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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

The nanophase iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

NASA Program Exobiology↗
NASA NTRS1992

Dielectric constant of liquid alkanes and hydrocarbon mixtures

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

NASA Program Exobiology↗
NASA NTRS1987

Deuterium hyperfine structure in interstellar C3HD

The deuterium nuclear quadrupole hyperfine structure of the transition 1(10)-1(01) of the ring molecule cyclopropenylidene-d1 (C3HD) has been observed in emission from interstellar molecular clouds. The narrowest linewidths (approximately 7 kHz) so far observed are in the cloud L1498. The derived D coupling constants Xzz = 186.9(1.4) kHz, eta=0.063(18) agree well with correlations based on other molecules.

NASA Program Exobiology↗
NASA NTRS1991

Imaging Jupiter's aurorae from H3+ emissions in the 3-4 micrometers band

Since H3+ was first spectroscopically detected on Jupiter, there has been considerable interest in using this simple molecular ion to probe conditions existing in the planet's auroral regions. Here we present a series of images of Jupiter recorded at wavelengths sensitive to emission by H3+, which reveal the spatial distribution of excited H3+ molecular ions in the jovian ionosphere, as seen from Earth. We believe that they provide high-spatial-resolution images of polar aurorae on Jupiter. They suggest that the intensity of the auroral emission can vary on a timescale of an hour, a shorter period than had previously been noted. We also find that the spatial distribution of H3+ emissions correlates only partially with the loci of auroral activity inferred from ultraviolet and longer-wavelength infrared observations. The H3+ emission may therefore be controlled by auroral processes that are different from those responsible for the ultraviolet and infrared emissions.

Non-NASA Center↗
NASA NTRS1991

Laboratory studies of the newly discovered infrared band at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io: the tentative identification of CO2

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

NASA Center ARC↗
NASA NTRS1992

Extraction technique for the determination of oxygen-18 in water using preevacuated glass vials

The need for a rapid, inexpensive technique for routine 18O/16O extraction from water has arisen recently through applications in the medical sciences and in hydrology. The traditional experimental technique for determining the oxygen isotope composition of water, the CO2-H2O equilibration method, is tedious, time consuming, and involves the use of custom-made glass apparatus. Furthermore, because of potential memory effects from one sample to the next, the glassware needs to be thoroughly cleaned between runs. A few attempts have been made to improve upon the method. Attempts to analyze water directly in the source of the mass spectrometer produced large memory effects and questionable results. Commercially available apparatus for automated extraction of 18O/16O from water is generally prohibitively expensive and often is designed to interface only with the manufacturer's own mass spectrometer. The method described in this paper utilizes inexpensive, off-the-shelf, preevacuated, glass vials. Preevacuated vials have been used by others for the isotopic analysis of breath CO2 and are well tested. The vials can be purchased in bulk from scientific apparatus suppliers at a relatively low cost. These are coupled with a simplified extraction line consisting of a stainless steel syringe needle and a glass cold trap. Vials are filled with CO2 and H2O and shaken in a constant-temperature water bath for at least 90 min. Since the vials are discarded after use, no cleaning is necessary, essentially eliminating any memory effect. Reproducibility is generally better than +/- 0.05%. The only reagents required are gaseous CO2 for equilibration, a dry ice/alcohol mixture for trapping water, and liquid nitrogen for transferring the CO2.

NASA Discipline Number 52-10↗
NASA NTRS1987

Radiogenic heating of comets by 26Al and implications for their time of formation

The effect of radiogenic heating on the thermal evolution of spherical icy bodies with radii 1 km < R < 100 km was investigated. The radioisotopes considered were 26Al, 40K, 232Th, 235U, and 238U. Except for the 26Al abundance, which was varied, the other initial abundances were kept fixed, at values derived from those of chondritic meteorites and corresponding to a gas-to-dust ratio of 1. The initial models were homogeneous and isothermal (To = 10 K) amorphous ice spheres, in a circular orbit at 10(4) AU from the Sun. The main object of this study was to examine the conditions under which the transition temperature from amorphous into cubic ice (Ta = 137 K) would be reached. It was shown that the influence of the short-lived radionuclide 26Al dominates the effect of other radioactive species for bodies of radii up to approximately 50 km. Consequently, if we require comets to retain their ice in amorphous form, as suggested by observations, an upper limit of approximately 4 x 10(-9) is obtained for the initial 26Al abundance in comets, a factor of 100 lower than that of the inclusions in the Allende meteorite. A lower limit for the formation time of comets may thus be derived. The possibility of a coexistence of molten cometary cores and extended amorphous ice mantles is ruled out. Larger icy spheres (R > 100 km) reached Ta even in the absence of 26Al, due to the decay of the other radionuclides. As a result, a crystalline core formed whose relative size depended on the composition assumed. Thus the outermost icy satellites in the solar system, which might have been formed of ice in the amorphous state, have probably undergone crystallization and may have exhibited eruptive activity when the gas trapped in the amorphous ice was released (e.g., Miranda).

Non-NASA Center↗
NASA NTRS1991

Isotopic composition of hydrogen in insoluble organic matter from cherts

Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

Non-NASA Center↗
NASA NTRS1991

Implanted 3He, 4He, and Xe in further studies of diamonds from Western Australia

In measurements of the noble gases in additional samples of diamonds from the Argyle and Ellendale lamproites in Western Australia we have failed to encounter any neon-rich stones such as showed solar-like isotopic compositions in earlier work. No neon was detected above the relatively high blank levels in our glass apparatus. White and brown diamonds showed no differences in noble gas content, nor did samples segregated by the color of long-wave UF fluorescence. The rare gas patterns in the 1.2 Ga Argyle pipe are largely consistent with implanted 3He, 4He, and fissiogenic Xe from U/Th in the matrix rock in which the diamonds have been stored for so long. These implanted species are absent in diamonds from the much younger (approximately 20 Ma) Ellendale pipe. We give implantation formulae for several models of inhomogeneously distributed U/Th. Differences in 3He content between pipe and alluvial Argyle samples are consistent with expected cosmogenic production in the latter. An expanded data base for helium and carbon isotopic data on the same samples supports a negative [4He]-delta 13C correlation seen earlier in work from our group, but if the Argyle samples, which contain light carbon, are corrected for implanted 4He, the correlation is considerably weakened. We no longer see an earlier 3He/4He-delta 13C correlation.

NASA Discipline Number 52-10↗
NASA NTRS1988

Trapping of gas mixtures by amorphous water ice

Our studies on gas trapping in amorphous water ice at 24-100 K were extended, by using mixtures of CH4, CO, N2, and Ar, rather than single gases. In 1:1 gas:(water vapor) mixtures, the competition among these gases on the available sites in the ice showed that the trapping capacity for the various gases is determined not only by the structure and dynamics of the ice, but is also influenced by the gas itself. Whereas at 24-35 K all four gases are trapped in the ice indiscriminantly, at 50-75 K there is a clear enhancement, in the order of CH4 > CO > N2 > or approximately Ar. This order is influenced by the gas-water interaction energy, the size of the trapped gas atom or molecule, the type of clathrate-hydrate formed (I or II) and, possibly, other factors. It seems that the gas can be trapped in the amorphous ice in several different locations, each being affected in a different way by the deposition temperature and gas composition. Once a gas atom or molecule is trapped in a specific location, it is predestined to emerge in one of eight different temperature ranges, which are associated with changes in the ice. The experimentally observed enhancements, together with the findings on the gas composition of comet Halley, might enable an estimation of the gas composition in the region of comet formation.

NASA Discipline Number 52-10↗
NASA NTRS1991

Ab initio study of C + H3+ reactions

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

NASA Discipline Exobiology↗
NASA NTRS1989

Theoretical studies of the infrared emission from circumstellar dust shells: the infrared characteristics of circumstellar silicates and the mass-loss rate of oxygen-rich late-type giants

We have modeled the infrared emission of spherically symmetric, circumstellar dust shells with the aim of deriving the infrared absorption properties of circumstellar silicate grains and the mass-loss rates of the central stars. As a basis for our numerical studies, a simple semianalytical formula has been derived that illustrates the essential characteristics of the infrared emission of such dust shells. A numerical radiative transfer program has been developed and applied to dust shells around oxygen-rich late-type giants. Free parameters in such models include the absorption properties and density distribution of the dust. An approximate, analytical expression is derived for the density distribution of circumstellar dust driven outward by radiation pressure from a central source. A large grid of models has been calculated to study the influence of the free parameters on the emergent spectrum. These results form the basis for a comparison with near-infrared observations. Observational studies have revealed a correlation between the near-infrared color temperature, Tc, and the strength of the 10 micrometers emission or absorption feature, A10. This relationship, which essentially measures the near-infrared optical depth in terms of the 10 micrometers optical depth, is discussed. Theoretical A10-Tc relations have been calculated and compared to the observations. The results show that this relation is a sensitive way to determine the ratio of the near-infrared to 10 micrometers absorption efficiency of circumstellar silicates. These results as well as previous studies show that the near-infrared absorption efficiency of circumstellar silicate grains is much higher than expected from terrestrial minerals. We suggest that this enhanced absorption is due to the presence of ferrous iron (Fe2+) color centers dissolved in the circumstellar silicates. By using the derived value for the ratio of the near-infrared to 10 micrometers absorption efficiency, the observed A10-Tc relation can be calibrated in terms of the total dust column density of the circumstellar shell and thus the mass-loss rate of late-type giants can easily be derived. Detailed models have been made of the infrared emission of three well-studied Miras: R Cas, IRC 10011, and OH 26.5+0.6, with the emphasis on the shape of the 10 micrometers emission or absorption feature. The results show that the intrinsic shape of the 10 micrometers resonance varies from a very broad feature in R Cas to a relatively narrower feature in OH 26.5+0.6, with IRC 10011 somewhere in between. Possible origins of this variation are discussed. The mass-loss rates from these objects are calculated to be 3 x 10(-7), 2 x 10(-5), and 2 x 10(-4) M Sun yr-1 for R Cas, IRC 10011, and OH 26.5+0.6, respectively. These results are compared to other determinations in the literature.

NASA Discipline Exobiology↗
NASA NTRS1990

Heating and melting of small icy satellites by the decay of 26Al

We study the effect of radiogenic heating due to 26Al on the thermal evolution of small icy satellites. Our object is to find the extent of internal melting as a function of the satellite radius and of the initial 26Al abundance. The implicit assumption, based on observations of young stars, is that planet and satellite accretion occurred on a time scale of approximately 10(6) yr (comparable with the lifetime of 26Al). The icy satellites are modeled as spheres of initially amorphous ice, with chondritic abundances of 40K, 232Th, 235U, 238U, corresponding to an ice/dust mass ratio of 1. Evolutionary calculations are carried out, spanning 4.5 x 10(9) yr, for different combinations of the two free parameters. Heat transfer by subsolidus convection is neglected for these small satellites. Our main conclusion is that the initial 26Al abundance capable of melting icy bodies of satellite size to a significant extent is more than 10 times lower than that prevailing in the interstellar medium (or that inferred from the Ca-Al rich inclusions of the Allende meteorite, approximately 7 x 10(-7) by mass). We find, for example, that an initial 26Al mass fraction of approximately 4 x 10(-8) is sufficient for melting almost completely icy spheres with radii of 800 km, typical of the larger icy planetary satellites. We also find that for any given 26Al abundance, there is a narrow range of radii below which only marginal melting occurs and above which most of the ice melts (and refreezes later). Since extensive melting may have important consequences, such as differentiation, gas release, and volcanic activity, the effect of 26Al should be included in future studies of satellite interiors.

Non-NASA Center↗
NASA NTRS1992

Sulfur and nitrogen reactions for cometary comae ion chemistry

The low pressure reactions of sulfur dioxide, carbon disulfide, and hydrazine with H2O+ and H3O+ were studied by the ion cyclotron resonance technique. These reactions are potentially important for sulphur chemistry in cometary comae. Rate coefficients and branching ratios of product channels are presented.

NASA Center JPL↗
NASA NTRS1992

Ab initio predictions on the rotational spectra of carbon-chain carbene molecules

We predict rotational constants for the carbon-chain molecules H2C=(C=)nC, n=3-8, using ab initio computations, observed values for the earlier members in the series, H2CCC and H2CCCC with n=1 and 2, and empirical geometry corrections derived from comparison of computation and experiment on related molecules. H2CCC and H2CCCC have already been observed by radioastronomy; higher members in the series, because of their large dipole moments, which we have calculated, are candidates for astronomical searches. Our predictions can guide searches and assist in both astronomical and laboratory detection.

NASA Discipline Number 52-10↗
NASA NTRS1988

The C4H7+ cation. A theoretical investigation

The potential energy surface of the C4H7+ cation has been investigated with ab initio quantum chemical theory. Extended basis set calculations, including electronic correlation, show that cyclobutyl and cyclopropylcarbinyl cation are equally stable isomers. The saddle point connecting these isomers lies 0.6 kcal/mol above the minima. The global C4H7+ minimum corresponds to the 1-methylallyl cation, which is 9.0 kcal/mol more stable than the cyclobutyl and the cyclopropylcarbinyl cation and 9.5 kcal/mol below the 2-methylallyl cation. These results are in excellent agreement with experimental data.

NASA Discipline Number 52-10↗
NASA NTRS1988

The 2.5-12 micrometers spectrum of comet Halley from the IKS-VEGA experiment

The infrared instrument IKS flown on board the VEGA space probes was designed for the detection of emission bands of parent molecules, and for a measurement of the size and temperature of the thermal emitting nuclear region. The instrument had three channels with cooled detectors: an "imaging channel" designed to modulate the signal of the nucleus and two spectroscopic channels operating at 2.5-5 and 6-12 micrometers, respectively, equipped with circular variable filters of resolving power approximately 50. This paper presents and discusses the results from the spectral channels. On VEGA 1, usable spectra were obtained at distances D from the comet nucleus ranging from 250,000 to 40,000 km corresponding to fields of view 4000 and 700 km in diameter, respectively. The important internal background signal caused by the instrument itself, which could not be cooled, had to be eliminated. Since no sky chopping was performed, we obtain difference spectra between the current spectrum and a reference spectrum with little or no cometary signal taken at the beginning of the observing sequence (D approximately 200,000 km). Final discrimination between cometary signal and instrumental background is achieved using their different time evolution, since the instrumental background is proportional to the slow temperature drift of the instrument, and the cometary signal due to parent molecules or dust grains is expected to vary in first order as D-1. The 2.5-5 micrometers IKS spectra definitely show strong narrow signals at 2.7 and 4.25 micrometers, attributed to the nu 3 vibrational bands of H2O and CO2, respectively, and a broader signal in the region 3.2-3.5 micrometers, which may be attributed to CH-bearing molecules. All these signals present the expected D-1 intensity variation. Weaker emission features at 3.6 and 4.7 micrometers could correspond to the nu 1 and nu 5 bands of H2CO and the (1 - 0) band of CO, respectively. Molecular production rates are derived from the observed emissions, assuming that they are due to resonance fluorescence excited by the Sun's infrared radiation. For the strong bands of H2O and CO2, the rovibrational lines are optically thick, and radiative transfer is taken into account. We derive production rates, at the moment of the VEGA 1 flyby, of approximately 10(30) sec-1 for H2O, approximately 2.7 x 10(28) sec-1 for CO2, approximately 5 x 10(28) sec-1 for CO, and 4 x 10(28) sec-1 for H2CO, if attributions to CO and H2CO are correct. The production rate of carbon atoms in CH-bearing molecules is approximately 9 x 10(29) sec-1 assuming fluorescence of molecules in the gas phase, but could be much less if the 3.2-3.5 micrometers emission is attributed to C-H stretch in polycyclic aromatic hydrocarbons or small organic grains. In addition, marginal features are present at 4.85 and 4.45 micrometers, tentatively attributed to OCS and molecules with the CN group, respectively. Broad absorption at 2.8-3.0 micrometers, as well as a narrow emission at 3.15 micrometers, which follow well the D-1 intensity variation, might be due to water ice. Emission at 2.8 micrometers is also possibly present, and might be due to OH created in vibrationally excited states after water photodissociation. The 6-12 micrometers spectrum does not show any molecular emission, nor emission in the 7.5-micrometers region. The spectrum is dominated by silicate emission showing a double structure with maxima at 9.0 and 11.2 micrometers, which suggests the presence of olivine.

NASA Discipline Number 52-10↗
NASA NTRS1995

Measurements of the H2(13)CO ortho/para ratio in cold dark molecular clouds

H2(13)CO has been detected for the first time toward cold dark molecular clouds using the NRAO 12 m telescope. The H2(13)CO ortho/para abundance ratio R for B335, which we report as R approximately 1.7, suggests equilibrium at the local kinetic temperature and appears to be distinctly different from that for both TMC-1 and L134N, where R is close to or higher than the statistical value 3. Since only B335 among the observed positions includes an imbedded IR source, this difference may result from heating of the grain surfaces, providing the energy necessary for desorption of formaldehyde formed on the grains.

NASA Discipline Exobiology↗