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NASA NTRS1984

Recent progress in the measurement of temperature and salinity by optical scattering

Recent progress is described in the use of Brillouin and Raman scattering for the measurement of temperature and salinity in the ocean. The use of Brillouin scattering is described for the measurement of the sound velocity, and the use of Raman scattering is described for the independent measurement of the temperature and salinity. Coupling these techniques permits the assessment of both temperature and salinity. The experimental techniques are described together with the results of recent experiments and an assessment of the errors to be expected.

Collins, D. J.↗

NASA NTRS1986

Rotational branch analysis of the excitation of the fundamental vibrational modes of CO2 by slow electron collisions

At 2 eV, the simultaneous rotational-vibrational cross sections for the fundamental modes are found to be well described by the Born formula with just long-range interactions. However, this result is not obtained for pure vibrational excitation (Q branch) in the Raman-active Fermi diads. At 3.8 eV, the infrared-active v2 and v3 cross sections agree with a previous theory incorporating resonant and direct scattering coherently. Measurements on the Raman-active v1 mode indicate that theories need to account for the Fermi resonance.

Antoni, TH.↗

NASA NTRS1986

Lidar method of measurement of atmospheric extinction and ozone profiles

A description of a method of measurement of atmospheric extinction and of ozone profiles by use of the backscatter signal from a monostatic lidar is given. The central feature of the procedure involves a measurement of the ratio of the Raman backscatter returns of both the oxygen and nitrogen atmospheric content. Because the ratio of the number density of both species is known to high accuracy, the measurement itself becomes a measure of the ratio of two transmissions to altitude along with a ratio of the two system constants. The calibration measurement for determining the value of the ratio of the two system constants or electro-optical conversion constants is accomplished by a lidar measurement of identical atmospheric targets while at the same time interchanging the two optical filters in the two optical channels of the receiver. More details of the procedure are discussed. Factoring this calibrated value into the measured O2/N2 profile ratio provides a measured value of the ratio of the two transmissions. Or equivalently, it provides a measurement of the difference of the two extinction coefficients at the O2 and N2 Raman wavelengths as a function of the height.

Cooney, J. A.↗

NASA NTRS1986

Infrared absorption and emission characteristics of interstellar PAHs

The mid-infrared interstellar emission spectrum with features at 3.28, 6.2, 7.7, 8.7 and 11.3 microns is discussed in terms of the Polycyclic Aromatic Hydrocarbon (PAH) hypothesis, which is based on the suggestive, but inconclusive comparison between the interstellar emission spectrum with the infrared absorption and Raman spectra of a few PAHs. The fundamental vibrations of PAHs and PAH-like species which determine the IR and Raman properties are discussed. Interstellar IR band emission is due to relaxation from highly vibrationally excited PAHs excited by ultraviolet photons. The excitation/emission process is described and the IR fluorescence from one PAH, chrysene, is traced. Generally, there is sufficient energy to populate several vibrational levels in each mode. Molecular vibrational potentials are anharmonic and emission from these higher levels will fall at lower frequencies and produce weak features to the red of the stronger fundamentals. This process is also described and can account for some spectroscopic details of the interstellar emission spectra previously unexplained. Analysis of the interstellar spectrum shows that PAHs contain between 20 and 30 carbon atoms are responsible for the emission.

Barker, J. R.↗

NASA NTRS1987

Structural models for nickel electrode active mass

Raman spectroscopic data allow one to distinguish nickel electrode active mass, alpha and beta phase materials. Discharges active mass is not isostructural with beta-Ni(OH)2. This is contrary to the generally accepted model for the discharged beta phase of active mass. It is concluded that charged active mass displays a disordered and nonstoichiometric, nonclose packed structure of the R3 bar m, NiOOH structure type. Raman spectral data and x ray diffraction data are analyzed and shown to be consistent with this structural model.

Cornilsen, Bahne C.↗

NASA NTRS1988

Laser Diagnostics for combustion temperature and species measurements

Laser optical diagnostic techniques for the measurement of combustion gaseous-phase temperatures and, or species concentrations are discussed. The techniques fall into two classes: incoherent (Rayleigh scattering, spontaneous Raman scattering, laser induced fluorescence spectroscopy) and coherent (coherent anti-Stokes Raman spectroscopy). The advantages, disadvantages and applicability of each method are outlined.

Eckbreth, Alan C.↗

NASA NTRS1987

Infrared absorption and emission characteristics of interstellar PAHs

Allamandola, L. J.↗

NASA NTRS1988

Aromatic components in cometary materials

The Raman spectra of interplanetary dust particles (IDPs) collected in the stratosphere show that two bands at about 1350 and 1600 delta/cm and a broader feature between 2200 and 3300 delta/cm that are characteristic of aromatic molecular units with ordered domains smaller than 25 A in diameter. This suggests that the carbonaceous material in IDPs may be similar to the polymeric component seen in meteorites, where this material is thought to consist of aromatic molecular units that are randomly interlinked by short aliphatic bridges. The features in the Raman spectra of IDPs are similar in position, and relative strength to interstellar infrared emission features that have been attributed to vibrational transitions in free molecular polycyclic aromatic hydrocarbons. Taken together, these observations suggest that some fraction of the carbonaceous materials in IDPs may have been produced in circumstellar dust shells and only slightly modified in interstellar space.

Allamandola, Louis J.↗

NASA NTRS1988

Structural models for nickel electrode active mass

Raman spectroscopic data allow one to distinguish nickel electrode active mass, alpha and beta phase materials. Discharges active mass is not isostructural with beta-Ni(OH)2. This is contrary to the generally accepted model for the discharged beta phase of active mass. It is concluded that charged active mass displays a disordered and nonstoichiometric, nonclose packed structure of the R3 bar m, NiOOH structure type. Raman spectral data and X ray diffraction data are analyzed and shown to be consistent with this structural model.

Cornilsen, B. C.↗

NASA NTRS1989

Structural comparison of nickel electrodes and precursor phases

Researchers summarize previous Raman spectroscopic results and discuss important structural differences in the various phases of active mass and active mass precursors. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to x rays (i.e., does not scatter x rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging are discussed. The oxidation states and dopant contents are explained in terms of the nonstoichiometric structures.

Cornilsen, Bahne C.↗

NASA NTRS1990

The oxidation of carbon monoxide using tin oxide based catalysts

The preparation conditions for precious metal/tin oxide catalysts were optimized for maximum carbon monoxide/oxygen recombination efficiency. This was achieved by controlling the tin digestion, the peptization to form the sol, the calcination process and the method of adding the precious metals. Extensive studies of the tin oxide structure were carried out over the temperature range 20 to 500 C in air or hydrogen environments using Raman scattering and X ray diffraction. Adsorbed species on tin oxide, generated in an environment containing carbon monoxide, gave rise to a Raman band at about 1600 cm(exp -1) which was assigned to carbonaceous groups, possible carbonate.

Sampson, Christopher F.↗

NASA NTRS1990

On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.

Rietmeijer, Frans J. M.↗

NASA NTRS1990

The ultraviolet continuum albedo of Uranus

A radiative transfer code explicitly treating the Raman scattering of solar protons by H2 is presently used to analyze the Uranus geometric albedo in the 2000-5000 A range. The Baines and Bergstralh (1986) baseline model used reproduces the geometric albedo peak produced by Raman scattering filling of solar absorption line cores, but is found to be excessively bright for wavelengths below 2400 A. This discrepancy is resolvable through inclusion of an absorbing stratospheric haze layer, and results are thereby obtained which are consistent with the Pollack et al. (1987) model, in which aerosols are generated stratospherically through photochemical effects on hydrocarbons.

Cochran, William D.↗

NASA NTRS1990

Structural comparison of nickel electrodes and precursor phases

In this paper the previous Raman spectroscopic results are summarized and important structural differences in the various phases of active mass and active mass precursors are discussed. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to X-rays (i.e., does not scatter X-rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging wil be discussed. The oxidation states and dopant contents are explained in terms of the nonstoichiometric structures.

Cornilsen, Bahne C.↗

NASA NTRS1990

Deposition of diamondlike films by electron cyclotron resonance microwave plasmas

Hard a-C:H films have been deposited through electron cyclotron resonance (ECR) microwave plasma decomposition of CH4 diluted with H2 gas. It has been found that hard diamondlike films could only be produced under a RF-induced negative self-bias of the substrate stage. Raman spectra indicate the deposition of two distinct film types: one film type exhibiting well-defined bands at 1360 and 1580/cm and another displaying a broad Raman peak centered at approximately 1500/cm. Variation of the mirror magnetic-field profile of the ECR system was examined, demonstrating the manipulation of film morphology through the extraction of different ion energies.

Pool, F. S.↗

NASA NTRS1990

Some optical and electron microscope comparative studies of excimer laser-assisted and nonassisted molecular-beam epitaxically grown thin GaAs films on Si

The quality of GaAs thin films grown via MBE under pulsed excimer laser irradiation on Si substrates is examined in both laser-irradiated and nonirradiated areas using Raman scattering, Rayleigh scattering, and by photoluminescence (PL), as a function of temperature, and by TEM. The temperature dependence of the PL and Raman peak positions indicates the presence of compressive stress in the thin GaAs films in both laser-irradiated and nonirradiated areas. This indicates incomplete homogeneous strain relaxation by dislocations at the growth temperature. The residual compressive strain at the growth temperature is large enough such that even with the introduction of tensile strain arising from the difference in thermal expansion coefficients of GaAs and Si, a compressive strain is still present at room temperature for these thin GaAs/Si films.

Lao, Pudong↗

NASA NTRS1990

Combustion interaction with radiation-cooled chambers

Over 15 hours of thruster operation at temperatures between 1916 and 2246 C without failure or erosion has been demonstrated using iridium-coated rhenium chamber materials with nitrogen tetroxide/monomethylhydrazine propellants operating over a mixture ratio range of 1.60-2.05. Research is now under way to provide a basic understanding of the mechanisms which make high-temperature operation possible and to extend the capability to a wider range of conditions, including other propellant combinations and chamber materials. Techniques have been demonstrated for studying surface fracture phenomena. These include surface Raman and Auger for study of oxide formation, surface Raman and X-ray diffraction to determine the oxide phase, Auger to study oxide stoichiometry, and sputter Auger to study interdiffusion of alloy species.

Rosenberg, S. D.↗

NASA NTRS1990

A self-seeded SRS system for the generation of 1.54-micron eye-safe radiation

A light source is described for the efficient generation of 1.54-micron for eye-safe aerosol lidar operation. The system is based upon an Nd:YAG laser at 1.06 micron which is then Raman-shifted in methane to produce light at the first Stokes wavelength of 1.54 micron. First Stokes light generated in the backward direction was retroreflected back into the Raman cell for amplification in the tail of the 10 ns pump beam. The energy conversion efficiency and the spatial beam quality of the amplified first Stokes were found to be adversely affected when operated at higher repetition rates due to a thermal gradient produced in the generation region. A Stokes energy of 25 mJ was obtained for a pumping energy of 140 mJ at a repetition rate of 10 Hz. The beam divergence of the amplified Stokes radiation was measured to be less than 1 mrad. The optimized results demonstrate the applicability of this radiation for eye-safe lidar measurements.

Chu, Z.↗