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At least 91 records · Page 5

The Structure of Ice Nanoclusters: Implications for Interstellar Ice Grains

Crystalline ice nanoclusters and thin-films of pure and impure water ice were deposited and studied in order to evaluate the extent to which surface-related effects control bulk properties. In pure water ice nanoclusters and thin-films of impure water ice, the cubic to hexagonal phase transformation occurs at lower temperatures than in thin-film deposits of pure water ice. In laboratory-grown crystalline ice nanoclusters, approx. 20 nm diameter, a significant proportion of water molecules exists in surface and near-surface environments which have an amorphous or nearly amorphous character. These disordered regions, which are highly reactive, serve to promote transformations or reactions which would otherwise be kinetically hindered. Likewise, dilute impurities such as methanol, sequestered to the surface of thin-films on crystallization, introduce defects into the ice network, thereby allowing sluggish structural transitions to proceed. These structural effects, which are surface phenomena, are believed to play an important role in promoting molecular reactions known to occur within interstellar ice grains in cold molecular clouds, where the first organic compounds are formed.

Delzeit, L.↗

Sublimation and reformation of icy grains in the primitive solar nebula

The quantity of water ice that sublimates during the free fall of grains into the solar nebula from a surrounding interstellar cloud varies from over 90 percent of the grain mass as 30 AU from the nebular center to less than 10 percent at more than 100 AU. Virtually all the water that is sublimated ultimately recondenses, since the cold nebular gas lying beyond 10 AU is unable to hold more than a small portion as vapor. The return of most of the gas to solid phase near the nebular ambient temperature, of about 50 K, may result in at least two grain populations consisting, in one case, of unaltered interstellar grains which did not undergo sublimation, and in the other of water ice which cocondensed with more volatile gases at nebular ambient temperatures to yield volatile-rich amorphous phases.

Lunine, Jonathan I.↗

HST-STIS Spectra of Saturn's Rings and Implications for Their Reddening Agent

We obtained HST-STIS spectra of Saturn's main rings in May 2011, using the G230L (and G430L) gratings, with final averaged radial resolution of 160 (and 330) km/pixel. The dataset filled a previous 200-330nm "spectral gap" between Cassini and ground-based spectra. The data provide radial profiles as a function of wavelength, but our most basic product at this point is a set of very low-noise spectra, radially averaged over broad regions of the rings (A, B, C, and Cassini Division). The raw spectra required special processing to remove artifacts due to extended-source grating scatter. We have modeled the spectra using a new particle surface model, which corrects for on-surface shadowing due to the likely very rough ring particle surfaces, and avoids overestimation of intra-mixed "neutral absorber". We correct for non-classical layer effects and finite ring optical depth, and relate our observed reflectivities to the spherical albedos of individual smooth particles. We model these smooth particle albedos using standard Hapke theory for regolith grain mixtures that are either homogeneous and "intramixed" (nonicy absorbers dispersed in water ice regolith grains) or heterogeneous "intimate" mixtures. As candidates for the nonicy contaminants we have considered amorphous carbon, aromatic-rich and aliphatic-rich organic tholins, silicates, hematite and iron metal. For the A and B rings, we find that iron metal (including a new theoretical estimate of the refractive indices of nanometer-sized grains of iron) is not spectrally steep enough in the 200-300nm range, and that aliphatic-rich tholins are either too steep at short wavelengths or too flat at long wavelengths. However, less than 1% by mass of aromatic-rich tholins provides a very good fit across the entire spectral range with no gratuitous "neutral absorber" needed, and a minimum of additional free parameters. The best fits require forward-scattering regolith grains. For the C Ring and Cassini Division, additional absorbers are needed (updated results will be given).

Saturn's Rings↗

Experimental studies of circumstellar, interstellar and interplanetary refractory grain analogs

Experimental techniques for studying the processes which occur during the life cycle of a refractory grain are reviewed. Consideration is given to the construction of a differentially-pumped beam-mass spectrometer which is expected to determine the relative stability of small clusters in the Fe-Mg-Si-O and Ca-Ti-Al-O systems as a function of temperature and pressure. Also, a smoke generator has been constructed to produce gram quantities of amorphous grains for use in thermal annealing and hydrous alteration studies of smokes containing Fe-Mg-Al-Ti-Ca-Si-O and Cl. Topics of the studies include the properties of grains produced in a flow condensation apparatus, the sorption efficiency of Si2O3 smokes for AR gas, the processing of ices containing refractory precursors such as SiH4 or Fe(CO)5 plus water, and the residue from 1 MeV bombardment and warming of an amorphous Fe-SiO smoke.

Nuth, J. A.↗

Flow of ices in the Ammonia-Water System

We have fabricated in the laboratory and subsequently deformed crystalline hydrates and partial melts of the water-rich end of the NH3-H2O system, with the aim of improving our understanding of physical processes occurring in icy moons of the outer solar system. Deformation experiments were carried out at constant strain rate. The range of experimental variables are given. Phase relationships in the NH3-H2O system indicate that water ice and ammonia dihydrate, NH3-2H2O, are the stable phases under our experiment conditions. X-ray diffraction of our samples usually revealed these as the dominant phases, but we have also observed an amorphous phase (in unpressurized samples only) and occasionally significant ammonia monohydrate, NH3-H2O. The onset of partial melting at the peritectic temperature at about 176 K appeared as a sharp transition in strength observed in samples of x(sub NH3) = 0.05 and 0.01, the effect of melt was less pronounced. For any given water ice + dihydrate alloy in the subsolidus region, we observed one rheological law over the entire temperature range from 175 K to about 140 K. Below 140 K, a shear instability similar to that occurring in pure water ice under the same conditions limited our ability to measure ductile flow. The rheological laws for the several alloys vary systematically from that of pure ice to that of dihydrate. Pure dihydrate is about 4 orders of magnitude less viscous than water ice just below the peritectic temperature, but because of a very pronounced temperature dependence in dihydrate (100 kJ/mol versus 43 kJ/mol for water ice) the viscosity of dihydrate equals or exceeds that of water ice at T less than 140 K. The large variation in viscosity of dihydrate with relatively small changes in temperature may be helpful in explaining the rich variety of tectonic and volcanic features seen on the surfaces of icy moons in the outer solar system.

Durham, W. B.↗

More About Arc-Welding Process for Making Carbon Nanotubes

High-quality batches of carbon nanotubes are produced at relatively low cost in a modified atmospheric-pressure electric-arc welding process that does not include the use of metal catalysts. What would normally be a welding rod and a weldment are replaced by an amorphous carbon anode rod and a wider, hollow graphite cathode rod. Both electrodes are water-cooled. The cathode is immersed in ice water to about 0.5 cm from the surface. The system is shielded from air by flowing helium during arcing. As the anode is consumed during arcing at 20 to 25 A, it is lowered to maintain it at an approximately constant distance above the cathode. The process causes carbon nanotubes to form on the lowest 5 cm of the anode. The arcing process is continued until the anode has been lowered to a specified height. The nanotube-containing material is then harvested. The additional information contained in the instant report consists mostly of illustrations of carbon nanotubes and a schematic diagram of the arc-welding setup, as modified for the production of carbon nanotubes.

Benavides, Jeanette M.↗

Dynamic compression effects of H 2 ⁡O in a dynamic diamond anvil cell: Origin of metastable ice VII and its crystal growth kinetics

We report on the structural verification of metastable ice VII solidifying in the phase space of ice VI at 1.80 GPa at room temperature. Using time-resolved (TR) x-ray diffraction and TR ruby luminescence paired with high-speed microphotography utilizing a dynamic diamond anvil cell, an initial compression rate range from 0.12 to 95.84 GPa/s was explored. The solidification pressure of metastable ice VII has a potential sigmoidal dependence upon compression rate with a turnover compression rate of ∼80 GPa/s. The preferred crystallization of ice VII in the stability field of ice VI is due to the increased nucleation rate of ice VII over ice VI at 1.77 GPa that is driven by the surface energy difference between the liquid and solid phases along with the change in Gibbs free energy of solidification. The dynamic pressure-volume–compression behaviors of ice phases (VI and VII) show a lattice stiffening in both phases, especially during the compression loading. It is also found that the compression rate greatly affects the solid-solid phase transition between ice VI and VII but does not affect the liquid-solid transition between water and ice VI as much. Lastly, a third phase transition was found to occur after metastable ice VII transforms into high-density amorphous (HDA) ice, which could be a disordered hydrogen-bonded network configuration of ice VII forming out of HDA ice facilitated by the decoupling of the oxygen movement and reorientation of the H 2⁡ O molecule. These results demonstrate the complexity of a seemingly simple molecule H 2⁡ O, how it can readily change its static properties with the modification of (de)compression rate, and highlight the need to use multiple TR structural and spectroscopic probes at higher time resolutions to realize the most comprehensive understanding.

Chemical bonding↗

Radiation-Induced Amorphization of Crystalline Ice

We study radiation-induced amorphization of crystalline ice, ana lyzing the resu lts of three decades of experiments with a variety of projectiles, irradiation energy, and ice temperature, finding a similar trend of increasing resistance of amorphization with temperature and inconsistencies in results from different laboratories. We discuss the temperature dependence of amorphization in terms of the 'thermal spike' model. We then discuss the common use of the 1.65 micrometer infrared absorption band of water as a measure of degree of crystallinity, an increasingly common procedure to analyze remote sensing data of astronomical icy bodies. The discussion is based on new, high quality near-infrared refl ectance absorption spectra measured between 1.4 and 2.2 micrometers for amorphous and crystalline ices irradiated with 225 keV protons at 80 K. We found that, after irradiation with 10(exp 15) protons per square centimeter, crystalline ice films thinner than the ion range become fully amorphous, and that the infrared absorption spectra show no significant changes upon further irradiation. The complete amorphization suggests that crystalline ice observed in the outer Solar System, including trans-neptunian objects, may results from heat from internal sources or from the impact of icy meteorites or comets.

Fama, M.↗

Revisiting the reactivity between HCO and CH 3 on interstellar grain surfaces

The formation of interstellar complex organic molecules is currently thought to be dominated by the barrierless coupling between radicals on the interstellar icy grain surfaces. Previous standard density functional theory (DFT) results on the reactivity between CH 3 and HCO on amorphous water surfaces showed that the formation of CH 4 + CO by H transfer from HCO to CH 3 assisted by water molecules of the ice was the dominant channel. In contrast, the adopted description of the electronic structure of the biradical (i.e. CH 3 /HCO) system was inadequate [without the broken-symmetry (BS) approach]. In this work, we revisit the original results by means of BS-DFT both in gas phase and with one water molecule simulating the role of the ice. Results indicate that the adoption of BS-DFT is mandatory to describe properly biradical systems. In the presence of the single water molecule, the water-assisted H transfer exhibits a high energy barrier. In contrast, CH 3 CHO formation is found to be barrierless. Yet, direct H transfer from HCO to CH 3 to give CO and CH 4 presents a very low energy barrier, hence being a potential competitive channel to the radical coupling and indicating, moreover, that the physical insights of the original work remain valid.

79 ASTRONOMY AND ASTROPHYSICS↗

Applying state diagrams to food processing and development

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Non-NASA Center↗

The Effect of Solution Chemistries and Freezing Temperatures on the Morphology of Cryogenic Opal-A (COA): Implications for Past Climates on Mars

Cryogenic opal-A (COA) is a type of hydrated amorphous silica that forms when silica-rich geothermal fluids erupt sub-aerially and are exposed to air temperatures below 0 °C. As the fluid cools and water-ice forms, the solution increases in ionic strength and reaches saturation of opal-A. This results in the precipitation of opal-A between water ice crystals. Natural COA is found embedded within frozen fluids near hydrothermal sources, and has been shown to preserve signs of biological activity. In this study, two solution chemistries (hydrochloric acid (HCl) and sulfuric acid (H2SO4)) and three freezing temperatures (-20, -80, -196 ºC) were used to synthesize COA in the lab. SEM analyses showed that COA frozen at -20 ºC in HCl solutions produced smooth silica branches similar to what was observed in previous studies. COA precipitated at lower freezing temperatures demonstrated progressively smaller particle sizes and unique morphologies such as halite dendrites within silica, desiccation cracks, and pores. COA made in H2SO4 solutions was more angular and fragmented than COA made in HCl solutions. Particle size also decreased with decreasing freezing temperature. COA textures have implications for terrestrial samples as well as future samples returned from Mars because they can provide information about past climate and fluid chemistry.

J V Hogancamp↗

Proton irradiation of SiH4-Fe(CO)5-H2O ices - Production of refractory silicates and implications for the solar nebula

The results of a number of experiments are reported in which SiH4-Fe(CO)5-H2O ice mixtures were irradiated by 1 MeV protons at 15 K and then warmed to room temperature in approximately 50 K steps. The properties of a sample were monitored by observing its infrared absorption spectrum as a function of its processing history. In each experiment in which ice samples containing SiH4 were irradiated, a refractory amorphous silicate residue remained after warming to room temperature. In addition to the usual broad silicate features at 10 and 20 microns, features due to water or hydroxyl at 3 and 6.2 microns, and a feature due to CO at 5 microns, a surprisingly stable infrared feature at 4.6 microns, attributed to the SiH stretching fundamental, was observed.

Nuth, J. A.↗

Dione’s Wispy Terrain: A Cryovolcanic Story?

We examine the H2O ice phase on the surface of Dione, one of Saturn's icy satellites, to investigate whether it might harbor cryovolcanic activity induced by a subcrustal body of water. Several studies have searched for such a signature, as summarized in Buratti et al.; however, none has yet produced sufficient evidence to dissipate doubts. In the radiation environment characteristic of Saturn's icy moons, the presence of crystalline H2O ice has been used as a marker of a high-temperature region. Because ion bombardment will, over time, drive crystalline ice toward an increasingly amorphous state, the current phase of the H2O ice can be used to gauge the temporal temperature evolution of the surface. We adopt a technique described by Dalle Ore et al. to map the fraction of amorphous to crystalline H2O ice on Dione's surface, observed by the Cassini Visible and Infrared Mapping Spectrometer, and provide an ice exposure age. We focus on a region observed at high spatial resolution and centered on one of the faults of the Wispy Terrain, which is measured to be fully crystalline. By assuming an amorphous to crystalline ice fraction of 5% (i.e., 95% crystallinity), significantly higher than the actual measurement, we obtain an upper limit for the age of the fault of 152 Ma. This implies that the studied fault has been active in the last ~100 Ma, supporting the hypothesis that Dione might still be active or was active a very short time ago, and similarly to Enceladus, might still be harboring a body of liquid water under its crust.

Saturnian satellites↗

Volatile-rich Asteroids in the Inner Solar System

Bennu (101195), target of the Origins, Spectral Interpretation, Resource Identification, Security, Regolith Explorer (OSIRIS-REx) mission, is a type-B asteroid with abundant spectral evidence for hydrated silicates, low thermal inertia “boulders” and frequent bursts of particle emission. We suggest that Bennu’s parent body formed in the outer solar system before it was perturbed into the asteroid belt and then evolved into a near-Earth object. We show that this is consistent with models of planetesimal evolution. Bennu has many characteristics expected for a dormant comet, and could potentially contain a minimum of 1 wt.% adsorbed water if its gross mineralogy is consistent with the Orgueil meteorite. This is in addition to any ice or water contained within the hydrous minerals themselves. Based on this hypothesis, we predict the properties of the samples that will be returned to Earth by the OSIRIS-REx mission, including abundant phyllosilicate minerals, amorphous hydrated silicates and low-density, very high-porosity aggregates, already observed by the OSIRIS-REx instrument suite. We predict enrichments in D/H and 15N/14N, high C/Mg ratios (>∼7 wt%), and a greater range of organic compositions than found in meteorites, including an organic component poor in aromatics, and a more labile organic fraction. Ammonium salts, ranging from NH4Cl to ammonium–organic acid salts could carry much of the nitrogen in comets, yet only NH4CH3COO and heavier salts are sufficiently stable to be found in these returned samples. Water adsorbed onto highly porous grains should also be detected provided that the sample return capsule remains below 300 K during Earth return, and this water should be isotopically heavy.

Joseph A. Nuth, III↗

The Hydrothermal System at Home Plate in Gusev Crater, Mars: Formation of High Silica Material by Acid-Sulfate Alteration of Basalt

The Alpha Particle X-ray Spectrometer (APXS) instrument on the Mars Exploration Rover (MER) Spirit measured three targets on or adjacent to Home Plate in Gusev Crater that have unusually high SiO2 concentrations (68% to 91%), unusually low FeO concentrations (1% to 7%, with total Fe as FeO), and unusually high TiO2/FeO ratios (0.2 to 1.2 by weight) [1]. Two targets (Kenosha Comets and Lefty Ganote) are located on high albedo soil (Gertrude Weise) that was exposed by the rover wheels, and one target is a float rock called Fuzzy Smith. Kenosha Comets has the highest SiO2 concentration, lowest FeO concentration, and highest TiO2/FeO ratio. Mineralogical evidence from the MER Miniature Thermal Emission Spectrometer (Mini-TES) suggests that the SiO2 is present as amorphous (noncrystalline) SiO2 at Gertrude Weise and nearby targets [2,3]. Mini-TES data were not acquired for Fuzzy Smith. Home Plate is considered to have an explosive volcanic origin, resulting when basaltic magma came into contact with ground water or ice [4]. Within ~50 m to 1 km of Home Plate are sulfate rich soil deposits (Paso Robles class soils with 22-35% SO3) which are considered to be probable fumarolic and/or hydrothermal deposits associated with the volcanism [5]. We develop the model here, suggested by [5], that the high-silica materials are another manifestation of acid-sulfate processes associated with fumarolic and hydrothermal activity at Home Plate. This is done by analogy with basaltic materials altered by acid sulfate processes on the Island of Hawaii.

Morris, R. V.↗

The Detection of Water Ice in Comet Hale-Bopp

We present spectra of Comet Hale-Bopp (C/1995 01) covering the range 1.4-2.5 micron that were recorded when the comet was 7 AU from the Sun. These show I)road absorption features at 1.5 and 2.05 micron. We show that some, but not all, of this absorption could be matched by an intimate mixture of water ice and a low albedo material such as carbon on the nucleus. However, we recognize that it is more likely that the ice features are produced by scattering from icy grains in the coma. The absence of absorption at 1.65 micron suggests that this ice is probably in the amorphous state. An unidentified additional component may be required to account for the downward slope at the longwavelength end of the spectrum.

Davies, John K.↗

Detection of Water Ice on Saturn's Satellite Phoebe

The near-infrared reflectance spectrum of Saturn's satellite Phoebe shows a broad absorption band at 2.0 micrometers and absorption at lambda > 2.2 micrometers, both characteristic of H2O ice. We have successfully modeled the surface of Phoebe with an intimate (granular) mix of H2O ice (3% by weight, grain size 500 micrometers) mixed with fine grains of H2O ice (0.25%) with amorphous carbon (grain size 900 micrometers) as the dominant component. This model reproduces the shape of the measured spectrum and the observed albedo of 0.10 for Phoebe, but it is not unique. The presence of ice establishes Phoebe as an original member of the outer Solar System rather than a renegade asteroid.

Owen, T. C.↗

Formation of model polar stratospheric cloud films

Fourier transform infrared spectroscopy was used to examine the competitive growth of films representative of polar stratospheric clouds. These experiments show that either crystalline nitric acid trihydrate (beta-NAT) or amorphous films with H2O:HNO3 ratios close to 3:1 formed at temperatures 3-7 K warmer than the ice frost point under stratospheric pressure conditions. In addition, with higher HNO3 pressure, we observed nitric acid dihydrate (NAD) formation at temperatures warmer than ice formation. However, our experiments also show that NAD surfaces converted to beta-NAT upon exposure to stratospheric water pressures. Finally, we determined that the net uptake coefficient for HNO3 on beta-NAT is close to unity, whereas the net uptake coefficient for H2O is much less.

Middlebrook, Ann M.↗