the brominated species relative to CFCl3 as about 0.84 using a semiempirical model.

Nelson, D. D., Jr.↗
NASA NTRS1993

Molecular processes in comets

Classical trajectory calculations of the cross sections for vibrational and rotational energy exchange in direct and reactive collisions of hydrogen atoms and hydrogen molecules have been carried out. To test the sensitivity, three potential energy surfaces have been used. For the exchange transitions which occur at small internuclear distances, the rate coefficients for the three surfaces agree quite well. For the direct transitions, there are significant differences for the pure rotational transitions from j=0 to 2 and from j=1 to j=3 in which there is no change in vibration. For higher j the differences tend to disappear, suggesting that the rotational angular momentum can couple to the orbital angular momentum to overcome the centrifugal barrier. Complete numerically exact quantum mechanical calculations for the process in which vJ changes have been performed. Dr. M. A'Hearn has provided data on the fluorescent population of the NH rotational and fine-structure levels from which we should be able to predict accurate photodissociation lifetimes. The distribution rate of C2 is being investigated. A review of H3(+) in terrestrial and extraterrestrial environments was prepared for a volume of Advances in Atomic, Molecular and Optical Physics.

Dalgarno, A.↗
NASA NTRS1980

Neutral cometary atmospheres. III - Acceleration of cometary CN by solar radiation pressure

The acceleration of cometary CN radicals due to solar radiation pressure has been determined by fitting Monte Carlo models to nine observed sunward-tailward pairs of brightness profiles of the (0-0) band of CN at 3883 A. The profiles were determined from spectrograms of comets Bennett 1970 II and West 1976 VI. The values of the observed acceleration agree with those computed from resonance fluorescence calculations to within the expected uncertainties. This provides an independent confirmation of the identification of the observed scale lengths with the photochemical lifetimes and velocities associated with the production of observed cometary CN by the photodissociation of HCN. The ratio of the intensity of the (0-1) band of CN at 4216 A to the (0-0) band at 3883 A has been determined from spectrograms of comet West, and is compared with theoretical values.

Combi, M. R.↗
NASA NTRS1990

Billion shot flashlamp for spaceborne lasers

A billion-shot flashlamp developed under a NASA contract for spaceborne laser missions is presented. Lifetime-limiting mechanisms are identified and addressed. Two energy loadings of 15 and 44 Joules were selected for the initial accelerated life testing. A fluorescence-efficiency test station was used for measuring the useful-light output degradation of the lamps. The design characteristics meeting NASA specifications are outlined. Attention is focused on the physical properties of tungsten-matrix cathodes, the chemistry of dispenser cathodes, and anode degradation. It is reported that out of the total 83 lamps tested in the program, 4 lamps reached a billion shots and one lamp is beyond 1.7 billion shots, while at 44 Joules, 4 lamps went beyond 100 million shots and one lamp reached 500 million shots.

Richter, Linda↗
NASA NTRS1983

Fluorescence branching ratios from the A2Sigma + (v-prime = 0) state of NO

The emission spectrum of NO from several rotational levels in the first excited state has been recorded. Branching ratios have been measured and Franck-Condon Factors calculated from the experimental data. Lifetimes of the lines used have been measured and Einstein A-values calculated.

Mcgee, T. J.↗
NASA NTRS2003

High-Temperature Sprayable Phosphor Coating Developed for Measuring Surface Temperatures

The use of phosphor thermography for noncontact temperature measurements in harsh environments has been proven over the last decade, but it has suffered from difficult application procedures such as vapor deposition or sputtering techniques. We have developed a high-temperature-sensitive paint that is easily applied with commercially available paint-spraying equipment and have successfully demonstrated it to temperatures up to 1500 C. Selected phosphors have also shown measurable signals to 1700 C, thus allowing a combination of phosphors to be used in high-temperature binders to make surface temperature measurements from ambient to over 1500 C. Phosphor thermography is an optical technique that measures the time response of fluorescence light, which is a function of the phosphor temperature. The phosphors are excited with short wavelength light (ultraviolet or blue), and they emit light at a longer wavelength. This technique has a benefit over other temperature measurements, such as thermocouples and infrared thermography, in difficult environments such as high blackbody backgrounds, vibration, flames, high electromagnetic noise, or where special windows may be needed. In addition, the sprayable phosphor paints easily cover large or complicated structures, providing full-surface information with a single measurement. Oak Ridge National Laboratories developed and tested the high-temperature binders and phosphors under the direction of the NASA Glenn Research Center. Refractory materials doped with rare earth metals were selected for their performance at high temperature. Survivability, adhesion, and material compatibility tests were conducted at high temperatures in a small furnace while the fluorescent response from the phosphors was being measured. A painted sample in a furnace with a clearly visible fluorescing dot excited by a pulsed laser is shown. Measuring the decay time of this fluorescence yields the surface temperature. One new paint was recently tested in a rocket test stand at Glenn. The floor of a square duct nozzle was painted, and full-field lifetime decay measurements were acquired for multiple firings of the rocket. Good agreement with predicted results was obtained, matching temperature gradients along the length of the nozzle and clearly showing shock structures. These good results were very satisfactory given that the measurements were made looking through the combustion plume. Infrared pyrometry was incapable of making the surface measurements because of the interference from the rocket exhaust, which contaminated the infrared signature.

Bencic, Timothy J.↗
NASA NTRS1988

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗
NASA NTRS2015

New Insights into Amino Acid Preservation in the Early Oceans Using Modern Analytical Techniques

Protein- and non-protein-amino acids likely occupied the oceans at the time of the origin and evolution of life. Primordial soup-, hydrothermal vent-, and meteoritic-processes likely contributed to this early chemical inventory. Prebiotic synthesis and carbonaceous meteorite studies suggest that non-protein amino acids were likely more abundant than their protein-counterparts. Amino acid preservation before abiotic and biotic destruction is key to biomarker availability in paleoenvironments and remains an important uncertainty. To constrain primitive amino acid lifetimes, a 1992 archived seawater/beach sand mixture was spiked with D,L-alanine, D,L-valine (Val), alpha-aminoisobutyric acid (alpha-AIB), D,L-isovaline (Iva), and glycine (Gly). Analysis by high performance liquid chromatography with fluorescence detection (HPLC-FD) showed that only D-Val and non-protein amino acids were abundant after 2250 days. The mixture was re-analyzed in 2012 using HPLC-FD and a triple quadrupole mass spectrometer (QqQ-MS). The analytical results 20 years after the inception of the experiment were strikingly similar to those after 2250 days. To confirm that viable microorganisms were still present, the mixture was re-spiked with Gly in 2012. Aliquots were collected immediately after spiking, and at 5- and 9-month intervals thereafter. Final HPLC-FD/QqQ-MS analyses were performed in 2014. The 2014 analyses revealed that only alpha-AIB, D,L-Iva, and D-Val remained abundant. The disappearance of Gly indicated that microorganisms still lived in the mixture and were capable of consuming protein amino acids. These findings demonstrate that non-protein amino acids are minimally impacted by biological degradation and thus have very long lifetimes under these conditions. Primitive non-protein amino acids from terrestrial synthesis, or meteorite in-fall, likely experienced great-er preservation than protein amino acids in paleo-oceanic environments. Such robust molecules may have reached a steady state concentration dependent on ocean circulation through hydrothermal systems and synthetic input processes. We are presently trying to estimate this concentration.

Parker, Eric T.↗
NASA NTRS1979

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

Kurylo, M. J.↗
NASA NTRS2004

Synthesis, Characterization, and Optical Properties of a Cyano-Functionalized 4,5,9,10-tetraaryl-l,6-dioxapyrene

5,10-Di(4-cyanophenyl)-4,9-di(4-methylphenyl)-1,6-dioxapyrene ( CN-diox), a symmetrically substituted 4,5,9,10-tetraaryldioxapyrene, was synthesized in seven steps from 1,4-dihydroxynaphthalene. The synthetic methodology incorporated a base-catalyzed ring-closure process followed by dehydration to introduce the first tetraaryl- 1,6-dioxapyrene. Crystal structure and electrochemical analysis were performed to directly compare the properties of CN-diox to previously reported dioxapyrene derivatives, specifically 1,6-dioxapyrene (Diox) and 4,9-diethyl-2,7-dimethyl- 1,6-dioxapyrene (Alkyl-diox). Optical spectroscopy studies were performed to evaluate the potential of the 1,6-dioxapyrenes as fluorescent probes. CN-diox revealed a broad absorption centered near 450 nm (epsilon = 31,900/M/cm) in THF with a corresponding fluorescence at 619 nm (Phi(sub f) = 0.011). This was in sharp contrast to both Diox and Alkyl-diox which displayed broad absorption bands near 400 nm (epsilon approx. 5,000-10,000/M/cm) in THF with corresponding fluorescence near 500 nm (Phi(sub f) = 0.059 and 0.082 for Diox and Alkyl-diox, respectively). The luminescence of CN-diox was found to be solvatochromic (lambda(sub max) = 619 nm-644 nm) with single exponential lifetimes of less than 1.3 ns. Neither Diox nor Alkyl-diox showed solvatochromic properties.

Tyson, Daniel S.↗
NASA NTRS1973

Inelastic Light Scattering Processes

Five different inelastic light scattering processes will be denoted by, ordinary Raman scattering (ORS), resonance Raman scattering (RRS), off-resonance fluorescence (ORF), resonance fluorescence (RF), and broad fluorescence (BF). A distinction between fluorescence (including ORF and RF) and Raman scattering (including ORS and RRS) will be made in terms of the number of intermediate molecular states which contribute significantly to the scattered amplitude, and not in terms of excited state lifetimes or virtual versus real processes. The theory of these processes will be reviewed, including the effects of pressure, laser wavelength, and laser spectral distribution on the scattered intensity. The application of these processes to the remote sensing of atmospheric pollutants will be discussed briefly. It will be pointed out that the poor sensitivity of the ORS technique cannot be increased by going toward resonance without also compromising the advantages it has over the RF technique. Experimental results on inelastic light scattering from I(sub 2) vapor will be presented. As a single longitudinal mode 5145 A argon-ion laser line was tuned away from an I(sub 2) absorption line, the scattering was observed to change from RF to ORF. The basis, of the distinction is the different pressure dependence of the scattered intensity. Nearly three orders of magnitude enhancement of the scattered intensity was measured in going from ORF to RF. Forty-seven overtones were observed and their relative intensities measured. The ORF cross section of I(sub 2) compared to the ORS cross section of N2 was found to be 3 x 10(exp 6), with I(sub 2) at its room temperature vapor pressure.

Fouche, Daniel G.↗
NASA NTRS2011

Sustainability of the Catalytic Activity of a Silica-Titania Composite (STC) for Long-Term Indoor Air Quality Control

TiO2-assisted photocatalytic oxidation (PCO) is an emerging technology for indoor air quality control and is also being evaluated as an alternative trace contaminant control technology for crew habitats in space exploration. Though there exists a vast range of literature on the development of photocatalysts and associated reactor systems, including catalyst performance and performance-influencing factors, the critical question of whether photocatalysts can sustain their initial catalytic activity over an extended period of operation has not been adequately addressed. For a catalyst to effectively serve as an air quality control product, it must be rugged enough to withstand exposure to a multitude of low concentration volatile organic compounds (VOCs) over long periods of time with minimal loss of activity. The objective of this study was to determine the functional lifetime of a promising photocatalyst - the silica-titania composite (STC) from Sol Gel Solutions, LLC in a real-world scenario. A bench-scale STC-packed annular reactor under continuous irradiation by a UV-A fluorescent black-light blue lamp ((lambda)max = 365 nm) was exposed to laboratory air continuously at an apparent contact time of 0.27 sand challenged with a known concentration of ethanol periodically to assess any changes in catalytic activity. Laboratory air was also episodically spiked with halocarbons (e.g., octafluoropropane), organosulfur compounds (e.g., sulfur hexafluoride), and organosilicons (e.g., siloxanes) to simulate accidental releases or leaks of such VOCs. Total organic carbon (TOC) loading and contaminant profiles of the laboratory air were also monitored. Changes in STC photocatalytic performance were evaluated using the ethanol mineralization rate, mineralization efficiency, and oxidation intermediate (acetaldehyde) formation. Results provide insights to any potential catalyst poisoning by trace halocarbons and organosulfur compounds.

Coutts, Janelle L.↗
NASA NTRS1995

Miniature X-Ray Tubes

Miniature x-ray tubes proposed for use in portable instruments used to analyze minerals. Electrons from field emitter (instead of thermionic emitter) accelerated to target to generate x-rays. Fabricated from silicon wafers, micromachined field emitters (MFEs) not subject to breakage or restrictions on lifetimes, and tolerate vacuums that filaments cannot. Miniature x-ray tubes very robust, immune to shock and vibration, and permanently sealed with getter for continued pumping. Combined with solid-state x-ray detectors for analysis of x-ray fluorescence.

Bearman, Gregory H.↗
NASA NTRS1971

Stabilities of nitrogen containing heterocyclic radicals and geometrical influences on non-radiative processes in organic molecules

Theoretical and experimental work on generating radicals by removal of a hydrogen atom from pyrrole, imidazole, indole, and carbazole is reported. Photophysical studies on indolizine and related aza-derivatives show that materials having large S2-S1 energy gaps might exhibit upper state fluorescence. Photodecomposition quantum yields of a series of sterically hindered p-aminobenzene diazonium cations in water were found structurally and wavelength dependent and unquenched in aqueous sodium bromide solutions. Photodecomposition of diazonium materials did not produce a metastable species with a longer lifetime than 1 msec.

Evleth, E. M.↗
NASA NTRS2011

Hypersonic Wake Diagnostics Using Laser Induced Fluorescence Techniques

A review of recent research performed in iodine that involves a two photon absorption of light at 193 nm will be discussed, and it's potential application to velocimetry measurements in a hypersonic flow field will be described. An alternative seed atom, Krypton, will be presented as a good candidate for performing nonintrusive hypersonic flow diagnostics. Krypton has a metastable state with a lifetime of approximately 43 s which would prove useful for time of flight measurement (TOF) and a sensitivity to collisions that can be utilized for density measurements. Calculations using modest laser energies and experimental values show an efficiency of excited state production to be on the order of 10(exp -6) for a two photon absorption at 193 nm.

Mills, Jack L.↗
NASA NTRS1991

The upper atmosphere of Uranus

Voyager measurements of the upper atmosphere of Uranus are analyzed and developed. The upper atmosphere of Uranus is predominantly H2, with at most 10 percent He by volume, and the dominant constituent of the exosphere is H. The thermosphere is warm, with an asymptotic isothermal temperature of about 800 K. Atomic hydrogen at this temperature forms an extensive thermal corona and creates gas drag that severely limits the lifetime of small ring particles. The upper atmosphere emits copious amounts of UV radiation from pressures greater than 0.01 microbar. The depth of this emission level imposes a powerful constraint on permissible emission mechanisms. Electron excitation from a thin layer near the exobase appears to violate this constraint. Solar fluorescence is consistent with the observed trend in solar zenith-angle variation of the emissions and is absent from the night side of the planet. On Uranus, it accounts for the observed Lyman beta to H2 bands intensity ratio and an important fraction of the observed intensity (about 55 percent).

Strobel, Darrell F.↗