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NASA NTRS1985

Structure-property relations in lanthanide borate glasses

Glass formation in the system Ln2O3-B2O3 (Ln = Nd, Sm) was studied. Glasses could be formed in the range from 0 to 28 mol pct rare-earth oxide (Ln2O3), but liquid immiscibility in these systems limits the range of homogeneous glasses to 0 to 1.5 and 25 to 28 mol pct Ln2O3. The infrared spectra indicate that the rare-earth-rich glasses are structurally similar to rare-earth metaborates (LnB3O6) which contain (B3O6)-infinity chains. The variation in density, transformation temperature, thermal expansion coefficient, and transformation-range viscosity of these glasses with the size of the rare-earth ion is discussed. Glasses near the metaborate composition have a transformation temperature of about 700 C, which is high for binary borate glasses. Glasses could not be formed in the systems Eu2O3-, Gd2O3-, Ho2O3-, and Er2O3-B2O3, even by quenching at 1300 C/s. The sudden lack of glass formation in the system Ln2O3-B2O3 with Ln(3+) ions smaller than Sm(3+) is explained on the basis of the size effect of the Ln(3+) ion on the stability of (B3O6)-infinity chains in these metaborates.

Chakraborty, I. N.↗

NASA NTRS1986

Working Group on Circumstellar/Interstellar Relationships

Stars of various types are believed to be the main source of interstellar (IS) dust grans. The most important confirmed source is evolved giant and supergiant stars. Supernovae also contribute to the mass loss. The differences between circumstellar (CS) and IS dust were reviewed using the following topics: alteration of CS dust grains, size distribution, space observation of CS and IS dust, comparison of infrared spectra, isotopic signatures, Magellanic clouds and nearby galaxies, life cycles of dust grains, and physical and chemical data.

Glassgold, A. E.↗

NASA NTRS1986

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 polydimethlsiloxane, 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 deploymerization of the fluid molecule.

Gulino, D. A.↗

NASA NTRS1985

Polyimide analysis using diffuse reflectance-FTIR

The thermal imidization of a number of polyimide precursors in the form of powders, films, and prepregs was examined by an in situ diffuse reflectance-FTIR technique where infrared spectra were determined while the material was being heated. An analysis of these spectra revealed that, with the exception of one water soluble adhesive, each precursor developed an anhydride band around 1850 cm/cu during imidization. This band diminished in intensity during final stages of cure. Efforts were made to quantify the amount of anhydride in several samples. Evidence obtained could be interpreted to mean that poly(amic acid) resins undergo an initial reduction in molecular weight during imidization before recombining to achieve their ultimate molecular weights as polyimides. Several reports in the literature are cited to support this interpretation. This report serves both to document anhydride formation during imidization and to increase our fundamental understanding of how polyimides cure.

Young, P. R.↗

NASA NTRS1985

The photochemistry of methane and carbon monoxide in the troposphere in 1950 and 1985

The roughly 1 percent/year increase in tropospheric methane and roughly 2 percent/year increase in tropospheric carbon monoxide deduced from recent analyses of ground-based solar infrared spectra recorded in 1950 and 1951 have very important implications for the photochemistry and chemistry of the troposphere. Photochemical calculations indicate that as a result of the increase of methane and carbon monoxide since 1950-51, levels of the hydroxyl radical, the key species in the photochemistry of the troposphere, may have decreased by about 25 percent.

Levine, J. S.↗

NASA NTRS1986

Detection of stratospheric N2O5 by infrared remote sounding

Measurements of N2O5 absorption (1230 and 1260 per cm) in infrared spectra were carried out using the Atmospheric Trace Molecule Spectroscopy (ATMOS) instruments on board Spacelab 3. The detection of stratospheric N2O5, a temporary reservoir species whose photolysis products catalyze ozone destruction, was confirmed. Preliminary analysis of spectra recorded at sunrise on 1 May 1985 indicates a peak volume mixing ratio of 1.6 x 10 the -9th at 35 km an altitude of 35 km, or a broad concentration peak pf 4 x 10 to the 8th molecules per cu cm between 21 and 35 km. Absorption was not detected in spectra measured at sunset due to the depletion of N2O5 by photolysis during the day. The volume mixing ratio profile of N2O5 between 0 and 75 km altitude is reproduced in graphic form.

Toon, G. C.↗

NASA NTRS1986

Time dependent chemistry in dense molecular clouds. III - Infrared band cross sections of molecules in the solid state at 10 K

Thin film transmission infrared spectra and a list of integrated absorbance values (band strengths) of bands in the 2.5 to 20 micron range of various molecular solids deposited on a CsI window cooled to 10 K are presented. These solids include molecules known or suspected to be present on interstellar grains such as H2O, CO, NH3 and CH4 and mixtures of these molecules as well as various hydrocarbons. The method is described by which the absorbance values derived can be used to estimate column densities of species adsorbed on interstellar grains and other solids associated with celestial IR sources.

Dhendecourt, L. B.↗

NASA NTRS1986

Planetary infrared astronomy using a cryogenic postdisperser on Fourier transform spectrometers

High resolution infrared spectra of planets from ground-based observatories were analyzed and instrumentation to improve sensitivity was developed. A cryogenic postdisperser (a narrow bandpass spectral filter) for use with Fourier transform spectrometers (FTS's) at facility observatories was constructed. This instrument has improved the sensitivity of FTS observations at 8 to 20 microns by about an order of magnitude. Spectra of Jupiter, Saturn and Comet Halley were obtained using the postdisperser with FTS facilities at the Kitt Peak 4-meter and McMath telescopes. Spectral resolution as high as 0.01/cm was achieved.

Jennings, D. E.↗

NASA NTRS1986

Asteroid team

Work on asteroid classification continued was rewarded with the discovery of two Earth-approaching M asteroids. The M class is rare and these are the first found among the near-Earth asteroids to have the spectral albedo characteristic of this class. The two asteroids are newly discovered 1986 DA and 1986 EB which were observed at N and Q bandpasses (i.e., 10 and 20 microns) with the 3 m IRTF telescope and at five wavelengths from 0.36 to 0.85 microns from Kitt peak National Observatory's 0.36 m telescope. The derived diameters are about 2 km for both objects. In the asteroid radiometry program N or Q photometry was obtained for more than 40 asteroids in Feb. 1986. Radiometric diameter calibration support were provided for stellar occultations of stars by 230 Athamantis and 129 Antigone. The data were reduced but not analyzed. Infrared spectra (0.8 to 2.6 microns) of 60 asteroids were reduced and are now ready for compositional analysis.

Matson, D. L.↗

NASA NTRS1987

Thermal-infrared spectral observations of geologic materials in emission

The thermal-infrared spectra of geologic materials in emission were studied using the prototype Thermal Emission Spectrometer (TES). A variety of of processes and surface modifications that may influence or alter the spectra of primary rock materials were studied. It was confirmed that thermal emission spectra contain the same absorption features as those observed in transmission and reflection spectra. It was confirmed that the TES instrument can be used to obtain relevant spectra for analysis of rock and mineral composition.

Christensen, Philip R.↗

NASA NTRS1987

Preliminary results of spectral reflectance studies of tycho crater

The preliminary analysis and interpretation of near infrared spectra obtained for both the interior and exterior deposits associated with the Tycho crater is presented. Specific objectives were: (1) to determine the composition and stratigraphy of the highland crust in the Tycho target site; (2) to determine the likely composition of the primary ejecta which may be present in ray deposits; (3) to investigate the nature of spectral units defined in previous studies; (4) to further investigate the nature and origin of both the bright and dark haloes around the rim crest; and (5) to compare the compositions determined for the Tycho units with those of the Aristarchus crater as well as typical highland deposits. The spectra obtained for the interior areas exhibit similar spectral features. These include relatively strong 1 micron absorption bands whose minima are centered between 0.97 and 0.99 microns and shallow to intermediate continuum slopes. The spectra generally exhibit indications of a 1.3 micron feature consistent with the presence of Fe(2+) bearing plagioclase feldspar. The strong 1 micron absorption features indicate a dominant high Ca clinopyroxene component. Results obtained from the ejecta deposits show that the spectrum of the inner, bright halo is almost identical with those obtained for interior units. The spectrum of the dark halo exhibits a wide, relatively shallow absorption feature centered at 1.01 microns, a 1.3 micron absorption, and a steep continuum slope. This spectrum is interpreted as indicating the presence of pyroxene, Fe-bearing feldspar, and a significant component of Fe-bearing impact melt glass. Finally, the spectra of spots inside Tycho show similarity with certain spectra for Aristarchus. However, the suite of spectra obtained for Tycho exhibits a different trend in terms of band center versus width.

Hawke, B. R.↗

NASA NTRS1987

Far-infrared properties of optically-selected quasars and Seyfert galaxies

Pointed IRAS observations and ground based observations are used to determine the infrared properties of optically selected galaxies and quasars. The use of complete, unbiased, optically selected samples means that statistical tests can be applied to probe the underlying properties of active galactic nuclei (AGNs). The near infrared to millimeter spectral energy distributions (SEDs) were studied of the CfA Seyfert galaxies, a well defined, unbiased sample of 25 Type 1 and 23 Type 2 Seyfert galaxies selected by optical spectroscopy. Data given show strong trends in the infrared SEDs. Strong evidence is also given that the infrared spectra of Seyfert 2 galaxies are dominated by thermal emission from warm dust, while nonthermal emission is more important in the spectra of quasars and luminous Seyfert 1 nuclei.

Edelson, R. A.↗

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.↗