Computer Modeling of the Thermal Conductivity of Cometary Ice

NASA Technical Reports Server (NTRS)

Bunch, Theodore E.; Wilson, Michael A.; Pohorille, Andrew

1998-01-01

The main objective of this research was to estimate the thermal conductivity of cometry ices from computer simulations of model amorphous ices. This was divided into four specific tasks: (1) Generating samples of amorphous water ices at different microporosities; (2) Comparing the resulting molecular structures of the ices with experimental results, for those densities where data was available; (3) Calculating the thermal conductivities of liquid water and bulk amorphous ices and comparing these results with experimentally determined thermal conductivities; and (4) Investigating how the thermal conductivity of amorphous ice depends upon the microscopic porosity of the samples. The thermal conductivity was found to be only weakly dependent on the microstructure of the amorphous ice. In general, the amorphous ices were found to have thermal conductivities of the same order of magnitude as liquid water. This is in contradiction to recent experimental estimates of the thermal conductivity of amorphous ice, and it is suggested that the extremely low value obtained experimentally is due to larger-scale defects in the ice, such as cracks, but it is not an intrinsic property of the bulk amorphous ice.

Measurement of the accumulation of water ice on optical components in cryogenic vacuum environments

NASA Astrophysics Data System (ADS)

Moeller, Trevor M.; Montgomery Smith, L.; Collins, Frank G.; Labello, Jesse M.; Rogers, James P.; Lowry, Heard S.; Crider, Dustin H.

2012-11-01

Standard vacuum practices mitigate the presence of water vapor and contamination inside cryogenic vacuum chambers. However, anomalies can occur in the facility that can cause the accumulation of amorphous water ice on optics and test articles. Under certain conditions, the amorphous ice on optical components shatters, which leads to a reduction in signal or failure of the component. An experiment was performed to study and measure the deposition of water (H2O) ice on optical surfaces under high-vacuum cryogenic conditions. Water was introduced into a cryogenic vacuum chamber, via a hydrated molecular sieve zeolite, through an effusion cell and impinged upon a quartz-crystal microbalance (QCM) and first-surface gold-plated mirror. A laser and photodiode setup, external to the vacuum chamber, monitored the multiple-beam interference reflectance of the ice-mirror configuration while the QCM measured the mass deposition. Data indicates that water ice, under these conditions, accumulates as a thin film on optical surfaces to thicknesses over 45 microns and can be detected and measured by nonintrusive optical methods which are based upon multiple-beam interference phenomena. The QCM validated the interference measurements. This experiment established proof-of-concept for a miniature system for monitoring ice accumulation within the chamber.

Magnetospheric considerations for solar system ice state

NASA Astrophysics Data System (ADS)

Paranicas, C.; Hibbitts, C. A.; Kollmann, P.; Ligier, N.; Hendrix, A. R.; Nordheim, T. A.; Roussos, E.; Krupp, N.; Blaney, D.; Cassidy, T. A.; Clark, G.

2018-03-01

The current lattice configuration of the water ice on the surfaces of the inner satellites of Jupiter and Saturn is likely shaped by many factors. But laboratory experiments have found that energetic proton irradiation can cause a transition in the structure of pure water ice from crystalline to amorphous. It is not known to what extent this process is competitive with other processes in solar system contexts. For example, surface regions that are rich in water ice may be too warm for this effect to be important, even if the energetic proton bombardment rate is very high. In this paper, we make predictions, based on particle flux levels and other considerations, about where in the magnetospheres of Jupiter and Saturn the ∼MeV proton irradiation mechanism should be most relevant. Our results support the conclusions of Hansen and McCord (2004), who related relative level of radiation on the three outer Galilean satellites to the amorphous ice content within the top 1 mm of surface. We argue here that if magnetospheric effects are considered more carefully, the correlation is even more compelling. Crystalline ice is by far the dominant ice state detected on the inner Saturnian satellites and, as we show here, the flux of bombarding energetic protons onto these bodies is much smaller than at the inner Jovian satellites. Therefore, the ice on the Saturnian satellites also corroborates the correlation.

Laboratory studies on low-energy electron penetration depths into amorphous ice - consequence to astrobiology on icy surfaces

NASA Astrophysics Data System (ADS)

Gudipati, M. S.; Li, I.; Lignell, A. A.

2009-12-01

Penetration of electrons through icy surfaces plays an important role in radiation processing of solar system icy bodies. However, to date, there is no quantitative data available on the penetration depths of electrons through cryogenic water-ices. Penetration of high-energy incident electrons also results in the in-situ formation of secondary low-energy electrons, such as on the surface of Europa (Herring-Captain et al., 2005; Johnson et al., 2004). Low-energy electrons can also be produced through photoionization process such as on comet surfaces, or through bombardment by solar wind on icy surfaces (Bodewits et al., 2004). Present models use the laboratory penetration data of high-energy (>10 keV) electrons through silicon as a proxy for the ice (Cooper et al., 2001), normalized by the density of the medium. So far no laboratory studies have been conducted that deal with the penetration of electrons through amorphous or crystalline ices. In order to address this issue, we adopted a new experimental strategy by using aromatic molecules as probes. To begin with, we carried out systematic studies on the penetration depths of low-energy electrons (5 eV - 2 keV) through amorphous ice films of defined thickness at cryogenic temperatures (5 - 30 K). The results of these experiments will be analyzed and their relevance to survival of organic material on solar system icy surfaces will be presented. References: Bodewits, D., et al., 2004. X-ray and Far-Ultraviolet emission from comets: Relevant charge exchange processes. Physica Scripta. 70, C17-C20. Cooper, J. F., et al., 2001. Energetic ion and electron irradiation of the icy Galilean satellites. Icarus. 149, 133-159. Herring-Captain, J., et al., 2005. Low-energy (5-250 eV) electron-stimulated desorption of H+, H2+, and H+(H2O)nfrom low-temperature water ice surfaces. Physical Review B. 72, 035431-10. Johnson, R. E., et al., Radiation Effects on the Surfaces of the Galilean Satellites. In: F. Bagenal, et al., Eds.), Jupiter - The Planet, Satellites and Magnetosphere. Cambridge University Press, 2004, pp. 485-512.

High-Density Amorphous Ice, the Frost on Interstellar Grains

NASA Technical Reports Server (NTRS)

Jenniskens, P.; Blake, D. F.; Wilson, M. A.; Pohorille, A.

1995-01-01

Most water ice in the universe is in a form which does not occur naturally on Earth and of which only minimal amounts have been made in the laboratory. We have encountered this 'high-density amorphous ice' in electron diffraction experiments of low-temperature (T less than 30 K) vapor-deposited water and have subsequently modeled its structure using molecular dynamics simulations. The characteristic feature of high-density amorphous ice is the presence of 'interstitial' oxygen pair distances between 3 and 4 A. However, we find that the structure is best described as a collapsed lattice of the more familiar low-density amorphous form. These distortions are frozen in at temperatures below 38 K because, we propose, it requires the breaking of one hydrogen bond, on average, per molecule to relieve the strain and to restructure the lattice to that of low-density amorphous ice. Several features of astrophysical ice analogs studied in laboratory experiments are readily explained by the structural transition from high-density amorphous ice into low-density amorphous ice. Changes in the shape of the 3.07 gm water band, trapping efficiency of CO, CO loss, changes in the CO band structure, and the recombination of radicals induced by low-temperature UV photolysis all covary with structural changes that occur in the ice during this amorphous to amorphous transition. While the 3.07 micrometers ice band in various astronomical environments can be modeled with spectra of simple mixtures of amorphous and crystalline forms, the contribution of the high-density amorphous form nearly always dominates.

Computer Modeling of the Thermal Conductivity of Cometary Ice

NASA Technical Reports Server (NTRS)

Bunch, Theodore E.; Wilson, Michael A.; Pohorille, Andrew

1998-01-01

The thermal conductivity was found to be only weakly dependent on the microstructure of the amorphous ice. In general, the amorphous ices were found to have thermal conductivities of the same order of magnitude as liquid water. This is in contradiction to recent experimental estimates of the thermal conductivity of amorphous ice, and it is suggested that the extremely low value obtained experimentally is due to larger-scale defects in the ice, such as cracks, but is not an intrinsic property of the bulk amorphous ice.

The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

NASA Astrophysics Data System (ADS)

Enrique-Romero, J.; Rimola, A.; Ceccarelli, C.; Balucani, N.

2016-06-01

Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

Heavy ion irradiation of crystalline water ice. Cosmic ray amorphisation cross-section and sputtering yield

NASA Astrophysics Data System (ADS)

Dartois, E.; Augé, B.; Boduch, P.; Brunetto, R.; Chabot, M.; Domaracka, A.; Ding, J. J.; Kamalou, O.; Lv, X. Y.; Rothard, H.; da Silveira, E. F.; Thomas, J. C.

2015-04-01

Context. Under cosmic irradiation, the interstellar water ice mantles evolve towards a compact amorphous state. Crystalline ice amorphisation was previously monitored mainly in the keV to hundreds of keV ion energies. Aims: We experimentally investigate heavy ion irradiation amorphisation of crystalline ice, at high energies closer to true cosmic rays, and explore the water-ice sputtering yield. Methods: We irradiated thin crystalline ice films with MeV to GeV swift ion beams, produced at the GANIL accelerator. The ice infrared spectral evolution as a function of fluence is monitored with in-situ infrared spectroscopy (induced amorphisation of the initial crystalline state into a compact amorphous phase). Results: The crystalline ice amorphisation cross-section is measured in the high electronic stopping-power range for different temperatures. At large fluence, the ice sputtering is measured on the infrared spectra, and the fitted sputtering-yield dependence, combined with previous measurements, is quadratic over three decades of electronic stopping power. Conclusions: The final state of cosmic ray irradiation for porous amorphous and crystalline ice, as monitored by infrared spectroscopy, is the same, but with a large difference in cross-section, hence in time scale in an astrophysical context. The cosmic ray water-ice sputtering rates compete with the UV photodesorption yields reported in the literature. The prevalence of direct cosmic ray sputtering over cosmic-ray induced photons photodesorption may be particularly true for ices strongly bonded to the ice mantles surfaces, such as hydrogen-bonded ice structures or more generally the so-called polar ices. Experiments performed at the Grand Accélérateur National d'Ions Lourds (GANIL) Caen, France. Part of this work has been financed by the French INSU-CNRS programme "Physique et Chimie du Milieu Interstellaire" (PCMI) and the ANR IGLIAS.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space

NASA Astrophysics Data System (ADS)

Clements, Aspen R.; Berk, Brandon; Cooke, Ilsa R.; Garrod, Robin T.

2018-02-01

Using an off-lattice kinetic Monte Carlo model we reproduce experimental laboratory trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature. Extrapolation of the model to conditions appropriate to protoplanetary disks and interstellar dark clouds indicate that these ices may be less porous than laboratory ices.

Ultrastructure in frozen/etched saline solutions: on the internal cleansing of ice.

PubMed

Menger, Fredric M; Galloway, Ashley L; Chlebowski, Mary E; Apkarian, Robert P

2004-05-19

Seawater, with its 3.5% salt content, freezes into hexagonal ice (Ih) that encloses concentrated brine within its matrix. When unsubmerged sea ice reaches a certain height and temperature, the brine drains downward through narrow channels. This mechanism was now modeled by frozen 2-3.5% saline as investigated by cryo-etch high-resolution secondary electron microscopy. Thus, saline was either plunge-frozen in liquid ethane at -183 degrees C or else high-pressure frozen to -105 degrees C in 5-6 ms. Ice from a freshly exposed surface was then subjected to a high-vacuum sublimation ("etching"), a procedure that removes pure bulk ice in preference to ice from frozen hydrated salt. After chromium-coating the etched surface with a 2-nm film, the sample was examined by cryo-HRSEM. Granular icy "fences" were seen surrounding empty areas where amorphous ice had originally resided. Since the fences, about 1-2 mum high, survived the etching, it is likely that they consist of frozen brine. The presence of such fences suggests that, during freezing, saline can purge itself of salt with remarkable speed (5-6 ms). Alternatively, channels (perhaps routed around submicroscopic crystallites of cubic ice (Ic) embedded in the amorphous ice at -105 degrees C) can guide the migration of salt to the periphery of ice patches. Macromolecules fail to form fences because they diffuse too slowly or because they are too large to pass through the channels.

Limits of metastability in amorphous ices: the neutron scattering Debye-Waller factor.

PubMed

Amann-Winkel, Katrin; Löw, Florian; Handle, Philip H; Knoll, Wiebke; Peters, Judith; Geil, Burkhard; Fujara, Franz; Loerting, Thomas

2012-12-21

Recently, it became clear that relaxation effects in amorphous ices play a very important role that has previously been overlooked. The thermodynamic history of amorphous samples strongly affects their transition behavior. In particular, well-relaxed samples show higher thermal stability, thereby providing a larger window to investigate their glass transitions. We here present neutron scattering experiments using fixed elastic window scans on relaxed forms of amorphous ice, namely expanded high density amorphous ice (eHDA), a variant of low density amorphous ice (LDA-II) and hyperquenched glassy water (HGW). These amorphous ices are expected to be true glassy counterparts of deeply supercooled liquid water, therefore fast precursor dynamics of structural relaxation are expected to appear below the calorimetric glass transition temperature. The Debye-Waller factor shows a very weak sub-T(g) anomaly in some of the samples, which might be the signature of such fast precursor dynamics. However, we cannot find this behavior consistently in all samples at all reciprocal length scales of momentum transfer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligier, N.; Poulet, F.; Carter, J.

We present new insights into Europa’s surface composition on the global scale from linear spectral modeling of a high spectral resolution data set acquired during a ground-based observation campaign using SINFONI{sup 4}, an adaptive optics near-infrared instrument on the Very Large Telescope (ESO). The spectral modeling confirms the typical “bullseye” distribution of sulfuric acid hydrate on the trailing hemisphere, which is consistent with Iogenic sulfur ion implantation. However, the traditional hypothesis of the presence of sulfate salts on the surface of the satellite is challenged as Mg-bearing chlorinated species (chloride, chlorate, and perchlorate) are found to provide improved spectral fits.more » The derived global distribution of Mg-chlorinated salts (and particularly chloride) is correlated with large-scale geomorphologic units such as chaos and darker areas, thus suggesting an endogenous origin. Based on the 1.65 μ m water-ice absorption band shape and position, the surface temperature is estimated to be in the range 110–130 K, and water ice is found to be predominantly in its crystalline state rather than amorphous. While amorphous water ice exhibits a strong correlation with the expected intensity of the Ionian plasma torus bombardment, crystalline water ice is instead more associated with distinct geomorphological units. Endogenous processes such as jets and ice heating due to active geology may explain this relationship. Otherwise, no evidence of a correlation between grain size for the water ice and the sputtering rate has been detected so far.« less

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Experimental evidence for a crossover between two distinct mechanisms of amorphization in ice Ih under pressure.

PubMed

Strässle, Thierry; Klotz, Stefan; Hamel, Gérard; Koza, Michael M; Schober, Helmut

2007-10-26

We report neutron scattering data which reveal the central role of phonon softening leading to a negative melting line, solid-state amorphization, and negative thermal expansion of ice. We find that pressure-induced amorphization is due to mechanical melting at low temperatures, while at higher temperatures amorphization is governed by thermal melting (violations of Born's and Lindemann's criteria, respectively). This confirms earlier conjectures of a crossover between two distinct amorphization mechanisms and provides a natural explanation for the strong annealing observed in high-density amorphous ice.

Experimental study of the polyamorphism of water. I. The isobaric transitions from amorphous ices to LDA at 4 MPa.

PubMed

Handle, Philip H; Loerting, Thomas

2018-03-28

The existence of more than one solid amorphous state of water is an extraordinary feature. Since polyamorphism might be connected to the liquid-liquid critical point hypothesis, it is particularly important to study the relations amongst the different amorphous ices. Here we study the polyamorphic transformations of several high pressure amorphous ices to low-density amorphous ice (LDA) at 4 MPa by isobaric heating utilising in situ volumetry and ex situ X-ray diffraction. We find that very-high density amorphous ice (VHDA) and unannealed high density amorphous ice (HDA) show significant relaxation before transforming to LDA, whereby VHDA is seen to relax toward HDA. By contrast, expanded HDA shows almost no relaxation prior to the transformation. The transition to LDA itself obeys criteria for a first-order-like transition in all cases. In the case of VHDA, even macroscopic phase separation is observed. These findings suggest that HDA and LDA are two clearly distinct polyamorphs. We further present evidence that HDA reaches the metastable equilibrium at 140 K and 0.1 GPa but only comes close to that at 140 K and 0.2 GPa. The most important is the path independence of the amorphous phase reached at 140 K and 0.1 GPa.

Experimental study of the polyamorphism of water. I. The isobaric transitions from amorphous ices to LDA at 4 MPa

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Loerting, Thomas

2018-03-01

The existence of more than one solid amorphous state of water is an extraordinary feature. Since polyamorphism might be connected to the liquid-liquid critical point hypothesis, it is particularly important to study the relations amongst the different amorphous ices. Here we study the polyamorphic transformations of several high pressure amorphous ices to low-density amorphous ice (LDA) at 4 MPa by isobaric heating utilising in situ volumetry and ex situ X-ray diffraction. We find that very-high density amorphous ice (VHDA) and unannealed high density amorphous ice (HDA) show significant relaxation before transforming to LDA, whereby VHDA is seen to relax toward HDA. By contrast, expanded HDA shows almost no relaxation prior to the transformation. The transition to LDA itself obeys criteria for a first-order-like transition in all cases. In the case of VHDA, even macroscopic phase separation is observed. These findings suggest that HDA and LDA are two clearly distinct polyamorphs. We further present evidence that HDA reaches the metastable equilibrium at 140 K and 0.1 GPa but only comes close to that at 140 K and 0.2 GPa. The most important is the path independence of the amorphous phase reached at 140 K and 0.1 GPa.

Radiation-Induced Amorphization of Crystalline Ice

NASA Technical Reports Server (NTRS)

Fama, M.; Loeffler, M. J.; Raut, U.; Baragiola, R. A.

2009-01-01

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.

Theory of amorphous ices.

PubMed

Limmer, David T; Chandler, David

2014-07-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens.

Infrared Spectra and Thermodynamic Properties of Co2/Methanol Ices

NASA Astrophysics Data System (ADS)

Maté, Belén; Gálvez, Óscar; Herrero, Víctor J.; Escribano, Rafael

2009-01-01

Ices of mixtures of carbon dioxide and methanol have been studied in a range of temperatures relevant for star-forming regions, comets, polar caps of planets and satellites, and other solar system bodies. We have performed temperature-programmed desorption measurements and recorded IR spectra of various types of samples. The presence of two slightly different structures of CO2 is manifest. A distorted CO2 structure is characterized by bandshifts between 5 cm-1 (ν3) and 10 cm-1 (ν2) with respect to normal CO2. If the samples are heated above 130 K, the distorted CO2 sublimates and only the normal structure remains. The latter can stay trapped until the sublimation of crystalline methanol (150 K). The desorption energy (E d ~ 20 kJ mol-1) of CO2 from methanol ice, and the specific adsorption surface area (6 m2 g-1) of amorphous CH3OH ice, have been determined. CO2 does not penetrate into crystalline ice. Whereas the desorption energy is similar to that of CO2/H2O samples, the specific surface of methanol is much smaller than that of amorphous solid water (ASW). The interaction of CO2 molecules with water and methanol is similar but ices of CH3OH are much less porous than ASW. The inclusion of CO2 into previously formed ices containing these two species would take place preferentially into ASW. However, in processes of simultaneous deposition, methanol ice can admit a larger amount of CO2 than water ice. CO2/CH3OH ices formed by simultaneous deposition admit two orders of magnitude more CO2 than sequentially deposited ices. These findings can have direct relevance to the interpretation of observations from protostellar environments (e.g., RAFGL7009S) and comet nuclei.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasuga, Toshihiro; Usui, Fumihiko; Hasegawa, Sunao

Primitive, outer-belt asteroids are generally of low albedo, reflecting carbonaceous compositions like those of CI and CM meteorites. However, a few outer-belt asteroids having high albedos are known, suggesting the presence of unusually reflective surface minerals or, conceivably, even exposed water ice. Here, we present near-infrared (1.1-2.5 {mu}m) spectra of four outer-belt C-complex asteroids with albedos {>=}0.1. We find no absorption features characteristic of water ice (near 1.5 and 2.0 {mu}m) in the objects. Intimate mixture models set limits to the water ice by weight {<=}2%. Asteroids (723) Hammonia and (936) Kunigunde are featureless and have (60%-95%) amorphous Mg pyroxenesmore » that might explain the high albedos. Asteroid (1276) Ucclia also shows a featureless reflection spectrum with (50%-60%) amorphous Mg pyroxenes. Asteroid (1576) Fabiola shows a possible weak, broad absorption band (1.5-2.1 {mu}m). The feature can be reproduced by (80%) amorphous Mg pyroxenes or orthopyroxene (crystalline silicate), either of which is likely to cause its high albedo. We discuss the origin of high-albedo components in primitive asteroids.« less

Theory of amorphous ices

PubMed Central

Limmer, David T.; Chandler, David

2014-01-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens. PMID:24858957

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure.

PubMed

Accolla, Mario; Congiu, Emanuele; Dulieu, François; Manicò, Giulio; Chaabouni, Henda; Matar, Elie; Mokrane, Hakima; Lemaire, Jean Louis; Pirronello, Valerio

2011-05-07

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ϕ(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous. This journal is © the Owner Societies 2011

Investigation of vapor-deposited amorphous ice and irradiated ice by molecular dynamics simulation.

PubMed

Guillot, Bertrand; Guissani, Yves

2004-03-01

With the purpose of clarifying a number of points raised in the experimental literature, we investigate by molecular dynamics simulation the thermodynamics, the structure and the vibrational properties of vapor-deposited amorphous ice (ASW) as well as the phase transformations experienced by crystalline and vitreous ice under ion bombardment. Concerning ASW, we have shown that by changing the conditions of the deposition process, it is possible to form either a nonmicroporous amorphous deposit whose density (approximately 1.0 g/cm3) is essentially invariant with the temperature of deposition, or a microporous sample whose density varies drastically upon temperature annealing. We find that ASW is energetically different from glassy water except at the glass transition temperature and above. Moreover, the molecular dynamics simulation shows no evidence for the formation of a high-density phase when depositing water molecules at very low temperature. In order to model the processing of interstellar ices by cosmic ray protons and heavy ions coming from the magnetospheric radiation environment around the giant planets, we bombarded samples of vitreous ice and cubic ice with 35 eV water molecules. After irradiation the recovered samples were found to be densified, the lower the temperature, the higher the density of the recovered sample. The analysis of the structure and vibrational properties of this new high-density phase of amorphous ice shows a close relationship with those of high-density amorphous ice obtained by pressure-induced amorphization. Copyright 2004 American Institute of Physics

Composition and physical properties of Enceladus' surface

USGS Publications Warehouse

Brown, R.H.; Clark, R.N.; Buratti, B.J.; Cruikshank, D.P.; Barnes, J.W.; Mastrapa, R.M.E.; Bauer, J.; Newman, S.; Momary, T.; Baines, K.H.; Bellucci, G.; Capaccioni, F.; Cerroni, P.; Combes, M.; Coradini, A.; Drossart, P.; Formisano, V.; Jaumann, R.; Langavin, Y.; Matson, D.L.; McCord, T.B.; Nelson, R.M.; Nicholson, P.D.; Sicardy, B.; Sotin, Christophe

2006-01-01

Observations of Saturn's satellite Enceladus using Cassini's Visual and Infrared Mapping Spectrometer instrument were obtained during three flybys of Enceladus in 2005. Enceladus' surface is composed mostly of nearly pure water ice except near its south pole, where there are light organics, CO2, and amorphous and crystalline water ice, particularly in the region dubbed the "tiger stripes." An upper limit of 5 precipitable nanometers is derived for CO in the atmospheric column above Enceladus, and 2% for NH 3 in global surface deposits. Upper limits of 140 kelvin (for a filled pixel) are derived for the temperatures in the tiger stripes.

Peculiarities of Vibration Characteristics of Amorphous Ices

NASA Astrophysics Data System (ADS)

Gets, Kirill V.; Subbotin, Oleg S.; Belosludov, Vladimir R.

2012-03-01

Dynamic properties of low (LDA), high (HDA) and very high (VHDA) density amorphous ices were investigated within the approach based on Lattice Dynamics simulations. In this approach, we assume that the short-range molecular order mainly determines the dynamic and thermodynamic properties of amorphous ices. Simulation cell of 512 water molecules with periodical boundary conditions and disordering allows us to study dynamical properties and dispersion curves in the Brillouin zone of pseudo-crystal. Existence of collective phenomena in amorphous ices which is usual for crystals but anomalous for disordered phase was confirmed in our simulations. Molecule amplitudes of delocalized (collective) as well as localized vibrations have been considered.

Far-infrared spectral studies of phase changes in water ice induced by proton irradiation

NASA Technical Reports Server (NTRS)

Moore, Marla H.; Hudson, Reggie L.

1992-01-01

Changes in the FIR spectrum of crystalline and amorphous water ice as a function of temperature are reported. The dramatic differences between the spectra of these ices in the FIR are used to examine the effect of proton irradiation on the stability of the crystalline and amorphous ice phases from 13 to 77 K. In particular, the spectra near 13 K show interconversion between the amorphous and crystalline ice phases beginning at doses near 2 eV/molecule and continuing cyclically with increased dose. The results are used to estimate the stability of irradiated ices in astronomical environments.

Surface composition of Europa based on VLT observations

NASA Astrophysics Data System (ADS)

Ligier, N.; Poulet, F.; Carter, J.

2016-12-01

Jupiter's moon Europa may harbor a global salty ocean under an 80-170 km thick outer layer consisting of an icy crust (Anderson et al. 1998). Meanwhile, the 10-50 My old surface, dated by cratering rates (Pappalardo et al. 1999) implies rapid surface recycling and reprocessing that could result in tectonic activity (Kattenhorn et al. 2014) and plumes (Roth et al. 2014). The surface could thus exhibit fingerprints of chemical species, as minerals characteristics of an ocean-mantle interaction and/or organics of exobiological interest, directly originating from the subglacial ocean. In order to re-investigate the composition of Europa's surface, a global mapping campaign of the satellite was performed with the near-infrared integral field spectrograph SINFONI on the Very Large Telescope (VLT) in Chile. The high spectral binning of this instrument (0.5 nm) and large signal noise ratio in comparison to previous observations are adequate to detect sharp absorptions in the wavelength range 1.45-2.45 μm. In addition, the spatially resolved spectra we obtained over five epochs nearly cover the entire surface of Europa with a pixel scale of 12.5 by 25 m.a.s ( 35 by 70 km on Europa's surface), thus permitting a global scale study. Several icy and non-icy compounds were detected and mapped at <100 km resolution. They are unevenly distributed on the moon's surface. Amorphous and crystalline water ice are both present and, in spite of a particularly strong amorphization process likely engendered by the Io plasma torus, the crystalline form is found to be approximately twice as abundant as the amorphous ice based on the analysis of the 1.65 μm band. If the surface is dominated by small and mid-sized water ice grains (25-200 μm), crystalline water-ice grains exhibit spatial inhomogeneities in their distribution. The sulfuric acid hydrate distribution exhibits the typical "bullseye" feature on the trailing hemisphere. The presence of Mg-bearing chlorinated salts (chloride, chlorate, and perchlorate) is supported by linear spectral modeling of the data, while the presence of sulfate salts is challenged. The distribution of some of these species is inconsistent with exogenic processes mainly impacting the trailing orbital hemisphere. These species may be traces of endogenous processes occurring on Europa.

FIRST INFRARED BAND STRENGTHS FOR AMORPHOUS CO{sub 2}, AN OVERLOOKED COMPONENT OF INTERSTELLAR ICES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerakines, Perry A.; Hudson, Reggie L., E-mail: Reggie.Hudson@NASA.gov

2015-08-01

Solid carbon dioxide (CO{sub 2}) has long been recognized as a component of both interstellar and solar system ices, but a recent literature search has revealed significant qualitative and quantitative discrepancies in the laboratory spectra on which the abundances of extraterrestrial CO{sub 2} are based. Here we report new infrared (IR) spectra of amorphous CO{sub 2}-ice along with band intensities (band strengths) of four mid-IR absorptions, the first such results in the literature. A possible thickness dependence for amorphous-CO{sub 2} IR band shapes and positions also is investigated, and the three discordant reports of amorphous CO{sub 2} spectra in themore » literature are addressed. Applications of our results are discussed with an emphasis on laboratory investigations and results from astronomical observations. A careful comparison with earlier work shows that the IR spectra calculated from several databases for CO{sub 2} ices, all ices being made near 10 K, are not for amorphous CO{sub 2}, but rather for crystalline CO{sub 2} or crystalline-amorphous mixtures.« less

The Metastable Persistence of Vapor-Deposited Amorphous Ice at Anomalously High Temperatures

NASA Technical Reports Server (NTRS)

Blake, David F.; Jenniskens, Peter; DeVincenzi, Donald L. (Technical Monitor)

1995-01-01

Studies of the gas release, vaporization behavior and infrared (IR) spectral properties of amorphous and crystalline water ice have direct application to cometary and planetary outgassing phenomena and contribute to an understanding of the physical properties of astrophysical ices. Several investigators report anomalous phenomena related to the warming of vapor-deposited astrophysical ice analogs. However gas release, ice volatilization and IR spectral features are secondary or tertiary manifestations of ice structure or morphology. These observations are useful in mimicking the bulk physical and chemical phenomena taking place in cometary and other extraterrestrial ices but do not directly reveal the structural changes which are their root cause. The phenomenological interpretation of spectral and gas release data is probably the cause of somewhat contradictory explanations invoked to account for differences in water ice behavior in similar temperature regimes. It is the microstructure, micromorphology and microchemical heterogeneity of astrophysical ices which must be characterized if the mechanisms underlying the observed phenomena are to be understood. We have been using a modified Transmission Electron Microscope to characterize the structure of vapor-deposited astrophysical ice analogs as a function of their deposition, temperature history and composition. For the present experiments, pure water vapor is deposited at high vacuum onto a 15 K amorphous carbon film inside an Hitachi H-500H TEM. The resulting ice film (approx. 0.05 micrometers thick) is warmed at the rate of 1 K per minute and diffraction patterns are collected at 1 K intervals. These patterns are converted into radial intensity distributions which are calibrated using patterns of crystalline gold deposited on a small part of the carbon substrate. The small intensity contributed by the amorphous substrate is removed by background subtraction. The proportions of amorphous and crystalline material in each pattern are determined by subtracting a percentage of crystalline component relative to amorphous and pure crystalline endmembers. Vapor-deposited water ice undergoes two amorphous to amorphous structural transformations in the temperature range 15-130 K with important astrophysical implications. The onset of cubic crystallization occurs at 142-160 K (at 1K per minute heating rates) during which the 220 and 311 diffraction maxima appear and 0.1 micrometer crystallites can be seen in bright field images. This transition is time dependent.

On the state of water ice on saturn's moon Titan and implications to icy bodies in the outer solar system.

PubMed

Zheng, Weijun; Jewitt, David; Kaiser, Ralf I

2009-10-22

The crystalline state of water ice in the Solar System depends on the temperature history of the ice and the influence of energetic particles to which it has been exposed. We measured the infrared absorption spectra of amorphous and crystalline water ice in the 10-50 K and 10-140 K temperature ranges, respectively, and conducted a systematic experimental study to investigate the amorphization of crystalline water ice via ionizing radiation irradiation at doses of up to 160 +/- 30 eV per molecule. We found that crystalline water ice can be converted only partially to amorphous ice by electron irradiation. The experiments showed that a fraction of the 1.65 microm band, which is characteristic for crystalline water ice, survived the irradiation, to a degree that strongly depends on the temperature. Quantitative kinetic fits of the temporal evolution of the 1.65 mum band clearly demonstrate that there is a balance between thermal recrystallization and irradiation-induced amorphization, with thermal recrystallizaton dominant at higher temperatures. Our experiments show the amorphization at 40 K was incomplete, in contradiction to Mastrapa and Brown's conclusion (Icarus 2006, 183, 207.). At 50 K, the recrystallization due to thermal effects is strong, and most of the crystalline ice survived. Temperatures of most icy objects in the Solar System, including Jovian satellites, Saturnian satellites (including Titan), and Kuiper Belt Objects, are equal to or above 50 K; this explains why water ice detected on those objects is mostly crystalline.

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

PubMed

Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

2006-03-07

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

Spatial averaging for small molecule diffusion in condensed phase environments

NASA Astrophysics Data System (ADS)

Plattner, Nuria; Doll, J. D.; Meuwly, Markus

2010-07-01

Spatial averaging is a new approach for sampling rare-event problems. The approach modifies the importance function which improves the sampling efficiency while keeping a defined relation to the original statistical distribution. In this work, spatial averaging is applied to multidimensional systems for typical problems arising in physical chemistry. They include (I) a CO molecule diffusing on an amorphous ice surface, (II) a hydrogen molecule probing favorable positions in amorphous ice, and (III) CO migration in myoglobin. The systems encompass a wide range of energy barriers and for all of them spatial averaging is found to outperform conventional Metropolis Monte Carlo. It is also found that optimal simulation parameters are surprisingly similar for the different systems studied, in particular, the radius of the point cloud over which the potential energy function is averaged. For H2 diffusing in amorphous ice it is found that facile migration is possible which is in agreement with previous suggestions from experiment. The free energy barriers involved are typically lower than 1 kcal/mol. Spatial averaging simulations for CO in myoglobin are able to locate all currently characterized metastable states. Overall, it is found that spatial averaging considerably improves the sampling of configurational space.

Reversible pressure-induced crystal-amorphous structural transformation in ice Ih

NASA Astrophysics Data System (ADS)

English, Niall J.; Tse, John S.

2014-08-01

Molecular dynamics (MD) simulation of depressurised high-density amorphous ice (HDA) at 80 K and at negative pressures has been performed. Over several attempts, HDA recrystallised to a form close to hexagonal ice Ih, albeit with some defects. The results support the hypothesis that compression of ice-Ih to HDA is a reversible first-order phase transition, with a large hysteresis. Therefore, it would appear that LDA is not truly amorphous. The elastic energy estimated from the area of the hysteresis loop is ca. 4.5 kJ/mol, in some way consistent with experimentally-determined accumulated successive heats of transformations from recovered HDA → ice Ih.

New transformations between crystalline and amorphous ice

NASA Technical Reports Server (NTRS)

Hemley, R. J.; Chen, L. C.; Mao, H. K.

1989-01-01

High-pressure optical and spectroscopic techniques were used to obtain directly the ice I(h) - hda-ice transformation in a diamond-anvil cell, and the stability of the amorphous form is examined as functions of pressure and temperature. It is demonstrated that hda-ice transforms abruptly at 4 GPa and 77 K to a crystalline phase close in structure to orientationally disordered ice-VII and to a more highly ordered, ice-VIII-like structure at higher temperatures. This is the first time that an amorphous solid is observed to convert to a crystalline solid at low temperatures by compression alone. Phase transitions of this type may be relevant on icy planetary satellites, and there may also be implications for the high-pressure behavior of silica.

New Optical Constants for Amorphous and Crystalline H2O-ice

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We have used the infrared spectra of laboratory ices to calculate the real and imaginary indices of refraction for amorphous and crystalline H2O-ice. We create H2O-ice samples in vacuum (approx. 10(exp ^-8)Torr). We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows and then collect transmission spectra of the samples in the wavelength range 1.25-22 micrometers. Using the ice thickness and transmission spectrum we calculate the imaginary part of the index of refraction. A Kramers-Kronig calculation is then used to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We will summarize the differences between the amorphous and crystalline H2O-ice spectra. These include weakening of features and shifting of features to shorter wavelength in amorphous H,O-ice spectra. We will also discuss methods of using band area ratios to quickly estimate the fraction of amorphous to crystalline H2O-ice. We acknowledge financial support from the NASA Origins of the Solar System Program, the NASA Planetary Geology and Geophysics Program, and the NASA Postdoctoral Program.

Polyamorphism in Water: Amorphous Ices and their Glassy States

NASA Astrophysics Data System (ADS)

Amann-Winkel, K.; Boehmer, R.; Fujara, F.; Gainaru, C.; Geil, B.; Loerting, T.

2015-12-01

Water is ubiquitous and of general importance for our environment. But it is also known as the most anomalous liquid. The fundamental origin of the numerous anomalies of water is still under debate. An understanding of these anomalous properties of water is closely linked to an understanding of the phase diagram of the metastable non-crystalline states of ice. The process of pressure induced amorphization of ice was first observed by Mishima et al. [1]. The authors pressurized hexagonal ice at 77 K up to a pressure of 1.6 GPa to form high density amorphous ice (HDA). So far three distinct structural states of amorphous water are known [2], they are called low- (LDA), high- (HDA) and very high density amorphous ice (VHDA). Since the discovery of multiple distinct amorphous states it is controversy discussed whether this phenomenon of polyamorphism at high pressures is connected to the occurrence of more than one supercooled liquid phase [3]. Alternatively, amorphous ices have been suggested to be of nanocrystalline nature, unrelated to liquids. Indeed inelastic X-ray scattering measurements indicate sharp crystal-like phonons in the amorphous ices [4]. In case of LDA the connection to the low-density liquid (LDL) was inferred from several experiments including the observation of a calorimetric glass-to-liquid transition at 136 K and ambient pressure [5]. Recently also the glass transition in HDA was observed at 116 K at ambient pressure [6] and at 140 K at elevated pressure of 1 GPa [7], using calorimetric measurements as well as dielectric spectroscopy. We discuss here the general importance of amorphous ices and their liquid counterparts and present calorimetric and dielectric measurements on LDA and HDA. The good agreement between dielectric and calorimetric results convey for a clearer picture of water's vitrification phenomenon. [1] O. Mishima, L. D. Calvert, and E. Whalley, Nature 314, 76, 1985 [2] D.T. Bowron, J. L. Finney, A. Hallbrucker, et al., J. Chem. Phys. 125, 2006 [3] P.G. Debenedetti, J. Phys.: Condens. Matter 15, R1669, 2003 [4] H. Schober, M.M. Koza et al., PRL 85, 4100, 2000 [5] G.P. Johari, A. Hallbrucker and E. Mayer Nature 330, 552, 1987 [6] K. Amann-Winkel, C. Gainaru, et al., PNAS 110, 17720, 2013 [7] Andersson, O., PNAS 108, 11013, 2011

Ultra-slow dynamics in low density amorphous ice revealed by deuteron NMR: indication of a glass transition.

PubMed

Löw, Florian; Amann-Winkel, Katrin; Loerting, Thomas; Fujara, Franz; Geil, Burkhard

2013-06-21

The postulated glass-liquid transition of low density amorphous ice (LDA) is investigated with deuteron NMR stimulated echo experiments. Such experiments give access to ultra-slow reorientations of water molecules on time scales expected for structural relaxation of glass formers close to the glass-liquid transition temperature. An involved data analysis is necessary to account for signal contributions originating from a gradual crystallization to cubic ice. Even if some ambiguities remain, our findings support the view that pressure amorphized LDA ices are of glassy nature and undergo a glass-liquid transition before crystallization.

Influence of sample preparation on the transformation of low-density to high-density amorphous ice: An explanation based on the potential energy landscape

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Starr, Francis W.; Poole, Peter H.

2017-07-01

Experiments and computer simulations of the transformations of amorphous ices display different behaviors depending on sample preparation methods and on the rates of change of temperature and pressure to which samples are subjected. In addition to these factors, simulation results also depend strongly on the chosen water model. Using computer simulations of the ST2 water model, we study how the sharpness of the compression-induced transition from low-density amorphous ice (LDA) to high-density amorphous ice (HDA) is influenced by the preparation of LDA. By studying LDA samples prepared using widely different procedures, we find that the sharpness of the LDA-to-HDA transformation is correlated with the depth of the initial LDA sample in the potential energy landscape (PEL), as characterized by the inherent structure energy. Our results show that the complex phenomenology of the amorphous ices reported in experiments and computer simulations can be understood and predicted in a unified way from knowledge of the PEL of the system.

The relation between high-density and very-high-density amorphous ice.

PubMed

Loerting, Thomas; Salzmann, Christoph G; Winkel, Katrin; Mayer, Erwin

2006-06-28

The exact nature of the relationship between high-density (HDA) and very-high-density (VHDA) amorphous ice is unknown at present. Here we review the relation between HDA and VHDA, concentrating on experimental aspects and discuss these with respect to the relation between low-density amorphous ice (LDA) and HDA. On compressing LDA at 125 K up to 1.5 GPa, two distinct density steps are observable in the pressure-density curves which correspond to the LDA --> HDA and HDA --> VHDA conversion. This stepwise formation process LDA --> HDA --> VHDA at 125 K is the first unambiguous observation of a stepwise amorphous-amorphous-amorphous transformation sequence. Density values of amorphous ice obtained in situ between 0.3 and 1.9 GPa on isobaric heating up to the temperatures of crystallization show a pronounced change of slope at ca. 0.8 GPa which could indicate formation of a distinct phase. We infer that the relation between HDA and VHDA is very similar to that between LDA and HDA except for a higher activation barrier between the former. We further discuss the two options of thermodynamic phase transition versus kinetic densification for the HDA --> VHDA conversion.

Laboratory studies of cometary ice analogues

NASA Astrophysics Data System (ADS)

Schmitt, B.; Espinasse, S.; Grim, R. J. A.; Greenberg, J. M.; Klinger, J.

1989-12-01

Laboratory studies were performed in order to simulate the physico-chemical processes that are likely to occur in the near surface layers of short and intermediate period comets. Pure H2O ice as well as CO:H2O, CO2:H2O, CH4:H2O, CO:CO2:H2O, and NH3:H2O ice mixtures were studied in the temperature range between 10 and 180 K. The evolution of the composition of ice mixtures, the crystallization of H2O ice as well as the formation and decompostion of clathrate hydrate by different processes were studied as a function of temperature and time. Using the results together with numerical modeling, predictions are made about the survival of amorphous ice, CO, CO2, CH4, and NH3 in the near surface layers of short period comets. The likeliness of finding clathrate and molecular hydrates is discussed. It is proposed that the analytical methods developed here could be fruitfully adapted to the analysis of returned comet samples.

OPTICAL CONSTANTS AND BAND STRENGTHS OF CH{sub 4}:C{sub 2}H{sub 6} ICES IN THE NEAR- AND MID-INFRARED

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molpeceres, Germán; Ortigoso, Juan; Escribano, Rafael

2016-07-10

We present a spectroscopic study of methane–ethane ice mixtures. We have grown CH{sub 4}:C{sub 2}H{sub 6} mixtures with ratios 3:1, 1:1, and 1:3 at 18 and 30 K, plus pure methane and ethane ices, and have studied them in the near-infrared (NIR) and mid-infrared (MIR) ranges. We have determined densities of all species mentioned above. For amorphous ethane grown at 18 and 30 K we have obtained a density of 0.41 and 0.54 g cm{sup −3}, respectively, lower than a previous measurement of the density of the crystalline species, 0.719 g cm{sup −3}. As far as we know this ismore » the first determination of the density of amorphous ethane ice. We have measured band shifts of the main NIR methane and ethane features in the mixtures with respect to the corresponding values in the pure ices. We have estimated band strengths of these bands in the NIR and MIR ranges. In general, intensity decay in methane modes was detected in the mixtures, whereas for ethane no clear tendency was observed. Optical constants of the mixtures at 30 and 18 K have also been evaluated. These values can be used to trace the presence of these species in the surface of trans-Neptunian objects. Furthermore, we have carried out a theoretical calculation of these ice mixtures. Simulation cells for the amorphous solids have been constructed using a Metropolis Monte Carlo procedure. Relaxation of the cells and prediction of infrared spectra have been carried out at density functional theory level.« less

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

A model calculation of coherence effects in the elastic backscattering of very low energy electrons (1-20 eV) from amorphous ice.

PubMed

Liljequist, David

2012-01-01

Backscattering of very low energy electrons in thin layers of amorphous ice is known to provide experimental data for the elastic and inelastic cross sections and indicates values to be expected in liquid water. The extraction of cross sections was based on a transport analysis consistent with Monte Carlo simulation of electron trajectories. However, at electron energies below 20 eV, quantum coherence effects may be important and trajectory-based methods may be in significant error. This possibility is here investigated by calculating quantum multiple elastic scattering of electrons in a simple model of a very small, thin foil of amorphous ice. The average quantum multiple elastic scattering of electrons is calculated for a large number of simulated foils, using a point-scatterer model for the water molecule and taking inelastic absorption into account. The calculation is compared with a corresponding trajectory simulation. The difference between average quantum scattering and trajectory simulation at energies below about 20 eV is large, in particular in the forward scattering direction, and is found to be almost entirely due to coherence effects associated with the short-range order in the amorphous ice. For electrons backscattered at the experimental detection angle (45° relative to the surface normal) the difference is however small except at electron energies below about 10 eV. Although coherence effects are in general found to be strong, the mean free path values derived by trajectory-based analysis may actually be in fair agreement with the result of an analysis based on quantum scattering, at least for electron energies larger than about 10 eV.

Radiation Synthesis of Carbon Dioxide in Ice-coated Carbon: Implications for Interstellar Grains and Icy Moons

NASA Astrophysics Data System (ADS)

Raut, U.; Fulvio, D.; Loeffler, M. J.; Baragiola, R. A.

2012-06-01

We report the synthesis of carbon dioxide on an amorphous carbon-13 substrate coated with amorphous water ice from irradiation with 100 keV protons at 20 K and 120 K. The quantitative studies show that the CO2 is dispersed in the ice; its column density increases with ion fluence to a maximum value (in 1015 molecules cm-2) of ~1 at 20 K and ~3 at 120 K. The initial yield is 0.05 (0.1) CO2 per incident H+ at 20 (120) K. The CO2 destruction process, which limits the maximum column density, occurs with an effective cross section of ~2.5 (4.1) × 10-17 cm2 at 20 (120) K. We discuss radiation-induced oxidation by reactions of radicals in water with the carbon surface and demonstrate that these reactions can be a significant source of condensed carbon dioxide in interstellar grains and in icy satellites in the outer solar system.

Physical State of Ices in the Outer Solar System. Revised

NASA Technical Reports Server (NTRS)

Roush, Ted L.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Comparison of the identity and abundances of ices observed around protostars and those associated with comets clearly suggests that comets preserve the heritage of the interstellar materials that aggregated to form them. However, the ability to identify these same species on icy satellites in the outer solar system is a complex function of the composition of the original ices, their subsequent thermal histories, and their exposure to various radiation environments. Our ability to identify the ices currently present on objects in the outer solar system relies upon observational and laboratory, and theoretical efforts. To date there is ample observational evidence for crystalline water ice throughout the outer solar system. In addition, there is growing evidence that amorphous ice may be present on some bodies. More volatile ices, e.g. N2, CH4. CO, and other species, e.g. ammonia hydrate, are identified on objects lying at and beyond Uranus. Both photolysis and radiolysis play important roles in altering the original surfaces due to chemical reactions and erosion of the surface. Ultraviolet photolysis appears to dominate alteration of the upper few hundred Angstroms, although sputtering the surface can sometimes be a significantly competitative process; dominating on icy surfaces embedded in a strong planetary magnetospheric field. There is growing observational evidence that the by-products of photolysis and radiolysis, suggested on a theoretical basis, are present on icy surfaces.

Polyamorphism in tetrahedral substances: Similarities between silicon and ice

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2015-07-01

Tetrahedral substances, such as silicon, water, germanium, and silica, share various unusual phase behaviors. Among them, the so-called polyamorphism, i.e., the existence of more than one amorphous form, has been intensively investigated in the last three decades. In this work, we study the metastable relations between amorphous states of silicon in a wide range of pressures, using Monte Carlo simulations. Our results indicate that the two amorphous forms of silicon at high pressures, the high density amorphous (HDA) and the very high density amorphous (VHDA), can be decompressed from high pressure (˜20 GPa) down to the tensile regime, where both convert into the same low density amorphous. Such behavior is also observed in ice. While at high pressure (˜20 GPa), HDA is less stable than VHDA, at the pressure of 10 GPa both forms exhibit similar stability. On the other hand, at much lower pressure (˜5 GPa), HDA and VHDA are no longer the most stable forms, and, upon isobaric annealing, an even less dense form of amorphous silicon emerges, the expanded high density amorphous, again in close similarity to what occurs in ice.

Clathrate hydrate formation in amorphous cometary ice analogs in vacuo

NASA Technical Reports Server (NTRS)

Blake, David; Allamandola, Louis; Sandford, Scott; Hudgins, Doug; Freund, Friedemann

1991-01-01

Experiments conducted in clathrate hydrates with a modified electron microscope have demonstrated the possibility of such compounds' formation during the warming of vapor-deposited amorphous ices in vacuo, through rearrangements in the solid state. Subsolidus crystallization of compositionally complex amorphous ices may therefore be a general and ubiquitous process. Phase separations and microporous textures thus formed may be able to account for such anomalous cometary phenomena as the release of gas at large radial distances from the sun and the retention of volatiles to elevated temperatures.

The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K.

PubMed

Crouse, J; Loock, H-P; Cann, N M

2015-07-21

Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atom desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H2O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H2O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice, arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.

Short, intermediate and long range order in amorphous ices

NASA Astrophysics Data System (ADS)

Martelli, Fausto; Torquato, Salvatore; Giovanbattista, Nicolas; Car, Roberto

Water exhibits polyamorphism, i.e., it exists in more than one amorphous state. The most common forms of glassy water are the low-density amorphous (LDA) and the high-density amorphous (HDA) ices. LDA, the most abundant form of ice in the Universe, transforms into HDA upon isothermal compression. We model the transformation of LDA into HDA under isothermal compression with classical molecular dynamics simulations. We analyze the molecular structures with a recently introduced scalar order metric to measure short and intermediate range order. In addition, we rank the structures by their degree of hyperuniformity, i.e.,the extent to which long range density fluctuations are suppressed. F.M. and R.C. acknowledge support from the Department of Energy (DOE) under Grant No. DE-SC0008626.

Peeling the astronomical onion.

PubMed

Rosu-Finsen, Alexander; Marchione, Demian; Salter, Tara L; Stubbing, James W; Brown, Wendy A; McCoustra, Martin R S

2016-11-23

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H 2 O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol -1 on the silica surface below 25 K and 0 kJ mol -1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.

Porosity effects on crystallization kinetics of Amorphous Solid Water: Implications for cold icy objects in the Outer Solar System

NASA Astrophysics Data System (ADS)

Mitchell, Emily H.; Raut, Ujjwal; Baragiola, Raul A.

2015-11-01

Crystalline ice has been identified on the cold surfaces of most icy satellites and TNOs [1]. This is surprising since accretion of water vapor at temperatures (T < 100 K) should result in the amorphous phase [2]. There are several possible explanations for the unexpected presence of crystalline ice on cold bodies, including cryovolcanism [3] and pulsed heating by micrometeoritic impacts [4].A salient feature of ice films condensed at low T is microporosity, known to increase with deposition angle [5]. Here we investigate the dependence of the crystallization rate on the ice porosity, which could contribute to the observed variation in crystallization time τc reported in the literature [2]. Such dependence is noted in other porous materials such as zeolites and titania [6, 7].Amorphous ice films were deposited on a CsI substrate from a collimated water vapor source at 10 K at incidences varying from 0 to 70°, as well as from an omnidirectional water vapor source. The films were heated to temperatures between 130 and 140 K following deposition. The isothermal transition from amorphous to fully crystalline phase was characterized by analyzing the time-dependent evolution of the OH-stretch absorption band using transmission infrared spectroscopy. Our initial results show that τc decreases with increasing porosity; for instance, a film deposited at 45° was observed to crystallize ~6 times faster than a film deposited at 0°. The preliminary estimate of the porosity of the 45° film is ~50% higher than that of the film deposited at normal incidence. Our findings can explain the reported variation in temperature-dependent τc [2] and contribute to the understanding of crystalline ice on cold bodies in the Outer Solar System.1. Mastrapa, R.M.E. et al. In: Gudipati, M.S. & Castillo-Rogez, J., Eds, The Science of Solar System Ices, Springer, New York, 2013.2. Baragiola, R.A. In: Devlin & Buch, Eds, Water in Confining Geometries, Springer-Verlag, 2003.3. Jewitt, D.C. & Luu, J., Nature 432, 731, 2004.4. Porter, S.B. et al. Icarus 208, 492, 2010.5. Stevenson, K.P., et al. Science 283, 1505, 1999.6. Francis, R.J. & O’Hare, D., J. Chem. Soc., Dalton Trans., 3133, 1998.7. Kirsch, B.L. et al., J. Phys. Chem. B., 108, 12698, 2004.

Experimental study of the polyamorphism of water. II. The isobaric transitions between HDA and VHDA at intermediate and high pressures.

PubMed

Handle, Philip H; Loerting, Thomas

2018-03-28

Since the first report of very-high density amorphous ice (VHDA) in 2001 [T. Loerting et al., Phys. Chem. Chem. Phys. 3, 5355-5357 (2001)], the status of VHDA as a distinct amorphous ice has been debated. We here study VHDA and its relation to expanded high density amorphous ice (eHDA) on the basis of isobaric heating experiments. VHDA was heated at 0.1 ≤ p ≤ 0.7 GPa, and eHDA was heated at 1.1 ≤ p ≤ 1.6 GPa to achieve interconversion. The behavior upon heating is monitored using in situ volumetry as well as ex situ X-ray diffraction and differential scanning calorimetry. We do not observe a sharp transition for any of the isobaric experiments. Instead, a continuous expansion (VHDA) or densification (eHDA) marks the interconversion. This suggests that a continuum of states exists between VHDA and HDA, at least in the temperature range studied here. This further suggests that VHDA is the most relaxed amorphous ice at high pressures and eHDA is the most relaxed amorphous ice at intermediate pressures. It remains unclear whether or not HDA and VHDA experience a sharp transition upon isothermal compression/decompression at low temperature.

Experimental study of the polyamorphism of water. II. The isobaric transitions between HDA and VHDA at intermediate and high pressures

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Loerting, Thomas

2018-03-01

Since the first report of very-high density amorphous ice (VHDA) in 2001 [T. Loerting et al., Phys. Chem. Chem. Phys. 3, 5355-5357 (2001)], the status of VHDA as a distinct amorphous ice has been debated. We here study VHDA and its relation to expanded high density amorphous ice (eHDA) on the basis of isobaric heating experiments. VHDA was heated at 0.1 ≤ p ≤ 0.7 GPa, and eHDA was heated at 1.1 ≤ p ≤ 1.6 GPa to achieve interconversion. The behavior upon heating is monitored using in situ volumetry as well as ex situ X-ray diffraction and differential scanning calorimetry. We do not observe a sharp transition for any of the isobaric experiments. Instead, a continuous expansion (VHDA) or densification (eHDA) marks the interconversion. This suggests that a continuum of states exists between VHDA and HDA, at least in the temperature range studied here. This further suggests that VHDA is the most relaxed amorphous ice at high pressures and eHDA is the most relaxed amorphous ice at intermediate pressures. It remains unclear whether or not HDA and VHDA experience a sharp transition upon isothermal compression/decompression at low temperature.

Atypical water lattices and their possible relevance to the amorphous ices: A density functional study

NASA Astrophysics Data System (ADS)

Anick, David J.

2013-04-01

Of the fifteen known crystalline forms of ice, eleven consist of a single topologically connected hydrogen bond network with four H-bonds at every O. The other four, Ices VI-VIII and XV, consist of two topologically connected networks, each with four H-bonds at every O. The networks interpenetrate but do not share H-bonds. This article presents two new periodic water lattice families whose topological connectivity is "atypical": they consist of many two-dimensional layers that share no H-bonds. Layers are held together only by dispersion forces. Within each layer there are still four H-bonds at each O. Called "Hexagonal Bilayer Water" (HBW) and "Pleated Sheet Water" (PSW), they have computed densities of about 1.1 g/mL and 1.3 g/mL respectively, and nearest neighbor O-coordination is 4.5 to 5.5 and 6 to 8 respectively. Using density functional theory (BLYP-D/TZVP), various proton ordered forms of HBW and PSW are optimized and categorized. There are simple pathways connecting Ice-Ih to HBW and HBW to PSW. Their computed properties suggest similarities to the high density and very high density amorphous ices (HDA and VHDA) respectively. It is unknown whether HDA, VHDA, and Low Density Amorphous Ice (LDA) are fully disordered glasses down to the molecular level, or whether there is some short-range local order. Based on estimated radial distribution functions (RDFs), one proton ordered form of HBW matches HDA best. The idea is explored that HDA could contain islands with this underlying structure, and likewise, that VHDA could contain regions of PSW. A "microlattice model version 1" (MLM1) is presented as a device to compare key experimental data on the amorphous ices with these atypical structures and with a microlattice form of Ice-XI for LDA. Resemblances are found with the amorphs' RDFs, densities, Raman spectra, and transition behaviors. There is not enough information in the static models to assign either a microlattice structure or a partial microlattice structure to any amorphous ice phase.

A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

NASA Astrophysics Data System (ADS)

Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

2016-11-01

Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crouse, J.; Loock, H.-P., E-mail: hploock@chem.queensu.ca; Cann, N. M., E-mail: ncann@chem.queensu.ca

2015-07-21

Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atommore » desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H{sub 2}O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H{sub 2}O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice, arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.« less

Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

PubMed

Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

2015-11-28

We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

Quantifying atom addition reactions on amorphous solid water: a review of recent laboratory advances

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco

2018-06-01

Complex organic molecules found in space are mostly formed on and in the ice mantle covering interstellar dust grains. In clouds where ionizing irradiation is insignificant, chemical reactions on the ice mantle are dominated by thermal processes. Modeling of grain surface chemistry requires detailed information from the laboratory, including sticking coefficients, binding energies, diffusion energy barriers, mechanism of reaction, and chemical desorption rates. In this talk, recent laboratory advances in obtaining these information would be reviewed. Specifically, this talk will focus on the efforts in our group in: 1) Determining the mechanism of atomic hydrogen addition reactions on amorphous solid water (ASW); 2) Measuring the chemical desorption coefficient of H+O3-->O2+OH using the time-resolved scattering technique; and 3) Measuring the diffusion energy barrier of volatile molecules on ASW. Further laboratory studies will be suggested.This research was supported by NSF Astronomy & Astrophysics Research Grant #1615897.

Thon rings from amorphous ice and implications of beam-induced Brownian motion in single particle electron cryo-microscopy.

PubMed

McMullan, G; Vinothkumar, K R; Henderson, R

2015-11-01

We have recorded dose-fractionated electron cryo-microscope images of thin films of pure flash-frozen amorphous ice and pre-irradiated amorphous carbon on a Falcon II direct electron detector using 300 keV electrons. We observe Thon rings [1] in both the power spectrum of the summed frames and the sum of power spectra from the individual frames. The Thon rings from amorphous carbon images are always more visible in the power spectrum of the summed frames whereas those of amorphous ice are more visible in the sum of power spectra from the individual frames. This difference indicates that while pre-irradiated carbon behaves like a solid during the exposure, amorphous ice behaves like a fluid with the individual water molecules undergoing beam-induced motion. Using the measured variation in the power spectra amplitude with number of electrons per image we deduce that water molecules are randomly displaced by a mean squared distance of ∼1.1 Å(2) for every incident 300 keV e(-)/Å(2). The induced motion leads to an optimal exposure with 300 keV electrons of 4.0 e(-)/Å(2) per image with which to observe Thon rings centred around the strong 3.7 Å scattering peak from amorphous ice. The beam-induced movement of the water molecules generates pseudo-Brownian motion of embedded macromolecules. The resulting blurring of single particle images contributes an additional term, on top of that from radiation damage, to the minimum achievable B-factor for macromolecular structure determination. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

High-density amorphous ice: A path-integral simulation

NASA Astrophysics Data System (ADS)

Herrero, Carlos P.; Ramírez, Rafael

2012-09-01

Structural and thermodynamic properties of high-density amorphous (HDA) ice have been studied by path-integral molecular dynamics simulations in the isothermal-isobaric ensemble. Interatomic interactions were modeled by using the effective q-TIP4P/F potential for flexible water. Quantum nuclear motion is found to affect several observable properties of the amorphous solid. At low temperature (T = 50 K) the molar volume of HDA ice is found to increase by 6%, and the intramolecular O-H distance rises by 1.4% due to quantum motion. Peaks in the radial distribution function of HDA ice are broadened with respect to their classical expectancy. The bulk modulus, B, is found to rise linearly with the pressure, with a slope ∂B/∂P = 7.1. Our results are compared with those derived earlier from classical and path-integral simulations of HDA ice. We discuss similarities and discrepancies with those earlier simulations.

Can xenon in water inhibit ice growth? Molecular dynamics of phase transitions in water-Xe system.

PubMed

Artyukhov, Vasilii I; Pulver, Alexander Yu; Peregudov, Alex; Artyuhov, Igor

2014-07-21

Motivated by recent experiments showing the promise of noble gases as cryoprotectants, we perform molecular dynamics modeling of phase transitions in water with xenon under cooling. We follow the structure and dynamics of xenon water solution as a function of temperature. Homogeneous nucleation of clathrate hydrate phase is observed and characterized. As the temperature is further reduced we observe hints of dissociation of clathrate due to stronger hydrophobic hydration, pointing towards a possible instability of clathrate at cryogenic temperatures and conversion to an amorphous phase comprised of "xenon + hydration shell" Xe·(H2O)21.5 clusters. Simulations of ice-xenon solution interface in equilibrium and during ice growth reveal the effects of xenon on the ice-liquid interface, where adsorbed xenon causes roughening of ice surface but does not preferentially form clathrate. These results provide evidence against the ice-blocker mechanism of xenon cryoprotection.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

PubMed

Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

2018-02-21

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Detection of cryogenic water ice contaminants and the IR AI&T environment

NASA Astrophysics Data System (ADS)

Lynch, David K.; Russell, Ray W.

2000-12-01

Several remote sensing/infrared space surveillance programs in the midst of assembly, integration and test have recently experienced delays when water vapor was deposited as ice on cold surfaces in a sensor under test or calibration. When these surfaces were at critical locations, the sensitivity or response of the sensor decreased significantly because the ice absorbed the incoming signal. The source of water vapor could be from a chamber leak or outgassing from the sensor system or the vacuum chamber itself. In order to quantify the effects of ice deposits on signals in various spectral bands, published optical constants for amorphous and crystalline water ice have been used to calculate the transmission of water ice films as a function of wavelength from 1 to 20 microns. The results are presented in two ways: spectra of the physical thickness of a layer of ice whose absorption optical depth is unity, and transmission spectra for several characteristic layer thicknesses. These tools can be used in estimating the amount of ice - and by inference water vapor - present in the system. Related calculations can also be used to assess the probability that a given hardware setup or resulting data set is showing signs of degradation of response due to ice absorption, and the implications for those trying to interpret the results.

Far infrared spectra of amorphous and crystalline water ice and changes in these phases as the result of proton irradiation

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Moore, Marla H.

1992-01-01

Far infrared spectra from 20 microns (500 cm(sup -1)) to 100 microns (100 cm(sup -1)) of water ice were measured. Amorphous ice deposited at 13 K has one absorption band at 45 microns (220 cm(sup -1)). Amorphous ice evolves into a crystalline form with absorptions at 44 microns (229 cm(sup -1)) and 62 microns (162 cm(sup -1)) as the temperature is increased to 155 K. Spectra documenting this phase change are presented as well as spectra of crystalline ice at temperatures between 13 K and 155 K. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation are also presented. Changes in these two forms are discussed in relation to ices in comets, grains, and planetary satellites in various radiation environments. Observations of non-terrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over forty years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. A methanol (CH3OH) clathrate hydrate, using a recently published procedure, was prepared and its far-IR spectrum investigated. The spectrum is quite differenct from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

Laboratory Spectroscopy of Ices of Astrophysical Interest

NASA Technical Reports Server (NTRS)

Hudson, Reggie; Moore, M. H.

2011-01-01

Ongoing and future NASA and ESA astronomy missions need detailed information on the spectra of a variety of molecular ices to help establish the identity and abundances of molecules observed in astronomical data. Examples of condensed-phase molecules already detected on cold surfaces include H2O, CO, CO2, N2, NH3, CH4, SO2, O2, and O3. In addition, strong evidence exists for the solid-phase nitriles HCN, HC3N, and C2N2 in Titan's atmosphere. The wavelength region over which these identifications have been made is roughly 0.5 to 100 micron. Searches for additional features of complex carbon-containing species are in progress. Existing and future observations often impose special requirements on the information that comes from the laboratory. For example, the measurement of spectra, determination of integrated band strengths, and extraction of complex refractive indices of ices (and icy mixtures) in both amorphous and crystalline phases at relevant temperatures are all important tasks. In addition, the determination of the index of refraction of amorphous and crystalline ices in the visible region is essential for the extraction of infrared optical constants. Similarly, the measurement of spectra of ions and molecules embedded in relevant ices is important. This laboratory review will examine some of the existing experimental work and capabilities in these areas along with what more may be needed to meet current and future NASA and ESA planetary needs.

Hydration of polar and nonpolar molecules at the surface of amorphous solid water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souda, Ryutaro

2004-10-15

On the basis of time-of-flight secondary ion mass spectrometry, properties of amorphous solid water above the glass transition temperature (136 K) and the hydration of polar (HCOOH,C{sub 3}H{sub 7}OH) and nonpolar (C{sub 6}H{sub 14},C{sub 6}F{sub 14}) molecules on the D{sub 2}O-ice surface have been investigated. No evidence was obtained for the irreversible transition of the amorphous solid water into the crystalline phase: the self-diffusion of water molecules occurs above 140 K irrespective of the preparation temperatures of the water-ice film ranging from 15 K to 165 K, whereas the morphology of the film changes drastically at 165 K due tomore » the evolution of liquidlike water. It is also demonstrated that the change in conformation of the hydrated HCOOH molecule, as well as the occurrence of hydrophilic/hydrophobic hydration of the C{sub 3}H{sub 7}OH molecule, can be analyzed successfully from the temperature evolutions of the secondary-ion intensities. These polar molecules basically stay on the surface and tend to quench the morphological change of the water film due to the reduction of surface tension. The nonpolar C{sub 6}H{sub 14} and C{sub 6}F{sub 14} molecules readily dissolve in the D{sub 2}O layer below 100 K and dehydration of the incorporated molecules occurs at 165 K concomitantly with the evolution of the liquidlike water. It is thus concluded that the hydrophobic hydration of nonpolar molecules is intimately related to the properties of water films.« less

New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

Infrared Spectra and Band Strengths of Amorphous and Crystalline N2O

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Loeffler, M. J.; Gerakines, P. A.

2017-01-01

Infrared transmission spectra from 4000 to 400 cm (exp -1), and associated band strengths and absorption coefficients, are presented for the first time for both amorphous and crystalline N2O. Changes in the spectra as a function of ice thickness and ice temperature are shown. New measurements of density, refractive index, and specific refraction are reported for amorphous and crystalline N2O. Comparisons are made to published results, and the most-likely reason for some recent disagreements in the literature is discussed. As with CO2, its isoelectronic congener, the formation of amorphous N2O is found to require greater care than the formation of amorphous solids from more-polar molecules.

Monte Carlo kinetics simulations of ice-mantle formation on interstellar grains

NASA Astrophysics Data System (ADS)

Garrod, Robin

2015-08-01

The majority of interstellar dust-grain chemical kinetics models use rate equations, or alternative population-based simulation methods, to trace the time-dependent formation of grain-surface molecules and ice mantles. Such methods are efficient, but are incapable of considering explicitly the morphologies of the dust grains, the structure of the ices formed thereon, or the influence of local surface composition on the chemistry.A new Monte Carlo chemical kinetics model, MIMICK, is presented here, whose prototype results were published recently (Garrod 2013, ApJ, 778, 158). The model calculates the strengths and positions of the potential mimima on the surface, on the fly, according to the individual pair-wise (van der Waals) bonds between surface species, allowing the structure of the ice to build up naturally as surface diffusion and chemistry occur. The prototype model considered contributions to a surface particle's potential only from contiguous (or "bonded") neighbors; the full model considers contributions from surface constituents from short to long range. Simulations are conducted on a fully 3-D user-generated dust-grain with amorphous surface characteristics. The chemical network has also been extended from the simple water system previously published, and now includes 33 chemical species and 55 reactions. This allows the major interstellar ice components to be simulated, such as water, methane, ammonia and methanol, as well as a small selection of more complex molecules, including methyl formate (HCOOCH3).The new model results indicate that the porosity of interstellar ices are dependent on multiple variables, including gas density, the dust temperature, and the relative accretion rates of key gas-phase species. The results presented also have implications for the formation of complex organic molecules on dust-grain surfaces at very low temperatures.

Ice in space: An experimental and theoretical investigation. [with applications to comets

NASA Technical Reports Server (NTRS)

Patashnick, H.; Rupprecht, G.

1976-01-01

The thermodynamics of water ice formation was experimentally investigated under a wide variety of conditions, including those of outer space. This information, and in particular, the lifetime of ice particles as a function of solar distance is an absolute requirement for proper interpretation of photometric profiles of comets. The sublimation of ice particles in a nonequilibrium situation was studied. An oscillating fiber microbalance was used to measure the sublimation rate of water droplets (which were suspended on a long quartz fiber which was oscillating in a vacuum chamber). The influence of particle size, surface temperature, and the index refraction from simulated solar radiation were studied in relation to ice formation. Also examined was the influence of impurities (clathrates) on ice formation. Windows in the vacuum chamber allowed the ice particles to be exposed to a 1 kilowatt xenon arc lamp which was used to simulate solar radiation. Ice is proposed as a possible energy source for comets, as amorphous water ice and ammonia in low temperature and pressure environments demonstrated a clear energy release upon warming. Motion pictures of ice formation were taken and photographs are shown.

Fourier transform infrared studies of the interaction of HCl with model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Koehler, Birgit G.; Mcneill, Laurie S.; Middlebrook, Ann M.; Tolbert, Margaret A.

1993-01-01

Heterogeneous reactions involving hydrochloric acid adsorbed on the surfaces of polar stratospheric clouds (PSCs) are postulated to contribute to polar ozone loss. Using FTIR spectroscopy to probe the condensed phase, we have examined the interaction of HCl with ice and nitric acid trihydrate (NAT) films representative of types II and I PSCs, respectively. For HCl pressures in the range of 10 exp -7 to 10 exp -5 Torr, our FTIR studies show that a small amount of crystalline HCl-6H2O formed on or in ice at 155 K. However, for higher HCl pressures, we observed that the entire film of ice rapidly converted into an amorphous 4:1 H2O:HCl mixture. From HCl-uptake experiments with P(HCl) = 8 x 10 exp -7 Torr, we estimate roughly that the diffusion coefficient of HCl in ice is around 2 x 10 exp -12 sq cm/s at 158 K. For higher temperatures more closely approximating those found in the stratosphere, we were unable to detect bulk HCl uptake by ice. Indirect evidence suggests that HCl adsorption onto the surface of model PSC films inhibited the evaporation of both ice and NAT by 3-5 K.

Comet 67p/Churyumov-Gerasimenko, possible origin of the depression Hatmehit

NASA Astrophysics Data System (ADS)

Kossacki, Konrad J.; Czechowski, Leszek

2018-05-01

On the nucleus of comet 67P/Churyumov-Gerasimenko numerous pits and depressions of different sizes are identified. In the present work the origin of depression Hatmehit is investigated. We propose a mechanism that includes recession of the surface due to sub-dust sublimation together with formation of cavities. Recession of the surface is calculated taking into account the sub-dust sublimation of water ice with volatile organic components, formation of a strengthened ice-dust crust due to sintering of ice grains and the increase of the gas pressure in pores due to release of gaseous CO. Our simulations indicate, that the formation of a 300 m deep depression due to the sub-dust sublimation of ice can take as little as 50 orbital periods assuming that the heliocentric distance at perihelion is close to its present value (Ip. et al., 2016). When amorphous water ice is present at small depth the release of gaseous CO may cause either compression of low-strength material beneath the strengthened crust, or ejection of the crust. In both cases a cavity is formed and grows due to the sublimation of ice from the wall and the floor.

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Chemical Evolution of Interstellar Methanol Ice Analogs upon Ultraviolet Irradiation: The Role of the Substrate

NASA Astrophysics Data System (ADS)

Ciaravella, A.; Jiménez-Escobar, A.; Cosentino, G.; Cecchi-Pestellini, C.; Peres, G.; Candia, R.; Collura, A.; Barbera, M.; Di Cicca, G.; Varisco, S.; Venezia, A. M.

2018-05-01

An important issue in the chemistry of interstellar ices is the role of dust materials. In this work, we study the effect of an amorphous water-rich magnesium silicate deposited onto ZnSe windows on the chemical evolution of ultraviolet-irradiated methanol ices. For comparison, we also irradiate similar ices deposited onto bare ZnSe windows. Silicates are produced at relatively low temperatures exploiting a sol–gel technique. The chemical composition of the synthesized material reflects the forsterite stoichiometry. Si–OH groups and magnesium carbonates are incorporated during the process. The results show that the substrate material does affect the chemical evolution of the ice. In particular, the CO2/CO ratio within the ice is larger for methanol ices deposited onto the silicate substrate as a result of concurrent effects: the photolysis of carbonates present in the adopted substrate as a source of CO2, CO, and carbon and oxygen atoms; reactions of water molecules and hydroxyl radicals released from the substrate with the CO formed in the ice by the photolysis of the methanol ice; and changes in the structure and energy of the silicate surface by ultraviolet irradiation, leading to more favorable conditions for chemical reactions or catalysis at the grain surface. The results of our experiments allow such chemical effects contributed by the various substrate material components to be disentangled.

Enhanced Heterogeneous Nitrates Photolysis on Ice and Potential Impacts on NOx Emissions

NASA Astrophysics Data System (ADS)

Ayotte, P.; Marcotte, G.; Pronovost, S.; Marchand, P.; Laffon, C.; Parent, P.

2015-12-01

Nitrates photolysis plays a key role in the chemistry of the polar boundary layer and of the lower troposphere over snow-covered areas (1). Using a combination of vibrational (2) and photo-absorption spectroscopies (3), we show that nitric acid is mostly dissociated upon its adsorption onto, and its dissolution within ice at temperatures as low 20K. Using amorphous solid water as a model substrate for the disordered surface layer at the interstitial air-ice interface, UV irradiation in the environmentally relevant n-π* transition uncovers the fact that the photolysis rates are significantly higher for surface-bound nitrates compared to those dissolved within the bulk. The complex coupled interfacial transport and reaction kinetics result in the formation of a thin photochemically active layer at the surface of ice which may magnify the impact of surface-enhanced nitrates photolysis rates on ice thereby providing a significant contribution to the intense photochemical NOxfluxes observed to emanate from the sunlit snowpack upon polar sunrise.(4) (1) F. Dominé, P.B. Shepson, Science, 297, 1506-1510 (2002).(2) P. Marchand, G. Marcotte, and P. Ayotte, Spectroscopic Study of HNO3 Dissociation on Ice, J. Phys. Chem. A 116, 12112-12122 (2012).(3) G. Marcotte, P. Ayotte, A. Bendounan, F. Sirotti, C. Laffon and P. Parent, J. Phys. Chem. Lett. 4, 2643-2648 (2013).(4) G. Marcotte, P. Marchand, S. Pronovost, P. Ayotte, C. Laffon and P. Parent, J. Phys. Chem. A 119, 1996-2005 (2015).

High-density amorphous ice: nucleation of nanosized low-density amorphous ice

NASA Astrophysics Data System (ADS)

Tonauer, Christina M.; Seidl-Nigsch, Markus; Loerting, Thomas

2018-01-01

The pressure dependence of the crystallization temperature of different forms of expanded high-density amorphous ice (eHDA) was scrutinized. Crystallization at pressures 0.05-0.30 GPa was followed using volumetry and powder x-ray diffraction. eHDA samples were prepared via isothermal decompression of very high-density amorphous ice at 140 K to different end pressures between 0.07-0.30 GPa (eHDA0.07-0.3). At 0.05-0.17 GPa the crystallization line T x (p) of all eHDA variants is the same. At pressures  >0.17 GPa, all eHDA samples decompressed to pressures  <0.20 GPa exhibit significantly lower T x values than eHDA0.2 and eHDA0.3. We rationalize our findings with the presence of nanoscaled low-density amorphous ice (LDA) seeds that nucleate in eHDA when it is decompressed to pressures  <0.20 GPa at 140 K. Below ~0.17 GPa, these nanosized LDA domains are latent within the HDA matrix, exhibiting no effect on T x of eHDA<0.2. Upon heating at pressures  ⩾0.17 GPa, these nanosized LDA nuclei transform to ice IX nuclei. They are favored sites for crystallization and, hence, lower T x . By comparing crystallization experiments of bulk LDA with the ones involving nanosized LDA we are able to estimate the Laplace pressure and radius of ~0.3-0.8 nm for the nanodomains of LDA. The nucleation of LDA in eHDA revealed here is evidence for the first-order-like nature of the HDA  →  LDA transition, supporting water’s liquid-liquid transition scenarios.

Ice crystallization in ultrafine water-salt aerosols: nucleation, ice-solution equilibrium, and internal structure.

PubMed

Hudait, Arpa; Molinero, Valeria

2014-06-04

Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by solution. We predict that micrometer-sized particles and nanoparticles have the same equilibrium internal structure. The variation of liquid-vapor surface tension with solute concentration is a key factor in determining whether a solution-embedded ice core or vapor-exposed ice cap is the equilibrium structure of the aerosols. In agreement with experiments, we predict that the structure of mixed-phase HNO3-water particles, representative of polar stratospheric clouds, consists of an ice core surrounded by freeze-concentrated solution. The results of this work are important to determine the phase state and internal structure of sea spray ultrafine aerosols and other mixed-phase particles under atmospherically relevant conditions.

Ice polyamorphism in the minimal Mercedes-Benz model of water.

PubMed

Cartwright, Julyan H E; Piro, Oreste; Sánchez, Pedro A; Sintes, Tomás

2012-12-28

We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore, we find a reversible transformation between two amorphous structures of high and low density; however, we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.

Ice polyamorphism in the minimal Mercedes-Benz model of water

NASA Astrophysics Data System (ADS)

Cartwright, Julyan H. E.; Piro, Oreste; Sánchez, Pedro A.; Sintes, Tomás

2012-12-01

We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore, we find a reversible transformation between two amorphous structures of high and low density; however, we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.

Glass polymorphism in glycerol–water mixtures: II. Experimental studies

PubMed Central

Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolas

2016-01-01

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s–1–10 K h–1) and for the whole range of glycerol mole fractions, χ g. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χ g ≥ 0.20), ice (χ g ≤ 0.32), and/or “distorted ice” (0 < χ g ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χ g ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol–water mixtures is shown to be possible only up to χ g ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χ g < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χ g ≈ 0.38. Accordingly, in the range 0.32 < χ g < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χ g ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 < χ g ≤ 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (χ g ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex “phase” behavior of glassy binary mixtures due to phase-separation (ice formation) and polyamorphism, and the relevance of sample preparation, concentration as well as cooling rates. The presence of the distorted ice (called “interphase” by us) also explains the debated “drift anomaly” upon melting. These results are compatible with the high-pressure study by Suzuki and Mishima indicating disappearance of polyamorphism at P ≈ 0.03–0.05 GPa at χ g ≈ 0.12–0.15 [J. Chem. Phys., 2014, 141, 094505]. PMID:27044677

Non-thermal processes on ice and liquid micro-jet surfaces

NASA Astrophysics Data System (ADS)

Olanrewaju, Babajide O.

The primary focus of this research is to investigate non-thermal processes occurring on ice surfaces and the photo-ejection of ions from liquid surfaces. Processes at the air-water/ice interface are known to play a very important role in the release of reactive halogen species with atmospheric aerosols serving as catalysts. The ability to make different types of ice with various morphologies, hence, different adsorption and surface properties in vacuum, provide a useful way to probe the catalytic effect of ice in atmospheric reactions. Also, the use of the liquid jet technique provides the rare opportunity to probe liquid samples at the interface; hitherto impossible to investigate with traditional surface science techniques. In Chapter 2, the effect of ice morphology on the release of reactive halogen species from photodissociation of adsorbed organic halides on ice will be presented. Quantum state resolved measurements of neutral atomic iodine from the photon irradiation of submonolayer coverages of methyl iodide adsorbed on low temperature water ice were conducted. Temperature programmed desorption (TPD) studies of methyl iodide adsorbed on ice were performed to provide information on the effect of ice morphology on the adsorption of submonolayer methyl iodide. The interaction and autoionization of HCl on low-temperature (80{140 K) water ice surfaces has been studied using low-energy (5-250 eV) electron-stimulated desorption (ESD) and temperature programmed desorption (TPD). A detailed ESD study of the interactions of low concentrations of HCl with low-temperature porous amorphous solid water (PASW), amorphous solid water (ASW) and crystalline ice (CI) surfaces will be presented in Chapter 3. The ESD cation yields from HCl adsorbed on ice, as well as the coverage dependence, kinetic energy distributions and TPD measurements were all monitored. Probing liquid surface using traditional surface science technique is usually difficult because of the problem of keeping the liquid surface clean and the distortion of information by the interference of equilibrium dense vapor above the liquid. By using the liquid jet technique the ejection of ions from surface of micron sized liquid can be adequately probed with a linear time-of-flight mass spectrometer. The photoionization of pure water and aqueous solutions of NaOH, NaCl and HCl is presented in Chapter 4. The aim of this investigation was to provide a fundamental understanding of the structure of water/vacuum interfaces. In Chapter 5, the ejection of ions from salt solutions containing divalent cations is also presented. The goal of the experiment was to figure out the solvation structure and reaction dynamics of divalent metal ions, M2+ on the surface of aqueous solution. A lot of work has been done in the gas phase either by a pickup-type cluster source or by collision induced dissociation of ejected ions from electrospray. For the first time the direct monitoring of ions ejected from liquid into gas phase is explored. Possible ejection mechanisms for the ejection of cations are discussed extensively in both Chapters 4 and 5. The results presented in this thesis is a combination of experiments performed at the Georgia Institute of Technology and the Pacific Northwest National Laboratory (PNNL) which includes experiments on ice and micro-jet respectively. The results in Chapters 2 and 3 have been submitted to the Journal of Chemical Physics and the Journal of Physical Chemistry respectively. It is important to note that the data presented in Chapter 3 was originally taken by Dr Janine Herring-Captain as part of her thesis work. It is also presented in this thesis due to effort in analyzing the data and preparation of the submitted manuscript. Chapter 4 and 5 represents papers which will also be submitted for publication in the open scientific literature. All the work leading to the results presented in these two chapters were done during my visit to PNNL and I would like to acknowledge that the instrumentation and data acquisition were done in collaboration with Nikolai Petrik and Greg Kimmel.

Modeling Subsidence-Like Events on Cometary Nuclei

NASA Astrophysics Data System (ADS)

Rosenberg, Eric; Prialnik, Dina

2017-10-01

There is ample evidence, particularly from the Rosetta mission, that cometary nuclei have very low tensile strength. Consequently, morphological changes are expected to occur, caused by buildup of pressure due to gas release in the interior of the nucleus. Such changes have been observed on the surface of comet 67P/Churyumov-Gerasimenko, as reported for example by Groussin et al.(2015). A mechanism for explaining comet surface depressions has been recently proposed by Prialnik & Sierks (2017). Here we report on a numerical study, elaborating on this mechanism. Essentially, the model considers a cometary nucleus composed of a low-density mixture of ice and dust, assuming that the ice is amorphous and traps volatile gasses, such as CO and CO2. The model assumes that the tensile strength of the subsurface material is low and that the surface is covered by a thin crust of low permeability. As the comet evolves, the amorphous ice crystallizes, and the crystallization front recedes from the surface, releasing the trapped gasses, which accumulate beneath the surface, building up pressure. The gas pressure weakens the material strength, but sustains the gas-filled layer against hydrostatic pressure. Eventually, the gas will break its way through the outer crust in an outburst. The rapid pressure drop may cause the collapse of the gas depleted layer, as seen on the nucleus of 67P/Churyumov-Gerasimenko. This mechanism is similar to subsidence events in gas fields on earth.We have performed quasi-3D numerical simulations in an attempt to determine the extent of the area that would be affected by such a mechanism. The frequency of such subsidence events and the depth of the collapse are investigated as functions of solar angle and spin axis inclination. The necessary conditions for outburst-induced collapse are determined and confronted with observations.References:Groussin, O., Sierks, H., et al. 2015, A&A, 583, A35Prialnik, D. & Sierks, H., 2017, MNRAS, in press

Amorphous Phases on the Surface of Mars

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Morris, R. V.; Ruff, S. W.; Horgan, B.; Dehouck, E.; Achilles, C. N.; Ming, D. W.; Bish, D. L.; Chipera, S. J.

2014-01-01

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.

New measurements of the sticking coefficient and binding energy of molecules on non-porous amorphous solid water in the submonolayer regime

NASA Astrophysics Data System (ADS)

He, Jiao; Acharyya, Kinsuk; Emtiaz, S. M.; Vidali, Gianfranco

2016-06-01

Sticking and adsorption of molecules on dust grains are two important processes in gas-grain interactions. We accurately measured both the sticking coefficient and the binding energy of several key molecules on the surface of amorphous solid water as a function of coverage.A time-resolved scattering technique was used to measure sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on non-porous amorphous solid water (np-ASW) in the low coverage limit over a wide range of surface temperatures. We found that the time-resolved scattering technique is advantageous over the conventional King-Wells method that underestimates the sticking coefficient. Based on the measured values we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy.We measured the binding energy of N2, CO, O2, CH4, and CO2 on np-ASW, and of N2 and CO on porous amorphous solid water (p-ASW). We were able to measure binding energies down to a fraction of 1% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO2 forms clusters on np-ASW surface even at very low coverage; this may help in explaining the segregation of CO2 in ices. The binding energies of N2, CO, O2, and CH4 on np-ASW decrease with coverage in the submonolayer regime. Their values in the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold dense clouds and hot core models. We found that owing to the higher value of desorption energy in the sub-monlayer regime a fraction of all these ices stays much longer and to higher temperature on the grain surface compared to the case using single value energies as currently done in astrochemical models.This work was supported in part by a grant to GV from NSF --- Astronomy & Astrophysics Division (#1311958)

Does deposition freezing really exist? At least different as we thought

NASA Astrophysics Data System (ADS)

Abdelmonem, Ahmed

2017-04-01

The structural and chemical properties of the surface of an IN-particle (INP) play a major role in its IN ability. This role is not well explored in terms of water/INP-surface molecular-level interactions. Recent MD simulations on deposition freezing showed that water first deposits as liquid clusters and then crystallize isothermally from there [1]. We probe freezing of water on INPs of different structural and chemical properties under varying supersaturation conditions using non-linear optical spectroscopy, mainly second harmonic generation (SHG) and sum frequency generation (SFG) [2, 3]. This presentation will show very recent preliminary experimental results comparing deposition, condensation and immersion freezing (DF, CF and IF respectively) on an atmospheric relevant metal oxide surface (mica) using supercooled SHG measurements. It is found that the signal drops upon the formation of a thin film regardless of 1) the freezing path (DF or CF), 2) the formed phase (ice or liquid), indicating a similar molecular structuring. The observed structuring similarity between DF, CF and LC films is a kick-off experimental confirmation of those computational results. References 1. Lupi, L., N. Kastelowitz, and V. Molinero, Vapor deposition of water on graphitic surfaces: Formation of amorphous ice, bilayer ice, ice I, and liquid water. The Journal of Chemical Physics, 2014. 141(18): p. 18C508. 2. Abdelmonem, A., J. Lützenkirchen, and T. Leisner, Probing ice-nucleation processes on the molecular level using second harmonic generation spectroscopy. Atmospheric Measurement Techniques, 2015. 8(8): p. 3519-3526. 3. Abdelmonem, A., et al., Surface charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001). Angewandte Chemie (Submitted), 2017.

Near-infrared spatially resolved spectroscopy of (136108) Haumea's multiple system

NASA Astrophysics Data System (ADS)

Gourgeot, F.; Carry, B.; Dumas, C.; Vachier, F.; Merlin, F.; Lacerda, P.; Barucci, M. A.; Berthier, J.

2016-08-01

Context. The transneptunian region of the solar system is populated by a wide variety of icy bodies showing great diversity in orbital behavior, size, surface color, and composition. Aims: The dwarf planet (136108) Haumea is among the largest transneptunian objects (TNOs) and is a very fast rotator (~3.9 h). This dwarf planet displays a highly elongated shape and hosts two small moons that are covered with crystalline water ice, similar to their central body. A particular region of interest is the Dark Red Spot (DRS) identified on the surface of Haumea from multiband light-curve analysis (Lacerda et al. 2008). Haumea is also known to be the largest member of the sole TNO family known to date, and an outcome of a catastrophic collision that is likely responsible for the unique characteristics of Haumea. Methods: We report here on the analysis of a new set of near-infrared Laser Guide Star assisted observations of Haumea obtained with the Integral Field Unit (IFU) Spectrograph for INtegral Field Observations in the Near Infrared (SINFONI) at the European Southern Observatory (ESO) Very Large Telescope (VLT) Observatory. Combined with previous data published by Dumas et al. (2011), and using light-curve measurements in the optical and far infrared to associate each spectrum with its corresponding rotational phase, we were able to carry out a rotationally resolved spectroscopic study of the surface of Haumea. Results: We describe the physical characteristics of the crystalline water ice present on the surface of Haumea for both regions, in and out of the DRS, and analyze the differences obtained for each individual spectrum. The presence of crystalline water ice is confirmed over more than half of the surface of Haumea. Our measurements of the average spectral slope (1.45 ± 0.82% by 100 nm) confirm the redder characteristic of the spot region. Detailed analysis of the crystalline water-ice absorption bands do not show significant differences between the DRS and the remaining part of the surface. We also present the results of applying Hapke modeling to our data set. The best spectral fit is obtained with a mixture of crystalline water ice (grain sizes smaller than 60 μm) with a few percent of amorphous carbon. Improvements to the fit are obtained by adding ~10% of amorphous water ice. Additionally, we used the IFU-reconstructed images to measure the relative astrometric position of the largest satellite Hi`iaka and determine its orbital elements. An orbital solution was computed with our genetic-based algorithm GENOID and our results are in full agreement with recent results. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile, Program ID: 60.A-9235.

Heterogeneous Ice Nucleation by Soufriere Hills Volcanic Ash Immersed in Water Droplets.

PubMed

Mangan, T P; Atkinson, J D; Neuberg, J W; O'Sullivan, D; Wilson, T W; Whale, T F; Neve, L; Umo, N S; Malkin, T L; Murray, B J

2017-01-01

Fine particles of ash emitted during volcanic eruptions may sporadically influence cloud properties on a regional or global scale as well as influencing the dynamics of volcanic clouds and the subsequent dispersion of volcanic aerosol and gases. It has been shown that volcanic ash can trigger ice nucleation, but ash from relatively few volcanoes has been studied for its ice nucleating ability. In this study we quantify the efficiency with which ash from the Soufriere Hills volcano on Montserrat nucleates ice when immersed in supercooled water droplets. Using an ash sample from the 11th February 2010 eruption, we report ice nucleating efficiencies from 246 to 265 K. This wide range of temperatures was achieved using two separate droplet freezing instruments, one employing nanolitre droplets, the other using microlitre droplets. Soufriere Hills volcanic ash was significantly more efficient than all other ash samples that have been previously examined. At present the reasons for these differences are not understood, but may be related to mineralogy, amorphous content and surface chemistry.

Heterogeneous Ice Nucleation by Soufriere Hills Volcanic Ash Immersed in Water Droplets

PubMed Central

Atkinson, J. D.; Neuberg, J. W.; O’Sullivan, D.; Wilson, T. W.; Whale, T. F.; Neve, L.; Umo, N. S.; Malkin, T. L.; Murray, B. J.

2017-01-01

Fine particles of ash emitted during volcanic eruptions may sporadically influence cloud properties on a regional or global scale as well as influencing the dynamics of volcanic clouds and the subsequent dispersion of volcanic aerosol and gases. It has been shown that volcanic ash can trigger ice nucleation, but ash from relatively few volcanoes has been studied for its ice nucleating ability. In this study we quantify the efficiency with which ash from the Soufriere Hills volcano on Montserrat nucleates ice when immersed in supercooled water droplets. Using an ash sample from the 11th February 2010 eruption, we report ice nucleating efficiencies from 246 to 265 K. This wide range of temperatures was achieved using two separate droplet freezing instruments, one employing nanolitre droplets, the other using microlitre droplets. Soufriere Hills volcanic ash was significantly more efficient than all other ash samples that have been previously examined. At present the reasons for these differences are not understood, but may be related to mineralogy, amorphous content and surface chemistry. PMID:28056077

AB-stacked square-like bilayer ice in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Bai, Jaeil; Zeng, Xiao Cheng; Wu, HengAn

2016-08-10

Water, when constrained between two graphene sheets and under ultrahigh pressure, can manifest dramatic differences from its bulk counterparts such as the van der Waals pressure induced water-to-ice transformation, known as the metastability limit of two-dimensional (2D) liquid. Here, we present result of a new crystalline structure of bilayer ice with the AB-stacking order, observed from molecular dynamics simulations of constrained water. This AB-stacked bilayer ice (BL-ABI) is transformed from the puckered monolayer square-like ice (pMSI) under higher lateral pressure in the graphene nanocapillary at ambient temperature. BL-ABI is a proton-ordered ice with square-like pattern. The transition from pMSI to BL-ABI is through crystal-to-amorphous-to-crystal pathway with notable hysteresis-loop in the potential energy during the compression/decompression process, reflecting the compression/tensile limit of the 2D monolayer/bilayer ice. In a superheating process, the BL-ABI transforms into the AB-stacked bilayer amorphous ice with the square-like pattern.

An aerosol chamber investigation of the heterogeneous ice nucleating potential of refractory nanoparticles

NASA Astrophysics Data System (ADS)

Saunders, R. W.; Möhler, O.; Schnaiter, M.; Benz, S.; Wagner, R.; Saathoff, H.; Connolly, P. J.; Burgess, R.; Gallagher, M.; Wills, R.; Murray, B. J.; Plane, J. M. C.

2009-11-01

Nanoparticles of iron oxide (crystalline and amorphous), silicon oxide and magnesium oxide were investigated for their propensity to nucleate ice over the temperature range 180-250 K, using the AIDA chamber in Karlsruhe, Germany. All samples were observed to initiate ice formation via the deposition mode at threshold ice super-saturations (RHi thresh) ranging from 105% to 140% for temperatures below 220 K. Approximately 10% of amorphous Fe2O3 particles (modal diameter = 30 nm) generated in situ from a photochemical aerosol reactor, led to ice nucleation at RHi thresh = 140% at an initial chamber temperature of 182 K. Quantitative analysis using a singular hypothesis treatment provided a fitted function [ns (190 K) = 10(3.33×sice)+8.16] for the variation in ice-active surface site density (ns: m-2) with ice saturation (sice) for Fe2O3 nanoparticles. This was implemented in an aerosol-cloud model to determine a predicted deposition (mass accommodation) coefficient for water vapour on ice of 0.1 at temperatures appropriate for the upper atmosphere. Classical nucleation theory was used to determine representative contact angles (θ) for the different particle compositions. For the in situ generated Fe2O3 particles, a slight inverse temperature dependence was observed with θ = 10.5° at 182 K, decreasing to 9.0° at 200 K (compared with 10.2° and 11.4°, respectively for the SiO2 and MgO particle samples at the higher temperature). These observations indicate that such refractory nanoparticles are relatively efficient materials for the nucleation of ice under the conditions studied in the chamber which correspond to cirrus cloud formation in the upper troposphere. The results also show that Fe2O3 particles do not act as ice nuclei under conditions pertinent for tropospheric mixed phase clouds, which necessarily form above ~233 K. At the lower temperatures (<150 K) where noctilucent clouds form during summer months in the high latitude mesosphere, higher contact angles would be expected, which may reduce the effectiveness of these particles as ice nuclei in this part of the atmosphere.

An aerosol chamber investigation of the heterogeneous ice nucleating potential of refractory nanoparticles

NASA Astrophysics Data System (ADS)

Saunders, R. W.; Möhler, O.; Schnaiter, M.; Benz, S.; Wagner, R.; Saathoff, H.; Connolly, P. J.; Burgess, R.; Murray, B. J.; Gallagher, M.; Wills, R.; Plane, J. M. C.

2010-02-01

Nanoparticles of iron oxide (crystalline and amorphous), silicon oxide and magnesium oxide were investigated for their propensity to nucleate ice over the temperature range 180-250 K, using the AIDA chamber in Karlsruhe, Germany. All samples were observed to initiate ice formation via the deposition mode at threshold ice super-saturations (RHithresh) ranging from 105% to 140% for temperatures below 220 K. Approximately 10% of amorphous Fe2O3 particles (modal diameter = 30 nm) generated in situ from a photochemical aerosol reactor, led to ice nucleation at RHithresh = 140% at an initial chamber temperature of 182 K. Quantitative analysis using a singular hypothesis treatment provided a fitted function [ns(190 K)=10(3.33×sice)+8.16] for the variation in ice-active surface site density (ns:m-2) with ice saturation (sice) for Fe2O3 nanoparticles. This was implemented in an aerosol-cloud model to determine a predicted deposition (mass accommodation) coefficient for water vapour on ice of 0.1 at temperatures appropriate for the upper atmosphere. Classical nucleation theory was used to determine representative contact angles (θ) for the different particle compositions. For the in situ generated Fe2O3 particles, a slight inverse temperature dependence was observed with θ = 10.5° at 182 K, decreasing to 9.0° at 200 K (compared with 10.2° and 11.4° respectively for the SiO2 and MgO particle samples at the higher temperature). These observations indicate that such refractory nanoparticles are relatively efficient materials for the nucleation of ice under the conditions studied in the chamber which correspond to cirrus cloud formation in the upper troposphere. The results also show that Fe2O3 particles do not act as ice nuclei under conditions pertinent for tropospheric mixed phase clouds, which necessarily form above ~233 K. At the lower temperatures (<150 K) where noctilucent clouds form during summer months in the high latitude mesosphere, higher contact angles would be expected, which may reduce the effectiveness of these particles as ice nuclei in this part of the atmosphere.

EXPERIMENTAL INVESTIGATION OF THE ORTHO/PARA RATIO OF NEWLY FORMED MOLECULAR HYDROGEN ON AMORPHOUS SOLID WATER

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavilan, L.; Lemaire, J. L.; Dulieu, F.

2012-11-20

Several astronomical observations have shown that the ortho/para ratio (OPR) of H{sub 2} can differ from the expected statistical value of 3 or the local thermodynamic equilibrium (LTE) value at the gas or dust temperature. It is thus important to know the OPR of H{sub 2} newly formed on dust grain surfaces, in order to clarify the dependence of the observed OPR in space on the formation process. Using an experimental setup designed to mimic interstellar medium environments, we measured the OPR of H{sub 2} and D{sub 2} formed on the surface of porous amorphous water ice held at 10more » K. We report for the first time the OPR value for newly formed D{sub 2}, consistent with the expected LTE value at the high-temperature limit found by previous theoretical and experimental works on the determination of the OPR upon H{sub 2} formation on surfaces at low temperature.« less

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

Communication: Disorder-suppressed vibrational relaxation in vapor-deposited high-density amorphous ice

NASA Astrophysics Data System (ADS)

Shalit, Andrey; Perakis, Fivos; Hamm, Peter

2014-04-01

We apply two-dimensional infrared spectroscopy to differentiate between the two polyamorphous forms of glassy water, low-density (LDA) and high-density (HDA) amorphous ices, that were obtained by slow vapor deposition at 80 and 11 K, respectively. Both the vibrational lifetime and the bandwidth of the 1-2 transition of the isolated OD stretch vibration of HDO in H2O exhibit characteristic differences when comparing hexagonal (Ih), LDA, and HDA ices, which we attribute to the different local structures - in particular the presence of interstitial waters in HDA ice - that cause different delocalization lengths of intermolecular phonon degrees of freedom. Moreover, temperature dependent measurements show that the vibrational lifetime closely follows the structural transition between HDA and LDA phases.

Insight into Nucleation Mechanisms of Tetrahedral Materials from Advanced Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Bi, Yuanfei

This dissertation studies the nucleation mechanisms of ice, clathrate hydrate and silicon clathrate which all belong to tetrahedral materials and carry significant importance to modern society. Because of the stochastic nature and the ultra-fine scale of nucleation, the mechanisms through which these important tetrahedral materials form from liquid remain poorly understood. Our goal is to address the current knowledge gap between experiment and theory on the nucleation mechanisms by conducting molecular dynamics (MD) studies. To overcome the rare event nature of nucleation, an advanced sampling method Forward Flux Sampling (FFS) is integrated with classical MD simulations. This integration allows obtaining not only nucleation rate explicitly but also an ensemble of nucleation trajectories with their correct statistical weights. By analyzing the ensemble of trajectories obtained from FFS, we reveal the important details of nucleation at the molecular level, particular at the early stage of nucleation. By combining Backward Flux Sampling (BFS) with FFS, we can also compute the free energy profile of nucleation explicitly, which allows a comparison against the classical nucleation theory (CNT). We began our investigation by studying heterogeneous ice nucleation, which is the most relevant form of ice formation. In this part of study, we aim to understand the key microscopic factors that control ice formation, including surface hydrophilicity, surface crystallinity, and surface geometry. Our simulations reveal that heterogeneous ice nucleation on graphitic surfaces is controlled by the coupling of surface crystallinity and surface hydrophilicity. In particular, our analysis shows that the crystalline graphitic lattice with an appropriate hydrophilicity may indeed template ice basal plane by forming a strained ice layer, thus significantly enhance its ice nucleation efficiency. The templating effect is further found to transit from within the first contact layer of water to the second as the surface hydrophilicity increases, which yields an oscillating distinction between the crystalline and amorphous graphitic surfaces in their ice nucleation efficiency. With this understanding, we then shifted our focus on the role of surface geometry, where we find that an atomically sharp, concave wedge can further promote ice nucleation. Remarkably, our molecular analysis shows a significant enhancement of ice nucleation can emerge both when the geometry of a wedge matches the ice lattice and when such lattice match does not exist. We then investigated the nucleation of gas hydrate, a binary compound composed of water and natural gas, e.g., methane. To facilitate the application of FFS in studying gas hydrate nucleation, we proposed a new order parameter: Half-Cage Order Parameter (H-COP), based on the topological signature of hydrate structure, and conducted a pB histogram analysis to verify the effectiveness of the H-COP order parameter. Our analyses show that the nucleation of M-hydrate (M can be methane or carbon dioxide) starts in the vicinity of water-M interface, and gradually transit from amorphous to crystalline structures. This is the direct support to the proposed two-step nucleation mechanism of methane hydrate. However, within the ensemble of nucleation trajectories, we also identified some direct crystallization pathways without going through a amorphous phase in the nucleation of both M-hydrate and L-hydrate. Remarkably the free energy profile of L-hydrate nucleation, which is obtained independent of nucleation theory, is found to fit well against the CNT, albeit with noticeable differences when the nucleus is small. Therefore, the CNT-like free energy profile and the existence of multiple nucleation pathways indicate the near degeneracy of these pathways in their free energy profiles and highlight the complexity of hydrate nucleation. On the basis of these results, we further proposed a new perspective of gas hydrate nucleation, which can be considered to be an entropically driven, kinetic process that proceeds via multiple pathways that have similar free energy profiles. Finally, inspired by our insight gained in studying gas hydrate nucleation, we proposed a novel synthesis route to obtain inert gas silicon clathrate, which has an attractive opto-electronic property for energy application, but remains as an experimental challenge for synthesis. We thoroughly examined this proposal through high-throughput computational studies that show the novel phases of silicon could form spontaneously from liquid silicon in the presence of noble gases under high pressure and high temperature. In particular, our results show that a medium size of noble gas, e.g., Ar, can trigger the nucleation and growth of inert-gas silicon clathrate, whereas a small noble gas such as He is able to induce the formation of an unconventional, inclusion-type compound Si2He. Our findings, along with the gained molecular insights, thus strongly suggest it is viable to experimentally synthesize novel silicon phases with noble gas through high pressure and high temperature. (Abstract shortened by ProQuest.).

The glass transition in high-density amorphous ice

PubMed Central

Loerting, Thomas; Fuentes-Landete, Violeta; Handle, Philip H.; Seidl, Markus; Amann-Winkel, Katrin; Gainaru, Catalin; Böhmer, Roland

2015-01-01

There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K. In the last decade some work has also been devoted to the study of the glass transition in high-density amorphous ice (HDA) which is in the focus of the present review. At ambient pressure HDA is metastable against both ice I and LDA, whereas at > 0.2 GPa HDA is no longer metastable against LDA, but merely against high-pressure forms of crystalline ice. The first experimental observation interpreted as the glass transition of HDA was made using in situ methods by Mishima, who reported a glass transition temperature Tg of 160 K at 0.40 GPa. Soon thereafter Andersson and Inaba reported a much lower glass transition temperature of 122 K at 1.0 GPa. Based on the pressure dependence of HDA's Tg measured in Innsbruck, we suggest that they were in fact probing the distinct glass transition of very high-density amorphous ice (VHDA). Very recently the glass transition in HDA was also observed at ambient pressure at 116 K. That is, LDA and HDA show two distinct glass transitions, clearly separated by about 20 K at ambient pressure. In summary, this suggests that three glass transition lines can be defined in the p–T plane for LDA, HDA, and VHDA. PMID:25641986

The glass transition in high-density amorphous ice.

PubMed

Loerting, Thomas; Fuentes-Landete, Violeta; Handle, Philip H; Seidl, Markus; Amann-Winkel, Katrin; Gainaru, Catalin; Böhmer, Roland

2015-01-01

There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K. In the last decade some work has also been devoted to the study of the glass transition in high-density amorphous ice (HDA) which is in the focus of the present review. At ambient pressure HDA is metastable against both ice I and LDA, whereas at > 0.2 GPa HDA is no longer metastable against LDA, but merely against high-pressure forms of crystalline ice. The first experimental observation interpreted as the glass transition of HDA was made using in situ methods by Mishima, who reported a glass transition temperature T g of 160 K at 0.40 GPa. Soon thereafter Andersson and Inaba reported a much lower glass transition temperature of 122 K at 1.0 GPa. Based on the pressure dependence of HDA's T g measured in Innsbruck, we suggest that they were in fact probing the distinct glass transition of very high-density amorphous ice (VHDA). Very recently the glass transition in HDA was also observed at ambient pressure at 116 K. That is, LDA and HDA show two distinct glass transitions, clearly separated by about 20 K at ambient pressure. In summary, this suggests that three glass transition lines can be defined in the p-T plane for LDA, HDA, and VHDA.

Weak interactions between water and clathrate-forming gases at low pressures

DOE PAGES

Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; ...

2015-07-17

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10 –1 mbar methane or 10 –5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 10 7 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10 –5 mbar methane does not alter their morphology, suggestingmore » that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

THE EFFECTS OF CRACKING ON THE SURFACE POTENTIAL OF ICY GRAINS IN SATURN’S E-RING: LABORATORY STUDIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bu, Caixia; Bahr, David A.; Dukes, Catherine A.

2016-07-10

Within Saturn's E-ring, dust grains are coated by water vapor co-released with ice grains from the geyser-like eruptions of Enceladus. These ice-coated grains have intrinsic surface potential and interact synergistically with the ions and electrons of Saturn's magnetospheric plasmas. We perform laboratory experiments to investigate the effects of water-ice growth on the surface potential, using amorphous solid water (ASW) films. We estimate the growth of the surface potential to be ∼ 2.5 mV (Earth) yr{sup 1} and 112 mV yr{sup 1} for E-ring grains at ∼4.5 R {sub s} and 3.95 R {sub s} outside Enceladus’s plume, respectively. In addition,more » our measurements show that the linear relationship between the surface potential and the film thickness, as described in previous studies, has an upper limit, where the film spontaneously cracks above a porosity-dependent critical thickness. Heating of the cracked films with (and without) deposited charge shows that significant positive (and negative) surface potentials are retained at temperatures above 110 K, contrary to the minimal values (roughly zero) for thin, transparent ASW films. The significant surface potentials observed on micron-scale cracked ice films after thermal cycling, (5–20) V, are consistent with Cassini measurements, which indicate a negative charge of up to 5 V for E-ring dust particles at ∼5 R {sub s}. Therefore, the native grain surface potential resulting from water-vapor coating must be included in modeling studies of interactions between E-ring icy surfaces and Saturn's magnetospheric plasma.« less

Infrared Spectra and Optical Constants of Elusive Amorphous Methane

NASA Technical Reports Server (NTRS)

Gerakines, Perry A.; Hudson, Reggie L.

2015-01-01

New and accurate laboratory results are reported for amorphous methane (CH4) ice near 10 K for the study of the interstellar medium (ISM) and the outer Solar System. Near- and mid-infrared (IR) data, including spectra, band strengths, absorption coefficients, and optical constants, are presented for the first time for this seldom-studied amorphous solid. The apparent IR band strength near 1300 cm(exp -1) (7.69 micrometer) for amorphous CH4 is found to be about 33% higher than the value long used by IR astronomers to convert spectral observations of interstellar CH4 into CH4 abundances. Although CH4 is most likely to be found in an amorphous phase in the ISM, a comparison of results from various laboratory groups shows that the earlier CH4 band strength at 1300 cm(exp -1) (7.69 micrometer) was derived from IR spectra of ices that were either partially or entirely crystalline CH4 Applications of the new amorphous-CH4 results are discussed, and all optical constants are made available in electronic form.

Centaurs and Activity Beyond the Water Sublimation Zone

NASA Astrophysics Data System (ADS)

Jewitt, David

2017-08-01

Centaurs are icy objects in dynamical transition between the Kuiper belt, where they originate, and the Jupiter family comets. Water ice in inward drifting Centaurs should begin to sublimate measurably when their perihelion reaches the orbit of Jupiter (5 AU). Instead, a fraction of Centaurs become active (have a cometary appearance) even with perihelia at Saturn (10 AU). Of the many suggestions made for the origin of this distant activity, the current favorite and the one with the largest impact on cometary science is the crystallization of amorphous water ice. Amorphous ice is an excellent carrier of supervolatiles (e.g. CO, N2) which are released upon the exothermic transition to crystalline ice. If Centaur ice is amorphous, then so must be Kuiper belt ice, setting strong constraints on the internal temperature vs. time history of the Kuiper belt objects. If the crystallization hypothesis is correct, we should never find an active Centaur with a perihelion substantially beyond the so-called crystallization line at about 12 AU (because temperatures there are too low to trigger crystallization). We propose a simple search for distant activity in Centaurs with perihelia 15 to 20 AU, in which crystallization cannot occur, in order to challenge the crystallization hypothesis. The search is made possible by the tight and stable point spread function and sensitivity to near-nucleus coma of HST.

Nonequilibrium Phase Transitions in Supercooled Water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2012-02-01

We present results of a simulation study of water driven out of equilibrium. Using transition path sampling, we can probe stationary path distributions parameterize by order parameters that are extensive in space and time. We find that by coupling external fields to these parameters, we can drive water through a first order dynamical phase transition into amorphous ice. By varying the initial equilibrium distributions we can probe pathways for the creation of amorphous ices of low and high densities.

Hydrocarbon ices in extra-red TNOs and Centaurs

NASA Astrophysics Data System (ADS)

Dalle Ore, C. M.; Barucci, M.; Emery, J. P.; Cruikshank, D. P.; Merlin, F.; Perna, D.

2012-12-01

We present an analysis of the reddest trans-neptunian objects (TNOs) and Centaurs - those belonging to the RR taxon. The RR class contains more than ¼ of the population of TNOs for which photometric colors are available, including a variety of dynamically different objects. The available data cover the spectral range from 0.3 to 2.2 μm. Previous work investigated possible relations between spectral characteristics and other physical and dynamical parameters. The distribution of ices on TNOs has been analyzed as a function of the object absolute magnitude, taxonomy and dynamical class. In a sample of 76 objects for which visible and near-IR spectroscopic measurements are available, CH3OH ice was detected only on three objects belonging to the RR taxonomic class (5145 Pholus, 55638 2002 VE95 and 90377 Sedna). These three objects are among the reddest, they belong to different dynamical classes, and they have different dimensions. However, all three have similar compositions with Sedna showing a more significant heterogeneity in the kind of hydrocarbon ices found on its surface than the others. To further investigate the presence of hydrocarbon ices, and in particular CH3OH, as part of the composition of the RR taxon we used Spitzer IRAC data available for a subgroup of nine objects. Both methanol and methane have a strong absorption at 3.6 μm, the first of the Spitzer IRAC channels, and a much higher albedo at the following channel at 4.5 μm. This albedo pattern is characteristic of some hydrocarbon ices and is very different from H2O ice that shows instead very low albedos at both channels. Our technique makes use of a large database of models including H2O, CH3OH, CH4, and N 2 ices combined with tholins, amorphous carbon, hydrogenated amorphous carbon, serpentine and olivine in different combinations of relative abundances and grain sizes. We automatically extract the models that match the observations at all color wavelengths therefore obtaining for each object a set of compositions that are consistent with its colors. We detect hydrocarbon ices on most objects in our sample. The presence of methanol, or more generally hydrocarbons, on these extra red objects could imply that they exhibit an almost primordial surface. In fact, laboratory experiments of irradiation of compounds rich in methanol show strong reddening. The reddening effect on a Centaur or TNO depends on the composition of the object and on the irradiation history while the thickness of the organic crust depends on the irradiation dose. These objects, following the hypothesis of Brown et al (2011) that objects that formed farther away might be able to retain their methanol ice, have the surface composition and colors set by formation-location-dependent volatile loss in the early solar system. The results of the current work also support the hypothesis that a substantial mixing has occurred after the TNOs formation but cannot exclude the hypothesis of initial heterogeneity.

Relaxation Time of High-Density Amorphous Ice

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Seidl, Markus; Loerting, Thomas

2012-06-01

Amorphous water plays a fundamental role in astrophysics, cryoelectron microscopy, hydration of matter, and our understanding of anomalous liquid water properties. Yet, the characteristics of the relaxation processes taking place in high-density amorphous ice (HDA) are unknown. We here reveal that the relaxation processes in HDA at 110-135 K at 0.1-0.2 GPa are of collective and global nature, resembling the alpha relaxation in glassy material. Measured relaxation times suggest liquid-like relaxation characteristics in the vicinity of the crystallization temperature at 145 K. By carefully relaxing pressurized HDA for several hours at 135 K, we produce a state that is closer to the ideal glass state than all HDA states discussed so far in literature.

Dynamics anomaly in high-density amorphous ice between 0.7 and 1.1 GPa

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Loerting, Thomas

2016-02-01

We studied high-density amorphous ices between 0.004 and 1.6 GPa by isobaric in situ volumetry and by subsequent ex situ x-ray diffraction and differential scanning calorimetry at 1 bar. Our observations indicate two processes, namely, relaxation in the amorphous matrix and crystallization, taking place at well-separated time scales. For this reason, we are able to report rate constants of crystallization kX and glass-transition temperatures Tg in an unprecedented pressure range. Tg's agree within ±3 K with earlier work in the small pressure range where there is overlap. Both Tg and kX show a pressure anomaly between 0.7 and 1.1 GPa, namely, a kX minimum and a Tg maximum. This anomalous pressure dependence suggests a continuous phase transition from high- (HDA) to very-high-density amorphous ice (VHDA) and faster hydrogen bond dynamics in VHDA. We speculate this phenomenology can be rationalized by invoking the crossing of a Widom line between 0.7 and 1.1 GPa emanating from a low-lying HDA-VHDA critical point. Furthermore, we interpret the volumetric relaxation of the amorphous matrix to be accompanied by viscosity change to explain the findings such that the liquid state can be accessed prior to the crystallization temperature TX at <0.4 GPa and >0.8 GPa.

SURVIVAL DEPTH OF ORGANICS IN ICES UNDER LOW-ENERGY ELECTRON RADIATION ({<=}2 keV)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnett, Irene Li; Lignell, Antti; Gudipati, Murthy S., E-mail: gudipati@jpl.nasa.gov

2012-03-01

Icy surfaces in our solar system are continually modified and sputtered with electrons, ions, and photons from solar wind, cosmic rays, and local magnetospheres in the cases of Jovian and Saturnian satellites. In addition to their prevalence, electrons specifically are expected to be a principal radiolytic agent on these satellites. Among energetic particles (electrons and ions), electrons penetrate by far the deepest into the ice and could cause damage to organic material of possible prebiotic and even biological importance. To determine if organic matter could survive and be detected through remote sensing or in situ explorations on these surfaces, suchmore » as water ice-rich Europa, it is important to obtain accurate data quantifying electron-induced chemistry and damage depths of organics at varying incident electron energies. Experiments reported here address the quantification issue at lower electron energies (100 eV-2 keV) through rigorous laboratory data analysis obtained using a novel methodology. A polycyclic aromatic hydrocarbon molecule, pyrene, embedded in amorphous water ice films of controlled thicknesses served as an organic probe. UV-VIS spectroscopic measurements enabled quantitative assessment of organic matter survival depths in water ice. Eight ices of various thicknesses were studied to determine damage depths more accurately. The electron damage depths were found to be linear, approximately 110 nm keV{sup -1}, in the tested range which is noticeably higher than predictions by Monte Carlo simulations by up to 100%. We conclude that computational simulations underestimate electron damage depths in the energy region {<=}2 keV. If this trend holds at higher electron energies as well, present models utilizing radiation-induced organic chemistry in icy solar system bodies need to be revisited. For interstellar ices of a few micron thicknesses, we conclude that low-energy electrons generated through photoionization processes in the interstellar medium could penetrate through ice grains significantly and trigger organic reactions several hundred nanometers deep-bulk chemistry thus competing with surface chemistry of astrophysical ice grains.« less

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

The presence of clathrates in comet 67P/Churyumov-Gerasimenko

PubMed Central

Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A.; Lunine, Jonathan I.; Marty, Bernard; Mandt, Kathleen E.; Wurz, Peter; Rubin, Martin

2016-01-01

Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate. PMID:27152351

The presence of clathrates in comet 67P/Churyumov-Gerasimenko.

PubMed

Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A; Lunine, Jonathan I; Marty, Bernard; Mandt, Kathleen E; Wurz, Peter; Rubin, Martin

2016-04-01

Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate.

Laboratory Studies of Ethane Ice Relevant to Outer Solar System Surfaces

NASA Technical Reports Server (NTRS)

Moore, Marla H.; Hudson, Reggie; Raines, Lily

2009-01-01

Oort Cloud comets, as well as TNOs Makemake (2045 FYg), Quaoar, and Pluto, are known to contain ethane. However, even though this molecule is found on several outer Solar System objects relatively little information is available about its amorphous and crystalline phases. In new experiments, we have prepared ethane ices at temperatures applicable to the outer Solar System, and have heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry using mid-IR spectroscopy (2.2 - 16.6 microns). Included in our work is the meta-stable phase that exists at 35 - 55 K. These results, including newly obtained optical constants, are relevant to ground-based observational campaigns, the New Horizons mission, and supporting laboratory work. An improved understanding of solid-phase ethane may contribute to future searches for this and other hydrocarbons in the outer Solar System.

Kinetic boundaries and phase transformations of ice i at high pressure.

PubMed

Wang, Yu; Zhang, Huichao; Yang, Xue; Jiang, Shuqing; Goncharov, Alexander F

2018-01-28

Raman spectroscopy in diamond anvil cells has been employed to study phase boundaries and transformation kinetics of H 2 O ice at high pressures up to 16 GPa and temperatures down to 15 K. Ice i formed at nearly isobaric cooling of liquid water transforms on compression to high-density amorphous (HDA) ice at 1.1-3 GPa at 15-100 K and then crystallizes in ice vii with the frozen-in disorder (ice vii') which remains stable up to 14.1 GPa at 80 K and 15.9 GPa at 100 K. Unexpectedly, on decompression of ice vii', it transforms to ice viii in its domain of metastability, and then it relaxes into low-density amorphous (LDA) ice on a subsequent pressure release and warming up. On compression of ice i at 150-170 K, ice ix is crystallized and no HDA ice is found; further compression of ice ix results in the sequential phase transitions to stable ices vi and viii. Cooling ice i to 210 K at 0.3 GPa transforms it to a stable ice ii. Our extensive investigations provide previously missing information on the phase diagram of water, especially on the kinetic paths that result in formation of phases which otherwise are not accessible; these results are keys for understanding the phase relations including the formation of metastable phases. Our observations inform on the ice modifications that can occur naturally in planetary environments and are not accessible for direct observations.

Kinetic boundaries and phase transformations of ice i at high pressure

NASA Astrophysics Data System (ADS)

Wang, Yu; Zhang, Huichao; Yang, Xue; Jiang, Shuqing; Goncharov, Alexander F.

2018-01-01

Raman spectroscopy in diamond anvil cells has been employed to study phase boundaries and transformation kinetics of H2O ice at high pressures up to 16 GPa and temperatures down to 15 K. Ice i formed at nearly isobaric cooling of liquid water transforms on compression to high-density amorphous (HDA) ice at 1.1-3 GPa at 15-100 K and then crystallizes in ice vii with the frozen-in disorder (ice vii') which remains stable up to 14.1 GPa at 80 K and 15.9 GPa at 100 K. Unexpectedly, on decompression of ice vii', it transforms to ice viii in its domain of metastability, and then it relaxes into low-density amorphous (LDA) ice on a subsequent pressure release and warming up. On compression of ice i at 150-170 K, ice ix is crystallized and no HDA ice is found; further compression of ice ix results in the sequential phase transitions to stable ices vi and viii. Cooling ice i to 210 K at 0.3 GPa transforms it to a stable ice ii. Our extensive investigations provide previously missing information on the phase diagram of water, especially on the kinetic paths that result in formation of phases which otherwise are not accessible; these results are keys for understanding the phase relations including the formation of metastable phases. Our observations inform on the ice modifications that can occur naturally in planetary environments and are not accessible for direct observations.

Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

NASA Astrophysics Data System (ADS)

Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

2018-03-01

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Vacuum ultraviolet and infrared spectra of condensed methyl acetate on cold astrochemical dust analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivaraman, B.; Nair, B. G.; Mason, N. J.

2013-12-01

Following the recent report of the first identification of methyl acetate (CH{sub 3}COOCH{sub 3}) in the interstellar medium (ISM), we have carried out vacuum ultraviolet (VUV) and infrared (IR) spectroscopy studies on methyl acetate from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. We present the first VUV and IR spectra of methyl acetate relevant to ISM conditions. Spectral signatures clearly showed molecular reorientation to have started in the ice by annealing the amorphous ice formed at 10 K. An irreversible phase change from amorphous to crystalline methyl acetate ice was found to occur between 110more » K and 120 K.« less

Neutron diffraction study of water freezing on aircraft engine combustor soot.

PubMed

Tishkova, V; Demirdjian, B; Ferry, D; Johnson, M

2011-12-14

The study of the formation of condensation trails and cirrus clouds on aircraft emitted soot particles is important because of its possible effects on climate. In the present work we studied the freezing of water on aircraft engine combustor (AEC) soot particles under conditions of pressure and temperature similar to the upper troposphere. The microstructure of the AEC soot was found to be heterogeneous containing both primary particles of soot and metallic impurities (Fe, Cu, and Al). We also observed various surface functional groups such as oxygen-containing groups, including sulfate ions, that can act as active sites for water adsorption. Here we studied the formation of ice on the AEC soot particles by using neutron diffraction. We found that for low amount of adsorbed water, cooling even up to 215 K did not lead to the formation of hexagonal ice. Whereas, larger amount of adsorbed water led to the coexistence of liquid water (or amorphous ice) and hexagonal ice (I(h)); 60% of the adsorbed water was in the form of ice I(h) at 255 K. Annealing of the system led to the improvement of the crystal quality of hexagonal ice crystals as demonstrated from neutron diffraction.

Formation of model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Middlebrook, Ann M.; Koehler, Birgit G.; Mcneill, Laurie S.; Tolbert, Margaret A.

1992-01-01

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.

Acrylonitrile characterization and high energetic photochemistry at Titan temperatures

NASA Astrophysics Data System (ADS)

Toumi, A.; Piétri, N.; Chiavassa, T.; Couturier-Tamburelli, I.

2016-05-01

Laboratory infrared spectra of amorphous and crystalline acrylonitrile (C2H3CN) ices were recorded between 4000 and 650 cm-1. Heating up the acrylonitrile sample to 160 K shows details on the transition between amorphous and crystalline ice at ∼94 K. This molecule can be used as an indicator of the surface temperature of Titan since it is known also to be ∼94 K. The desorption energy of acrylonitrile was determined using two methods (IRTF and mass spectrometries) to be around 35 kJ mol-1. Solid phase acrylonitrile was irradiated with vacuum ultraviolet (VUV) light at low temperatures (20, 70, 95 and 130 K) using a microwave-discharge hydrogen flow lamp. Isoacrylonitrile, cyanoacetylene (HC3N), isocyanoacetylene (HC2NC), acetylene (C2H2) and hydrogen cyanide (HCN) were identified as photoproducts by using FTIR spectroscopy. The branching ratio of each pathway has been calculated for the different temperatures. We have estimated the acrylonitrile, HCN and HC3N νCtbnd N stretching band strengths to be respectively A = 3.98 ×10-18 , A = 1.38 ×10-18 and A = 2.92 ×10-18cmmolecule-1 .

The distribution, structure, and composition of freshwater ice deposits in Bolivian salt lakes

USGS Publications Warehouse

Hurlbert, S.H.; Chang, Cecily C.Y.

1988-01-01

Freshwater ice deposits are described from seven, high elevation (4117-4730 m), shallow (mean depth <30 cm), saline (10-103 g l-1) lakes in the southwestern corner of Bolivia. The ice deposits range to several hundred meters in length and to 7 m in height above the lake or playa surface. They are located near the lake or salar margins; some are completely surrounded by water, others by playa deposits or salt crusts. Upper surfaces and sides of the ice deposits usually are covered by 20-40 cm of white to light brown, dry sedimentary materials. Calcite is the dominant crystalline mineral in these, and amorphous materials such as diatom frustules and volcanic glass are also often abundant. Beneath the dry overburden the ice occurs primarily as horizontal lenses 1-1000 mm thick, irregularly alternating with strata of frozen sedimentary materials. Ice represents from 10 to 87% of the volume of the deposits and yields freshwater (TFR <3 g l-1) when melted. Oxygen isotope ratios for ice are similar to those for regional precipitation and shoreline seeps but much lower than those for the lakewaters. Geothermal flux is high in the region as evidenced by numerous hot springs and deep (3.0-3.5 m) sediment temperatures of 5-10??C. This flux is one cause of the present gradual wasting away of these deposits. Mean annual air temperatures for the different lakes probably are all in the range of -2 to 4??C, and mean midwinter temperatures about 5??C lower. These deposits apparently formed during colder climatic conditions by the freezing of low salinity porewaters and the building up of segregation ice lenses. ?? 1988 Dr W. Junk Publishers.

Infrared Spectra and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Anderson, Carrie; Ferrante, Robert F.; Moore, W. James; Hudson, Reggie; Moore, Marla H.

2011-01-01

Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

Heating of Porous Icy Dust Aggregates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirono, Sin-iti

At the beginning of planetary formation, highly porous dust aggregates are formed through coagulation of dust grains. Outside the snowline, the main component of an aggregate is H{sub 2}O ice. Because H{sub 2}O ice is formed in amorphous form, its thermal conductivity is extremely small. Therefore, the thermal conductivity of an icy dust aggregate is low. There is a possibility of heating inside an aggregate owing to the decay of radionuclides. It is shown that the temperature increases substantially inside an aggregate, leading to crystallization of amorphous ice. During the crystallization, the temperature further increases sufficiently to continue sintering. Themore » mechanical properties of icy dust aggregates change, and the collisional evolution of dust aggregates is affected by the sintering.« less

Superheating of monolayer ice in graphene nanocapillaries

NASA Astrophysics Data System (ADS)

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-04-01

The freezing and melting of low-dimensional materials, either via a first-order phase transition or without any discontinuity in thermodynamic, still remain a matter of debate. Melting (superheating) in two-dimensional (2D) ice is fundamentally different from that in bulk counterpart. Here, we perform comprehensive molecular dynamics simulations of the superheating of monolayer ice in graphene nanocapillaries to understand the nature of melting transition in 2D water/ice. We find four different superheating (melting) scenarios can happen in the superheating of monolayer square-like ice, which are closely related to the lateral pressure and the channel width. The anomalous two-stage melting transition with arisen coexistence phase is found, which reveals the unknown extraordinary characteristics of melting in 2D water/ice. Under ultrahigh lateral pressure, the intermediate monolayer triangular amorphous ice will be formed during the superheating of monolayer square-like ice with both continuous-like and first-order phase transitions. Whereas, under low lateral pressure, the melting in monolayer square-like ice manifests typical discontinuity with notable hysteresis-loop in potential energy during the heating/cooling process. Moreover, we also find that highly puckered monolayer square-like ice can transform into bilayer AB-stacked amorphous ice with square pattern in the superheating process. The superheating behavior under high lateral pressure can be partly regarded as the compression limit of superheated monolayer water. The intrinsic phenomena in our simulated superheating of monolayer ice may be significant for understanding the melting behavior in 2D water/ice.

Superheating of monolayer ice in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-04-07

The freezing and melting of low-dimensional materials, either via a first-order phase transition or without any discontinuity in thermodynamic, still remain a matter of debate. Melting (superheating) in two-dimensional (2D) ice is fundamentally different from that in bulk counterpart. Here, we perform comprehensive molecular dynamics simulations of the superheating of monolayer ice in graphene nanocapillaries to understand the nature of melting transition in 2D water/ice. We find four different superheating (melting) scenarios can happen in the superheating of monolayer square-like ice, which are closely related to the lateral pressure and the channel width. The anomalous two-stage melting transition with arisen coexistence phase is found, which reveals the unknown extraordinary characteristics of melting in 2D water/ice. Under ultrahigh lateral pressure, the intermediate monolayer triangular amorphous ice will be formed during the superheating of monolayer square-like ice with both continuous-like and first-order phase transitions. Whereas, under low lateral pressure, the melting in monolayer square-like ice manifests typical discontinuity with notable hysteresis-loop in potential energy during the heating/cooling process. Moreover, we also find that highly puckered monolayer square-like ice can transform into bilayer AB-stacked amorphous ice with square pattern in the superheating process. The superheating behavior under high lateral pressure can be partly regarded as the compression limit of superheated monolayer water. The intrinsic phenomena in our simulated superheating of monolayer ice may be significant for understanding the melting behavior in 2D water/ice.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shephard, Jacob J.; Vickers, Martin; Salzmann, Christoph G., E-mail: c.salzmann@ucl.ac.uk

Low-density amorphous (LDA) ice is involved in critical cosmological processes and has gained prominence as one of the at least two distinct amorphous forms of ice. Despite these accolades, we still have an incomplete understanding of the structural diversity that is encompassed within the LDA state and the dynamic processes that take place upon heating LDA. Heating the high-pressure ice VIII phase at ambient pressure is a remarkable example of temperature-induced amorphisation yielding LDA. We investigate this process in detail using X-ray diffraction and Raman spectroscopy and show that the LDA obtained from ice VIII is structurally different from themore » more “traditional” states of LDA which are approached upon thermal annealing. This new structural relaxation pathway involves an increase of structural order on the intermediate range length scale. In contrast with other LDA materials the local structure is more ordered initially and becomes slightly more disordered upon annealing. We also show that the cascade of phase transitions upon heating ice VIII at ambient pressure includes the formation of ice IX which may be connected with the structural peculiarities of LDA from ice VIII. Overall, this study shows that LDA is a structurally more diverse material than previously appreciated.« less

Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

2016-05-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -39.0 and -37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

Activation of weak IR fundamentals of two species of astrochemical interest in the T(d) point group--the importance of amorphous ices.

PubMed

Hudson, R L; Gerakines, P A; Loeffler, M J

2015-05-21

New measurements are reported on the weak ν1 and ν2 fundamentals of frozen CH4, a solid of considerable astrochemical interest. Infrared spectra in the ν1 and ν2 regions are presented for three CH4-ice phases at 10-30 K with new absorption coefficients and band strengths to quantify the results. In contrast to the situation with the two crystalline phases of CH4, both ν1 and ν2 were seen clearly in methane's amorphous phase. To support our CH4 work, we also present new results for NH4SH, a component of Jupiter's atmosphere, showing that the ν2 vibration of NH4(+) undergoes a dramatic loss of intensity during an amorphous-to-crystalline phase transition, but is regenerated in equally-dramatic fashion by radiation-induced amorphization of the sample. Results are compared to work recently published in this journal and elsewhere.

Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

NASA Technical Reports Server (NTRS)

Blake, D. F.; Allamandola, L. J.; Sandford, S.; Hudgins, D.; Freund, F.

1991-01-01

In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.

Spectroscopy from Space

NASA Astrophysics Data System (ADS)

Clark, R. N.; Swayze, G. A.; Carlson, R.; Grundy, W.; Noll, K.

2014-01-01

This chapter reviews detection of materials on solid and liquid (lakes and ocean) surfaces in the solar system using ultraviolet to infrared spectroscopy from space, or near space (high altitude aircraft on the Earth), or in the case of remote objects, earth-based and earth-orbiting telescopes. Point spectrometers and imaging spectrometers have been probing the surfaces of our solar system for decades. Spacecraft carrying imaging spectrometers are currently in orbit around Mercury, Venus, Earth, Mars, and Saturn, and systems have recently visited Jupiter, comets, asteroids, and one spectrometer-carrying spacecraft is on its way to Pluto. Together these systems are providing a wealth of data that will enable a better understanding of the composition of condensed matter bodies in the solar system. Minerals, ices, liquids, and other materials have been detected and mapped on the Earth and all planets and/or their satellites where the surface can be observed from space, with the exception of Venus whose thick atmosphere limits surface observation. Basaltic minerals (e.g., pyroxene and olivine) have been detected with spectroscopy on the Earth, Moon, Mars and some asteroids. The greatest mineralogic diversity seen from space is observed on the Earth and Mars. The Earth, with oceans, active tectonic and hydrologic cycles, and biological processes, displays the greatest material diversity including the detection of amorphous and crystalline inorganic materials, organic compounds, water and water ice. Water ice is a very common mineral throughout the Solar System and has been unambiguously detected or inferred in every planet and/or their moon(s) where good spectroscopic data has been obtained. In addition to water ice, other molecular solids have been observed in the solar system using spectroscopic methods. Solid carbon dioxide is found on all systems beyond the Earth except Pluto, although CO2 sometimes appears to be trapped in other solids rather than as an ice on some objects. The largest deposits of carbon dioxide ice are found on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn's moon Titan probably has the most complex active extra-terrestrial surface chemistry involving organic compounds. Some of the observed or inferred compounds include ices of benzene (C6H6), cyanoacetylene (HC3N), toluene (C7H8), cyanogen (C2N2), acetonitrile (CH3CN), water (H2O), carbon dioxide (CO2), and ammonia (NH3). Confirming compounds on Titan is hampered by its thick smoggy atmosphere, where in relative terms the atmospheric interferences that hamper surface characterization lie between that of Venus and Earth. In this chapter we exclude discussion of the planets Jupiter, Saturn, Uranus, and Neptune because their thick atmospheres preclude observing the surface, even if surfaces exist. However, we do discuss spectroscopic observations on a number of the extra-terrestrial satellite bodies. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with possible exceptions on Charon and possible trace amounts on some of the Saturnian satellites. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces from spectroscopy. Only two asteroids have had a direct detection of surface water ice, although its presence can be inferred in others.

Jovian magnetospheric weathering of Europa's nonice surface material

NASA Astrophysics Data System (ADS)

Hibbitts, Charles A.; Paranicas, Christopher; Blaney, Diana L.; Murchie, Scott; Seelos, Frank

2016-10-01

Jovian plasma and energetic charged particles bombard the Galilean satellites. These satellites vary from volcanically active (Io) to a nearly primordial surface (Callisto). These satellites are imbedded in a harsh and complex particle radiation environment that weathers their surfaces, and thus are virtual laboratories for understanding how particle bombardment alters the surfaces of airless bodies. Europa orbits deeply in the Jovian radiation belts and may have an active surface, where space weathering and geologic processes can interact in complex ways with a range of timescales. At Europa's surface temperature of 80K to 130K, the hydrated nonice material and to a lesser extent, water ice, will be thermally stable over geologic times and will exhibit the effects of weathering. The ice on the surface of Europa is amorphous and contains trace products such as H2O2 [1] due to weathering. The nonice material, which likely has an endogenic component [2] may also be partially amorphous and chemically altered as a result of being weathered by electrons, Iogenic sulfur, or other agents [3]. This hydrated salt or frozen brine likely compositionally 'matures' over time as the more weakly bound constituents are preferentially removed compared with Ca and Mg [4]. Electron bombardment induces chemical reactions through deposition of energy (e.g., ionizations) possibly explaining some of the nonice material's redness [5,6]. Concurrently, micrometeroid gardening mixes the upper surface burying weathered and altered material while exposing both fresh material and previous altered material, potentially with astrobiological implications. Our investigation of the spectral alteration of nonice analog materials irradiated by 10s keV electrons demonstrates the prevalence of this alteration and we discuss relevance to potential measurements by the Europa MISE instrument.References: [1] Moore, M. and R. Hudson, (2000), Icarus, 145, 282-288; [2] McCord et al., (1998), Science, 280, 1242; [3] Carlson et al., (2002), Icarus, 157, 456-463; [4] McCord et al., (2001), JGR, 106, E2, 3311-3319; [5] Hand, K. and R. Carlson, (2015), GRL, 10.1002/2015GRL063559. [6] Hibbitts, C.A. and Paranicas, C., ACS conference, Aug., 2016.

X-Ray Absorption Spectra of Amorphous Ices from GW Quasiparticle Calculation

NASA Astrophysics Data System (ADS)

Kong, Lingzhu; Car, Roberto

2013-03-01

We use a GW approach[2] to compute the x-ray absorption spectra of model low- and high-density amorphous ice structures(LDA and HDA)[3]. We include the structural effects of quantum zero point motion using colored-noise Langevin molecular dynamics[4]. The calculated spectra differences in the main and post edge region between LDA and HDA agree well with experimental observations. We attribute these differences to the presence of interstitial molecules within the first coordination shell range in HDA. This assignment is further supported by a calculation of the spectrum of ice VIII, a high-pressure structure that maximizes the number of interstitial molecules and, accordingly, shows a much weaker post-edge feature. We further rationalize the spectral similarity between HDA and liquid water, and between LDA and ice Ih in terms of the respective similarities in the H-bond network topology and bond angle distributions. Supported by grants DOE-DE-SC0005180, DOE DE-SC0008626 and NSF-CHE-0956500.

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

PubMed Central

Kim, Chae Un; Tate, Mark W.; Gruner, Sol M.

2015-01-01

Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water. PMID:26351671

Compression Freezing Kinetics of Water to Ice VII

DOE PAGES

Gleason, A. E.; Bolme, C. A.; Galtier, E.; ...

2017-07-11

Time-resolved x-ray diffraction (XRD) of compressed liquid water shows transformation to ice VII in 6 nsec, revealing crystallization rather than amorphous solidification during compression freezing. Application of classical nucleation theory indicates heterogeneous nucleation and one-dimensional (e.g., needlelike) growth. In conclusion, these first XRD data demonstrate rapid growth kinetics of ice VII with implications for fundamental physics of diffusion-mediated crystallization and thermodynamic modeling of collision or impact events on ice-rich planetary bodies.

Compression Freezing Kinetics of Water to Ice VII

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gleason, A. E.; Bolme, C. A.; Galtier, E.

Time-resolved x-ray diffraction (XRD) of compressed liquid water shows transformation to ice VII in 6 nsec, revealing crystallization rather than amorphous solidification during compression freezing. Application of classical nucleation theory indicates heterogeneous nucleation and one-dimensional (e.g., needlelike) growth. In conclusion, these first XRD data demonstrate rapid growth kinetics of ice VII with implications for fundamental physics of diffusion-mediated crystallization and thermodynamic modeling of collision or impact events on ice-rich planetary bodies.

Potential Energy Landscape of the Liquid-Liquid Phase Transition in Water and the transformation between Low-Density and High-Density Amorphous Ice

NASA Astrophysics Data System (ADS)

Giovambattista, N.; Sciortino, F.; Starr, F. W.; Poole, P. H.

The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics for describing supercooled liquids and glasses. We use the PEL formalism and computer simulations to study the transformation between low-density (LDL) and high-density liquid (HDL) water, and between low-density (LDA) and high-density amorphous ice (HDA). We employ the ST2 water model that exhibits a LDL-HDL first-order phase transition and a sharp LDA-HDA transformation, as observed in experiments. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that LDL configurations are located in the same megabasin as LDA, and that HDL configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid and the amorphous ice differ. We also study the liquid-to-ice-VII first-order phase transition. The PEL properties across this transition are qualitatively similar to the changes found during the LDA-HDA transformation, supporting the interpretation that the LDA-HDA transformation is a first-order-like phase transition between out-of-equilibrium states.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model

NASA Astrophysics Data System (ADS)

Engstler, Justin; Giovambattista, Nicolas

2017-08-01

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (Ih), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice Ih and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice Ih occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and Ih-to-HDA transformations.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model.

PubMed

Engstler, Justin; Giovambattista, Nicolas

2017-08-21

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (I h ), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice I h and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice I h occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and I h -to-HDA transformations.

Polarized Raman spectroscopic study of relaxed high density amorphous ices under pressure.

PubMed

Suzuki, Yoshiharu; Tominaga, Yasunori

2010-10-28

We have made high density amorphous ice (HDA) by the pressure-induced amorphization of hexagonal ice at 77 K and measured the volume change on isobaric heating in a pressure range between 0.1 and 1.5 GPa. The volume of HDA on heating below ∼0.35 GPa increases, while the volume of HDA on heating above ∼0.35 GPa decreases. The polarized OH-stretching Raman spectra of the relaxed HDAs are compared with that of the unannealed HDA. The relaxed HDAs are prepared at 0.2 GPa at 130 K and 1.5 GPa at 160 K. It is found that the relatively strong totally symmetric OH-stretching vibration mode around 3100 cm(-1) exists in the depolarized reduced Raman spectrum χ(VH)(") of the unannealed HDA and that its intensity rapidly decreases by relaxation. The χ(VH)(") profiles of the relaxed HDA are similar to those of liquid water. These results indicate that the HDA reaches a nearly equilibrium state by annealing and the intrinsic state of HDA relates to a liquid state. The pressure-volume curve of the relaxed HDA at 140 K seems to be smooth in the pressure range below 1.5 GPa.

Formation and decomposition of CO2-filled ice.

PubMed

Massani, B; Mitterdorfer, C; Loerting, T

2017-10-07

Recently it was shown that CO 2 -filled ice is formed upon compression of CO 2 -clathrate hydrate. Here we show two alternative routes of its formation, namely, by decompression of CO 2 /ice VI mixtures at 250 K and by isobaric heating of CO 2 /high-density amorphous ice mixtures at 0.5-1.0 GPa above 200 K. Furthermore, we show that filled ice may either transform into the clathrate at an elevated pressure or decompose to "empty" hexagonal ice at ambient pressure and low temperature. This complements the literature studies in which decomposition to ice VI was favoured at high pressures and low temperatures.

Formation and decomposition of CO2-filled ice

NASA Astrophysics Data System (ADS)

Massani, B.; Mitterdorfer, C.; Loerting, T.

2017-10-01

Recently it was shown that CO2-filled ice is formed upon compression of CO2-clathrate hydrate. Here we show two alternative routes of its formation, namely, by decompression of CO2/ice VI mixtures at 250 K and by isobaric heating of CO2/high-density amorphous ice mixtures at 0.5-1.0 GPa above 200 K. Furthermore, we show that filled ice may either transform into the clathrate at an elevated pressure or decompose to "empty" hexagonal ice at ambient pressure and low temperature. This complements the literature studies in which decomposition to ice VI was favoured at high pressures and low temperatures.

Sticking of Molecules on Nonporous Amorphous Water Ice

NASA Astrophysics Data System (ADS)

He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

2016-05-01

Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King-Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas-grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

STICKING OF MOLECULES ON NONPOROUS AMORPHOUS WATER ICE

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Vidali, Gianfranco; Acharyya, Kinsuk, E-mail: gvidali@syr.edu

2016-05-20

Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H{sub 2}, D{sub 2}, N{sub 2}, O{sub 2}, CO, CH{sub 4}, and CO{sub 2} on nonporous amorphous solid water. The sticking coefficient was measured over a widemore » range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.« less

Small-angle neutron scattering study of micropore collapse in amorphous solid water.

PubMed

Mitterdorfer, Christian; Bauer, Marion; Youngs, Tristan G A; Bowron, Daniel T; Hill, Catherine R; Fraser, Helen J; Finney, John L; Loerting, Thomas

2014-08-14

Vapor-deposited amorphous solid water (ASW) is the most abundant solid molecular material in space, where it plays a direct role in both the formation of more complex chemical species and the aggregation of icy materials in the earliest stages of planet formation. Nevertheless, some of its low temperature physics such as the collapse of the micropore network upon heating are still far from being understood. Here we characterize the nature of the micropores and their collapse using neutron scattering of gram-quantities of D2O-ASW of internal surface areas up to 230 ± 10 m(2) g(-1) prepared at 77 K. The model-free interpretation of the small-angle scattering data suggests micropores, which remain stable up to 120-140 K and then experience a sudden collapse. The exact onset temperature to pore collapse depends on the type of flow conditions employed in the preparation of ASW and, thus, the specific surface area of the initial deposit, whereas the onset of crystallization to cubic ice is unaffected by the flow conditions. Analysis of the small-angle neutron scattering signal using the Guinier-Porod model suggests that a sudden transition from three-dimensional cylindrical pores with 15 Å radius of gyration to two-dimensional lamellae is the mechanism underlying the pore collapse. The rather high temperature of about 120-140 K of micropore collapse and the 3D-to-2D type of the transition unraveled in this study have implications for our understanding of the processing and evolution of ices in various astrophysical environments.

Theoretical models for ice mixtures in outer solar system bodies

NASA Astrophysics Data System (ADS)

Escribano, R. M.; Gómez, P. C.; Molpeceres, G.; Timón, V.; Moreno, M. A.; Maté, B.

2016-12-01

In a recent work [1], we have measured the optical constants and band strengths of methane/ethane ice mixtures in the near- and mid-infrared ranges. We present here recent calculations on models for these and other ice mixtures containing water. Methane and ethane are constituents of planetary ices in our solar system. Methane has been detected in outer solar system bodies like Titan, Pluto, Charon, Triton, or other TNO's [2]. Ethane has also been identified in some of those objects [2]. The motivation of this work has been to provide new laboratory data and theoretical models that may contribute to the understanding of those systems, in the new era of TNO's knowledge opened up by the New Horizons mission [3,4]. The models are designed to cover a range of mixtures of molecular species that match the composition and density of some of the systems in outer solar systems bodies. The calculations include several steps: first, amorphous samples are generated, via a Metropolis Montecarlo procedure (see Figure, left); next, the amorphous structures are relaxed to reach a minimum in the potential energy surface; at this point, the harmonic vibrational spectrum is predicted. Finally, the relaxed structures are processed by ab initio molecular dynamics simulations with the final aim of obtaining an anharmonic prediction of the spectra, which includes the near-infrared region (see Figure, right). Both the harmonic and anharmonic spectra are compared to experimental measurements in the mid- and near-infrared regions. All calculations are carried out by means of Materials Studio software, using the Density Functional Theory method, with GGA-PBE functionals and Grimme D2 dispersion correction. Acknowledgements This research has been supported by the Spanish MINECO, Projects FIS2013-48087-C2-1-P. G.M. acknowledges MINECO PhD grant BES-2014-069355. We are grateful to V. J. Herrero and I. Tanarro for discussions. References [1] G. Molpeceres et al., Astrophys. J, accepted (2016). [2] D.P. Cruikshank et al., Icarus, 246, 82-92, 2015. [3] A. Stern et al., Science, 350, 260-292, 2015. [4] W.M. Grundy et al. Science, 351, 1283, 2016. Figure caption Left: Representation of an amorphous mixture with 1 methane and 3 water molecules; right: spectra predicted in the near-IR from a molecular dynamics calculation.

Structure and Evolution of Kuiper Belt Objects and Dwarf Planets

NASA Astrophysics Data System (ADS)

McKinnon, W. B.; Prialnik, D.; Stern, S. A.; Coradini, A.

Kuiper belt objects (KBOs) accreted from a mélange of volatile ices, carbonaceous matter, and rock of mixed interstellar and solar nebular provenance. The transneptunian region, where this accretion took place, was likely more radially compact than today. This and the influence of gas drag during the solar nebula epoch argue for more rapid KBO accretion than usually considered. Early evolution of KBOs was largely the result of heating due to radioactive decay, the most important potential source being 26Al, whereas long-term evolution of large bodies is controlled by the decay of U, Th, and 40K. Several studies are reviewed dealing with the evolution of KBO models, calculated by means of one-dimensional numerical codes that solve the heat and mass balance equations. It is shown that, depending on parameters (principally rock content and porous conductivity), KBO interiors may have reached relatively high temperatures. The models suggest that KBOs likely lost ices of very volatile species during early evolution, whereas ices of less-volatile species should be retained in cold, less-altered subsurface layers. Initially amorphous ice may have crystallized in KBO interiors, releasing volatiles trapped in the amorphous ice, and some objects may have lost part of these volatiles as well. Generally, the outer layers are far less affected by internal evolution than the inner part, which in the absence of other effects (such as collisions) predicts a stratified composition and altered porosity distribution. Kuiper belt objects are thus unlikely to be "the most pristine objects in the solar system," but they do contain key information as to how the early solar system accreted and dynamically evolved. For large (dwarf planet) KBOs, long-term radiogenic heating alone may lead to differentiated structures -- rock cores, ice mantles, volatile-ice-rich "crusts," and even oceans. Persistence of oceans and (potential) volcanism to the present day depends strongly on body size and the melting-point depression afforded by the presence of salts, ammonia, etc. (we review the case for Charon in particular). The surface color and compositional classes of KBOs are usually discussed in terms of "nature vs. nurture," i.e., a generic primordial composition vs. surface processing, but the true nature of KBOs also depends on how they have evolved. The broad range of albedos now found in the Kuiper belt, deep water-ice absorptions on some objects, evidence for differentiation of Pluto and 2003 EL61, and a range of densities incompatible with a single, primordial composition and variable porosity strongly imply significant, intrinsic compositional differences among KBOs. The interplay of formation zone (accretion rate), body size, and dynamical (collisional) history may yield KBO compositional classes (and their spectral correlates) that recall the different classes of asteroids in the inner solar system, but whose members are broadly distributed among the KBO dynamical subpopulations.

Fast surface crystallization of amorphous griseofulvin below T g.

PubMed

Zhu, Lei; Jona, Janan; Nagapudi, Karthik; Wu, Tian

2010-08-01

To study crystal growth rates of amorphous griseofulvin (GSF) below its glass transition temperature (T (g)) and the effect of surface crystallization on the overall crystallization kinetics of amorphous GSF. Amorphous GSF was generated by melt quenching. Surface and bulk crystal growth rates were determined using polarized light microscope. X-ray powder diffraction (XRPD) and Raman microscopy were used to identify the polymorph of the crystals. Crystallization kinetics of amorphous GSF powder stored at 40 degrees C (T (g)-48 degrees C) and room temperature (T (g)-66 degrees C) was monitored using XRPD. Crystal growth at the surface of amorphous GSF is 10- to 100-fold faster than that in the bulk. The surface crystal growth can be suppressed by an ultrathin gold coating. Below T (g), the crystallization of amorphous GSF powder was biphasic with a rapid initial crystallization stage dominated by the surface crystallization and a slow or suspended late stage controlled by the bulk crystallization. GSF exhibits the fastest surface crystallization kinetics among the known amorphous pharmaceutical solids. Well below T (g), surface crystallization dominated the overall crystallization kinetics of amorphous GSF powder. Thus, surface crystallization should be distinguished from bulk crystallization in studying, modeling and controlling the crystallization of amorphous solids.

Infrared Spectra and Optical Constants of Astronomical Ices: I. Amorphous and Crystalline Acetylene

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Ferrante, R. F.; Moore, M. H.

2013-01-01

Here we report recent measurements on acetylene (C2H2) ices at temperatures applicable to the outer Solar System and the interstellar medium. New near- and mid-infrared data, including optical constants (n, k), absorption coefficients (alpha), and absolute band strengths (A), are presented for both amorphous and crystalline phases of C2H2 that exist below 70 K. Comparisons are made to earlier work. Electronic versions of the data are made available, as is a computer routine to use our reported n and k values to simulate the observed IR spectra. Suggestions are given for the use of the data and a comparison to a spectrum of Makemake is made.

Search for the First-Order Liquid-to-Liquid Phase Transition in Low-Temperature Confined Water by Neutron Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I

2013-01-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaricmore » temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the alpha-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.« less

Search for the first-order liquid-to-liquid phase transition in low-temperature confined water by neutron scattering

NASA Astrophysics Data System (ADS)

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I.; Zhang, Yang; Liu, Kao-Hsiang

2013-02-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaric temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the α-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.

Trapping of Methanol, Hydrogen Cyanide, and n-Hexane in Water Ice, above Its Transformation Temperature to the Crystalline Form

NASA Astrophysics Data System (ADS)

Notesco, G.; Bar-Nun, A.

1997-04-01

HCN and n-C 6H 14were found experimentally to be trapped in water ice, when codeposited with water vapor on a cold plate, at 140 K and CH 3OH even at 160 K. At these temperatures at least part of the water ice is cystalline. These three gases have relatively high sublimation temperatures, whereas the gases studied earlier, Ar, Kr, Xe, CO, CH 4, and N 2, which have lower sublimination temperatures, are trapped only in amorphous water ice, up to ˜100 K. It seems that the major factor determining the efficiency of gas trapping by water ice, during codeposition of a gas-water vapor mixture on a cold plate, is the sublimation temperatures of the gases to be trapped. Those with a high sublimation temperature remain, during codeposition, longer in the pores of the water ice which are open to the surface, until they are covered by additional ice layers. Only methanol seems to form a clathrate hydrate, in agreement with the experimental results of D. Blake et al.(1991), Science254, 548-551), which points to the importance of the interaction of the gas molecules with the water molecules in the ice. Consequently, comets and icy satellites that were formed in the Jupiter-Saturn region and their subnebulae could trap CH 3OH, HCN, and heavy hydrocarbons, whereas comets and icy satellites that were formed in the Uranus-Neptune region, at the outskirts of the Saturnian subnebulae (Titan), and beyond the planets in the Kuiper belt could trap also gases having lower sublimation temperatures.

The Search for Pluto Water

NASA Astrophysics Data System (ADS)

Cook, Jason C.; Cruikshank, Dale P.; Dalle Ore, Cristina M.; Ennico, Kimberly; Grundy, William M.; Olkin, Cathy B.; Protopapa, Silvia; Stern, S. Alan; Weaver, Harold A.; Young, Leslie A.

2015-11-01

On July 14, 2015, the New Horizons spacecraft made its closest approach to Pluto at about ~12,000 km from Pluto's surface. The LEISA (Linear Etalon Imaging Spectral Array) component of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Sci. Rev. 140, 129) obtained spatially resolved near infrared spectra at scales as small as 3 km/pix. LEISA covers the wavelength range 1.25 to 2.5 μm at a spectral resolution (λ/Δλ) of 240, and the 2.1 to 2.25 μm range at a resolution of 560. The observations from this instrument are being used to map the distribution of Pluto's known ices such as N2, CH4, CO and C2H6 as well as search for H2O-ice. To date, H2O-ice has evaded detection from Earth bound observatories. Observations based on LORRI, the LOng Range Reconnaissance Imager, suggest H2O-ice is a major component of several mountain ranges around the western perimeter of the landmass informally named Tombaugh Regio. If true, H2O-ice may be found in small isolated regions around Pluto. We will present our analysis of all LESIA data of Pluto in hand to search for and understand the distribution of H2O-ice. If found, we will also discuss limits on crystalline vs. amorphous H2O-ice and temperature measurements based on the 1.65 µm crystalline H2O-ice feature. This work was supported by NASA's New Horizons project.

Mid- and far-infrared spectroscopic studies of the influence of temperature, ultraviolet photolysis and ion irradiation on cosmic-type ices.

PubMed

Moore, M H; Hudson, R L; Gerakines, P A

2001-03-15

Infrared (IR) studies of laboratory ices can provide information on the evolution of cosmic-type ices as a function of different simulated space environments involving thermal, ultraviolet (UV), or ion processing. Laboratory radiation experiments can lead to the formation of complex organic molecules. However, because of our lack of knowledge about UV photon and ion fluxes, and exposure lifetimes, it is not certain how well our simulations represent space conditions. Appropriate laboratory experiments are also limited by the absence of knowledge about the composition, density, and temperature of ices in different regions of space. Our current understanding of expected doses due to UV photons and cosmic rays is summarized here, along with an inventory of condensed-phase molecules identified on outer solar system surfaces, comets and interstellar grains. Far-IR spectra of thermally cycled H2O are discussed since these results reflect the dramatic difference between the amorphous and crystalline phases of H2O ice, the most dominant condensed-phase molecule in cosmic ices. A comparison of mid-IR spectra of products in proton-irradiated and UV-photolyzed ices shows that few differences are observed for these two forms of processing for the simple binary mixtures studied to date. IR identification of radiation products and experiments to determine production rates of new molecules in ices during processing are discussed. A new technique for measuring intrinsic IR band strengths of several unstable molecules is presented. An example of our laboratory results applied to Europa observations is included.

Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice.

PubMed

Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W; Poole, Peter H

2016-12-14

The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W.; Poole, Peter H.

2016-12-01

The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

Molecular dynamics simulations of energy dissipation and non-thermal diffusion on amorphous solid water.

PubMed

Fredon, A; Cuppen, H M

2018-02-21

Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. Especially, saturated, hydrogen-rich molecules are formed through surface chemistry where the interstellar grains act as a meeting place and absorbing energy. Here we present the results of thousands of molecular dynamics simulations to quantify the outcome of an energy dissipation process. Admolecules on top of an amorphous solid water surface have been given translational energy between 0.5 and 5 eV. Three different surface species are considered, CO 2 , H 2 O and CH 4 , spanning a range in binding energies, number of internal degrees of freedom and molecular weight. The results are compared against a previous study using a crystalline water ice surface. Possible outcomes of a dissipation process are adsorption - possibly after long-range diffusion-, desorption and desorption of a surface molecule. The three admolecules were found to bind at different locations on the surface, particularly in terms of height. Water preferably binds on top of the surface, whereas methane fills the nanopores on the surface. This has direct consequences for desorption, travelled distance, and kick-out probabilities. The admolecules are found to frequently travel several tens of angstroms before stabilizing on a binding site, allowing follow-up reactions en route. We present kick-out probabilities and we have been able to quantify the desorption probability which depends on the binding energy of the species, the translational excitation, and a factor that accounts for difference in binding site height. We provide expressions that can be incorporated in astrochemical models to predict grain surface formation and return into the gas phase of these products.

Ethane Ices in the Outer Solar System: Spectroscopy and Chemistry

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Moore, M. H.; Raines, L. L.

2009-01-01

We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons

Ethane Ices in the Outer Solar System: Spectroscopy and Chemistry

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Moore, M. H.; Raines, L. L.

2009-01-01

We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons,

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices.

PubMed

Kofman, V; Witlox, M J A; Bouwman, J; Ten Kate, I L; Linnartz, H

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools-UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry-can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, n λ , of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices

NASA Astrophysics Data System (ADS)

Kofman, V.; Witlox, M. J. A.; Bouwman, J.; ten Kate, I. L.; Linnartz, H.

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools—UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry—can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, nλ, of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization.

PubMed

Salim, Michael A; Willow, Soohaeng Yoo; Hirata, So

2016-05-28

Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D2O ice greater than that of H2O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born-Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of acoustic phonons is observed starting around 2 GPa. They constitute a computational detection of a mechanical instability in ice Ih and the resulting pressure-induced amorphization to HDA.

Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization

NASA Astrophysics Data System (ADS)

Salim, Michael A.; Willow, Soohaeng Yoo; Hirata, So

2016-05-01

Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D2O ice greater than that of H2O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born-Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of acoustic phonons is observed starting around 2 GPa. They constitute a computational detection of a mechanical instability in ice Ih and the resulting pressure-induced amorphization to HDA.

Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salim, Michael A.; Willow, Soohaeng Yoo; Hirata, So, E-mail: sohirata@illinois.edu

Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D{sub 2}O ice greater than that of H{sub 2}O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials ismore » taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born–Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of acoustic phonons is observed starting around 2 GPa. They constitute a computational detection of a mechanical instability in ice Ih and the resulting pressure-induced amorphization to HDA.« less

Pressure-induced transformations in amorphous silicon: A computational study

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2014-02-01

We study the transformations between amorphous phases of Si through molecular simulations using the environment dependent interatomic potential (EDIP) for Si. Our results show that upon pressure, the material undergoes a transformation from the low density amorphous (LDA) Si to the high density amorphous (HDA) Si. This transformation can be reversed by decompressing the material. This process, however, exhibits clear hysteresis, suggesting that the transformation LDA ↔ HDA is first-order like. The HDA phase is predominantly five-fold coordinated, whereas the LDA phase is the normal tetrahedrally bonded amorphous Si. The HDA phase at 400 K and 20 GPa was submitted to an isobaric annealing up to 800 K, resulting in a denser amorphous phase, which is structurally distinct from the HDA phase. Our results also show that the atomic volume and structure of this new amorphous phase are identical to those of the glass obtained by an isobaric quenching of the liquid in equilibrium at 2000 K and 20 GPa down to 400 K. The similarities between our results and those for amorphous ices suggest that this new phase is the very high density amorphous Si.

Temperature, grain size, and CO2-clathrate hydrates maps of Enceladus and Dione

NASA Astrophysics Data System (ADS)

Taffin, C.; Combe, J.; Grasset, O.; Le Menn, E.; McCord, T. B.; Bollengier, O.; Oancea, A.; Giraud, M.; Tobie, G.

2011-12-01

Reflectance spectra of water ice have absorption bands at 1.30 and 1.50 μm that depend on temperature and grain size. Band shape measurements can be used to characterize the surface properties of icy celestial bodies1,2,3. Moreover, CO2-clathrates have a diagnostic and unique absorption band at 2.7 μm. Mapping of these properties and components of the surface can be used to better constrain the internal activity and surface tectonics. We present an analysis of the 1.30 and 1.50 μm water ice absorption bands and the 2.7-μm CO2-clathrates absorption band in reflectance spectra from VIMS on Cassini in order to understand the geological history of the South Pole of Enceladus and an equatorial area of Dione. We have synthesized samples of pure ice Ih grains and acquired reflectance spectra between 1 and 5 μm with a Nicolet Fourier Transform spectrometer to investigate the characteristics of near-IR spectra using temperature and pressure ranges relevant for the icy satellites of Saturn. Forty-seven spectra of crystalline water ice have been acquired. We have derived two empirical laws to calculate temperature and grain size from pure crystalline water ice spectrum4. We have also synthesized samples of CO2-clathrates and acquired reflectance spectra for the band. These two spectra have been used as end-member. A linear sum is computed using the end-member spectra: [CRF×(clathrate)+(1-CRF)×(pure water ice)], where CRF is the to-be-determined clathrate ratio factor, 'clathrate' and 'pure water ice' are the reference spectra (end-member). Figure 1 shows results on one equatorial area where craters and ridges can be observed. Temperature appears to be higher besides the ridges (Figure 1f), but this may indicate that water ice is amorphous, which results in overestimating the temperature. Along the ridge, grain size is larger (Figure 1e), and CO2-clathrates have higher concentration near the ridges (Figure 1d). All these clues indicate a recent activity that we are planning to interpret in more details. 1)Fink and Larson, Icarus, 1975. 2)Leto et al. Mem. S.A.It. Suppl. 2005. 3)Grundy, Icarus, 1999. 4)Taffin et al., PSS, 2011

The use of inverse phase gas chromatography to measure the surface energy of crystalline, amorphous, and recently milled lactose.

PubMed

Newell, H E; Buckton, G; Butler, D A; Thielmann, F; Williams, D R

2001-05-01

To assess differences in surface energy due to processing induced disorder and to understand whether the disorder dominated the surfaces of particles. Inverse gas chromatography was used to compare the surface energies of crystalline, amorphous, and ball milled lactose. The milling process made ca 1% of the lactose amorphous, however the dispersive contribution to surface energy was 31.2, 37.1, and 41.6 mJ m(-2) for crystalline, spray dried and milled lactose, respectively. A physical mixture of crystalline (99%) and amorphous (1%) material had a dispersive surface energy of 31.5 mJ m(-2). Milling had made the surface energy similar to that of the amorphous material in a manner that was very different to a physical mixture of the same amorphous content. The milled material will have similar interfacial interactions to the 100% amorphous material.

Spontaneous crystalline-to-amorphous phase transformation of organic or medicinal compounds in the presence of porous media, part 2: amorphization capacity and mechanisms of interaction.

PubMed

Qian, Ken K; Suib, Steven L; Bogner, Robin H

2011-11-01

Amorphization of crystalline compounds using mesoporous media is a promising technique to improve the solubility and dissolution rate of poorly soluble compounds. The objective of this paper is to determine the capacity of amorphization and understand the mechanisms of phase transformation. Commercial grades of mesoporous silicon dioxide (SiO(2)) samples (5- to 30-nm mean pore diameters) with either constant surface area or constant pore volume were used. The amorphization capacity of naphthalene was not proportional to either the surface area or the pore volume measured using adsorption chambers. Instead, the amorphization capacity correlated with surface curvature, that is, the smaller the pore diameter and the higher the surface curvature, the greater the amorphization capacity. The change in surface chemistry due to a highly curved surface may be responsible for the enhanced amorphization capacity as well. The amorphization of crystalline compounds was facilitated through capillary condensation, with the decrease in pore volume as the direct experimental evidence. The amorphization capacity was also enhanced by the dipole-dipole or dipole-induced dipole interaction, promoted by the hydroxyl groups on the surface of SiO(2). The enthalpy of vapor-solid condensation of crystalline compounds was a useful indicator to predict the rank order of amorphization capacity. Copyright © 2011 Wiley-Liss, Inc.

Bibliography on Cold Regions Science and Technology, Volume 45, Part 1

DTIC Science & Technology

1991-12-01

Island. High pressure ice, Amorphous ice, Molecular struc- tVelikaia prilednikovala sistema stoka Severnol Ev- over the past three years. The work has...Maad land shelf III detrmine the eel5 uty andu stra in 1Ii the eI t he netl t I \\ A -In iinosmasuet n ihei toC . I SN- it-i H ului-cho - nasurenrenis

The preparation and structure of salty ice VII under pressure

NASA Astrophysics Data System (ADS)

Klotz, Stefan; Bove, Livia E.; Strässle, Thierry; Hansen, Thomas C.; Saitta, Antonino M.

2009-05-01

It is widely accepted that ice, no matter what phase, is unable to incorporate large amounts of salt into its structure. This conclusion is based on the observation that on freezing of salt water, ice expels the salt almost entirely as brine. Here, we show that this behaviour is not an intrinsic physico-chemical property of ice phases. We demonstrate by neutron diffraction that substantial amounts of dissolved LiCl can be built homogeneously into the ice VII structure if it is produced by recrystallization of its glassy (amorphous) state under pressure. Such `alloyed' ice VII has significantly different structural properties compared with pure ice VII, such as an 8% larger unit cell volume, 5 times larger displacement factors, an absence of a transition to an ordered ice VIII structure and plasticity. Our study suggests that there could be a whole new class of `salty' high-pressure ice forms.

The preparation and structure of salty ice VII under pressure.

PubMed

Klotz, Stefan; Bove, Livia E; Strässle, Thierry; Hansen, Thomas C; Saitta, Antonino M

2009-05-01

It is widely accepted that ice, no matter what phase, is unable to incorporate large amounts of salt into its structure. This conclusion is based on the observation that on freezing of salt water, ice expels the salt almost entirely as brine. Here, we show that this behaviour is not an intrinsic physico-chemical property of ice phases. We demonstrate by neutron diffraction that substantial amounts of dissolved LiCl can be built homogeneously into the ice VII structure if it is produced by recrystallization of its glassy (amorphous) state under pressure. Such 'alloyed' ice VII has significantly different structural properties compared with pure ice VII, such as an 8% larger unit cell volume, 5 times larger displacement factors, an absence of a transition to an ordered ice VIII structure and plasticity. Our study suggests that there could be a whole new class of 'salty' high-pressure ice forms.

Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photometric and spectroscopic evidence for a dense ring system around Centaur Chariklo

NASA Astrophysics Data System (ADS)

Duffard, R.; Pinilla-Alonso, N.; Ortiz, J. L.; Alvarez-Candal, A.; Sicardy, B.; Santos-Sanz, P.; Morales, N.; Colazo, C.; Fernández-Valenzuela, E.; Braga-Ribas, F.

2014-08-01

Context. A stellar occultation observed on 3rd June 2013 revealed the presence of two dense and narrow rings separated by a small gap around the Centaur object (10 199) Chariklo. The composition of these rings is not known. We suspect that water ice is present in the rings, as is the case for Saturn and other rings around the giant planets. Aims: In this work, we aim to determine if the variability in the absolute magnitude of Chariklo and the temporal variation of the spectral ice feature, even when it disappeared in 2007, can be explained by an icy ring system whose aspect angle changes with time. Methods: We explained the variations on the absolute magnitude of Chariklo and its ring by modeling the light reflected by a system as the one described above. Using X-shooter at VLT, we obtained a new reflectance spectra. We compared this new set of data with the ones available in the literature. We showed how the water ice feature is visible in 2013 in accordance with the ring configuration, which had an opening angle of nearly 34° in 2013. Finally, we also used models of light scattering to fit the visible and near-infrared spectra that shows different characteristics to obtain information on the composition of Chariklo and its rings. Results: We showed that absolute photometry of Chariklo from the literature and new photometric data that we obtained in 2013 can be explained by a ring of particles whose opening angle changes as a function of time. We used the two possible pole solutions for the ring system and found that only one of them, α = 151.30 ± 0.5, δ = 41.48 ± 0.2° (λ = 137.9 ± 0.5, β = 27.7 ± 0.2°), provides the right variation of the aspect angle with time to explain the photometry, whereas the other possible pole solution fails to explain the photometry. From spectral modeling, we derived the composition of the Chariklo surface and that of the rings using the result on the pole solution. Chariklo surface is composed with about 60% of amorphous carbon, 30% of silicates and 10% of organics; no water ice was found on the surface. The ring, on the other hand, contains 20% of water ice, 40-70% of silicates, and 10-30% of tholins and small quantities of amorphous carbon. Partially based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile. DDT 291.C-5035(A). Based on observations carried out at the Complejo Astronómico El Leoncito, which is operated under agreement between the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina and the National Universities of La Plata, Córdoba, and San Juan.

Outbursts of H2O in Comet P/Halley

NASA Astrophysics Data System (ADS)

Larson, H. P.; Hu, H.-Y.; Mumma, M. J.; Weaver, H. A.

1990-07-01

Comet Halley gas-production monitoring efforts in March 1986 with the NASA Kuiper Airborne Observatory's Fourier transform spectrometer have indicated rapid temporal variations in H2O emissions; a continuous record of an H2O outburst was thus obtained. The event, in which H2O brightness increased by a factor of 2.2 in less than 10 min, is ascribable to an energetic process in the nucleus whose character may have been that of amorphous H2O ice crystallization, chemical explosion, thermal stress, or a compressed gas pocket. The timing and energy of the event appear to require an internal energy source; amorphous ice crystallization is held to be most consistent with compositional and thermal models of cometary nuclei as well as the observations.

Experimental evidence of a liquid-liquid transition in interfacial water

NASA Astrophysics Data System (ADS)

Zanotti, J.-M.; Bellissent-Funel, M.-C.; Chen, S.-H.

2005-07-01

At ambient pressure, bulk liquid water shows an anomalous increase of thermodynamic quantities and apparent divergences of dynamic properties on approaching a temperature Ts of 228 K. At normal pressure, supercooled water spontaneously freezes below the homogeneous nucleation temperature, TH = 235 K. Upon heating, the two forms of Amorphous Solid Water (ASW), LDA (Low Density Amorphous Ice) and HDA (High Density Amorphous Ice), crystallise above TX = 150 K. As a consequence, up to now no experiment has been able to explore the properties of liquid water in this very interesting temperature range between 150 and 235 K. We present nanosecond-time-scale measurements of local rotational and translational dynamics of interfacial, non-crystalline, water from 77 to 280 K. These experimental dynamic results are combined with calorimetric and diffraction data to show that after exhibiting a glass transition at 165 K, interfacial water experiences a first-order liquid-liquid transition at 240 K from a low-density to a high-density liquid. This is the first direct evidence of the existence of a liquid-liquid transition involving water.

Possible fossil H2O liquid-ice interfaces in the Martian crust

USGS Publications Warehouse

Soderblom, L.A.; Wenner, D.B.

1978-01-01

Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H2O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H2O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H2O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H2O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9 images suggest interaction of impact, volcanic, and gravitational processes with the ice-laden layer. Finally, volcanic eruptions into ice produces a highly oxidized friable amorphous rock, palagonite. Based on spectral reflectance properties, these materials may provide the best analog to Martian surface materials. They are easily eroded, providing vast amounts of eolian debris, and have been suggested (Toulmin et al., 1977) as possible source rocks for the materials observed at the Viking landing sites. ?? 1978.

Milling induced amorphisation and recrystallization of α-lactose monohydrate.

PubMed

Badal Tejedor, Maria; Pazesh, Samaneh; Nordgren, Niklas; Schuleit, Michael; Rutland, Mark W; Alderborn, Göran; Millqvist-Fureby, Anna

2018-02-15

Preprocessing of pharmaceutical powders is a common procedure to condition the materials for a better manufacturing performance. However, such operations may induce undesired material properties modifications when conditioning particle size through milling, for example. Modification of both surface and bulk material structure will change the material properties, thus affecting the processability of the powder. Hence it is essential to control the material transformations that occur during milling. Topographical and mechanical changes in surface properties can be a preliminary indication of further material transformations. Therefore a surface evaluation of the α-lactose monohydrate after short and prolonged milling times has been performed. Unprocessed α-lactose monohydrate and spray dried lactose were evaluated in parallel to the milled samples as reference examples of the crystalline and amorphous lactose structure. Morphological differences between unprocessed α-lactose, 1 h and 20 h milled lactose and spray dried lactose were detected from SEM and AFM images. Additionally, AFM was used to simultaneously characterize particle surface amorphicity by measuring energy dissipation. Extensive surface amorphicity was detected after 1 h of milling while prolonged milling times showed only a moderate particle surface amorphisation. Bulk material characterization performed with DSC indicated a partial amorphicity for the 1 h milled lactose and a fully amorphous thermal profile for the 20 h milled lactose. The temperature profiles however, were shifted somewhat in the comparison to the amorphous reference, particularly after extended milling, suggesting a different amorphous state compared to the spray-dried material. Water loss during milling was measured with TGA, showing lower water content for the lactose amorphized through milling compared to spray dried amorphous lactose. The combined results suggest a surface-bulk propagation of the amorphicity during milling in combination with a different amorphous structural conformation to that of the amorphous spray dried lactose. The hardened surface may be due to either surface crystallization of lactose or to formation of a low-water glass transition. Copyright © 2017 Elsevier B.V. All rights reserved.

Dynamic signatures of the transition from stacking disordered to hexagonal ice: Dielectric and nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Gainaru, C.; Vynokur, E.; Köster, K. W.; Fuentes-Landete, V.; Spettel, N.; Zollner, J.; Loerting, T.; Böhmer, R.

2018-04-01

Using various temperature-cycling protocols, the dynamics of ice I were studied via dielectric spectroscopy and nuclear magnetic resonance relaxometry on protonated and deuterated samples obtained by heating high-density amorphous ices as well as crystalline ice XII. Previous structural studies of ice I established that at temperatures of about 230 K, the stacking disorder of the cubic/hexagonal oxygen lattice vanishes. The present dielectric and nuclear magnetic resonance investigations of spectral changes disclose that the memory of the existence of a precursor phase is preserved in the hydrogen matrix up to 270 K. This finding of hydrogen mobility lower than that of the undoped hexagonal ice near the melting point highlights the importance of dynamical investigations of the transitions between various ice phases and sheds new light on the dynamics in ice I in general.

Laboratory Research. [spectroscopic analysis, photochemical reactions, and proton irradiation of ice

NASA Technical Reports Server (NTRS)

Donn, B.

1981-01-01

To properly interpret the rapidly growing body of data from comet observations, many types of laboratory measurements are needed. These include: (1) molecular spectroscopy in the visible, ultraviolet, infrared and microwave region of the spectra; (2) laser fluorescent spectroscopy of photofragments; (3) laboratory cross-section or reaction rate measurements using flow tube techniques, fluorescent spectroscopy detection for neutrals and ion-molecule reaction techniques; (4) experiments to simulate solar-wind interactions with comets; (5) studies of the properties and behavior of ice mixtures; (6) experiments on the sublimation rate of ice, and the phase transition from amorphous to crystalline ice; (7) investigations of the irradiation of ice; and (8) the electron impact dissociation and excitation of molecules of cometary interest. A nearly completed experiment on the proton irradiation of ice is described.

Inhibiting surface crystallization of amorphous indomethacin by nanocoating.

PubMed

Wu, Tian; Sun, Ye; Li, Ning; de Villiers, Melgardt M; Yu, Lian

2007-04-24

An amorphous solid (glass) may crystallize faster at the surface than through the bulk, making surface crystallization a mechanism of failure for amorphous pharmaceuticals and other materials. An ultrathin coating of gold or polyelectrolytes inhibited the surface crystallization of amorphous indomethacin (IMC), an anti-inflammatory drug and model organic glass. The gold coating (10 nm) was deposited by sputtering, and the polyelectrolyte coating (3-20 nm) was deposited by an electrostatic layer-by-layer assembly of cationic poly(dimethyldiallyl ammonium chloride) (PDDA) and anionic sodium poly(styrenesulfonate) (PSS) in aqueous solution. The coating also inhibited the growth of existing crystals. The inhibition was strong even with one layer of PDDA. The polyelectrolyte coating still permitted fast dissolution of amorphous IMC and improved its wetting and flow. The finding supports the view that the surface crystallization of amorphous IMC is enabled by the mobility of a thin layer of surface molecules, and this mobility can be suppressed by a coating of only a few nanometers. This technique may be used to stabilize amorphous drugs prone to surface crystallization, with the aqueous coating process especially suitable for drugs of low aqueous solubility.

A fibre-coupled UHV-compatible variable angle reflection-absorption UV/visible spectrometer

NASA Astrophysics Data System (ADS)

Stubbing, J. W.; Salter, T. L.; Brown, W. A.; Taj, S.; McCoustra, M. R. S.

2018-05-01

We present a novel UV/visible reflection-absorption spectrometer for determining the refractive index, n, and thicknesses, d, of ice films. Knowledge of the refractive index of these films is of particular relevance to the astrochemical community, where they can be used to model radiative transfer and spectra of various regions of space. In order to make these models more accurate, values of n need to be recorded under astronomically relevant conditions, that is, under ultra-high vacuum (UHV) and cryogenic cooling. Several design considerations were taken into account to allow UHV compatibility combined with ease of use. The key design feature is a stainless steel rhombus coupled to an external linear drive (z-shift) allowing a variable reflection geometry to be achieved, which is necessary for our analysis. Test data for amorphous benzene ice are presented as a proof of concept, the film thickness, d, was found to vary linearly with surface exposure, and a value for n of 1.43 ± 0.07 was determined.

Rotationally resolved spectroscopy of Jupiter Trojans (624) Hektor and (911) Agamemnon

NASA Astrophysics Data System (ADS)

Perna, D.; Bott, N.; Hromakina, T.; Mazzotta Epifani, E.; Dotto, E.; Doressoundiram, A.

2018-03-01

We present the first-ever rotationally resolved spectroscopic investigation of (624) Hektor and (911) Agamemnon, the two largest Jupiter Trojans. The visible and near-infrared spectra that we have obtained at the TNG telescope (La Palma, Spain) do not show any feature or hints of heterogeneity. In particular, we found no hints of water-related absorptions. No cometary activity was detected down to ˜23.5 R mag arcsec-2 based on the complementary photometric data. We estimated upper limits on the dust production rates of Hektor and Agamemnon to be ≈30 and ≈24 kg s-1, respectively. We modelled complete visible and near-infrared spectra of our targets using the Shkuratov formalism to define the upper limit to the presence of water ice and more in general to constrain their surface composition. For both objects, successful models include amorphous carbon, magnesium-rich pyroxene, and kerogen, with an upper limit to the amount of water ice of a few per cent.

Electron affinity of liquid water

DOE PAGES

Gaiduk, Alex P.; Pham, Tuan Anh; Govoni, Marco; ...

2018-01-16

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential ofmore » the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.« less

Electron affinity of liquid water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaiduk, Alex P.; Pham, Tuan Anh; Govoni, Marco

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential ofmore » the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.« less

Determining the Equation of State (EoS) Parameters for Ballistic Gelatin

DTIC Science & Technology

2015-09-01

standard deviation. The specific heat measured at room temperature reported in (Winter 1975) is approximately 1.13 cal/g/°C (= 4.73 J /g/K). Fig. 4...Piatt 2010) Table 3 Specific heat capacity, average heat capacity, and standard deviation Temperature (°C) Cp [ J /(g·K)] Cp Cp Cp Average Cp...density amorphous ice and their implications on pressure induced amorphization. J Chem Physics. 2005;122:124710. Appleby-Thomas GJ, Hazell PJ

The length and time scales of water's glass transitions

NASA Astrophysics Data System (ADS)

Limmer, David T.

2014-06-01

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

The length and time scales of water's glass transitions.

PubMed

Limmer, David T

2014-06-07

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

Diffusive dynamics during the high-to-low density transition in amorphous ice

DOE PAGES

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix; ...

2017-06-26

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

NASA Astrophysics Data System (ADS)

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkühler, Felix; Sprung, Michael; Mariedahl, Daniel; Sellberg, Jonas A.; Pathak, Harshad; Späh, Alexander; Cavalca, Filippo; Schlesinger, Daniel; Ricci, Alessandro; Jain, Avni; Massani, Bernhard; Aubree, Flora; Benmore, Chris J.; Loerting, Thomas; Grübel, Gerhard; Pettersson, Lars G. M.; Nilsson, Anders

2017-08-01

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distribution function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. The diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid-liquid transition in the ultraviscous regime.

Direct Measurement of Water States in Cryopreserved Cells Reveals Tolerance toward Ice Crystallization

PubMed Central

Huebinger, Jan; Han, Hong-Mei; Hofnagel, Oliver; Vetter, Ingrid R.; Bastiaens, Philippe I.H.; Grabenbauer, Markus

2016-01-01

Complex living systems such as mammalian cells can be arrested in a solid phase by ultrarapid cooling. This allows for precise observation of cellular structures as well as cryopreservation of cells. The state of water, the main constituent of biological samples, is crucial for the success of cryogenic applications. Water exhibits many different solid states. If it is cooled extremely rapidly, liquid water turns into amorphous ice, also called vitreous water, a glassy and amorphous solid. For cryo-preservation, the vitrification of cells is believed to be mandatory for cell survival after freezing. Intracellular ice crystallization is assumed to be lethal, but experimental data on the state of water during cryopreservation are lacking. To better understand the water conditions in cells subjected to freezing protocols, we chose to directly analyze their subcellular water states by cryo-electron microscopy and tomography, cryoelectron diffraction, and x-ray diffraction both in the cryofixed state and after warming to different temperatures. By correlating the survival rates of cells with their respective water states during cryopreservation, we found that survival is less dependent on ice-crystal formation than expected. Using high-resolution cryo-imaging, we were able to directly show that cells tolerate crystallization of extra- and intracellular water. However, if warming is too slow, many small ice crystals will recrystallize into fewer but bigger crystals, which is lethal. The applied cryoprotective agents determine which crystal size is tolerable. This suggests that cryoprotectants can act by inhibiting crystallization or recrystallization, but they also increase the tolerance toward ice-crystal growth. PMID:26541066

Interfacial Free Energy as the Key to the Pressure-Induced Deceleration of Ice Nucleation

NASA Astrophysics Data System (ADS)

Espinosa, Jorge R.; Zaragoza, Alberto; Rosales-Pelaez, Pablo; Navarro, Caridad; Valeriani, Chantal; Vega, Carlos; Sanz, Eduardo

2016-09-01

The avoidance of water freezing is the holy grail in the cryopreservation of biological samples, food, and organs. Fast cooling rates are used to beat ice nucleation and avoid cell damage. This strategy can be enhanced by applying high pressures to decrease the nucleation rate, but the physics behind this procedure has not been fully understood yet. We perform computer experiments to investigate ice nucleation at high pressures consisting in embedding ice seeds in supercooled water. We find that the slowing down of the nucleation rate is mainly due to an increase of the ice I -water interfacial free energy with pressure. Our work also clarifies the molecular mechanism of ice nucleation for a wide pressure range. This study is not only relevant to cryopreservation, but also to water amorphization and climate change modeling.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasuga, Toshihiro; Shirahata, Mai; Usui, Fumihiko

Most outer main-belt asteroids have low albedos because of their carbonaceouslike bodies. However, infrared satellite surveys have revealed that some asteroids have high albedos, which may suggest the presence of unusual surface minerals for those primitive objects. We present new near-infrared (1.1–2.5 μm) spectra of four outer main-belt asteroids with albedos ≥ 0.1. The C-complex asteroids (555) Norma and (2542) Calpurnia are featureless and have (50%–60%) amorphous Mg pyroxenes that might explain the high albedos. Asteroids (701) Oriola (which is a C-complex asteroid) and (2670) Chuvashia (a D/T-type or M-type asteroid) show possible broad absorption bands (1.5–2.1 μm). The featuremore » can be reproduced by either Mg-rich amorphous pyroxene (with 50%–60% and 80%–95% Mg, respectively) or orthopyroxene (crystalline silicate), which might be responsible for the high albedos. No absorption features of water ice (near 1.5 and 2.0 μm) are detected in the objects. We discuss the origin of high albedo components in the outer main-belt asteroids and their physical relations to comets.« less

Structure and Evolution of Kuiper Belt Objects: The Case for Compositional Classes

NASA Astrophysics Data System (ADS)

McKinnon, William B.; Prialnik, D.; Stern, S. A.

2007-10-01

Kuiper belt objects (KBOs) accreted from a mélange of ices, carbonaceous matter, and rock of mixed interstellar and solar nebular provenance. The transneptunian region, where this accretion took place, was likely more radially compact than today. This and the influence of gas drag during the solar nebula epoch argue for more rapid KBO accretion than usually considered. Early evolution of KBOs was largely the result of radiogenic heating, with both short-term and long-term contributions being potentially important. Depending on rock content and porous conductivity, KBO interiors may have reached relatively high temperatures. Models suggest that KBOs likely lost very volatile ices during early evolution, whereas less volatile ices should be retained in cold, less altered subsurface layers; initially amorphous ice may have crystallized in the interior as well, releasing trapped volatiles. Generally, KBOs should be stratified in terms of composition and porosity, albeit subject to impact disruption and collisional stripping. KBOs are thus unlikely to be "the most pristine objects in the Solar System.” Large (dwarf planet) KBOs may be fully differentiated. KBO surface color and compositional classes are usually discussed in terms of "nature vs. nurture,” i.e., a generic primordial composition vs. surface processing, but the true nature of KBOs also depends on how they have evolved. The broad range of albedos now found in the Kuiper belt, deep water-ice absorptions on some objects, evidence for differentiation of Pluto and 2003 EL61, and a range of densities incompatible with a single, primordial composition and variable porosity strongly imply significant, intrinsic compositional differences among KBOs. The interplay of formation zone (accretion rate), body size, and dynamical (collisional) history may yield KBO compositional classes (and their spectral correlates) that recall the different classes of asteroids in the inner Solar System, but whose members are broadly distributed among the KBO dynamical subpopulations.

Infrared Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Moore, Marla; Ferrante, Robert; Moore, William; Hudson, Reggie

2010-01-01

Spectra and optical constants of nitrite ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 per cm ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C 2H5CN, propionitrile; and HC3N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous- and crystallinephase at 670 nm. Spectra were measured and optical constants were calculated for each nitrite at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous- and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data.

The use of inverse phase gas chromatography to study the change of surface energy of amorphous lactose as a function of relative humidity and the processes of collapse and crystallisation.

PubMed

Newell, H E; Buckton, G; Butler, D A; Thielmann, F; Williams, D R

2001-04-17

The purpose of this study was to assess the effect of relative humidity (RH) on the surface energy of amorphous lactose. Two samples of amorphous lactose were investigated; a spray dried 100% amorphous material and a ball milled sample of crystalline lactose. The milled sample had less than 1% amorphous content by mass, but on investigation at 0% RH, yielded surface energies comparable to those obtained from the 100% amorphous material, indicating that the surface was amorphous. The effect of increasing humidity was to reduce the dispersive surface energy of the two samples from 36.0 +/- 0.14 and 41.6 +/- 1.4 mJ m(-2) at 0% RH for the spray dried and milled samples respectively, to a value comparable to that obtained for the crystalline alpha-lactose monohydrate of 31.3 +/- 0.41 mJ m(-2). The change in surface energy due to water sorption was only reversible up to 20% RH; after exposure to higher RH values subsequent drying did not result in a return to the original surface energy of the amorphous form. This shows that the surface is reorganising as the glass transition temperature (Tg) is reduced, even though the sample has not collapsed or crystallised. It was possible to follow the collapse behaviour in the column with ease, using a number of different methods.

Giant-Planet Chemistry: Ammonium Hydrosulfide (NH4SH), Its IR Spectra and Thermal and Radiolytic Stabilities

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.; Chanover, Nancy J.; Simon, Amy A.

2015-01-01

Here we present our recent studies of proton-irradiated and unirradiated ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. We irradiated both crystalline and amorphous NH4SH at 10-160 K and used IR spectroscopy to observe and identify reaction products in the ice, specifically NH3 and long-chained sulfur-containing ions. Crystalline NH4SH was amorphized during irradiation at all temperatures studied with the rate being the fastest at the lowest temperatures. Irradiation of amorphous NH4SH at approximately 10-75 K showed that 60-80% of the NH4 + remained when equilibrium was reached, and that NH4SH destruction rates were relatively constant within this temperature range. Irradiations at higher temperatures produced different dose dependence and were accompanied by pressure outbursts that, in some cases, fractured the ice. The thermal stability of irradiated NH4SH was found to be greater than that of unirradiated NH4SH, suggesting that an irradiated giant-planet cloud precipitate can exist at temperatures and altitudes not previously considered.

Compensated amorphous silicon solar cell

DOEpatents

Devaud, Genevieve

1983-01-01

An amorphous silicon solar cell including an electrically conductive substrate, a layer of glow discharge deposited hydrogenated amorphous silicon over said substrate and having regions of differing conductivity with at least one region of intrinsic hydrogenated amorphous silicon. The layer of hydrogenated amorphous silicon has opposed first and second major surfaces where the first major surface contacts the electrically conductive substrate and an electrode for electrically contacting the second major surface. The intrinsic hydrogenated amorphous silicon region is deposited in a glow discharge with an atmosphere which includes not less than about 0.02 atom percent mono-atomic boron. An improved N.I.P. solar cell is disclosed using a BF.sub.3 doped intrinsic layer.

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics

PubMed Central

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-01-01

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics. PMID:25297473

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics.

PubMed

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-10-09

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics.

Amorphous and Crystalline H20 Ice at Rhea's Inktomi Crater

NASA Technical Reports Server (NTRS)

Lewis, Emma M.; Dalle Ore, Cristina M.; Cruikshank, Dale P.; White, Oliver L.

2014-01-01

We present the analysis of Cassini spectral data from spectral mapping of Saturnian icy moons Dione and Rhea, to investigate possible effects of impact crater formation on the relative abundances of crystalline and amorphous water ice in the moons' ice crusts. Both moons display morphologically young ray craters as well as older craters. Possible changes in ice properties due to crater formation are conjectured to be more visible in younger craters, and as such Rhea's well imaged ray crater Inktomi is analysed, as are older craters for comparison. We used data from Cassini's Visual and Infrared Mapping Spectrometer (VIMS). For each pixel in the VIMS maps, spectral data were extracted in the near-infrared range (1.75 micrometers less than lambda less than 2.45 micrometers). Analysis was begun by fitting a single Gaussian to the peak in absorption at 2.0 micrometers, which was then subtracted from the data, leaving residuals with a minimum on either side of the original 2.0-micrometers band. The spectra of the individual spatial pixels were then clustered by the differences between these minima, which are sensitive to changes in both ice grain size and crystallinity. This yielded preliminary maps which approximated the physical characteristics of the landscape and were used to identify candidates for further analysis. Spectra were then clustered by the properties of the 1.5-micrometers band, to divide the map into regions based on inferred grain size. For each region, the predicted differences in minima from the Gaussian residuals, over a range of crystallinities, were calculated based on the found grain sizes. This model was used to find the crystallinity of each pixel via grain size and characteristics of the residual function. Preliminary results show a greater degree of crystallization of young crater interiors, particularly in Rhea's ray crater Inktomi, where ice showed crystalline ice abundances between 33 percent and 61 percent. These patterns in ice crystallization are possibly attributable to increased heat generated during crater formation.

Calorimetric study of water's two glass transitions in the presence of LiCl

PubMed Central

Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

2018-01-01

A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

Infrared optical constants of H2O ice, amorphous nitric acid solutions, and nitric acid hydrates

NASA Technical Reports Server (NTRS)

Toon, Owen B.; Koehler, Birgit G.; Middlebrook, Ann M.; Tolbert, Margaret A.; Jordon, Joseph

1994-01-01

We determined the infrared optical constants of nitric acid trihydrate, nitric acid dihydrate, nitric acid monohydrate, and solid amorphous nitric acid solutions which crystallize to form these hydrates. We have also found the infrared optical constants of H2O ice. We measured the transmission of infrared light throught thin films of varying thickness over the frequency range from about 7000 to 500/cm at temperatures below 200 K. We developed a theory for the transmission of light through a substrate that has thin films on both sides. We used an iterative Kramers-Kronig technique to determine the optical constants which gave the best match between measured transmission spectra and those calculated for a variety of films of different thickness. These optical constants should be useful for calculations of the infrared spectrum of polar stratospheric clouds.

DIFFERENT ORIGINS OR DIFFERENT EVOLUTIONS? DECODING THE SPECTRAL DIVERSITY AMONG C-TYPE ASTEROIDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vernazza, P.; Marsset, M.; Groussin, O.

Anhydrous pyroxene-rich interplanetary dust particles (IDPs) have been proposed as surface analogs for about two-thirds of all C-complex asteroids. However, this suggestion appears to be inconsistent with the presence of hydrated silicates on the surfaces of some of these asteroids, including Ceres. Here, we report the presence of enstatite (pyroxene) on the surface of two C-type asteroids (Ceres and Eugenia) based on their spectral properties in the mid-infrared range. The presence of this component is particularly unexpected in the case of Ceres, because most thermal evolution models predict a surface consisting of hydrated compounds only. The most plausible scenario is that Ceres’more » surface has been partially contaminated by exogenous enstatite-rich material, possibly coming from the Beagle asteroid family. This scenario questions a similar origin for Ceres and the remaining C-types, and it possibly supports recent results obtained by the Dawn mission (NASA) that Ceres may have formed in the very outer solar system. Concerning the smaller D  ∼ 200 km C-types such as Eugenia, both their derived surface composition (enstatite and amorphous silicates) and low density (<1.5 g cm{sup −3}) suggest that these bodies accreted from the same building blocks, namely chondritic porous, pyroxene-rich IDPs and volatiles (mostly water ice), and that a significant volume fraction of these bodies has remained unaffected by hydrothermal activity likely implying a late accretion. In addition, their current heliocentric distance may best explain the presence or absence of water ice at their surfaces. Finally, we raise the possibility that CI chondrites, Tagish-Lake-like material, or hydrated IDPs may be representative samples of the cores of these bodies.« less

Different Origins or Different Evolutions? Decoding the Spectral Diversity Among C-type Asteroids

NASA Astrophysics Data System (ADS)

Vernazza, P.; Castillo-Rogez, J.; Beck, P.; Emery, J.; Brunetto, R.; Delbo, M.; Marsset, M.; Marchis, F.; Groussin, O.; Zanda, B.; Lamy, P.; Jorda, L.; Mousis, O.; Delsanti, A.; Djouadi, Z.; Dionnet, Z.; Borondics, F.; Carry, B.

2017-02-01

Anhydrous pyroxene-rich interplanetary dust particles (IDPs) have been proposed as surface analogs for about two-thirds of all C-complex asteroids. However, this suggestion appears to be inconsistent with the presence of hydrated silicates on the surfaces of some of these asteroids, including Ceres. Here, we report the presence of enstatite (pyroxene) on the surface of two C-type asteroids (Ceres and Eugenia) based on their spectral properties in the mid-infrared range. The presence of this component is particularly unexpected in the case of Ceres, because most thermal evolution models predict a surface consisting of hydrated compounds only. The most plausible scenario is that Ceres’ surface has been partially contaminated by exogenous enstatite-rich material, possibly coming from the Beagle asteroid family. This scenario questions a similar origin for Ceres and the remaining C-types, and it possibly supports recent results obtained by the Dawn mission (NASA) that Ceres may have formed in the very outer solar system. Concerning the smaller D ˜ 200 km C-types such as Eugenia, both their derived surface composition (enstatite and amorphous silicates) and low density (<1.5 g cm-3) suggest that these bodies accreted from the same building blocks, namely chondritic porous, pyroxene-rich IDPs and volatiles (mostly water ice), and that a significant volume fraction of these bodies has remained unaffected by hydrothermal activity likely implying a late accretion. In addition, their current heliocentric distance may best explain the presence or absence of water ice at their surfaces. Finally, we raise the possibility that CI chondrites, Tagish-Lake-like material, or hydrated IDPs may be representative samples of the cores of these bodies.

Method for improving the stability of amorphous silicon

DOEpatents

Branz, Howard M.

2004-03-30

A method of producing a metastable degradation resistant amorphous hydrogenated silicon film is provided, which comprises the steps of growing a hydrogenated amorphous silicon film, the film having an exposed surface, illuminating the surface using an essentially blue or ultraviolet light to form high densities of a light induced defect near the surface, and etching the surface to remove the defect.

Flow of ices in the Ammonia-Water System

NASA Technical Reports Server (NTRS)

Durham, W. B.; Kirby, S. H.; Stern, L. A.

1993-01-01

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.

Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

NASA Astrophysics Data System (ADS)

Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

2017-12-01

The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

Investigation of Celestial Solid Analogs

NASA Technical Reports Server (NTRS)

Sievers, A. J.

2003-01-01

Our far infrared studies of both hydrophobic and hydrophilic aerogel grains have demonstrated that the mm and sub-mm wave absorption produced by the fundamental two level systems (TLS) mechanism represents a more significant contribution for these open grain structures than for bulk amorphous silicate grains. We found that the region with the anomalous temperature dependence of the spectral index due to the TLS excitations can extend in a fluffy material up to 80 per cm, which is well beyond its typical upper limit for bulk glasses. Currently there is no theoretical explanation for this surprising result. The effects of reduced dimensionality on the optical properties of carbonaceous grains have been studied with a systematic investigation of carbon aerogels. This spectroscopic approach has permitted a more reliable determination of the single grain mass normalized absorption coefficient based on the experimentally determined characteristics of the fluffy material rather than on first principles calculations involving the bulk properties of the substance. Our finding is that the electrical connectivity of the material is the main factor affecting its far infrared absorption coefficient. Another one of the main constituents of the interstellar dust, amorphous ice, has been investigated in the mm-wave region both in the high (HDA) and low (LDA) density amorphous phases and as a function of impurities. We found that doping either phase with ionic (LiCl) or molecular (methanol) impurities decreases the difference in the mm-wave absorption coefficient between the HDA and LDA ice phases so that the HDA spectrum can be used as an analog for impure ice absorption in the far infrared spectral region.

Experimental studies of the far-infrared spectra of cosmic-type ices

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.

1992-01-01

Work performed during the period is reported. The abstract of a paper presented at the Second International Workshop on the Nature of Cometary Organic Matter is included. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation is presented. Also, a study of clathrate hydrates was conducted in which a methanol (CH3OH) clathrate hydrate was prepared and its far-infrared spectrum investigated. This paper is also included.

Time-Domain Terahertz Spectroscopy (0.3 - 7.5 THz) of Molecular Ices of Simple Alcohols

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Ioppolo, Sergio; Allodi, Marco A.; de Vries, Xander; Finneran, Ian; Carroll, Brandon; Blake, Geoffrey

2014-06-01

We have recently constructed a time-domain TeraHertz (THz) spectrometer for the study of molecular ices in the far-infrared. Here, we present the results of a study of amorphous and crystalline ices of simple alcohols from methanol (CH_3OH) through butanol (CH_3(CH_2)_3OH) in the region of 0.3 - 7.5 THz. We examine the effects of the length and degree of branching of the carbon chain on the observed spectra arising from the bulk, large-amplitude motions which are prominent in this spectral region. We also discuss these results in an astrochemical context: the application of these spectra to astronomical observations of interstellar ices with Herschel PACS/SPIRE and SOFIA.

Amorphization and thermal stability of aluminum-based nanoparticles prepared from the rapid cooling of nanodroplets: effect of iron addition.

PubMed

Xiao, Shifang; Li, Xiaofan; Deng, Huiqiu; Deng, Lei; Hu, Wangyu

2015-03-07

Despite an intensive investigation on bimetallic nanoparticles, little attention has been paid to their amorphization in the past few decades. The study of amorphization on a nanoscale is of considerable significance for the preparation of amorphous nanoparticles and bulk metallic glass. Herein, we pursue the amorphization process of Al-based nanoparticles with classic molecular dynamics simulations and local structural analysis techniques. By a comparative study of the amorphization of pure Al and Fe-doped Al-based nanodroplets in the course of rapid cooling, we find that Fe addition plays a very important role in the vitrification of Al-based nanodroplets. Owing to the subsurface segregated Fe atoms with their nearest neighbors tending to form relatively stable icosahedral (ICO) clusters, the Fe-centred cluster network near the surface effectively suppresses the crystallization of droplets from surface nucleation and growth as the concentration of Fe attains a certain value. The glass formation ability of nanodroplets is suggested to be enhanced by the high intrinsic inner pressure as a result of small size and surface tension, combined with the dopant-inhibited surface nucleation. In addition, the effect of the size and the added concentration of nanoparticles on amorphization and the thermal stability of the amorphous nanoparticles are discussed. Our findings reveal the amorphization mechanism in Fe-doped Al-based nanoparticles and provide a theoretical guidance for the design of amorphous materials.

Extremely hard amorphous-crystalline hybrid steel surface produced by deformation induced cementite amorphization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Wei; Meng, Yifei; Zhang, Xie

Amorphous and nanograined (NG) steels are two categories of strong steels. However, over the past decade, their application has been hindered by their limited plasticity, the addition of expensive alloying elements, and processing challenges associated with producing bulk materials. Here in this work, we report that the surface of a carburized Fe-Mn-Si martensitic steel with extremely low elemental alloying additions can be economically fabricated into an amorphous-nanocrystalline hybrid structure. Atom probe tomography and nanobeam diffraction of a hard turned steel surface together with molecular dynamics (MD) simulations reveal that the original cementite surface structure experiences a size-dependent amorphization and phasemore » transformation during heavy plastic deformation. MD simulations further show that the martensite-cementite interface serves as a nucleation site for cementite amorphization, and that cementite can become disordered if further strained when the cementite particles are relatively small. These graded structures exhibit a surface hardness of ~16.2 GPa, which exceeds the value of ~8.8 GPa for the original nanocrystalline martensitic steel and most nanocrystalline steels reported before. Finally, this practical and cost-efficient approach for producing a hard surface with retained bulk ductility and toughness can provide expanded opportunities for producing an amorphous-crystalline hybrid structure in steels and other alloy systems.« less

Extremely hard amorphous-crystalline hybrid steel surface produced by deformation induced cementite amorphization

DOE PAGES

Guo, Wei; Meng, Yifei; Zhang, Xie; ...

2018-04-11

Amorphous and nanograined (NG) steels are two categories of strong steels. However, over the past decade, their application has been hindered by their limited plasticity, the addition of expensive alloying elements, and processing challenges associated with producing bulk materials. Here in this work, we report that the surface of a carburized Fe-Mn-Si martensitic steel with extremely low elemental alloying additions can be economically fabricated into an amorphous-nanocrystalline hybrid structure. Atom probe tomography and nanobeam diffraction of a hard turned steel surface together with molecular dynamics (MD) simulations reveal that the original cementite surface structure experiences a size-dependent amorphization and phasemore » transformation during heavy plastic deformation. MD simulations further show that the martensite-cementite interface serves as a nucleation site for cementite amorphization, and that cementite can become disordered if further strained when the cementite particles are relatively small. These graded structures exhibit a surface hardness of ~16.2 GPa, which exceeds the value of ~8.8 GPa for the original nanocrystalline martensitic steel and most nanocrystalline steels reported before. Finally, this practical and cost-efficient approach for producing a hard surface with retained bulk ductility and toughness can provide expanded opportunities for producing an amorphous-crystalline hybrid structure in steels and other alloy systems.« less

[Microcosmic mechanisms of amorphous indomethacin crystallization and the influence of nano-coating on crystallization].

PubMed

Hui, Ou-Yang; Yi, Tao; Zheng, Qin; Liu, Feng

2011-06-01

Amorphous drugs have higher solubility, better oral bioavailability and are easier to be absorbed than their crystalline counterparts. However, the amorphous drugs, with weak stability, are so easy to crystallize that they will lose the original advantages. Polarization microscope, scanning electron microscope, differential scanning calorimetry, X-ray diffractomer and Raman spectroscopy were used to study the microcosmic crystallization mechanisms of amorphous indometacin and the performance of the drug crystals. The results showed that the growth rate of amorphous indometacin crystals at the free surface was markedly faster than that through the bulk, and that the crystal growth rate decreased observably after spraying an ultrathin melting gold (10 nm) at the free surface of the drug. These results indicated that the high growth rates of amorphous drugs crystals at the free surface were the key to their stability and that an ultrathin coating could be applied to enhance the stability of amorphous drugs.

CHEMICAL PROCESSING OF PURE AMMONIA AND AMMONIA-WATER ICES INDUCED BY HEAVY IONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bordalo, V.; Da Silveira, E. F.; Lv, X. Y.

Cosmic rays are possibly the main agents to prevent the freeze-out of molecules onto grain surfaces in cold dense clouds. Ammonia (NH{sub 3}) is one of the most abundant molecules present in dust ice mantles, with a concentration of up to 15% relative to water (H{sub 2}O). FTIR spectroscopy is used to monitor pure NH{sub 3} and NH{sub 3}-H{sub 2}O ice samples as they are irradiated with Ni and Zn ion beams (500-600 MeV) at GANIL/France. New species, such as hydrazine (N{sub 2}H{sub 4}), diazene (N{sub 2}H{sub 2} isomers), molecular hydrogen (H{sub 2}), and nitrogen (N{sub 2}) were identified aftermore » irradiation of pure NH{sub 3} ices. Nitrous oxide (N{sub 2}O), nitrogen oxide (NO), nitrogen dioxide (NO{sub 2}), and hydroxylamine (NH{sub 2}OH) are some of the products of the NH{sub 3}-H{sub 2}O ice radiolysis. The spectral band at 6.85 {mu}m was observed after irradiation of both types of ice. Besides the likely contribution of ammonium (NH{sub 4}{sup +}) and amino (NH{sub 2}) radicals, data suggest a small contribution of NH{sub 2}OH to this band profile after high fluences of irradiation of NH{sub 3}-H{sub 2}O ices. The spectral shift of the NH{sub 3} ''umbrella'' mode (9.3 {mu}m) band is parameterized as a function of NH{sub 3}/H{sub 2}O ratio in amorphous ices. Ammonia and water destruction cross-sections are obtained, as well as the rate of NH{sub 3}-H{sub 2}O (1:10) ice compaction, measured by the OH dangling bond destruction cross-section. Ammonia destruction is enhanced in the presence of H{sub 2}O in the ice and a power law relationship between stopping power and NH{sub 3} destruction cross-section is verified. Such results may provide relevant information for the evolution of molecular species in dense molecular clouds.« less

Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals

DOEpatents

Farmer, Joseph C.; Wong, Frank M.G.; Haslam, Jeffery J.; Yang, Nancy; Lavernia, Enrique J.; Blue, Craig A.; Graeve, Olivia A.; Bayles, Robert; Perepezko, John H.; Kaufman, Larry; Schoenung, Julie; Ajdelsztajn, Leo

2014-07-15

A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).

Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals

DOEpatents

Farmer, Joseph C [Tracy, CA; Wong, Frank M. G. [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Yang, Nancy [Lafayette, CA; Lavernia, Enrique J [Davis, CA; Blue, Craig A [Knoxville, TN; Graeve, Olivia A [Reno, NV; Bayles, Robert [Annandale, VA; Perepezko, John H [Madison, WI; Kaufman, Larry [Brookline, MA; Schoenung, Julie [Davis, CA; Ajdelsztajn, Leo [Walnut Creek, CA

2009-11-17

A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).

[H2O ortho-para spin conversion in aqueous solutions as a quantum factor of Konovalov paradox].

PubMed

Pershin, S M

2014-01-01

Recently academician Konovalov and co-workers observed an increase in electroconductivity and biological activity simultaneously with diffusion slowing (or nanoobject diameter increasing) and extremes of other parameters (ζ-potential, surface tension, pH, optical activity) in low concentration aqueous solutions. This phenomenon completely disappeared when samples were shielded against external electromagnetic fields by a Faraday cage. A conventional theory of water and water solutions couldn't explain "Konovalov paradox" observed in numerous experiments (representative sampling about 60 samples and 7 parameters). The new approach was suggested to describe the physics of water and explain "Konovalov paradox". The proposed concept takes into account the quantum differences of ortho-para spin isomers of H2O in bulk water (rotational spin-selectivity upon hydration and spontaneous formation of ice-like structures, quantum beats and spin conversion induced in the presence of a resonant electromagnetic radiation). A size-dependent self-assembly of amorphous complexes of H2O molecules more than 275 leading to the ice Ih structure observed in the previous experiments supports this concept.

Radiation effects in astrophysical ices

NASA Astrophysics Data System (ADS)

Boduch, Philippe; Dartois, Emmanuel; de Barros, Ana L. F.; da Silveira, Enio F.; Domaracka, Alicja; Lv, Xue-Yang; Palumbo, Maria Elisabetta; Pilling, Sergio; Rothard, Hermann; Seperuelo Duarte, Eduardo; Strazzulla, Giovanni

2015-07-01

The interaction of heavy ions with astrophysical ices was studied at different beamlines of GANIL by infrared absorption spectroscopy. This allowed simulating in the laboratory the physico-chemical modifications induced in icy objects in space, exposed to radiation fields such as the solar wind, magnetospheric particles and interstellar cosmic rays. We briefly discuss sputtering, destruction and formation of molecules, amorphization and compaction, implantation, and finally the formation of organic molecules. This latter topic is related to the question of the initial conditions for the emergence of life.

Different structural morphologies of the two surfaces in some Co-based amorphous ribbons

NASA Astrophysics Data System (ADS)

Bordin, G.; Buttino, G.

1992-12-01

In nearly zero magnetostriction Co-based Metglas amorphous ribbons, the anomalous Hall effect is used to investigate the behaviour of the surfaces (dull or shiny). The electronic transport properties of a double-layer film, where one of the two layers examined is ferromagnetic and amorphous, and the other is a non-magnetic film, are interpreted on the basis of the mean free path method of Bergmann and Fuchs-Sondheimer theory. The results obtained confirm the different structural morphology of the amorphous surfaces (dull or shiny) already observed by means of bending effects on the initial permeability that depends on the way of winding the ribbons in toroidal samples of the same amorphous materials.

Distinct ice patterns on solid surfaces with various wettabilities

PubMed Central

Liu, Jie; Zhu, Chongqin; Liu, Kai; Jiang, Ying; Song, Yanlin; Francisco, Joseph S.; Zeng, Xiao Cheng; Wang, Jianjun

2017-01-01

No relationship has been established between surface wettability and ice growth patterns, although ice often forms on top of solid surfaces. Here, we report experimental observations obtained using a process specially designed to avoid the influence of nucleation and describe the wettability-dependent ice morphology on solid surfaces under atmospheric conditions and the discovery of two growth modes of ice crystals: along-surface and off-surface growth modes. Using atomistic molecular dynamics simulation analysis, we show that these distinct ice growth phenomena are attributable to the presence (or absence) of bilayer ice on solid surfaces with different wettability; that is, the formation of bilayer ice on hydrophilic surface can dictate the along-surface growth mode due to the structural match between the bilayer hexagonal ice and the basal face of hexagonal ice (ice Ih), thereby promoting rapid growth of nonbasal faces along the hydrophilic surface. The dramatically different growth patterns of ice on solid surfaces are of crucial relevance to ice repellency surfaces. PMID:29073045

Distinct ice patterns on solid surfaces with various wettabilities.

PubMed

Liu, Jie; Zhu, Chongqin; Liu, Kai; Jiang, Ying; Song, Yanlin; Francisco, Joseph S; Zeng, Xiao Cheng; Wang, Jianjun

2017-10-24

No relationship has been established between surface wettability and ice growth patterns, although ice often forms on top of solid surfaces. Here, we report experimental observations obtained using a process specially designed to avoid the influence of nucleation and describe the wettability-dependent ice morphology on solid surfaces under atmospheric conditions and the discovery of two growth modes of ice crystals: along-surface and off-surface growth modes. Using atomistic molecular dynamics simulation analysis, we show that these distinct ice growth phenomena are attributable to the presence (or absence) of bilayer ice on solid surfaces with different wettability; that is, the formation of bilayer ice on hydrophilic surface can dictate the along-surface growth mode due to the structural match between the bilayer hexagonal ice and the basal face of hexagonal ice (ice I h ), thereby promoting rapid growth of nonbasal faces along the hydrophilic surface. The dramatically different growth patterns of ice on solid surfaces are of crucial relevance to ice repellency surfaces. Published under the PNAS license.

Surface Ice and Tholins on the Extreme Centaur 2012 DR30

NASA Astrophysics Data System (ADS)

Szabó, Gy. M.; Kiss, Cs.; Pinilla-Alonso, N.; Hsiao, E. Y.; Marion, G. H.; Györgyey Ries, J.; Duffard, R.; Alvarez-Candal, A.; Sárneczky, K.; Vinkó, J.

2018-04-01

2012 {DR}}30 is one of the known solar system objects with the largest aphelion distance, exceeding 2200 au, on a high inclination orbit (i = 78°). It has been recognized to be either a borderline representative of high inclination, high perihelion distance (HiHq) objects, or even a new class of bodies, similar to HiHq objects for orbit but with an aphelion in the inner Oort Cloud. Here, we present photometry using long-term data from 2000 to 2013 taken by the SDSS sky survey, ESO MPG 2.2 m and McDonald 2.1 m telescopes, and a visual+near-infrared spectrum taken with the Southern Astrophysical Research Telescope and Magellan telescopes, providing insights into the surface composition of this body. Our best fit suggests that the surface contains 60% of complex organics (30% of Titan and 30% of Triton tholins) with a significant fraction of ice (30%, including pure water and water with inclusions of complex organics) and 10% silicates. The models also suggest a low limit of amorphous carbons, and hence the fragmentation of long-chained complex organics is slower than their rate of generation. 2012 {DR}}30 just recently passed the perihelion, and the long-term photometry of the object suggested ambiguous signs of activity, since the long-term photometric scatter well exceeded the supposed measurement errors and the expected brightness variation related to rotation. Photometric colors put 2012 {DR}}30 exactly between dark neutral and red objects, thus it either can be in a transition phase between the two classes or have differing surface properties from these populated classes.

The Detection of Water Ice in Comet Hale-Bopp

NASA Technical Reports Server (NTRS)

Davies, John K.; Roush, Ted L.; Cruikshank, Dale P.; Bartholomew, Mary Jane; Geballe, Thomas R.; Owen, Tobias

1996-01-01

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.

Elucidation of Compression-Induced Surface Crystallization in Amorphous Tablets Using Sum Frequency Generation (SFG) Microscopy.

PubMed

Mah, Pei T; Novakovic, Dunja; Saarinen, Jukka; Van Landeghem, Stijn; Peltonen, Leena; Laaksonen, Timo; Isomäki, Antti; Strachan, Clare J

2017-05-01

To investigate the effect of compression on the crystallization behavior in amorphous tablets using sum frequency generation (SFG) microscopy imaging and more established analytical methods. Tablets containing neat amorphous griseofulvin with/without excipients (silica, hydroxypropyl methylcellulose acetate succinate (HPMCAS), microcrystalline cellulose (MCC) and polyethylene glycol (PEG)) were prepared. They were analyzed upon preparation and storage using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM) and SFG microscopy. Compression-induced crystallization occurred predominantly on the surface of the neat amorphous griseofulvin tablets, with minimal crystallinity being detected in the core of the tablets. The presence of various types of excipients was not able to mitigate the compression-induced surface crystallization of the amorphous griseofulvin tablets. However, the excipients affected the crystallization rate of amorphous griseofulvin in the core of the tablet upon compression and storage. SFG microscopy can be used in combination with ATR-FTIR spectroscopy and SEM to understand the crystallization behaviour of amorphous tablets upon compression and storage. When selecting excipients for amorphous formulations, it is important to consider the effect of the excipients on the physical stability of the amorphous formulations.

Shrinking water's no man's land by lifting its low-temperature boundary

NASA Astrophysics Data System (ADS)

Seidl, Markus; Fayter, Alice; Stern, Josef N.; Zifferer, Gerhard; Loerting, Thomas

2015-04-01

Investigation of the properties and phase behavior of noncrystalline water is hampered by rapid crystallization in the so-called "no man's land." We here show that it is possible to shrink the no man's land by lifting its low-temperature boundary, i.e., the pressure-dependent crystallization temperature Tx(p ) . In particular, we investigate two types of high-density amorphous ice (HDA) in the pressure range of 0.10 -0.50 GPa and show that the commonly studied unannealed state, uHDA, is up to 11 K less stable against crystallization than a pressure-annealed state called eHDA. We interpret this finding based on our previously established microscopic picture of uHDA and eHDA, respectively [M. Seidl et al., Phys. Rev. B 88, 174105 (2013), 10.1103/PhysRevB.88.174105]. In this picture the glassy uHDA matrix contains ice Ih-like nanocrystals, which simply grow upon heating uHDA at pressures ≤0.20 GPa . By contrast, they experience a polymorphic phase transition followed by subsequent crystal growth at higher pressures. In comparison, upon heating purely glassy eHDA, ice nuclei of a critical size have to form in the first step of crystallization, resulting in a lifted Tx(p ) . Accordingly, utilizing eHDA enables the study of amorphous ice at significantly higher temperatures at which we regard it to be in the ultraviscous liquid state. This will boost experiments aiming at investigating the proposed liquid-liquid phase transition.

Square ice in graphene nanocapillaries.

PubMed

Algara-Siller, G; Lehtinen, O; Wang, F C; Nair, R R; Kaiser, U; Wu, H A; Geim, A K; Grigorieva, I V

2015-03-26

Bulk water exists in many forms, including liquid, vapour and numerous crystalline and amorphous phases of ice, with hexagonal ice being responsible for the fascinating variety of snowflakes. Much less noticeable but equally ubiquitous is water adsorbed at interfaces and confined in microscopic pores. Such low-dimensional water determines aspects of various phenomena in materials science, geology, biology, tribology and nanotechnology. Theory suggests many possible phases for adsorbed and confined water, but it has proved challenging to assess its crystal structure experimentally. Here we report high-resolution electron microscopy imaging of water locked between two graphene sheets, an archetypal example of hydrophobic confinement. The observations show that the nanoconfined water at room temperature forms 'square ice'--a phase having symmetry qualitatively different from the conventional tetrahedral geometry of hydrogen bonding between water molecules. Square ice has a high packing density with a lattice constant of 2.83 Å and can assemble in bilayer and trilayer crystallites. Molecular dynamics simulations indicate that square ice should be present inside hydrophobic nanochannels independently of their exact atomic nature.

Square ice in graphene nanocapillaries

NASA Astrophysics Data System (ADS)

Algara-Siller, G.; Lehtinen, O.; Wang, F. C.; Nair, R. R.; Kaiser, U.; Wu, H. A.; Geim, A. K.; Grigorieva, I. V.

2015-03-01

Bulk water exists in many forms, including liquid, vapour and numerous crystalline and amorphous phases of ice, with hexagonal ice being responsible for the fascinating variety of snowflakes. Much less noticeable but equally ubiquitous is water adsorbed at interfaces and confined in microscopic pores. Such low-dimensional water determines aspects of various phenomena in materials science, geology, biology, tribology and nanotechnology. Theory suggests many possible phases for adsorbed and confined water, but it has proved challenging to assess its crystal structure experimentally. Here we report high-resolution electron microscopy imaging of water locked between two graphene sheets, an archetypal example of hydrophobic confinement. The observations show that the nanoconfined water at room temperature forms `square ice'--a phase having symmetry qualitatively different from the conventional tetrahedral geometry of hydrogen bonding between water molecules. Square ice has a high packing density with a lattice constant of 2.83 Å and can assemble in bilayer and trilayer crystallites. Molecular dynamics simulations indicate that square ice should be present inside hydrophobic nanochannels independently of their exact atomic nature.

Low-energy electron irradiation induced top-surface nanocrystallization of amorphous carbon film

NASA Astrophysics Data System (ADS)

Chen, Cheng; Fan, Xue; Diao, Dongfeng

2016-10-01

We report a low-energy electron irradiation method to nanocrystallize the top-surface of amorphous carbon film in electron cyclotron resonance plasma system. The nanostructure evolution of the carbon film as a function of electron irradiation density and time was examined by transmission electron microscope (TEM) and Raman spectroscopy. The results showed that the electron irradiation gave rise to the formation of sp2 nanocrystallites in the film top-surface within 4 nm thickness. The formation of sp2 nanocrystallite was ascribed to the inelastic electron scattering in the top-surface of carbon film. The frictional property of low-energy electron irradiated film was measured by a pin-on-disk tribometer. The sp2 nanocrystallized top-surface induced a lower friction coefficient than that of the original pure amorphous film. This method enables a convenient nanocrystallization of amorphous surface.

Comparative surface dynamics of amorphous and semicrystalline polymer films

PubMed Central

Becker, James S.; Brown, Ryan D.; Killelea, Daniel R.; Yuan, Hanqiu; Sibener, S. J.

2011-01-01

The surface dynamics of amorphous and semicrystalline polymer films have been measured using helium atom scattering. Time-of-flight data were collected to resolve the elastic and inelastic scattering components in the diffuse scattering of neutral helium atoms from the surface of a thin poly(ethylene terephthalate) film. Debye–Waller attenuation was observed for both the amorphous and semicrystalline phases of the polymer by recording the decay of elastically scattered helium atoms with increasing surface temperature. Thermal attenuation measurements in the specular scattering geometry yielded perpendicular mean-square displacements of 2.7•10-4 Å2 K-1 and 3.1•10-4 Å2 K-1 for the amorphous and semicrystalline surfaces, respectively. The semicrystalline surface was consistently ∼15% softer than the amorphous across a variety of perpendicular momentum transfers. The Debye–Waller factors were also measured at off-specular angles to characterize the parallel mean-square displacements, which were found to increase by an order of magnitude over the perpendicular mean-square displacements for both surfaces. In contrast to the perpendicular motion, the semicrystalline state was ∼25% stiffer than the amorphous phase in the surface plane. These results were uniquely accessed through low-energy neutral helium atom scattering due to the highly surface-sensitive and nonperturbative nature of these interactions. The goal of tailoring the chemical and physical properties of complex advanced materials requires an improved understanding of interfacial dynamics, information that is obtainable through atomic beam scattering methods. PMID:20713734

The effect of processing on the surface physical stability of amorphous solid dispersions.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Moffat, Jonathan; Craig, Duncan; Qi, Sheng

2014-11-01

The focus of this study was to investigate the effect of processing on the surface crystallization of amorphous molecular dispersions and gain insight into the mechanisms underpinning this effect. The model systems, amorphous molecular dispersions of felodipine-EUDRAGIT® E PO, were processed both using spin coating (an ultra-fast solvent evaporation based method) and hot melt extrusion (HME) (a melting based method). Amorphous solid dispersions with drug loadings of 10-90% (w/w) were obtained by both processing methods. Samples were stored under 75% RH/room temperatures for up to 10months. Surface crystallization was observed shortly after preparation for the HME samples with high drug loadings (50-90%). Surface crystallization was characterized by powder X-ray diffraction (PXRD), ATR-FTIR spectroscopy and imaging techniques (SEM, AFM and localized thermal analysis). Spin coated molecular dispersions showed significantly higher surface physical stability than hot melt extruded samples. For both systems, the progress of the surface crystal growth followed zero order kinetics on aging. Drug enrichment at the surfaces of HME samples on aging was observed, which may contribute to surface crystallization of amorphous molecular dispersions. In conclusion it was found the amorphous molecular dispersions prepared by spin coating had a significantly higher surface physical stability than the corresponding HME samples, which may be attributed to the increased process-related apparent drug-polymer solubility and reduced molecular mobility due to the quenching effect caused by the rapid solvent evaporation in spin coating. Copyright © 2014 Elsevier B.V. All rights reserved.

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

PubMed Central

Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

2012-01-01

Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

2012-05-01

Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models - one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT.

Heterogeneous water oxidation: surface activity versus amorphization activation in cobalt phosphate catalysts.

PubMed

González-Flores, Diego; Sánchez, Irene; Zaharieva, Ivelina; Klingan, Katharina; Heidkamp, Jonathan; Chernev, Petko; Menezes, Prashanth W; Driess, Matthias; Dau, Holger; Montero, Mavis L

2015-02-16

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate-containing Co oxide (CoCat). X-ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5-8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high-TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high-TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte-exposed "outer surface", within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ices on Charon: Distribution of H2O and NH3 from New Horizons LEISA observations

NASA Astrophysics Data System (ADS)

Dalle Ore, C. Morea; Protopapa, S.; Cook, J. C.; Grundy, W. M.; Cruikshank, D. P.; Verbiscer, A. J.; Ennico, K.; Olkin, C. B.; Stern, S. A.; Weaver, H. A.; Young, L. A.; New Horizons Science Team

2018-01-01

Charon, the largest moon of Pluto, appeared as a fairly homogeneous, gray, icy world to New Horizons during closest approach on July 14th, 2015. Charon's sub-Pluto hemisphere was scanned by the Ralph/LEISA near-IR spectrograph providing an unprecedented opportunity to measure its surface composition. We apply a statistical clustering tool to identify spectrally distinct terrains and a radiative transfer approach to study the variations of the 2.0-μm H2O ice band. We map the distribution of the ices previously reported to be present on Charon's surface, namely H2O and the products of NH3 in H2O. We find that H2O ice is mostly in the crystalline phase, confirming previous studies. The regions with the darkest albedos show the strongest signature of amorphous-phase ice, although the crystalline component is still strong. The brighter albedo regions, often corresponding to crater ejecta blankets, are characterized by larger H2O grains, possibly an indication of a younger age. We observe two different behaviors for the two absorption bands representing NH3 in H2O. The 2.21-μm band tends to cluster more in the northern areas compared to the ∼2.01-μm band. Both bands are present in the brighter crater rays, but not all craters show both bands. The 2.21-μm band is also clearly present on the smaller moons Hydra and Nix. These results hint that different physical conditions may determine the appearance or absence of these two different forms of NH3 in H2O ice in the Pluto system. We also investigate the blue slope affecting the spectrum at wavelengths longer than ∼1.8 μm previously reported by several authors. We find that the slope is common among the objects in the Pluto system, Charon, the smaller moons Nix and Hydra, and the darkest terrains on Pluto. It also characterizes the analog ice tholin obtained from irradiation of Pluto-specific materials (a mixture of N2, CH4, and CO ices) in the laboratory. Our modeling results show that Pluto ice tholins are widespread almost uniformly on Charon suggesting a common distribution possibly part of the original reservoir of materials that made up Charon. This was irradiated over the years to yield the gray color characteristic of Charon today. On top of the 'primordial' Pluto ice tholin there is the redder component produced by irradiation of the CH4 provided by Pluto's atmospheric contribution as illustrated by Grundy et al. (2016a).

From Interstellar Polycyclic Aromatic Hydrocarbons and Ice to the Origin of Life

NASA Technical Reports Server (NTRS)

Allamandola, Louis

2004-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. The first part of this talk will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, abundances, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the presolar nebula, the materials frozen into the interstellar/precometary ices are photoprocessed by ultraviolet light and produce more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex materials on the early Earth and their composition may be related to the origin of life.

Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Moore, Marla; Hudson, Reggie; Ferrante, Robert; Moore, William

Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 cm-1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2 N2 , cyanogen; CH3 CN, acetonitrile; C2 H5 CN, propionitrile; and HC3 N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous-and crystalline-phase at 670 nm. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous-and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryo-stat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data. We acknowledge Mark Loeffler who recently joined in our refractive index measurements. The authors also acknowledge support from the Cassini Data Analysis Program. RLH and MHM acknowledge additional funding from NASA's PGG and Outer Planets Programs, and the Goddard Center for Astrobiology.

A significant reduction of ice adhesion on nanostructured surfaces that consist of an array of single-walled carbon nanotubes: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Bao, Luyao; Huang, Zhaoyuan; Priezjev, Nikolai V.; Chen, Shaoqiang; Luo, Kai; Hu, Haibao

2018-04-01

It is well recognized that excessive ice accumulation at low-temperature conditions can cause significant damage to civil infrastructure. The passive anti-icing surfaces provide a promising solution to suppress ice nucleation and enhance ice removal. However, despite extensive efforts, it remains a challenge to design anti-icing surfaces with low ice adhesion. Using all-atom molecular dynamics (MD) simulations, we show that surfaces with single-walled carbon nanotube array (CNTA) significantly reduce ice adhesion due to the extremely low solid areal fraction. It was found that the CNTA surface exhibits up to a 45% decrease in the ice adhesion strength in comparison with the atomically smooth graphene surface. The details of the ice detachment from the CNTA surface were examined for different water-carbon interaction energies and temperatures of the ice cube. Remarkably, the results of MD simulations demonstrate that the ice detaching strength depends linearly on the ratio of the ice-surface interaction energy and the ice temperature. These results open the possibility for designing novel robust surfaces with low ice adhesion for passive anti-icing applications.

Replication of surface features from a master model to an amorphous metallic article

DOEpatents

Johnson, William L.; Bakke, Eric; Peker, Atakan

1999-01-01

The surface features of an article are replicated by preparing a master model having a preselected surface feature thereon which is to be replicated, and replicating the preselected surface feature of the master model. The replication is accomplished by providing a piece of a bulk-solidifying amorphous metallic alloy, contacting the piece of the bulk-solidifying amorphous metallic alloy to the surface of the master model at an elevated replication temperature to transfer a negative copy of the preselected surface feature of the master model to the piece, and separating the piece having the negative copy of the preselected surface feature from the master model.

Amorphous metal formulations and structured coatings for corrosion and wear resistance

DOEpatents

Farmer, Joseph C.

2014-07-15

A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.

Amorphous metal formulations and structured coatings for corrosion and wear resistance

DOEpatents

Farmer, Joseph C [Tracy, CA

2011-12-13

A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.

Formation of Hydroxylamine on Dust Grains via Ammonia Oxidation

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco; Lemaire, Jean-Louis; Garrod, Robin T.

2015-01-01

The quest to detect prebiotic molecules in space, notably amino acids, requires an understanding of the chemistry involving nitrogen atoms. Hydroxylamine (NH2OH) is considered a precursor to the amino acid glycine. Although not yet detected, NH2OH is considered a likely target of detection with ALMA. We report on an experimental investigation of the formation of hydroxylamine on an amorphous silicate surface via the oxidation of ammonia. The experimental data are then fed into a simulation of the formation of NH2OH in dense cloud conditions. On ices at 14 K and with a modest activation energy barrier, NH2OH is found to be formed with an abundance that never falls below a factor 10 with respect to NH3. Suggestions of conditions for future observations are provided.

Systems and Methods for Fabricating Objects Including Amorphous Metal Using Techniques Akin to Additive Manufacturing

NASA Technical Reports Server (NTRS)

Hofmann, Douglas (Inventor)

2017-01-01

Systems and methods in accordance with embodiments of the invention fabricate objects including amorphous metals using techniques akin to additive manufacturing. In one embodiment, a method of fabricating an object that includes an amorphous metal includes: applying a first layer of molten metallic alloy to a surface; cooling the first layer of molten metallic alloy such that it solidifies and thereby forms a first layer including amorphous metal; subsequently applying at least one layer of molten metallic alloy onto a layer including amorphous metal; cooling each subsequently applied layer of molten metallic alloy such that it solidifies and thereby forms a layer including amorphous metal prior to the application of any adjacent layer of molten metallic alloy; where the aggregate of the solidified layers including amorphous metal forms a desired shape in the object to be fabricated; and removing at least the first layer including amorphous metal from the surface.

Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.

On liquid phases in cometary nuclei

NASA Astrophysics Data System (ADS)

Miles, Richard; Faillace, George A.

2012-06-01

In this paper we review the relevant literature and investigate conditions likely to lead to melting of H2O ice, methanol (CH3OH) ice, ethane (C2H6) ice and other volatile ices in cometary nuclei. On the basis of a heat balance model which takes account of volatiles loss, we predict the formation of occasional aqueous and hydrocarbon liquid phases in subsurface regions at heliocentric distances, rh of 1-3 AU, and 5-12 AU, respectively. Low triple-point temperatures and low vapour pressures of C2H6, C3H8, and some higher-order alkanes and alkenes, favour liquid phase formation in cometary bodies at high rh. Microporosity and the formation of a stabilization crust occluding the escape of volatiles facilitate liquid-phase formation. Characteristics of the near-surface which favour subsurface melting include; low effective surface emissivity (at low rh), high amorphous carbon content, average pore sizes of ˜10 μm or less, presence of solutes (e.g. CH3OH), mixtures of C2-C6 hydrocarbons (for melting at high rh), diurnal thermal cycling, and slow rotation rate. Applying the principles of soil mechanics, capillary forces are shown to initiate pre-melting phenomena and subsequent melting, which is expected to impart considerable strength of ˜104 Pa in partially saturated layers, reducing porosity and permeability, enhancing thermal conductivity and heat transfer. Diurnal thermal cycling is expected to have a marked effect on the composition and distribution of H2O ice in the near-surface leading to frost heave-type phenomena even where little if any true melting occurs. Where melting does take place, capillary suction in the wetted zone has the potential to enhance heat transfer via capillary wetting in a low-gravity environment, and to modify surface topography creating relatively smooth flat-bottomed features, which have a tendency to be located within small depressions. An important aspect of the "wetted layer" model is the prediction that diurnal melt-freeze cycles alter the mixing ratio vs. depth of solutes present, or of other miscible components, largely through a process of fractional crystallization, but also potentially involving frost heave. Wetted layers are potentially durable and can involve significant mass transport of volatile materials in the near-surface, increasing in extent over many rotations of the nucleus prior to and just after perihelion passage, and causing stratification and trapping of the lowest-melting mixtures at depths of several metres. A possible mechanism for cometary outbursts is proposed involving a heat pulse reaching the liquid phase in the deepest wetted zone, leading to supersaturation and triggering the sudden release under pressure of dissolved gases, in particular CO2, CO, CH4 or N2, contained beneath a consolidated near-surface layer. This study indicates that liquid water can persist for long periods of time in the near-surface of some intermediate-sized bodies (102-103 km radius) within protoplanetary discs.

Radiation Effects in Hydrogen-Laden Porous Water Ice Films: Implications for Interstellar Ices

NASA Astrophysics Data System (ADS)

Raut, Ujjwal; Baragiola, Raul; Mitchell, Emma; Shi, Jianming

H _{2} is the dominant gas in the dense clouds of the interstellar medium (ISM). At densities of 10 (5) cm (-3) , an H _{2} molecule arrives at the surface of a 0.1 mum-sized, ice-covered dust grain once every few seconds [1]. At 10 K, H _{2} can diffuse into the pores of the ice mantle and adsorb at high-energy binding sites, loading the ice with hydrogen over the lifetime of the cloud. These icy grains are also impacted by galactic cosmic rays and stellar winds (in clouds with embedded protostar). Based on the available cosmic proton flux spectrum [2], we estimate a small impact rate of nearly 1 hit per year on a 0.1 μm sized grain, or 10 (-7) times the impact frequency of the neutral H _{2}. The energy deposited by such impacts can release the adsorbed H _{2} into the gas phase (impact desorption or sputtering). Recently, we have reported on a new process of ion-induced enhanced adsorption, where molecules from the gas phase are incorporated into the film when irradiation is performed in the presence of ambient gas [3]. The interplay between ion-induced ejection and adsorption can be important in determining the gas-solid balance in the ISM. To understand the effects of cosmic rays/stellar winds impacts on interstellar ice immersed in H _{2} gas, we have performed irradiation of porous amorphous ice films loaded with H _{2} through co-deposition or adsorption following growth. The irradiations were performed with 100 keV H (+) using fluxes of 10 (10) -10 (12) H (+) cm (-2) s (-1) at 7 K, in presence of ambient H _{2} at pressures ranging from 10 (-5) to 10 (-8) Torr. Our initial results show a net loss in adsorbed H _{2} during irradiation, from competing ion-induced ejection and adsorption. The H _{2} loss per ion decreases exponentially with fluence, with a cross-section of 10 (-13) cm (2) . In addition to hydrogen removal, irradiation also leads to trapping of H _{2} in the ice film, from closing of the pores during irradiation [4]. As a result, 2.6 percent H _{2} molar remains trapped in the ice even upon removal of ambient gas-phase H _{2}, and is stable to 170 K, where the ice film desorbs. We will describe the dependence of net loss of adsorbed hydrogen on important parameters such as ice film thickness and the ratio of ion flux (f) to H _{2} flux (F _{H}). Both fluxes are higher by orders of magnitude than interstellar values. However, the information obtained from these experiments, especially the behavior in the limit of low flux (f << F _{H}) should be relevant to the interstellar case. Furthermore, we will discuss the effects of the presence of H _{2} in radiation chemistry of water ice, in particular, the observed suppression in H _{2}O _{2} synthesis. References: 1.Tielens, A.G.G.M., The Physics and Chemistry of the Interstellar Medium. 2005: Cambridge University Press. 2.Webber, W.R. and S.M. Yushak, A measurement of the energy spectra and relative abundance of the cosmic-ray H and He isotopes over a broad energy range. Astrophysical Journal, 1983. 275: p. 391-404. 3.Shi, J., B.D. Teolis, and R.A. Baragiola, Irradiation-enhanced adsorption and trapping of O2 on nanoporous water ice. Physical Review B, 2009. 79(23): p. 235422. 4.Raut, U., et al., Compaction of microporous amorphous solid water by ion irradiation. Journal of Chemical Physics, 2007. 126(24): p. 244511.

The Effect of Shock on the Amorphous Component in Altered Basalt

NASA Technical Reports Server (NTRS)

Eckley, S. A.; Wright, S. P.; Rampe, E. B.; Niles, P. B.

2017-01-01

Investigation of the geochemical and mineralogical composition of the Martian surface provides insight into the geologic history of the predominantly basaltic crust. The Chemistry and Mineralogy (CheMin) instrument onboard the Curiosity rover has returned the first X-Ray diffraction data from the Martian surface. However, large proportions (27 +/- 14 with some estimates as high as 50 weight percentage) of an amorphous component have been reported. As a remedy to this problem, mass balance equations using geochemistry, volatile chemistry, and mineralogy have been employed to constrain the geochemistry of the amorphous component. However, "the nature and number of amorphous phases that constitute the amorphous component is not unequivocally known". Multiple hypotheses have been proposed to explain the origin of this amorphous component: Allophane (Al2O); Basaltic glass (Volcanic and impact); Palagonite (Altered basaltic glass); Hisingerite (Fe (sup 3 plus)-bearing phyllosilicate); S/Cl-rich component (sulfates and/or akaganeite); Nanophase ferric oxide component (npOx). Establishing a multi-phase amorphous component from a basaltic precursor that has undergone physical and chemical weathering within geochemical constraints is of paramount importance to better understand the composition of a large portion of the Martian surface (up to 50 weight percentage). Shocked basalts from Lonar Crater in India are valuable analogs for the Martian surface because it is a well-preserved impact crater in a basaltic target. Having undergone pre- and post-shock aqueous alteration, these rocks provide crucial data regarding the effect of shock on the amorphous component in altered basalt. By conducting mass balance equations similar to what has been performed for Gale crater materials, we attempt to calculate the geochemistry of the amorphous component in altered basalts ranging from unshocked to Class 5 (Table 1). This has the potential to reveal the nature and origin (i.e. primary igneous, shock metamorphic, and/or aqueous alteration occurring before or after the impact event) of the amorphous component in shocked basalt with the goal of unravelling the history of the Martian surface.

Imaging of Crystalline and Amorphous Surface Regions Using Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS): Application to Pharmaceutical Materials.

PubMed

Iuraş, Andreea; Scurr, David J; Boissier, Catherine; Nicholas, Mark L; Roberts, Clive J; Alexander, Morgan R

2016-04-05

The structure of a material, in particular the extremes of crystalline and amorphous forms, significantly impacts material performance in numerous sectors such as semiconductors, energy storage, and pharmaceutical products, which are investigated in this paper. To characterize the spatial distribution for crystalline-amorphous forms at the uppermost molecular surface layer, we performed time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) measurements for quench-cooled amorphous and recrystallized samples of the drugs indomethacin, felodipine, and acetaminophen. Polarized light microscopy was used to localize crystallinity induced in the samples under controlled conditions. Principal component analysis was used to identify the subtle changes in the ToF-SIMS spectra indicative of the amorphous and crystalline forms for each drug. The indicators of amorphous and crystalline surfaces were common in type across the three drugs, and could be explained in general terms of crystal packing and intermolecular bonding, leading to intramolecular bond scission in the formation of secondary ions. Less intramolecular scission occurred in the amorphous form, resulting in a greater intensity of molecular and dimer secondary ions. To test the generality of amorphous-crystalline differentiation using ToF-SIMS, a different recrystallization method was investigated where acetaminophen single crystals were recrystallized from supersaturated solutions. The findings indicated that the ability to assign the crystalline/amorphous state of the sample using ToF-SIMS was insensitive to the recrystallization method. This demonstrates that ToF-SIMS is capable of detecting and mapping ordered crystalline and disordered amorphous molecular materials forms at micron spatial resolution in the uppermost surface of a material.

Gelatin Nano-coating for Inhibiting Surface Crystallization of Amorphous Drugs.

PubMed

Teerakapibal, Rattavut; Gui, Yue; Yu, Lian

2018-01-05

Inhibit the fast surface crystallization of amorphous drugs with gelatin nano-coatings. The free surface of amorphous films of indomethacin or nifedipine was coated by a gelatin solution (type A or B) and dried. The coating's effect on surface crystallization was evaluated. Coating thickness was estimated from mass change after coating. For indomethacin (weak acid, pK a  = 4.5), a gelatin coating of either type deposited at pH 5 and 10 inhibited its fast surface crystal growth. The coating thickness was 20 ± 10 nm. A gelatin coating deposited at pH 3, however, provided no protective effect. These results suggest that an effective gelatin coating does not require that the drug and the polymer have opposite charges. The ineffective pH 3 coating might reflect the poor wetting of indomethacin's neutral, hydrophobic surface by the coating solution. For nifedipine (weak base, pK a  = 2.6), a gelatin coating of either type deposited at pH 5 inhibited its fast surface crystal growth. Gelatin nano-coatings can be conveniently applied to amorphous drugs from solution to inhibit fast surface crystallization. Unlike strong polyelectrolyte coatings, a protective gelatin coating does not require strict pairing of opposite charges. This could make gelatin coating a versatile, pharmaceutically acceptable coating for stabilizing amorphous drugs.

Pyroelectricity of water ice.

PubMed

Wang, Hanfu; Bell, Richard C; Iedema, Martin J; Schenter, Gregory K; Wu, Kai; Cowin, James P

2008-05-22

Water ice usually is thought to have zero pyroelectricity by symmetry. However, biasing it with ions breaks the symmetry because of the induced partial dipole alignment. This unmasks a large pyroelectricity. Ions were soft-landed upon 1 mum films of water ice at temperatures greater than 160 K. When cooled below 140-150 K, the dipole alignment locks in. Work function measurements of these films then show high and reversible pyroelectric activity from 30 to 150 K. For an initial approximately 10 V induced by the deposited ions at 160 K, the observed bias below 150 K varies approximately as 10 Vx(T/150 K)2. This implies that water has pyroelectric coefficients as large as that of many commercial pyroelectrics, such as lead zirconate titanate (PZT). The pyroelectricity of water ice, not previously reported, is in reasonable agreement with that predicted using harmonic analysis of a model system of SPC ice. The pyroelectricity is observed in crystalline and compact amorphous ice, deuterated or not. This implies that for water ice between 0 and 150 K (such as astrophysical ices), temperature changes can induce strong electric fields (approximately 10 MV/m) that can influence their chemistry, ion trajectories, or binding.

Characterization of thin film CO2 ice through the infrared ν1 + ν3 combination mode

NASA Astrophysics Data System (ADS)

He, Jiao; Vidali, Gianfranco

2018-01-01

Carbon dioxide is abundant in ice mantles of dust grains; some is found in the pure crystalline form as inferred from the double peak splitting of the bending profile at about 650 cm-1. To study how CO2 segregates into the pure form from water-rich mixtures of ice mantles and how it then crystallizes, we used Reflection Absorption InfraRed Spectroscopy to study the structural change of pure CO2 ice as a function of both ice thickness and temperature. We found that the ν1 + ν3 combination mode absorption profile at 3708 cm-1 provides an excellent probe to quantify the degree of crystallinity in CO2 ice. We also found that between 20 and 30 K, there is an ordering transition that we attribute to reorientation of CO2 molecules, while the diffusion of CO2 becomes significant at much higher temperatures. In the formation of pure crystalline CO2 in interstellar medium ices, the rate limiting process is the diffusion/segregation of CO2 molecules in the ice instead of the phase transition from amorphous to crystalline after clusters/islands of CO2 are formed.

Enhanced Physical Stability of Amorphous Drug Formulations via Dry Polymer Coating.

PubMed

Capece, Maxx; Davé, Rajesh

2015-06-01

Although amorphous solid drug formulations may be advantageous for enhancing the bioavailability of poorly soluble active pharmaceutical ingredients, they exhibit poor physical stability and undergo recrystallization. To address this limitation, this study investigates stability issues associated with amorphous solids through analysis of the crystallization behavior for acetaminophen (APAP), known as a fast crystallizer, using a modified form of the Avrami equation that kinetically models both surface and bulk crystallization. It is found that surface-enhanced crystallization, occurring faster at the free surface than in the bulk, is the major impediment to the stability of amorphous APAP. It is hypothesized that a novel use of a dry-polymer-coating process referred to as mechanical-dry-polymer-coating may be used to inhibit surface crystallization and enhance stability. The proposed process, which is examined, simultaneously mills and coats amorphous solids with polymer, while avoiding solvents or solutions, which may otherwise cause stability or crystallization issues during coating. It is shown that solid dispersions of APAP (64% loading) with a small particle size (28 μm) could be prepared and coated with the polymer, carnauba wax, in a vibratory ball mill. The resulting amorphous solid was found to have excellent stability as a result of inhibition of surface crystallization. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Surface plasmon effects in the absorption enhancements of amorphous silicon solar cells with periodical metal nanowall and nanopillar structures.

PubMed

Lin, Hung-Yu; Kuo, Yang; Liao, Cheng-Yuan; Yang, C C; Kiang, Yean-Woei

2012-01-02

The authors numerically investigate the absorption enhancement of an amorphous Si solar cell, in which a periodical one-dimensional nanowall or two-dimensional nanopillar structure of the Ag back-reflector is fabricated such that a dome-shaped grating geometry is formed after Si deposition and indium-tin-oxide coating. In this investigation, the effects of surface plasmon (SP) interaction in such a metal nanostructure are of major concern. Absorption enhancement in most of the solar spectral range of significant amorphous Si absorption (320-800 nm) is observed in a grating solar cell. In the short-wavelength range of high amorphous Si absorption, the weakly wavelength-dependent absorption enhancement is mainly caused by the broadband anti-reflection effect, which is produced through the surface nano-grating structures. In the long-wavelength range of diminishing amorphous Si absorption, the highly wavelength-sensitive absorption enhancement is mainly caused by Fabry-Perot resonance and SP interaction. The SP interaction includes the contributions of surface plasmon polariton and localized surface plasmon.

Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

2016-04-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice nucleation of secondary organic aerosol produced from ozonolysis of α-pinene, Atmos. Chem. Phys. Discuss., 15, 35719-35752, doi:10.5194/acpd-15-35719-2015, 2015. Järvinen, E. et al., Observation of viscosity transition in α-pinene secondary organic aerosol, Atmos. Chem. Phys. Discuss., 15, 28575-28617, doi:10.5194/acpd-15-28575-2015, 2015.

Coma in Comet C/2012 S1 (ISON) at ~4 au

NASA Astrophysics Data System (ADS)

Videen, Gorden; Zubko, Evgenij; Hines, Dean C.; Shkuratov, Yuriy; Kaydash, Vadym; Muinonen, Karri; Knight, Matthew W.; Sitko, Michael L.; Lisse, Carrey M.; Mutchler, Max; Wooden, Diane H.; Li, Jian-Yang; Kobayashi, Hiroshi

2015-11-01

We analyze HST observations of Comet ISON (C/2012 S1) at heliocentric distance ~4 au and phase angle ~12-14 degree. The inner coma (< 5000 km) reveals two polarimetric features, positive degree of linear polarization P = (2.48 ± 0.45)% at projected distances less than 236 km and negative polarization P = - (1.6 ± 0.45)% at 1000 - 5000 km [Hines et al. 2014: ApJL 780, L32]. At these projected distances, average color slope was found to be ~6% per 100 nm [Li et al. 2013: ApJL 779, L3]. When considered simultaneously, these two features place significant constraint on the physical and chemical properties of dust particles [Zubko et al. 2015: Planet. Space Sci., http://dx.doi.org/10.1016/j.pss.2015.08.002].We model this response with agglomerated debris particles, having highly irregular morphology and density of constituent material being consistent with in situ studies of comets. We consider particles of 28 different refractive indices that correspond to in situ studies of comets and plausible assumptions on chemical composition of cometary dust and ices. What emerges from our analysis is that the ISON coma was chemically heterogeneous at the epoch of observation. The positive polarization at small projected distances suggests a high spatial concentration of highly absorbing materials, such as amorphous carbon and/or organics highly irradiated with UV radiation. At larger distances, the negative polarization P = - (1.6 ± 0.45)% and color slope ~6% per 100 nm appear consistent with organics slightly processed with UV radiation, tholins, Mg-Fe silicates, and Mg-rich silicates contaminated with ~10% (by volume) amorphous carbon. A significant abundance of pure water-ice particles and/or pure Mg-rich silicates must be ruled out in this region. These materials have been found in situ in other comets and also detected with imaging polarimetry in the circumnucleus halo regions. Analyses of polarimetric images suggest that Mg-rich silicates could originate from a refractory surface layer on the surface of cometary nuclei [Zubko et al. 2012: A&A 544, L8]. A depletion of such particles in Comet ISON could imply an absence of such a layer on its nucleus.

Heterogeneous Ice Nucleation: Interplay of Surface Properties and Their Impact on Water Orientations.

PubMed

Glatz, Brittany; Sarupria, Sapna

2018-01-23

Ice is ubiquitous in nature, and heterogeneous ice nucleation is the most common pathway of ice formation. How surface properties affect the propensity to observe ice nucleation on that surface remains an open question. We present results of molecular dynamics studies of heterogeneous ice nucleation on model surfaces. The models surfaces considered emulate the chemistry of kaolinite, an abundant component of mineral dust. We investigate the interplay of surface lattice and hydrogen bonding properties in affecting ice nucleation. We find that lattice matching and hydrogen bonding are necessary but not sufficient conditions for observing ice nucleation at these surfaces. We correlate this behavior to the orientations sampled by the metastable supercooled water in contact with the surfaces. We find that ice is observed in cases where water molecules not only sample orientations favorable for bilayer formation but also do not sample unfavorable orientations. This distribution depends on both surface-water and water-water interactions and can change with subtle modifications to the surface properties. Our results provide insights into the diverse behavior of ice nucleation observed at different surfaces and highlight the complexity in elucidating heterogeneous ice nucleation.

Development of a novel nanoscratch technique for quantitative measurement of ice adhesion strength

NASA Astrophysics Data System (ADS)

Loho, T.; Dickinson, M.

2018-04-01

The mechanism for the way that ice adheres to surfaces is still not well understood. Currently there is no standard method to quantitatively measure how ice adheres to surfaces which makes ice surface studies difficult to compare. A novel quantitative lateral force adhesion measurement at the micro-nano scale for ice was created which shears micro-nano sized ice droplets (less than 3 μm in diameter and 100nm in height) using a nanoindenter. By using small ice droplets, the variables associated with bulk ice measurements were minimised which increased data repeatability compared to bulk testing. The technique provided post- testing surface scans to confirm that the ice had been removed and that measurements were of ice adhesion strength. Results show that the ice adhesion strength of a material is greatly affected by the nano-scale surface roughness of the material with rougher surfaces having higher ice adhesion strength.

Reducing Ice Adhesion on Nonsmooth Metallic Surfaces: Wettability and Topography Effects.

PubMed

Ling, Edwin Jee Yang; Uong, Victor; Renault-Crispo, Jean-Sébastien; Kietzig, Anne-Marie; Servio, Phillip

2016-04-06

The effects of ice formation and accretion on external surfaces range from being mildly annoying to potentially life-threatening. Ice-shedding materials, which lower the adhesion strength of ice to its surface, have recently received renewed research attention as a means to circumvent the problem of icing. In this work, we investigate how surface wettability and surface topography influence the ice adhesion strength on three different surfaces: (i) superhydrophobic laser-inscribed square pillars on copper, (ii) stainless steel 316 Dutch-weave meshes, and (iii) multiwalled carbon nanotube-covered steel meshes. The finest stainless steel mesh displayed the best performance with a 93% decrease in ice adhesion relative to polished stainless steel, while the superhydrophobic square pillars exhibited an increase in ice adhesion by up to 67% relative to polished copper. Comparisons of dynamic contact angles revealed little correlation between surface wettability and ice adhesion. On the other hand, by considering the ice formation process and the fracture mechanics at the ice-substrate interface, we found that two competing mechanisms governing ice adhesion strength arise on nonplanar surfaces: (i) mechanical interlocking of the ice within the surface features that enhances adhesion, and (ii) formation of microcracks that act as interfacial stress concentrators, which reduce adhesion. Our analysis provides insight toward new approaches for the design of ice-releasing materials through the use of surface topographies that promote interfacial crack propagation.

Sink or Swim: Ions and Organics at the Ice-Air Interface.

PubMed

Hudait, Arpa; Allen, Michael T; Molinero, Valeria

2017-07-26

The ice-air interface is an important locus of environmental chemical reactions. The structure and dynamics of the ice surface impact the uptake of trace gases and kinetics of reactions in the atmosphere and snowpack. At tropospheric temperatures, the ice surface is partially premelted. Experiments indicate that ions increase the liquidity of the ice surface but hydrophilic organics do not. However, it is not yet known the extent of the perturbation solutes induce at the ice surface and what is the role of the disordered liquid-like layer in modulating the interaction between solutes and their mobility and aggregation at the ice surface. Here we use large-scale molecular simulations to investigate the effect of ions and glyoxal, one of the most abundant oxygenated volatile organic compounds in the atmosphere, on the structure, dynamics, and solvation properties of the ice surface. We find that the premelted surface of ice has unique solvation properties, different from those of liquid water. The increase in surface liquidity resulting from the hydration of ions leads to a water-mediated attraction of ions at the ice surface. Glyoxal molecules, on the other hand, perturb only slightly the surface of ice and do not experience water-driven attraction. They nonetheless accumulate as dry agglomerates at the ice surface, driven by direct interactions between the organic molecules. The enhanced attraction and clustering of ions and organics at the ice surface may play a significant role in modulating the mechanism and rate of heterogeneous chemical reactions occurring at the surface of atmospheric ice particles.

Conformal coating of highly structured surfaces

DOEpatents

Ginley, David S.; Perkins, John; Berry, Joseph; Gennett, Thomas

2012-12-11

Method of applying a conformal coating to a highly structured substrate and devices made by the disclosed methods are disclosed. An example method includes the deposition of a substantially contiguous layer of a material upon a highly structured surface within a deposition process chamber. The highly structured surface may be associated with a substrate or another layer deposited on a substrate. The method includes depositing a material having an amorphous structure on the highly structured surface at a deposition pressure of equal to or less than about 3 mTorr. The method may also include removing a portion of the amorphous material deposited on selected surfaces and depositing additional amorphous material on the highly structured surface.

Fabrication of micro-patterned aluminum surfaces for low ice adhesion strength

NASA Astrophysics Data System (ADS)

Jeon, Jaehyeon; Jang, Hanmin; Chang, Jinho; Lee, Kwan-Soo; Kim, Dong Rip

2018-05-01

We report a fabrication method to obtain a low-ice-adhesion aluminum surface by surface texturing using solution etching and subsequent thin-film coating. Specifically, the textured surface has microstructures of a low aspect ratio, that is, with a much smaller height than width. Such microstructures can effectively reduce ice-adhesion strengths by sliding the ice during detachment. Because our method is based on solution etching, it can be applied to curved surfaces with complex shapes for uniformly constructing the morphology of a low-ice-adhesion aluminum surface. Finally, the low-ice-adhesion aluminum surface reduces the ice-adhesion strengths by up to 95%.

Amorphous titanium-oxide supercapacitors.

PubMed

Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko

2016-10-21

The electric capacitance of an amorphous TiO 2-x surface increases proportionally to the negative sixth power of the convex diameter d. This occurs because of the van der Waals attraction on the amorphous surface of up to 7 mF/cm 2 , accompanied by extreme enhanced electron trapping resulting from both the quantum-size effect and an offset effect from positive charges at oxygen-vacancy sites. Here we show that a supercapacitor, constructed with a distributed constant-equipment circuit of large resistance and small capacitance on the amorphous TiO 2-x surface, illuminated a red LED for 37 ms after it was charged with 1 mA at 10 V. The fabricated device showed no dielectric breakdown up to 1,100 V. Based on this approach, further advances in the development of amorphous titanium-dioxide supercapacitors might be attained by integrating oxide ribbons with a micro-electro mechanical system.

Amorphous titanium-oxide supercapacitors

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko

2016-10-01

The electric capacitance of an amorphous TiO2-x surface increases proportionally to the negative sixth power of the convex diameter d. This occurs because of the van der Waals attraction on the amorphous surface of up to 7 mF/cm2, accompanied by extreme enhanced electron trapping resulting from both the quantum-size effect and an offset effect from positive charges at oxygen-vacancy sites. Here we show that a supercapacitor, constructed with a distributed constant-equipment circuit of large resistance and small capacitance on the amorphous TiO2-x surface, illuminated a red LED for 37 ms after it was charged with 1 mA at 10 V. The fabricated device showed no dielectric breakdown up to 1,100 V. Based on this approach, further advances in the development of amorphous titanium-dioxide supercapacitors might be attained by integrating oxide ribbons with a micro-electro mechanical system.

Ice sheet topography by satellite altimetry

USGS Publications Warehouse

Brooks, R.L.; Campbell, W.J.; Ramseier, R.O.; Stanley, H.R.; Zwally, H.J.

1978-01-01

The surface elevation of the southern Greenland ice sheet and surface features of the ice flow are obtained from the radar altimeter on the GEOS 3 satellite. The achieved accuracy in surface elevation is ???2 m. As changes in surface elevation are indicative of changes in ice volume, the mass balance of the present ice sheets could be determined by repetitive mapping of the surface elevation and the surface could be monitored to detect surging or significant changes in ice flow. ?? 1978 Nature Publishing Group.

Where's the Water in (Salty) Ice?

NASA Astrophysics Data System (ADS)

Kahan, T.; Malley, P.

2017-12-01

Solutes can have large effects on reactivity in ice and at ice surfaces. Freeze concentration ("the salting out effect") forms liquid regions containing high solute concentrations surrounded by relatively solute-free ice. Thermodynamics can predict the fraction of ice that is liquid for a given temperature and (pre-frozen) solute concentration, as well as the solute concentration within these liquid regions, but they do not inform on the spatial distribution of the solutes and the liquid regions within the ice. This leads to significant uncertainty in predictions of reaction kinetics in ice and at ice surfaces. We have used Raman microscopy to determine the location of liquid regions within ice and at ice surface in the presence of sodium chloride (NaCl). Under most conditions, liquid channels are observed at the ice surface and throughout the ice bulk. The fraction of the ice that is liquid, as well as the widths of these channels, increases with increasing temperature. Below the eutectic temperature (-21.1 oC), no liquid is observed. Patches of NaCl.2H2O ("hydrohalite") are observed at the ice surface under these conditions. These results will improve predictions of reaction kinetics in ice and at ice surfaces.

Significance of Thermal Fluvial Incision and Bedrock Transfer due to Ice Advection on Greenland Ice Sheet Topography

NASA Astrophysics Data System (ADS)

Crozier, J. A.; Karlstrom, L.; Yang, K.

2017-12-01

Ice sheet surface topography reflects a complicated combination of processes that act directly upon the surface and that are products of ice advection. Using recently-available high resolution ice velocity, imagery, ice surface elevation, and bedrock elevation data sets, we seek to determine the domain of significance of two important processes - thermal fluvial incision and transfer of bedrock topography through the ice sheet - on controlling surface topography in the ablation zone. Evaluating such controls is important for understanding how melting of the GIS surface during the melt season may be directly imprinted in topography through supraglacial drainage networks, and indirectly imprinted through its contribution to basal sliding that affects bedrock transfer. We use methods developed by (Karlstrom and Yang, 2016) to identify supraglacial stream networks on the GIS, and use high resolution surface digital elevation models as well as gridded ice velocity and melt rate models to quantify surface processes. We implement a numerically efficient Fourier domain bedrock transfer function (Gudmundsson, 2003) to predict surface topography due to ice advection over bedrock topography obtained from radar. Despite a number of simplifying assumptions, the bedrock transfer function predicts the observed ice sheet surface in most regions of the GIS with ˜90% accuracy, regardless of the presence or absence of supraglacial drainage networks. This supports the hypothesis that bedrock is the most significant driver of ice surface topography on wavelengths similar to ice thickness. Ice surface topographic asymmetry on the GIS is common, with slopes in the direction of ice flow steeper than those faced opposite to ice flow, consistent with bedrock transfer theory. At smaller wavelengths, topography consistent with fluvial erosion by surface hydrologic features is evident. We quantify the effect of ice advection versus fluvial thermal erosion on supraglacial longitudinal stream profiles, as a function of location on the GIS (hence ice thickness and background melt rate) using spectral techniques to quantify longitudinal stream profiles. This work should provide a predictive guide for which processes are responsible for ice sheet topography scales from several m (DEM resolution) up to several ice thicknesses.

Surface and basal ice shelf mass balance processes of the Southern McMurdo Ice Shelf determined through radar statistical reconnaissance

NASA Astrophysics Data System (ADS)

Grima, C.; Koch, I.; Greenbaum, J. S.; Soderlund, K. M.; Blankenship, D. D.; Young, D. A.; Fitzsimons, S.

2017-12-01

The McMurdo ice shelves (northern and southern MIS), adjacent to the eponymous station and the Ross Ice Shelf, Antarctica, are known for large gradients in surface snow accumulation and snow/ice impurities. Marine ice accretion and melting are important contributors to MIS's mass balance. Due to erosive winds, the southern MIS (SMIS) shows a locally negative surface mass balance. Thus, marine ice once accreted at the ice shelf base crops out at the surface. However, the exact processes that exert primary control on SMIS mass balance have remained elusive. Radar statistical reconnaissance (RSR) is a recent technique that has been used to characterize the surface properties of the Earth's cryosphere, Mars, and Titan from the stochastic character of energy scattered by the surface. Here, we apply RSR to map the surface density and roughness of the SMIS and extend the technique to derive the basal reflectance and scattering coefficients of the ice-ocean interface. We use an airborne radar survey grid acquired over the SMIS in the 2014-2015 austral summer by the University of Texas Institute for Geophysics with the High Capability Radar Sounder (HiCARS2; 60-MHz center frequency and 15-MHz bandwidth). The RSR-derived snow density values and patterns agree with directly -measured ice shelf surface accumulation rates. We also compare the composition of SMIS ice surface samples to test the ability of RSR to discriminate ices with varying dielectric properties (e.g., marine versus meteoric ice) and hypothesize relationships between the RSR-derived basal reflectance/scattered coefficients and accretion or melting at the ice-ocean interface. This improved knowledge of air-ice and ice-ocean boundaries provides a new perspective on the processes governing SMIS surface and basal mass balance.

Inverted amorphous silicon solar cell utilizing cermet layers

DOEpatents

Hanak, Joseph J.

1979-01-01

An amorphous silicon solar cell incorporating a transparent high work function metal cermet incident to solar radiation and a thick film cermet contacting the amorphous silicon opposite to said incident surface.

A molecular model for ice nucleation and growth, attachment 1

NASA Technical Reports Server (NTRS)

Plummer, P. L. M.

1981-01-01

The quantum mechanical technique is used to study ionic, configurational, and impurity defects in the ice surface. In addition to static calculations of the energetics of the water monomer-ice surface interactions, molecular dynamics studies were initiated. The calculations of the monomer-ice surface interaction, molecular dynamics studies were initiated. The calculations of monomer-ice surface interactions indicate that many adsorption sites exist on the ice surfaces and that the barriers between bonding sites are relatively low. Bonding on the prism face of ice is preferentially above lattice sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swarctz, Christopher; Alijallis, Elias; Hunter, Scott Robert

In this study, a closed loop low-temperature wind tunnel was custom-built and uniquely used to investigate the anti-icing mechanism of superhydrophobic surfaces in regulated flow velocities, temperatures, humidity, and water moisture particle sizes. Silica nanoparticle-based hydrophobic coatings were tested as superhydrophobic surface models. During tests, images of ice formation were captured by a camera and used for analysis of ice morphology. Prior to and after wind tunnel testing, apparent contact angles of water sessile droplets on samples were measured by a contact angle meter to check degradation of surface superhydrophobicity. A simple peel test was also performed to estimate adhesionmore » of ice on the surfaces. When compared to an untreated sample, superhydrophobic surfaces inhibited initial ice formation. After a period of time, random droplet strikes attached to the superhydrophobic surfaces and started to coalesce with previously deposited ice droplets. These sites appear as mounds of accreted ice across the surface. The appearance of the ice formations on the superhydrophobic samples is white rather than transparent, and is due to trapped air. These ice formations resemble soft rime ice rather than the transparent glaze ice seen on the untreated sample. Compared to untreated surfaces, the icing film formed on superhydrophobic surfaces was easy to peel off by shear flows.« less

Intrinsic stress evolution during amorphous oxide film growth on Al surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flötotto, D., E-mail: d.floetotto@is.mpg.de; Wang, Z. M.; Jeurgens, L. P. H.

2014-03-03

The intrinsic stress evolution during formation of ultrathin amorphous oxide films on Al(111) and Al(100) surfaces by thermal oxidation at room temperature was investigated in real-time by in-situ substrate curvature measurements and detailed atomic-scale microstructural analyses. During thickening of the oxide a considerable amount of growth stresses is generated in, remarkably even amorphous, ultrathin Al{sub 2}O{sub 3} films. The surface orientation-dependent stress evolutions during O adsorption on the bare Al surfaces and during subsequent oxide-film growth can be interpreted as a result of (i) adsorption-induced surface stress changes and (ii) competing processes of free volume generation and structural relaxation, respectively.

Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A. M.; Cheap, A.; Champagnon, B.; Bessueille, F.; Coulm, J.; Bois, L.; Vouagner, D.

2015-10-01

Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential interest in the field of Raman distributed sensors, which use the amorphous SiO2 core of optical fibers as a transducer to make temperature measurements.

Using Airborne Radar Stratigraphy to Model Surface Accumulation Anomaly and Basal Control over Deformed Basal Ice in Greenland

NASA Astrophysics Data System (ADS)

Das, I.; Bell, R. E.; Creyts, T. T.; Wolovick, M.

2013-12-01

Large deformed ice structures have been imaged at the base of northern Greenland ice sheet by IceBridge airborne radar. Numerous deformed structures lie along the base of both Petermann Glacier and Northeast Ice stream catchments covering 10-13% of the catchment area. These structures may be combinations of basal freeze-on and folded ice that overturns and inverts stratigraphy. In the interior, where the ice velocity is low, the radar imaged height of the deformed structures are frequently a significant fraction of the ice thickness. They are related to basal freeze on and stick-slip at the base of the ice sheet and may be triggered by subglacial water, sediments or local geological conditions. The larger ones (at times up to 700 m thick and 140 km long) perturb the ice stratigraphy and create prominent undulations on the ice surface and modify the local surface mass balance. Here, we investigate the relationship between the deformed structures and surface processes using shallow and deep ice radar stratigraphy. The surface undulations caused by the deformed structures modulate the pattern of local surface snow accumulation. Using normalized differences of several near-surface stratigraphic layers, we have calculated the accumulation anomaly over these deformed structures. The accumulation anomalies can be as high as 20% of the local surface accumulation over some of the larger surface depressions caused by these deformed structures. We observe distinct differences in the phases of the near-surface internal layers on the Petermann and Northeast catchments. These differences indicate that the deformed bodies over Petermann are controlled by conditions at the bed different from the Northeast Ice stream. The distinctly different near-surface stratigraphy over the deformed structures in the Petermann and Northeast catchments have opened up a number of questions including their formation and how they influence the ice dynamics, ice stratigraphy and surface mass balance. In this study we will model the different physical conditions at the bed and ice rheology from their distinct signatures in the near-surface strata. The results will identify the distinct mechanisms that form these bodies and their control over the surface morphology and snow accumulation.

Antarctic ice shelf potentially stabilized by export of meltwater in surface river.

PubMed

Bell, Robin E; Chu, Winnie; Kingslake, Jonathan; Das, Indrani; Tedesco, Marco; Tinto, Kirsty J; Zappa, Christopher J; Frezzotti, Massimo; Boghosian, Alexandra; Lee, Won Sang

2017-04-19

Meltwater stored in ponds and crevasses can weaken and fracture ice shelves, triggering their rapid disintegration. This ice-shelf collapse results in an increased flux of ice from adjacent glaciers and ice streams, thereby raising sea level globally. However, surface rivers forming on ice shelves could potentially export stored meltwater and prevent its destructive effects. Here we present evidence for persistent active drainage networks-interconnected streams, ponds and rivers-on the Nansen Ice Shelf in Antarctica that export a large fraction of the ice shelf's meltwater into the ocean. We find that active drainage has exported water off the ice surface through waterfalls and dolines for more than a century. The surface river terminates in a 130-metre-wide waterfall that can export the entire annual surface melt over the course of seven days. During warmer melt seasons, these drainage networks adapt to changing environmental conditions by remaining active for longer and exporting more water. Similar networks are present on the ice shelf in front of Petermann Glacier, Greenland, but other systems, such as on the Larsen C and Amery Ice Shelves, retain surface water at present. The underlying reasons for export versus retention remain unclear. Nonetheless our results suggest that, in a future warming climate, surface rivers could export melt off the large ice shelves surrounding Antarctica-contrary to present Antarctic ice-sheet models, which assume that meltwater is stored on the ice surface where it triggers ice-shelf disintegration.

Antarctic Ice Shelf Potentially Stabilized by Export of Meltwater in Surface River

NASA Technical Reports Server (NTRS)

Bell, Robin E.; Chu, Winnie; Kingslake, Jonathan; Das, Indrani; Tedesco, Marco; Tinto, Kirsty J.; Zappa, Christopher J.; Frezzotti, Massimo; Boghosian, Alexandra; Lee, Won Sang

2017-01-01

Meltwater stored in ponds and crevasses can weaken and fracture ice shelves, triggering their rapid disintegration. This ice-shelf collapse results in an increased flux of ice from adjacent glaciers and ice streams, thereby raising sea level globally. However, surface rivers forming on ice shelves could potentially export stored meltwater and prevent its destructive effects. Here we present evidence for persistent active drainage networks-interconnected streams, ponds and rivers-on the Nansen Ice Shelf in Antarctica that export a large fraction of the ice shelf's meltwater into the ocean. We find that active drainage has exported water off the ice surface through waterfalls and dolines for more than a century. The surface river terminates in a 130-metre-wide waterfall that can export the entire annual surface melt over the course of seven days. During warmer melt seasons, these drainage networks adapt to changing environmental conditions by remaining active for longer and exporting more water. Similar networks are present on the ice shelf in front of Petermann Glacier, Greenland, but other systems, such as on the Larsen C and Amery Ice Shelves, retain surface water at present. The underlying reasons for export versus retention remain unclear. Nonetheless our results suggest that, in a future warming climate, surface rivers could export melt off the large ice shelves surrounding Antarctica-contrary to present Antarctic ice-sheet models, which assume that meltwater is stored on the ice surface where it triggers ice-shelf disintegration.

Antarctic ice shelf potentially stabilized by export of meltwater in surface river

NASA Astrophysics Data System (ADS)

Bell, Robin E.; Chu, Winnie; Kingslake, Jonathan; Das, Indrani; Tedesco, Marco; Tinto, Kirsty J.; Zappa, Christopher J.; Frezzotti, Massimo; Boghosian, Alexandra; Lee, Won Sang

2017-04-01

Meltwater stored in ponds and crevasses can weaken and fracture ice shelves, triggering their rapid disintegration. This ice-shelf collapse results in an increased flux of ice from adjacent glaciers and ice streams, thereby raising sea level globally. However, surface rivers forming on ice shelves could potentially export stored meltwater and prevent its destructive effects. Here we present evidence for persistent active drainage networks—interconnected streams, ponds and rivers—on the Nansen Ice Shelf in Antarctica that export a large fraction of the ice shelf’s meltwater into the ocean. We find that active drainage has exported water off the ice surface through waterfalls and dolines for more than a century. The surface river terminates in a 130-metre-wide waterfall that can export the entire annual surface melt over the course of seven days. During warmer melt seasons, these drainage networks adapt to changing environmental conditions by remaining active for longer and exporting more water. Similar networks are present on the ice shelf in front of Petermann Glacier, Greenland, but other systems, such as on the Larsen C and Amery Ice Shelves, retain surface water at present. The underlying reasons for export versus retention remain unclear. Nonetheless our results suggest that, in a future warming climate, surface rivers could export melt off the large ice shelves surrounding Antarctica—contrary to present Antarctic ice-sheet models, which assume that meltwater is stored on the ice surface where it triggers ice-shelf disintegration.

COHESION OF AMORPHOUS SILICA SPHERES: TOWARD A BETTER UNDERSTANDING OF THE COAGULATION GROWTH OF SILICATE DUST AGGREGATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimura, Hiroshi; Wada, Koji; Senshu, Hiroki

2015-10-10

Adhesion forces between submicrometer-sized silicate grains play a crucial role in the formation of silicate dust agglomerates, rocky planetesimals, and terrestrial planets. The surface energy of silicate dust particles is the key to their adhesion and rolling forces in a theoretical model based on contact mechanics. Here we revisit the cohesion of amorphous silica spheres by compiling available data on the surface energy for hydrophilic amorphous silica in various circumstances. It turned out that the surface energy for hydrophilic amorphous silica in a vacuum is a factor of 10 higher than previously assumed. Therefore, the previous theoretical models underestimated themore » critical velocity for the sticking of amorphous silica spheres, as well as the rolling friction forces between them. With the most plausible value of the surface energy for amorphous silica spheres, theoretical models based on the contact mechanics are in harmony with laboratory experiments. Consequently, we conclude that silicate grains with a radius of 0.1 μm could grow to planetesimals via coagulation in a protoplanetary disk. We argue that the coagulation growth of silicate grains in a molecular cloud is advanced either by organic mantles rather than icy mantles or, if there are no mantles, by nanometer-sized grain radius.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range frommore » −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.« less

Amorphous surface layers in Ti-implanted Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knapp, J.A.; Follstaedt, D.M.; Picraux, S.T.

1979-01-01

Implanting Ti into high-purity Fe results in an amorphous surface layer which is composed of not only Fe and Ti, but also C. Implantations were carried out at room temperature over the energy range 90 to 190 keV and fluence range 1 to 2 x 10/sup 16/ at/cm/sup 2/. The Ti-implanted Fe system has been characterized using transmission electron microscopy (TEM), ion backscattering and channeling analysis, and (d,p) nuclear reaction analysis. The amorphous layer was observed to form at the surface and grow inward with increasing Ti fluence. For an implant of 1 x 10/sup 17/ Ti/cm/sup 2/ at 180more » keV the layer thickness was 150 A, while the measured range of the implanted Ti was approx. 550 A. This difference is due to the incorporation of C into the amorphous alloy by C being deposited on the surface during implantation and subsequently diffusing into the solid. Our results indicate that C is an essential constituent of the amorphous phase for Ti concentrations less than or equal to 10 at. %. For the 1 x 10/sup 17/ Ti/cm/sup 2/ implant, the concentration of C in the amorphous phase was approx. 25 at. %, while that of Ti was only approx. 3 at. %. A higher fluence implant of 2 x 10/sup 17/ Ti/cm/sup 2/ produced an amorphous layer with a lower C concentration of approx. 10 at. % and a Ti concentration of approx. 20 at. %.« less

Effects of Atmospheric Water and Surface Wind on Passive Microwave Retrievals of Sea Ice Concentration: a Simulation Study

NASA Astrophysics Data System (ADS)

Shin, D.; Chiu, L. S.; Clemente-Colon, P.

2006-05-01

The atmospheric effects on the retrieval of sea ice concentration from passive microwave sensors are examined using simulated data typical for the Arctic summer. The simulation includes atmospheric contributions of cloud liquid water, water vapor and surface wind on the microwave signatures. A plane parallel radiative transfer model is used to compute brightness temperatures at SSM/I frequencies over surfaces that contain open water, first-year (FY) ice and multi-year (MY) ice and their combinations. Synthetic retrievals in this study use the NASA Team (NT) algorithm for the estimation of sea ice concentrations. This study shows that if the satellite sensor's field of view is filled with only FY ice the retrieval is not much affected by the atmospheric conditions due to the high contrast between emission signals from FY ice surface and the signals from the atmosphere. Pure MY ice concentration is generally underestimated due to the low MY ice surface emissivity that results in the enhancement of emission signals from the atmospheric parameters. Simulation results in marginal ice areas also show that the atmospheric effects from cloud liquid water, water vapor and surface wind tend to degrade the accuracy at low sea ice concentration. FY ice concentration is overestimated and MY ice concentration is underestimated in the presence of atmospheric water and surface wind at low ice concentration. This compensating effect reduces the retrieval uncertainties of total (FY and MY) ice concentration. Over marginal ice zones, our results suggest that strong surface wind is more important than atmospheric water in contributing to the retrieval errors of total ice concentrations in the normal ranges of these variables.

Investigating the Effects of Environmental Solutes on the Reaction Environment in Ice and at Ice Surfaces

NASA Astrophysics Data System (ADS)

Malley, Philip Patrick Anthony

The reaction environments present in water, ice, and at ice surfaces are physically distinct from one another and studies have shown that photolytic reactions can take place at different rates in the different media. Kinetics of reactions in frozen media are measured in snow and ice prepared from deionized water. This reduces experimental artifacts, but is not relevant to snow in the environment, which contains solutes. We have monitored the effect of nonchromophoric (will not absorb sunlight) organic matter on the photolytic fate of the polycyclic aromatic hydrocarbons (PAHs) phenanthrene, pyrene, and anthracene in ice and at ice surfaces. Nonchromophoric organic matter reduced photolysis rates to below our detection limit in bulk ice, and reduced rates at ice surfaces to a lesser extent due to the PAHs partially partitioning to the organics present. In addition, we have monitored the effect of chromophoric (will absorb sunlight) dissolved organic matter (cDOM) on the fate of anthracene in water, ice, and ice surfaces. cDOM reduced rates in all three media. Suppression in liquid water was due to physical interactions between anthracene and the cDOM, rather than to competitive photon absorbance. More suppression was observed in ice cubes and ice granules than in liquid water due to a freeze concentrating effect. Sodium Chloride (NaCl) is another ubiquitous environmental solute that can influence reaction kinetics in water, ice, and at ice surfaces. Using Raman microscopy, we have mapped the surface of ice of frozen NaCl solutions at 0.02M and 0.6M, as well as the surface of frozen samples of Sargasso Sea Water. At temperatures above and below the eutectic temperature (-21.1°C). Above the eutectic, regions of ice and liquid water were observed in all samples. Liquid regions generally took the form of channels. Channel widths and fractional liquid surface coverage increased with NaCl concentration and temperature. Volume maps of the three samples at temperatures above the eutectic point, showed that liquid channels were distributed throughout the ice sample. Liquid fractions were similar at ice surfaces and in the bulk at depths of at least 80 microm.

From Interstellar PAHs and Ices to the Origin of Life

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In dense molecular clouds, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier interstellar chemistry standards, is widespread throughout the Universe. The first part of this lecture will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, concentrations, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the solar nebula during the star and planet formation stage, the materials frozen into interstellar/precometary ices are photoprocessed by ultraviolet light, producing more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the early Earth. As these materials are thought to be the building blocks of comets and related to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex organic materials on the early Earth and their composition may be related to the origin of life.

Mass Balance Changes and Ice Dynamics of Greenland and Antarctic Ice Sheets from Laser Altimetry

NASA Astrophysics Data System (ADS)

Babonis, G. S.; Csatho, B.; Schenk, T.

2016-06-01

During the past few decades the Greenland and Antarctic ice sheets have lost ice at accelerating rates, caused by increasing surface temperature. The melting of the two big ice sheets has a big impact on global sea level rise. If the ice sheets would melt down entirely, the sea level would rise more than 60 m. Even a much smaller rise would cause dramatic damage along coastal regions. In this paper we report about a major upgrade of surface elevation changes derived from laser altimetry data, acquired by NASA's Ice, Cloud and land Elevation Satellite mission (ICESat) and airborne laser campaigns, such as Airborne Topographic Mapper (ATM) and Land, Vegetation and Ice Sensor (LVIS). For detecting changes in ice sheet elevations we have developed the Surface Elevation Reconstruction And Change detection (SERAC) method. It computes elevation changes of small surface patches by keeping the surface shape constant and considering the absolute values as surface elevations. We report about important upgrades of earlier results, for example the inclusion of local ice caps and the temporal extension from 1993 to 2014 for the Greenland Ice Sheet and for a comprehensive reconstruction of ice thickness and mass changes for the Antarctic Ice Sheets.

EM Bias-Correction for Ice Thickness and Surface Roughness Retrievals over Rough Deformed Sea Ice

NASA Astrophysics Data System (ADS)

Li, L.; Gaiser, P. W.; Allard, R.; Posey, P. G.; Hebert, D. A.; Richter-Menge, J.; Polashenski, C. M.

2016-12-01

The very rough ridge sea ice accounts for significant percentage of total ice areas and even larger percentage of total volume. The commonly used Radar altimeter surface detection techniques are empirical in nature and work well only over level/smooth sea ice. Rough sea ice surfaces can modify the return waveforms, resulting in significant Electromagnetic (EM) bias in the estimated surface elevations, and thus large errors in the ice thickness retrievals. To understand and quantify such sea ice surface roughness effects, a combined EM rough surface and volume scattering model was developed to simulate radar returns from the rough sea ice `layer cake' structure. A waveform matching technique was also developed to fit observed waveforms to a physically-based waveform model and subsequently correct the roughness induced EM bias in the estimated freeboard. This new EM Bias Corrected (EMBC) algorithm was able to better retrieve surface elevations and estimate the surface roughness parameter simultaneously. In situ data from multi-instrument airborne and ground campaigns were used to validate the ice thickness and surface roughness retrievals. For the surface roughness retrievals, we applied this EMBC algorithm to co-incident LiDAR/Radar measurements collected during a Cryosat-2 under-flight by the NASA IceBridge missions. Results show that not only does the waveform model fit very well to the measured radar waveform, but also the roughness parameters derived independently from the LiDAR and radar data agree very well for both level and deformed sea ice. For sea ice thickness retrievals, validation based on in-situ data from the coordinated CRREL/NRL field campaign demonstrates that the physically-based EMBC algorithm performs fundamentally better than the empirical algorithm over very rough deformed sea ice, suggesting that sea ice surface roughness effects can be modeled and corrected based solely on the radar return waveforms.

Molecular simulations of heterogeneous ice nucleation. I. Controlling ice nucleation through surface hydrophilicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cox, Stephen J.; Kathmann, Shawn M.; Slater, B.

2015-05-14

Ice formation is one of the most common and important processes on earth and almost always occurs at the surface of a material. A basic understanding of how the physicochemical properties of a material’s surface affect its ability to form ice has remained elusive. Here, we use molecular dynamics simulations to directly probe heterogeneous ice nucleation at a hexagonal surface of a nanoparticle of varying hydrophilicity. Surprisingly, we find that structurally identical surfaces can both inhibit and promote ice formation and analogous to a chemical catalyst, it is found that an optimal interaction between the surface and the water existsmore » for promoting ice nucleation.We use our microscopic understanding of the mechanism to design a modified surface in silico with enhanced ice nucleating ability. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.« less

Characterizing Arctic Sea Ice Topography Using High-Resolution IceBridge Data

NASA Technical Reports Server (NTRS)

Petty, Alek; Tsamados, Michel; Kurtz, Nathan; Farrell, Sinead; Newman, Thomas; Harbeck, Jeremy; Feltham, Daniel; Richter-Menge, Jackie

2016-01-01

We present an analysis of Arctic sea ice topography using high resolution, three-dimensional, surface elevation data from the Airborne Topographic Mapper, flown as part of NASA's Operation IceBridge mission. Surface features in the sea ice cover are detected using a newly developed surface feature picking algorithm. We derive information regarding the height, volume and geometry of surface features from 2009-2014 within the Beaufort/Chukchi and Central Arctic regions. The results are delineated by ice type to estimate the topographic variability across first-year and multi-year ice regimes.

Heterogeneous nucleation of ice on carbon surfaces.

PubMed

Lupi, Laura; Hudait, Arpa; Molinero, Valeria

2014-02-26

Atmospheric aerosols can promote the heterogeneous nucleation of ice, impacting the radiative properties of clouds and Earth's climate. The experimental investigation of heterogeneous freezing of water droplets by carbonaceous particles reveals widespread ice freezing temperatures. It is not known which structural and chemical characteristics of soot account for the variability in ice nucleation efficiency. Here we use molecular dynamics simulations to investigate the nucleation of ice from liquid water in contact with graphitic surfaces. We find that atomically flat carbon surfaces promote heterogeneous nucleation of ice, while molecularly rough surfaces with the same hydrophobicity do not. Graphitic surfaces and other surfaces that promote ice nucleation induce layering in the interfacial water, suggesting that the order imposed by the surface on liquid water may play an important role in the heterogeneous nucleation mechanism. We investigate a large set of graphitic surfaces of various dimensions and radii of curvature and find that variations in nanostructures alone could account for the spread in the freezing temperatures of ice on soot in experiments. We conclude that a characterization of the nanostructure of soot is needed to predict its ice nucleation efficiency.

Some fundamental properties and reactions of ice surfaces at low temperatures.

PubMed

Park, Seong-Chan; Moon, Eui-Seong; Kang, Heon

2010-10-14

Ice surfaces offer a unique chemical environment in which reactions occur quite differently from those in liquid water or gas phases. In this article, we examine the basic properties of ice surfaces below the surface premelting temperature and discuss some of the recent investigations carried out on reactions at the ice surfaces. The static and dynamic properties of an ice surface as a reaction medium, such as its structure, molecule diffusion and proton transfer dynamics, and the surface preference of hydronium and hydroxide ions, are discussed in relation to the reactivity of the surface.

A Continuing Analysis of Possible Activity Drivers for the Enigmatic Comet 29P/Schwassmann-Wachmann 1

NASA Astrophysics Data System (ADS)

Schambeau, Charles; Fernández, Yanga; Samarasinha, Nalin H.; Mueller, Beatrice E. A.; Sarid, Gal; Meech, Karen Jean; Woodney, Laura

2016-01-01

We present results from our effort to understand activity drivers in Comet 29P/Schwassmann-Wachmann 1 (SW1). In a nearly circular orbit around 6 AU, outside of the water-sublimation zone, SW1 is continuously active and experiences frequent outbursts. Our group's effort is focusing on finding constraints on physical and dynamical properties of SW1's nucleus and their incorporation into a thermophysical model [1,2] to explain this behavior. We are currently analyzing coma morphology of SW1 before, during, and after outburst placing constraints on the spin-pole direction, spin period, and surface areas of activity. In addition, we are using the thermal model to investigate if the continuous activity comes from one or multiple processes, such as the release of trapped supervolatiles during the amorphous to crystalline (A-C) water ice phase transition and/or the direct sublimation of pockets of supervolatile ices. The supervolatile ices may be primordial or from the condensation of gases released during the A-C phase transition. To explain the possibly quasi-periodic but frequent outbursts, we are looking into subsurface cavities where internal pressures can build, reaching and exceeding surrounding material strengths [3,4] and/or thermal waves reaching a pocket of supervolatile ices, causing a rapid increase in the sublimation rate. For all these phenomena, the model is constrained by comparing the output dust mass loss rate and its variability with what has been observed through optical imaging of the comet at various points in its orbit. We will present preliminary thermal modeling of a homogeneous progenitor nucleus that evolves into a body showing internal material layering, the generation of CO and CO2 ice pockets, and the production of outbursts, thus bringing us closer to explaining the behavior of this intriguing comet. [1] Sarid, G., et al.: 2005, PASP, 117, 843. [2] Sarid, G.: 2009, PhD Thesis, Tel Aviv Univ. [3] Gronkowski, P., 2014, Astron. Nachr./AN 2, No. 335, 124-134. [4] Gronkowski, P. and Wesolowski, M., 2015, MNRAS, 451, 3068-3077. We thank the NASA Outer Planets Research Program (NNX12AK50G) and the Center for Lunar and Asteroid Surface Science (CLASS, NNA14AB05A) for support of this work.

Experimental evidence for modifying the current physical model for ice accretion on aircraft surfaces

NASA Technical Reports Server (NTRS)

Olsen, W.; Walker, E.

1986-01-01

Closeup movies, still photographs, and other experimental data suggest that the current physical model for ice accretion needs significant modification. At aircraft airspeeds there was no flow of liquid over the surface of the ice after a short initial flow, even at barely subfreezing temperatures. Instead, there were very large stationary drops on the ice surface that lose water from their bottoms by freezing and replenish their liquid by catching the microscopic cloud droplets. This observation disagrees with the existing physical model, which assumes there is a thin liquid film continuously flowing over the ice surface. With no such flow, the freezing-fraction concept of the model fails when a mass balance is performed on the surface water. Rime ice does, as the model predicts, form when the air temperature is low enough to cause the cloud droplets to freeze almost immediately on impact. However, the characteristic shapes of horn-glaze ice or rime ice are primarily caused by the ice shape affecting the airflow locally and consequently the droplet catch and the resulting ice shape. Ice roughness greatly increases the heat transfer coefficient, stops the movement of drops along the surface, and may also affect the airflow initially and thereby the droplet catch. At high subreezing temperatures the initial flow and shedding of surface drops have a large effect on the ice shape. At the incipient freezing limit, no ice forms.

Variability in Arctic sea ice topography and atmospheric form drag: Combining IceBridge laser altimetry with ASCAT radar backscatter.

NASA Astrophysics Data System (ADS)

Petty, A.; Tsamados, M.; Kurtz, N. T.

2016-12-01

Here we present atmospheric form drag estimates over Arctic sea ice using high resolution, three-dimensional surface elevation data from NASA's Operation IceBridge Airborne Topographic Mapper (ATM), and surface roughness estimates from the Advanced Scatterometer (ASCAT). Surface features of the ice pack (e.g. pressure ridges) are detected using IceBridge ATM elevation data and a novel surface feature-picking algorithm. We use simple form drag parameterizations to convert the observed height and spacing of surface features into an effective atmospheric form drag coefficient. The results demonstrate strong regional variability in the atmospheric form drag coefficient, linked to variability in both the height and spacing of surface features. This includes form drag estimates around 2-3 times higher over the multiyear ice north of Greenland, compared to the first-year ice of the Beaufort/Chukchi seas. We compare results from both scanning and linear profiling to ensure our results are consistent with previous studies investigating form drag over Arctic sea ice. A strong correlation between ASCAT surface roughness estimates (using radar backscatter) and the IceBridge form drag results enable us to extrapolate the IceBridge data collected over the western-Arctic across the entire Arctic Ocean. While our focus is on spring, due to the timing of the primary IceBridge campaigns since 2009, we also take advantage of the autumn data collected by IceBridge in 2015 to investigate seasonality in Arctic ice topography and the resulting form drag coefficient. Our results offer the first large-scale assessment of atmospheric form drag over Arctic sea ice due to variable ice topography (i.e. within the Arctic pack ice). The analysis is being extended to the Antarctic IceBridge sea ice data, and the results are being used to calibrate a sophisticated form drag parameterization scheme included in the sea ice model CICE, to improve the representation of form drag over Arctic and Antarctic sea ice in global climate models.

Multiscale crack initiator promoted super-low ice adhesion surfaces.

PubMed

He, Zhiwei; Xiao, Senbo; Gao, Huajian; He, Jianying; Zhang, Zhiliang

2017-09-27

Preventing icing on exposed surfaces is important for life and technology. While suppressing ice nucleation by surface structuring and local confinement is highly desirable and yet to be achieved, a realistic roadmap of icephobicity is to live with ice, but with lowest possible ice adhesion. According to fracture mechanics, the key to lower ice adhesion is to maximize crack driving forces at the ice-substrate interface. Herein, we present a novel integrated macro-crack initiator mechanism combining nano-crack and micro-crack initiators, and demonstrate a new approach to designing super-low ice adhesion surfaces by introducing sub-structures into smooth polydimethylsiloxane coatings. Our design promotes the initiation of macro-cracks and enables the reduction of ice adhesion by at least ∼50% regardless of the curing temperature, weight ratio and size of internal holes, reaching a lowest ice adhesion of 5.7 kPa. The multiscale crack initiator mechanisms provide an unprecedented and versatile strategy towards designing super-low ice adhesion surfaces.

An approach to tune the amplitude of surface ripple patterns

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Tanuj; Kanjilal, D.; Kumar, Ashish

An approach is presented to tune the amplitude of ripple patterns using ion beam. By varying the depth location of amorphous/crystalline interface, ripple patterns of different amplitude with similar wavelength were grown on the surface of Si (100) using 50 keV Ar{sup +} beam irradiation. Atomic force microscopy study demonstrates the tuning of amplitude of ripples patterns for wide range. Rutherford backscattering channeling measurement was performed to measure the depth location of amorphous/crystalline interface. It is postulated that the ion beam stimulated solid flow inside the amorphous layer controls the wavelength, whereas mass rearrangement at amorphous/crystalline interface controls the amplitude.

Bioinspired Surfaces with Superwettability for Anti-Icing and Ice-Phobic Application: Concept, Mechanism, and Design.

PubMed

Zhang, Songnan; Huang, Jianying; Cheng, Yan; Yang, Hui; Chen, Zhong; Lai, Yuekun

2017-12-01

Ice accumulation poses a series of severe issues in daily life. Inspired by the nature, superwettability surfaces have attracted great interests from fundamental research to anti-icing and ice-phobic applications. Here, recently published literature about the mechanism of ice prevention is reviewed, with a focus on the anti-icing and ice-phobic mechanisms, encompassing the behavior of condensate microdrops on the surface, wetting, ice nucleation, and freezing. Then, a detailed account of the innovative fabrication and fundamental research of anti-icing materials with special wettability is summarized with a focus on recent progresses including low-surface energy coatings and liquid-infused layered coatings. Finally, special attention is paid to a discussion about advantages and disadvantages of the technologies, as well as factors that affect the anti-icing and ice-phobic efficiency. Outlooks and the challenges for future development of the anti-icing and ice-phobic technology are presented and discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Meltwater storage in low-density near-surface bare ice in the Greenland ice sheet ablation zone

NASA Astrophysics Data System (ADS)

Cooper, Matthew G.; Smith, Laurence C.; Rennermalm, Asa K.; Miège, Clément; Pitcher, Lincoln H.; Ryan, Jonathan C.; Yang, Kang; Cooley, Sarah W.

2018-03-01

We document the density and hydrologic properties of bare, ablating ice in a mid-elevation (1215 m a.s.l.) supraglacial internally drained catchment in the Kangerlussuaq sector of the western Greenland ice sheet. We find low-density (0.43-0.91 g cm-3, μ = 0.69 g cm-3) ice to at least 1.1 m depth below the ice sheet surface. This near-surface, low-density ice consists of alternating layers of water-saturated, porous ice and clear solid ice lenses, overlain by a thin (< 0.5 m), even lower density (0.33-0.56 g cm-3, μ = 0.45 g cm-3) unsaturated weathering crust. Ice density data from 10 shallow (0.9-1.1 m) ice cores along an 800 m transect suggest an average 14-18 cm of specific meltwater storage within this low-density ice. Water saturation of this ice is confirmed through measurable water levels (1-29 cm above hole bottoms, μ = 10 cm) in 84 % of cryoconite holes and rapid refilling of 83 % of 1 m drilled holes sampled along the transect. These findings are consistent with descriptions of shallow, depth-limited aquifers on the weathered surface of glaciers worldwide and confirm the potential for substantial transient meltwater storage within porous low-density ice on the Greenland ice sheet ablation zone surface. A conservative estimate for the ˜ 63 km2 supraglacial catchment yields 0.009-0.012 km3 of liquid meltwater storage in near-surface, porous ice. Further work is required to determine if these findings are representative of broader areas of the Greenland ice sheet ablation zone, and to assess the implications for sub-seasonal mass balance processes, surface lowering observations from airborne and satellite altimetry, and supraglacial runoff processes.

Graphene Coating via Chemical Vapor Deposition for Improving Friction and Wear of Gray Cast Iron at Interfaces.

PubMed

Tripathi, Khagendra; Gyawali, Gobinda; Lee, Soo Wohn

2017-09-20

This study reports the influence of CVD-graphene on the tribological performance of gray cast iron (GCI) from the internal combustion engine (ICE) cylinder liners by performing a ball-on-disk friction tests. The graphene-coated specimen exhibited a significant reduction (∼53%) of friction as compared to that of the uncoated specimen, whereas wear resistance increased by 2- and 5-fold regarding the wear of specimen and ball, respectively. Extremely low shear strength and highly lubricating nature of graphene contribute to the formation of a lubricative film between the sliding surfaces and decreases the interaction between surfaces in the dry environment. Under the applied load, a uniform film of iron oxides such as Fe 2 O 3 , Fe 3 O 4 , and FeOOH is found to be formed between the surfaces. It is proposed that the graphene encapsulation with the metal debris and oxides formed between the specimens increases the lubricity and decreases the shear force. The transformation of graphene/graphite into nanocrystalline graphites across the contact interfaces following the amorphization trajectory further increases the lubricity of the film that ultimately reduces friction and wear of the material.

Relating sub-surface ice features to physiological stress in a climate sensitive mammal, the American pika (Ochotona princeps).

PubMed

Wilkening, Jennifer L; Ray, Chris; Varner, Johanna

2015-01-01

The American pika (Ochotona princeps) is considered a sentinel species for detecting ecological effects of climate change. Pikas are declining within a large portion of their range, and ongoing research suggests loss of sub-surface ice as a mechanism. However, no studies have demonstrated physiological responses of pikas to sub-surface ice features. Here we present the first analysis of physiological stress in pikas living in and adjacent to habitats underlain by ice. Fresh fecal samples were collected non-invasively from two adjacent sites in the Rocky Mountains (one with sub-surface ice and one without) and analyzed for glucocorticoid metabolites (GCM). We also measured sub-surface microclimates in each habitat. Results indicate lower GCM concentration in sites with sub-surface ice, suggesting that pikas are less stressed in favorable microclimates resulting from sub-surface ice features. GCM response was well predicted by habitat characteristics associated with sub-surface ice features, such as lower mean summer temperatures. These results suggest that pikas inhabiting areas without sub-surface ice features are experiencing higher levels of physiological stress and may be more susceptible to changing climates. Although post-deposition environmental effects can confound analyses based on fecal GCM, we found no evidence for such effects in this study. Sub-surface ice features are key to water cycling and storage and will likely represent an increasingly important component of water resources in a warming climate. Fecal samples collected from additional watersheds as part of current pika monitoring programs could be used to further characterize relationships between pika stress and sub-surface ice features.

N2 and CO Desorption Energies from Water Ice

NASA Astrophysics Data System (ADS)

Fayolle, Edith C.; Balfe, Jodi; Loomis, Ryan; Bergner, Jennifer; Graninger, Dawn; Rajappan, Mahesh; Öberg, Karin I.

2016-01-01

The relative desorption energies of CO and N2 are key to interpretations of observed interstellar CO and N2 abundance patterns, including the well-documented CO and N2H+ anti-correlations in disks, protostars, and molecular cloud cores. Based on laboratory experiments on pure CO and N2 ice desorption, the difference between CO and N2 desorption energies is small; the N2-to-CO desorption energy ratio is 0.93 ± 0.03. Interstellar ices are not pure, however, and in this study we explore the effect of water ice on the desorption energy ratio of the two molecules. We present temperature programmed desorption experiments of different coverages of 13CO and 15N2 on porous and compact amorphous water ices and, for reference, of pure ices. In all experiments, 15N2 desorption begins a few degrees before the onset of 13CO desorption. The 15N2 and 13CO energy barriers are 770 and 866 K for the pure ices, 1034-1143 K and 1155-1298 K for different submonolayer coverages on compact water ice, and 1435 and 1575 K for ˜1 ML of ice on top of porous water ice. For all equivalent experiments, the N2-to-CO desorption energy ratio is consistently 0.9. Whenever CO and N2 ice reside in similar ice environments (e.g., experience a similar degree of interaction with water ice) their desorption temperatures should thus be within a few degrees of one another. A smaller N2-to-CO desorption energy ratio may be present in interstellar and circumstellar environments if the average CO ice molecules interacts more with water ice compared to the average N2 molecules.

Facile Synthesis of Highly Efficient Amorphous Mn-MIL-100 Catalysts: Formation Mechanism and Structure Changes during Application in CO Oxidation.

PubMed

Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin

2018-06-21

A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts for CO oxidation. This study focused on explaining the crystalline-amorphous-crystalline transformations during thermolysis of Mn-MIL-100 and studying the structure changes during the CO oxidation reaction. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250 °C (a-Mn-250) showed a smaller specific surface area (4 m 2  g -1 ) but high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction. When a-Mn-250 was treated with reaction atmosphere at high temperature (giving used-a-Mn-250-S), the amorphous catalysts transformed into Mn 2 O 3 . Meanwhile, the BET surface area (164 m 2  g -1 ) and catalytic performance both sharply increased. In addition, used-a-Mn-250-S catalyst transformed from Mn 2 O 3 into Mn 3 O 4 , and this resulted in a slight decrease of catalytic activity in the presence of 1 vol % water vapor in the feed stream. A schematic mechanism of the structure changes during the reaction process was proposed. The success of the synthesis relies on the increase in BET surface area by using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a large quantity of surface active oxygen species, oxygen vacancies, and good low-temperature reduction behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predictive model for ice formation on superhydrophobic surfaces.

PubMed

Bahadur, Vaibhav; Mishchenko, Lidiya; Hatton, Benjamin; Taylor, J Ashley; Aizenberg, Joanna; Krupenkin, Tom

2011-12-06

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies. © 2011 American Chemical Society

Toward Surface Mass Balance Modeling over Antarctic Peninsula with Improved Snow/Ice Physics within WRF

NASA Astrophysics Data System (ADS)

Villamil-Otero, G.; Zhang, J.; Yao, Y.

2017-12-01

The Antarctic Peninsula (AP) has long been the focus of climate change studies due to its rapid environmental changes such as significantly increased glacier melt and retreat, and ice-shelf break-up. Progress has been continuously made in the use of regional modeling to simulate surface mass changes over ice sheets. Most efforts, however, focus on the ice sheets of Greenland with considerable fewer studies in Antarctica. In this study the Weather Research and Forecasting (WRF) model, which has been applied to the Antarctic region for weather modeling, is adopted to capture the past and future surface mass balance changes over AP. In order to enhance the capabilities of WRF model simulating surface mass balance over the ice surface, we implement various ice and snow processes within the WRF and develop a new WRF suite (WRF-Ice). The WRF-Ice includes a thermodynamic ice sheet model that improves the representation of internal melting and refreezing processes and the thermodynamic effects over ice sheet. WRF-Ice also couples a thermodynamic sea ice model to improve the simulation of surface temperature and fluxes over sea ice. Lastly, complex snow processes are also taken into consideration including the implementation of a snowdrift model that takes into account the redistribution of blowing snow as well as the thermodynamic impact of drifting snow sublimation on the lower atmospheric boundary layer. Intensive testing of these ice and snow processes are performed to assess the capability of WRF-Ice in simulating the surface mass balance changes over AP.

Surfacing behavior and gas release of the physostome sprat (Sprattus sprattus) in ice-free and ice-covered waters.

PubMed

Solberg, Ingrid; Kaartvedt, Stein

2014-01-01

Upward-facing echosounders that provided continuous, long-term measurements were applied to address the surfacing behavior and gas release of the physostome sprat ( Sprattus sprattus ) throughout an entire winter in a 150-m-deep Norwegian fjord. During ice-free conditions, the sprat surfaced and released gas bubbles at night with an estimated surfacing rate of 3.5 times per fish day -1 . The vertical swimming speeds during surfacing were considerably higher (~10 times) than during diel vertical migrations, especially when returning from the surface, and particularly when the fjord was not ice covered. The sprat released gas a few hours after surfacing, suggesting that the sprat gulped atmospheric air during its excursions to the surface. While the surface activity increased after the fjord became ice covered, the records of gas release decreased sharply. The under-ice fish then displayed a behavior interpreted as "searching for the surface" by repeatedly ascending toward the ice, apparently with limited success of filling the swim bladder. This interpretation was supported by lower acoustic target strength in ice-covered waters. The frequent surfacing behavior demonstrated in this study indicates that gulping of atmospheric air is an important element in the life of sprat. While at least part of the population endured overwintering in the ice-covered habitat, ice covering may constrain those physostome fishes that lack a gas-generating gland in ways that remain to be established.

Origin of the ices agglomerated by Comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Mousis, Olivier; Lunine, Jonathan I.; Luspay-Kuti, Adrienn; Guillot, Tristan; Marty, Bernard; Wurz, Peter; Ali-Dib, Mohamad; Altwegg, Kathrin; Hässig, Myrtha; Rubin, Martin; Vernazza, Pierre; Waite, Jack H.

2015-11-01

The nature of the icy material accreted by comets during their formation in the outer regions of the protosolar nebula is a major open question in planetary science. Some scenarios of comet formation predict that these bodies agglomerated from clathrates crystallized in the protosolar nebula. Concurrently, alternative scenarios suggest that comets accreted amorphous ice originating from the interstellar cloud. Here we show that the recent N2/CO and Ar/CO ratios measured in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko by the ROSINA instrument aboard the European Space Agency's Rosetta spacecraft can help disentangling between these two scenarios.

Inflammatory cell response to ultra-thin amorphous and crystalline hydroxyapatite surfaces.

PubMed

Rydén, Louise; Omar, Omar; Johansson, Anna; Jimbo, Ryo; Palmquist, Anders; Thomsen, Peter

2017-01-01

It has been suggested that surface modification with a thin hydroxyapatite (HA) coating enhances the osseointegration of titanium implants. However, there is insufficient information about the biological processes involved in the HA-induced response. This study aimed to investigate the inflammatory cell response to titanium implants with either amorphous or crystalline thin HA. Human mononuclear cells were cultured on titanium discs with a machined surface or with a thin, 0.1 μm, amorphous or crystalline HA coating. Cells were cultured for 24 and 96 h, with and without lipopolysaccharide (LPS) stimulation. The surfaces were characterized with respect to chemistry, phase composition, wettability and topography. Biological analyses included the percentage of implant-adherent cells and the secretion of pro-inflammatory cytokine (TNF-α) and growth factors (BMP-2 and TGF-β1). Crystalline HA revealed a smooth surface, whereas the amorphous HA displayed a porous structure, at nano-scale, and a hydrophobic surface. Higher TNF-α secretion and a higher ratio of adherent cells were demonstrated for the amorphous HA compared with the crystalline HA. TGF-β1 secretion was detected in all groups, but without any difference. No BMP-2 secretion was detected in any of the groups. The addition of LPS resulted in a significant increase in TNF-α in all groups, whereas TGF-β1 was not affected. Taken together, the results show that thin HA coatings with similar micro-roughness but a different phase composition, nano-scale roughness and wettability are associated with different monocyte responses. In the absence of strong inflammatory stimuli, crystalline hydroxyapatite elicits a lower inflammatory response compared with amorphous hydroxyapatite.

Annealing to optimize the primary drying rate, reduce freezing-induced drying rate heterogeneity, and determine T(g)' in pharmaceutical lyophilization.

PubMed

Searles, J A; Carpenter, J F; Randolph, T W

2001-07-01

In a companion paper we show that the freezing of samples in vials by shelf-ramp freezing results in significant primary drying rate heterogeneity because of a dependence of the ice crystal size on the nucleation temperature during freezing.1 The purpose of this study was to test the hypothesis that post-freezing annealing, in which the product is held at a predetermined temperature for a specified duration, can reduce freezing-induced heterogeneity in sublimation rates. In addition, we test the impact of annealing on primary drying rates. Finally, we use the kinetics of relaxations during annealing to provide a simple measurement of T(g)', the glass transition temperature of the maximally freeze-concentrated amorphous phase, under conditions and time scales most appropriate for industrial lyophilization cycles. Aqueous solutions of hydroxyethyl starch (HES), sucrose, and HES:sucrose were either frozen by placement on a shelf while the temperature was reduced ("shelf-ramp frozen") or by immersion into liquid nitrogen. Samples were then annealed for various durations over a range of temperatures and partially lyophilized to determine the primary drying rate. The morphology of fully dried liquid nitrogen-frozen samples was examined using scanning electron microscopy. Annealing reduced primary drying rate heterogeneity for shelf-ramp frozen samples, and resulted in up to 3.5-fold increases in the primary drying rate. These effects were due to increased ice crystal sizes, simplified amorphous structures, and larger and more numerous holes on the cake surface of annealed samples. Annealed HES samples dissolved slightly faster than their unannealed counterparts. Annealing below T(g)' did not result in increased drying rates. We present a simple new annealing-lyophilization method of T(g)' determination that exploits this phenomenon. It can be carried out with a balance and a freeze-dryer, and has the additional advantage that a large number of candidate formulations can be evaluated simultaneously.

Key roles of sea ice in inducing contrasting modes of glacial AMOC and climate

NASA Astrophysics Data System (ADS)

Sherriff-Tadano, S.; Abe-Ouchi, A.

2017-12-01

Gaining a better understanding of glacial Atlantic meridional overturning circulation (AMOC) is important to interpret the glacial climate changes such as the Heinrich event. Recent studies suggest that changes in sea ice over the North Atlantic largely affect the surface wind. Since changes in surface wind have a large impact on the AMOC, this implies a role of sea ice in modifying the AMOC though surface wind. However, the impact of sea ice on the surface winds and the impact of changes in the winds on the AMOC remain unclear. In this study, we first assess the impact of sea ice expansion on the winds. We then explore whether the changes in winds play a role in modifying the AMOC and climate. For this purpose, results from MIROC4m are analyzed (Kawamura et al. 2017). To clarify the impact of changes in sea ice on the surface wind, sensitivity experiments are conducted with an atmospheric general circulation model (AGCM). In the AGCM experiments, we modify the sea ice to extract the impact of sea ice on the winds. Partial decouple experiments are conducted with the coupled model MIROC4m, which we modify the surface winds to assess the impact of changes in the surface wind due to sea ice expansion on the AMOC. Results show that expansion of sea ice substantially weakens the surface wind over the northern North Atlantic. AGCM experiments show that a drastic decrease in surface temperature duo to a suppression of sensible heat flux plays a dominant role in weakening the surface winds through increasing the static stability of the air column near the surface. Partial decouple experiments with MIROC4m show that the weakening of the surface wind due to the expansion of sea ice plays an important role in maintaining the weak AMOC. Thus, these experiments show that the weakening of the surface winds due to sea ice expansion plays a role in stabilizing the AMOC.

Surface nanoporosity has a greater influence on osteogenic and bacterial cell adhesion than crystallinity and wettability

NASA Astrophysics Data System (ADS)

Rodriguez-Contreras, Alejandra; Guadarrama Bello, Dainelys; Nanci, Antonio

2018-07-01

There has been much emphasis on the influence of crystallinity and wettability for modulating cell activity, particularly for bone biomaterials. In this context, we have generated titanium oxide layers with similar mesoporous topography and surface roughness but with amorphous or crystalline oxide layers and differential wettability. We then investigated their influence on the behavior of MC3T3 osteoblastic and bacterial cells. There was no difference in cell adhesion, spreading and growth on amorphous and crystalline surfaces. The number of focal adhesions was similar, however, cells on the amorphous surface exhibited a higher frequency of mature adhesions. The crystallinity of the surface layers also had no bearing on bacterial adhesion. While it cannot be excluded that surface crystallinity, roughness and wettability contribute to some degree to determining cell behavior, our data suggest that physical characteristics of surfaces represent the major determinant.

Spatial scales of light transmission through Antarctic pack ice: Surface flooding vs. floe-size distribution

NASA Astrophysics Data System (ADS)

Arndt, S.; Meiners, K.; Krumpen, T.; Ricker, R.; Nicolaus, M.

2016-12-01

Snow on sea ice plays a crucial role for interactions between the ocean and atmosphere within the climate system of polar regions. Antarctic sea ice is covered with snow during most of the year. The snow contributes substantially to the sea-ice mass budget as the heavy snow loads can depress the ice below water level causing flooding. Refreezing of the snow and seawater mixture results in snow-ice formation on the ice surface. The snow cover determines also the amount of light being reflected, absorbed, and transmitted into the upper ocean, determining the surface energy budget of ice-covered oceans. The amount of light penetrating through sea ice into the upper ocean is of critical importance for the timing and amount of bottom sea-ice melt, biogeochemical processes and under-ice ecosystems. Here, we present results of several recent observations in the Weddell Sea measuring solar radiation under Antarctic sea ice with instrumented Remotely Operated Vehicles (ROV). The combination of under-ice optical measurements with simultaneous characterization of surface properties, such as sea-ice thickness and snow depth, allows the identification of key processes controlling the spatial distribution of the under-ice light. Thus, our results show how the distinction between flooded and non-flooded sea-ice regimes dominates the spatial scales of under-ice light variability for areas smaller than 100-by-100m. In contrast, the variability on larger scales seems to be controlled by the floe-size distribution and the associated lateral incidence of light. These results are related to recent studies on the spatial variability of Arctic under-ice light fields focusing on the distinctly differing dominant surface properties between the northern (e.g. summer melt ponds) and southern (e.g. year-round snow cover, surface flooding) hemisphere sea-ice cover.

Applying state diagrams to food processing and development

NASA Technical Reports Server (NTRS)

Roos, Y.; Karel, M.

1991-01-01

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.

Ice recrystallization inhibition in ice cream by propylene glycol monostearate.

PubMed

Aleong, J M; Frochot, S; Goff, H D

2008-11-01

The effectiveness of propylene glycol monostearate (PGMS) to inhibit ice recrystallization was evaluated in ice cream and frozen sucrose solutions. PGMS (0.3%) dramatically reduced ice crystal sizes in ice cream and in sucrose solutions frozen in a scraped-surface freezer before and after heat shock, but had no effect in quiescently frozen solutions. PGMS showed limited emulsifier properties by promoting smaller fat globule size distributions and enhanced partial coalescence in the mix and ice cream, respectively, but at a much lower level compared to conventional ice cream emulsifier. Low temperature scanning electron microscopy revealed highly irregular crystal morphology in both ice cream and sucrose solutions frozen in a scraped-surface freezer. There was strong evidence to suggest that PGMS directly interacts with ice crystals and interferes with normal surface propagation. Shear during freezing may be required for its distribution around the ice and sufficient surface coverage.

Path-integral simulation of ice Ih: The effect of pressure

NASA Astrophysics Data System (ADS)

Herrero, Carlos P.; Ramírez, Rafael

2011-12-01

The effect of pressure on structural and thermodynamic properties of ice Ih has been studied by means of path-integral molecular dynamics simulations at temperatures between 50 and 300 K. Interatomic interactions were modeled by using the effective q-TIP4P/F potential for flexible water. Positive (compression) and negative (tension) pressures have been considered, which allowed us to approach the limits for the mechanical stability of this solid water phase. We have studied the pressure dependence of the crystal volume, bulk modulus, interatomic distances, atomic delocalization, and kinetic energy. The spinodal point at both negative and positive pressures is derived from the vanishing of the bulk modulus. For P<0, the spinodal pressure changes from -1.38 to - 0.73 GPa in the range from 50 to 300 K. At positive pressure the spinodal is associated with ice amorphization, and at low temperatures it is found to be between 1.1 and 1.3 GPa. Quantum nuclear effects cause a reduction of the metastability region of ice Ih.

Modeling of surface roughness effects on glaze ice accretion

NASA Technical Reports Server (NTRS)

Hansman, R. John, Jr.; Yamaguchi, Keiko; Berkowitz, Brian M.; Potapczuk, Mark

1990-01-01

A series of experimental investigations focused on studying the cause and effect of roughness on accreting glaze ice surfaces were conducted. Detailed microvideo observations were made of glaze ice accretions on 1 to 4 inch diameter cylinders in three icing wind tunnels (the Data Products of New England six inch test facility, the NASA Lewis Icing Research Tunnel, and the B. F. Goodrich Ice Protection Research Facility). Infrared thermal video recordings were made of accreting ice surfaces in the Goodrich facility. Distinct zones of surface water behavior were observed; a smooth wet zone in the stagnation region with a uniform water film; a rough zone where surface tension effects caused coalescence of surface water into stationary beads; a horn zone where roughness elements grow into horn shapes; a runback zone where surface water ran back as rivulets; and a dry zone where rime feathers formed. The location of the transition from the smooth to the rough zone was found to migrate with time towards the stagnation point. The behavior of the transition appeared to be controlled by boundary layer transition and bead formation mechanisms at the interface between the smooth and rough zones. Regions of wet ice growth and enhanced heat transfer were clearly visible in the infrared video recordings of glaze ice surfaces. A simple multi-zone modification to the current glaze ice accretion model was proposed to include spatial variability in surface roughness.

Factors affecting projected Arctic surface shortwave heating and albedo change in coupled climate models.

PubMed

Holland, Marika M; Landrum, Laura

2015-07-13

We use a large ensemble of simulations from the Community Earth System Model to quantify simulated changes in the twentieth and twenty-first century Arctic surface shortwave heating associated with changing incoming solar radiation and changing ice conditions. For increases in shortwave absorption associated with albedo reductions, the relative influence of changing sea ice surface properties and changing sea ice areal coverage is assessed. Changes in the surface sea ice properties are associated with an earlier melt season onset, a longer snow-free season and enhanced surface ponding. Because many of these changes occur during peak solar insolation, they have a considerable influence on Arctic surface shortwave heating that is comparable to the influence of ice area loss in the early twenty-first century. As ice area loss continues through the twenty-first century, it overwhelms the influence of changes in the sea ice surface state, and is responsible for a majority of the net shortwave increases by the mid-twenty-first century. A comparison with the Arctic surface albedo and shortwave heating in CMIP5 models indicates a large spread in projected twenty-first century change. This is in part related to different ice loss rates among the models and different representations of the late twentieth century ice albedo and associated sea ice surface state. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Factors affecting projected Arctic surface shortwave heating and albedo change in coupled climate models

PubMed Central

Holland, Marika M.; Landrum, Laura

2015-01-01

We use a large ensemble of simulations from the Community Earth System Model to quantify simulated changes in the twentieth and twenty-first century Arctic surface shortwave heating associated with changing incoming solar radiation and changing ice conditions. For increases in shortwave absorption associated with albedo reductions, the relative influence of changing sea ice surface properties and changing sea ice areal coverage is assessed. Changes in the surface sea ice properties are associated with an earlier melt season onset, a longer snow-free season and enhanced surface ponding. Because many of these changes occur during peak solar insolation, they have a considerable influence on Arctic surface shortwave heating that is comparable to the influence of ice area loss in the early twenty-first century. As ice area loss continues through the twenty-first century, it overwhelms the influence of changes in the sea ice surface state, and is responsible for a majority of the net shortwave increases by the mid-twenty-first century. A comparison with the Arctic surface albedo and shortwave heating in CMIP5 models indicates a large spread in projected twenty-first century change. This is in part related to different ice loss rates among the models and different representations of the late twentieth century ice albedo and associated sea ice surface state. PMID:26032318

Amorphization strategy affects the stability and supersaturation profile of amorphous drug nanoparticles.

PubMed

Cheow, Wean Sin; Kiew, Tie Yi; Yang, Yue; Hadinoto, Kunn

2014-05-05

Amorphous drug nanoparticles have recently emerged as a promising bioavailability enhancement strategy of poorly soluble drugs attributed to the high supersaturation solubility generated by the amorphous state and fast dissolution afforded by the nanoparticles. Herein we examine the effects of two amorphization strategies in the nanoscale, i.e., (1) molecular mobility restrictions and (2) high energy surface occupation, both by polymer excipient stabilizers, on the (i) morphology, (ii) colloidal stability, (iii) drug loading, (iv) amorphous state stability after three-month storage, and (v) in vitro supersaturation profiles, using itraconazole (ITZ) as the model drug. Drug-polyelectrolyte complexation is employed in the first strategy to prepare amorphous ITZ nanoparticles using dextran sulfate as the polyelectrolyte (ITZ nanoplex), while the second strategy employs pH-shift precipitation using hydroxypropylmethylcellulose as the surface stabilizer (nano-ITZ), with both strategies resulting in >90% ITZ utilization. Both amorphous ITZ nanoparticles share similar morphology (∼300 nm spheres) with the ITZ nanoplex exhibiting better colloidal stability, albeit at lower ITZ loading (65% versus 94%), due to the larger stabilizer amount used. The ITZ nanoplex also exhibits superior amorphous state stability, attributed to the ITZ molecular mobility restriction by electrostatic complexation with dextran sulfate. The higher stability, however, is obtained at the expense of slower supersaturation generation, which is maintained over a prolonged period, compared to the nano-ITZ. The present results signify the importance of selecting the optimal amorphization strategy, in addition to formulating the excipient stabilizers, to produce amorphous drug nanoparticles having the desired characteristics.

Liquid-infused nanostructured surfaces with extreme anti-ice and anti-frost performance.

PubMed

Kim, Philseok; Wong, Tak-Sing; Alvarenga, Jack; Kreder, Michael J; Adorno-Martinez, Wilmer E; Aizenberg, Joanna

2012-08-28

Ice-repellent coatings can have significant impact on global energy savings and improving safety in many infrastructures, transportation, and cooling systems. Recent efforts for developing ice-phobic surfaces have been mostly devoted to utilizing lotus-leaf-inspired superhydrophobic surfaces, yet these surfaces fail in high-humidity conditions due to water condensation and frost formation and even lead to increased ice adhesion due to a large surface area. We report a radically different type of ice-repellent material based on slippery, liquid-infused porous surfaces (SLIPS), where a stable, ultrasmooth, low-hysteresis lubricant overlayer is maintained by infusing a water-immiscible liquid into a nanostructured surface chemically functionalized to have a high affinity to the infiltrated liquid and lock it in place. We develop a direct fabrication method of SLIPS on industrially relevant metals, particularly aluminum, one of the most widely used lightweight structural materials. We demonstrate that SLIPS-coated Al surfaces not only suppress ice/frost accretion by effectively removing condensed moisture but also exhibit at least an order of magnitude lower ice adhesion than state-of-the-art materials. On the basis of a theoretical analysis followed by extensive icing/deicing experiments, we discuss special advantages of SLIPS as ice-repellent surfaces: highly reduced sliding droplet sizes resulting from the extremely low contact angle hysteresis. We show that our surfaces remain essentially frost-free in which any conventional materials accumulate ice. These results indicate that SLIPS is a promising candidate for developing robust anti-icing materials for broad applications, such as refrigeration, aviation, roofs, wires, outdoor signs, railings, and wind turbines.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Investigation of the influence of pretreatment parameters on the surface characteristics of amorphous metal for use in power industry

NASA Astrophysics Data System (ADS)

Nieroda, Jolanta; Rybak, Andrzej; Kmita, Grzegorz; Sitarz, Maciej

2018-05-01

Metallic glasses are metallic materials, which exhibit an amorphous structure. These are mostly three or more component alloys, and some of them are magnetic metals. Materials of this kind are characterized by high electrical resistivity and at the same time exhibit very good magnetic properties (e.g. low-magnetization loss). The above mentioned properties are very useful in electrical engineering industry and this material is more and more popular as a substance for high-efficiency electrical devices production. This industry area is still evolving, and thus even higher efficiency of apparatus based on amorphous material is expected. A raw material must be carefully investigated and characterized before the main production process is started. Presented work contains results of complementary examination of amorphous metal Metglas 2605. Studies involve two ways to obtain clean and oxidized surface with high reactivity, namely degreasing followed by annealing process and plasma treatment. The amorphous metal parameters were examined by means of several techniques: surface free energy (SFE) measurements by sessile drop method, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and both ex situ and in situ Raman spectroscopy. Additionally, influence of plasma parameters on wetting properties were optimized in systematic way with Design of Experiments (DOE) method. A wide range of used methods allow to fully investigate the amorphous metal material during preliminary preparation of surface. Obtained results provide information about appropriate parameters that should be applied in order to obtain highly reactive surface with functional oxide layer on it.

A mechanism for comet surface collapse as observed by Rosetta on 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Prialnik, D.; Sierks, H.

2017-07-01

We explore a possible mechanism that may explain sudden depressions of surface areas on a comet nucleus, as suggested by observations of the Rosetta mission on comet 67P/Churyumov-Gerasimenko (hereafter, 67P/C-G). Assuming the area is covered by a thin, compact dust layer of low permeability to gas flow compared to deeper, porous layers, gas can accumulate below the surface when a surge of gas release from amorphous ice occurs upon crystallization. The gas pressure is found to exceed the hydrostatic pressure down to a depth of a few metres. The rapid build-up of pressure may weaken the already fragile, highly porous structure. Eventually, the high pressure gradient that arises drives the gas out and the pressure falls well below the hydrostatic pressure. The rapid pressure drop may result in collapse. Since the crystallization front lies at some depth below the surface, the location on the orbit when this phenomenon occurs is determined by the thermal lag, which, in turn, depends on the thermal conductivity. Numerical simulations show that mostly such activity occurs post-perihelion, but it may also occur pre-perihelion. When permeability is uniform, crystallization still causes increased gas production, but the gas pressure inside the nucleus remains below hydrostatic pressure.

Challenges for understanding Antarctic surface hydrology and ice-shelf stability

NASA Astrophysics Data System (ADS)

Kingslake, J.; Bell, R. E.; Banwell, A. F.; Boghosian, A.; Spergel, J.; Trusel, L. D.

2017-12-01

It is widely hypothesized that surface meltwater can contribute to ice mass loss in Antarctica through its impact on ice-shelf stability. Meltwater potentially expedites ice-shelf calving by flowing into and enlarging existing crevasses, and could even trigger ice-shelf disintegration via stresses generated by melt ponds. When ice shelves collapse, the adjacent grounded ice accelerates and thins, which contributes to sea-level rise. How these mechanisms mediate the interactions between the atmosphere, the ocean and the ice sheet is the subject of long-standing research efforts. The drainage of water across the surface of the Antarctic Ice Sheet and its ice shelves is beginning to be recognized as another important aspect of the system. Recent studies have revealed that surface meltwater drainage is more widespread than previously thought and that surface hydrological systems in Antarctica may expand and proliferate this century. Contrasting hypotheses regarding the impact of the proliferation of drainage systems on ice-shelf stability have emerged. Surface drainage could deliver meltwater to vulnerable area or export meltwater from ice shelves entirely. Which behavior dominates may have a large impact on the future response of the Antarctic Ice Sheet to atmospheric warming. We will discuss these recent discoveries and hypotheses, as well as new detailed studies of specific areas where hydrological systems are well developed, such as Amery and Nimrod Ice Shelves. We will highlight analogies that can be drawn with Greenlandic (near-)surface hydrology and, crucially, where hydrological systems on the two ice sheets are very different, leading to potentially important gaps in our understanding. Finally, we will look ahead to the key questions that we argue will need to be if we are to determine the role Antarctic surface hydrology could play in the future of the ice sheet. These include: Where does meltwater pond today and how will this change this century? What coupled glaciological-hydrological dynamics control how drainage systems will change as melt rates increase this century? How do we incorporate surface hydrology into ice-sheet models? While we may be currently unable to answer these and related questions, we aim to start the discussion on how the community can move towards answering them in the future.

Relating Sub-Surface Ice Features to Physiological Stress in a Climate Sensitive Mammal, the American Pika (Ochotona princeps)

PubMed Central

Wilkening, Jennifer L.; Ray, Chris; Varner, Johanna

2015-01-01

The American pika (Ochotona princeps) is considered a sentinel species for detecting ecological effects of climate change. Pikas are declining within a large portion of their range, and ongoing research suggests loss of sub-surface ice as a mechanism. However, no studies have demonstrated physiological responses of pikas to sub-surface ice features. Here we present the first analysis of physiological stress in pikas living in and adjacent to habitats underlain by ice. Fresh fecal samples were collected non-invasively from two adjacent sites in the Rocky Mountains (one with sub-surface ice and one without) and analyzed for glucocorticoid metabolites (GCM). We also measured sub-surface microclimates in each habitat. Results indicate lower GCM concentration in sites with sub-surface ice, suggesting that pikas are less stressed in favorable microclimates resulting from sub-surface ice features. GCM response was well predicted by habitat characteristics associated with sub-surface ice features, such as lower mean summer temperatures. These results suggest that pikas inhabiting areas without sub-surface ice features are experiencing higher levels of physiological stress and may be more susceptible to changing climates. Although post-deposition environmental effects can confound analyses based on fecal GCM, we found no evidence for such effects in this study. Sub-surface ice features are key to water cycling and storage and will likely represent an increasingly important component of water resources in a warming climate. Fecal samples collected from additional watersheds as part of current pika monitoring programs could be used to further characterize relationships between pika stress and sub-surface ice features. PMID:25803587

Generating gradient germanium nanostructures by shock-induced amorphization and crystallization

PubMed Central

Zhao, Shiteng; Kad, Bimal; Wehrenberg, Christopher E.; Remington, Bruce A.; Hahn, Eric N.; More, Karren L.; Meyers, Marc A.

2017-01-01

Gradient nanostructures are attracting considerable interest due to their potential to obtain superior structural and functional properties of materials. Applying powerful laser-driven shocks (stresses of up to one-third million atmospheres, or 33 gigapascals) to germanium, we report here a complex gradient nanostructure consisting of, near the surface, nanocrystals with high density of nanotwins. Beyond there, the structure exhibits arrays of amorphous bands which are preceded by planar defects such as stacking faults generated by partial dislocations. At a lower shock stress, the surface region of the recovered target is completely amorphous. We propose that germanium undergoes amorphization above a threshold stress and that the deformation-generated heat leads to nanocrystallization. These experiments are corroborated by molecular dynamics simulations which show that supersonic partial dislocation bursts play a role in triggering the crystalline-to-amorphous transition. PMID:28847926

Generating gradient germanium nanostructures by shock-induced amorphization and crystallization.

PubMed

Zhao, Shiteng; Kad, Bimal; Wehrenberg, Christopher E; Remington, Bruce A; Hahn, Eric N; More, Karren L; Meyers, Marc A

2017-09-12

Gradient nanostructures are attracting considerable interest due to their potential to obtain superior structural and functional properties of materials. Applying powerful laser-driven shocks (stresses of up to one-third million atmospheres, or 33 gigapascals) to germanium, we report here a complex gradient nanostructure consisting of, near the surface, nanocrystals with high density of nanotwins. Beyond there, the structure exhibits arrays of amorphous bands which are preceded by planar defects such as stacking faults generated by partial dislocations. At a lower shock stress, the surface region of the recovered target is completely amorphous. We propose that germanium undergoes amorphization above a threshold stress and that the deformation-generated heat leads to nanocrystallization. These experiments are corroborated by molecular dynamics simulations which show that supersonic partial dislocation bursts play a role in triggering the crystalline-to-amorphous transition.

Growth of GaAs “nano ice cream cones” by dual wavelength pulsed laser ablation

NASA Astrophysics Data System (ADS)

Schamp, C. T.; Jesser, W. A.; Shivaram, B. S.

2007-05-01

Harmonic generation crystals inherently offer the possibility of using multiple wavelengths of light in a single laser pulse. In the present experiment, the fundamental (1064 nm) and second harmonic (532 nm) wavelengths from an Nd:YAG laser are focused together on GaAs and GaSb targets for ablation. Incident energy densities up to about 45 J/cm 2 at 10 Hz with substrate temperatures between 25 and 600 °C for durations of about 60 s have been used in an ambient gas pressure of about 10 -6 Torr. The ablated material was collected on electron-transparent amorphous carbon films for TEM analysis. Apart from a high density of isolated nanocrystals, the most common morphology observed consists of a crystalline GaAs cone-like structure in contact with a sphere of liquid Ga, resembling an "ice cream cone", typically 50-100 nm in length. For all of the heterostuctures of this type, the liquid/solid/vacuum triple junction is found to correspond to the widest point on the cone. These heterostructures likely form by preferential evaporation of As from molten GaAs drops ablated from the target. The resulting morphology minimizes the interfacial and surface energies of the liquid Ga and solid GaAs.

Ice sintering timescales at the surface of Europa and implications for surface properties

NASA Astrophysics Data System (ADS)

Phillips, C. B.; Molaro, J.; Meirion-Griffith, G.

2017-12-01

The planned exploration of Europa by NASA's Europa Clipper Mission and the possibility of a future Europa lander have driven the need to characterize its surface strength, roughness, porosity, thermal conductivity, and regolith depth in order to accurately interpret remote sensing data and develop appropriate spacecraft landing systems. Many processes contribute to Europa's landscape evolution, such as sputtering, mass wasting, thermal segregation, and impact gardening, driving the creation and distribution of icy regolith across the surface. While the efficacy of these processes are not well constrained, any amount of regolith emplaced at the surface will undergo subsequent processing due to sintering. Ice sintering is a form of frost metamorphism whereby contacting ice grains experience the diffusion of material into their contact region, forming a "neck" between them and densifying over time. Over long enough timescales, ice aggregates will sinter into solid material, which may contribute to the incorporation of non-ice material into Europa's subsurface and help to drive subsurface chemistry. Sintering also interacts with other processes, adding to the complexity of icy surface evolution. For example, sputtering preferentially removes larger grains and may enhance sintering rates, and changes in ice porosity may affect the response of the surface to micrometeorite impacts. Quantifying the effects of ice sintering will allow us to predict the microstructural properties of Europa's surface at spacecraft scales. To this end, we have modeled pressure-less (no overburden) sintering of spherical water-ice grains and validated the results with a laboratory experiment. We also modeled ice at the surface of Europa to obtain a first-order approximation of the sintering timescale and surface properties. Preliminary results indicate that ice grains will experience neck growth but not significant densification over Europa's surface age, suggesting that loose surface ice forms a weak and porous crust. Furthermore, our results suggest that existing models do not accurately quantify all stages of the sintering process for ice, emphasizing the need for more laboratory studies on this topic.

Greenland ice sheet motion insensitive to exceptional meltwater forcing.

PubMed

Tedstone, Andrew J; Nienow, Peter W; Sole, Andrew J; Mair, Douglas W F; Cowton, Thomas R; Bartholomew, Ian D; King, Matt A

2013-12-03

Changes to the dynamics of the Greenland ice sheet can be forced by various mechanisms including surface-melt-induced ice acceleration and oceanic forcing of marine-terminating glaciers. We use observations of ice motion to examine the surface melt-induced dynamic response of a land-terminating outlet glacier in southwest Greenland to the exceptional melting observed in 2012. During summer, meltwater generated on the Greenland ice sheet surface accesses the ice sheet bed, lubricating basal motion and resulting in periods of faster ice flow. However, the net impact of varying meltwater volumes upon seasonal and annual ice flow, and thus sea level rise, remains unclear. We show that two extreme melt events (98.6% of the Greenland ice sheet surface experienced melting on July 12, the most significant melt event since 1889, and 79.2% on July 29) and summer ice sheet runoff ~3.9 σ above the 1958-2011 mean resulted in enhanced summer ice motion relative to the average melt year of 2009. However, despite record summer melting, subsequent reduced winter ice motion resulted in 6% less net annual ice motion in 2012 than in 2009. Our findings suggest that surface melt-induced acceleration of land-terminating regions of the ice sheet will remain insignificant even under extreme melting scenarios.

Large-area homogeneous periodic surface structures generated on the surface of sputtered boron carbide thin films by femtosecond laser processing

NASA Astrophysics Data System (ADS)

Serra, R.; Oliveira, V.; Oliveira, J. C.; Kubart, T.; Vilar, R.; Cavaleiro, A.

2015-03-01

Amorphous and crystalline sputtered boron carbide thin films have a very high hardness even surpassing that of bulk crystalline boron carbide (≈41 GPa). However, magnetron sputtered B-C films have high friction coefficients (C.o.F) which limit their industrial application. Nanopatterning of materials surfaces has been proposed as a solution to decrease the C.o.F. The contact area of the nanopatterned surfaces is decreased due to the nanometre size of the asperities which results in a significant reduction of adhesion and friction. In the present work, the surface of amorphous and polycrystalline B-C thin films deposited by magnetron sputtering was nanopatterned using infrared femtosecond laser radiation. Successive parallel laser tracks 10 μm apart were overlapped in order to obtain a processed area of about 3 mm2. Sinusoidal-like undulations with the same spatial period as the laser tracks were formed on the surface of the amorphous boron carbide films after laser processing. The undulations amplitude increases with increasing laser fluence. The formation of undulations with a 10 μm period was also observed on the surface of the crystalline boron carbide film processed with a pulse energy of 72 μJ. The amplitude of the undulations is about 10 times higher than in the amorphous films processed at the same pulse energy due to the higher roughness of the films and consequent increase in laser radiation absorption. LIPSS formation on the surface of the films was achieved for the three B-C films under study. However, LIPSS are formed under different circumstances. Processing of the amorphous films at low fluence (72 μJ) results in LIPSS formation only on localized spots on the film surface. LIPSS formation was also observed on the top of the undulations formed after laser processing with 78 μJ of the amorphous film deposited at 800 °C. Finally, large-area homogeneous LIPSS coverage of the boron carbide crystalline films surface was achieved within a large range of laser fluences although holes are also formed at higher laser fluences.

Method for producing silicon thin-film transistors with enhanced forward current drive

DOEpatents

Weiner, K.H.

1998-06-30

A method is disclosed for fabricating amorphous silicon thin film transistors (TFTs) with a polycrystalline silicon surface channel region for enhanced forward current drive. The method is particularly adapted for producing top-gate silicon TFTs which have the advantages of both amorphous and polycrystalline silicon TFTs, but without problem of leakage current of polycrystalline silicon TFTs. This is accomplished by selectively crystallizing a selected region of the amorphous silicon, using a pulsed excimer laser, to create a thin polycrystalline silicon layer at the silicon/gate-insulator surface. The thus created polysilicon layer has an increased mobility compared to the amorphous silicon during forward device operation so that increased drive currents are achieved. In reverse operation the polysilicon layer is relatively thin compared to the amorphous silicon, so that the transistor exhibits the low leakage currents inherent to amorphous silicon. A device made by this method can be used, for example, as a pixel switch in an active-matrix liquid crystal display to improve display refresh rates. 1 fig.

Method for producing silicon thin-film transistors with enhanced forward current drive

DOEpatents

Weiner, Kurt H.

1998-01-01

A method for fabricating amorphous silicon thin film transistors (TFTs) with a polycrystalline silicon surface channel region for enhanced forward current drive. The method is particularly adapted for producing top-gate silicon TFTs which have the advantages of both amorphous and polycrystalline silicon TFTs, but without problem of leakage current of polycrystalline silicon TFTs. This is accomplished by selectively crystallizing a selected region of the amorphous silicon, using a pulsed excimer laser, to create a thin polycrystalline silicon layer at the silicon/gate-insulator surface. The thus created polysilicon layer has an increased mobility compared to the amorphous silicon during forward device operation so that increased drive currents are achieved. In reverse operation the polysilicon layer is relatively thin compared to the amorphous silicon, so that the transistor exhibits the low leakage currents inherent to amorphous silicon. A device made by this method can be used, for example, as a pixel switch in an active-matrix liquid crystal display to improve display refresh rates.

Investigation of surface water behavior during glaze ice accretion

NASA Technical Reports Server (NTRS)

Hansman, R. John, Jr.; Turnock, Stephen R.

1990-01-01

A series of experimental investigations that focused on isolating the primary factors that control the behavior of unfrozen surface water during glaze ice accretion were conducted. Detailed microvideo observations were made of glaze ice accretions on 2.54 cm diam cylinders in a closed-loop refrigerated wind tunnel. Distinct zones of surface water behavior were observed; a smooth wet zone in the stagnation region with a uniform water film, a rough zone where surface tension effects caused coalescence of surface water into stationary beads, and a zone where surface water ran back as rivulets. The location of the transition from the smooth to the rough zone was found to migrate towards the stagnation point with time. Comparative tests were conducted to study the effect of the substrate thermal and roughness properties on ice accretion. The importance of surface water behavior was evaluated by the addition of a surface tension reducing agent to the icing tunnel water supply, which significantly altered the accreted glaze ice shape. Measurements were made to determine the contact angle behavior of water droplets on ice. A simple multizone modification to current glaze ice accretion models was proposed to include the observed surface roughness behavior.

Wave-Ice and Air-Ice-Ocean Interaction During the Chukchi Sea Ice Edge Advance

DTIC Science & Technology

2014-09-30

During cruise CU-B UAF UW Airborne expendable Ice Buoy (AXIB) Ahead, at and inside ice edge Surface meteorology T, SLP ~1 year CU-B UW...Balance (IMB) buoys Inside ice edge w/ >50cm thickness Ice mass balance T in snow-ice-ocean, T, SLP at surface ~1 year WHOI CRREL (SeaState DRI

Low-dose electron energy-loss spectroscopy using electron counting direct detectors.

PubMed

Maigné, Alan; Wolf, Matthias

2018-03-01

Since the development of parallel electron energy loss spectroscopy (EELS), charge-coupled devices (CCDs) have been the default detectors for EELS. With the recent development of electron-counting direct-detection cameras, micrographs can be acquired under very low electron doses at significantly improved signal-to-noise ratio. In spectroscopy, in particular in combination with a monochromator, the signal can be extremely weak and the detection limit is principally defined by noise introduced by the detector. Here we report the use of an electron-counting direct-detection camera for EEL spectroscopy. We studied the oxygen K edge of amorphous ice and obtained a signal noise ratio up to 10 times higher than with a conventional CCD.We report the application of electron counting to record time-resolved EEL spectra of a biological protein embedded in amorphous ice, revealing chemical changes observed in situ while exposed by the electron beam. A change in the fine structure of nitrogen K and the carbon K edges were recorded during irradiation. A concentration of 3 at% nitrogen was detected with a total electron dose of only 1.7 e-/Å2, extending the boundaries of EELS signal detection at low electron doses.

Effect of Viscosity on the Crystallization of Undercooled Liquids

NASA Technical Reports Server (NTRS)

2003-01-01

There have been numerous studies of glasses indicating that low-gravity processing enhances glass formation. NASA PI s are investigating the effect of low-g processing on the nucleation and crystal growth rates. Dr. Ethridge is investigating a potential mechanism for glass crystallization involving shear thinning of liquids in 1-g. For shear thinning liquids, low-g (low convection) processing will enhance glass formation. The study of the viscosity of glass forming substances at low shear rates is important to understand these new crystallization mechanisms. The temperature dependence of the viscosity of undercooled liquids is also very important for NASA s containerless processing studies. In general, the viscosity of undercooled liquids is not known, yet knowledge of viscosity is required for crystallization calculations. Many researchers have used the Turnbull equation in error. Subsequent nucleation and crystallization calculations can be in error by many orders of magnitude. This demonstrates the requirement for better methods for interpolating and extrapolating the viscosity of undercooled liquids. This is also true for undercooled water. Since amorphous water ice is the predominant form of water in the universe, astrophysicists have modeled the crystallization of amorphous water ice with viscosity relations that may be in error by five orders-of-magnitude.

Bio-inspired design of ice-retardant devices based on benthic marine invertebrates: the effect of surface texture

PubMed Central

Mehrabani, Homayun; Ray, Neil; Tse, Kyle

2014-01-01

Growth of ice on surfaces poses a challenge for both organisms and for devices that come into contact with liquids below the freezing point. Resistance of some organisms to ice formation and growth, either in subtidal environments (e.g., Antarctic anchor ice), or in environments with moisture and cold air (e.g., plants, intertidal) begs examination of how this is accomplished. Several factors may be important in promoting or mitigating ice formation. As a start, here we examine the effect of surface texture alone. We tested four candidate surfaces, inspired by hard-shelled marine invertebrates and constructed using a three-dimensional printing process. We examined sub-polar marine organisms to develop sample textures and screened them for ice formation and accretion in submerged conditions using previous methods for comparison to data for Antarctic organisms. The sub-polar organisms tested were all found to form ice readily. We also screened artificial 3-D printed samples using the same previous methods, and developed a new test to examine ice formation from surface droplets as might be encountered in environments with moist, cold air. Despite limitations inherent to our techniques, it appears surface texture plays only a small role in delaying the onset of ice formation: a stripe feature (corresponding to patterning found on valves of blue mussels, Mytilus edulis, or on the spines of the Antarctic sea urchin Sterechinus neumayeri) slowed ice formation an average of 25% compared to a grid feature (corresponding to patterning found on sub-polar butterclams, Saxidomas nuttalli). The geometric dimensions of the features have only a small (∼6%) effect on ice formation. Surface texture affects ice formation, but does not explain by itself the large variation in ice formation and species-specific ice resistance observed in other work. This suggests future examination of other factors, such as material elastic properties and surface coatings, and their interaction with surface pattern. PMID:25279268

Frost flowers on young Arctic sea ice: The climatic, chemical, and microbial significance of an emerging ice type

NASA Astrophysics Data System (ADS)

Barber, D. G.; Ehn, J. K.; Pućko, M.; Rysgaard, S.; Deming, J. W.; Bowman, J. S.; Papakyriakou, T.; Galley, R. J.; Søgaard, D. H.

2014-10-01

Ongoing changes in Arctic sea ice are increasing the spatial and temporal range of young sea ice types over which frost flowers can occur, yet the significance of frost flowers to ocean-sea ice-atmosphere exchange processes remains poorly understood. Frost flowers form when moisture from seawater becomes available to a cold atmosphere and surface winds are low, allowing for supersaturation of the near-surface boundary layer. Ice grown in a pond cut in young ice at the mouth of Young Sound, NE Greenland, in March 2012, showed that expanding frost flower clusters began forming as soon as the ice formed. The new ice and frost flowers dramatically changed the radiative and thermal environment. The frost flowers were about 5°C colder than the brine surface, with an approximately linear temperature gradient from their base to their upper tips. Salinity and δ18O values indicated that frost flowers primarily originated from the surface brine skim. Ikaite crystals were observed to form within an hour in both frost flowers and the thin pond ice. Average ikaite concentrations were 1013 µmol kg-1 in frost flowers and 1061 µmol kg-1 in the surface slush layer. Chamber flux measurements confirmed an efflux of CO2 at the brine-wetted sea ice surface, in line with expectations from the brine chemistry. Bacteria concentrations generally increased with salinity in frost flowers and the surface slush layer. Bacterial densities and taxa indicated that a selective process occurred at the ice surface and confirmed the general pattern of primary oceanic origin versus negligible atmospheric deposition.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Widespread surface meltwater drainage in Antarctica

NASA Astrophysics Data System (ADS)

Kingslake, J.; Ely, J.; Das, I.; Bell, R. E.

2016-12-01

Surface meltwater is thought to cause ice-shelf disintegration, which accelerates the contribution of ice sheets to sea-level rise. Antarctic surface melting is predicted to increase and trigger further ice-shelf disintegration during this century. These climate-change impacts could be modulated by an active hydrological network analogous to the one in operation in Greenland. Despite some observations of Antarctic surface and sub-surface hydrological systems, large-scale active surface drainage in Antarctica has rarely been studied. We use satellite imagery and aerial photography to reveal widespread active hydrology on the surface of the Antarctic Ice Sheet as far south as 85o and as high as 1800 m a.s.l., often near mountain peaks that protrude through the ice (nunataks) and relatively low-albedo `blue-ice areas'. Despite predominantly sub-zero regional air temperatures, as simulated by a regional climate model, Antarctic active drainage has persisted for decades, transporting water through surface streams and feeding vast melt ponds up to 80 km long. Drainage networks (the largest are over 100 km in length) form on flat ice shelves, steep outlet glaciers and ice-sheet flanks across the West and East Antarctica Ice Sheets. Motivated by the proximity of many drainage systems to low-albedo rock and blue-ice areas, we hypothesize a positive feedback between exposed-rock extent, BIA formation, melting and ice-sheet thinning. This feedback relies on drainage moving water long distances from areas near exposed rock, across the grounding line onto and across ice shelves - a process we observe, but had previously thought to be unlikely in Antarctica. This work highlights previously-overlooked processes, not captured by current regional-scale models, which may accelerate the retreat of the Antarctic Ice Sheet.

Monitoring the recrystallisation of amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering.

PubMed

Palomäki, Emmi; Ahvenainen, Patrik; Ehlers, Henrik; Svedström, Kirsi; Huotari, Simo; Yliruusi, Jouko

2016-07-11

In this paper we present a fast model system for monitoring the recrystallization of quench-cooled amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering. The use of these two methods enables comparison between surface and bulk crystallization. Non-ordered mesoporous silica micro-particles were added to the system in order to alter the rate of crystallization of the amorphous xylitol. Raman measurements showed that adding silica to the system increased the rate of surface crystallization, while X-ray measurements showed that the rate of bulk crystallization decreased. Using this model system it is possible to measure fast changes, which occur in minutes or within a few hours. Raman-spectroscopy and wide-angle X-ray scattering were found to be complementary techniques when assessing surface and bulk crystallization of amorphous xylitol. Copyright © 2016 Elsevier B.V. All rights reserved.

Anti-icing properties of superhydrophobic ZnO/PDMS composite coating

NASA Astrophysics Data System (ADS)

Yang, Chao; Wang, Fajun; Li, Wen; Ou, Junfei; Li, Changquan; Amirfazli, Alidad

2016-01-01

We present the excellent anti-icing performance for a superhydrophobic coating surface based on ZnO/polydimethylsiloxane (ZnO/PDMS) composite. The superhydrophobic ZnO/PDMS coating surface was prepared by a facile solution mixing, drop coating, room-temperature curing and surface abrading procedure. The superhydrophobic ZnO/PDMS composite coating possesses a water contact angle of 159.5° and a water sliding angle of 8.3° at room temperature (5 °C). The anti-icing properties of the superhydrophobic coating were investigated by continuously dropping cold-water droplets (about 0 °C) onto the pre-cooled surface using a home-made apparatus. The sample was placed at different tilting angle (0° and 10°) and pre-cooled to various temperatures (-5, -10 and -15 °C) prior to measure. The pure Al surface was also studied for comparison. It was found that icing accretion on the surface could be reduced apparently because the water droplets merged together and slid away from the superhydrophobic surface at all of the measuring temperatures when the surface is horizontally placed. In addition, water droplet slid away completely from the superhydrophobic surface at -5 and -10 °C when the surface is tilted at 10°, which demonstrates its excellent anti-icing properties at these temperatures. When the temperature decreased to -15 °C, though ice accretion on the tilted superhydrophobic coating surface could not be avoided absolutely, the amount of ice formed on the surface is very small, which indicated that the coating surface with superhydrophobicity could significantly reduce ice accumulation on the surface at very low temperature (-15 °C). Importantly, the sample is also stable against repeated icing/deicing cycles. More meaningfully, once the superhydrophobic surface is damaged, it can be repaired easily and rapidly.

Methods and systems for detection of ice formation on surfaces

NASA Technical Reports Server (NTRS)

Alfano, Robert R. (Inventor); Wang, Wubao (Inventor); Sztul, Henry (Inventor); Budansky, Yury (Inventor)

2007-01-01

A system for detecting ice formation on metal, painted metal and other material surfaces can include a transparent window having an exterior surface upon which ice can form; a light source and optics configured and arranged to illuminate the exterior surface of the window from behind the exterior surface; and a detector and optics configured and arranged to receive light backscattered by the exterior surface and any ice disposed on the exterior surface and determine the thickness of the ice layer. For example, the system can be used with aircraft by placing one or more windows in the wings of the aircraft. The system is used for a novel optical method for real-time on-board detection and warning of ice formation on surfaces of airplanes, unmanned aerial vehicles (UAVs), and other vehicles and stationary structures to improve their safety and operation.

Studies of cavitation and ice nucleation in 'doubly-metastable' water: time-lapse photography and neutron diffraction.

PubMed

Barrow, Matthew S; Williams, P Rhodri; Chan, Hoi-Houng; Dore, John C; Bellissent-Funel, Marie-Claire

2012-10-14

High-speed photographic studies and neutron diffraction measurements have been made of water under tension in a Berthelot tube. Liquid water was cooled below the normal ice-nucleation temperature and was in a doubly-metastable state prior to a collapse of the liquid state. This transition was accompanied by an exothermic heat release corresponding with the rapid production of a solid phase nucleated by cavitation. Photographic techniques have been used to observe the phase transition over short time scales in which a solidification front is observed to propagate through the sample. Significantly, other images at a shorter time interval reveal the prior formation of cavitation bubbles at the beginning of the process. The ice-nucleation process is explained in terms of a mechanism involving hydrodynamically-induced changes in tension in supercooled water in the near vicinity of an expanding cavitation bubble. Previous explanations have attributed the nucleation of the solid phase to the production of high positive pressures. Corresponding results are presented which show the initial neutron diffraction pattern after ice-nucleation. The observed pattern does not exhibit the usual crystalline pattern of hexagonal ice [I(h)] that is formed under ambient conditions, but indicates the presence of other ice forms. The composite features can be attributed to a mixture of amorphous ice, ice-I(h)/I(c) and the high-pressure form, ice-III, and the diffraction pattern continues to evolve over a time period of about an hour.

Possible Mechanisms for Turbofan Engine Ice Crystal Icing at High Altitude

NASA Technical Reports Server (NTRS)

Tsao, Jen-Ching; Struk, Peter M.; Oliver, Michael

2014-01-01

A thermodynamic model is presented to describe possible mechanisms of ice formation on unheated surfaces inside a turbofan engine compression system from fully glaciated ice crystal clouds often formed at high altitude near deep convective weather systems. It is shown from the analysis that generally there could be two distinct types of ice formation: (1) when the "surface freezing fraction" is in the range of 0 to 1, dominated by the freezing of water melt from fully or partially melted ice crystals, the ice structure is formed from accretion with strong adhesion to the surface, and (2) when the "surface melting fraction" is the range of 0 to 1, dominated by the further melting of ice crystals, the ice structure is formed from accumulation of un-melted ice crystals with relatively weak bonding to the surface. The model captures important qualitative trends of the fundamental ice-crystal icing phenomenon reported earlier1,2 from the research collaboration work by NASA and the National Research Council (NRC) of Canada. Further, preliminary analysis of test data from the 2013 full scale turbofan engine ice crystal icing test3 conducted in the NASA Glenn Propulsion Systems Laboratory (PSL) has also suggested that (1) both types of ice formation occurred during the test, and (2) the model has captured some important qualitative trend of turning on (or off) the ice crystal ice formation process in the tested engine low pressure compressor (LPC) targeted area under different icing conditions that ultimately would lead to (or suppress) an engine core roll back (RB) event.

Possible Mechanisms for Turbofan Engine Ice Crystal Icing at High Altitude

NASA Technical Reports Server (NTRS)

Tsao, Jen-Ching; Struk, Peter M.; Oliver, Michael J.

2016-01-01

A thermodynamic model is presented to describe possible mechanisms of ice formation on unheated surfaces inside a turbofan engine compression system from fully glaciated ice crystal clouds often formed at high altitude near deep convective weather systems. It is shown from the analysis that generally there could be two distinct types of ice formation: (1) when the "surface freezing fraction" is in the range of 0 to 1, dominated by the freezing of water melt from fully or partially melted ice crystals, the ice structure is formed from accretion with strong adhesion to the surface, and (2) when the "surface melting fraction" is the range of 0 to 1, dominated by the further melting of ice crystals, the ice structure is formed from accumulation of un-melted ice crystals with relatively weak bonding to the surface. The model captures important qualitative trends of the fundamental ice-crystal icing phenomenon reported earlier (Refs. 1 and 2) from the research collaboration work by NASA and the National Research Council (NRC) of Canada. Further, preliminary analysis of test data from the 2013 full scale turbofan engine ice crystal icing test (Ref. 3) conducted in the NASA Glenn Propulsion Systems Laboratory (PSL) has also suggested that (1) both types of ice formation occurred during the test, and (2) the model has captured some important qualitative trend of turning on (or off) the ice crystal ice formation process in the tested engine low pressure compressor (LPC) targeted area under different icing conditions that ultimately would lead to (or suppress) an engine core roll back (RB) event.

Field-Induced Crystalline-to-Amorphous Phase Transformation on the Si Nano-Apex and the Achieving of Highly Reliable Si Nano-Cathodes

PubMed Central

Huang, Yifeng; Deng, Zexiang; Wang, Weiliang; Liang, Chaolun; She, Juncong; Deng, Shaozhi; Xu, Ningsheng

2015-01-01

Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation. PMID:25994377

Barrier coated drug layered particles for enhanced performance of amorphous solid dispersion dosage form.

PubMed

Puri, Vibha; Dantuluri, Ajay K; Bansal, Arvind K

2012-01-01

Amorphous solid dispersions (ASDs) may entail tailor-made dosage form design to exploit their solubility advantage. Surface phenomena dominated the performance of amorphous celecoxib solid dispersion (ACSD) comprising of amorphous celecoxib (A-CLB), polyvinylpyrrolidone, and meglumine (7:2:1, w/w). ACSD cohesive interfacial interactions hindered its capsule dosage form dissolution (Puri V, Dhantuluri AK, Bansal AK 2011. J Pharm Sci 100:2460-2468). Furthermore, ACSD underwent significant devitrification under environmental stress. In the present study, enthalpy relaxation studies revealed its free surface to contribute to molecular mobility. Based on all these observations, barrier coated amorphous CLB solid dispersion layered particles (ADLP) were developed by Wurster process, using microcrystalline cellulose as substrate and polyvinyl alcohol (PVA), inulin, and polyvinyl acetate phthalate (PVAP) as coating excipients. Capsule formulations of barrier coated-ADLP could achieve rapid dispersibility and high drug release. Evaluation under varying temperature and RH conditions suggested the crystallization inhibitory efficiency in order of inulin < PVA ≈ PVAP; however, under only temperature treatment, crystallization inhibition increased with increase in T(g) of the coating material. Simulated studies using DSC evidenced drug-polymer mixing at the interface as a potential mechanism for surface stabilization. In conclusion, surface modification yielded a fast dispersing robust high drug load ASD based dosage form. Copyright © 2011 Wiley-Liss, Inc.

The Role of Basal Channels in Ice Shelf Calving.

NASA Astrophysics Data System (ADS)

Dow, C. F.; Lee, W. S.; Greenbaum, J. S.; Greene, C. A.; Blankenship, D. D.; Poinar, K.; Forrest, A.; Young, D. A.; Zappa, C. J.

2017-12-01

Increased rates of ice shelf break-up drives acceleration of grounded glacial ice into the ocean, resulting in sea-level rise. Ice shelves are vulnerable to thinning, which make them more susceptible to calving. Here, we examine basal channels under three ice shelves that locally thin the ice and drive formation of transverse ice shelf fractures. The basal channels also cause surface depressions due to hydrostatic buoyancy effects and can draw in surface water to form rivers. These rivers exacerbate thinning by surface melting and hydraulic loading, and can accelerate rifting when they flow into the transverse fractures. Our investigation focuses on Nansen Ice Shelf in the Ross Sea Embayment, East Antarctica. We use ice-sounding radar and single-beam laser altimeter data from two aerogeophysical campaigns conducted in 2011 and 2014, ice surface DEM reconstruction, and satellite imagery analysis, to examine the role of a substantial basal channel in the stability of this ice shelf. Nansen Ice Shelf calved two large icebergs totaling 214 km2 in area in April 2016. The transverse fracture that eventually rifted to form these icebergs initiated directly over the basal channel in 1987. In years when surface water formed on Nansen Ice Shelf, a river flowed into the transverse fracture. In November 2016, we identified a new fracture over the basal channel during in-situ data collection. We compare the Nansen Ice Shelf fractures with those at other vulnerable ice-shelf systems, including Petermann Glacier in Greenland and Totten Glacier in East Antarctica, to evaluate the role that basal channels may play in simultaneous basal and surface weakening and their consequent effect on ice-shelf rifting and stability.

Magnetic slippery extreme icephobic surfaces

PubMed Central

Irajizad, Peyman; Hasnain, Munib; Farokhnia, Nazanin; Sajadi, Seyed Mohammad; Ghasemi, Hadi

2016-01-01

Anti-icing surfaces have a critical footprint on daily lives of humans ranging from transportation systems and infrastructure to energy systems, but creation of these surfaces for low temperatures remains elusive. Non-wetting surfaces and liquid-infused surfaces have inspired routes for the development of icephobic surfaces. However, high freezing temperature, high ice adhesion strength, and high cost have restricted their practical applications. Here we report new magnetic slippery surfaces outperforming state-of-the-art icephobic surfaces with a ice formation temperature of −34 °C, 2–3 orders of magnitude higher delay time in ice formation, extremely low ice adhesion strength (≈2 Pa) and stability in shear flows up to Reynolds number of 105. In these surfaces, we exploit the magnetic volumetric force to exclude the role of solid–liquid interface in ice formation. We show that these inexpensive surfaces are universal and can be applied to all types of solids (no required micro/nano structuring) with no compromise to their unprecedented properties. PMID:27824053

Effects of the addition of Co, Ni or Cr on the decolorization properties of Fe-Si-B amorphous alloys

NASA Astrophysics Data System (ADS)

Zhang, Changqin; Zhu, Zhengwang; Zhang, Haifeng

2017-11-01

Fe-based amorphous alloys show great potential in degrading azo dyes and other organic pollutants, and are widely investigated as a kind of environmental-friendly materials for wastewater remediation. In this paper, the effects of Co, Ni or Cr addition on the decolorization properties of Fe-Si-B amorphous alloys were studied, and the mechanism of their different effects was analyzed. Co addition could lower the activation energy of Fe-Si-B amorphous alloys in decolorizing azo dyes, and had no weakening effect on the decolorization capability of Fe-Si-B amorphous alloys. Ni addition led to partial crystallization of Fe-Si-B amorphous alloys, and the decolorization mechanism at low temperatures changed from chemical degradation to physical adsorption. Cr addition could enhance the corrosion resistance of Fe-Si-B amorphous alloys, but the amorphous alloys completely lost the decolorization capability no matter at lower or higher temperatures. The results of X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) indicated that the addition of Co, Ni or Cr could generate different surface structures that had significant influences on the decolorization process. Our work demonstrated that the effiecient decolorization of azo dyes by Fe-based alloys could be realized only when amorphous nature and incompact surface structure were simultaneously achieved for the alloys.

Generating gradient germanium nanostructures by shock-induced amorphization and crystallization

DOE PAGES

Zhao, Shiteng; Kad, Bimal; Wehrenberg, Christopher E.; ...

2017-08-28

Gradient nanostructures are attracting considerable interest due to their potential to obtain superior structural and functional properties of materials. Applying powerful laser-driven shocks (stresses of up to one-third million atmospheres, or 33 gigapascals) to germanium, we report a complex gradient nanostructure consisting of, near the surface, nanocrystals with high density of nanotwins. Beyond there, the structure exhibits arrays of amorphous bands which are preceded by planar defects such as stacking faults generated by partial dislocations. At a lower shock stress, the surface region of the recovered target is completely amorphous. Here, we propose that germanium undergoes amorphization above a thresholdmore » stress and that the deformation-generated heat leads to nanocrystallization. These experiments are corroborated by molecular dynamics simulations which show that supersonic partial dislocation bursts play a role in triggering the crystalline-to-amorphous transition.« less

How does spallation microdamage nucleate in bulk amorphous alloys under shock loading?

NASA Astrophysics Data System (ADS)

Huang, X.; Ling, Z.; Zhang, H. S.; Ma, J.; Dai, L. H.

2011-11-01

Specially designed plate-impact experiments have been conducted on a Zr-based amorphous alloy using a single-stage light gas gun. To understand the microdamage nucleation process in the material, the samples are subjected to dynamic tensile loadings of identical amplitude (˜ 3.18 GPa) but with different durations (83-201 ns). A cellular pattern with an equiaxed shape is observed on the spallation surface, which shows that spallation in the tested amorphous alloy is a typical ductile fracture and that microvoids have been nucleated during the process. Based on the observed fracture morphologies of the spallation surface and free-volume theory, we propose a microvoid nucleation model of bulk amorphous alloys. It is found that nucleation of microvoids at the early stage of spallation in amorphous alloys results from diffusion and coalescence of free volume, and that high mean tensile stress plays a dominant role in microvoid nucleation.

Generating gradient germanium nanostructures by shock-induced amorphization and crystallization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Shiteng; Kad, Bimal; Wehrenberg, Christopher E.

Gradient nanostructures are attracting considerable interest due to their potential to obtain superior structural and functional properties of materials. Applying powerful laser-driven shocks (stresses of up to one-third million atmospheres, or 33 gigapascals) to germanium, we report a complex gradient nanostructure consisting of, near the surface, nanocrystals with high density of nanotwins. Beyond there, the structure exhibits arrays of amorphous bands which are preceded by planar defects such as stacking faults generated by partial dislocations. At a lower shock stress, the surface region of the recovered target is completely amorphous. Here, we propose that germanium undergoes amorphization above a thresholdmore » stress and that the deformation-generated heat leads to nanocrystallization. These experiments are corroborated by molecular dynamics simulations which show that supersonic partial dislocation bursts play a role in triggering the crystalline-to-amorphous transition.« less

Impact of surface roughness on L-band emissivity of the sea ice

NASA Astrophysics Data System (ADS)

Miernecki, M.; Kaleschke, L.; Hendricks, S.; Søbjærg, S. S.

2015-12-01

In March 2014 a joint experiment IRO2/SMOSice was carried out in the Barents Sea. R/V Lance equipped with meteorological instruments, electromagnetic sea ice thickness probe and engine monitoring instruments, was performing a series of tests in different ice conditions in order to validate the ice route optimization (IRO) system, advising on his route through pack ice. In parallel cal/val activities for sea ice thickness product obtained from SMOS (Soil Moisture and Ocean Salinity mission) L-band radiometer were carried out. Apart from helicopter towing the EMbird thickness probe, Polar 5 aircraft was serving the area during the experiment with L-band radiometer EMIRAD2 and Airborne Laser Scanner (ALS) as primary instruments. Sea ice Thickness algorithm using SMOS brightness temperature developed at University of Hamburg, provides daily maps of thin sea ice (up to 0.5-1 m) in polar regions with resolution of 35-50 km. So far the retrieval method was not taking into account surface roughness, assuming that sea ice is a specular surface. Roughness is a stochastic process that can be characterized by standard deviation of surface height σ and by shape of the autocorrelation function R to estimate it's vertical and horizontal scales respectively. Interactions of electromagnetic radiation with the surface of the medium are dependent on R and σ and they scales with respect to the incident wavelength. During SMOSice the radiometer was observing sea ice surface at two incidence angles 0 and 40 degrees and simultaneously the surface elevation was scanned with ALS with ground resolution of ~ 0.25 m. This configuration allowed us to calculate σ and R from power spectral densities of surface elevation profiles and quantify the effect of surface roughness on the emissivity of the sea ice. First results indicate that Gaussian autocorrelation function is suitable for deformed ice, for other ice types exponential function is the best fit.

Si amorphization by focused ion beam milling: Point defect model with dynamic BCA simulation and experimental validation.

PubMed

Huang, J; Loeffler, M; Muehle, U; Moeller, W; Mulders, J J L; Kwakman, L F Tz; Van Dorp, W F; Zschech, E

2018-01-01

A Ga focused ion beam (FIB) is often used in transmission electron microscopy (TEM) analysis sample preparation. In case of a crystalline Si sample, an amorphous near-surface layer is formed by the FIB process. In order to optimize the FIB recipe by minimizing the amorphization, it is important to predict the amorphous layer thickness from simulation. Molecular Dynamics (MD) simulation has been used to describe the amorphization, however, it is limited by computational power for a realistic FIB process simulation. On the other hand, Binary Collision Approximation (BCA) simulation is able and has been used to simulate ion-solid interaction process at a realistic scale. In this study, a Point Defect Density approach is introduced to a dynamic BCA simulation, considering dynamic ion-solid interactions. We used this method to predict the c-Si amorphization caused by FIB milling on Si. To validate the method, dedicated TEM studies are performed. It shows that the amorphous layer thickness predicted by the numerical simulation is consistent with the experimental data. In summary, the thickness of the near-surface Si amorphization layer caused by FIB milling can be well predicted using the Point Defect Density approach within the dynamic BCA model. Copyright © 2017 Elsevier B.V. All rights reserved.

The Effect of Surface Ice and Topography on the Atmospheric Circulation and Distribution of Nitrogen Ice on Pluto

NASA Astrophysics Data System (ADS)

Rafkin, Scot C. R.; Soto, Alejandro; Michaels, Timothy I.

2016-10-01

A newly developed general circulation model (GCM) for Pluto is used to investigate the impact of a heterogeneous distribution of nitrogen surface ice and large scale topography on Pluto's atmospheric circulation. The GCM is based on the GFDL Flexible Modeling System (FSM). Physics include a gray model radiative-conductive scheme, subsurface conduction, and a nitrogen volatile cycle. The radiative-conductive model takes into account the 2.3, 3.3 and 7.8 μm bands of CH4 and CO, including non-local thermodynamic equilibrium effects. including non-local thermodynamic equilibrium effects. The nitrogen volatile cycle is based on a vapor pressure equilibrium assumption between the atmosphere and surface. Prior to the arrival of the New Horizons spacecraft, the expectation was that the volatile ice distribution on the surface of Pluto would be strongly controlled by the latitudinal temperature gradient. If this were the case, then Pluto would have broad latitudinal bands of both ice covered surface and ice free surface, as dictated by the season. Further, the circulation, and the thus the transport of volatiles, was thought to be driven almost exclusively by sublimation and deposition flows associated with the volatile cycle. In contrast to expectations, images from New Horizon showed an extremely complex, heterogeneous distribution of surface ices draped over substantial and variable topography. To produce such an ice distribution, the atmospheric circulation and volatile transport must be more complex than previously envisioned. Simulations where topography, surface ice distributions, and volatile cycle physics are added individually and in various combinations are used to individually quantify the importance of the general circulation, topography, surface ice distributions, and condensation flows. It is shown that even regional patches of ice or large craters can have global impacts on the atmospheric circulation, the volatile cycle, and hence, the distribution of surface ices. The work demonstrates that explaining Pluto's volatile cycle and the expression of that cycle in the surface ice distributions requires consideration of atmospheric processes beyond simple vapor pressure equilibrium arguments.

Addressing the amorphous content issue in quantitative phase analysis: the certification of NIST standard reference material 676a.

PubMed

Cline, James P; Von Dreele, Robert B; Winburn, Ryan; Stephens, Peter W; Filliben, James J

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum (α-Al(2)O(3)) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% ± 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

Amorphous Diamond for MEMS

NASA Astrophysics Data System (ADS)

Sullivan, J. P.

2002-03-01

Pure carbon films can exhibit surprising complexity in structure and properties. Amorphous diamond (tetrahedrally-coordinated amorphous carbon) is an amorphous quasi-two phase mixture of four-fold and three-fold coordinated carbon which is produced by pulsed excimer laser deposition, an energetic deposition process that leads to film growth by sub-surface carbon implantation and the creation of local metastability in carbon bonding. Modest annealing, < 900K, produces significant irreversible strain relaxation which is thermally activated with activation energies ranging from < 1 eV to > 2 eV. During annealing the material remains amorphous, but there is a detectable increase in medium-range order as measured by fluctuation microscopy. The strain relaxation permits the residual strain in the films to be reduced to < 0.00001, which is a critical requirement for the fabrication of microelectromechanical systems (MEMS). Amorphous diamond MEMS have been fabricated in order to evaluate the mechanical properties of this material under tension and flexure, and this has enabled the determination of elastic modulus (800 GPa), tensile strength (8 GPa), and fracture toughness (8 MPa m^1/2). In addition, amorphous diamond MEMS structures have been fabricated to measure internal dissipation and surface adhesion. The high hardness and strength and hydrophobic nature of the surface makes this material particularly suitable for the fabrication of high wear resistance and low stiction MEMS. Sandia is a multiprogram laboratory operated by Sandia Corp., a Lockheed Martin Co., for the U.S. Dept. of Energy under contract DE-AC04-94AL85000.

An Imminent Revolution in Modeling Interactions of Ice Sheets With Climate

NASA Astrophysics Data System (ADS)

Hughes, T.

2008-12-01

Modeling continental ice sheets was inaugurated by meteorologists William Budd and Uwe Radok, with mathematician Richard Jenssen, in 1971. Their model calculated the thermal and mechanical regime using measured surface accumulation rates, temperatures, and elevations, and bed topography. This top-down approach delivered a basal thermal regime of temperatures or melting rates for an assumed basal geothermal heat flux. When Philippe Huybrechts and others incorporated time, largely unknownpast surface conditions had a major effect on present basal thermal conditions. This approach produced ice-sheet models with only a slow response to external forcing, whereas the glacial geological record and climate records from ice and ocean cores show that ice sheets can have rapid changes in size and shape independent of external forcing. These top-down models were wholly inadequate for reconstructing former ice sheets at the LGM for CLIMAP in 1981. Ice-sheet areas,elevations, and volumes provided the albedo, surface topography, and sea-surface area as input to climate models. A bottom-up model based on dated glacial geology was developed to provide the areal extent and basal thermal regime of ice sheets at the LGM. Basal thermal conditions determined ice-bed coupling and therefore the elevation of ice sheets. High convex ice surfaces for slow sheet flow lower about 20 percent when a frozen bed becomes thawed. As further basal melting drowns bedrock bumps that "pin" basal ice, the ice surface becomes concave in fast stream flow that ends as low floating ice shelves at marine ice margins. A revolution in modeling interactions between glaciation, climate, and sea level is driven by new Greenland and Antarctic data from Earth-orbiting satellites, airborne and surface traverses, and deep drilling. We anticipate continuous data acquisition of surface albedo, accumulation/ablation rates, elevations, velocities, and temperatures over a whole ice sheet, mapping basal thermal conditions by radar, seismic, and magnetic profiling, and direct measurement of basal conditions by deep drilling and coring into the ice and the bed. These data allow calculating the geothermal heat flux and mapping flow of basal meltwater from geothermal sources to sinks at the termini of ice streams, which discharge up to 90 percent of the ice. James Fastook has a preliminary solution of the full momentum equation needed to model ice streams. Douglas MacAyeal has pioneered modeling catastrophic ice-shelf disintegration that releases "armadas" of icebergs into the world ocean, to extract heat from ocean surface water and thereby reduce the critical ocean-to-atmosphere heat exchange that drives global climate. Ice sheets are the only component of Earth's climate machine that can destroy itself-- swiftly--and thereby radically and rapidly alter global climate and sea level.

Algae Drive Enhanced Darkening of Bare Ice on the Greenland Ice Sheet

NASA Astrophysics Data System (ADS)

Stibal, Marek; Box, Jason E.; Cameron, Karen A.; Langen, Peter L.; Yallop, Marian L.; Mottram, Ruth H.; Khan, Alia L.; Molotch, Noah P.; Chrismas, Nathan A. M.; Calı Quaglia, Filippo; Remias, Daniel; Smeets, C. J. P. Paul; van den Broeke, Michiel R.; Ryan, Jonathan C.; Hubbard, Alun; Tranter, Martyn; van As, Dirk; Ahlstrøm, Andreas P.

2017-11-01

Surface ablation of the Greenland ice sheet is amplified by surface darkening caused by light-absorbing impurities such as mineral dust, black carbon, and pigmented microbial cells. We present the first quantitative assessment of the microbial contribution to the ice sheet surface darkening, based on field measurements of surface reflectance and concentrations of light-absorbing impurities, including pigmented algae, during the 2014 melt season in the southwestern part of the ice sheet. The impact of algae on bare ice darkening in the study area was greater than that of nonalgal impurities and yielded a net albedo reduction of 0.038 ± 0.0035 for each algal population doubling. We argue that algal growth is a crucial control of bare ice darkening, and incorporating the algal darkening effect will improve mass balance and sea level projections of the Greenland ice sheet and ice masses elsewhere.

Thin-film limit formalism applied to surface defect absorption.

PubMed

Holovský, Jakub; Ballif, Christophe

2014-12-15

The thin-film limit is derived by a nonconventional approach and equations for transmittance, reflectance and absorptance are presented in highly versatile and accurate form. In the thin-film limit the optical properties do not depend on the absorption coefficient, thickness and refractive index individually, but only on their product. We show that this formalism is applicable to the problem of ultrathin defective layer e.g. on a top of a layer of amorphous silicon. We develop a new method of direct evaluation of the surface defective layer and the bulk defects. Applying this method to amorphous silicon on glass, we show that the surface defective layer differs from bulk amorphous silicon in terms of light soaking.

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

PubMed

Ueta, Hirokazu; Watanabe, Naoki; Hama, Tetsuya; Kouchi, Akira

2016-06-24

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16 K. Within a narrow temperature window of 8 K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2}  s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Surface and Basal Roughness in Radar Sounding Data: Obstacle and Opportunity

NASA Astrophysics Data System (ADS)

Schroeder, D. M.; Grima, C.; Haynes, M.

2015-12-01

The surface and basal roughness of glaciers, ice sheets, and ice shelves can pose a significant obstacle to the visual interpretation and quantitative analysis of radar sounding data. Areas of high surface roughness - including grounding zones, shear margins, and crevasse fields - can produce clutter and side-lobe signals that obscure the interpretation of englacial and subglacial features. These areas can also introduce significant variation in bed echo strength profiles as a result of losses from two-way propagation through rough ice surfaces. Similarly, reflections from rough basal interfaces beneath ice sheets and ice shelves can also result in large, spatially variable losses in bed echo power. If unmitigated and uncorrected, these effects can degrade or prevent the definitive interpretation of material and geometric properties at the base of ice sheets and ice shelves using radar reflectivity and bed echo character. However, these effects also provide geophysical signatures of surface and basal interface character - including surface roughness, firn density, subglacial bedform geometry, ice shelf basal roughness, marine-ice/brine detection, and crevasse geometry - that can be observed and constrained by exploiting roughness effects in radar sounding data. We present a series of applications and approaches for characterizing and correcting surface and basal roughness effects for airborne radar sounding data collected in Antarctica. We also present challenges, insights, and opportunities for extending these techniques to the orbital radar sounding of Europa's ice shell.

Electro-suppression of water nano-droplets' solidification in no man's land: Electromagnetic fields' entropic trapping of supercooled water

NASA Astrophysics Data System (ADS)

Nandi, Prithwish K.; Burnham, Christian J.; English, Niall J.

2018-01-01

Understanding water solidification, especially in "No Man's Land" (NML) (150 K < T < 235 K) is crucially important (e.g., upper-troposphere cloud processes) and challenging. A rather neglected aspect of tropospheric ice-crystallite formation is inevitably present electromagnetic fields' role. Here, we employ non-equilibrium molecular dynamics of aggressively quenched supercooled water nano-droplets in the gas phase under NML conditions, in externally applied electromagnetic (e/m) fields, elucidating significant differences between effects of static and oscillating fields: although static fields induce "electro-freezing," e/m fields exhibit the contrary - solidification inhibition. This anti-freeze action extends not only to crystal-ice formation but also restricts amorphisation, i.e., suppression of low-density amorphous ice which forms otherwise in zero-field NML environments. E/m-field applications maintain water in the deeply supercooled state in an "entropic trap," which is ripe for industrial impacts in cryo-freezing, etc.

Surface Brillouin scattering study of the surface excitations in amorphous silicon layers produced by ion bombardment

NASA Astrophysics Data System (ADS)

Zhang, X.; Comins, J. D.; Every, A. G.; Stoddart, P. R.; Pang, W.; Derry, T. E.

1998-11-01

Thin amorphous silicon layers on crystalline silicon substrates have been produced by argon-ion bombardment of (001) silicon surfaces. Thermally induced surface excitations characteristic of this example of a soft-on-hard system have been investigated by surface Brillouin scattering (SBS) as a function of scattering-angle and amorphous-layer thickness. At large scattering angles or for sufficiently large layer thickness, a second peak is present in the SBS spectrum near the low-energy threshold for the continuum of bulk excitations of the system. The measured spectra are analyzed on the basis of surface elastodynamic Green's functions, which successfully simulate their detailed appearance and identify the second peak as either a Sezawa wave (true surface wave) or a pseudo-Sezawa wave (attenuated surface wave) depending on the scattering parameters. The attributes of the pseudo-Sezawa wave are described; these include its asymmetrical line shape and variation in intensity with k∥d (the product of the surface excitation wave vector and the layer thickness), and its emergence as the Sezawa wave from the low-energy side of the Lamb shoulder at a critical value of k∥d. Furthermore, the behavior of a pronounced minimum in the Lamb shoulder near the longitudinal wave threshold observed in the experiments is reported and is found to be in good agreement with the calculated spectra. The elastic constants of the amorphous silicon layer are determined from the velocity dispersion of the Rayleigh surface acoustic wave and the minimum in the Lamb shoulder.

Ice sintering timescales at the surface of Europa and implications for surface properties

NASA Astrophysics Data System (ADS)

Molaro, Jamie; Phillips, Cynthia B.; Meirion-Griffith, Gareth

2017-10-01

The planned exploration of Europa by NASA’s Europa Clipper Mission and the possibility of a future Europa lander have driven the need to characterize its surface strength, roughness, porosity, thermal conductivity, and regolith depth in order to accurately interpret remote sensing data and develop appropriate spacecraft landing systems. Many processes contribute to Europa’s landscape evolution, such as sputtering, mass wasting, thermal segregation, and impact gardening, driving the creation and distribution of icy regolith across the surface. While the efficacy of these processes are not well constrained, any amount of regolith emplaced at the surface will undergo subsequent processing due to sintering. Ice sintering is a form of frost metamorphism whereby contacting ice grains experience the diffusion of material into their contact region, forming a “neck” between them and densifying over time. Over long enough timescales, ice aggregates will sinter into solid material, which may contribute to the incorporation of non-ice material into Europa’s subsurface and help to drive subsurface chemistry. Sintering also interacts with other processes, adding to the complexity of icy surface evolution. For example, sputtering preferentially removes larger grains and may enhance sintering rates, and changes in ice porosity may affect the response of the surface to micrometeorite impacts.Quantifying the effects of ice sintering will allow us to predict the microstructural properties of Europa’s surface at spacecraft scales. To this end, we have modeled pressure-less (no overburden) sintering of spherical water-ice grains and validated the results with a laboratory experiment. We also modeled ice at the surface of Europa to obtain a first-order approximation of the sintering timescale and surface properties. Preliminary results indicate that ice grains will experience neck growth but not significant densification over Europa’s surface age, suggesting that loose surface ice forms a weak and porous crust. Furthermore, our results suggest that existing models do not accurately quantify all stages of the sintering process for ice, emphasizing the need for more laboratory studies on this topic.

Surface Nanocrystallization and Amorphization of Dual-Phase TC11 Titanium Alloys under Laser Induced Ultrahigh Strain-Rate Plastic Deformation

PubMed Central

Luo, Sihai; Zhou, Liucheng; Wang, Xuede; Cao, Xin; Nie, Xiangfan

2018-01-01

As an innovative surface technology for ultrahigh strain-rate plastic deformation, laser shock peening (LSP) was applied to the dual-phase TC11 titanium alloy to fabricate an amorphous and nanocrystalline surface layer at room temperature. X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy (HRTEM) were used to investigate the microstructural evolution, and the deformation mechanism was discussed. The results showed that a surface nanostructured surface layer was synthesized after LSP treatment with adequate laser parameters. Simultaneously, the behavior of dislocations was also studied for different laser parameters. The rapid slipping, accumulation, annihilation, and rearrangement of dislocations under the laser-induced shock waves contributed greatly to the surface nanocrystallization. In addition, a 10 nm-thick amorphous structure layer was found through HRTEM in the top surface and the formation mechanism was attributed to the local temperature rising to the melting point, followed by its subsequent fast cooling. PMID:29642379

Surface Nanocrystallization and Amorphization of Dual-Phase TC11 Titanium Alloys under Laser Induced Ultrahigh Strain-Rate Plastic Deformation.

PubMed

Luo, Sihai; Zhou, Liucheng; Wang, Xuede; Cao, Xin; Nie, Xiangfan; He, Weifeng

2018-04-06

As an innovative surface technology for ultrahigh strain-rate plastic deformation, laser shock peening (LSP) was applied to the dual-phase TC11 titanium alloy to fabricate an amorphous and nanocrystalline surface layer at room temperature. X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy (HRTEM) were used to investigate the microstructural evolution, and the deformation mechanism was discussed. The results showed that a surface nanostructured surface layer was synthesized after LSP treatment with adequate laser parameters. Simultaneously, the behavior of dislocations was also studied for different laser parameters. The rapid slipping, accumulation, annihilation, and rearrangement of dislocations under the laser-induced shock waves contributed greatly to the surface nanocrystallization. In addition, a 10 nm-thick amorphous structure layer was found through HRTEM in the top surface and the formation mechanism was attributed to the local temperature rising to the melting point, followed by its subsequent fast cooling.

Investigation of surface water behavior during glaze ice accretion

NASA Technical Reports Server (NTRS)

Hansman, R. John, Jr.; Turnock, Stephen R.

1988-01-01

Microvideo observations of glaze ice accretions on 1-in-diameter cylinders in a closed-loop refrigerated wind tunnel were obtained to study factors controlling the behavior of unfrozen surface water during glaze ice accretion. Three zones of surface water behavior were noted, each with a characteristic roughness. The effect of substrate thermal and roughness properties on ice accretions was also studied. The contact angle and hysteresis were found to increase sharply at temperatures just below 0 C, explaining the high resistance to motion of water beads observed on accreting glaze ice surfaces. Based on the results, a simple multizone modification to the current glaze ice accretion model is proposed.

Electron impact dissociation of amorphous cis-methyl acetate ice analogs

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Mukherjee, R.; Subramanian, K. P.; Banerjee, S. B.

2014-08-01

We have carried out, for the first time, electron irradiation on methyl acetate (CH3COOCH3) ices grown, under astrochemical condition, at 85 K and the chemical changes were probed by FTIR spectroscopy in the mid-IR region (4000-500 cm-1). Carbon dioxide (CO2), carbon monoxide (CO) molecules were found to be the major products indicating a competing dissociation pathway along with the by-products ethane (C2H6) and dimethyl ether (CH3OCH3), respectively. CH3OH (methyl alcohol) formation showed the possibility of acetate to alcohol conversion by keV electron irradiation. In addition irradiation induced aggregation of CH3COOCH3 molecules is also proposed.

Bayesian inference of ice thickness from remote-sensing data

NASA Astrophysics Data System (ADS)

Werder, Mauro A.; Huss, Matthias

2017-04-01

Knowledge about ice thickness and volume is indispensable for studying ice dynamics, future sea-level rise due to glacier melt or their contribution to regional hydrology. Accurate measurements of glacier thickness require on-site work, usually employing radar techniques. However, these field measurements are time consuming, expensive and sometime downright impossible. Conversely, measurements of the ice surface, namely elevation and flow velocity, are becoming available world-wide through remote sensing. The model of Farinotti et al. (2009) calculates ice thicknesses based on a mass conservation approach paired with shallow ice physics using estimates of the surface mass balance. The presented work applies a Bayesian inference approach to estimate the parameters of a modified version of this forward model by fitting it to both measurements of surface flow speed and of ice thickness. The inverse model outputs ice thickness as well the distribution of the error. We fit the model to ten test glaciers and ice caps and quantify the improvements of thickness estimates through the usage of surface ice flow measurements.

Global warming related transient albedo feedback in the Arctic and its relation to the seasonality of sea ice

NASA Astrophysics Data System (ADS)

Andry, Olivier; Bintanja, Richard; Hazeleger, Wilco

2015-04-01

The Arctic is warming two to three times faster than the global average. Arctic sea ice cover is very sensitive to this warming and has reached historic minima in late summer in recent years (i.e. 2007, 2012). Considering that the Arctic Ocean is mainly ice-covered and that the albedo of sea ice is very high compared to that of open water, the change in sea ice cover is very likely to have a strong impact on the local surface albedo feedback. Here we quantify the temporal changes in surface albedo feedback in response to global warming. Usually feedbacks are evaluated as being representative and constant for long time periods, but we show here that the strength of climate feedbacks in fact varies strongly with time. For instance, time series of the amplitude of the surface albedo feedback, derived from future climate simulations (CIMP5, RCP8.5 up to year 2300) using a kernel method, peaks around the year 2100. This maximum is likely caused by an increased seasonality in sea-ice cover that is inherently associated with sea ice retreat. We demonstrate that the Arctic average surface albedo has a strong seasonal signature with a maximum in spring and a minimum in late summer/autumn. In winter when incoming solar radiation is minimal the surface albedo doesn't have an important effect on the energy balance of the climate system. The annual mean surface albedo is thus determined by the seasonality of both downwelling shortwave radiation and sea ice cover. As sea ice cover reduces the seasonal signature is modified, the transient part from maximum sea ice cover to its minimum is shortened and sharpened. The sea ice cover is reduced when downwelling shortwave radiation is maximum and thus the annual surface albedo is drastically smaller. Consequently the change in annual surface albedo with time will become larger and so will the surface albedo feedback. We conclude that a stronger seasonality in sea ice leads to a stronger surface albedo feedback, which accelerates melting of sea ice. Hence, the change in seasonality and the associated change in feedback strength is an integral part of the positive surface albedo feedback leading to Arctic amplification and diminishing sea ice cover in the next century when global climate warms.

Discharge of New Subglacial Lake on Whillians Ice Stream: Implication for Ice Stream Flow Dynamics.

NASA Astrophysics Data System (ADS)

Sergienko, O. V.; Fricker, H. A.; Bindschadler, R. A.; Vornberger, P. L.; Macayeal, D. R.

2006-12-01

One of the surprise discoveries made possible by the ICESat laser altimeter mission of 2004-2006 is the presence of a large subglacial lake below the grounding zone of Whillians Ice Stream (dubbed here `Lake Helen' after the discoverer, Helen Fricker). What is even more surprising is the fact that this lake discharged a substantial portion of its volume during the ICESat mission, and changes in lake volume and surface elevation of the ice stream are documented in exquisite detail [Fricker et al., in press]. The presence and apparent dynamism of large subglacial lakes in the grounding zone of a major ice stream raises questions about their effects on ice-stream dynamics. Being liquid and movable, water modifies basal friction spatially and temporally. Melting due to shear heating and geothermal flux reduces basal traction, making the ice stream move fast. However, when water collects in a depression to form a lake, it potentially deprives the surrounding bed of lubricating water, and additionally makes the ice surface flat, thereby locally decreasing the ice stream driving stress. We study the effect of formation and discharge of a subglacial lake at the mouth of and ice stream using a two dimensional, vertically integrated, ice-stream model. The model is forced by the basal friction, ice thickness and surface elevation. The basal friction is obtained by inversion of the ice surface velocity, ice thickness and surface elevation come from observations. To simulate the lake formation we introduce zero basal friction and "inflate" the basal elevation of the ice stream at the site of the lake. Sensitivity studies of the response of the surrounding ice stream and ice shelf flow are performed to delineate the influence of near-grounding-line subglacial water storage for ice streams in general.

Hydrogen-Bonding Surfaces for Ice Mitigation

NASA Technical Reports Server (NTRS)

Smith, Joseph G., Jr.; Wohl, Christopher J.; Kreeger, Richard E.; Hadley, Kevin R.; McDougall, Nicholas

2014-01-01

Ice formation on aircraft, either on the ground or in-flight, is a major safety issue. While ground icing events occur predominantly during the winter months, in-flight icing can happen anytime during the year. The latter is more problematic since it could result in increased drag and loss of lift. Under a Phase I ARMD NARI Seedling Activity, coated aluminum surfaces possessing hydrogen-bonding groups were under investigation for mitigating ice formation. Hydroxyl and methyl terminated dimethylethoxysilanes were prepared via known chemistries and characterized by spectroscopic methods. These materials were subsequently used to coat aluminum surfaces. Surface compositions were based on pure hydroxyl and methyl terminated species as well as mixtures of the two. Coated surfaces were characterized by contact angle goniometry. Receding water contact angle data suggested several potential surfaces that may exhibit reduced ice adhesion. Qualitative icing experiments performed under representative environmental temperatures using supercooled distilled water delivered via spray coating were inconclusive. Molecular modeling studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition. Chain mobility resulted from the creation of "pockets" of increased free volume for longer chains to occupy.

Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

NASA Astrophysics Data System (ADS)

Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

2014-10-01

A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO2 modification increased more than six times. And the adsorption of Pb2+ on the MnO2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

Remote Characterization of Ice Shelf Surface and Basal Processes: Examples from East Antarctica

NASA Astrophysics Data System (ADS)

Greenbaum, J. S.; Blankenship, D. D.; Grima, C.; Schroeder, D. M.; Soderlund, K. M.; Young, D. A.; Kempf, S. D.; Siegert, M. J.; Roberts, J. L.; Warner, R. C.; van Ommen, T. D.

2017-12-01

The ability to remotely characterize surface and basal processes of ice shelves has important implications for conducting systematic, repeatable, and safe evaluations of their stability in the context of atmospheric and oceanic forcing. Additionally, techniques developed for terrestrial ice shelves can be adapted to orbital radar sounding datasets planned for forthcoming investigations of icy moons. This has been made possible through recent advances in radar signal processing that enable these data to be used to test hypotheses derived from conceptual and numerical models of ice shelf- and ice shell-ocean interactions. Here, we present several examples of radar sounding-derived characterizations of surface and basal processes underway on ice shelves in East Antarctica. These include percolation of near-surface meltwater in warm austral summers, brine infiltration along ice shelf calving fronts, basal melt rate and distribution, and basal freeze distribution. On Europa, near-surface brines and their migration may impact local geological variability, while basal processes likely control the distribution of melt and freeze. Terrestrially, we emphasize radar-sounding records of the Totten Glacier Ice Shelf which hosts each of these processes as well as the highest known density of basal melt channels of any terrestrial ice shelf. Further, with a maximum floating ice thickness of over 2.5 km, the pressure at Totten's basal interface may be similar to that at Europa's ice-ocean interface; therefore, evaluating surface and basal processes of Totten Glacier and other ice shelves could serve as analogs for understanding melting processes of Europa's ice shell.

connecting the dots between Greenland ice sheet surface melting and ice flow dynamics (Invited)

NASA Astrophysics Data System (ADS)

Box, J. E.; Colgan, W. T.; Fettweis, X.; Phillips, T. P.; Stober, M.

2013-12-01

This presentation is of a 'unified theory' in glaciology that first identifies surface albedo as a key factor explaining total ice sheet mass balance and then surveys a mechanistic self-reinforcing interaction between melt water and ice flow dynamics. The theory is applied in a near-real time total Greenland mass balance retrieval based on surface albedo, a powerful integrator of the competing effects of accumulation and ablation. New snowfall reduces sunlight absorption and increases meltwater retention. Melting amplifies absorbed sunlight through thermal metamorphism and bare ice expansion in space and time. By ';following the melt'; we reveal mechanisms linking existing science into a unified theory. Increasing meltwater softens the ice sheet in three ways: 1.) sensible heating given the water temperature exceeds that of the ice sheet interior; 2.) Some infiltrating water refreezes, transferring latent heat to the ice; 3.) Friction from water turbulence heats the ice. It has been shown that for a point on the ice sheet, basal lubrication increases ice flow speed to a time when an efficient sub-glacial drainage network develops that reduces this effect. Yet, with an increasing melt duration the point where the ice sheet glides on a wet bed increases inland to a larger area. This effect draws down the ice surface elevation, contributing to the ';elevation feedback'. In a perpetual warming scenario, the elevation feedback ultimately leads to ice sheet loss reversible only through much slower ice sheet growth in an ice age environment. As the inland ice sheet accelerates, the horizontal extension pulls cracks and crevasses open, trapping more sunlight, amplifying the effect of melt accelerated ice. As the bare ice area increases, the direct sun-exposed crevassed and infiltration area increases further allowing the ice warming process to occur more broadly. Considering hydrofracture [a.k.a. hydrofracking]; surface meltwater fills cracks, attacking the ice integrity. Because water is 'heavier' than ice, water-filled cracks have unlimited capacity to hydraulically ';jack' open fractures, penetrating, fracturing and disaggregating a solid ice body. This process promotes iceberg calving at more than 150, 1km wide marine terminating Greenland glacier fronts. Resulting from a rising trend of surface melting and sea water temperature, meltwater ejection at the underwater front of marine glaciers drives a an increasing turbulent heat exchange between the glacier front and relatively warm sea water melting it faster. Underwater melting promotes an undercutting of the glacier front leading to ice berg calving. Calving through hydrofracture or marine undercutting provide a direct and immediate ice flow speed response mechanism for surface meltwater production. Ice flow speed reacts because calving reduces flow resistance. The above physical processes interact. Cooling shuts these processes down. Negative feedbacks dampen the warming impulse. Live 21 June, 2013 is a new Danish Web site1 that exploits total mass balance rate of decline as a function of albedo to predict GRACE mass rate of change with 80% explained variance. While surface mass balance explains the mass rate of change slightly higher, surface albedo is an observable quantity as is gravity change.

In situ observations of Arctic cloud properties across the Beaufort Sea marginal ice zone

NASA Astrophysics Data System (ADS)

Corr, C.; Moore, R.; Winstead, E.; Thornhill, K. L., II; Crosbie, E.; Ziemba, L. D.; Beyersdorf, A. J.; Chen, G.; Martin, R.; Shook, M.; Corbett, J.; Smith, W. L., Jr.; Anderson, B. E.

2016-12-01

Clouds play an important role in Arctic climate. This is particularly true over the Arctic Ocean where feedbacks between clouds and sea-ice impact the surface radiation budget through modifications of sea-ice extent, ice thickness, cloud base height, and cloud cover. This work summarizes measurements of Arctic cloud properties made aboard the NASA C-130 aircraft over the Beaufort Sea during ARISE (Arctic Radiation - IceBridge Sea&Ice Experiment) in September 2014. The influence of surface-type on cloud properties is also investigated. Specifically, liquid water content (LWC), droplet concentrations, and droplet size distributions are compared for clouds sampled over three distinct regimes in the Beaufort Sea: 1) open water, 2) the marginal ice zone, and 3) sea-ice. Regardless of surface type, nearly all clouds intercepted during ARISE were liquid-phase clouds. However, differences in droplet size distributions and concentrations were evident for the surface types; clouds over the MIZ and sea-ice generally had fewer and larger droplets compared to those over open water. The potential implication these results have for understanding cloud-surface albedo climate feedbacks in Arctic are discussed.

Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition

NASA Astrophysics Data System (ADS)

Mao, Yougang; Ba, Yong

2006-09-01

This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

Comparing the ice nucleation efficiencies of ice nucleating substrates to natural mineral dusts

NASA Astrophysics Data System (ADS)

Steinke, Isabelle; Funk, Roger; Höhler, Kristina; Haarig, Moritz; Hoffmann, Nadine; Hoose, Corinna; Kiselev, Alexei; Möhler, Ottmar; Leisner, Thomas

2014-05-01

Mineral dust particles in the atmosphere may act as efficient ice nuclei over a wide range of temperature and relative humidity conditions. The ice nucleation capability of dust particles mostly depends on the particle surface area and the associated physico-chemical surface properties. It has been observed that the surface-related ice nucleation efficiency of different dust particles and mineral species can vary by several orders of magnitude. However, the relation between aerosol surface properties and observed ice nucleation efficiency is still not completely understood due to the large variability of chemical compositions and morphological features. In order to gain a better understanding of small scale freezing processes, we investigated the freezing of several hundreds of small droplets (V=0.4 nl) deposited on materials with reasonably well defined surfaces such as crystalline silicon wafers, graphite and freshly cleaved mica sheets under atmospherically relevant conditions. These substrates are intended to serve as simple model structures compared to the surface of natural aerosol particles. To learn more about the impact of particle morphology on ice nucleation processes, we also investigated micro-structured silicon wafers with prescribed trenches. The ice nucleation efficiencies deduced from these experiments are expressed as ice nucleation active surface site density values. With this approach, the freezing properties of the above-described substrates could be compared to those of natural mineral dusts such as agricultural soil dusts, volcanic ash and fossil diatoms, which have been investigated in AIDA cloud chamber experiments. All tested ice nucleating substrates were consistently less efficient at nucleating ice than the natural mineral dusts. Crystalline silicon only had a negligible influence on the freezing of small droplets, leading to freezing near the homogeneous freezing temperature threshold. Applying surface structures to silicon led to a shift towards heterogeneous freezing. However, the measured ice nucleation active surface site densities were still smaller than those of mineral dusts.

Influence of hydrophobicity on ice accumulation process under sleet and wind conditions

NASA Astrophysics Data System (ADS)

Xu, Ke; Hu, Jianlin; Shu, Lichun; Jiang, Xingliang; Huang, Zhengyong

2018-03-01

Glaze, the most dangerous ice type in natural environment, forms during sleet weather, which is usually accompanied with wind. The icing performance of hydrophobic coatings under the impact of wind needs further research. This paper studies the influence of hydrophobicity on ice accumulation process under sleet and wind conditions by computer simulations and icing tests. The results indicate that the heat dissipation process of droplets on samples with various hydrophobicity will be accelerated by wind significantly and that a higher hydrophobicity cannot reduce the cooling rate effectively. However, on different hydrophobic surfaces, the ice accumulation process has different characteristics. On a hydrophilic surface, the falling droplets form continuously water film, which will be cooled fast. On superhydrophobic surface, the frozen droplets form ice bulges, which can shield from wind and slow down the heat dissipation process. These ice accumulation characteristics lead to the difference in ice morphology and make a higher hydrophobic surface to have a lower ice mass growth rate in long period icing tests. As a conclusion, superhydrophobic coating remain icephobic under wind and sleet conditions.

Primary spectrum and composition with IceCube/IceTop

NASA Astrophysics Data System (ADS)

Gaisser, Thomas K.; IceCube Collaboration

2016-10-01

IceCube, with its surface array IceTop, detects three different components of extensive air showers: the total signal at the surface, GeV muons in the periphery of the showers and TeV muons in the deep array of IceCube. The spectrum is measured with high resolution from the knee to the ankle with IceTop. Composition and spectrum are extracted from events seen in coincidence by the surface array and the deep array of IceCube. The muon lateral distribution at the surface is obtained from the data and used to provide a measurement of the muon density at 600 meters from the shower core up to 30 PeV. Results are compared to measurements from other experiments to obtain an overview of the spectrum and composition over an extended range of energy. Consistency of the surface muon measurements with hadronic interaction models and with measurements at higher energy is discussed.

Does hydrophilicity of carbon particles improve their ice nucleation ability?

PubMed

Lupi, Laura; Molinero, Valeria

2014-09-04

Carbonaceous particles account for 10% of the particulate matter in the atmosphere. Atmospheric oxidation and aging of soot modulates its ice nucleation ability. It has been suggested that an increase in the ice nucleation ability of aged soot results from an increase in the hydrophilicity of the surfaces upon oxidation. Oxidation, however, also impacts the nanostructure of soot, making it difficult to assess the separate effects of soot nanostructure and hydrophilicity in experiments. Here we use molecular dynamics simulations to investigate the effect of changes in hydrophilicity of model graphitic surfaces on the freezing temperature of ice. Our results indicate that the hydrophilicity of the surface is not in general a good predictor of ice nucleation ability. We find a correlation between the ability of a surface to promote nucleation of ice and the layering of liquid water at the surface. The results of this work suggest that ordering of liquid water in contact with the surface plays an important role in the heterogeneous ice nucleation mechanism.

Observing the seasonal cycle of the upper ocean in the Ross Sea, Antarctica, with autonomous profiling floats

NASA Astrophysics Data System (ADS)

Porter, D. F.; Springer, S. R.; Padman, L.; Fricker, H. A.; Bell, R. E.

2017-12-01

The upper layers of the Southern Ocean where it meets the Antarctic ice sheet undergoes a large seasonal cycle controlled by surface radiation and by freshwater fluxes, both of which are strongly influenced by sea ice. In regions where seasonal sea ice and icebergs limit use of ice-tethered profilers and conventional moorings, autonomous profiling floats can sample the upper ocean. The deployment of seven Apex floats (by sea) and six ALAMO floats (by air) provides unique upper ocean hydrographic data in the Ross Sea close to the Ross Ice Shelf front. A novel choice of mission parameters - setting parking depth deeper than the seabed - limits their drift, allowing us to deploy the floats close to the ice shelf front, while sea ice avoidance algorithms allow the floats to to sample through winter under sea ice. Hydrographic profiles show the detailed development of the seasonal mixed layer close to the Ross front, and interannual variability of the seasonal mixed layer and deeper water masses on the central Ross Sea continental shelf. After the sea ice breakup in spring, a warm and fresh surface mixed layer develops, further warming and deepening throughout the summer. The mixed layer deepens, with maximum temperatures exceeding 0ºC in mid-February. By March, the surface energy budget becomes negative and sea ice begins to form, creating a cold, saline and dense surface layer. Once these processes overcome the stable summer stratification, convection erodes the surface mixed layer, mixing some heat downwards to deeper layers. There is considerable interannual variability in the evolution and strength of the surface mixed layer: summers with shorter ice-free periods result in a cooler and shallower surface mixed layer, which accumulates less heat than the summers with longer ice-free periods. Early ice breakup occurred in all floats in 2016/17 summer, enhancing the absorbed solar flux leading to a warmer surface mixed layer. Together, these unique measurements from autonomous profilers provide insight into the hydrographic state of the Ross Sea at the start of the spring period of sea-ice breakup, and how ocean mixing and sea ice interact to initiate the summer open-water season.

Physical and Chemical Behaviors of HCl on Ice Surface: Insights from an XPS and NEXAFS Study

NASA Astrophysics Data System (ADS)

Kong, X.; Waldner, A.; Orlando, F.; Birrer, M.; Artiglia, L.; Ammann, M.; Bartels-Rausch, T.

2016-12-01

Ice and snow play active roles for the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. Trace gases can be taken up by ice, and physical and chemical fates of the impurities could modify surface properties significantly and consequently influence atmospheric chemistry and the climate system. However, the understanding of chemical behaviour of impurities on ice surface are very poor, which is largely limited by the difficulties to apply high sensitivity experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray photoelectron spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art near-ambient pressure photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS, on volatile surfaces, i.e. ice at temperatures approaching 0°C. XPS and NEXAFS together provide unique information of hydrogen bonding network, dopants surface concentration, dopant depth profile, and acidic dissociation on the surfaces1. Taking the advantages of the highly sensitive techniques, the adsorption, dissociation and depth profile of Hydrogen Chloride (HCl) on ice were studied. In brief, two states of Chloride on ice surface are identified from the adsorbed HCl, and they are featured with different depth profiles along the ice layers. Combining our results and previously reported constants from literatures (e.g. HCl diffusion coefficients in ice)2, a layered kinetic model has been constructed to fit the depth profiles of two states of Chloride. On the other side, pure ice and doped ice are compared for their surface structure change caused by temperature and the presence of HCl, which shows how the strong acid affect the ice surface in turn. 1. Orlando, F., et al., Top Catal 2016, 59, 591-604. 2. Huthwelker, T.; Malmstrom, M. E.; Helleis, F.; Moortgat, G. K.; Peter, T., J Phys Chem A 2004, 108, 6302-6318.

Fluxing purification and its effect on magnetic properties of high-Bs FeBPSiC amorphous alloy

NASA Astrophysics Data System (ADS)

Pang, Jing; Wang, Anding; Yue, Shiqiang; Kong, Fengyu; Qiu, Keqiang; Chang, Chuntao; Wang, Xinmin; Liu, Chain-Tsuan

2017-07-01

A high-Bs amorphous alloy with the base composition Fe83B11P3Si2C1 was used to study the effects of fluxing purification on amorphous forming ability and magnetic properties of the alloy prepared with raw materials in industrialization. By using fluxing purification, the surface crystallization was suppressed and fully amorphous Fe83B11P3Si2C1 ribbons with a maximum thickness of 48 μm were successfully achieved by using an industrial process and materials. The amorphous ribbons made with industrial-purified alloys exhibit excellent magnetic properties, containing high-Bs of 1.65 T, low Hc of 2.0 A/m, and high μe of 9.7 × 103 at 1 kHz. Impurities in the melting alloys exist in three forms and have different effluences on magnetic properties. The surface crystallization was triggered by the impurities which exist as high melting point inclusions serving as nuclei. Thus, fluxing purification is a feasible way for industrialization of high-Bs FeBPSiC amorphous alloys.

Thermal conductivity of the cryoprotective cocktail DP6 in cryogenic temperatures, in the presence and absence of synthetic ice modulators

PubMed Central

Ehrlich, Lili E.; Malen, Jonathan A.; Rabin, Yoed

2016-01-01

The thermal conductivity of the cryoprotective agent (CPA) cocktail DP6 in combination with synthetic ice modulators (SIMs) is measured in this study, using a transient hot-wire method. DP6 is a mixture of 3M dimethyl sulfoxide (DMSO) and 3M propylene glycol, which received significant attention in the cryobiology community in recent years. Tested SIMs include 6% 1,3Cyclohexanediol, 6% 2,3Butanediol, and 12% PEG400 (percentage by volume). This study integrates the scanning cryomacroscope for visual verification of crystallization and vitrification events. It is demonstrated that the thermal conductivity of the vitrifying CPA cocktail decreases monotonically with the decreasing temperature down to −180°C. By contrast, the thermal conductivity of the crystalline material increases with decreasing temperature in the same temperature range. Results of this study demonstrate that the thermal conductivity may vary by three fold between the amorphous and crystalline phases of DP6 below the glass transition temperature of DP6 (Tg = −119°C). The selected SIMs demonstrate the ability to inhibit crystallization in DP6, even at subcritical cooling rates. An additional ice suppression capability is observed by the Euro-Collins as a vehicle solution, disproportionate to its volume ratio in the cocktail. The implication of the observed thermal conductivity differences between the amorphous and crystalline phases of the same cocktail on cryopreservation simulations is significant in some cases and must be taken into account in thermal analyses of cryopreservation protocols. PMID:27471057

Thermal conductivity of the cryoprotective cocktail DP6 in cryogenic temperatures, in the presence and absence of synthetic ice modulators.

PubMed

Ehrlich, Lili E; Malen, Jonathan A; Rabin, Yoed

2016-10-01

The thermal conductivity of the cryoprotective agent (CPA) cocktail DP6 in combination with synthetic ice modulators (SIMs) is measured in this study, using a transient hot-wire method. DP6 is a mixture of 3 M dimethyl sulfoxide (DMSO) and 3 M propylene glycol, which received significant attention in the cryobiology community in recent years. Tested SIMs include 6% 1,3Cyclohexanediol, 6% 2,3Butanediol, and 12% PEG400 (percentage by volume). This study integrates the scanning cryomacroscope for visual verification of crystallization and vitrification events. It is demonstrated that the thermal conductivity of the vitrifying CPA cocktail decreases monotonically with the decreasing temperature down to -180 °C. By contrast, the thermal conductivity of the crystalline material increases with decreasing temperature in the same temperature range. Results of this study demonstrate that the thermal conductivity may vary by three fold between the amorphous and crystalline phases of DP6 below the glass transition temperature of DP6 (Tg = -119 °C). The selected SIMs demonstrate the ability to inhibit crystallization in DP6, even at subcritical cooling rates. An additional ice suppression capability is observed by the Euro-Collins as a vehicle solution, disproportionate to its volume ratio in the cocktail. The implication of the observed thermal conductivity differences between the amorphous and crystalline phases of the same cocktail on cryopreservation simulations is significant in some cases and must be taken into account in thermal analyses of cryopreservation protocols. Copyright © 2016. Published by Elsevier Inc.

The distribution of ground ice on Mars

NASA Technical Reports Server (NTRS)

Mellon, M. T.; Jakosky, B. M.

1993-01-01

A wealth of geologic evidence indicates that subsurface water ice has played an important role in the evolution of Martian landforms. Theoretical models of the stability of ground ice show that in the near-surface regolith ice is currently stable at latitudes poleward of about +/- 40 deg and below a depth of a few centimeters to a meter, with some variations with longitude. If ice is not previously present at a particular location where it is stable, atmospheric water will diffuse into the regolith and condense as ice, driven by the annual subsurface thermal oscillations. The lower boundary of this ice deposit is found to occur at a depth (typically a few meters) where the annual thermal oscillations give way to the geothermal gradient. In the equatorial regions near-surface ice is currently not stable, resulting in the sublimation of any existing ice and subsequent loss to the atmosphere. However, subliming ice might be maintained at a steady-state depth, where diffusion and loss to the atmosphere are balanced by resupply from a possible deeper source of water (either deeper, not yet depleted, ice deposits or ground water). This depth is typically a few tens to hundreds of meters and depends primarily on the surface temperature and the nature of the geothermal gradient, being deeper for a higher surface temperature and a lower geothermal gradient. Such an equatorial deposit is characterized by the regolith ice content being low nearer the surface and increasing with depth in the deposit. Oscillations in the orbit will affect this picture of ground ice in two ways: by causing periodic changes in the pattern of near-surface stability and by producing subsurface thermal waves that may be capable of driving water ice deeper into the regolith.

Surface-atmosphere decoupling limits accumulation at Summit, Greenland.

PubMed

Berkelhammer, Max; Noone, David C; Steen-Larsen, Hans Christian; Bailey, Adriana; Cox, Christopher J; O'Neill, Michael S; Schneider, David; Steffen, Konrad; White, James W C

2016-04-01

Despite rapid melting in the coastal regions of the Greenland Ice Sheet, a significant area (~40%) of the ice sheet rarely experiences surface melting. In these regions, the controls on annual accumulation are poorly constrained owing to surface conditions (for example, surface clouds, blowing snow, and surface inversions), which render moisture flux estimates from myriad approaches (that is, eddy covariance, remote sensing, and direct observations) highly uncertain. Accumulation is partially determined by the temperature dependence of saturation vapor pressure, which influences the maximum humidity of air parcels reaching the ice sheet interior. However, independent proxies for surface temperature and accumulation from ice cores show that the response of accumulation to temperature is variable and not generally consistent with a purely thermodynamic control. Using three years of stable water vapor isotope profiles from a high altitude site on the Greenland Ice Sheet, we show that as the boundary layer becomes increasingly stable, a decoupling between the ice sheet and atmosphere occurs. The limited interaction between the ice sheet surface and free tropospheric air reduces the capacity for surface condensation to achieve the rate set by the humidity of the air parcels reaching interior Greenland. The isolation of the surface also acts to recycle sublimated moisture by recondensing it onto fog particles, which returns the moisture back to the surface through gravitational settling. The observations highlight a unique mechanism by which ice sheet mass is conserved, which has implications for understanding both past and future changes in accumulation rate and the isotopic signal in ice cores from Greenland.

Surface-atmosphere decoupling limits accumulation at Summit, Greenland

PubMed Central

Berkelhammer, Max; Noone, David C.; Steen-Larsen, Hans Christian; Bailey, Adriana; Cox, Christopher J.; O’Neill, Michael S.; Schneider, David; Steffen, Konrad; White, James W. C.

2016-01-01

Despite rapid melting in the coastal regions of the Greenland Ice Sheet, a significant area (~40%) of the ice sheet rarely experiences surface melting. In these regions, the controls on annual accumulation are poorly constrained owing to surface conditions (for example, surface clouds, blowing snow, and surface inversions), which render moisture flux estimates from myriad approaches (that is, eddy covariance, remote sensing, and direct observations) highly uncertain. Accumulation is partially determined by the temperature dependence of saturation vapor pressure, which influences the maximum humidity of air parcels reaching the ice sheet interior. However, independent proxies for surface temperature and accumulation from ice cores show that the response of accumulation to temperature is variable and not generally consistent with a purely thermodynamic control. Using three years of stable water vapor isotope profiles from a high altitude site on the Greenland Ice Sheet, we show that as the boundary layer becomes increasingly stable, a decoupling between the ice sheet and atmosphere occurs. The limited interaction between the ice sheet surface and free tropospheric air reduces the capacity for surface condensation to achieve the rate set by the humidity of the air parcels reaching interior Greenland. The isolation of the surface also acts to recycle sublimated moisture by recondensing it onto fog particles, which returns the moisture back to the surface through gravitational settling. The observations highlight a unique mechanism by which ice sheet mass is conserved, which has implications for understanding both past and future changes in accumulation rate and the isotopic signal in ice cores from Greenland. PMID:27386509

Discrete Surface Evolution and Mesh Deformation for Aircraft Icing Applications

NASA Technical Reports Server (NTRS)

Thompson, David; Tong, Xiaoling; Arnoldus, Qiuhan; Collins, Eric; McLaurin, David; Luke, Edward; Bidwell, Colin S.

2013-01-01

Robust, automated mesh generation for problems with deforming geometries, such as ice accreting on aerodynamic surfaces, remains a challenging problem. Here we describe a technique to deform a discrete surface as it evolves due to the accretion of ice. The surface evolution algorithm is based on a smoothed, face-offsetting approach. We also describe a fast algebraic technique to propagate the computed surface deformations into the surrounding volume mesh while maintaining geometric mesh quality. Preliminary results presented here demonstrate the ecacy of the approach for a sphere with a prescribed accretion rate, a rime ice accretion, and a more complex glaze ice accretion.

Photochromic amorphous molecular materials and their applications

NASA Astrophysics Data System (ADS)

Shirota, Yasuhiko; Utsumi, Hisayuki; Ujike, Toshiki; Yoshikawa, Satoru; Moriwaki, Kazuyuki; Nagahama, Daisuke; Nakano, Hideyuki

2003-01-01

Two novel classes of photochromic amorphous molecular materials based on azobenzene and dithienylethene were designed and synthesized. They were found to readily form amorphous glasses with well-defined glass-transition temperatures when the melt samples were cooled on standing in air and to exhibit photochromism in their amorphous films as well as in solution. Photochromic properties of these materials are discussed in relation to their molecular structures. Surface relief grating was formed on the amorphous films of azobenzene-based photochromic amorphous molecular materials by irradiation with two coherent Ar + laser beams. Dual image was formed at the same location of the films of dithienylethene-based photochromic amorphous molecular materials by irradiation with two linearly polarized light beams perpendicular to each other.

Effects of surface roughness and energy on ice adhesion strength

NASA Astrophysics Data System (ADS)

Zou, M.; Beckford, S.; Wei, R.; Ellis, C.; Hatton, G.; Miller, M. A.

2011-02-01

The aim of this study is to investigate the effects of surface roughness and surface energy on ice adhesion strength. Sandblasting technique was used to prepare samples with high roughness. Silicon-doped hydrocarbon and fluorinated-carbon thin films were employed to alter the surface energy of the samples. Silicon-doped hydrocarbon films were deposited by plasma-enhanced chemical vapor deposition, while fluorinated-carbon films were produced using deep reactive ion etching equipment by only activating the passivation step. Surface topographies were characterized using scanning electron microscopy and a stylus profilometer. The surface wetting properties were characterized by a video-based contact angle measurement system. The adhesion strength of ice formed from a water droplet on these surfaces was studied using a custom-built shear force test apparatus. It was found that the ice adhesion strength is correlated to the water contact angles of the samples only for surfaces with similar roughness: the ice adhesion strength decreases with the increase in water contact angle. The study also shows that smoother as-received sample surfaces have lower ice adhesion strength than the much rougher sandblasted surfaces.

Aircraft Icing Handbook. Volume 2

DTIC Science & Technology

1991-03-01

an airfoil surface. icenhobig - A surface property exhibiting a reduced adhesion to ice; literally, "ice-hating." light icing - The rate of...power, and are a light weight system of reasonable cost. K. ill I-I1 1.I.2 Pneumatic Impulse Ice Protection A Pneumatic Impulse Ice Protection System...should be about 5 to 6 seconds. During moderate icing a 60 second cycle is suggested, while for light icing, longer accretion times of 3 to 4 minutes

Effects of an Arctic under-ice phytoplankton bloom on bio-optical properties of surface waters during the Norwegian Young Sea Ice Cruise (N-ICE2015)

NASA Astrophysics Data System (ADS)

Pavlov, A. K.; Granskog, M. A.; Hudson, S. R.; Taskjelle, T.; Kauko, H.; Hamre, B.; Assmy, P.; Mundy, C. J.; Nicolaus, M.; Kowalczuk, P.; Stedmon, C. A.; Fernandez Mendez, M.

2016-02-01

A thinner and younger Arctic sea-ice cover has led to an increase in solar light transmission into the surface ocean, especially during late spring and summer. A description of the seasonal evolution of polar surface water optical properties is essential, in order to understand how changes are affecting light availability for photosynthetic organisms and the surface ocean energy budget. The development of the bio-optical properties of Arctic surface waters under predominantly first-year sea ice in the southern Nansen Basin were studied from January to June 2015 during the Norwegian Young Sea Ice Cruise (N-ICE2015). Observations included inherent optical properties, absorption by colored dissolved organic matter and particles, as well as radiometric measurements. We documented a rapid transition from relatively clear and transparent waters in winter to turbid waters in late May and June. This transition was associated with a strong under-ice phytoplankton bloom detected first under the compact ice pack and then monitored during drift across the marginal ice zone. We discuss potential implications of underwater light availability for photosynthesis, heat redistribution in the upper ocean layer, and energy budget of the sea-ice - ocean system.

Review of behaviour of oil in freezing environments.

PubMed

Fingas, M F; Hollebone, B P

2003-01-01

The current knowledge of the physical fate and behaviour of crude oil and petroleum products spilled in Arctic situations is reviewed. The fate and final deposition of oil in marine conditions is presented as based on the extant literature. Spreading models were evaluated for oil on ice, under ice, in snow, in brash ice, and between blocks of ice. Models of oil transport under sheet and broken ice were considered, both for sea and river conditions. The ability of ice sheets to trap oil is discussed in relation to oil storage capacity. The effects of oil on a growing ice sheet were examined, both in terms of ice formation and the thermal effects of oil inclusions in ice. The migration of oil through ice was reviewed, focussing primarily on the movement through brine channels. The effects of oil on the surface of ice were considered, with emphasis on the effects of surface pools on ice melt. Similar consideration was given to the effects of oil on snow on the surface of ice. The few quantitative studies of oil in open and dynamic ice conditions are reviewed. Observations of intentional small-scale spills in leads and ice fields are reviewed and compared with observations from real spills. The conditions under which "oil pumping" from leads occurs were quantified. The most common ultimate fate of oil in an ice field is to be released onto the water surface.

Ice Surface Temperature Variability in the Polar Regions and the Relationships to 2 Meter Air Temperatures

NASA Astrophysics Data System (ADS)

Hoyer, J.; Madsen, K. S.; Englyst, P. N.

2017-12-01

Determining the surface and near surface air temperature from models or observations in the Polar Regions is challenging due to the extreme conditions and the lack of in situ observations. The errors in near surface temperature products are typically larger than for other regions of the world, and the potential for using Earth Observations is large. As part of the EU project, EUSTACE, we have developed empirical models for the relationship between the satellite observed skin ice temperatures and 2m air temperatures. We use the Arctic and Antarctic Sea and sea ice Surface Temperatures from thermal Infrared satellite sensors (AASTI) reanalysis to estimate daily surface air temperature over land ice and sea ice for the Arctic and the Antarctic. Large efforts have been put into collecting and quality controlling in situ observations from various data portals and research projects. The reconstruction is independent of numerical weather prediction models and thus provides an important alternative to modelled air temperature estimates. The new surface air temperature data record has been validated against more than 58.000 independent in situ measurements for the four surface types: Arctic sea ice, Greenland ice sheet, Antarctic sea ice and Antarctic ice sheet. The average correlations are 92-97% and average root mean square errors are 3.1-3.6°C for the four surface types. The root mean square error includes the uncertainty of the in-situ measurement, which ranges from 0.5 to 2°C. A comparison with ERA-Interim shows a consistently better performance of the satellite based air temperatures than the ERA-Interim for the Greenland ice sheet, when compared against observations not used in any of the two estimates. This is encouraging and demonstrates the values of these products. In addition, the procedure presented here works on satellite observations that are available in near real time and this opens up for a near real time estimation of the surface air temperature over ice from satellites.

Present-day Exposures of Water Ice in the Northern Mid-latitudes of Mars

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Kanner, Lisa C.

2007-01-01

Water ice is exposed in the martian north polar cap, but is rarely exposed beyond the cap boundary. Orbital gamma ray spectrometry data strongly imply the presence of water ice within meters of the surface at latitudes north of approximately 60deg. We have examined mid-latitude areas of the northern plains displaying residual ice-rich layers, and report evidence of present-day surface exposures of water ice. These exposures, if confirmed, could con-strain the latitudinal and temporal stability of surface ice on Mars.

Greenland Ice Sheet Surface Temperature, Melt, and Mass Loss: 2000-2006

NASA Technical Reports Server (NTRS)

Hall, Dorothy K.; Williams, Richard S., Jr.; Luthcke, Scott B.; DiGirolamo, Nocolo

2007-01-01

Extensive melt on the Greenland Ice Sheet has been documented by a variety of ground and satellite measurements in recent years. If the well-documented warming continues in the Arctic, melting of the Greenland Ice Sheet will likely accelerate, contributing to sea-level rise. Modeling studies indicate that an annual or summer temperature rise of 1 C on the ice sheet will increase melt by 20-50% therefore, surface temperature is one of the most important ice-sheet parameters to study for analysis of changes in the mass balance of the ice-sheet. The Greenland Ice Sheet contains enough water to produce a rise in eustatic sea level of up to 7.0 m if the ice were to melt completely. However, even small changes (centimeters) in sea level would cause important economic and societal consequences in the world's major coastal cities thus it is extremely important to monitor changes in the ice-sheet surface temperature and to ultimately quantify these changes in terms of amount of sea-level rise. We have compiled a high-resolution, daily time series of surface temperature of the Greenland Ice Sheet, using the I-km resolution, clear-sky land-surface temperature (LST) standard product from the Moderate-Resolution Imaging Spectroradiometer (MODIS), from 2000 - 2006. We also use Gravity Recovery and Climate Experiment (GRACE) data, averaged over 10-day periods, to measure change in mass of the ice sheet as it melt and snow accumulates. Surface temperature can be used to determine frequency of surface melt, timing of the start and the end of the melt season, and duration of melt. In conjunction with GRACE data, it can also be used to analyze timing of ice-sheet mass loss and gain.

A method to evaluate the effect of contact with excipients on the surface crystallization of amorphous drugs.

PubMed

Zhang, Si-Wei; Yu, Lian; Huang, Jun; Hussain, Munir A; Derdour, Lotfi; Qian, Feng; de Villiers, Melgardt M

2014-12-01

Amorphous drugs are used to improve the solubility, dissolution, and bioavailability of drugs. However, these metastable forms of drugs can transform into more stable, less soluble, crystalline counterparts. This study reports a method for evaluating the effect of commonly used excipients on the surface crystallization of amorphous drugs and its application to two model amorphous compounds, nifedipine and indomethacin. In this method, amorphous samples of the drugs were covered by excipients and stored in controlled environments. An inverted light microscope was used to measure in real time the rates of surface crystal nucleation and growth. For nifedipine, vacuum-dried microcrystalline cellulose and lactose monohydrate increased the nucleation rate of the β polymorph from two to five times when samples were stored in a desiccator, while D-mannitol and magnesium stearate increased the nucleation rate 50 times. At 50% relative humidity, the nucleation rates were further increased, suggesting that moisture played an important role in the crystallization caused by the excipients. The effect of excipients on the crystal growth rate was not significant, suggesting that contact with excipients influences the physical stability of amorphous nifedipine mainly through the effect on crystal nucleation. This effect seems to be drug specific because for two polymorphs of indomethacin, no significant change in the nucleation rate was observed under the excipients.

Experimental exploration of the hydrodynamic effect polishing machinability for different types of material

NASA Astrophysics Data System (ADS)

Peng, W. Q.; Li, Y.; Wang, Z.; Li, S. Y.

2018-01-01

Hydrodynamic effect polishing (HEP), in which the material removal relies on the chemisorption between nanoparticles and the workpiece surface in elastic mode, can realize automatic level smooth surface without surface/subsurface damage. The machinability of different types of optical material (such as monocrystalline silicon and crystalline quartz, amorphous silicate glass, Zerodur and so on) were investigated experimentally. The workpiece surfaces before and after being polished by HEP was observed by atomic force microscopy. The experimental results show the surface roughness of monocrystalline silicon and quartz, amorphous silicate glass have decreased from Rms 0.737nm to Rms 0.175nm, Rms 0.490nm to Rms 0.187nm, Rms 0.469nm to Rms 0.157nm respectively, and meanwhile all the defects and bumpy structures have been removed clearly. However the surface roughness has increased from Rms 0.213nm to Rms 0.321nm with the obvious increment of micro unevenness. By comparison, we can conclude that excellent performance is shown when HEP is applied on the optical material structure with a single monocrystalline or amorphous component. However the ultrasmooth surface cannot be obtained when HEP was applied on the combinational materials such as Zerodur glass. The micro unevenness increases gradually along with polishing process due to the different material removal of the monocrystalline and amorphous component.

Challenges in molecular simulation of homogeneous ice nucleation

NASA Astrophysics Data System (ADS)

Brukhno, Andrey V.; Anwar, Jamshed; Davidchack, Ruslan; Handel, Richard

2008-12-01

We address the problem of recognition and growth of ice nuclei in simulation of supercooled bulk water. Bond orientation order parameters based on the spherical harmonics analysis are shown to be ineffective when applied to ice nucleation. Here we present an alternative method which robustly differentiates between hexagonal and cubic ice forms. The method is based on accumulation of the maximum projection of bond orientations onto a set of predetermined vectors, where different terms can contribute with opposite signs with the result that the irrelevant or incompatible molecular arrangements are damped out. We also introduce an effective cluster size by assigning a quality weight to each molecule in an ice-like cluster. We employ our cluster analysis in Monte Carlo simulation of homogeneous ice formation. Replica-exchange umbrella sampling is used for biasing the growth of the largest cluster and calculating the associated free energy barrier. Our results suggest that the ice formation can be seen as a two-stage process. Initially, short tetrahedrally arranged threads and rings are present; these become correlated and form a diffuse ice-genic network. Later, hydrogen bond arrangements within the amorphous ice-like structure gradually settle down and simultaneously 'tune-up' nearby water molecules. As a result, a well-shaped ice core emerges and spreads throughout the system. The process is very slow and diverse owing to the rough energetic landscape and sluggish molecular motion in supercooled water, while large configurational fluctuations are needed for crystallization to occur. In the small systems studied so far the highly cooperative molecular rearrangements eventually lead to a relatively fast percolation of the forming ice structure through the periodic boundaries, which inevitably affects the simulation results.

Landcover Mapping of the McMurdo Ice Shelf Using Landsat and WorldView Image Data

NASA Astrophysics Data System (ADS)

Hansen, E. K.; Macdonald, G.; Mayer, D. P.; MacAyeal, D. R.

2016-12-01

Ice shelves bound approximately half of the Antarctic coast and act to buttress the glaciers that feed them. The collapse of the Larsen B Ice Shelf on the Antarctic Peninsula highlights the importance of processes at the surface for an ice shelf's stability. The McMurdo Ice Shelf is unique among Antarctic ice shelves in that it exists in a relatively warm climate zone and is thus more vulnerable to climate change than colder ice shelves at similar latitudes. However, little is known quantitatively about the surface cover types across the ice shelf, impeding the study of its hydrology and of the origins of its features. In particular, no work has been done linking field observations of supraglacial channels to shelf-wide surface hydrology. We will present the first satellite-derived multiscale landcover map of the McMurdo Ice Shelf based on Landsat 8 and WorldView-2 image data. Landcover types are extracted using supervised classification methods referenced to field observations. Landsat 8 provides coverage of the entire ice shelf ( 5,000 km2) at 30 m/pixel, sufficient to distinguish glacial ice, debris cover, and large supraglacial lakes. WorldView data cover a smaller area— 300 km2 at 2 m/pixel—and thus allow detailed mapping of features that are not spatially resolved by Landsat, such as supraglacial channels and small fractures across the ice shelf's surface. We take advantage of the higher resolution of WorldView-2 data to calculate the area of mid-summer surface water in channels and melt ponds within a detailed study area and use this as the basis for a spectral mixture model in order to estimate the total surface water area across the ice shelf. We intend to use the maps to guide strategic planning of future field research into the seasonal surface hydrology and climate stability of the McMurdo Ice Shelf.

Threshold irradiation dose for amorphization of silicon carbide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snead, L.L.; Zinkle, S.J.

1997-04-01

The amorphization of silicon carbide due to ion and electron irradiation is reviewed with emphasis on the temperature-dependent critical dose for amorphization. The effect of ion mass and energy on the threshold dose for amorphization is summarized, showing only a weak dependence near room temperature. Results are presented for 0.56 MeV silicon ions implanted into single crystal 6H-SiC as a function of temperature and ion dose. From this, the critical dose for amorphization is found as a function of temperature at depths well separated from the implanted ion region. Results are compared with published data generated using electrons and xenonmore » ions as the irradiating species. High resolution TEM analysis is presented for the Si ion series showing the evolution of elongated amorphous islands oriented such that their major axis is parallel to the free surface. This suggests that surface of strain effects may be influencing the apparent amorphization threshold. Finally, a model for the temperature threshold for amorphization is described using the Si ion irradiation flux and the fitted interstitial migration energy which was found to be {approximately}0.56 eV. This model successfully explains the difference in the temperature-dependent amorphization behavior of SiC irradiated with 0.56 MeV silicon ions at 1 x 10{sup {minus}3} dpa/s and with fission neutrons irradiated at 1 x 10{sup {minus}6} dpa/s irradiated to 15 dpa in the temperature range of {approximately}340 {+-} 10K.« less

Amorphous ZnO Quantum Dot/Mesoporous Carbon Bubble Composites for a High-Performance Lithium-Ion Battery Anode.

PubMed

Tu, Zhiming; Yang, Gongzheng; Song, Huawei; Wang, Chengxin

2017-01-11

Due to its high theoretical capacity (978 mA h g -1 ), natural abundance, environmental friendliness, and low cost, zinc oxide is regarded as one of the most promising anode materials for lithium-ion batteries (LIBs). A lot of research has been done in the past few years on this topic. However, hardly any research on amorphous ZnO for LIB anodes has been reported despite the fact that the amorphous type could have superior electrochemical performance due to its isotropic nature, abundant active sites, better buffer effect, and different electrochemical reaction details. In this work, we develop a simple route to prepare an amorphous ZnO quantum dot (QDs)/mesoporous carbon bubble composite. The composite consists of two parts: mesoporous carbon bubbles as a flexible skeleton and monodisperse amorphous zinc oxide QDs (smaller than 3 nm) encapsulated in an amorphous carbon matrix as a continuous coating tightly anchored on the surface of mesoporous carbon bubbles. With the benefits of abundant active sites, amorphous nature, high specific surface area, buffer effect, hierarchical pores, stable interconnected conductive network, and multidimensional electron transport pathways, the amorphous ZnO QD/mesoporous carbon bubble composite delivers a high reversible capacity of nearly 930 mA h g -1 (at current density of 100 mA g -1 ) with almost 90% retention for 85 cycles and possesses a good rate performance. This work opens the possibility to fabricate high-performance electrode materials for LIBs, especially for amorphous metal oxide-based materials.

Linking atmospheric synoptic transport, cloud phase, surface energy fluxes, and sea-ice growth: observations of midwinter SHEBA conditions

NASA Astrophysics Data System (ADS)

Persson, P. Ola G.; Shupe, Matthew D.; Perovich, Don; Solomon, Amy

2017-08-01

Observations from the Surface Heat Budget of the Arctic Ocean (SHEBA) project are used to describe a sequence of events linking midwinter long-range advection of atmospheric heat and moisture into the Arctic Basin, formation of supercooled liquid water clouds, enhancement of net surface energy fluxes through increased downwelling longwave radiation, and reduction in near-surface conductive heat flux loss due to a warming of the surface, thereby leading to a reduction in sea-ice bottom growth. The analyses provide details of two events during Jan. 1-12, 1998, one entering the Arctic through Fram Strait and the other from northeast Siberia; winter statistics extend the results. Both deep, precipitating frontal clouds and post-frontal stratocumulus clouds impact the surface radiation and energy budget. Cloud liquid water, occurring preferentially in stratocumulus clouds extending into the base of the inversion, provides the strongest impact on surface radiation and hence modulates the surface forcing, as found previously. The observations suggest a minimum water vapor threshold, likely case dependent, for producing liquid water clouds. Through responses to the radiative forcing and surface warming, this cloud liquid water also modulates the turbulent and conductive heat fluxes, and produces a thermal wave penetrating into the sea ice. About 20-33 % of the observed variations of bottom ice growth can be directly linked to variations in surface conductive heat flux, with retarded ice growth occurring several days after these moisture plumes reduce the surface conductive heat flux. This sequence of events modulate pack-ice wintertime environmental conditions and total ice growth, and has implications for the annual sea-ice evolution, especially for the current conditions of extensive thinner ice.

Ice Nucleation Efficiency of Hydroxylated Organic Surfaces Is Controlled by Their Structural Fluctuations and Mismatch to Ice.

PubMed

Qiu, Yuqing; Odendahl, Nathan; Hudait, Arpa; Mason, Ryan; Bertram, Allan K; Paesani, Francesco; DeMott, Paul J; Molinero, Valeria

2017-03-01

Heterogeneous nucleation of ice induced by organic materials is of fundamental importance for climate, biology, and industry. Among organic ice-nucleating surfaces, monolayers of long chain alcohols are particularly effective, while monolayers of fatty acids are significantly less so. As these monolayers expose to water hydroxyl groups with an order that resembles the one in the basal plane of ice, it was proposed that lattice matching between ice and the surface controls their ice-nucleating efficiency. Organic monolayers are soft materials and display significant fluctuations. It has been conjectured that these fluctuations assist in the nucleation of ice. Here we use molecular dynamic simulations and laboratory experiments to investigate the relationship between the structure and fluctuations of hydroxylated organic surfaces and the temperature at which they nucleate ice. We find that these surfaces order interfacial water to form domains with ice-like order that are the birthplace of ice. Both mismatch and fluctuations decrease the size of the preordered domains and monotonously decrease the ice freezing temperature. The simulations indicate that fluctuations depress the freezing efficiency of monolayers of alcohols or acids to half the value predicted from lattice mismatch alone. The model captures the experimental trend in freezing efficiencies as a function of chain length and predicts that alcohols have higher freezing efficiency than acids of the same chain length. These trends are mostly controlled by the modulation of the structural mismatch to ice. We use classical nucleation theory to show that the freezing efficiencies of the monolayers are directly related to their free energy of binding to ice. This study provides a general framework to relate the equilibrium thermodynamics of ice binding to a surface and the nonequilibrium ice freezing temperature and suggests that these could be predicted from the structure of interfacial water.

Molecular Insight into the Slipperiness of Ice.

PubMed

Weber, Bart; Nagata, Yuki; Ketzetzi, Stefania; Tang, Fujie; Smit, Wilbert J; Bakker, Huib J; Backus, Ellen H G; Bonn, Mischa; Bonn, Daniel

2018-05-16

Measurements of the friction coefficient of steel-on-ice over a large temperature range reveal very high friction at low temperatures (-100 °C) and a steep decrease in the friction coefficient with increasing temperature. Very low friction is only found over the limited temperature range typical for ice skating. The strong decrease in the friction coefficient with increasing temperature exhibits Arrhenius behavior with an activation energy of E a ≈ 11.5 kJ mol -1 . Remarkably, molecular dynamics simulations of the ice-air interface reveal a very similar activation energy for the mobility of surface molecules. Weakly hydrogen-bonded surface molecules diffuse over the surface in a rolling motion, their number and mobility increasing with increasing temperature. This correlation between macroscopic friction and microscopic molecular mobility indicates that slippery ice arises from the high mobility of its surface molecules, making the ice surface smooth and the shearing of the weakly bonded surface molecules easy.

Saltwater icephobicity: Influence of surface chemistry on saltwater icing

PubMed Central

Carpenter, Katherine; Bahadur, Vaibhav

2015-01-01

Most studies on icephobicity focus on ice formation with pure water. This manuscript presents studies to understand the influence of surfaces on saltwater ice nucleation and propagation. Experiments are conducted to quantify the influence of surface chemistry on saltwater ice nucleation and to understand the utility of superhydrophobic surfaces for saltwater icephobicity. These experiments are conducted with pure water and two sodium chloride solutions, which represent the salinity of seawater and briny produced water. It is seen that the presence of salt slows down the ice front propagation velocity significantly. Saltwater droplet impact dynamics on superhydrophobic surfaces are also different from pure water. Saltwater droplets retract more and a greater fraction of impacting liquid is repelled from the superhydrophobic surface. It is seen that the greater bounciness of saltwater droplets is a result of slower ice nucleation propagation kinetics. These experiments indicate that superhydrophobic surfaces will have better resistance to impact icing with saltwater than pure water and can remain useful at temperatures as low as −40 °C. Overall, this work is a starting point for further studies on heterogeneous nucleation in saltwater and serves as a bridge between the widely studied freshwater icephobic surfaces and saltwater-related applications. PMID:26626958

Addressing the amorphous content issue in quantitative phase analysis : the certification of NIST SRM 676a.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cline, J. P.; Von Dreele, R. B.; Winburn, R.

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Addressing the Amorphous Content Issue in Quantitative Phase Analysis: The Certification of NIST Standard Reference Material 676a

DOE Office of Scientific and Technical Information (OSTI.GOV)

J Cline; R Von Dreele; R Winburn

2011-12-31

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Mechanical contact induced transformation from the amorphous to the crystalline state in metallic glass

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1984-01-01

Friction and wear tests were conducted with 3.2- and 6.4-millimeter-diameter aluminum oxide spheres sliding, in reciprocating motion, on a Fe67Co18B14Si1 metallic foil. Crystallites with a size range of 10 to 150 nanometers were produced on the wear surface of the amorphous alloy. A strong interaction between transition metals and metalloids such as silicon and boron results in strong segregation during repeated sliding, provides preferential transition metal-metalloid clustering in the amorphous alloy, and subsequently produces the diffused honeycomb structure formed by dark grey bands and primary crystals, that is, alpha-Fe in the matrix. Large plastic flow occurs on an amorphous alloy surface with sliding and the flow film of the alloy transfers to the aluminum oxide pin surface. Multiple slip bands due to shear deformation are observed on the side of the wear track. Two distinct types of wear debris were observed as a result of sliding: an alloy wear debris, and/or powdery-whiskery oxide debris.

Evaporation of ice in planetary atmospheres: Ice-covered rivers on Mars

NASA Technical Reports Server (NTRS)

Wallace, D.; Sagan, C.

1978-01-01

The evaporation rate of water ice on the surface of a planet with an atmosphere involves an equilibrium between solar heating and radiative and evaporative cooling of the ice layer. The thickness of the ice is governed principally by the solar flux which penetrates the ice layer and then is conducted back to the surface. Evaporation from the surface is governed by wind and free convection. In the absence of wind, eddy diffusion is caused by the lower density of water vapor in comparison to the density of the Martian atmosphere. For mean martian insolations, the evaporation rate above the ice is approximately 10 to the minus 8th power gm/sq cm/s. Evaporation rates are calculated for a wide range of frictional velocities, atmospheric pressures, and insolations and it seems clear that at least some subset of observed Martian channels may have formed as ice-chocked rivers. Typical equilibrium thicknesses of such ice covers are approximately 10m to 30 m; typical surface temperatures are 210 to 235 K.

Multiscale physics of rubber-ice friction

NASA Astrophysics Data System (ADS)

Tuononen, Ari J.; Kriston, András; Persson, Bo

2016-09-01

Ice friction plays an important role in many engineering applications, e.g., tires on icy roads, ice breaker ship motion, or winter sports equipment. Although numerous experiments have already been performed to understand the effect of various conditions on ice friction, to reveal the fundamental frictional mechanisms is still a challenging task. This study uses in situ white light interferometry to analyze ice surface topography during linear friction testing with a rubber slider. The method helps to provide an understanding of the link between changes in the surface topography and the friction coefficient through direct visualization and quantitative measurement of the morphologies of the ice surface at different length scales. Besides surface polishing and scratching, it was found that ice melts locally even after one sweep showing the refrozen droplets. A multi-scale rubber friction theory was also applied to study the contribution of viscoelasticity to the total friction coefficient, which showed a significant level with respect to the smoothness of the ice; furthermore, the theory also confirmed the possibility of local ice melting.

A calving law for ice sheet models; Investigating the role of surface melt on dynamics of Greenland outlet glaciers

NASA Astrophysics Data System (ADS)

Nick, F. M.; van der Veen, C. J.; Vieli, A.

2008-12-01

alving of icebergs accounts for perhaps as much as half the ice transferred from the Greenland Ice Sheet into the surrounding ocean, and virtually all of the ice loss from the Antarctic Ice Sheet. We have formulated a calving model that can be readily incorporated into time-evolving numerical ice-flow models. Our model is based on downward penetration of water-filled surface crevasses and upward propagation of basal crevasses. A calving event occurs when the depth of the surface crevasse (which increases as melting progresses through the summer) reaches the height of the basal crevasse. Our numerical ice sheet model is able to reproduce observed seasonal changes of Greenland outlet glaciers, such as fluctuations in flow speed and terminus positions. We have applied the model to Helheim Glacier on the east coast, and Petermann Glacier in the northwest. Our model suggests that rapid retreat of the claving front is highly affected by the amplified calving rate due to increasing water level in surface crevasses during warmer summers. Our results show little response to seasonally enhanced basal lubrication from surface melt. This modeling study provides insights into the role of surface and basal hydrology to ice sheet dynamics and on how to incorporate calving in ice sheet models and therefore advances our ability to predict future ice sheet change.

Influence of ice thickness and surface properties on light transmission through Arctic sea ice.

PubMed

Katlein, Christian; Arndt, Stefanie; Nicolaus, Marcel; Perovich, Donald K; Jakuba, Michael V; Suman, Stefano; Elliott, Stephen; Whitcomb, Louis L; McFarland, Christopher J; Gerdes, Rüdiger; Boetius, Antje; German, Christopher R

2015-09-01

The observed changes in physical properties of sea ice such as decreased thickness and increased melt pond cover severely impact the energy budget of Arctic sea ice. Increased light transmission leads to increased deposition of solar energy in the upper ocean and thus plays a crucial role for amount and timing of sea-ice-melt and under-ice primary production. Recent developments in underwater technology provide new opportunities to study light transmission below the largely inaccessible underside of sea ice. We measured spectral under-ice radiance and irradiance using the new Nereid Under-Ice (NUI) underwater robotic vehicle, during a cruise of the R/V Polarstern to 83°N 6°W in the Arctic Ocean in July 2014. NUI is a next generation hybrid remotely operated vehicle (H-ROV) designed for both remotely piloted and autonomous surveys underneath land-fast and moving sea ice. Here we present results from one of the first comprehensive scientific dives of NUI employing its interdisciplinary sensor suite. We combine under-ice optical measurements with three dimensional under-ice topography (multibeam sonar) and aerial images of the surface conditions. We investigate the influence of spatially varying ice-thickness and surface properties on the spatial variability of light transmittance during summer. Our results show that surface properties such as melt ponds dominate the spatial distribution of the under-ice light field on small scales (<1000 m 2 ), while sea ice-thickness is the most important predictor for light transmission on larger scales. In addition, we propose the use of an algorithm to obtain histograms of light transmission from distributions of sea ice thickness and surface albedo.

Ice nucleation on nanotextured surfaces: the influence of surface fraction, pillar height and wetting states.

PubMed

Metya, Atanu K; Singh, Jayant K; Müller-Plathe, Florian

2016-09-29

In this work, we address the nucleation behavior of a supercooled monatomic cylindrical water droplet on nanoscale textured surfaces using molecular dynamics simulations. The ice nucleation rate at 203 K on graphite based textured surfaces with nanoscale roughness is evaluated using the mean fast-passage time method. The simulation results show that the nucleation rate depends on the surface fraction as well as the wetting states. The nucleation rate enhances with increasing surface fraction for water in the Cassie-Baxter state, while contrary behavior is observed for the case of Wenzel state. Based on the spatial histogram distribution of ice formation, we observed two pathways for ice nucleation. Heterogeneous nucleation is observed at a high surface fraction. However, the probability of homogeneous ice nucleation events increases with decreasing surface fraction. We further investigate the role of the nanopillar height in ice nucleation. The nucleation rate is enhanced with increasing nanopillar height. This is attributed to the enhanced contact area with increasing nanopillar height and the shift in nucleation events towards the three-phase contact line associated with the nanotextured surface. The ice-surface work of adhesion for the Wenzel state is found to be 1-2 times higher than that in the Cassie-Baxter state. Furthermore, the work of adhesion of ice in the Wenzel state is found to be linearly dependent on the contour length of the droplet, which is in line with that reported for liquid droplets.

Comparisons of Cubed Ice, Crushed Ice, and Wetted Ice on Intramuscular and Surface Temperature Changes

PubMed Central

Dykstra, Joseph H; Hill, Holly M; Miller, Michael G; Cheatham, Christopher C; Michael, Timothy J; Baker, Robert J

2009-01-01

Context: Many researchers have investigated the effectiveness of different types of cold application, including cold whirlpools, ice packs, and chemical packs. However, few have investigated the effectiveness of different types of ice used in ice packs, even though ice is one of the most common forms of cold application. Objective: To evaluate and compare the cooling effectiveness of ice packs made with cubed, crushed, and wetted ice on intramuscular and skin surface temperatures. Design: Repeated-measures counterbalanced design. Setting: Human performance research laboratory. Patients or Other Participants: Twelve healthy participants (6 men, 6 women) with no history of musculoskeletal disease and no known preexisting inflammatory conditions or recent orthopaedic injuries to the lower extremities. Intervention(s): Ice packs made with cubed, crushed, or wetted ice were applied to a standardized area on the posterior aspect of the right gastrocnemius for 20 minutes. Each participant was given separate ice pack treatments, with at least 4 days between treatment sessions. Main Outcome Measure(s): Cutaneous and intramuscular (2 cm plus one-half skinfold measurement) temperatures of the right gastrocnemius were measured every 30 seconds during a 20-minute baseline period, a 20-minute treatment period, and a 120-minute recovery period. Results: Differences were observed among all treatments. Compared with the crushed-ice treatment, the cubed-ice and wetted-ice treatments produced lower surface and intramuscular temperatures. Wetted ice produced the greatest overall temperature change during treatment and recovery, and crushed ice produced the smallest change. Conclusions: As administered in our protocol, wetted ice was superior to cubed or crushed ice at reducing surface temperatures, whereas both cubed ice and wetted ice were superior to crushed ice at reducing intramuscular temperatures. PMID:19295957

Germanium detector passivated with hydrogenated amorphous germanium

DOEpatents

Hansen, William L.; Haller, Eugene E.

1986-01-01

Passivation of predominantly crystalline semiconductor devices (12) is provided for by a surface coating (21) of sputtered hydrogenated amorphous semiconductor material. Passivation of a radiation detector germanium diode, for example, is realized by sputtering a coating (21) of amorphous germanium onto the etched and quenched diode surface (11) in a low pressure atmosphere of hydrogen and argon. Unlike prior germanium diode semiconductor devices (12), which must be maintained in vacuum at cryogenic temperatures to avoid deterioration, a diode processed in the described manner may be stored in air at room temperature or otherwise exposed to a variety of environmental conditions. The coating (21) compensates for pre-existing undesirable surface states as well as protecting the semiconductor device (12) against future impregnation with impurities.

Comparison of skating kinetics and kinematics on ice and on a synthetic surface.

PubMed

Stidwill, T J; Pearsall, David; Turcotte, Rene

2010-03-01

The recent popularization and technological improvements of synthetic or artificial ice surfaces provide an attractive alternative to real ice in venues where the latter is impractical to install. Potentially, synthetic ice (SI) may be installed in controlled laboratory settings to permit detailed biomechanical analysis of skating manoeuvres. Unknown, however, is the extent to which skating on SI replicates skating on traditional ice (ICE). Hence, the purpose of this study was to compare kinetic and kinematic forward skating parameters between SI and ICE surfaces. With 11 male hockey players, a portable strain gauge system adhered to the outside of the skate blade holder was used to measure skate propulsive force synchronized with electrogoniometers for tracking dynamic knee and ankle movements during forward skating acceleration. In general, the kinetic and kinematic variables investigated in this study showed minimal differences between the two surfaces (P > 0.06), and no individual variable differences were identified between the two surfaces (P > or = 0.1) with the exception of greater knee extension on SI than ICE (15.2 degrees to 11.0 degrees; P < or = 0.05). Overall, SI surfaces permit comparable mechanics for on-ice forward skating, and thus offer the potential for valid analogous conditions for in-lab testing and training.

Yield surface evolution for columnar ice

NASA Astrophysics Data System (ADS)

Zhou, Zhiwei; Ma, Wei; Zhang, Shujuan; Mu, Yanhu; Zhao, Shunpin; Li, Guoyu

A series of triaxial compression tests, which has capable of measuring the volumetric strain of the sample, were conducted on columnar ice. A new testing approach of probing the experimental yield surface was performed from a single sample in order to investigate yield and hardening behaviors of the columnar ice under complex stress states. Based on the characteristic of the volumetric strain, a new method of defined the multiaxial yield strengths of the columnar ice is proposed. The experimental yield surface remains elliptical shape in the stress space of effective stress versus mean stress. The effect of temperature, loading rate and loading path in the initial yield surface and deformation properties of the columnar ice were also studied. Subsequent yield surfaces of the columnar ice have been explored by using uniaxial and hydrostatic paths. The evolution of the subsequent yield surface exhibits significant path-dependent characteristics. The multiaxial hardening law of the columnar ice was established experimentally. A phenomenological yield criterion was presented for multiaxial yield and hardening behaviors of the columnar ice. The comparisons between the theoretical and measured results indicate that this current model is capable of giving a reasonable prediction for the multiaxial yield and post-yield properties of the columnar ice subjected to different temperature, loading rate and path conditions.

Pressure-induced transformations in computer simulations of glassy water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2013-11-14

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Pressure-induced transformations in computer simulations of glassy water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2013-11-01

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Gossan Hill, Victoria Island, Northwest Territories: An analogue for mine waste reactions within permafrost and implication for the subsurface mineralogy of Mars

NASA Astrophysics Data System (ADS)

Peterson, Ronald C.; Williamson, Marie-Claude; Rainbird, Robert H.

2014-08-01

Gossan Hill is located within the Minto Inlier in central Victoria Island, Northwest Territories (N 71.36697°, W 114.95155°). A study of the mineralogical associations and geological setting of this deposit indicates that it is an arrested hydrothermal system frozen in permafrost. From above, the hill stands out because of the topographic relief of 75 m and the orange-brown color of the surficial material. The surface of the hill is marked by areas of concentric color zonation up to 3 m across, with light gray centers surrounded by a yellow-orange ring that is surrounded by an orange-brown color that covers the rest of the surface of the hill. Trenches dug into these areas reveal that the central zone contains quartz and pyrite +/- native sulfur in a loose aggregate of sand-sized grains. This central area is surrounded by a zone dominated by gypsum and quartz with some jarosite. Beyond this, the surrounding surface consists of quartz, hematite, and amorphous iron oxides. The radial arrangement of the mineral assemblage indicates an increase in oxidation of sulfur from the center outward. Analysis of isotopic composition of the sulfur indicates the source of sulfur could be the underlying strata. The hill is underlain by inter-bedded carbonate and sulfate-evaporite sedimentary rocks of the Kilian formation in the upper part of the Neoproterozoic Shaler Super group. The sedimentary rocks were intruded by diabase sills of the 720 Ma Franklin igneous event, which crop out 2 km to the south of Gossan Hill. The soft friable nature of the deposit and the topographic relief of the hill indicate a post-glacial (Pleistocene) age of formation. Permafrost has maintained the disequilibrium mineral assemblage since the cessation of fluid flow. Extraction of the permafrost ice from the central zone yields a liquid with a pH of 2.3. The observed long-term persistence of pyrite encased within the acidic permafrost indicates that oxidation and dissolution reactions common in mine waste are slowed, if not stopped, in such an environment. The predicted rise of Arctic temperatures will cause the active layer to move deeper and result in the release of the acidic solutions frozen in the permafrost. Water ice or frozen CO2 just below the Martian surface would also preserve such mineral disequilibrium for very long periods of time. No region exists on Earth where ice has existed continuously for millions of years, but the Gossan Hill deposit is an excellent terrestrial analogue. On Mars, the subsurface ice may be very old. Ancient reactive Martian mineral assemblages and the fluids associated with them will reflect conditions that existed in the past.

H2-rich interstellar grain mantles: An equilibrium description

NASA Technical Reports Server (NTRS)

Dissly, Richard W.; Allen, Mark; Anicich, Vincent G.

1994-01-01

Experiments simulating the codeposition of molecular hydrogen and water ice on interstellar grains demonstrate that amorphous water ice at 12 K can incorporate a substantial amount of H2, up to a mole ratio of H2/H2O = 0.53. We find that the physical behavior of approximately 80% of the hydrogen can be explained satisfactorily in terms of an equilibrium population, thermodynamically governed by a wide distribution of binding site energies. Such a description predicts that gas phase accretion could lead to mole fractions of H2 in interstellar grain mantles of nearly 0.3; for the probable conditions of WL5 in the rho Ophiuchi cloud, an H2 mole fraction of between 0.05 and 0.3 is predicted, in possible agreement with the observed abundance reported by Sandford, Allamandola, & Geballe. Accretion of gas phase H2 onto grain mantles, rather than photochemical production of H2 within the ice, could be a general explanation for frozen H2 in interstellar ices. We speculate on the implications of such a composition for grain mantle chemistry and physics.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C; Wong, Frank M.G.; Haslam, Jeffery J; Ji, Xiaoyan; Day, Sumner D; Blue, Craig A; Rivard, John D.K.; Aprigliano, Louis F; Kohler, Leslie K; Bayles, Robert; Lemieux, Edward J; Yang, Nancy; Perepezko, John H; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J

2013-09-03

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C.; Wong, Frank M. G.; Haslam, Jeffery J.; Ji, Xiaoyan; Day, Sumner D.; Blue, Craig A.; Rivard, John D. K.; Aprigliano, Louis F.; Kohler, Leslie K.; Bayles, Robert; Lemieux, Edward J.; Yang, Nancy; Perepezko, John H.; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J.

2013-07-09

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

The Impact of Cloud Properties on Young Sea Ice during Three Winter Storms at N-ICE2015

NASA Astrophysics Data System (ADS)

Murphy, S. Y.; Walden, V. P.; Cohen, L.; Hudson, S. R.

2017-12-01

The impact of clouds on sea ice varies significantly as cloud properties change. Instruments deployed during the Norwegian Young Sea Ice field campaign (N-ICE2015) are used to study how differing cloud properties influence the cloud radiative forcing at the sea ice surface. N-ICE2015 was the first campaign in the Arctic winter since SHEBA (1997/1998) to study the surface energy budget of sea ice and the associated effects of cloud properties. Cloud characteristics, surface radiative and turbulent fluxes, and meteorological properties were measured throughout the field campaign. Here we explore how cloud macrophysical and microphysical properties affect young, thin sea ice during three winter storms from 31 January to 15 February 2015. This time period is of interest due to the varying surface and atmospheric conditions, which showcase the variety of conditions the newly-formed sea ice can experience during the winter. This period was characterized by large variations in the ice surface and near-surface air temperatures, with highs near 0°C when warm, moist air was advected into the area and lows reaching -40°C during clear, calm periods between storms. The advection of warm, moist air into the area influenced the cloud properties and enhanced the downwelling longwave flux. For most of the period, downwelling longwave flux correlates closely with the air temperature. However, at the end of the first storm, a drop in downwelling longwave flux of about 50 Wm-2 was observed, independent of any change in surface or air temperature or cloud fraction, indicating a change in cloud properties. Lidar data show an increase in cloud height during this period and a potential shift in cloud phase from ice to mixed-phase. This study will describe the cloud properties during the three winter storms and discuss their impacts on surface energy budget.

What Controls the Limit of Supercooling and Superheating of Pinned Ice Surfaces?

PubMed

Naullage, Pavithra M; Qiu, Yuqing; Molinero, Valeria

2018-04-05

Cold-adapted organisms produce antifreeze proteins and glycoproteins to control the growth, melting and recrystallization of ice. It has been proposed that these molecules pin the crystal surface, creating a curvature that arrests the growth and melting of the crystal. Here we use thermodynamic modeling and molecular simulations to demonstrate that the curvature of the superheated or supercooled surface depends on the temperature and distances between ice-binding molecules, but not the details of their interactions with ice. We perform simulations of ice pinned with the antifreeze protein TmAFP, polyvinyl alcohol with different degrees of polymerization, and model ice-binding molecules to determine the thermal hystereses on melting and freezing, i.e. the maximum curvature that can be attained before, respectively, ice melts or grows irreversibly over the ice-binding molecules. We find that the thermal hysteresis is controlled by the bulkiness of the ice-binding molecules and their footprint at the ice surface. We elucidate the origin of the asymmetry between freezing and melting hysteresis found in experiments and propose guidelines to design synthetic antifreeze molecules with potent thermal hysteresis activity.

Open-source algorithm for detecting sea ice surface features in high-resolution optical imagery

NASA Astrophysics Data System (ADS)

Wright, Nicholas C.; Polashenski, Chris M.

2018-04-01

Snow, ice, and melt ponds cover the surface of the Arctic Ocean in fractions that change throughout the seasons. These surfaces control albedo and exert tremendous influence over the energy balance in the Arctic. Increasingly available meter- to decimeter-scale resolution optical imagery captures the evolution of the ice and ocean surface state visually, but methods for quantifying coverage of key surface types from raw imagery are not yet well established. Here we present an open-source system designed to provide a standardized, automated, and reproducible technique for processing optical imagery of sea ice. The method classifies surface coverage into three main categories: snow and bare ice, melt ponds and submerged ice, and open water. The method is demonstrated on imagery from four sensor platforms and on imagery spanning from spring thaw to fall freeze-up. Tests show the classification accuracy of this method typically exceeds 96 %. To facilitate scientific use, we evaluate the minimum observation area required for reporting a representative sample of surface coverage. We provide an open-source distribution of this algorithm and associated training datasets and suggest the community consider this a step towards standardizing optical sea ice imagery processing. We hope to encourage future collaborative efforts to improve the code base and to analyze large datasets of optical sea ice imagery.

Arctic Sea Ice Classification and Mapping for Surface Albedo Parameterization in Sea Ice Modeling

NASA Astrophysics Data System (ADS)

Nghiem, S. V.; Clemente-Colón, P.; Perovich, D. K.; Polashenski, C.; Simpson, W. R.; Rigor, I. G.; Woods, J. E.; Nguyen, D. T.; Neumann, G.

2016-12-01

A regime shift of Arctic sea ice from predominantly perennial sea ice (multi-year ice or MYI) to seasonal sea ice (first-year ice or FYI) has occurred in recent decades. This shift has profoundly altered the proportional composition of different sea ice classes and the surface albedo distribution pertaining to each sea ice class. Such changes impacts physical, chemical, and biological processes in the Arctic atmosphere-ice-ocean system. The drastic changes upset the traditional geophysical representation of surface albedo of the Arctic sea ice cover in current models. A critical science issue is that these profound changes must be rigorously and systematically observed and characterized to enable a transformative re-parameterization of key model inputs, such as ice surface albedo, to ice-ocean-atmosphere climate modeling in order to obtain re-analyses that accurately reproduce Arctic changes and also to improve sea ice and weather forecast models. Addressing this challenge is a strategy identified by the National Research Council study on "Seasonal to Decadal Predictions of Arctic Sea Ice - Challenges and Strategies" to replicate the new Arctic reality. We review results of albedo characteristics associated with different sea ice classes such as FYI and MYI. Then we demonstrate the capability for sea ice classification and mapping using algorithms developed by the Jet Propulsion Laboratory and by the U.S. National Ice Center for use with multi-sourced satellite radar data at L, C, and Ku bands. Results obtained with independent algorithms for different radar frequencies consistently identify sea ice classes and thereby cross-verify the sea ice classification methods. Moreover, field observations obtained from buoy webcams and along an extensive trek across Elson Lagoon and a sector of the Beaufort Sea during the BRomine, Ozone, and Mercury EXperiment (BROMEX) in March 2012 are used to validate satellite products of sea ice classes. This research enables the mapping of Arctic sea ice classes over multiple decades using multiple satellite radar datasets with both coarse resolution for synoptic scales and high resolution for local and regional scales, which are crucial for realistic surface albedo parameterization to significantly advance sea ice forecast and projection models.

The seasonal cycle of snow cover, sea ice and surface albedo

NASA Technical Reports Server (NTRS)

Robock, A.

1980-01-01

The paper examines satellite data used to construct mean snow cover caps for the Northern Hemisphere. The zonally averaged snow cover from these maps is used to calculate the seasonal cycle of zonally averaged surface albedo. The effects of meltwater on the surface, solar zenith angle, and cloudiness are parameterized and included in the calculations of snow and ice albedo. The data allows a calculation of surface albedo for any land or ocean 10 deg latitude band as a function of surface temperature ice and snow cover; the correct determination of the ice boundary is more important than the snow boundary for accurately simulating the ice and snow albedo feedback.

Ice sheet radar altimetry

NASA Technical Reports Server (NTRS)

Zwally, J.

1988-01-01

The surface topography of the Greenland and Antarctic ice sheets between 72 degrees north and south was mapped using radar altimetry data from the U.S. Navy GEOSAT. The glaciological objectives of this activity were to study the dynamics of the ice flow, changes in the position of floating ice-shelf fronts, and ultimately to measure temporal changes in ice surface elevation indicative of ice sheet mass balance.

Revealing Surface Waters on an Antifreeze Protein by Fusion Protein Crystallography Combined with Molecular Dynamic Simulations.

PubMed

Sun, Tianjun; Gauthier, Sherry Y; Campbell, Robert L; Davies, Peter L

2015-10-08

Antifreeze proteins (AFPs) adsorb to ice through an extensive, flat, relatively hydrophobic surface. It has been suggested that this ice-binding site (IBS) organizes surface waters into an ice-like clathrate arrangement that matches and fuses to the quasi-liquid layer on the ice surface. On cooling, these waters join the ice lattice and freeze the AFP to its ligand. Evidence for the generality of this binding mechanism is limited because AFPs tend to crystallize with their IBS as a preferred protein-protein contact surface, which displaces some bound waters. Type III AFP is a 7 kDa globular protein with an IBS made up two adjacent surfaces. In the crystal structure of the most active isoform (QAE1), the part of the IBS that docks to the primary prism plane of ice is partially exposed to solvent and has clathrate waters present that match this plane of ice. The adjacent IBS, which matches the pyramidal plane of ice, is involved in protein-protein crystal contacts with few surface waters. Here we have changed the protein-protein contacts in the ice-binding region by crystallizing a fusion of QAE1 to maltose-binding protein. In this 1.9 Å structure, the IBS that fits the pyramidal plane of ice is exposed to solvent. By combining crystallography data with MD simulations, the surface waters on both sides of the IBS were revealed and match well with the target ice planes. The waters on the pyramidal plane IBS were loosely constrained, which might explain why other isoforms of type III AFP that lack the prism plane IBS are less active than QAE1. The AFP fusion crystallization method can potentially be used to force the exposure to solvent of the IBS on other AFPs to reveal the locations of key surface waters.

Detection of Deuterium in Icy Surfaces and the D/H Ratio of Icy Objects

NASA Astrophysics Data System (ADS)

Clark, Roger Nelson; Brown, Robert H.; Swayze, Gregg A.; Cruikshank, Dale P.

2017-10-01

Water ice in crystalline or amorphous form is orientationally disordered, which results in very broad absorptions. Deuterium in trace amounts goes into an ordered position, so is not broadened like H2O absorptions. The D-O stretch is located at 4.13 microns with a width of 0.027 micron. Laboratory spectral measurements on natural H2O and deuterium doped ice show the absorption is slightly asymmetric and in reflectance the band shifts from 4.132 to 4.137 microns as abundance decreases. We derive a preliminary absorption coefficient of ~ 80,000 cm^-1 for the D-O stretch compared to about 560 cm^-1 in H2O ice at 4.13 microns, enabling the detection of deuterium at levels less than Vienna Standard Mean Ocean Water (VSMOW), depending on S/N. How accurate the D/H ratios can be derived will require additional lab work and radiative transfer modeling to simultaneously derive the grain size distribution, the abundance of any contaminants, and deuterium abundance. To first order, the grain size distribution can be compensated by computing the D-O stretch band depth to 2-micron H2O ice band depth ratio, which we call Dratio. Colorado fresh water (~80% of VSMOW) has a Dratio of 0.036, at a D/H = 0.0005, the Dratio = 0.15, and at a D/H = 0.0025, the Dratio = 0.42. The VSMOW Dratio is ~ 0.045.We have used VIMS data from the Cassini spacecraft to compute large spectral averages to detect the deuterium in the rings and on the icy satellite surfaces. A B-ring, 21,882 pixel average, at 640 ms/pixel, or 3.89 hours of integration time, shows a 3.5% O-D stretch band depth and a Dratio = 0.045, indicating deuterium abundance equal to VSMOW. Rhea, using 1.89 hours of integration time shows Dratio = 0.052, or slightly higher than VSMOW. Phoebe has an unusually deep O-D stretch band of 1.85% considering the high abundance of dark material suppressing the ice absorptions. We measure a Dratio = 0.11, an enhancement of ~2.4 over VSMOW, but detailed radiative transfer modeling is needed to derive a more accurate ratio. The enhancement is consistent with previous studies that suggest Phoebe's origin might be external to the Saturn system. More satellites and radiative transfer modeling results will be shown at the meeting.

Experimental Studies on the Formation of D2O and D2O2 by Implantation of Energetic D+ Ions into Oxygen Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Ennis, Courtney P.; Kaiser, Ralf I.

2014-02-01

The formation of water (H2O) in the interstellar medium is intrinsically linked to grain-surface chemistry; thought to involve reactions between atomic (or molecular) hydrogen with atomic oxygen (O), molecular oxygen (O2), and ozone (O3). Laboratory precedent suggests that H2O is produced efficiently when O2 ices are exposed to H atoms (~100 K). This leads to the sequential generation of the hydroxyperoxyl radical (HO2), then hydrogen peroxide (H2O2), and finally H2O and a hydroxyl radical (OH); despite a barrier of ~2300 K for the last step. Recent detection of the four involved species toward ρ Oph A supports this general scenario; however, the precise formation mechanism remains undetermined. Here, solid O2 ice held at 12 K is exposed to a monoenergetic beam of 5 keV D+ ions. Products formed during the irradiation period are monitored through FTIR spectroscopy. O3 is observed through seven archetypal absorptions. Three additional bands found at 2583, 2707, and 1195 cm -1 correspond to matrix isolated DO2 (ν1) and D2O2 (ν1, ν5), and D2O (ν2), respectively. During subsequent warming, the O2 ice sublimates, revealing a broad band at 2472 cm-1 characteristic of amorphous D2O (ν1, ν3). Sublimating D2, D2O, D2O2, and O3 products were confirmed through their subsequent detection via quadrupole mass spectrometry. Reaction schemes based on both thermally accessible and suprathermally induced chemistries were developed to fit the observed temporal profiles are used to elucidate possible reaction pathways for the formation of D2-water. Several alternative schemes to the hydrogenation pathway (O2→HO2→H2O2→H2O) were identified; their astrophysical implications are briefly discussed.

Impact of surface nanostructure on ice nucleation.

PubMed

Zhang, Xiang-Xiong; Chen, Min; Fu, Ming

2014-09-28

Nucleation of water on solid surface can be promoted noticeably when the lattice parameter of a surface matches well with the ice structure. However, the characteristic length of the surface lattice reported is generally less than 0.5 nm and is hardly tunable. In this paper, we show that a surface with nanoscale roughness can also remarkably promote ice nucleation if the characteristic length of the surface structure matches well with the ice crystal. A series of surfaces composed of periodic grooves with same depth but different widths are constructed in molecular dynamics simulations. Water cylinders are placed on the constructed surfaces and frozen at constant undercooling. The nucleation rates of the water cylinders are calculated in the simulation using the mean first-passage time method and then used to measure the nucleation promotion ability of the surfaces. Results suggest that the nucleation behavior of the supercooled water is significantly sensitive to the width of the groove. When the width of the groove matches well with the specific lengths of the ice crystal structure, the nucleation can be promoted remarkably. If the width does not match with the ice crystal, this kind of promotion disappears and the nucleation rate is even smaller than that on the smooth surface. Simulations also indicate that even when water molecules are adsorbed onto the surface structure in high-humidity environment, the solid surface can provide promising anti-icing ability as long as the characteristic length of the surface structure is carefully designed to avoid geometric match.

Influence of amorphous content on compaction behaviour of anhydrous alpha-lactose.

PubMed

Ziffels, S; Steckel, H

2010-03-15

Modified lactoses are widely used as filler-binders in direct compression of tablets. Until today, little about the compaction behaviour of anhydrous alpha-lactose is known. In this study, a new method to prepare anhydrous alpha-lactose from alpha-lactose monohydrate by desiccation with heated ethanol was evaluated and the influence of amorphous content in the lactose powder prior to modification on powder properties, compaction behaviour and storage stability was determined. The modification process led to anhydrous alpha-lactose with decreased bulk and tapped density, increased flow rate and significantly higher specific surface area. Due to the higher specific surface area, the compaction behaviour of the anhydrous alpha-lactose was found to be significantly better than the compaction behaviour of powder blends consisting of alpha-lactose monohydrate and amorphous lactose. An influence of the amorphous content prior to modification could be observed only at higher compaction forces. In general, tablets of modified powders needed longer time to disintegrate directly after compression. However, the storage stability of modified tablets was found to be better compared to the amorphous-crystalline tablets which were influenced by storage conditions, initial crushing strength as well as amorphous content due to the re-crystallization of amorphous lactose during storage. 2009 Elsevier B.V. All rights reserved.

Burial of gas-phase HNO(3) by growing ice surfaces under tropospheric conditions.

PubMed

Ullerstam, Maria; Abbatt, Jonathan P D

2005-10-21

The uptake of gas-phase nitric acid by ice surfaces undergoing growth by vapor deposition has been performed for the first time under conditions of the free troposphere. The investigation was performed using a coated-wall flow tube coupled to a chemical ionization mass spectrometer, at nitric acid partial pressures between 10(-7) and 10(-6) hPa, at 214, 229 and 239 K. Ice surfaces were prepared as smooth ice films from ultra-pure water. During the experiments an excess flow of water vapor was added to the carrier gas flow and the existing ice surfaces grew by depositing water vapor. The average growth rates ranged from 0.7-5 microm min(-1), values similar to those which prevail in some portions of the atmosphere. With growing ice the long term uptake of nitric acid is significantly enhanced compared to an experiment performed at equilibrium, i.e. at 100% relative humidity (RH) with respect to ice. The fraction of HNO(3) that is deposited onto the growing ice surface is independent of the growth rate and may be driven by the solubility of the nitric acid in the growing ice film rather than by condensation kinetics alone.

Extenstional terrain formation in icy satellites: Implications for ocean-surface interaction

NASA Astrophysics Data System (ADS)

Howell, Samuel M.; Pappalardo, Robert T.

2017-10-01

Europa and Ganymede, Galilean satellites of Jupiter, exhibit geologic activity in their outer H2O ice shells that might convey material from water oceans within the satellites to their surfaces. Imagery from the Voyager and Galileo spacecraft reveal surfaces rich with tectonic deformation, including dilational bands on Europa and groove lanes on Ganymede. These features are generally attributed to the extension of a brittle ice lithosphere overlaying a possibly convecting ice asthenosphere. To explore band formation and interaction with interior oceans, we employ fully visco-elasto-plastic 2-D models of faulting and convection with complex, realistic pure ice rheologies. In these models, material entering from below is tracked and considered to be “fossilized ocean,” ocean material that has frozen into the ice shell and evolves through geologic time. We track the volume fraction of fossil ocean material in the ice shell as a function of depth, and the exposure of both fresh ice and fossil ocean material at the ice shell surface. To explore the range in extensional terrains, we vary ice shell thickness, fault localization, melting-temperature ice viscosity, and the presence of pre-existing weaknesses. Mechanisms which act to weaken the ice shell and thin the lithosphere (e.g. vigorous convection, thinner shells, pre-existing weaknesses) tend to plastically yield to form smooth bands at high strains, and are more likely to incorporate fossil ocean material in the ice shell and expose it at the surface. In contrast, lithosphere strengthened by rapid fault annealing or increased viscosity, for example, exhibits large-scale tectonic rifting at low strains superimposed over pre-existing terrains, and inhibits the incorporation and delivery of fossil ocean material to the surface. Thus, our results identify a spectrum of extensional terrain formation mechanisms as linked to lithospheric strength, rather than specific mechanisms that are unique to each type of band, and discuss where in this spectrum ocean material incorporated at the bottom of the ice shell may be exposed on the satellite surface.

Observation of Sea Ice Surface Thermal States Under Cloud Cover

NASA Technical Reports Server (NTRS)

Nghiem, S. V.; Perovich, D. K.; Gow, A. J.; Kwok, R.; Barber, D. G.; Comiso, J. C.; Zukor, Dorothy J. (Technical Monitor)

2001-01-01

Clouds interfere with the distribution of short-wave and long-wave radiations over sea ice, and thereby strongly affect the surface energy balance in polar regions. To evaluate the overall effects of clouds on climatic feedback processes in the atmosphere-ice-ocean system, the challenge is to observe sea ice surface thermal states under both clear sky and cloudy conditions. From laboratory experiments, we show that C-band radar (transparent to clouds) backscatter is very sensitive to the surface temperature of first-year sea ice. The effect of sea ice surface temperature on the magnitude of backscatter change depends on the thermal regimes of sea ice thermodynamic states. For the temperature range above the mirabilite (Na2SO4.10H20) crystallization point (-8.2 C), C-band data show sea ice backscatter changes by 8-10 dB for incident angles from 20 to 35 deg at both horizontal and vertical polarizations. For temperatures below the mirabilite point but above the crystallization point of MgCl2.8H2O (-18.0 C), relatively strong backwater changes between 4-6 dB are observed. These backscatter changes correspond to approximately 8 C change in temperature for both cases. The backscattering mechanism is related to the temperature which determines the thermodynamic distribution of brine volume in the sea ice surface layer. The backscatter is positively correlated to temperature and the process is reversible with thermodynamic variations such as diurnal insolation effects. From two different dates in May 1993 with clear and overcast conditions determined by the Advanced Very High Resolution Radiometer (AVHRR), concurrent Earth Resources Satellite 1 (ERS-1) C-band ice observed with increases in backscatter over first-year sea ice, and verified by increases in in-situ sea ice surface temperatures measured at the Collaborative-Interdisciplinary Cryosphere Experiment (C-ICE) site.

Extensional terrain formation on Europa and Ganymede: Implications for ocean-surface interaction

NASA Astrophysics Data System (ADS)

Howell, S. M.; Pappalardo, R. T.

2017-12-01

Europa and Ganymede, Galilean satellites of Jupiter, exhibit geologic activity in their outer H2O ice shells that might convey material from water oceans within the satellites to their surfaces. Imagery from the Voyager and Galileo spacecraft reveal surfaces rich with tectonic deformation, including dilational bands on Europa and groove lanes on Ganymede. These features are generally attributed to the extension of a brittle ice lithosphere overlaying a possibly convecting ice asthenosphere. To explore band formation and interaction with interior oceans, we employ fully visco-elasto-plastic 2-D models of faulting and convection with complex, realistic pure ice rheologies. In these models, material entering from below is tracked and considered to be "fossilized ocean," ocean material that has frozen into the ice shell and evolves through geologic time. We track the volume fraction of fossil ocean material in the ice shell as a function of depth, and the exposure of both fresh ice and fossil ocean material at the ice shell surface. We vary ice shell thickness, fault localization, melting-temperature ice viscosity, and the presence of pre-existing weaknesses. Mechanisms which act to weaken the ice shell and thin the lithosphere (e.g. vigorous convection, thinner shells, pre-existing weaknesses) tend to plastically yield to form smooth bands at high strains, and are more likely to incorporate fossil ocean material in the ice shell and expose it at the surface. In contrast, lithosphere strengthened by rapid fault annealing or increased viscosity, for example, exhibits large-scale tectonic rifting at low strains superimposed over pre-existing terrains, and inhibits the incorporation and delivery of fossil ocean material to the surface. Thus, our results identify a spectrum of extensional terrain formation mechanisms as linked to lithospheric strength, rather than any specific mechanism being unique to each type of band, and where in this spectrum ocean material incorporated at the bottom of the ice shell may be exposed on the satellite surface.

High-Albedo Salt Crusts on the Tropical Ocean of Snowball Earth: Measurements and Modeling

NASA Astrophysics Data System (ADS)

Carns, R.; Light, B.; Warren, S. G.

2014-12-01

During a Snowball Earth event, almost all of the ocean surface first freezes as sea ice. As in modern sea ice, trapped inclusions of liquid brine permeate the ice cover. As the ice grows and cools, salt crystals precipitate within the inclusions. At -23C, the most abundant salt in seawater, sodium chloride, begins to precipitate as the dihydrate mineral hydrohalite (NaCl·2H2O). Crystals of hydrohalite within the sea ice scatter light. Measurements of cold, natural sea ice show a broadband albedo increase of 10-20% when salt precipitates. Such snow-free natural sea ice with a surface temperature below -23C is rare on modern Earth, but would have been common in tropical regions of a Snowball Earth where evaporation exceeded precipitation. The persistent cold and lack of summer melt on the Snowball ocean surface, combined with net evaporation, is hypothesized to yield lag deposits of hydrohalite crystals on the ice surface. To investigate this process, we prepared laboratory-grown sea ice in a 1000 liter tank in a walk-in freezer laboratory. The ice was cooled below -23 C and the surface sprayed with a 23% NaCl solution to create a layer of hydrohalite-enriched ice, a proxy for lag deposits that would have formed over long periods of surface sublimation. We have developed a novel technique for measuring the spectral albedo of ice surfaces in the laboratory; this technique was used to monitor the evolution of the surface albedo of our salt crust as the ice matrix sublimated away leaving a layer of fine-grained hydrohalite crystals. Measurements of this hydrohalite surface crust show a very high albedo, comparable to fresh snow at visible wavelengths and significantly larger than fresh snow at near infrared wavelengths. Broadband albedos are 0.55 for bare artificial sea ice at -30C, 0.75 for ice containing 25% hydrohalite by volume, 0.84 after five days of desiccation and 0.93 after 47 days of desiccation. Using our laboratory measurements, along with estimates of grain size and crust optical depth, as inputs to Mie scattering and radiative transfer models allowed us to infer the imaginary refractive index of hydrohalite. The model can calculate albedo for pure hydrohalite crusts of varying thickness and for mixtures of ice and hydrohalite. A parameterization is presented for albedo as a function of the thickness of the hydrohalite crust.

A review of the physics of ice surface friction and the development of ice skating.

PubMed

Formenti, Federico

2014-01-01

Our walking and running movement patterns require friction between shoes and ground. The surface of ice is characterised by low friction in several naturally occurring conditions, and compromises our typical locomotion pattern. Ice skates take advantage of this slippery nature of ice; the first ice skates were made more than 4000 years ago, and afforded the development of a very efficient form of human locomotion. This review presents an overview of the physics of ice surface friction, and discusses the most relevant factors that can influence ice skates' dynamic friction coefficient. It also presents the main stages in the development of ice skating, describes the associated implications for exercise physiology, and shows the extent to which ice skating performance improved through history. This article illustrates how technical and materials' development, together with empirical understanding of muscle biomechanics and energetics, led to one of the fastest forms of human powered locomotion.

Microwave and physical properties of sea ice in the winter marginal ice zone

NASA Technical Reports Server (NTRS)

Tucker, W. B., III; Perovich, D. K.; Gow, A. J.; Grenfell, T. C.; Onstott, R. G.

1991-01-01

Surface-based active and passive microwave measurements were made in conjunction with ice property measurements for several distinct ice types in the Fram Strait during March and April 1987. Synthesis aperture radar imagery downlinked from an aircraft was used to select study sites. The surface-based radar scattering cross section and emissivity spectra generally support previously inferred qualitative relationships between ice types, exhibiting expected separation between young, first-year and multiyear ice. Gradient ratios, calculated for both active and passive data, appear to allow clear separation of ice types when used jointly. Surface flooding of multiyear floes, resulting from excessive loading and perhaps wave action, causes both active and passive signatures to resemble those of first-year ice. This effect could possibly cause estimates of ice type percentages in the marginal ice zone to be in error when derived from aircraft- or satellite-born sensors.

Surface water hydrology and the Greenland Ice Sheet

NASA Astrophysics Data System (ADS)

Smith, L. C.; Yang, K.; Pitcher, L. H.; Overstreet, B. T.; Chu, V. W.; Rennermalm, A. K.; Cooper, M. G.; Gleason, C. J.; Ryan, J.; Hubbard, A.; Tedesco, M.; Behar, A.

2016-12-01

Mass loss from the Greenland Ice Sheet now exceeds 260 Gt/year, raising global sea level by >0.7 mm annually. Approximately two-thirds of this total mass loss is now driven by negative ice sheet surface mass balance (SMB), attributed mainly to production and runoff of meltwater from the ice sheet surface. This new dominance of runoff as a driver of GrIS total mass loss will likely persist owing to anticipated further increases in surface melting, reduced meltwater storage in firn, and the waning importance of dynamical mass losses (ice calving) as the ice sheets retreat from their marine-terminating margins. It also creates the need and opportunity for integrative research pairing traditional surface water hydrology approaches with glaciology. As one example, we present a way to measure supraglacial "runoff" (i.e. specific discharge) at the supraglacial catchment scale ( 101-102 km2), using in situ measurements of supraglacial river discharge and high-resolution satellite/drone mapping of upstream catchment area. This approach, which is standard in terrestrial hydrology but novel for ice sheet science, enables independent verification and improvement of modeled SMB runoff estimates used to project sea level rise. Furthermore, because current SMB models do not consider the role of fluvial watershed processes operating on the ice surface, inclusion of even a simple surface routing model materially improves simulations of runoff delivered to moulins, the critical pathways for meltwater entry into the ice sheet. Incorporating principles of surface water hydrology and fluvial geomorphology and into glaciological models will thus aid estimates of Greenland meltwater runoff to the global ocean as well as connections to subglacial hydrology and ice sheet dynamics.

Kuiper Belt Objects of different sizes and average densities: thermal evolution scenarios and modern structure of matter

NASA Astrophysics Data System (ADS)

Shchuko, O. B.; Shchuko, S. D.; Kartashov, D.; Orosei, R.

2012-04-01

Thermal evolution of accretion-formed Kuiper Belt Objects (KBOs) with modern sizes from 200 to 2000 km and average densities from 1100 to 3200 kg/m3 has been studied by mathematical simulation methods. The values range of physical parameters of the accretion material and ultimate radionuclide content, securing KBO existence at present, have been found. The solid dust material of protosolar cloud fringe regions and fine-fractured H2O condensate in the form of amorphous ice are considered to have been the building matter for these objects. This material was represented by small dust particles of different chemical and mineralogical composition, embedded with radionuclides 238U, 235U, 232Th, 40K providing the sources of radiogenic heat. H2O condensate secured the presence of amorphous ice in the forming body's matter. Radiogenic heat leads to H2O phase transitions which define a body's interior matter differentiation. The radionuclide content at the initial time of the body formation determined the dynamically changing degree of the interior matter differentiation at different KBO depths for the whole period from the initial up to the present time. For the models of the celestial objects considered, the dynamically changing boundaries of spherically symmetric regions with different degree of matter differentiation have been determined.

Reaction Dynamics Following Ionization of Ammonia Dimer Adsorbed on Ice Surface.

PubMed

Tachikawa, Hiroto

2016-09-22

The ice surface provides an effective two-dimensional reaction field in interstellar space. However, how the ice surface affects the reaction mechanism is still unknown. In the present study, the reaction of an ammonia dimer cation adsorbed both on water ice and cluster surface was theoretically investigated using direct ab initio molecular dynamics (AIMD) combined with our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) method, and the results were compared with reactions in the gas phase and on water clusters. A rapid proton transfer (PT) from NH3(+) to NH3 takes place after the ionization and the formation of intermediate complex NH2(NH4(+)) is found. The reaction rate of PT was significantly affected by the media connecting to the ammonia dimer. The time of PT was calculated to be 50 fs (in the gas phase), 38 fs (on ice), and 28-33 fs (on water clusters). The dissociation of NH2(NH4(+)) occurred on an ice surface. The reason behind the reaction acceleration on an ice surface is discussed.

Rapid heat treatment for anatase conversion of titania nanotube orthopedic surfaces

NASA Astrophysics Data System (ADS)

Bhosle, Sachin M.; Friedrich, Craig R.

2017-10-01

The amorphous to anatase transformation of anodized nanotubular titania surfaces has been studied by x-ray diffraction and transmission electron microscopy (TEM). A more rapid heat treatment for conversion of amorphous to crystalline anatase favorable for orthopedic implant applications was demonstrated. Nanotube titania surfaces were fabricated by electrochemical anodization of Ti6Al4V in an electrolyte containing 0.2 wt% NH4F, 60% ethylene glycol and 40% deionized water. The resulting surfaces were systematically heat treated in air with isochronal and isothermal experiments to study the temperature and time dependent transformation respectively. Energy dispersive spectroscopy shows that the anatase phase transformation of TiO2 in the as-anodized amorphous nanotube layer can be achieved in as little as 5 min at 350 °C in contrast to reports of higher temperature and much longer time. Crystallinity analysis at different temperatures and times yield transformation rate coefficients and activation energy for crystalline anatase coalescence. TEM confirms the (101) TiO2 presence within the nanotubes. These results confirm that for applications where amorphous titania nanotube surfaces are converted to crystalline anatase, a 5 min production flow-through heating process could be used instead of a 3 h batch process, reducing time, cost, and complexity.

Effects of morphology parameters on anti-icing performance in superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Binh; Park, Seungchul; Lim, Hyuneui

2018-03-01

In this paper, we report the contributions of actual ice-substrate contact area and nanopillar height to passive anti-icing performance in terms of adhesion force and freezing time. Well-textured nanopillars with various parameters were fabricated via colloidal lithography and a dry etching process. The nanostructured quartz surface was coated with low-energy material to confer water-repellent properties. These superhydrophobic surfaces were investigated to determine the parameters essential for reducing adhesion strength and delaying freezing time. A well-textured surface with nanopillars of very small top diameter, regardless of height, could reduce adhesion force and delay freezing time in a subsequent de-icing process. Small top diameters of nanopillars also ensured the metastable Cassie-Baxter state based on energy barrier calculations. The results demonstrated the important role of areal fraction in anti-icing efficiency, and the negligible contribution of texture height. This insight into icing phenomena should lead to design of improved ice-phobic surfaces in the future.

Albedo and its relationship with seasonal surface roughness using repeat UAV survey across the Kangerlussuaq sector of the Greenland Ice Sheet

NASA Astrophysics Data System (ADS)

Hubbard, A., II; Ryan, J.; Box, J. E.; Snooke, N.

2015-12-01

Surface albedo is a primary control on absorbed radiation and hence ice surface darkening is a powerful amplifier of melt across the margin of the Greenland ice sheet. To investigate the relationship between ice surface roughness and variations in albedo in space and time at ~dm resolution, a suite of Unmanned Aerial Vehicles (UAVs) were deployed from the margin of Russell Glacier between June and August, 2014. The UAVs were equipped with digital and multispectral cameras, GoPros, fast response broadband pyranometers and temperature and humidity sensors. The primary mission was regular repeat longitudinal transects attaining data from the margin to the equilibrium line 80 km into the ice sheet interior and which were complimented by selected watershed and catchment surveys. The pyranometers reliably measure bare ice surface albedo between 0.34 and 0.58 that correlate well against concurrent MODIS data (where available). Repeat digital photogrammetric analysis enables investigation of relationship between changing meso- and micro-scale albedo and melt processes modulated by ice surface roughness that, in turn, are related to the seasonally evolving surface energy balance recorded at three AWS on the flight path.

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars.

PubMed

Sklute, Elizabeth C; Rogers, A Deanne; Gregerson, Jason C; Jensen, Heidi B; Reeder, Richard J; Dyar, M Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multi-component (Fe 2 (SO 4 ) 3 ± Ca, Na, Mg, Fe, Cl, HCO 3 ) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

NASA Astrophysics Data System (ADS)

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multicomponent (Fe2(SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21 °C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

PubMed Central

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-01-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca–, Na–, Mg– and Fe–chloride brines and multi-component (Fe2 (SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe–chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials. PMID:29670302

Endmembers of Ice Shelf Melt

NASA Astrophysics Data System (ADS)

Boghosian, A.; Child, S. F.; Kingslake, J.; Tedesco, M.; Bell, R. E.; Alexandrov, O.; McMichael, S.

2017-12-01

Studies of surface melt on ice shelves have defined a spectrum of meltwater behavior. On one end the storage of meltwater in persistent surface ponds can trigger ice shelf collapse as in the 2002 event leading to the disintegration of the Larsen B Ice Shelf. On the other, meltwater export by rivers can stabilize an ice shelf as was recently shown on the Nansen Ice Shelf. We explore this dichotomy by quantifying the partitioning between stored and transported water on two glaciers adjacent to floating ice shelves, Nimrod (Antarctica) and Peterman (Greenland). We analyze optical satellite imagery (LANDSAT, WorldView), airborne imagery (Operation IceBridge, Trimetrogon Aerial Phototography), satellite radar (Sentinel-1), and digital elevation models (DEMs) to categorize surface meltwater fate and map the evolution of ice shelf hydrology and topographic features through time. On the floating Peterman Glacier tongue a sizable river exports water to the ocean. The surface hydrology of Nimrod Glacier, geometrically similar to Peterman but with ten times shallower surface slope, is dominated by storage in surface lakes. In contrast, the Nansen has the same surface slope as Nimrod but transports water through surface rivers. Slope alone is not the sole control on ice shelf hydrology. It is essential to track the storage and transport volumes for each of these systems. To estimate water storage and transport we analyze high resolution (40 cm - 2 m) modern and historical DEMs. We produce historical (1957 onwards) DEMs with structure-from-motion photogrammetry. The DEMs are used to constrain water storage potential estimates of observed basins and water routing/transport potential. We quantify the total volume of water stored seasonally and interannually. We use the normalize difference water index to map meltwater extent, and estimate lake water depth from optical data. We also consider the role of stored water in subsurface aquifers in recharging surface water after observing a pond and river reemerge after apparently freezing during the 2016-17 melt season. Using the ponds/rivers endmember scheme helps us to constrain the role storage and transport play on stabilizing ice shelves. By extending this analysis to other ice tongues and shelves we can better understand their vulnerability to a warming world.

Coating Reduces Ice Adhesion

NASA Technical Reports Server (NTRS)

Smith, Trent; Prince, Michael; DwWeese, Charles; Curtis, Leslie

2008-01-01

The Shuttle Ice Liberation Coating (SILC) has been developed to reduce the adhesion of ice to surfaces on the space shuttle. SILC, when coated on a surface (foam, metal, epoxy primer, polymer surfaces), will reduce the adhesion of ice by as much as 90 percent as compared to the corresponding uncoated surface. This innovation is a durable coating that can withstand several cycles of ice growth and removal without loss of anti-adhesion properties. SILC is made of a binder composed of varying weight percents of siloxane(s), ethyl alcohol, ethyl sulfate, isopropyl alcohol, and of fine-particle polytetrafluoroethylene (PTFE). The combination of these components produces a coating with significantly improved weathering characteristics over the siloxane system alone. In some cases, the coating will delay ice formation and can reduce the amount of ice formed. SILC is not an ice prevention coating, but the very high water contact angle (greater than 140 ) causes water to readily run off the surface. This coating was designed for use at temperatures near -170 F (-112 C). Ice adhesion tests performed at temperatures from -170 to 20 F (-112 to -7 C) show that SILC is a very effective ice release coating. SILC can be left as applied (opaque) or buffed off until the surface appears clear. Energy dispersive spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS) data show that the coating is still present after buffing to transparency. This means SILC can be used to prevent ice adhesion even when coating windows or other objects, or items that require transmission of optical light. Car windshields are kept cleaner and SILC effectively mitigates rain and snow under driving conditions.

A Continuing Analysis of Possible Activity Drivers for the Enigmatic Comet 29P/Schwassmann-Wachmann 1

NASA Astrophysics Data System (ADS)

Schambeau, Charles Alfred; Fernandez, Yanga; Samarasinha, Nalin; Sarid, Gal; Mueller, Beatrice; Meech, Karen; Woodney, Laura

2015-11-01

We present results from our continuing effort to understand activity drivers in Comet 29P/Schwassmann-Wachmann 1 (SW1). While being in a nearly circular orbit around 6 AU, SW1 is continuously active and experiences frequent outbursts. Our group’s effort is focusing on finding constraints on physical and dynamical properties of SW1’s nucleus and their incorporation into a thermophysical model [1,2] to explain this behavior. Now we are analyzing coma morphology of SW1 before, during, and after outburst to place constraints on the spin-pole direction, spin period, and surface areas of activity (a spin period lower limit has been measured). Also, we are using the thermal model to investigate if the continuous activity comes from one or multiple processes, such as the release of trapped supervolatiles during the amorphous to crystalline (A-C) water ice phase transition and/or the direct sublimation of pockets of supervolatile ices, which may be primordial or from the condensation of gases released during the A-C phase transition. To explain the possibly quasi-periodic but frequent outbursts, we are looking into subsurface cavities where internal pressures can build, reaching and exceeding surrounding material strengths [3,4] and/or thermal waves reaching a pocket of supervolatile ices, causing a rapid increase in the sublimation rate. For all these phenomena, the model is constrained by comparing the output dust mass loss rate and its variability with what has been observed through optical imaging of the comet at various points in its orbit. We will present preliminary thermal modeling of a homogeneous progenitor nucleus that evolves into a body showing internal material layering, the generation of CO and CO2 ice pockets, and the production of outbursts, thus bringing us closer to explaining the behavior of this intriguing comet.[1] Sarid, G., et al.: 2005, PASP, 117, 843. [2] Sarid, G.: 2009, PhD Thesis, Tel Aviv Univ. [3] Gronkowski, P., 2014, Astron. Nachr./AN 2, No. 335, 124-134. [4] Gronkowski, P. and Wesolowski, M., 2015, MNRAS, 451, 3068-3077. We thank the NASA Outer Planets Research Program (NNX12AK50G) and the Center for Lunar and Asteroid Surface Science (CLASS, NNA14AB05A) for support of this work.

Modeling Pluto's Ice-Rich Surface and Its Interaction with Atmosphere

NASA Astrophysics Data System (ADS)

Wei, Q.; Hu, Y.

2016-12-01

Recent discoveries made available through NASA's New Horizon mission revealed a new world on Pluto with a plateau of "young" surface, the Sputnik Planum. It is a gigantic reservoir of volatile ice on top of an impact basin. The reason of such a high level of concentration of volatile ice is yet unknown. We are actively looking into explanations through atmospheric models and ice sheet models. Apart from the quantity of ice on SP, its surface age constrained by impact flux models to under 10Myr is significantly different from other parts of Pluto. Convection of solid nitrogen ice has been proposed as a viable cause. We endeavor to explore other possibilities that may have jointly contributed to this phenomena, including atmospheric condensation, ice sheet evolution, etc. Unique rheological properties of nitrogen ice, which is thought to dominate the Sputnik Planum, may hold the key to answering our questions. They are soft and easy to deform under its own weight even at Pluto's surface temperature of around 40K. Based on our initial simulations with numerical ice sheet models, we propose that once a crater is created on the Sputnik Planum, deformation under internal stress kicks in as a primary mechanism to flatten out craters. This could be done in a time scale of 100,000 years, significantly shorter than the maximum surface age contrained by crater densitiess models. As the surface arpproaches a flat state, such mechanism becomes weaker. The surface feature is then dominated by convection.

The Impact of Moisture Intrusions from Lower Latitudes on Arctic Net Surface Radiative Fluxes and Sea Ice Growth in Fall and Winter

NASA Astrophysics Data System (ADS)

Hegyi, B. M.; Taylor, P. C.

2017-12-01

The fall and winter seasons mark an important period in the evolution of Arctic sea ice, where energy is transferred away from the surface to facilitate the cooling of the surface and the growth of Arctic sea ice extent and thickness. Climatologically, these seasons are characterized by distinct periods of increased and reduced surface cooling and sea ice growth. Periods of reduced sea ice growth and surface cooling are associated with cloudy conditions and the transport of warm and moist air from lower latitudes, termed moisture intrusions. In the research presented, we explore the regional and Arctic-wide impact of moisture intrusions on the surface net radiative fluxes and sea ice growth for each fall and winter season from 2000/01-2015/16, utilizing MERRA2 reanalysis data, PIOMAS sea ice thickness data, and daily CERES radiative flux data. Consistent with previous studies, we find that positive anomalies in downwelling longwave surface flux are associated with increased temperature and water vapor content in the atmospheric column contained within the moisture intrusions. Interestingly, there are periods of increased downwelling LW flux anomalies that persist for one week or longer (i.e. longer than synoptic timescales) that are associated with persistent poleward flux of warm, moist air from lower latitudes. These persistent anomalies significantly reduce the regional growth of Arctic sea ice, and may in part explain the interannual variability of fall and winter Arctic sea ice growth.

A Mathematical Model of Melt Lake Development on an Ice Shelf

NASA Astrophysics Data System (ADS)

Buzzard, S. C.; Feltham, D. L.; Flocco, D.

2018-02-01

The accumulation of surface meltwater on ice shelves can lead to the formation of melt lakes. Melt lakes have been implicated in ice shelf collapse; Antarctica's Larsen B Ice Shelf was observed to have a large amount of surface melt lakes present preceding its collapse in 2002. Such collapse can affect ocean circulation and temperature, cause habitat loss and contribute to sea level rise through the acceleration of tributary glaciers. We present a mathematical model of a surface melt lake on an idealized ice shelf. The model incorporates a calculation of the ice shelf surface energy balance, heat transfer through the firn, the production and percolation of meltwater into the firn, the formation of ice lenses, and the development and refreezing of surface melt lakes. The model is applied to the Larsen C Ice Shelf, where melt lakes have been observed. This region has warmed several times the global average over the last century and the Larsen C firn layer could become saturated with meltwater by the end of the century. When forced with weather station data, our model produces surface melting, meltwater accumulation, and melt lake development consistent with observations. We examine the sensitivity of lake formation to uncertain parameters and provide evidence of the importance of processes such as lateral meltwater transport. We conclude that melt lakes impact surface melt and firn density and warrant inclusion in dynamic-thermodynamic models of ice shelf evolution within climate models, of which our model could form the basis for the thermodynamic component.

Amorphization of quartz by friction: Implication to silica-gel lubrication of fault surfaces

NASA Astrophysics Data System (ADS)

Nakamura, Yu; Muto, Jun; Nagahama, Hiroyuki; Shimizu, Ichiko; Miura, Takashi; Arakawa, Ichiro

2012-11-01

To understand physico-chemical processes at real contacts (asperities) on fault surfaces, we conducted pin-on-disk friction experiments at room temperature, using single crystalline quartz disks and quartz pins. Velocity weakening from friction coefficient μ ˜ 0.6 to 0.4 was observed under apparent normal stresses of 8-19 (18 > 19), when the slip rate was increased from 0.003 to 2.6 m/s. Frictional surfaces revealed ductile deformation of wear materials. The Raman spectra of frictional tracks showed blue shifts and broadening of quartz main bands, and appearance of new peaks at 490-520 and 610 cm-1. All these features are indicative of pressure- and strain-induced amorphization of quartz. The mapping analyses of Fourier transform infrared (FT-IR) spectroscopy at room dry conditions suggest selective hydration of wear materials. It is possible that the strained Si-O-Si bridges in amorphous silica preferentially react with water to form silica-gel. In natural fault systems, amorphous materials would be produced at real fault contacts and accumulate over the fault surfaces with displacements. Subsequent hydration would lead to significant reduction of fault strength during slip.

Convection from Hemispherical and Conical Model Ice Roughness Elements in Stagnation Region Flows

NASA Technical Reports Server (NTRS)

Hughes, Michael T.; Shannon, Timothy A.; McClain, Stephen T.; Vargas, Mario; Broeren, Andy

2016-01-01

To improve ice accretion prediction codes, more data regarding ice roughness and its effects on convective heat transfer are required. The Vertical Icing Studies Tunnel (VIST) at NASA Glenn Research was used to model realistic ice roughness in the stagnation region of a NACA 0012 airfoil. In the VIST, a test plate representing the leading 2% chord of the airfoil was subjected to flows of 7.62 m/s (25 ft/s), 12.19 m/s (40 ft/s), and 16.76 m/s (55 ft/s). The test plate was fitted with multiple surfaces or sets of roughness panels, each with a different representation of ice roughness. The sets of roughness panels were constructed using two element distribution patterns that were created based on a laser scan of an iced airfoil acquired in the Icing Research Tunnel at NASA Glenn. For both roughness patterns, surfaces were constructed using plastic hemispherical elements, plastic conical elements, and aluminum conical elements. Infrared surface thermometry data from tests run in the VIST were used to calculate area averaged heat transfer coefficient values. The values from the roughness surfaces were compared to the smooth control surface, showing convective enhancement as high as 400% in some cases. The data gathered during this study will ultimately be used to improve the physical modeling in LEWICE or other ice accretion codes and produce predictions of in-flight ice accretion on aircraft surfaces with greater confidence.

Implementation of Combined Feather and Surface-Normal Ice Growth Models in LEWICE/X

NASA Technical Reports Server (NTRS)

Velazquez, M. T.; Hansman, R. J., Jr.

1995-01-01

Experimental observations have shown that discrete rime ice growths called feathers, which grow in approximately the direction of water droplet impingement, play an important role in the growth of ice on accreting surfaces for some thermodynamic conditions. An improved physical model of ice accretion has been implemented in the LEWICE 2D panel-based ice accretion code maintained by the NASA Lewis Research Center. The LEWICE/X model of ice accretion explicitly simulates regions of feather growth within the framework of the LEWICE model. Water droplets impinging on an accreting surface are withheld from the normal LEWICE mass/energy balance and handled in a separate routine; ice growth resulting from these droplets is performed with enhanced convective heat transfer approximately along droplet impingement directions. An independent underlying ice shape is grown along surface normals using the unmodified LEWICE method. The resulting dual-surface ice shape models roughness-induced feather growth observed in icing wind tunnel tests. Experiments indicate that the exact direction of feather growth is dependent on external conditions. Data is presented to support a linear variation of growth direction with temperature and cloud water content. Test runs of LEWICE/X indicate that the sizes of surface regions containing feathers are influenced by initial roughness element height. This suggests that a previous argument that feather region size is determined by boundary layer transition may be incorrect. Simulation results for two typical test cases give improved shape agreement over unmodified LEWICE.

Tests of the Performance of Coatings for Low Ice Adhesion

NASA Technical Reports Server (NTRS)

Anderson, David N.; Reich, Allen D.

1997-01-01

This paper reports studies of the performance of low-ice-adhesion coatings by NASA Lewis and BFGoodrich. Studies used impact ice accreted both in the NASA Lewis Icing Research Tunnel (IRT) and in the BFGoodrich Icing Wind Tunnel (IWT) and static ice in a BFGoodrich bench-top parallel-plate shear rig. Early tests at NASA Lewis involved simple qualitative evaluations of the ease of removing impact ice from a surface. Coated surfaces were compared with uncoated ones. Some of the coatings were tested again with static ice at BFGoodrich to obtain quantitative measurements. Later, methods to establish the adhesion force on surfaces subjected to impact ice were explored at Lewis. This paper describes the various test programs and the results of testing some of the coatings looked at over the past 5 years. None of the coatings were found to be truly ice-phobic; however, the most effective coatings were found to reduce the adhesion of ice to about 1/2 that of an uncoated aluminum sample.

Encapsulation of lactase in Ca(II)-alginate beads: Effect of stabilizers and drying methods.

PubMed

Traffano-Schiffo, Maria Victoria; Castro-Giraldez, Marta; Fito, Pedro J; Santagapita, Patricio R

2017-10-01

The purpose of the present work was to analyze the effect of trehalose, arabic and guar gums on the preservation of β-galactosidase activity in freeze-dried and vacuum dried Ca(II)-alginate beads. Freezing process was also studied as a first step of freeze-drying. Trehalose was critical for β-galactosidase conservation, and guar gum as a second excipient showed the highest conservation effect (close to 95%). Systems with T g values ~40°C which were stables at ambient temperature were obtained, being trehalose the main responsible of the formation of an amorphous matrix. Vacuum dried beads showed smaller size (with Feret's diameter below 1.08±0.09mm), higher circularity (reaching 0.78±0.06) and large cracks in their surface than freeze-dried beads, which were more spongy and voluminous. Ice crystallization of the beads revealed that the crystallization of Ca(II)-alginate system follows the Avrami kinetics of nucleation and growth. Particularly, Ca(II)-alginate showed an Avrami index of 2.03±0.07, which means that crystal growing is bidimensional. Neither the addition of trehalose nor gums affected the dimension of the ice growing or its rate. These results open an opportunity in the development of new lactic products able to be consumed by lactose intolerance people. Copyright © 2017 Elsevier Ltd. All rights reserved.

The influence of Lifshitz forces and gas on premelting of ice within porous materials

NASA Astrophysics Data System (ADS)

Boström, M.; Malyi, O. I.; Thiyam, P.; Berland, K.; Brevik, I.; Persson, C.; Parsons, D. F.

2016-07-01

Premelting of ice within pores in earth materials is shown to depend on the presence of vapor layers. For thick vapor layers between ice and pore surfaces, a nanosized water sheet can be formed due to repulsive Lifshitz forces. In the absence of vapor layers, ice is inhibited from melting near pore surfaces. In between these limits, we find an enhancement of the water film thickness in silica and alumina pores. In the presence of metallic surface patches in the pore, the Lifshitz forces can dramatically widen the water film thickness, with potential complete melting of the ice surface.

Geodynamic Modeling of Planetary Ice-Oceans: Evolution of Ice-Shell Thickness in Convecting Two-Phase Systems

NASA Astrophysics Data System (ADS)

Allu Peddinti, D.; McNamara, A. K.

2016-12-01

Along with the newly unveiled icy surface of Pluto, several icy planetary bodies show indications of an active surface perhaps underlain by liquid oceans of some size. This augments the interest to explore the evolution of an ice-ocean system and its surface implications. The geologically young surface of the Jovian moon Europa lends much speculation to variations in ice-shell thickness over time. Along with the observed surface features, it suggests the possibility of episodic convection and conduction within the ice-shell as it evolved. What factors would control the growth of the ice-shell as it forms? If and how would those factors determine the thickness of the ice-shell and consequently the heat transfer? Would parameters such as tidal heating or initial temperature affect how the ice-shell grows and to what significance? We perform numerical experiments using geodynamical models of the two-phase ice-water system to study the evolution of planetary ice-oceans such as that of Europa. The models evolve self-consistently from an initial liquid ocean as it cools with time. The effects of presence, absence and magnitude of tidal heating on ice-shell thickness are studied in different models. The vigor of convection changes as the ice-shell continues to thicken. Initial modeling results track changes in the growth rate of the ice-shell as the vigor of the convection changes. The magnitude and temporal location of the rate change varies with different properties of tidal heating and values of initial temperature. A comparative study of models is presented to demonstrate how as the ice-shell is forming, its growth rate and convection are affected by processes such as tidal heating.

Convective Heat Transfer from Castings of Ice Roughened Surfaces in Horizontal Flight

NASA Technical Reports Server (NTRS)

Dukhan, Nihad; Vanfossen, G. James, Jr.; Masiulaniec, K. Cyril; Dewitt, Kenneth J.

1995-01-01

A technique was developed to cast frozen ice shapes that had been grown on a metal surface. This technique was applied to a series of ice shapes that were grown in the NASA Lewis Icing Research Tunnel on flat plates. Eight different types of ice growths, characterizing different types of roughness, were obtained from these plates, from which aluminum castings were made. Test strips taken from these castings were outfitted with heat flux gages, such that when placed in a dry wind tunnel, they could be used to experimentally map out the convective heat transfer coefficient in the direction of flow from the roughened surfaces. The effects on the heat transfer coefficient for parallel flow, which simulates horizontal flight, were studied. The results of this investigation can be used to help size heaters for wings, helicopter rotor blades, jet engine intakes, etc., or de-icing for anti-icing applications where the flow is parallel to the iced surface.

Temperature measurement of supercooled droplet in icing phenomenon by means of dual-luminescent imaging

NASA Astrophysics Data System (ADS)

Tanaka, M.; Morita, K.; Mamori, H.; Fukushima, N.; Yamamoto, M.

2017-08-01

The collision of a supercooled water droplet with a surface result an object creates ice accretion on the surface. The icing problem in any cold environments leads to severe damages on aircrafts, and a lot of studies on prevention and prediction techniques for icing have been conducted so far. Therefore, it is very important to know the detail of freezing mechanism of supercooled water droplets to improve the anti-and de-icing devices and icing simulation codes. The icing mechanism of a single supercooled water droplet impacting on an object surface would give us great insights for the purpose. In the present study, we develop a dual-luminescent imaging technique to measure the time-resolved temperature of a supercooled water droplet impacting on the surface under different temperature conditions. We apply this technique to measure the exact temperature of a water droplet, and to discuss the detail of the freezing process.

Temperature Distribution Measurement of The Wing Surface under Icing Conditions

NASA Astrophysics Data System (ADS)

Isokawa, Hiroshi; Miyazaki, Takeshi; Kimura, Shigeo; Sakaue, Hirotaka; Morita, Katsuaki; Japan Aerospace Exploration Agency Collaboration; Univ of Notre Dame Collaboration; Kanagawa Institute of Technology Collaboration; Univ of Electro-(UEC) Team, Comm

2016-11-01

De- or anti-icing system of an aircraft is necessary for a safe flight operation. Icing is a phenomenon which is caused by a collision of supercooled water frozen to an object. For the in-flight icing, it may cause a change in the wing cross section that causes stall, and in the worst case, the aircraft would fall. Therefore it is important to know the surface temperature of the wing for de- or anti-icing system. In aerospace field, temperature-sensitive paint (TSP) has been widely used for obtaining the surface temperature distribution on a testing article. The luminescent image from the TSP can be related to the temperature distribution. (TSP measurement system) In icing wind tunnel, we measured the surface temperature distribution of the wing model using the TSP measurement system. The effect of icing conditions on the TSP measurement system is discussed.

Reduced platelet adhesion and improved corrosion resistance of superhydrophobic TiO₂-nanotube-coated 316L stainless steel.

PubMed

Huang, Qiaoling; Yang, Yun; Hu, Ronggang; Lin, Changjian; Sun, Lan; Vogler, Erwin A

2015-01-01

Superhydrophilic and superhydrophobic TiO2 nanotube (TNT) arrays were fabricated on 316L stainless steel (SS) to improve corrosion resistance and hemocompatibility of SS. Vertically-aligned superhydrophilic amorphous TNTs were fabricated on SS by electrochemical anodization of Ti films deposited on SS. Calcination was carried out to induce anatase phase (superhydrophilic), and fluorosilanization was used to convert superhydrophilicity to superhydrophobicity. The morphology, structure and surface wettability of the samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle goniometry. The effects of surface wettability on corrosion resistance and platelet adhesion were investigated. The results showed that crystalline phase (anatase vs. amorphous) and wettability strongly affected corrosion resistance and platelet adhesion. The superhydrophilic amorphous TNTs failed to protect SS from corrosion whereas superhydrophobic amorphous TNTs slightly improved corrosion resistance of SS. Both superhydrophilic and superhydrophobic anatase TNTs significantly improved corrosion resistance of SS. The superhydrophilic amorphous TNTs minimized platelet adhesion and activation whereas superhydrophilic anatase TNTs activated the formation of fibrin network. On the contrary, both superhydrophobic TNTs (superhydrophobic amorphous TNTs and superhydrophobic anatase TNTs) reduced platelet adhesion significantly and improved corrosion resistance regardless of crystalline phase. Superhydrophobic anatase TNTs coating on SS surface offers the opportunity for the application of SS as a promising permanent biomaterial in blood contacting biomedical devices, where both reducing platelets adhesion/activation and improving corrosion resistance can be effectively combined. Copyright © 2014 Elsevier B.V. All rights reserved.

A study of the formation of amorphous calcium phosphate and hydroxyapatite on melt quenched Bioglass using surface sensitive shallow angle X-ray diffraction.

PubMed

Martin, R A; Twyman, H; Qiu, D; Knowles, J C; Newport, R J

2009-04-01

Melt quenched silicate glasses containing calcium, phosphorous and alkali metals have the ability to promote bone regeneration and to fuse to living bone. These glasses, including 45S5 Bioglass((R)) [(CaO)(26.9)(Na(2)O)(24.4)(SiO(2))(46.1)(P(2)O(5))(2.6)], are routinely used as clinical implants. Consequently there have been numerous studies on the structure of these glasses using conventional diffraction techniques. These studies have provided important information on the atomic structure of Bioglass((R)) but are of course intrinsically limited in the sense that they probe the bulk material and cannot be as sensitive to thin layers of near-surface dissolution/growth. The present study therefore uses surface sensitive shallow angle X-ray diffraction to study the formation of amorphous calcium phosphate and hydroxyapatite on Bioglass((R)) samples, pre-reacted in simulated body fluid (SBF). Unreacted Bioglass((R)) is dominated by a broad amorphous feature around 2.2 A(-1) which is characteristic of sodium calcium silicate glass. After reacting Bioglass((R)) in SBF a second broad amorphous feature evolves ~1.6 A(-1) which is attributed to amorphous calcium phosphate. This feature is evident for samples after only 4 h reacting in SBF and by 8 h the amorphous feature becomes comparable in magnitude to the background signal of the bulk Bioglass((R)). Bragg peaks characteristic of hydroxyapatite form after 1-3 days of reacting in SBF.

Stability of Glycine to Energetic Processing Under Astrophysical Conditions Investigated via Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Maté, Belén; Herrero, Victor Jose; Tanarro, Isabel; Escribano, Rafael

2015-06-01

Glycine, the simplest aminoacid, has been detected in comets and meteorites in our Solar System. Its detection in the interstellar medium is not improbable since other organic molecules of comparable complexity have been observed. Information of how complex organic molecules resist the energetic processing that they may suffer in different regions of space is of great interest for astrochemists and astrobiologists. Further to previous investigations we have studied in this work, via infrared spectroscopy, the effect of 2 keV electron bombardment on amorphous and crystalline glycine layers at low temperatures, to determine its destruction cross section under astrophysical conditions. Energetic electrons are known to be present in the solar wind and in planetary magnetospheres, and are also formed in the interaction of cosmic rays with matter. Moreover, we have probed the shielding effect of water ice layers grown on top of the glycine samples at 90 K. These experiment aim to mimic the conditions of the aminoacid in ice mantles on dust grains in the interstellar medium or in some outer Solar System objects, with a water ice surface crust. A residual material, product of glycine decomposition, was found at the end of the processing. A tentative assignment of the infrared spectra of the residue will be discussed in the presentation. E. Herbst and E. F. van Dishoeck, Annu. Rev. Astro. Astrophys. 2009, 47:427-480 B. Maté, Y. Rodriguez-Lazcano, O. Gálvez, I. Tanarro and R. Escribano, Phys Chem Chem Phys, 2011, 13, 12268. B. Maté, I. Tanarro, M.A. Moreno, M. Jiménez-Redondo, R. Escribano, and V. J. Herrero, Faraday Discussions, 2014, DOI: 10.1039/c3fd00132f.

Physical characteristics of summer sea ice across the Arctic Ocean

USGS Publications Warehouse

Tucker, W. B.; Gow, A.J.; Meese, D.A.; Bosworth, H.W.; Reimnitz, E.

1999-01-01

Sea ice characteristics were investigated during July and August on the 1994 transect across the Arctic Ocean. Properties examined from ice cores included salinity, temperature, and ice structure. Salinities measured near zero at the surface, increasing to 3-4??? at the ice-water interface. Ice crystal texture was dominated by columnar ice, comprising 90% of the ice sampled. Surface albedos of various ice types, measured with radiometers, showed integrated shortwave albedos of 0.1 to 0.3 for melt ponds, 0.5 for bare, discolored ice, and 0.6 to 0.8 for a deteriorated surface or snow-covered ice. Aerial photography was utilized to document the distribution of open melt ponds, which decreased from 12% coverage of the ice surface in late July at 76??N to almost none in mid-August at 88??N. Most melt ponds were shallow, and depth bore no relationship to size. Sediment was pervasive from the southern Chukchi Sea to the north pole, occurring in bands or patches. It was absent in the Eurasian Arctic, where it had been observed on earlier expeditions. Calculations of reverse trajectories of the sediment-bearing floes suggest that the southernmost sediment was entrained during ice formation in the Beaufort Sea while more northerly samples probably originated in the East Siberian Sea, some as far west as the New Siberian Islands.

Amorphization of hard crystalline materials by electrosprayed nanodroplet impact

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gamero-Castaño, Manuel, E-mail: mgameroc@uci.edu; Torrents, Anna; Borrajo-Pelaez, Rafael

2014-11-07

A beam of electrosprayed nanodroplets impacting on single-crystal silicon amorphizes a thin surface layer of a thickness comparable to the diameter of the drops. The phase transition occurs at projectile velocities exceeding a threshold, and is caused by the quenching of material melted by the impacts. This article demonstrates that the amorphization of silicon is a general phenomenon, as nanodroplets impacting at sufficient velocity also amorphize other covalently bonded crystals. In particular, we bombard single-crystal wafers of Si, Ge, GaAs, GaP, InAs, and SiC in a range of projectile velocities, and characterize the samples via electron backscatter diffraction and transmissionmore » electron microscopy to determine the aggregation state under the surface. InAs requires the lowest projectile velocity to develop an amorphous layer, followed by Ge, Si, GaAs, and GaP. SiC is the only semiconductor that remains fully crystalline, likely due to the relatively low velocities of the beamlets used in this study. The resiliency of each crystal to amorphization correlates well with the specific energy needed to melt it except for Ge, which requires projectile velocities higher than expected.« less

A predictive framework for the design and fabrication of icephobic polymers

PubMed Central

Golovin, Kevin; Tuteja, Anish

2017-01-01

Ice accretion remains a costly, hazardous concern worldwide. Icephobic coatings reduce the adhesion between ice and a surface. However, only a handful of the icephobic systems reported to date reduce the ice adhesion sufficiently for the facile and passive removal of ice, such as under its own weight or by mild winds. Most of these icephobic surfaces have relied on sacrificial lubricants, which may be depleted over time, drastically raising the ice adhesion. In contrast, surfaces that use interfacial slippage to lower their adhesion to ice can remain icephobic indefinitely. However, the mechanism of interfacial slippage, as it relates to ice adhesion, is largely unexplored. We investigate how interfacial slippage reduces the ice adhesion of polymeric materials. We propose a new, universally applicable framework that may be used to predict the reduction in the adhesion of ice to surfaces exhibiting interfacial slippage. This framework allows one to rationally engender icephobicity in essentially any polymeric system, including common thermoplastics. Hence, we present several new, extremely icephobic systems fabricated from a wide range of materials, including everyday engineering plastics and sustainable, natural oils. PMID:28948227

Impact of surface melt and ponding on the stability of Larsen C Ice Shelf, Antarctic Peninsula

NASA Astrophysics Data System (ADS)

Kulessa, Bernd; Luckman, Adrian; Hubbard, Bryn; Bevan, Suzanne; O'Leary, Martin; Ashmore, David; Kuipers Munneke, Peter; Jansen, Daniela; Booth, Adam; Sevestre, Heidi; Holland, Paul; McGrath, Daniel; Brisbourne, Alex; Rutt, Ian

2017-04-01

Several ice shelves on the Antarctic Peninsula have disintegrated rapidly in recent decades, and surface meltwater is strongly implicated as a driver. The Larsen C Ice Shelf is the largest ice shelf on the peninsula and one of the largest in Antarctica, and is subject to pronounced surface melting and meltwater ponding, especially in the northern sectors and landward inlets. As part of the MIDAS project we have investigated the structure and physical properties of the firn and ice layers in the 2014/15 and 2015/16 austral summers, using a combination of radar and seismic geophysical surveys together with hot water drilling and borehole optical televiewing and temperature measurements. We found that Larsen C's firn column and ice temperatures are modified strongly by surface melting and ponding, including the presence of massive ice bodies in the Cabinet and Whirlwind inlets. Numerical modelling reveals that these modifications have been altering ice shelf deformation, flow and fracture significantly. The findings from our MIDAS project thus suggest that the response of Antarctic ice shelves to climatic warming is more complex than previously thought.

Point defects at the ice (0001) surface

PubMed Central

Watkins, Matthew; VandeVondele, Joost; Slater, Ben

2010-01-01

Using density functional theory we investigate whether intrinsic defects in ice surface segregate. We predict that hydronium, hydroxide, and the Bjerrum L- and D-defects are all more stable at the surface. However, the energetic cost to create a D-defect at the surface and migrate it into the bulk crystal is smaller than its bulk formation energy. Absolute and relative segregation energies are sensitive to the surface structure of ice, especially the spatial distribution of protons associated with dangling hydrogen bonds. It is found that the basal plane surface of hexagonal ice increases the bulk concentration of Bjerrum defects, strongly favoring D-defects over L-defects. Dangling protons associated with undercoordinated water molecules are preferentially injected into the crystal bulk as Bjerrum D-defects, leading to a surface dipole that attracts hydronium ions. Aside from the disparity in segregation energies for the Bjerrum defects, we find the interactions between defect species to be very finely balanced; surface segregation energies for hydronium and hydroxide species and trapping energies of these ionic species with Bjerrum defects are equal within the accuracy of our calculations. The mobility of the ionic hydronium and hydroxide species is greatly reduced at the surface in comparison to the bulk due to surface sites with high trapping affinities. We suggest that, in pure ice samples, the surface of ice will have an acidic character due to the presence of hydronium ions. This may be important in understanding the reactivity of ice particulates in the upper atmosphere and at the boundary layer. PMID:20615938

Hydrophobic durability characteristics of butterfly wing surface after freezing cycles towards the design of nature inspired anti-icing surfaces

PubMed Central

Choy, Kwang-Leong

2018-01-01

The hydrophobicity and anti-icing performance of the surfaces of some artificial hydrophobic coatings degraded after several icing and de-icing cycles. In this paper, the frost formation on the surfaces of butterfly wings from ten different species was observed, and the contact angles were measured after 0 to 6 frosting/defrosting cycles. The results show that no obvious changes in contact angle for the butterfly wing specimens were not obvious during the frosting/defrosting process. Further, the conclusion was inferred that the topography of the butterfly wing surface forms a special space structure which has a larger space inside that can accommodate more frozen droplets; this behavior prevents destruction of the structure. The findings of this study may provide a basis and new concepts for the design of novel industrially important surfaces to inhibit frost/ice growth, such as durable anti-icing coatings, which may decrease or prevent the socio-economic loss. PMID:29385390

Hydrophobic durability characteristics of butterfly wing surface after freezing cycles towards the design of nature inspired anti-icing surfaces.

PubMed

Chen, Tingkun; Cong, Qian; Qi, Yingchun; Jin, Jingfu; Choy, Kwang-Leong

2018-01-01

The hydrophobicity and anti-icing performance of the surfaces of some artificial hydrophobic coatings degraded after several icing and de-icing cycles. In this paper, the frost formation on the surfaces of butterfly wings from ten different species was observed, and the contact angles were measured after 0 to 6 frosting/defrosting cycles. The results show that no obvious changes in contact angle for the butterfly wing specimens were not obvious during the frosting/defrosting process. Further, the conclusion was inferred that the topography of the butterfly wing surface forms a special space structure which has a larger space inside that can accommodate more frozen droplets; this behavior prevents destruction of the structure. The findings of this study may provide a basis and new concepts for the design of novel industrially important surfaces to inhibit frost/ice growth, such as durable anti-icing coatings, which may decrease or prevent the socio-economic loss.

Surface-enhanced Raman scattering of amorphous TiO2 thin films by gold nanostructures: Revealing first layer effect with thickness variation

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A.-M.; Bessueille, F.; Coulm, J.; Champagnon, B.; Vouagner, D.

2013-12-01

In this paper, amorphous titanium dioxide (TiO2) thin films have been deposited on a commercially available Klarite substrate using the sol-gel process to produce surface-enhanced Raman scattering (SERS). The substrate consists of square arrays of micrometer-sized pyramidal pits in silicon with a gold coating. Several thin TiO2 layers have been deposited on the surface to study the influence of film thickness. Ultimately, we obtained information on SERS of an amorphous TiO2 layer by gold nanostructures, whose range is less than a few nanometers. Mechanisms responsible for the enhancement are the product of concomitant chemical and electromagnetic effects with an important contribution from plasmon-induced charge transfer.

Surface modification by carbon ion implantation for the application of ni-based amorphous alloys as bipolar plate in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Kim, Min-Uk; Kim, Do-Hyang; Han, Seung-hee; Fleury, Eric; Seok, Hyun-Kwang; Cha, Pil-Ryung; Kim, Yu-Chan

2011-04-01

Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni60Nb20Ti10Zr10 alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.

Amorphization and nanocrystallization of silcon under shock compression

DOE PAGES

Remington, B. A.; Wehrenberg, C. E.; Zhao, S.; ...

2015-11-06

High-power, short-duration, laser-driven, shock compression and recovery experiments on [001] silicon unveiled remarkable structural changes above a pressure threshold. Two distinct amorphous regions were identified: (a) a bulk amorphous layer close to the surface and (b) amorphous bands initially aligned with {111} slip planes. Further increase of the laser energy leads to the re-crystallization of amorphous silicon into nanocrystals with high concentration of nano-twins. This amorphization is produced by the combined effect of high magnitude hydrostatic and shear stresses under dynamic shock compression. Shock-induced defects play a very important role in the onset of amorphization. Calculations of the free energymore » changes with pressure and shear, using the Patel-Cohen methodology, are in agreement with the experimental results. Molecular dynamics simulation corroborates the amorphization, showing that it is initiated by the nucleation and propagation of partial dislocations. As a result, the nucleation of amorphization is analyzed qualitatively by classical nucleation theory.« less