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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 235 records · Page 13
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NASA NTRS1978

Solid state photochemistry of polycarbonates

The quantum yield of photoFries rearrangement in a polycarbonate film has been analyzed as a function of temperature and humidity on the basis of previously reported (Koyler and Mann, 1977) experimental data. Results indicate that in the homogeneous amorphous phase, photoFries rearrangement is a concerted process proceeding either from the pi star reversed arrow n singlet, in which case it must be subject to considerable self quenching, or from a triplet, presumably the first triplet since the lifetime of higher triplets is expected to be very short in the solid phase. If the parent excited state is the first triplet, chain scission is possibly an independent process, probably occurring from the pi star reversed arrow n singlet. Evidence of chain scission on photodegradation in the solid state includes loss of C-O and C-C bond intensities revealed in the Fourier transform infrared spectra, gel permeation chromotography elution profiles of degraded film samples dissolved in CHCl3, and a decrease in tensile strength and T sub g as photodegradation proceeds. Chain scission is apparently inhibited as photoFries products accumulate.

Gupta, A.↗
NASA NTRS1979

Hydrogen atom initiated chemistry

H Atoms have been created by the photolysis of H2S. These then initiated reactions in mixtures involving acetylene-ammonia-water and ethylene-ammonia-water. In the case of the acetylene system, the products consisted of two amino acids, ethylene and a group of primarily cyclic thio-compounds, but no free sulfur. In the case of the ethylene systems, seven amino acids, including an aromatic one, ethane, free sulfur, and a group of solely linear thio-compounds were produced. Total quantum yields for the production of amino acids were about 3 x 10 to the -5th and about 2 x 10 to the -4th with ethylene and acetylene respectively as carbon substrates. Consideration is given of the mechanism for the formation of some of the products and implications regarding planetary atmosphere chemistry, particularly that of Jupiter, are explored.

Hong, J. H.↗
NASA NTRS1980

Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

Hampson, R. F., Jr.↗
NASA NTRS1979

Charge injection device as a candidate sensor for stellar tracking

Charge transfer devices (CTDs) are superior to the image dissector as stellar tracking sensors, considering their low voltage requirements, insensitivity to magnetic fields, good linearity, and low weight and power. An analysis of one type of CTD, called the charge injection device (CID), revealed an X-Y addressing capability which provides exceptional flexibility in array readout and results in enhanced S/N capability, a surface channel device which produces a larger dynamic range of operation, and exceptional and unique tolerance to optical overloads. A 128 row by 128 column CID array processed on silicon was evaluated in a cooled breadboard camera, and measured results indicate projected performance parameters of a large area CID array as follows: 20 micron square sensing site, noise not greater than 25 carriers per pixel, quantum yield of approximately 40% from 0.4 to 1.0 micron, and cooling requirements on the order of 0 degrees C.

Jones, C. S., Jr.↗
NASA NTRS1980

Possible existence and chemistry of ClO.O2 in the stratosphere

The influence of the existence and chemistry of the possible atmospheric constituent ClO.O2 on current models of stratospheric photochemistry is discussed. It is suggested that the formation of an asymmetric ClO.O2 complex may explain the observed suppression of the quantum yield in the chlorine-photosensitized decomposition of ozone in the presence of O2, and that the presence of the ClO.O2 formed may account for the current discrepancy between measurements and theoretical predictions of stratospheric ClO mixing ratio profiles. The presence of stratospheric ClO.O2 is also invoked as a possible mitigating influence on present estimates of ozone destruction due to chlorofluoromethane release.

Prasad, S. S.↗
NASA NTRS1980

Photodissociation of CO2 into CO plus O/1D/

It is shown that the photodissociation of CO2(1Sigma/g/plus) into CO(X1Sigma/plus/) plus O(1D) with a quantum yield of unity is consistent with all known data on the CO2 ultraviolet absorption band between 1675 and 1400 A. Astrophysical data from the atmospheres of Mars and Venus are not inconsistent with this interpretation and cometary data seem to support it.

Delsemme, A. H.↗
NASA NTRS1980

A laboratory study on the dissociative recombination of vibrationally excited O2/+/ions

The dissociative recombination of vibrationally excited O2(+) ions is studied in light of the possible importance of this reaction in upper atmospheric chemistry. A plasma spectroscopy experiment was performed in a microwave cavity filled by an argon-oxygen mixture, with O(1S) production monitored by measurements of the 5577-A afterglow, the O2(+) density and the electron concentration. Plasma and optical data reveal the predominant afterglow ions to be Ar2(+) and O2(+), with an effective O(1S) dissociative recombination coefficient of 2.1 x 10 to the -8th cu cm/sec, corresponding to a quantum yield of 10%. Experiments with an argon-krypton-oxygen mixture reveal that vibrationally excited O2(+) ions are the chief source of the O(1S) atoms, with a specific recombination coefficient for the dissociation of O2(+)(2 pi g) into O(1S) and O(1D) of 4.2 x 10 to the -9th cu cm/sec. A comparison of the laboratory results with Atmospheric Explorer data on the 5577-A airglow implies that O2(+) ions in the sunlit ionosphere are vibrationally excited to the same degree as in the laboratory, with the vibrational relaxation of these ions much slower than dissociative recombination. Results also predict a dawn-twilight asymmetry in the effective O(1S) yield due to the normal variation of electron content.

Zipf, E. C.↗
NASA NTRS1980

Asymmetrical ClO3 - Its possible formation from ClO and O2 and its possible reactions

An analysis of recent accurate experimental studies of Cl2-photosensitized O3 decomposition, in which O3 disappearance and OClO formation were directly monitored, suggests the possibility that the suppression of the quantum yield in the presence of O2 may be due to the formation of asymmetrical chlorine trioxide (ClO.O2). Other intermediaries, such as Cl2O2, which may also form in the system are not thought to explain the observations. In addition to its capacity to oxidize, which it shares with other peroxo compounds, asymmetrical ClO3 appears to undergo an interesting class of reactions in which the loosely bound O2 adduct is relatively easily displaced by reactive atoms and radicals such as chlorine.

Prasad, S. S.↗
NASA NTRS1981

Long wavelength carbonyl sulfide photodissociation

The aeronomic implications of a preliminary observation of weak OCS photoabsorption above 270 nm are investigated. It is argued that the measured cross section is consistent with a forbidden transition in this wavelength region. Model calculations are made for the OCS photodissociation rates in daylight, the OCS and SO2 distributions in the upper atmosphere, and the budgets of sulfur in the stratosphere and OCS in the troposphere, assuming various extrapolations of the measured OCS absorption cross sections and quantum yields to longer wavelengths. It is shown that weak OCS absorption above 300 nm can have important consequences for all of these quantities. Laboratory and field experiments are identified which might lead to a better understanding of the atmospheric OCS cycle.

Turco, R. P.↗
NASA NTRS1983

Mechanisms of degradation of graphite composites in a simulated space environment

Attention is given to degradation mechanisms for graphite/polysulfone and graphite/epoxy laminates exposed to ultraviolet and high-energy electron radiation in vacuum up to 960 equivalent sun hours and to 10 to the 9th rads, respectively. The materials showed good electron radiation stability as indicated by the low G values for gas formation and no evidence of mechanical property changes. Quantum yields for gas formation indicate poor stability to ultraviolet radiation. Mechanical property measurements did not show significant changes up to 960 ESH, with the possible exception of P1700/C6000. The main products of irradiation were identified as hydrogen and methane, along with high levels of CO and CO2.

Giori, C.↗
NASA NTRS1983

Photochemistry of acetylene at 1849 A

It is pointed out that the photochemistry of acetylene in the 1500-2000 A region at low pressure, particularly the quantum yield of C2H production and the reactions of C2H with H2 and hydrocarbons, is important in understanding the photochemistry of Jovian and Titan atmospheres. The present investigation was initiated to obtain information on these issues. The 1849 A light source used in the study was a sealed quartz tube containing a drop of Hg and 2 torr of Ar excited by a microwave generator. The lamp was attached to a Pyrex reaction cell. The amount of diacetylene produced was measured on the basis of absorption near 1650 A. Reaction mixtures of acetylene with N2, He, C2H6, or C3H8 were prepared. Attention is given to the absorption cross section, the photolysis of acetylene, and the photolysis of acetylene in the presence of other gases. It is found that the photochemical process of acetylene at 1849 A may represent that of acetylene in the Titan atmosphere.

Okabe, H.↗
NASA NTRS1983

Photodissociation of NH3 at 106-200 nm

The absorption and fluorescence cross sections for NH3 are measured in the 106-200 nm region using synchrotron radiation as the light source. The threshold wavelengths for the production of the NH (b to X) and NH (c to a) emissions from NH3 dissociation are measured and compared with previous measurements. The heat of formation of NH determined from these thresholds agrees well with the value determined from thermochemical data. The process of dissociation of NH3 into NH2(2AL) and H2(S) has a significant quantum yield whose maximum at 134 nm is about twice the NH(c) production yield. All the vibronic levels of the B and C states produce the NH2(2A1) emission, contrary to previous theoretical interpretations.

Suto, M.↗
NASA NTRS1984

Quantitative photoexcitation and fluorescence studies of C2H2 in vacuum ultraviolet

Synchrotron radiation light source measurements were conducted in the 105-155 nm region to obtain the photoabsorption and fluorescence cross sections of C2H2, and the quantum yield for producing the C2H-asterisk fluorescence from C2H2's photodissociation was measured in the 106-136.5 nm region. The products of the radiative lifetime quenching rate constant increase with excitation wavelengths. The data obtained on lifetimes, quenchings, and fluorescence spectra point to an upper state of the C2H-asterisk fluorescence that is well bound, while the lower state is a repulsive or weak-bound state.

Suto, M.↗
NASA NTRS1985

Identification and properties of molecular systems of potential use in solar-pumped lasers

The concepts and computational tools of theortical chemistry are used to investigate molecular properties needed in direct solar-pumped lasers. Compounds of the type RR'CXY, with R and R' organic groups, and X and Y halide atoms were identified as likely candidates because of their highly enhanced absorption coefficients over compounds with a single halide atom. The use of a combination of vibrational excitation followed by electronic excitation to enhance quantum yields at certain wavelengths is indicated. A self-consistent eikonal approximation to state-to-state transitions was tested for CH3I and is useful for other problems involving electronic energy and charge transfer. An approach to calculate potential energy surfaces and transition dipoles was developed which is based on the generation of eigenstates of the nonrelativisitc Hamiltonian followed by incorporation of the spin-orbit coupling by configuration interaction.

Micha, D. A.↗
NASA NTRS1985

Study of Kapton Degradation under Simulated Shuttle Environment

Weight loss and severe degradation of the surface of Kapton that occurs in low Earth orbit is studied. Atomic oxygen, the major ambient species at low Earth altitude and incident with approximately 5 eV energy in ram conditions, is the primary suspect, but a thorough study of oxygen-Kapton interactions has not yet been carried out. A low-energy ion source is used to simulate the shuttle low Earth orbit environment. This source, together with diagnostic tools including surface analysis and mass spectroscopic capability, is being used to carry out experiments from which quantum yields may be obtained.

Eck, T. G.↗
NASA NTRS1985

Photoabsorption cross section of CH3CN - Photodissociation rates by solar flux and interstellar radiation

The photoabsorption cross section of CH2CN vapor was measured in the 106-180 nm region using synchrotron radiation as a light source. The cross section and the quantum yield for the production of CN (A, B-X) fluorescence were measured and were used to infer the photodissociation cross section of CH3CN. The cross sections were used to calculate the photodissociation rates of CH3CN by the solar flux and by the interstellar radiation. In both the stratosphere and the troposphere, the solar photodissociation of CH3CN is negligible in comparison with chemical degradation.

Suto, M.↗
NASA NTRS1985

Direct observation of the excited-state proton transfer and decay kinetics of internally hydrogen-bonded photostabilizers in copolymer films

The excited-state dynamics of a 2-hydroxyphenylbenzotriazole (HPB) photostabilizer copolymerized with polystyrene are reported. HPB fluorescence from these copolymer films is observed at approximately 630 nm, characteristic of the proton-transferred excited state of HPB, and it has a risetime of less than 10 ps and a decay time of 28 + or - 4 ps at room temperature. Measurement of the relative fluorescence quantum yield as a function of temperature gives the activation energy for nonradiative decay of this state to be E/hc = 259 + or 25/cm.

Oconnor, D. B.↗
NASA NTRS1986

Carbon monoxide production in low energy oxygen ion bombardment of pyrolytic graphite and Kapton surfaces

The results of an investigtion of the interaction of low energy oxygen ions with pyrolytic graphite and Kapton surface are reported. CO molecules emitted from the surface as a result of the ion bombardment were detected by a mass spectrometer. Because the ion-induced signals were small compared to that arising from the CO background pressure in the vacuum system, the ion beam was modulated and the modulated component of the CO signal measured with a lock-in amplifier. The quantum yield (CO molecules emitted per incident oxygen ion) for graphite rose from 1.9 at 4.5 eV ion energy to 6.6 at 465 eV. Comparable yields were obtained for Kapton. The large size of the yields suggests contributions to the reaction process from the background O2 molecules in the vacuum system.

Horton, C. C.↗