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NASA NTRS1986

The ortho/para ratio of water vapor in Comet Halley

The ortho/para ratio of H2O is shown to be an invariant in the cometary coma. The dependence of ortho-para ratio on temperature in thermal equilibrium is given, and the nuclear-spin-temperature is defined. Its relation to the physical temperature of the cometary ices is discussed, and the prospects for using the observed ortho/para ratio to infer properties of the cometary nucleus are explored. The ortho/para ratio in Halley's comet is derived from high resolution infrared spectra of near 2.7 microns wavelength. On UT December 24.1, 1985 it was 2.73 + or - 0.17, and on UT March 22.7, 1986 it was 3.23 + or - 0.37. The nuclear-spin-temperature was 35 K (+9 K, -5 K) pre-perihelion, and less than 40 K post-perihelion, at the 67% confidence limit. Both numbers are consistent with modeled values of the equilibrium temperature of the cometary nucleus at aphelion (47 K). However, at the 95% confidence limit they are also fully consistent with temperatures less than 50 K, corresponding to an ortho/para ratio of about 3.0.

Mumma, Michael J.↗

NASA NTRS1987

Reactions of Atomic Oxygen (O(3P)) with Polybutadienes and Related Polymers

Thin films of the following polymers were exposed at ambient temperature to ground-state oxygen atoms (O(3P)), generated by a radio-frequency glow discharge in O2: cis- and trans-1,4-polybutadienes (CB and TB), amorphous 1,2-polybutadiene (VB), polybutadienes with different 1,4/1,2 contents, trans polypentenamer (TP), cis and trans polyoctenamers (CO and TO), and ethylene-propylene rubber (EPM). Transmission infrared spectra of CB and TB films revealed extensive surface recession, or etching, unaccompanied by any microstructural changes within the films, demonstrating that the reactions were confined to the surface layers. Contrary to the report by Rabek, Lucki, and Ranby (1979), there was no O(3P)-induced cis-trans isomerization in CB or TB. From weight-loss measurements, etch rates for polybutadienes were found to be markedly dependent on vinyl content, decreasing by two orders of magnitude from CB (2% 1,2) to structures with 30 to 40% 1,2 double bonds, thereafter increasing by half an order of magnitude to VB (97% 1,2). Relative etch rates for EMP and the polyalkenamers were in the order: EMP is greater than CO (or TO) is greater than TP is greater than CB. The sole non-elastomer examined, TB, had an etch rate about six times that of CB, ascribable to a morphology difference. Cis/trans content had a negligible effect on the etch rate of the polyalkenamers. Mechanisms involving crosslinking through units are proposed for the unexpected protection imparted to polybutadienes by the 1,2 double bonds.

Golub, Morton A.↗

NASA NTRS1987

Effect of an oxygen plasma on the physical and chemical properties of several fluids for the Liquid Droplet Radiator

The Liquid Droplet Radiator is one of several radiator systems currently under investigation by NASA Lewis Research Center. It involves the direct exposure of the radiator working fluid to the space environment. An area of concern is the potential harmful effects of the low-Earth-orbit atomic oxygen environment on the radiator working fluid. To address this issue, seven candidate fluids were exposed to an oxygen plasma environment in a laboratory plasma asher. The fluids studied included Dow Corning 705 Diffusion Pump Fluid, polymethylphenylsiloxane and polydimethylsiloxane, both of which are experimental fluids made by Dow Corning, Fomblin Z25, made by Montedison, and three fluids from the Krytox family of fluids, Krytox 143AB, 1502, and 16256, which are made by DuPont. The fluids were characterized by noting changes in visual appearance, physical state, mass, and infrared spectra. Of the fluids tested, the Fomblin and the three Krytoxes were the least affected by the oxygen plasma. The only effect noted was a change in mass, which was most likely due to an oxygen-catalyzed depolymerization of the fluid molecule.

Gulino, Daniel A.↗

NASA NTRS1987

A kinetic study of hydrous alteration of amorphous MgSiO smokes - Implications for cometary particles and chondrite matrix

Measurements of the rate of hydrous alteration of amorphous Mg-SiO smokes are reported as a function of temperature, as inferred by observing changes in the infrared spectra of these materials. It is shown that under the conditions reported for the nucleus of Comet Halley, based on measurements made by the Vega and Giotto missions, amorphous, anhydrous Mg-SiO smokes would become hydrated within several weeks in the dusty regolith observed on the surface. However, if such grains were released in 'jets' or from loose ice fragments, then previously amorphous grains would retain their anhydrous nature. Similarly, brief periods of aqueous activity on meteorite parent bodies would convert amorphous, fine-grained material to hydrated phyllosilicates much more rapidly than coarse mineral grains. A kinetic model might therefore be developed to explain the observed textural relationships in the matrices of carbonaceous chondrites such as Mokoia, where amorphous phyllosilicates are intimately associated with coarse anhydrous grains.

Nelson, Robert↗

NASA NTRS1987

Production of Cl2O2 from the self-reaction of the ClO radical

The species Cl2O2 has been generated in a gaseous flow system at 220-240 K by reacting Cl atoms with one of three different ClO precursors: O3, Cl2O, or OClO. The infrared spectra of the reactive mixture indicate that at least two different dimers are produced: a predominant form with bands centered at 1225 and 1057/cm attributed to ClOOCl, and a second form with a band at 650/cm attributed to ClOClO. The UV spectrum of the predominant form shows a maximum absorption cross section of about 6.5 x 10 to the -18th sq cm/molecule around 270 nm, with a wing extending beyond 300 nm. The implications of these results for the chemistry of the stratosphere are discussed.

Molina, L. T.↗

NASA NTRS1987

Simultaneous measurement of stratospheric O3, H2O, CH4, and N2O profiles from infrared limb thermal emissions

Thermal emission measurements of the earth's stratospheric limb were made with a cryogenically cooled high-resolution Michelson interferometer on a balloon flight launched from Palestine, TX, on Nov. 6, 1984. Infrared spectra for complete limb sequences were obtained over portions of the 700-1940/cm range with an unapodized spectral resolution of 0.03/cm for tangent heights varying from 13 to 39 km. The observed data from 1125 to 1425/cm have been analyzed for simultaneous measurement of O3, H2O, CH4, and N2O profiles. The analysis employs line-by-line and layer-by-layer radiative-transfer calculations, including curvature and refraction effects. The optimum use of geometric and spectral effects is made to obtain sharply peaked weighting functions. Contributions from stratospheric aerosol are included by measuring the light extinction within the window regions of the observed spectra. The retrieved constituent profiles are compared with measurements made with a variety of techniques by other groups. The comparison shows good agreement with the published data for all gases, indicating the capability of retrieving trace gas profiles from high-resolution thermal emission limb measurements.

Abbas, M. M.↗

NASA NTRS1987

Kinematic properties of the neutral gas outflow from comet P/Halley

High-resolution infrared spectra of H2O in Comet Halley, obtained by the Kuiper Airborne Observatory, were used to characterize the dynamics of the neutral gas outflow from the comet. The spatial distribution and the expansion velocity of the H2O molecules were deduced from the positions, widths, and shapes of the H2O lines. The character of line profiles suggested that the H2O distribution was anisotropic in the circular field-of-view of aproximately 10,000 radius centered on the nucleus. Direct observations of the H2O spatial brightness distribution showed that the outflow was concentrated in the sunward direction (although some H2O emission was also detected in the tail). An obvious property of the gas outflow from the Comet P/Halley was its variability. The specific intensities of the H2O lines demonstrated that the gas production from the comet varied significantly on many time scales; there were pre- and postperihelion asymmetries, day-to-day variations, and outbursts.

Larson, H. P.↗

NASA NTRS1988

Cometary dust composition

The earth based measurements and in situ sampling of Comet Halley have provided new data about the chemical composition of cometary grains. Recent progress in laboratory studies of interplanetary dust particles (IDPs) complement the comet data, allowing inferences about the mineralogy and physical structure of the comet dust to be drawn from the observed elemental composition and infrared spectra. The in situ dust composition measurements at Halley, the composition of IDPs and their relation to comet dust, and the origin of the 3.4 micron hydrocarbon feature is discussed. Related discussion is also presented on aromatic components in comets and the 3.4 micron feature. These topics are briefly summarized.

Gehrz, R. D.↗

NASA NTRS1988

Properties of interstellar dust in reflection nebulae

Observations of interstellar dust in reflection nebulae are the closest analog in the interstellar medium to studies of cometary dust in our solar system. The presence of a bright star near the reflection nebula dust provides the opportunity to study both the reflection and emission characteristics of interstellar dust. At 0.1 to 1 micrometer, the reflection nebula emission is due to starlight scattered by dust. The albedo and scattering phase function of the dust is determined from observations of the scattered light. At 50 to 200 micrometers, thermal emission from the dust in equilibrium with the stellar radiation field is observed. The derived dust temperature determines the relative values of the absorption coefficient of the dust at wavelengths where the stellar energy is absorbed and at far infrared wavelengths where the absorbed energy is reradiated. These emission mechanisms directly relate to those seen in the near and mid infrared spectra of comets. In a reflection nebula the dust is observed at much larger distances from the star than in our solar system, so that the equilibrium dust temperature is 50 K rather than 300 K. Thus, in reflection nebulae, thermal emission from dust is emitted at 50 to 200 micrometer.

Sellgren, Kristin↗

NASA NTRS1988

Chemistry of chlorinated species in the Antarctic stratosphere

The chemistry of Cl sub 2 O sub 2, the chlorine monoxide dimer, has been further investigated in order to better asses its potential role in catalytic ozone destruction cycles. The dimer has been generated in a flow system, in the 200 to 250 K temperature range, by using ozone and chlorine atoms as ClO precursors. The Cl-atoms are produced by a microwave discharge of either Cl sub 2, or of F sub 2 with subsequent addition of HCl. With this later scheme the dimer can be generated in the absence of Cl sub 2. The Fourier transform infrared spectra of the products clearly indicates the presence of two isomers, in agreement with earlier results (J. Phys. Shen., 91, 433, 1987). None of the observed IR bands can be attributed to a ClO-OClO adduct, since they all appear in the absence of any detectable amount of OCl. It is likely that the particles in the polar stratospheric clouds will have a relatively dilute nitric acid outer layer, even if the core is the nitric acid monohydrate, since the particles are in equilibrium with the ambient water vapor, which is present at levels of a few parts per million.

Molina, Mario J.↗

NASA NTRS1988

Hot components and circumstellar grains in M supergiant syncretic binaries

Ultraviolet and infrared spectra were obtained in order to study grains in cool star and hot star syncretic type binaries. Grains are found in only about half of the syncretic systems. The results suggest that grains have not formed in many syncretic systems because of ultraviolet radiation from the hot star. Circumstellar extinction could not be unambiguously detected in those systems with grains.

Buss, Richard H., Jr.↗

NASA NTRS1988

In situ composite cure monitoring using infrared transmitting optical fibers

The development of infrared-transmitting optical fibers as sensors for monitoring the cure of advanced composite materials is reported. Fourier transform infrared spectra are presented which were remotely sensed during the cure of a high performance polyimide resin and a graphite/polyimide matrix prepreg using an 0.1 mm O.D. x 3 m chalcogenide optical fiber. A discussion of the fiber and sensor element, absorption mechanism and potential applications is presented.

Young, Philip R.↗

NASA NTRS1989

Remote sensing and geologic studies of localized dark mantle deposits on the moon

Localized lunar dark mantle deposits (LDMD) are small, smooth low-albedo units of pyroclastic origin commonly found associated with endogenic source craters. Analysis of near-infrared spectra, multispectral images, and radar data obtained for 25 LDMD has led to the identification of three compositional groups of LDMD. Group 1 deposits are composed predominantly of highlands-rich wall rock but also contain a substantial juvenile component, Group 2 deposits are composed largely of mare plug rock material, while Group 3 deposits are rich in a mixture of olivine and pyroxene. Variations in eruption conditions are interpreted to be largely responsible for the varying mineralogy of these three types of deposits.

Hawke, B. R.↗

NASA NTRS1989

Bayesian learning

In 1983 and 1984, the Infrared Astronomical Satellite (IRAS) detected 5,425 stellar objects and measured their infrared spectra. In 1987 a program called AUTOCLASS used Bayesian inference methods to discover the classes present in these data and determine the most probable class of each object, revealing unknown phenomena in astronomy. AUTOCLASS has rekindled the old debate on the suitability of Bayesian methods, which are computationally intensive, interpret probabilities as plausibility measures rather than frequencies, and appear to depend on a subjective assessment of the probability of a hypothesis before the data were collected. Modern statistical methods have, however, recently been shown to also depend on subjective elements. These debates bring into question the whole tradition of scientific objectivity and offer scientists a new way to take responsibility for their findings and conclusions.

Denning, Peter J.↗

NASA NTRS1989

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier transform spectroscopy (FTIR)

The Laser Atmospheric Wind Sounder (LAWS) Program has as one of its goals the development of a satellite based carbon dioxide laser for making wind velocity measurements. The specifications for this laser include the requirement that the laser operate at a repetition rate of 10 Hertz continuously for three years. Earth-based carbon dioxide lasers can operate for only a short time on a single charge of gas because the lasing action causes the CO2 to break down into CO and O2. Therefore, earth-based CO2 lasers are generally operated in a flow through mode in which the spent gas is continually exhausted and fresh gas is continually added. For a satellite based system, however, a recirculation system is desired because it is not practical to send up extra tanks of CO2. A catalyst which could enable a recirculating CO2 laser to function continuously for three years needs to be developed. In the development of a catalyst system there are many variables. Obviously, not all possible formulations can be tested for three years, therefore, an accurate model which is based on the reaction mechanism is needed. The construction of a multistep reaction mechanism is similar to the construction of a jigsaw puzzle. Different techniques each supply a piece of the puzzle and the researcher must put the pieces together. Transmission infrared spectroscopy was shown to be very useful in supplying some of the information needed to elucidate reaction mechanisms. The purpose was to see what kind of information might be obtained about the NASA catalyst using infrared absorption spectroscopy. Approximately 200 infrared spectra of the prototype Pt/tin oxide catalyst and its precursor components are observed under a variety of different conditions. The most significant observations are summarized.

Keiser, Joseph T.↗

NASA NTRS1990

Space station contamination study: Assessment of contaminant spectral brightness

The results presented show that spectral emissions which arise as a result of vehicle-ambient atmospheric interactions are significant and can become competitive with the natural zodiacal background up to altitudes as high as 400 km for the Vacuun Ultraviolet (VUV) and Visible Infrared Spectra (VIS) for the worst case conditions used. The empirical database on the induced environment of space vehicles is very sparse, and these results are based on a number of assumptions and cannot be regarded as definitive at the present time. Since the technique for doing calculations of this kind was developed in its preliminary form for the purpose of this study, a list of greatly improved estimates are provided of the contamination irradiances. Tasks which are considered most important in order to achieve a higher confidence level for the preliminary conclusions drawn are provided.

Torr, D. G.↗

NASA NTRS1989

Fitting improved accretion disk models to the multiwavelength continua of quasars and active galactic nuclei

Fits to the ultraviolet-optical-infrared spectra of 60 quasars and active galactic nuclei (AGNs) are investigated, using black hole accretion disk models. The disk is assumed to be geometrically thin and optically thick. The observed spectrum from a black hole accretion disk, rotating (Kerr) or nonrotating (Schwarzschild), is transformed by the geometric inclination effect, Doppler shifts, gravitational redshifts, and gravitational focusing. These effects alter the locally emitted fluxes and produce harder spectra for an observer at higher inclination angles. The relativistic corrections are much more significant in the Kerr geometry since the inner edge of the disk is much closer to the rotating black hole. A simple inverse relation between the inferred black hole mass and the assumed inclination angle was found in the Kerr case, while the inferred accretion rate (solar masses/yr) remains independent of the angle. In the Schwarzschild case, the ratio of the inferred accretion rate to the black hole mass remains roughly constant when the viewing angle changes. In both geometries, low-redshift Seyfert galaxies have relatively low accretion rates, only a few percent of their Eddington luminosities, while the most luminous quasars are accreting near their Eddington limits.

Sun, Wei-Hsin↗

NASA NTRS1989

High-resolution near-infrared spectroscopy of water dimer

High-resolution near-infrared spectra are reported for all of the O-H stretch vibrational bands of the water dimer. The four O-H vibrations are characterized as essentially independent proton-donor or proton-acceptor motions. In addition to the rotational and vibrational information contained in these spectra, details are obtained concerning the internal tunneling dynamics in both the ground and excited vibrational states. These results show that, for tunneling motions which involve the interchange of the proton donor and acceptor molecules, the associated frequencies decrease substantially due to vibrational excitation. The predissociation lifetimes for the various states of the dimer are determined from linewidth measurements. These results clearly show that the predissociation dynamics is strongly dependent on the tunneling states, as well as the Ka quantum number, indicating that the internal tunneling dynamics plays an important role in determining the dissociation rate in this complex.

Huang, Z. S.↗