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Sample records for amorphous ice transition

  1. 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

  2. Molecular Reorientation Dynamics Govern the Glass Transitions of the Amorphous Ices.

    PubMed

    Shephard, J J; Salzmann, C G

    2016-06-16

    The glass transitions of low-density amorphous ice (LDA) and high-density amorphous ice (HDA) are the topic of controversial discussions. Understanding their exact nature may be the key to explaining the anomalies of liquid water but has also got implications in the general context of polyamorphism, the occurrence of multiple amorphous forms of the same material. We first show that the glass transition of hydrogen-disordered ice VI is associated with the kinetic unfreezing of molecular reorientation dynamics by measuring the calorimetric responses of the corresponding H2O, H2(18)O, and D2O materials in combination with X-ray diffraction. Well-relaxed LDA and HDA show identical isotopic-response patterns in calorimetry as ice VI, and we conclude that the glass transitions of the amorphous ices are also governed by molecular reorientation processes. This "reorientation scenario" seems to resolve the previously conflicting viewpoints and is consistent with the fragile-to-strong transition from water to the amorphous ices.

  3. Evidence for liquid water during the high-density to low-density amorphous ice transition

    PubMed Central

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

    2009-01-01

    Polymorphism of water has been extensively studied, but controversy still exists over the phase transition between high-density amorphous (HDA) and low-density amorphous (LDA) ice. We report the phase behavior of HDA ice inside high-pressure cryocooled protein crystals. Using X-ray diffraction, we demonstrate that the intermediate states in the temperature range from 80 to 170 K can be reconstructed as a linear combination of HDA and LDA ice, suggesting a first-order transition. We found evidence for a liquid state of water during the ice transition based on the protein crystallographic data. These observations open the possibility that the HDA ice induced by high-pressure cryocooling is a genuine glassy form of high-density liquid. PMID:19258453

  4. SURVIVAL OF AMORPHOUS WATER ICE ON CENTAURS

    SciTech Connect

    Guilbert-Lepoutre, Aurelie

    2012-10-01

    Centaurs are believed to be Kuiper Belt objects in transition between Jupiter and Neptune before possibly becoming Jupiter family comets. Some indirect observational evidence is consistent with the presence of amorphous water ice in Centaurs. Some of them also display a cometary activity, probably triggered by the crystallization of the amorphous water ice, as suggested by Jewitt and this work. Indeed, we investigate the survival of amorphous water ice against crystallization, using a fully three-dimensional thermal evolution model. Simulations are performed for varying heliocentric distances and obliquities. They suggest that crystallization can be triggered as far as 16 AU, though amorphous ice can survive beyond 10 AU. The phase transition is an efficient source of outgassing up to 10-12 AU, which is broadly consistent with the observations of the active Centaurs. The most extreme case is 167P/CINEOS, which barely crystallizes in our simulations. However, amorphous ice can be preserved inside Centaurs in many heliocentric distance-obliquity combinations, below a {approx}5-10 m crystallized crust. We also find that outgassing due to crystallization cannot be sustained for a time longer than 10{sup 4}-10{sup 4} years, leading to the hypothesis that active Centaurs might have recently suffered from orbital changes. This could be supported by both observations (although limited) and dynamical studies.

  5. 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.

  6. Structure and dynamics of amorphous water ice.

    PubMed

    Laufer, D; Kochavi, E; Bar-Nun, A

    1987-12-15

    Further insight into the structure and dynamics of amorphous water ice, at low temperatures, was obtained by trapping in it Ar, Ne, H2, and D2. Ballistic water-vapor deposition results in the growth of smooth, approximately 1 x 0.2 micrometer2, ice needles. The amorphous ice seems to exist in at least two separate forms, at T < 85 K and at 85 < T < 136.8 K, and transform irreversibly from one form to the other through a series of temperature-dependent metastable states. The channels formed by the water hexagons in the ice are wide enough to allow the free penetration of H2 and D2 into the ice matrix even in the relatively compact cubic ice, resulting in H2-(D2-) to-ice ratios (by number) as high as 0.63. The larger Ar atoms can penetrate only into the wider channels of amorphous ice, and Ne is an intermediate case. Dynamic percolation behavior explains the emergence of Ar and Ne (but not H2 and D2) for the ice, upon warming, in small and big gas jets. The big jets, each containing approximately 5 x 10(10) atoms, break and propel the ice needles. Dynamic percolation also explains the collapse of the ice matrix under bombardment by Ar , at a pressure exceeding 2.6 dyn cm-2, and the burial of huge amounts of gas inside the collapsed matrix, up to an Ar-to-ice of 3.3 (by number). The experimental results could be relevant to comets, icy satellites, and icy grain mantles in dense interstellar clouds.

  7. Structure and dynamics of amorphous water ice

    NASA Technical Reports Server (NTRS)

    Laufer, D.; Kochavi, E.; Bar-Nun, A.; Owen, T. (Principal Investigator)

    1987-01-01

    Further insight into the structure and dynamics of amorphous water ice, at low temperatures, was obtained by trapping in it Ar, Ne, H2, and D2. Ballistic water-vapor deposition results in the growth of smooth, approximately 1 x 0.2 micrometer2, ice needles. The amorphous ice seems to exist in at least two separate forms, at T < 85 K and at 85 < T < 136.8 K, and transform irreversibly from one form to the other through a series of temperature-dependent metastable states. The channels formed by the water hexagons in the ice are wide enough to allow the free penetration of H2 and D2 into the ice matrix even in the relatively compact cubic ice, resulting in H2-(D2-) to-ice ratios (by number) as high as 0.63. The larger Ar atoms can penetrate only into the wider channels of amorphous ice, and Ne is an intermediate case. Dynamic percolation behavior explains the emergence of Ar and Ne (but not H2 and D2) for the ice, upon warming, in small and big gas jets. The big jets, each containing approximately 5 x 10(10) atoms, break and propel the ice needles. Dynamic percolation also explains the collapse of the ice matrix under bombardment by Ar , at a pressure exceeding 2.6 dyn cm-2, and the burial of huge amounts of gas inside the collapsed matrix, up to an Ar-to-ice of 3.3 (by number). The experimental results could be relevant to comets, icy satellites, and icy grain mantles in dense interstellar clouds.

  8. 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

  9. Amorphous to amorphous transition in particle rafts

    NASA Astrophysics Data System (ADS)

    Varshney, Atul; Sane, A.; Ghosh, Shankar; Bhattacharya, S.

    2012-09-01

    Space-filling assemblies of athermal hydrophobic particles floating at an air-water interface, called particle rafts, are shown to undergo an unusual phase transition between two amorphous states, i.e., a low density “less-rigid” state and a high density “more-rigid” state, as a function of particulate number density (Φ). The former is shown to be a capillary bridged solid and the latter is shown to be a frictionally coupled one. Simultaneous studies involving direct imaging as well as measuring its mechanical response to longitudinal and shear stresses show that the transition is marked by a subtle structural anomaly and a weakening of the shear response. The structural anomaly is identified from the variation of the mean coordination number, mean area of the Voronoi cells, and spatial profile of the displacement field with Φ. The weakened shear response is related to local plastic instabilities caused by the depinning of the contact line of the underlying fluid on the rough surfaces of the particles.

  10. Amorphous to amorphous transition in particle rafts.

    PubMed

    Varshney, Atul; Sane, A; Ghosh, Shankar; Bhattacharya, S

    2012-09-01

    Space-filling assemblies of athermal hydrophobic particles floating at an air-water interface, called particle rafts, are shown to undergo an unusual phase transition between two amorphous states, i.e., a low density "less-rigid" state and a high density "more-rigid" state, as a function of particulate number density (Φ). The former is shown to be a capillary bridged solid and the latter is shown to be a frictionally coupled one. Simultaneous studies involving direct imaging as well as measuring its mechanical response to longitudinal and shear stresses show that the transition is marked by a subtle structural anomaly and a weakening of the shear response. The structural anomaly is identified from the variation of the mean coordination number, mean area of the Voronoi cells, and spatial profile of the displacement field with Φ. The weakened shear response is related to local plastic instabilities caused by the depinning of the contact line of the underlying fluid on the rough surfaces of the particles.

  11. Crystallization of amorphous water ice in the solar system

    NASA Technical Reports Server (NTRS)

    Jenniskens, P.; Blake, D. F.

    1996-01-01

    Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.

  12. Highly confined water: two-dimensional ice, amorphous ice, and clathrate hydrates.

    PubMed

    Zhao, Wen-Hui; Wang, Lu; Bai, Jaeil; Yuan, Lan-Feng; Yang, Jinlong; Zeng, Xiao Cheng

    2014-08-19

    Understanding phase behavior of highly confined water, ice, amorphous ice, and clathrate hydrates (or gas hydrates), not only enriches our view of phase transitions and structures of quasi-two-dimensional (Q2D) solids not seen in the bulk phases but also has important implications for diverse phenomena at the intersection between physical chemistry, cell biology, chemical engineering, and nanoscience. Relevant examples include, among others, boundary lubrication in nanofluidic and lab-on-a-chip devices, synthesis of antifreeze proteins for ice-growth inhibition, rapid cooling of biological suspensions or quenching emulsified water under high pressure, and storage of H2 and CO2 in gas hydrates. Classical molecular simulation (MD) is an indispensable tool to explore states and properties of highly confined water and ice. It also has the advantage of precisely monitoring the time and spatial domains in the sub-picosecond and sub-nanometer scales, which are difficult to control in laboratory experiments, and yet allows relatively long simulation at the 10(2) ns time scale that is impractical with ab initio molecular dynamics simulations. In this Account, we present an overview of our MD simulation studies of the structures and phase behaviors of highly confined water, ice, amorphous ice, and clathrate, in slit graphene nanopores. We survey six crystalline phases of monolayer (ML) ice revealed from MD simulations, including one low-density, one mid-density, and four high-density ML ices. We show additional supporting evidence on the structural stabilities of the four high-density ML ices in the vacuum (without the graphene confinement), for the first time, through quantum density-functional theory optimization of their free-standing structures at zero temperature. In addition, we summarize various low-density, high-density, and very-high-density Q2D bilayer (BL) ice and amorphous ice structures revealed from MD simulations. These simulations reinforce the notion that

  13. Matrix sublimation method for the formation of high-density amorphous ice

    NASA Astrophysics Data System (ADS)

    Kouchi, A.; Hama, T.; Kimura, Y.; Hidaka, H.; Escribano, R.; Watanabe, N.

    2016-08-01

    A novel method for the formation of amorphous ice involving matrix sublimation has been developed. A CO-rich CO:H2O mixed ice was deposited at 8-10 K under ultra-high vacuum condition, which was then allowed to warm. After the sublimation of matrix CO at 35 K, amorphous ice remained. The amorphous ice formed exhibits a highly porous microscale texture; however, it also rather exhibits a density similar to that of high-density amorphous ice formed under high pressure. Furthermore, unlike conventional vapor-deposited amorphous ice, the amorphous ice is stable up to 140 K, where it transforms directly to cubic ice Ic.

  14. Amorphous polymorphis in ice investigated by inelastic neutron scattering

    NASA Astrophysics Data System (ADS)

    Schober, H.; Koza, M.; Tölle, A.; Fujara, F.; Angell, C. A.; Böhmer, R.

    High-density I lda and low-density I lda amorphous have been investigated by inelastic neutron scattering (INS) with emphasis on the energy window from 0.5 to 20 meV. At variance with earlier measurements the spectra in the I lda phase show a simple ω2 behaviour in the acoustic region and the temperature dependence is found to be harmonic. I lda converts with a strongly temperature-dependent rate towards I lda ice. We have investigated in detail the time evolution of both the static and dynamic response functions at several temperatures. Elastic small-angle signals indicate the presence of strong heterogeneties at the early stages of the conversion process. At least two different time scales are present in the transition. The structural changes are reflected in the frequency distribution. The first peak in the phonon density-of-states softens appreciably when going from I lda to I lda. In the acoustic region there is evidence that I lda is softer than both I lda and crystalline cubic ice I c. No signs of a fast ps process related to melting can be detected in the dynamics.

  15. 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

    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.

  16. 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.

  17. 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.

  18. Mimas: Preliminary Evidence For Amorphous Water Ice from VIMS

    NASA Technical Reports Server (NTRS)

    Cruikshank, Dale P.; Marzo, G. A.; Pinilla-Alonso, N.; Roush, T. L.; Mastrapa, R. M.; DalleOre, C. M.; Buratti, B. J.; Stephan, K.

    2010-01-01

    We have conducted a statistical clustering analysis (1,2) on a mosaic of VIMS data cubes obtained on February 13, 2010, for Saturn s satellite Mimas. Seven VIMS cubes were geometrically projected and re-sampled to a common spatial resolution. The clustering technique consists of a partitioning algorithm coupled to a criterion that prevents sub-optimal solutions and tests for the influence of random noise in the measurements. The clustering technique is agnostic about the meaning of the clusters, and scientific interpretation requires their a posteriori evaluation. The preliminary results yielded five clusters, demonstrating that spectral variability across Mimas surface is statistically significant. The ratios of the means calculated for each of the clusters show structure within the 1.6- micron water ice band, as well as the shape and the central wavelength of the strong ice band at 2 micron, that map spatially in patterns apparently related to the topography of Mimas, in particular certain regions in and around Herschel crater. The mean spectra of the five clusters, show similarities with laboratory spectra of amorphous and crystalline H2O ice (3) that are suggestive of the presence of an amorphous ice component in certain regions of Mimas, notably on the central peak of Herschel, on the crater floor, and in faults surrounding the crater. This may represent a mixture of both ice phases, or perhaps a layer of amorphous ice on a base of crystalline ice. Another possible occurrence of amorphous ice appears southwest of Herschel, close to the south pole.

  19. Mimas: Preliminary Evidence For Amorphous Water Ice From VIMS

    NASA Astrophysics Data System (ADS)

    Cruikshank, Dale P.; Marzo, G. A.; Pinilla-Alonso, N.; Roush, T. L.; Mastrapa, R. M.; Dalle Ore, C. M.; Buratti, B. J.; Stephan, K.; VIMS Team

    2010-10-01

    We have conducted a statistical clustering analysis (1,2) on a mosaic of VIMS data cubes obtained on February 13, 2010, for Saturn's satellite Mimas. Seven VIMS cubes were geometrically projected and re-sampled to a common spatial resolution. The clustering technique consists of a partitioning algorithm coupled to a criterion that prevents sub-optimal solutions and tests for the influence of random noise in the measurements. The clustering technique is agnostic about the meaning of the clusters, and scientific interpretation requires their a posteriori evaluation. The preliminary results yielded five clusters, demonstrating that spectral variability across Mimas’ surface is statistically significant. The ratios of the means calculated for each of the clusters show structure within the 1.6-µm water ice band, as well as the shape and the central wavelength of the strong ice band at 2 µm that map spatially in patterns apparently related to the topography of Mimas, in particular certain regions in and around Herschel crater. The mean spectra of the five clusters, show similarities with laboratory spectra of amorphous and crystalline H2O ice (3) that are suggestive of the presence of an amorphous ice component in certain regions of Mimas, notably on the central peak of Herschel, on the crater floor, and in faults surrounding the crater. This may represent a mixture of both ice phases, or perhaps a layer of amorphous ice on a base of crystalline ice. Another possible occurrence of amorphous ice appears southwest of Herschel, close to the south pole. 1. Marzo, G. A. et al. J. Geophys. Res. 111, E03002, 2006 2. Marzo, G. A. et al. J. Geophys. Res. 113, E12009, 2008 3. Mastrapa, R. M., et al. Astrophys. J. 701, 1347-1356, 2009

  20. CO DIFFUSION INTO AMORPHOUS H{sub 2}O ICES

    SciTech Connect

    Lauck, Trish; Karssemeijer, Leendertjan; Cuppen, Herma M.; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I. E-mail: koberg@cfa.harvard.edu

    2015-03-10

    The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H{sub 2}O, and diffusion on external and internal (pore) surfaces of H{sub 2}O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H{sub 2}O-dominated ices at low temperatures (15–23 K), by measuring the mixing rate of initially layered H{sub 2}O(:CO{sub 2})/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H{sub 2}O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H{sub 2}O ice. The extracted energy barrier for CO diffusion into amorphous H{sub 2}O ice is ∼160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

  1. Mimas: Preliminary Evidence For Amorphous Water Ice From VIMS (Invited)

    NASA Astrophysics Data System (ADS)

    Cruikshank, D. P.; Marzo, G.; Pinilla-Alonso, N.; Roush, T. L.; Mastrapa, R. M.; Dalle Ore, C. M.; Buratti, B. J.; Stephan, K.; Brown, R. H.; Baines, K. H.; Clark, R. N.; Nicholson, P. D.; Sotin, C.; Cassini Vims Team

    2010-12-01

    We have conducted a statistical clustering analysis (1,2) on a mosaic of VIMS data cubes obtained on February 13, 2010, for Saturn’s satellite Mimas. Seven VIMS cubes were geometrically projected and re-sampled to a common spatial resolution. The clustering technique consists of a partitioning algorithm coupled to a criterion that prevents sub-optimal solutions and tests for the influence of random noise in the measurements. The clustering technique is agnostic about the meaning of the clusters, and scientific interpretation requires their a posteriori evaluation. The preliminary results yielded five clusters, demonstrating that spectral variability across Mimas’ surface is statistically significant. The ratios of the means calculated for each of the clusters show structure within the 1.6-µm water ice band, as well as the shape and the central wavelength of the strong ice band at 2 µm, that map spatially in patterns apparently related to the topography of Mimas, in particular certain regions in and around Herschel crater. The mean spectra of the five clusters, show similarities (band shape and central wavelength) with lab spectra of amorphous and crystalline H2O ice (3) that are suggestive of the presence of an amorphous (or “disordered”) ice component in certain regions of Mimas, notably on the central peak of Herschel, on the crater floor, and in faults surrounding the crater. Mimas is too warm to sustain H2O ice in a possibly original amorphous form for the great age of the surface, and its appearance may represent a mixture of both ice phases, or perhaps a layer of disordered ice on a base of crystalline ice. Another possible occurrence of non-crystalline ice appears southwest of Herschel, close to the south pole. (1) Marzo, G. A. et al. J. Geophys. Res. 111, E03002, 2006. (2) Marzo, G. A. et al. J. Geophys. Res. 113, E12009, 2008. (3) Mastrapa, R. M., et al. Astrophys. J. 701, 1347-1356, 2009.

  2. Computer simulation study of metastable ice VII and amorphous phases obtained by its melting

    NASA Astrophysics Data System (ADS)

    Slovák, Jan; Tanaka, Hideki

    2005-05-01

    Molecular dynamics simulations of metastable ice VII and cubic ice Ic are carried out in order to examine (1) the ability of commonly used water interaction potentials to reproduce the properties of ices, and (2) the possibility of generating low-density amorphous (LDA) structures by heating ice VII, which is known to transform to LDA at ˜135K at normal pressure [S. Klotz, J. M. Besson, G. Hamel, R. J. Nelmes, J. S. Loveday, and W. G. Marshall, Nature (London) 398, 681 (1999)]. We test four simple empirical interaction potentials of water: TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)], SPC/E [H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. B 91, 6269 (1987)], TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)], and ST2 [F. H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)]. We have found that TIP5P ice VII melts at 210 K, TIP4P at 90 K, and SPC/E at 70 K. Only TIP5P water after transition has a structure similar to that of LDA. TIP4P and SPC/E have almost identical structures, dissimilar to any known water or amorphous phases, but upon heating both slowly evolve towards LDA-like structure. ST2 ice VII is remarkably stable up to 430 K. TIP4P and SPC/E predict correctly the cubic ice collapse into a high-density amorphous ice (HDA) at ˜1GPa whereas TIP5P remains stable up to ˜5GPa. The densities of the simulated ice phases differ significantly, depending on the potential used, and are generally higher than experimental values. The importance of proper treatment of long-range electrostatic interactions is also discussed.

  3. Crystallization of CO2 ice and the absence of amorphous CO2 ice in space

    PubMed Central

    Escribano, Rafael M.; Muñoz Caro, Guillermo M.; Cruz-Diaz, Gustavo A.; Rodríguez-Lazcano, Yamilet; Maté, Belén

    2013-01-01

    Carbon dioxide (CO2) is one of the most relevant and abundant species in astrophysical and atmospheric media. In particular, CO2 ice is present in several solar system bodies, as well as in interstellar and circumstellar ice mantles. The amount of CO2 in ice mantles and the presence of pure CO2 ice are significant indicators of the temperature history of dust in protostars. It is therefore important to know if CO2 is mixed with other molecules in the ice matrix or segregated and whether it is present in an amorphous or crystalline form. We apply a multidisciplinary approach involving IR spectroscopy in the laboratory, theoretical modeling of solid structures, and comparison with astronomical observations. We generate an unprecedented highly amorphous CO2 ice and study its crystallization both by thermal annealing and by slow accumulation of monolayers from the gas phase under an ultrahigh vacuum. Structural changes are followed by IR spectroscopy. We also devise theoretical models to reproduce different CO2 ice structures. We detect a preferential in-plane orientation of some vibrational modes of crystalline CO2. We identify the IR features of amorphous CO2 ice, and, in particular, we provide a theoretical explanation for a band at 2,328 cm−1 that dominates the spectrum of the amorphous phase and disappears when the crystallization is complete. Our results allow us to rule out the presence of pure and amorphous CO2 ice in space based on the observations available so far, supporting our current view of the evolution of CO2 ice. PMID:23858474

  4. Phase transitions in biogenic amorphous calcium carbonate

    NASA Astrophysics Data System (ADS)

    Gong, Yutao

    Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

  5. Visual Observations of the Amorphous-Amorphous Transition in H2O Under Pressure.

    PubMed

    Mishima, O; Takemura, K; Aoki, K

    1991-10-18

    The vapor-deposited low-density amorphous phase of H(2)O was directly compressed at 77 kelvin with a diamond-anvil cell, and the boundary between the low-density amorphous phase and the high-density amorphous phase was observed while the sample was warmed under compression. The transition from the low-density amorphous phase to the high-density amorphous phase was distinct and reversible in an apparently narrow pressure range at approximately 130 to approximately 150 kelvin, which provided experimental evidence for polymorphism in amorphous H(2)O. PMID:17742228

  6. Evolution of Hydrogen Dynamics in Amorphous Ice with Density.

    PubMed

    Parmentier, A; Shephard, J J; Romanelli, G; Senesi, R; Salzmann, C G; Andreani, C

    2015-06-01

    The single-particle dynamics of hydrogen atoms in several of the amorphous ices are reported using a combination of deep inelastic neutron scattering (DINS) and inelastic neutron scattering (INS). The mean kinetic energies of the hydrogen nuclei are found to increase with increasing density, indicating the weakening of hydrogen bonds as well as a trend toward steeper and more harmonic hydrogen vibrational potential energy surfaces. DINS shows much more pronounced changes in the O-H stretching component of the mean kinetic energy going from low- to high-density amorphous ices than indicated by INS and Raman spectroscopy. This highlights the power of the DINS technique to retrieve accurate ground-state kinetic energies beyond the harmonic approximation. In a novel approach, we use information from DINS and INS to determine the anharmonicity constants of the O-H stretching modes. Furthermore, our experimental kinetic energies will serve as important benchmark values for path-integral Monte Carlo simulations.

  7. Vapor deposition of water on graphitic surfaces: Formation of amorphous ice, bilayer ice, ice I, and liquid water

    SciTech Connect

    Lupi, Laura; Kastelowitz, Noah; Molinero, Valeria

    2014-11-14

    Carbonaceous surfaces are a major source of atmospheric particles and could play an important role in the formation of ice. Here we investigate through molecular simulations the stability, metastability, and molecular pathways of deposition of amorphous ice, bilayer ice, and ice I from water vapor on graphitic and atomless Lennard-Jones surfaces as a function of temperature. We find that bilayer ice is the most stable ice polymorph for small cluster sizes, nevertheless it can grow metastable well above its region of thermodynamic stability. In agreement with experiments, the simulations predict that on increasing temperature the outcome of water deposition is amorphous ice, bilayer ice, ice I, and liquid water. The deposition nucleation of bilayer ice and ice I is preceded by the formation of small liquid clusters, which have two wetting states: bilayer pancake-like (wetting) at small cluster size and droplet-like (non-wetting) at larger cluster size. The wetting state of liquid clusters determines which ice polymorph is nucleated: bilayer ice nucleates from wetting bilayer liquid clusters and ice I from non-wetting liquid clusters. The maximum temperature for nucleation of bilayer ice on flat surfaces, T{sub B}{sup max} is given by the maximum temperature for which liquid water clusters reach the equilibrium melting line of bilayer ice as wetting bilayer clusters. Increasing water-surface attraction stabilizes the pancake-like wetting state of liquid clusters leading to larger T{sub B}{sup max} for the flat non-hydrogen bonding surfaces of this study. The findings of this study should be of relevance for the understanding of ice formation by deposition mode on carbonaceous atmospheric particles, including soot.

  8. Vapor deposition of water on graphitic surfaces: formation of amorphous ice, bilayer ice, ice I, and liquid water.

    PubMed

    Lupi, Laura; Kastelowitz, Noah; Molinero, Valeria

    2014-11-14

    Carbonaceous surfaces are a major source of atmospheric particles and could play an important role in the formation of ice. Here we investigate through molecular simulations the stability, metastability, and molecular pathways of deposition of amorphous ice, bilayer ice, and ice I from water vapor on graphitic and atomless Lennard-Jones surfaces as a function of temperature. We find that bilayer ice is the most stable ice polymorph for small cluster sizes, nevertheless it can grow metastable well above its region of thermodynamic stability. In agreement with experiments, the simulations predict that on increasing temperature the outcome of water deposition is amorphous ice, bilayer ice, ice I, and liquid water. The deposition nucleation of bilayer ice and ice I is preceded by the formation of small liquid clusters, which have two wetting states: bilayer pancake-like (wetting) at small cluster size and droplet-like (non-wetting) at larger cluster size. The wetting state of liquid clusters determines which ice polymorph is nucleated: bilayer ice nucleates from wetting bilayer liquid clusters and ice I from non-wetting liquid clusters. The maximum temperature for nucleation of bilayer ice on flat surfaces, T(B)(max) is given by the maximum temperature for which liquid water clusters reach the equilibrium melting line of bilayer ice as wetting bilayer clusters. Increasing water-surface attraction stabilizes the pancake-like wetting state of liquid clusters leading to larger T(B)(max) for the flat non-hydrogen bonding surfaces of this study. The findings of this study should be of relevance for the understanding of ice formation by deposition mode on carbonaceous atmospheric particles, including soot. PMID:25399173

  9. The sticking of atomic hydrogen on amorphous water ice

    SciTech Connect

    Veeraghattam, Vijay K.; Manrodt, Katie; Lewis, Steven P.; Stancil, P. C. E-mail: lewis@physast.uga.edu

    2014-07-20

    Using classical molecular dynamics, we have simulated the sticking and scattering process of a hydrogen atom on an amorphous ice film to predict the sticking probability of hydrogen on ice surfaces. A wide range of initial kinetic energies of the incident hydrogen atom (10 K-600 K) and two different ice temperatures (10 K and 70 K) were used to investigate this fundamental process in interstellar chemistry. We report here the sticking probability of atomic hydrogen as a function of incident kinetic energy, gas temperature, and substrate temperature, which can be used in astrophysical models. The current results are compared to previous theoretical and experimental studies that have reported a wide range in the sticking coefficient.

  10. Clathrate hydrate formation in amorphous cometary ice analogs in vacuo.

    PubMed

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

    1991-10-25

    The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena. PMID:11538372

  11. Clathrate hydrate formation in amorphous cometary ice analogs in vacuo.

    PubMed

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

    1991-10-25

    The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena.

  12. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark

    2016-06-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and to the interstellar medium, with an emphasis on amorphous and crystalline ices below ~ 120 K. Our goal is to update and add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on three of the simplest and most abundant components of interstellar and solar-system ices: methane (CH4), carbon dioxide (CO2), and methanol (CH3OH). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 120 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  13. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark

    2016-06-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and to the interstellar medium, with an emphasis on amorphous and crystalline ices below ~ 120 K. Our goal is to update and add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on three of the simplest and most abundant components of interstellar and solar-system ices: methane (CH4), carbon dioxide (CO2), and methanol (CH3OH). Infrared spectra from ∼ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 120 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  14. The structure and dynamics of amorphous and crystalline phases of ice

    SciTech Connect

    Klug, D. D.; Tse, J. S.; Tulk, C. A.; Svensson, E. C.; Swainson, I.; Loong, C.-K.

    2000-07-14

    The structures of the high and low-density amorphous phases of ice are studied using several techniques. The diffraction patterns of high and low density amorphous ice are analyzed using reverse Monte Carlo methods and compared with molecular dynamics simulations of these phases. The spectra of crystalline and amorphous phases of ice obtained by Raman and incoherent inelastic neutron scattering are analyzed to yield structural features for comparison with the results of molecular dynamics and Reverse Monte Carlo analysis. The structural details obtained indicate that there are significant differences between the structure of liquid water and the amorphous phases of ice.

  15. 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

  16. Amorphous and polycrystalline water ices in space environments

    NASA Astrophysics Data System (ADS)

    Andrade, Diana; Pilling, Sergio; Da Silveira, Enio; Barros, Ana

    2016-07-01

    Ices are an important reservoir of more complex molecular species in several space environments, containing information about the composition and formation of these regions. Water ice is the dominant constituent of interstellar ices in most lines of sight and is about 70 % of the composition in comets, being a key molecule in astrochemical models. It is believed that one of the reactive species possibly evaporated from the water ices is the hydronium ion, H_{3}O^{+}, which plays an important role in the oxygen chemistry network. This ion has been detected in the lunar surface of Enceladus and Titan, and toward the Sagittarius B2 molecular Clouds, where H_{2}O and OH were also identified. In this work, the ion desorption due to radiolysis in ices constituted by water at three different temperatures (40, 70 and 125 K) is studied, to investigate the different allotropic water ices. A discussion on the rate of H_{3}O^{+} and water delivered to gas phase, as well as the half-life of water ice grains, inside dense molecular clouds considering a constants cosmic ray flux is given. The ions desorbed from water ice have been mass/charge analyzed by a time-of-flight spectrometer. Among the results, it is seen that in the positive ion spectrum of high density amorphous water ice at 40 K the highest desorption yields (ejected ions/impact) correspond to H^{+}, H_{3}O^{+} and clusters formed by (H_{2}O)_{n}R^{+}, where R^{+} is H_{3}O^{+} and 1 ≤ n ≤ 25. At T = 125 K, the ice is in its low density polycrystalline form and new clusters are present, such as (H_{2}O)_{n}R^{+}, where R^{+} is H_{2}^{+} and H_{3}^{+} (for low n), beyond H_{3}O^{+}. Therefore, it is seen that (H_{2}O)_{n}H_{3}O^{+} series (with n between 1 and 25) is dominant in all cases. The H_{3}O^{+} desorption yield at 40 K is about 5times10^{-3} ions/impact. This value is 4-5 times higher than the one obtained at T > 125 K. This behavior is also seen to all series member and consequently to the sum (Yn).

  17. State transformations and ice nucleation in amorphous (semi-)solid organic aerosol

    NASA Astrophysics Data System (ADS)

    Baustian, K. J.; Wise, M. E.; Jensen, E. J.; Schill, G. P.; Freedman, M. A.; Tolbert, M. A.

    2013-06-01

    Amorphous (semi-)solid organic aerosol particles have the potential to serve as surfaces for heterogeneous ice nucleation in cirrus clouds. Raman spectroscopy and optical microscopy have been used in conjunction with a cold stage to examine water uptake and ice nucleation on individual amorphous (semi-)solid particles at atmospherically relevant temperatures (200-273 K). Three organic compounds considered proxies for atmospheric secondary organic aerosol (SOA) were used in this investigation: sucrose, citric acid and glucose. Internally mixed particles consisting of each organic and ammonium sulfate were also investigated. Results from water uptake experiments followed the shape of a humidity-induced glass transition (Tg(RH)) curve and were used to construct state diagrams for each organic and corresponding mixture. Experimentally derived Tg(RH) curves are in good agreement with theoretical predictions of Tg(RH) following the approach of Koop et al. (2011). A unique humidity-induced glass transition point on each state diagram, Tg'(RH), was used to quantify and compare results from this study to previous works. Values of Tg'(RH) determined for sucrose, glucose and citric acid glasses were 236, 230 and 220 K, respectively. Values of Tg'(RH) for internally mixed organic/sulfate particles were always significantly lower; 210, 207 and 215 K for sucrose/sulfate, glucose/sulfate and citric acid/sulfate, respectively. All investigated SOA proxies were observed to act as heterogeneous ice nuclei at tropospheric temperatures. Heterogeneous ice nucleation on pure organic particles occurred at Sice = 1.1-1.4 for temperatures below 235 K. Particles consisting of 1:1 organic-sulfate mixtures took up water over a greater range of conditions but were in some cases also observed to heterogeneously nucleate ice at temperatures below 202 K (Sice= 1.25-1.38). Polynomial curves were fitted to experimental water uptake data and then incorporated into the Community Aerosol Radiation

  18. Amorphous-crystalline transition in thermoelectric NbO2

    NASA Astrophysics Data System (ADS)

    Music, Denis; Chen, Yen-Ting; Bliem, Pascal; Geyer, Richard W.

    2015-06-01

    Density functional theory was employed to design enhanced amorphous NbO2 thermoelectrics. The covalent-ionic nature of Nb-O bonding is identical in amorphous NbO2 and its crystalline counterpart. However, the Anderson localisation occurs in amorphous NbO2, which may affect the transport properties. We calculate a multifold increase in the absolute Seebeck coefficient for the amorphous state. These predictions were critically appraised by measuring the Seebeck coefficient of sputtered amorphous and crystalline NbO2 thin films with the identical short-range order. The first-order phase transition occurs at approximately 550 °C, but amorphous NbO2 possesses enhanced transport properties at all temperatures. Amorphous NbO2, reaching  -173 μV K-1, exhibits up to a 29% larger absolute Seebeck coefficient value, thereby validating the predictions.

  19. Experimental Evidence for a Crossover between Two Distinct Mechanisms of Amorphization in Ice Ih under Pressure

    SciTech Connect

    Straessle, Thierry; Klotz, Stefan; Hamel, Gerard; 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.

  20. Dynamics of CO in amorphous water-ice environments

    SciTech Connect

    Karssemeijer, L. J.; Ioppolo, S.; Van der Avoird, A.; Cuppen, H. M.; Van Hemert, M. C.; Allodi, M. A.; Blake, G. A.

    2014-01-20

    The long-timescale behavior of adsorbed carbon monoxide on the surface of amorphous water ice is studied under dense cloud conditions by means of off-lattice, on-the-fly, kinetic Monte Carlo simulations. It is found that the CO mobility is strongly influenced by the morphology of the ice substrate. Nanopores on the surface provide strong binding sites, which can effectively immobilize the adsorbates at low coverage. As the coverage increases, these strong binding sites are gradually occupied leaving a number of admolecules with the ability to diffuse over the surface. Binding energies and the energy barrier for diffusion are extracted for various coverages. Additionally, the mobility of CO is determined from isothermal desorption experiments. Reasonable agreement on the diffusivity of CO is found with the simulations. Analysis of the 2152 cm{sup –1} polar CO band supports the computational findings that the pores in the water ice provide the strongest binding sites and dominate diffusion at low temperatures.

  1. Phase transitions in biogenic amorphous calcium carbonate.

    PubMed

    Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

    2012-04-17

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro. PMID:22492931

  2. Diffusion measurements of CO, HNCO, H2CO, and NH3 in amorphous water ice

    NASA Astrophysics Data System (ADS)

    Mispelaer, F.; Theulé, P.; Aouididi, H.; Noble, J.; Duvernay, F.; Danger, G.; Roubin, P.; Morata, O.; Hasegawa, T.; Chiavassa, T.

    2013-07-01

    Context. Water is the major component of the interstellar ice mantle. In interstellar ice, chemical reactivity is limited by the diffusion of the reacting molecules, which are usually present at abundances of a few percent with respect to water. Aims: We want to study the thermal diffusion of H2CO, NH3, HNCO, and CO in amorphous water ice experimentally to account for the mobility of these molecules in the interstellar grain ice mantle. Methods: In laboratory experiments performed at fixed temperatures, the diffusion of molecules in ice analogues was monitored by Fourier transform infrared spectroscopy. Diffusion coefficients were extracted from isothermal experiments using Fick's second law of diffusion. Results: We measured the surface diffusion coefficients and their dependence with the temperature in porous amorphous ice for HNCO, H2CO, NH3, and CO. They range from 10-15 to 10-11 cm2 s-1 for HNCO, H2CO, and NH3 between 110 K and 140 K, and between 5-8 × 10-13 cm2 s-1 for CO between 35 K and 40 K. The bulk diffusion coefficients in compact amorphous ice are too low to be measured by our technique and a 10-15 cm2 s-1 upper limit can be estimated. The amorphous ice framework reorganization at low temperature is also put in evidence. Conclusions: Surface diffusion of molecular species in amorphous ice can be experimentally measured, while their bulk diffusion may be slower than the ice mantle desorption kinetics.

  3. Phase behaviors of supercooled water: Reconciling a critical point of amorphous ices with spinodal instability

    NASA Astrophysics Data System (ADS)

    Tanaka, Hideki

    1996-09-01

    The anomalies of supercooled water in thermodynamic response functions at atmospheric pressure, the phase transition between low and high density amorphous ices (LDA and HDA), and a predicted fragile-strong transition are accounted for in a unified manner by reconciling an idea due to Stanley and co-workers introducing a second critical point separating LDA and HDA ices with a conjecture proposed by Speedy that LDA is a different phase from a normal water, called water II. The reconciliation is made on the basis of results from extensive molecular dynamics simulations at constant pressure and temperature. It is found that there exist large gaps around temperature 213 K in thermodynamic, structural, and dynamic properties at atmospheric pressure, suggesting liquid-liquid phase transition. This transition is identified with an extension of the experimentally observed LDA-HDA transition in high pressure to atmospheric pressure. Thus, we propose a new phase diagram where the locus of the second critical point is moved into negative pressure region. With this simple modification, it becomes possible to account for the divergence of the thermodynamic response functions at atmospheric pressure in terms of the critical point and the spinodal-like instability of HDA. The unstable HDA undergoes a transition to LDA phase in lower temperature. The transition is also observed in high pressure region such as 200 MPa while it disappears at negative pressure, -200 MPa. This reinforces our proposed phase diagram in which there is no continuous path from a supercooled state to LDA at atmospheric pressure. It is argued that the HDA-LDA transition is accompanied by a fragile-strong transition. A possible mechanism of avoiding crystallization of aqueous solutions is also discussed in terms of a difference in hydrogen bond number distribution between LDA and HDA.

  4. Mechanisms for pressure- and time-dependent amorphization of ice under pressure

    NASA Astrophysics Data System (ADS)

    Johari, G. P.; Andersson, Ove

    2004-11-01

    Amorphization of hexagonal ice under pressure at low temperatures has been studied by measuring the thermal conductivity with time, by keeping the ice in the temperature range 127-130K and pressure range 0.79-0.88GPa . The results have been used to examine the relative merits of the Lindemann melting and the Born instability as a mechanism for amorphization of ice. Thermal conductivity decreases continuously with time according to a stretched-exponential relation. This and the findings that, (i) amorphization pressure is lower than the available values calculated for an ideal ice crystal by using the Born theory, and (ii) amorphization of cubic ice occurs at about the same pressure as that of hexagonal ice, seem inconsistent with both mechanisms. The findings can be reconciled with the Born mechanism if the effect of the existing lattice faults and/or the lattice faults produced during the plastic deformation of uniaxially compressed ice are considered to produce a distribution of collapse pressure. It is argued that the difference between the amorphization and the low-density amorph to high-density amorph transformation pressures corresponds to the energy needed to collapse, or randomly distort, the ice crystallites to a structure whose energy spontaneously decreases by diffusion of a H2O molecule into the first coordination shell of the amorph’s known structure, and persist there as an interstitial molecule. The newly observed amorphization kinetics has a bearing on the computer-simulated inference on pressure-induced collapse and/or melting of crystals.

  5. New Optical Constants of Amorphous and Crystalline H2O-ice, 3-20_m

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel Michelle Elizab

    2008-01-01

    We will present new optical constants forth amorphous and crystalline H2O-ice in the spectral range 3-20 _m. Our new measurements provide high temperature resolution for crystalline H2O-ice, 10 K intervals from 20-150 K, including temperatures relevant to Solar System ices. We have found that the shape of the 3 _m feature in amorphous H2O-ice is strongly dependant on deposition temperature and the high and low density phases of amorphous H2O-ice are not easily distinguishable. We will present methods of measuring the change in band shape with phase and temperature. We acknowledge financial support from the NASA Origins of the Solar System Program and the NASA Planetary Geology and Geophysics Program.

  6. Stepwise morphological change of porous amorphous ice films observed through adsorption of methane

    NASA Astrophysics Data System (ADS)

    Horimoto, Noriko; Kato, Hiroyuki S.; Kawai, Maki

    2002-03-01

    Morphological change of amorphous ice films of D2O has been studied through adsorption of methane using thermal desorption spectroscopy (TDS) and infrared reflection absorption spectroscopy under ultrahigh vacuum. The investigated ice films were prepared under several different conditions; first, water (D2O) molecules are evaporated onto a Ru substrate at 25 K, and then subjected to an annealing process at various temperatures prior to methane deposition. On ice annealed at low temperatures, two desorption species of methane were observed in TDS: one was derived from methane adsorbed near the ice surface and the other was attributed to the desorption of methane encapsulated in ice during heating. Only the former species was observed when the annealing temperature exceeded 60 K. This indicates that reconstruction of ice occurs below 60 K, which inhibits the encapsulation of methane molecules from the amorphous ice. On the other hand, infrared spectra of ice covered with methane show that the micropores in ice start to collapse at ˜80 K, and ice becomes pore free at 120 K. We have found that the morphological change of amorphous ice induced by thermal relaxation takes place in a stepwise manner.

  7. 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

  8. 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

  9. 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.

  10. The structure of amorphous phases of ices prepared by high pressure and rapid quenching of water

    NASA Astrophysics Data System (ADS)

    Klug, Dennis D.; Tse, John S.; Tulk, Chris A.; Swainson, Ian; Svensson, Eric C.; Loong, C.-K.

    2000-03-01

    The structures of the amorphous ices are investigated using incoherent inelastic neutron scattering(1), neutron and x-ray scattering data, and reverse Monte Carlo methods to determine the relationship between liquid water under pressure or at 1 bar and the amorphous solids prepared by pressure amorphization and annealing or by rapid quenching of water. We show that the amorphous solids prepared by pressure amorphization are structurally different from liquid water and their structures are determined by the the mechanism for amorphization(2). References: 1) D.D. Klug, C.A. Tulk, E.C. Svensson, and C.-K. Loong, Phys. Rev. Lett. 83, 2584, 1999. 2) J.S. Tse, et al. Nature 400, 647 (1999).

  11. Phase diagram of amorphous solid water: low-density, high-density, and very-high-density amorphous ices.

    PubMed

    Giovambattista, Nicolas; Stanley, H Eugene; Sciortino, Francesco

    2005-09-01

    We calculate the phase diagram of amorphous solid water by performing molecular dynamics simulations using the extended simple point charge (SPC/E) model. Our simulations follow different paths in the phase diagram: isothermal compression/decompression, isochoric cooling/heating, and isobaric cooling/heating. We are able to identify low-density amorphous (LDA), high-density amorphous (HDA), and very-high density amorphous (VHDA) ices. The density rho of these glasses at different pressure P and temperature T agree well with experimental values. We also study the radial distribution functions of glassy water. In agreement with experiments, we find that LDA, HDA, and VHDA are characterized by a tetrahedral hydrogen-bonded network and that, as compared to LDA, HDA has an extra interstitial molecule between the first and second shell. VHDA appears to have two such extra molecules. We obtain VHDA, as in experiment, by isobaric heating of HDA. We also find that "other forms" of glassy water can be obtained upon isobaric heating of LDA, as well as amorphous ices formed during the transformation of LDA to HDA. We argue that these other forms of amorphous ices, as well as VHDA, are not altogether new glasses but rather are the result of aging induced by heating. Samples of HDA and VHDA with different densities are recovered at normal P, showing that there is a continuum of glasses. Furthermore, the two ranges of densities of recovered HDA and recovered VHDA overlap at ambient P. Our simulations reproduce the experimental findings of HDA --> LDA and VHDA --> LDA transformations. We do not observe a VHDA --> HDA transformation, and our final phase diagram of glassy water together with equilibrium liquid data suggests that for the SPC/E model the VHDA --> HDA transformation cannot be observed with the present heating rates accessible in simulations. Finally, we discuss the consequences of our findings for the understanding of the transformation between the different amorphous

  12. Extracellular ice phase transitions in insects.

    PubMed

    Hawes, T C

    2014-01-01

    At temperatures below their temperature of crystallization (Tc), the extracellular body fluids of insects undergo a phase transition from liquid to solid. Insects that survive the transition to equilibrium (complete freezing of the body fluids) are designated as freeze tolerant. Although this phenomenon has been reported and described in many Insecta, current nomenclature and theory does not clearly delineate between the process of transition (freezing) and the final solid phase itself (the frozen state). Thus freeze tolerant insects are currently, by convention, described in terms of the temperature at which the crystallization of their body fluids is initiated, Tc. In fact, the correct descriptor for insects that tolerate freezing is the temperature of equilibrium freezing, Tef. The process of freezing is itself a separate physical event with unique physiological stresses that are associated with ice growth. Correspondingly there are a number of insects whose physiological cryo-limits are very specifically delineated by this transitional envelope. The distinction also has considerable significance for our understanding of insect cryobiology: firstly, because the ability to manage endogenous ice growth is a fundamental segregator of cryotype; and secondly, because our understanding of internal ice management is still largely nascent.

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

    SciTech Connect

    Gerakines, Perry A.; Hudson, Reggie L.

    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 the 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.

  14. Interaction of acetonitrile with the surfaces of amorphous and crystalline ice

    SciTech Connect

    Schaff, J.E.; Roberts, J.T.

    1999-10-12

    The adsorption of acetonitrile (CH{sub 3}CN) on ultrathin films of ice under ultrahigh vacuum was investigated with temperature-programmed desorption ass spectrometry (TPD) and Fourier transform infrared reflection absorption spectroscopy (FTIRAS). Two types of film were studied, amorphous and crystalline. On the amorphous films, two sates of adsorbed acetonitrile were observed by TPD and FTIRAS. One of the states is attributed to acetonitrile that is hydrogen bonded to agree OH group at the ice surface; the other state is assigned to acetonitrile that is purely physiorbed. Evidence for the hydrogen-bonded state is two-fold. First, there is a large kinetic isotope effect for desorption from H{sub 2}O-and D{sub 2}O-ice: the desorption temperatures from ice-h{sub 2} and ice-d{sub 2} are {approximately}161 and {approximately}176 K, respectively. Second, the C{triple{underscore}bond}N stretching frequency (2,265 cm{sup {minus}1}) is 16 cm{sup {minus}1} is greater than that of physisorbed acetonitrile, and it is roughly equal to that of acetonitrile which is hydrogen bonded to an OH group at the air-liquid water interface. On the crystalline films, there is no evidence for a hydrogen-bonded state in the TPD spectra. The FTIRAS spectra do show that some hydrogen-bonded acetonitrile is present but at a maximum coverage that is roughly one-sixth of that on the amorphous surface. The difference between the amorphous and crystalline surfaces cannot be attributed to a difference n surface areas. Rather, this work provides additional evidence that the surface chemical properties of amorphous ice are different from those of crystalline ice.

  15. A new measurement of thermal conductivity of amorphous ice and its implications for the thermal evolution of comets

    NASA Technical Reports Server (NTRS)

    Kouchi, Akira; Greenberg, J. M.; Yamamoto, T.; Mukai, T.; Xing, Z. F.

    1992-01-01

    Very slowly deposited amorphous ice has a thermal conductivity about four orders of magnitude or more smaller than hitherto estimated. Using the exceedingly low value of the thermal conductivity of comets deduced from the properties of amorphous ice leads to the expectation that internal heating of comets is negligible below the outer several tens of centimeters.

  16. First-order transition in confined water between high-density liquid and low-density amorphous phases.

    PubMed

    Koga, K; Tanaka, H; Zeng, X C

    2000-11-30

    Supercooled water and amorphous ice have a rich metastable phase behaviour. In addition to transitions between high- and low-density amorphous solids, and between high- and low-density liquids, a fragile-to-strong liquid transition has recently been proposed, and supported by evidence from the behaviour of deeply supercooled bilayer water confined in hydrophilic slit pores. Here we report evidence from molecular dynamics simulations for another type of first-order phase transition--a liquid-to-bilayer amorphous transition--above the freezing temperature of bulk water at atmospheric pressure. This transition occurs only when water is confined in a hydrophobic slit pore with a width of less than one nanometre. On cooling, the confined water, which has an imperfect random hydrogen-bonded network, transforms into a bilayer amorphous phase with a perfect network (owing to the formation of various hydrogen-bonded polygons) but no long-range order. The transition shares some characteristics with those observed in tetrahedrally coordinated substances such as liquid silicon, liquid carbon and liquid phosphorus. PMID:11117739

  17. Neutron Scattering Analysis of Water's Glass Transition and Micropore Collapse in Amorphous Solid Water.

    PubMed

    Hill, Catherine R; Mitterdorfer, Christian; Youngs, Tristan G A; Bowron, Daniel T; Fraser, Helen J; Loerting, Thomas

    2016-05-27

    The question of the nature of water's glass transition has continued to be disputed over many years. Here we use slow heating scans (0.4  K min^{-1}) of compact amorphous solid water deposited at 77 K and an analysis of the accompanying changes in the small-angle neutron scattering signal, to study mesoscale changes in the ice network topology. From the data we infer the onset of rotational diffusion at 115 K, a sudden switchover from nondiffusive motion and enthalpy relaxation of the network at <121  K to diffusive motion across sample grains and sudden pore collapse at >121  K, in excellent agreement with the glass transition onset deduced from heat capacity and dielectric measurements. This indicates that water's glass transition is linked with long-range transport of water molecules on the time scale of minutes and, thus, clarifies its nature. Furthermore, the slow heating rates combined with the high crystallization resistance of the amorphous sample allow us to identify the glass transition end point at 136 K, which is well separated from the crystallization onset at 144 K-in contrast to all earlier experiments in the field. PMID:27284664

  18. Neutron Scattering Analysis of Water's Glass Transition and Micropore Collapse in Amorphous Solid Water

    NASA Astrophysics Data System (ADS)

    Hill, Catherine R.; Mitterdorfer, Christian; Youngs, Tristan G. A.; Bowron, Daniel T.; Fraser, Helen J.; Loerting, Thomas

    2016-05-01

    The question of the nature of water's glass transition has continued to be disputed over many years. Here we use slow heating scans (0.4 K min-1 ) of compact amorphous solid water deposited at 77 K and an analysis of the accompanying changes in the small-angle neutron scattering signal, to study mesoscale changes in the ice network topology. From the data we infer the onset of rotational diffusion at 115 K, a sudden switchover from nondiffusive motion and enthalpy relaxation of the network at <121 K to diffusive motion across sample grains and sudden pore collapse at >121 K , in excellent agreement with the glass transition onset deduced from heat capacity and dielectric measurements. This indicates that water's glass transition is linked with long-range transport of water molecules on the time scale of minutes and, thus, clarifies its nature. Furthermore, the slow heating rates combined with the high crystallization resistance of the amorphous sample allow us to identify the glass transition end point at 136 K, which is well separated from the crystallization onset at 144 K—in contrast to all earlier experiments in the field.

  19. A unified description of crystalline-to-amorphous transitions

    SciTech Connect

    Lam, N.Q.; Okamoto, P.R.; Devanathan, R. |; Meshii, M.

    1993-07-01

    Amorphous metallic alloys can now be synthesized by a variety of solid-state processes demonstrating the need for a more general approach to crystalline-to-amorphous (c-a) transitions. By focusing on static atomic displacements as a measure of chemical and topological disorder, we show that a unified description of c-a transformations can be based on a generalization of the phenomenological melting criterion proposed by Lindemann. The generalized version assumes that melting of a defective crystal occurs whenever the sum of thermal and static mean-square displacements exceeds a critical value identical to that for melting of the defect-free crystal. This implies that chemical or topological disorder measured by static displacements is thermodynamically equivalent to heating, and therefore that the melting temperature of the defective crystal will decrease with increasing amount of disorder. This in turn implies the existence of a critical state of disorder where the melting temperature becomes equal to a glass-transition temperature below which the metastable crystal melts to a glass. The generalized Lindemann melting criterion leads naturally to an interpretation of c-a transformations as defect-induced, low-temperature melting of critically disordered crystals. Confirmation of this criterion is provided by molecular-dynamics simulations of heat-induced melting and of defect-induced amorphization of intermetallic compounds caused either by the production of Frenkel pairs or anti-site defects. The thermodynamic equivalence between static atomic disorder and heating is reflected in the identical softening effects which they have on elastic properties and also in the diffraction analysis of diffuse scattering from disordered crystals, where the effect of static displacements appears as an artificially-enlarged thermal Debye-Waller factor. Predictions of this new, unified approach to melting and amorphization are compared with available experimental information.

  20. Formation of gas hydrate during crystallization of ethane-saturated amorphous ice

    NASA Astrophysics Data System (ADS)

    Faizullin, M. Z.; Vinogradov, A. V.; Skokov, V. N.; Koverda, V. P.

    2014-10-01

    Layers of ethane-saturated amorphous ice were prepared by depositing molecular beams of water and gas on a substrate cooled with liquid nitrogen. The heating of the layers was accompanied by vitrification (softening) followed by spontaneous crystallization. Crystallization of condensates under the conditions of deep metastability proceeded with gas hydrate formation. The vitrification and crystallization temperatures of the condensates were determined from the changes in their dielectric properties on heating. The thermal effects of transformations were recorded by differential thermal analysis. The crystallization of the amorphous water layers was studied by electron diffraction. Formation of a metastable packing with elements of a cubic diamond-like structure was noted.

  1. 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.

  2. Possible existence of two amorphous phases of D-mannitol related by a first-order transition

    SciTech Connect

    Zhu, Men; Yu, Lian; Wang, Jun-Qiang; Perepezko, John H.

    2015-06-28

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature T{sub g} (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near T{sub g} + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near T{sub g} with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.

  3. Possible existence of two amorphous phases of d-mannitol related by a first-order transition

    NASA Astrophysics Data System (ADS)

    Zhu, Men; Wang, Jun-Qiang; Perepezko, John H.; Yu, Lian

    2015-06-01

    We report that the common polyalcohol d-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of d-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of d-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from d-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and d-mannitol both strengthen the hydrogen bonds. In contrast to TPP, d-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make d-mannitol a valuable new model for understanding polyamorphism.

  4. Crystallization of amorphous ice as the cause of Comet P/Halley's outburst at 14 AU

    NASA Technical Reports Server (NTRS)

    Prialnik, D.; Bar-Nun, A.

    1992-01-01

    An explanation is provided for the postperihelion eruption of Comet P/Halley, detected in February 1991 and believed to have started three months earlier, namely, the crystallization of amorphous ice taking place in the interior of the porous nucleus, at depths of a few tens of meters, accompanied by the release of trapped gases. Numerical calculations show that for a bulk density of 0.5 g/cu cm and a pore size of 1 micron crystallization occurs on the outbound leg of Comet P/Halley's orbit, at heliocentric distances between 5 AU and 17 AU. The trapped gas is released and flows to the surface through the porous medium. It may also open wider channels, as the internal pressures obtained surpass the tensile strength of cometary ice. The outflowing gas carries with it grains of ice and dust, and thus can explain the large amounts of dust observed in the coma at 14.3 AU and beyond.

  5. 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.

  6. 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.

  7. The Infrared Spectra and Absorption Intensities of Amorphous Ices: Methane and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark J.

    2015-11-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and the interstellar medium, with an emphasis on amorphous and crystalline ices below ~70 K. Our goal is to add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on two of the simplest and most abundant components of icy bodies in the solar system - methane (CH4) and carbon dioxide (CO2). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 70 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  8. 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.

  9. Water formation through O2 + D pathway on cold silicate and amorphous water ice surfaces of interstellar interest.

    PubMed

    Chaabouni, H; Minissale, M; Manicò, G; Congiu, E; Noble, J A; Baouche, S; Accolla, M; Lemaire, J L; Pirronello, V; Dulieu, F

    2012-12-21

    The formation of the first monolayer of water molecules on bare dust grains is of primary importance to understand the growth of the icy mantles that cover dust in the interstellar medium. In this work, we explore experimentally the formation of water molecules from O(2) + D reaction on bare silicate surfaces that simulates the grains present in the diffuse interstellar clouds at visual extinctions (A(V) < 3 mag). For comparison, we also study the formation of water molecules on surfaces covered with amorphous water ice representing the dense clouds (A(V) ≥ 3 mag). Our studies focus on the formation of water molecules in the sub-monolayer and monolayer regimes using reflection absorption infrared spectroscopy and temperature-programmed desorption techniques. We provide the fractions of the products, such as D(2)O and D(2)O(2) molecules formed on three astrophysically relevant surfaces held at 10 K (amorphous olivine-type silicate, porous amorphous water ice, and nonporous amorphous water ice). Our results showed that the formation of D(2)O molecules occurs with an efficiency of about 55%-60% on nonporous amorphous water ice and about 18% on bare silicate grains surfaces. We explain the low efficiency of D(2)O water formation on the silicate surfaces by the desorption upon formation of certain products once the reaction occurs between O(2) and D atoms on the surface. A kinetic model taking into account the chemical desorption of newly formed water supports our conclusions.

  10. Radionuclides in Arctic sea ice: Tracers of sources, fates and ice transit time scales

    NASA Astrophysics Data System (ADS)

    Masqué, P.; Cochran, J. K.; Hirschberg, D. J.; Dethleff, D.; Hebbeln, D.; Winkler, A.; Pfirman, S.

    2007-08-01

    Arctic sea ice can incorporate sediment and associated chemical species during its formation in shallow shelf environments and can also intercept atmospherically transported material during transit. Release of this material in ice ablation areas (e.g. the Fram Strait) enhances fluxes of both sediments and associated species in such areas. We have used a suite of natural ( 7Be, 210Pb) and anthropogenic ( 137Cs, 239Pu, 240Pu) radionuclides in sea ice, sea-ice sediments (SIS), sediment trap material and bottom sediments from the Fram Strait to estimate transit times of sea ice from source to ablation areas, calculate radionuclide fluxes to the Fram Strait and investigate the role of sea-ice entrained sediments in sedimentation processes. Sea ice intercepts and transports the atmospherically supplied radionuclides 7Be and 210Pb, which are carried in the ice and are scavenged by any entrained SIS. All of the 7Be and most of the excess 210Pb measured in SIS collected in the Fram Strait are added to the ice during transit through the Arctic Ocean, and we use these radionuclides as chronometers to calculate ice transit times for individual ice floes. Transit times estimated from the 210Pb inventories in two ice cores are 1-3 years. Values estimated from the 7Be/ 210Pb excess activity ratio of SIS are about 3-5 years. Finally, equilibrium values of the activity ratio of 210Pb to its granddaughter 210Po in the ice cores indicate transit times of at least 2 years. These transit times are consistent with back-trajectory analyses of the ice floes. The latter, as well as the clay-mineral assemblage of the SIS (low smectite and high illite content), suggest that the sampled sea-ice floes originated from the eastern Siberian Arctic shelf seas such as the eastern Laptev Sea and the East Siberian Sea. This result is in agreement with the relatively low activities of 239,240Pu and 137Cs and the 240Pu/ 239Pu atom ratios (˜0.18, equivalent to that in global fallout) in SIS, indicating

  11. Photodissociation of methyl iodide adsorbed on low-temperature amorphous ice surfaces

    SciTech Connect

    DeSimone, Alice J.; Olanrewaju, Babajide O.; Grieves, Gregory A.; Orlando, Thomas M.

    2013-02-28

    Photodissociation dynamics of methyl iodide (CH{sub 3}I) adsorbed on both amorphous solid water (ASW) and porous amorphous solid water (PASW) has been investigated. The ejected ground-state I({sup 2}P{sub 3/2}) and excited-state I({sup 2}P{sub 1/2}) photofragments produced by 260- and 290-nm photons were detected using laser resonance-enhanced multiphoton ionization. In contrast to gas-phase photodissociation, (i) the I({sup 2}P{sub 3/2}) photofragment is favored compared to I({sup 2}P{sub 1/2}) at both wavelengths, (ii) I({sup 2}P{sub 3/2}) and I({sup 2}P{sub 1/2}) have velocity distributions that depend upon ice morphology, and (iii) I{sub 2} is produced on ASW. The total iodine [I({sup 2}P{sub 3/2})+I({sup 2}P{sub 1/2})+I{sub 2}] yield varies with substrate morphology, with greater yield from ASW than PASW using both 260- and 290-nm photons. Temperature-programmed desorption studies demonstrate that ice porosity enhances the trapping of adsorbed CH{sub 3}I, while pore-free ice likely allows monomer adsorption and the formation of two-dimensional CH{sub 3}I clusters. Reactions or collisions involving these clusters, I atomic fragments, or I-containing molecular fragments at the vacuum-surface interface can result in I{sub 2} formation.

  12. 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

  13. Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations

    NASA Astrophysics Data System (ADS)

    Mikhailov, E.; Vlasenko, S.; Martin, S. T.; Koop, T.; Pöschl, U.

    2009-12-01

    Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we present a conceptual framework for the interaction of amorphous aerosol particles with water vapor, outlining characteristic features and differences in comparison to crystalline particles. We used a hygroscopicity tandem differential mobility analyzer (H-TDMA) to characterize the hydration and dehydration of crystalline ammonium sulfate, amorphous oxalic acid and amorphous levoglucosan particles (diameter ~100 nm, relative humidity 5-95% at 298 K). The experimental data and accompanying Köhler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic growth. The results of these and related investigations lead to the following conclusions: (1) Many organic substances, including carboxylic acids, carbohydrates and proteins, tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous phases can be classified as glasses, rubbers, gels or viscous liquids. (2) Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at lower relative humidity than their crystalline counterparts. (3) In the course of hydration and dehydration, certain organic substances can form rubber- or gel-like structures (supramolecular networks) and undergo transitions between swollen and collapsed network structures. (4) Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water and may influence the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). Moreover, (semi-)solid amorphous phases may influence the uptake of gaseous photo-oxidants and the chemical transformation and aging of

  14. 2D ice from first principles: structures and phase transitions

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression the pentagonal structure becomes the most stable and persists up to ca. 2 GPa at which point square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. We also find a double layer AA stacked square ice phase, which clarifies the difference between experimental observations and earlier force field simulations. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and width.

  15. Crystallization of amorphous ice as the cause of comet P/Halley's outburst at 14 AU.

    PubMed

    Prialnik, D; Bar-Nun, A

    1992-01-01

    The post-perihelion eruption of comet P/Halley, detected in Feb. 1991 and believed to have started 3 months earlier, can be explained by crystallization of amorphous ice taking place in the interior of the porous nucleus, at depths a few tens of meters, accompanied by the release of trapped gases. Numerical calculations show that for a bulk density of 0.5 g cm-3 and a pore size of 1 millimicron crystallization occurs on the outbound leg of comet P/Halley's orbit, at heliocentric distances between 5 AU and 17 AU. The trapped gas is released and flows to the surface through the porous medium. It may also open wider channels, as the internal pressures obtained surpass the tensile strength of cometary ice. The outflowing gas carries with it grains of ice and dust, and thus can explain the large amounts of dust observed in the coma at 14.3 AU and beyond. The typical decline time of the process is found to be on the order of months, in agreement with observations. The rate of outgassing is two or three orders of magnitude higher than in quiescence. In an asymmetric, non-uniform nucleus--in contrast to the one-dimensional spherical model--the process should occur intermittently, such as was observed for comet P/Halley beyond 5 AU.

  16. Carbodiimide production from cyanamide by UV irradiation and thermal reaction on amorphous water ice.

    PubMed

    Duvernay, Fabrice; Chiavassa, Thierry; Borget, Fabien; Aycard, Jean-Pierre

    2005-02-01

    Cyanamide (NH(2)CN), an interstellar molecule, is a relevant molecule in prebiotic chemistry, because it can be converted into urea in liquid water. Carbodiimide (HNCNH), the most stable cyanamide isomer, is able to assemble amino acids into peptides. In this work, using FTIR spectroscopy, we show that carbodiimide can be formed from cyanamide at low temperature (10 K), by a photochemical process in argon matrix, in water matrix, or in solid film. We also report experimental evidence about the carbodiimide formation when cyanamide is condensed at low temperature (50-140 K) on an amorphous water ice surface, or when it is trapped in the water ice. The water ice acts as a catalyst. This isomerization reaction occurs at low temperature (T < 100 K), which agrees with those expected in the interstellar clouds composed of dust grains in which water is the most predominant compound. Finally, the hydrolysis reaction of cyanamide or carbodiimide leading to urea or isourea formation is not observed under our experimental conditions.

  17. 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.

  18. 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.

  19. 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.

  20. 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. PMID:26103047

  1. 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).

  2. Two Dimensional Ice from First Principles: Structures and Phase Transitions.

    PubMed

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J; Salzmann, Christoph G; Michaelides, Angelos

    2016-01-15

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ∼2  GPa, at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width.

  3. Two Dimensional Ice from First Principles: Structures and Phase Transitions

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J.; Salzmann, Christoph G.; Michaelides, Angelos

    2016-01-01

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ˜2 GPa , at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width.

  4. Two Dimensional Ice from First Principles: Structures and Phase Transitions.

    PubMed

    Chen, Ji; Schusteritsch, Georg; Pickard, Chris J; Salzmann, Christoph G; Michaelides, Angelos

    2016-01-15

    Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here, we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression, the pentagonal structure becomes the most stable and persists up to ∼2  GPa, at which point the square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and the width. PMID:26824547

  5. Effect of Water Ice Transition on Murchison Meteorite

    NASA Astrophysics Data System (ADS)

    Páchová, H.; Kletetschka, G.

    2014-12-01

    Uncertainty of magnetic field existence during formation of our solar system may be resolved by studying the details of carbonaceous meteorite. We chose Murchison meteorite to represent this group of carbonaceous meteorites. Murchison contains magnetic minerals like magnetite and pyrhottite. Their presence suggests that there were oxidizing conditions during the formation of these two minerals. This material may have been exposed to water-ice proximity that caused neo-formation of these two minerals. Such chemical change in magnetic mineralogy may resulted from multiple exposure of the meteorite material to transition between the liquid and solid water (ice). We expose Murchison fragments to multiple cycles of water/ice transition. Our data shows changes in both magnetic susceptibility and remanence. We interpret these findings in terms of the past nebular magnetic fields.

  6. 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.

  7. Crystallization of Gas-Laden Amorphous Water Ice, Activated by Heat Transport to its Subsurface Reservoirs, as Trigger of Huge Explosions of Comet 17P/Holmes

    NASA Astrophysics Data System (ADS)

    Sekanina, Zdenek

    2009-10-01

    Thick terrain layers, of the type recognized on the Deep Impact mission's close-up images of the nucleus of comet 9P/Tempel, and each 10^(13) to 10^(14) grams in mass, are suggested to be attractive candidate carriers of solid material released into the atmosphere during super-massive explosions (megabursts) and/or major fragmentation events. The properties of the 2007 megaburst of comet 17P/Holmes are shown to be consistent with the triggering mechanism being a transformation of gas-laden water ice from low-density amorphous phase to cubic phase (crystallization) in a reservoir located beneath a layer tens of meters thick. Molecules of highly volatile gases, carbon monoxide in particular, trapped in amorphous water ice and released during the phase transition (at 130 K to 150 K), are superheated, generating -- almost instantly in a runaway process -- a momentum needed to lift off, from the comet's nucleus, the mass of the layer and, after its collapse, to accelerate the pile of mostly microscopic dust debris to subkilometer-per-second velocities. Strongly temperature dependent, the crystallization rate increases progressively between about 100 K at aphelion and nearly 120 K (with about 10 percent of the ice in cubic phase) some 10 days before the megaburst and explosively afterwards, due to the release of the trapped volatiles and completion of the phase transition. The proposed model is in agreement with a wide range of relevant observations of the 2007 megaburst of comet 17P, including the event's post-perihelion timing, the water production rate, the CO-to-H_2O production rate ratio, the dust halo's expansion rate, and the energy involved. The observed recurrence rate of super-massive explosions of comet 17P is explained by heat transport through the terrain layers whose effective thermal conductivity is about 0.2 W m^(-1) K^(-1).

  8. Universal amorphous-amorphous transition in GexSe100‑x glasses under pressure

    NASA Astrophysics Data System (ADS)

    Yildirim, Can; Micoulaut, Matthieu; Boolchand, Punit; Kantor, Innokenty; Mathon, Olivier; Gaspard, Jean-Pierre; Irifune, Tetsuo; Raty, Jean-Yves

    2016-06-01

    Pressure induced structural modifications in vitreous GexSe100‑x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15–20 GPa, depending on the composition. This increase is attributed to the metallization event that can be traced with the red shift in Ge K edge energy which is also identified by the principal peak position of the structure factor. The densification mechanisms are studied in details by means of AIMD simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition.

  9. Universal amorphous-amorphous transition in GexSe100−x glasses under pressure

    PubMed Central

    Yildirim, Can; Micoulaut, Matthieu; Boolchand, Punit; Kantor, Innokenty; Mathon, Olivier; Gaspard, Jean-Pierre; Irifune, Tetsuo; Raty, Jean-Yves

    2016-01-01

    Pressure induced structural modifications in vitreous GexSe100−x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15–20 GPa, depending on the composition. This increase is attributed to the metallization event that can be traced with the red shift in Ge K edge energy which is also identified by the principal peak position of the structure factor. The densification mechanisms are studied in details by means of AIMD simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition. PMID:27273197

  10. Roughening transition in nanoporous hydrogenated amorphous germanium: Roughness correlation to film stress

    NASA Astrophysics Data System (ADS)

    Carroll, M. S.; Verley, J. C.; Sheng, J. J.; Banks, J.

    2007-03-01

    Hydrogenated amorphous germanium (a-Ge:H) is a material of interest for optoelectronic applications such as solar cells and radiation detectors because of the material's potential to extend the wavelength sensitivity of hydrogenated amorphous silicon (a-Si:H). An increase in porosity is observed in amorphous germanium compared to a-Si :H, and this increase in porosity has been correlated with a degradation of the electrical performance. Improved understanding of the mechanisms of porous formation in a-Ge :H films is therefore desirable in order to better control it. In this paper we describe a correlation between film stress and surface roughness, which evolves with increasing thickness of a-Ge :H. A roughening transition from planar two-dimensional growth to three-dimensional growth at a critical thickness less than 800Å results in a network of needlelike nanotrench cavities which stretch from the transition thickness to the surface in films up to 4000Å thick. Surface roughness measurements by atomic force microscope and transmission electron microscopy indicate that the transition is abrupt and that the roughness increases linearly after the transition thickness. The roughening transition thickness is, furthermore, found to correlate with the maxima of the integrated compressive stress. The compressive stress is reduced after this transition thickness due to the incorporation of nanovoids into the film that introduce tensile stress as the islands coalesce together. The roughening transition behavior is similar to that found in a general class of Volmer-Weber mode thin film deposition (e.g., Cu, Ag, and nonhydrogenated amorphous silicon), which offers additional insight into the underlying mechanisms of the stress and roughening in these a-Ge :H films. The suppression of the roughening transition by changing the kinetics of the deposition rates (e.g., slowing the deposition rate with a weak sputtering bias) is also observed and discussed.

  11. OPTICAL CONSTANTS OF AMORPHOUS AND CRYSTALLINE H{sub 2}O-ICE: 2.5-22 {mu}m (4000-455 cm{sup -1}) OPTICAL CONSTANTS OF H{sub 2}O-ICE

    SciTech Connect

    Mastrapa, R. M.; Dalle Ore, C. M.; Sandford, S. A.; Cruikshank, D. P.; Roush, T. L.

    2009-08-20

    Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H{sub 2}O-ice from 20-150 K in the wavelength range 2.5-22 {mu}m (4000-455 cm{sup -1}) and joined these results with previous measurement from 1.25 to 2.5 {mu}m. These optical constants improve on previous measurements by having better temperature and spectral resolution and can be used to create model spectra for comparison to spectra of solar system objects and interstellar materials. In this wavelength range, the infrared band shapes and positions of amorphous H{sub 2}O-ice are strongly dependent on deposition temperature. Amorphous and crystalline H{sub 2}O-ice have distinctive spectral bands at all wavelengths in this region with bands weakening and shifting to shorter wavelength in amorphous H{sub 2}O-ice compared to crystalline H{sub 2}O-ice. Some notable exceptions are the band near 6 {mu}m, which is stronger in amorphous H{sub 2}O-ice, and the bands near 4.5 {mu}m and 12.5 {mu}m, which shift to longer wavelength in amorphous H{sub 2}O-ice.

  12. Measurement of the adsorption energy difference between ortho- and para-D2 on an amorphous ice surface.

    PubMed

    Amiaud, L; Momeni, A; Dulieu, F; Fillion, J H; Matar, E; Lemaire, J-L

    2008-02-01

    Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

  13. Tuning electronic properties of graphene heterostructures by amorphous-to-crystalline phase transitions

    NASA Astrophysics Data System (ADS)

    Kulju, S.; Akola, J.; Prendergast, D.; Jones, R. O.

    2016-05-01

    The remarkable ability of phase change materials (PCM) to switch between amorphous and crystalline states on a nanosecond time scale could provide new opportunities for graphene engineering. We have used density functional calculations to investigate the structures and electronic properties of heterostructures of thin amorphous and crystalline films of the PCM GeTe (16 Å thick) and Ge2Sb2Te5 (20 Å) between graphene layers. The interaction between graphene and PCM is very weak, charge transfer is negligible, and the structures of the chalcogenide films differ little from those of bulk phases. A crystalline GeTe (111) layer induces a band gap opening of 80 meV at the Dirac point. This effect is absent for the amorphous film, but the Fermi energy shifts down along the Dirac cone by -60 meV. Ge2Sb2Te5 shows similar features, although inherent disorder in the crystalline rocksalt structure reduces the contrast in band structure from that in the amorphous structure. These features originate in charge polarization within the crystalline films, which show electromechanical response (piezoelectricity) upon compression, and show that the electronic properties of graphene structures can be tuned by inducing ultrafast structural transitions within the chalcogenide layers. Graphene can also be used to manipulate the structural state of the PCM layer and its electronic and optical properties.

  14. Helium Diffusion Through H2O and D2O Amorphous Ice: A Lattice Inverse Istope Effect

    SciTech Connect

    Daschbach, John L.; Schenter, Gregory K.; Ayotte, Patrick; Smith, R. Scott; Kay, Bruce D.

    2004-05-14

    The diffusion of helium through both H2O and D2O amorphous solid water (ASW) has been measured between 55K and 110K. We find the diffusion rate is dependent on the isotopic composition of the ASW lattice. This lattice isotope effect is the "inverse" of a normal isotope effect, in that diffusion is faster in the heavier (D2O) isotope. Transition state theory calculations show that the isotope effect is due to a tight transition state results in a large zero point vibrational energy differences at the transition state predominantly due to hindered rotations of water in the lattice.

  15. Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl4

    DOE PAGES

    Liu, Hanyu; Tse, John S.; Hu, Michael Y.; Bi, Wenli; Zhao, Jiyong; Alp, E. Ercan; Pasternak, Moshe; Taylor, R. Dean; Lashley, Jason C.

    2015-10-27

    The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres,more » we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.« less

  16. The use of inverse gas chromatography and gravimetric vapour sorption to study transitions in amorphous lactose.

    PubMed

    Ambarkhane, Ameet V; Pincott, Kim; Buckton, Graham

    2005-04-27

    The aim of this study was to measure the glass transition of amorphous lactose under well-controlled temperature and humidity, using inverse gas chromatography (IGC) and to relate these data to gravimetric vapour sorption experiments. Amorphous lactose (spray-dried) was exposed to a stepwise increment in the relative humidity (%RH) under isothermal conditions in an IGC. At the end of each conditioning step a decane injection was made, and the retention volumes were calculated using the maximum peak height (V(max)) method. The pressure drop across the column was recorded using the pressure transducers. These measurements were performed at various temperatures from 25 to 40 degrees C. The extent of water sorption at identical humidity (%RH) and temperature conditions was determined gravimetrically using dynamic vapour sorption (DVS). At each T, it was possible to determine: (1) a transition at low RH relating to the onset of mobility; (2) changes in retention volume relating to the point, where T(g) = T; (3) changes in pressure drop, which were related to the sample collapse. The rate and extent of water sorption was seen to alter at T(g) and also at a collapse point. Combinations of temperature and critical %RH (%cRH required to lower the dry glass transition temperature to the experimental temperature) obtained from IGC were comparable to those obtained from DVS. It was shown that at each T, the sample spontaneously crystallised, when T(g) was 32 degrees C below T. Inverse gas chromatograph can be used in this novel way to reveal the series of transitions that occur in amorphous materials.

  17. Interaction of atomic and molecular deuterium with a nonporous amorphous water ice surface between 8 and 30 K.

    PubMed

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

    2007-10-14

    Molecular and atomic interactions of hydrogen on dust grains covered with ice at low temperatures are key mechanisms for star formation and chemistry in dark interstellar clouds. We have experimentally studied the interaction of atomic and molecular deuterium on nonporous amorphous water ice surfaces between 8 and 30 K, in conditions compatible with an extrapolation to an astrophysical context. The adsorption energy of D(2) presents a wide distribution, as already observed on porous water ice surfaces. At low coverage, the sticking coefficient of D(2) increases linearly with the number of deuterium molecules already adsorbed on the surface. Recombination of atomic D occurs via a prompt reaction that releases molecules into the gas phase. Part of the newly formed molecules are in vibrationally excited states (v=1-7). The atomic recombination efficiency increases with the presence of D(2) molecules already adsorbed on the water ice, probably because these increase the sticking coefficient of the atoms, as in the case of incident D(2). We have measured the atomic recombination efficiency in the presence of already absorbed D(2), as it is expected to occur in the interstellar medium. The recombination efficiency decreases rapidly with increasing temperature and is zero at 13 K. This allows us to estimate an upper limit to the value of the atom adsorption energy E(a) approximately 29 meV, in agreement with previous calculations.

  18. Thermal analysis of frozen solutions: multiple glass transitions in amorphous systems.

    PubMed

    Sacha, Gregory A; Nail, Steven L

    2009-09-01

    Frozen aqueous solutions of sucrose exhibit two "glass transition-like" thermal events below the melting endotherm of ice when examined by DSC, but the physical basis of these events has been a source of some disagreement. In this study, a series of sugars, including sucrose, lactose, trehalose, maltose, fructose, galactose, fucose, mannose, and glucose were studied by modulated DSC and freeze-dry microscopy in order to better understand whether sucrose is unique in any way with respect to this behavior, as well as to explore the physical basis, and the pharmaceutical significance of these multiple transitions. Double transitions were found to be a common feature of all sugars examined. The results are consistent with both thermal events being glass transitions in that (1) both events have second-order characteristics that appear in the reversing signals, (2) annealing experiments reveal that enthalpy recovery is associated with each transition, and (3) Lissajous plots indicate that no detectable latent heat of melting is associated with either transition. The data in this study are consistent with the idea that the lower temperature transition arises from a metastable glassy mixture containing more water than that in the maximally freeze-concentrated solute. Freeze-dry microscopy observations show that for all of the sugars examined, it is the higher temperature transition that is associated with structural collapse during freeze-drying. There is no apparent pharmaceutical significance associated with the lower-temperature transition. PMID:19384925

  19. Molecular relaxation behavior and isothermal crystallization above glass transition temperature of amorphous hesperetin.

    PubMed

    Shete, Ganesh; Khomane, Kailas S; Bansal, Arvind Kumar

    2014-01-01

    The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature.

  20. Ice age at the Middle-Late Jurassic transition?

    NASA Astrophysics Data System (ADS)

    Dromart, G.; Garcia, J.-P.; Picard, S.; Atrops, F.; Lécuyer, C.; Sheppard, S. M. F.

    2003-08-01

    A detailed record of sea surface temperatures in the Northern Hemisphere based on migration of marine invertebrate fauna (ammonites) and isotopic thermometry (δ18O values of shark tooth enamel) indicates a severe cooling at the Middle-Late Jurassic transition (MLJT), about 160 Ma ago. The magnitude of refrigeration (1-3°C for lower middle latitudes) and its coincidence in time with an abrupt global-scale fall of sea level documented through sequence stratigraphy are both suggestive of continental ice formation at this time. Ice sheets may have developed over the high-latitude mountainous regions of Far-East Russia. The drastic cooling just post-dated the Middle-Late Callovian widespread deposition of organic-rich marine sediments (e.g. northwestern Europe, Central Atlantic, and Arabian Peninsula). This thermal deterioration can thus be ascribed to a downdraw in atmospheric CO2 via enhanced organic carbon burial which acted as a negative feedback effect (i.e. the inverse greenhouse effect). The glacial episode of the MLJT climaxed in the Late Callovian, lasted about 2.6 Myr, and had a pronounced asymmetrical pattern composed of an abrupt (˜0.8 Myr) temperature fall opposed to a long-term (˜1.8 Myr), stepwise recovery. The glacial conditions at the MLJT reveal that atmospheric CO2 levels could have dropped temporarily to values lower than 500 ppmv during Mesozoic times.

  1. Physico-ecobiogeochemistry of East Antarctic pack ice during the winter-spring transition

    NASA Astrophysics Data System (ADS)

    Meiners, Klaus M.; Norman, Louiza; Granskog, Mats A.; Krell, Andreas; Heil, Petra; Thomas, David N.

    2011-05-01

    Our study provides information on the relationships between physical, chemical, and biological properties of East Antarctic sea ice sampled as part of the Sea Ice Physics and Ecosystem eXperiment (SIPEX) during the winter-spring transition in 2007. The sampled sea ice showed a high contribution of granular ice, indicating the turbulent conditions during sea ice formation off East Antarctica. The sea ice was cold, with brine volumes often below or very close to the theoretical percolation threshold of sea ice. Dissolved inorganic nutrient concentrations showed both positive and negative deviations from theoretical dilution lines, indicating both nutrient uptake as well as nutrient remineralisation in sea ice brines. Cold temperatures, high brine salinities, and low brine volumes limited high ice algal biomass to the warmer and more porous sea ice layers at the ice-water interface. We hypothesise that East Antarctic sea ice shows generally low ice algal biomass accumulation due to a combination of relatively low snow-loading, relatively cold ice temperatures, and short persistence of sea ice into the warm forcing regime, all of which prevent the development of significant internal and surface communities.

  2. Upper critical fields and superconducting transition temperatures of some zirconium-base amorphous transition-metal alloys

    NASA Astrophysics Data System (ADS)

    Karkut, M. G.; Hake, R. R.

    1983-08-01

    Superconducting upper critical fields Hc2(T), transition temperatures Tc and normal-state electrical resistivities ρn have been measured in the amorphous transition-metal alloy series Zr1-xCox, Zr1-xNix, (Zr1-xTix)0.78Ni0.22, and (Zr1-xNbx)0.78Ni0.22. Structural integrity of these melt-spun alloys is indicated by x-ray, density, bend-ductility, normal-state electrical resistivity, superconducting transition width, and mixed-state flux-pinning measurements. The specimens display Tc=2.1-3.8 K, ρn=159-190 μΩ cm, and |(dHc2dT)Tc|=28-36 kG/K. These imply electron mean free paths l~2-6 Å, zero-temperature Ginzburg-Landau coherence distances ξG0~50-70 Å, penetration depths λG0~(7-10)×103 Å, and extremely high dirtiness parameters ξ0l~300-1300. All alloys display Hc2(T) curves with negative curvature and (with two exceptions) fair agreement with the standard dirty-limit theory of Werthamer, Helfand, Hohenberg, and Maki (WHHM) for physically reasonable values of spin-orbit-coupling induced, electron-spin-flip scattering time τso. This is in contrast to the anomalously elevated Hc2(T) behavior which is nearly linear in T that is observed by some, and the unphysically low-τso fits to WHHM theory obtained by others, for various amorphous alloys. Current ideas that such anomalies may be due to alloy inhomogeneity are supported by present results on two specimens for which relatively low-τso fits of Hc2(T) to WHHM theory are coupled with superconductive evidence for inhomogeneity: relatively broad transitions at Tc and Hc2 current-density-dependent transitions at Hc2 and (in one specimen) a J-dependent, high-H (>Hc2), resistive "beak effect." In the Zr1-xCox and Zr1-xNix series, Tc decreases linearly with x (and with unfilled-shell average electron-to-atom ratio < ea > in the range 5.05<=< ea ><=6.40 in fair agreement with previous results for these systems and contrary to the Tc vs < ea > behavior of both amorphous and crystalline transition-metal alloys formed

  3. Thermal history of comets during residence in the Oort cloud - Effect of radiogenic heating in combination with the very low thermal conductivity of amorphous ice

    NASA Technical Reports Server (NTRS)

    Haruyama, Jun'ichi; Yamamoto, Tetsuo; Mizutani, Hitoshi; Greenberg, J. M.

    1993-01-01

    The thermal history of long-period comets initially composed of amorphous ice is studied. It is shown that such comets with a small nucleus thermal conductivity (kappa) experience a runaway increase in the internal temperature during residence in the Oort cloud. The temperature increase is a result of rapid release of the latent heat at crystallization triggered by gradual heating due to decay of radioactive nuclides. The time of the runaway temperature increase is about ten to a hundred million years after the formation of the nucleus depending on the fraction of refractory grains which contain radioactive nuclides. Most of the amorphous ice in the nuclides except just beneath the surface transforms into crystalline ice due to the runaway temperature increase. This implies that the ice in short-period comets is crystalline from the initial time when the long-period comet becomes a short-period one. In comets with large kappa the temperature does not rise much compared to the small kappa case and the initial amorphous ice is preserved. A criterion for the crystallization of the nucleus ice is derived.

  4. Stoichiometry determined exchange interactions in amorphous ternary transition metal oxides: Theory and experiment

    SciTech Connect

    Hu, Shu-jun; Yan, Shi-shen Zhang, Yun-peng; Zhao, Ming-wen; Kang, Shi-shou; Mei, Liang-mo

    2014-07-28

    Amorphous transition metal oxides exhibit exotic transport and magnetic properties, while the absence of periodic structure has long been a major obstacle for the understanding of their electronic structure and exchange interaction. In this paper, we have formulated a theoretical approach, which combines the melt-quench approach and the spin dynamic Monte-Carlo simulations, and based on it, we explored amorphous Co{sub 0.5}Zn{sub 0.5}O{sub 1−y} ternary transition metal oxides. Our theoretical results reveal that the microstructure, the magnetic properties, and the exchange interactions of Co{sub 0.5}Zn{sub 0.5}O{sub 1−y} are strongly determined by the oxygen stoichiometry. In the oxygen-deficient sample (y > 0), we have observed the long-range ferromagnetic spin ordering which is associated with the non-stoichiometric cobalt-rich region rather than metallic clusters. On the other hand, the microstructure of stoichiometric sample takes the form of continuous random networks, and no long-range ferromagnetism has been observed in it. Magnetization characterization of experimental synthesized Co{sub 0.61}Zn{sub 0.39}O{sub 1−y} films verifies the relation between the spin ordering and the oxygen stoichiometry. Furthermore, the temperature dependence of electrical transport shows a typical feature of semiconductors, in agreement with our theoretical results.

  5. Phase transition of an ice-proton system into a Bernal-Fowler state

    NASA Astrophysics Data System (ADS)

    Ryzhkin, Ivan A.; Petrenko, Victor F.

    2000-11-01

    We present a microscopic model of an ice-proton system. A mean-field approximation was used to study the disorder-partial order transition in the proton subsystem of ice. This analysis revealed that ice rules arise as a result of the second-order phase transition. From the theoretical point of view, above the phase-transition temperature the protons should be distributed over all possible positions without any restrictions. However, in real ice under zero pressure the disordering of the proton lattice apparently leads to ice melting. We also derived the Landau-Ginzburg equation suitable for the model under consideration and showed that the theories based on ice rules must be modified when one is working in the region of the critical temperature.

  6. Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media.

    PubMed

    Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

    2014-10-01

    The commercial and clinical success of amorphous solid dispersions (ASD) in overcoming the low bioavailability of poorly soluble molecules has generated momentum among pharmaceutical scientists to advance the fundamental understanding of these complex systems. A major limitation of these formulations stems from the propensity of amorphous solids to crystallize upon exposure to aqueous media. This study was specifically focused on developing analytical techniques to evaluate the impact of polymers on the crystallization behavior during dissolution, which is critical in designing effective amorphous formulations. In the study, the crystallization and polymorphic conversions of a model compound, nifedipine, were explored in the absence and presence of polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and HPMC-acetate succinate (HPMC-AS). A combination of analytical approaches including Raman spectroscopy, polarized light microscopy, and chemometric techniques such as multivariate curve resolution (MCR) were used to evaluate the kinetics of crystallization and polymorphic transitions as well as to identify the primary route of crystallization, i.e., whether crystallization took place in the dissolving solid matrix or from the supersaturated solutions generated during dissolution. Pure amorphous nifedipine, when exposed to aqueous media, was found to crystallize rapidly from the amorphous matrix, even when polymers were present in the dissolution medium. Matrix crystallization was avoided when amorphous solid dispersions were prepared, however, crystallization from the solution phase was rapid. MCR was found to be an excellent data processing technique to deconvolute the complex phase transition behavior of nifedipine.

  7. Influence of compression on water sorption, glass transition, and enthalpy relaxation behavior of freeze-dried amorphous sugar matrices.

    PubMed

    Imamura, Koreyoshi; Kagotani, Ryo; Nomura, Mayo; Tanaka, Kazuhiro; Kinugawa, Kohshi; Nakanishi, Kazuhiro

    2011-04-15

    An amorphous matrix comprised of sugar molecules are frequently used in the pharmaceutical industry. The compression of the amorphous sugar matrix improves the handling. Herein, the influence of compression on the water sorption of an amorphous sugar matrix was investigated. Amorphous sugar samples were prepared by freeze-drying, using several types of sugars, and compressed at 0-443 MPa. The compressed amorphous sugar samples as well as uncompressed samples were rehumidified at given RHs, and the equilibrium water content and glass transition temperature (T(g)) were then measured. Compression resulted in a decrease in the equilibrium water content of the matrix, the magnitude of which was more significant for smaller sized sugars. Diffusivity of water vapor in the sample was also decreased to one-hundredth by the compression. The T(g) value for a given RH remained unchanged, irrespective of the compression. Accordingly, the decrease in T(g) with increasing water content increased as the result of compression. The structural relaxation of the amorphous sugar matrices were also examined and found to be accelerated to the level of a non-porous amorphous sugar matrix as the result of the compression. The findings indicate that pores contained in freeze-dried sugar samples interfere with the propagation of structural relaxation.

  8. Influence of compression on water sorption, glass transition, and enthalpy relaxation behavior of freeze-dried amorphous sugar matrices.

    PubMed

    Imamura, Koreyoshi; Kagotani, Ryo; Nomura, Mayo; Tanaka, Kazuhiro; Kinugawa, Kohshi; Nakanishi, Kazuhiro

    2011-04-15

    An amorphous matrix comprised of sugar molecules are frequently used in the pharmaceutical industry. The compression of the amorphous sugar matrix improves the handling. Herein, the influence of compression on the water sorption of an amorphous sugar matrix was investigated. Amorphous sugar samples were prepared by freeze-drying, using several types of sugars, and compressed at 0-443 MPa. The compressed amorphous sugar samples as well as uncompressed samples were rehumidified at given RHs, and the equilibrium water content and glass transition temperature (T(g)) were then measured. Compression resulted in a decrease in the equilibrium water content of the matrix, the magnitude of which was more significant for smaller sized sugars. Diffusivity of water vapor in the sample was also decreased to one-hundredth by the compression. The T(g) value for a given RH remained unchanged, irrespective of the compression. Accordingly, the decrease in T(g) with increasing water content increased as the result of compression. The structural relaxation of the amorphous sugar matrices were also examined and found to be accelerated to the level of a non-porous amorphous sugar matrix as the result of the compression. The findings indicate that pores contained in freeze-dried sugar samples interfere with the propagation of structural relaxation. PMID:21291973

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

    SciTech Connect

    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 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.

  10. Possible Existence of Two Amorphous Phases of D-Mannitol Related by a First-Order Transition

    NASA Astrophysics Data System (ADS)

    Zhu, Men; Wang, Jun-Qiang; Perepezko, John; Yu, Lian

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase (Phase X). The enthalpy of Phase X is roughly halfway between those of the known amorphous and crystalline phases. The amorphous nature of Phase X is suggested by its absence of birefringence, transparency, broad X-ray diffraction, and broad Raman and NIR spectra. Phase X has greater molecular spacing, higher molecular order, fewer intra- and more inter-molecular hydrogen bonds than the normal liquid. On fast heating, Phase X transforms back to SCL near 330 K. Upon temperature cycling, it shows a glass-transition-like change of heat capacity. The presence of D-sorbitol enables a first-order liquid-liquid transition (LLT) from SCL to Phase X. This is the first report of polyamorphism at 1 atm for a pharmaceutical relevant substance. As amorphous solids are explored for many applications, polyamorphism could offer a tool to engineer the properties of materials. (Ref: M. Zhu et al., J. Chem. Phys. 2015, 142, 244504)

  11. A calorimetric study on the low temperature dynamics of doped ice V and its reversible phase transition to hydrogen ordered ice XIII.

    PubMed

    Salzmann, Christoph G; Radaelli, Paolo G; Finney, John L; Mayer, Erwin

    2008-11-01

    Doped ice V samples made from solutions containing 0.01 M HCl (DCl), HF (DF), or KOH (KOD) in H(2)O (D(2)O) were slow-cooled from 250 to 77 K at 0.5 GPa. The effect of the dopant on the hydrogen disorder --> order transition and formation of hydrogen ordered ice XIII was studied by differential scanning calorimetry (DSC) with samples recovered at 77 K. DSC scans of acid-doped samples are consistent with a reversible ice XIII <--> ice V phase transition at ambient pressure, showing an endothermic peak on heating due to the hydrogen ordered ice XIII --> disordered ice V phase transition, and an exothermic peak on subsequent cooling due to the ice V --> ice XIII phase transition. The equilibrium temperature (T(o)) for the ice V <--> ice XIII phase transition is 112 K for both HCl doped H(2)O and DCl doped D(2)O. From the maximal enthalpy change of 250 J mol(-1) on the ice XIII --> ice V phase transition and T(o) of 112 K, the change in configurational entropy for the ice XIII --> ice V transition is calculated as 2.23 J mol(-1) K(-1) which is 66% of the Pauling entropy. For HCl, the most effective dopant, the influence of HCl concentration on the formation of ice XIII was determined: on decreasing the concentration of HCl from 0.01 to 0.001 M, its effectiveness is only slightly lowered. However, further HCl decrease to 0.0001 M drastically lowered its effectiveness. HF (DF) doping is less effective in inducing formation of ice XIII than HCl (DCl) doping. On heating at a rate of 5 K min(-1), kinetic unfreezing starts in pure ice V at approximately 132 K, whereas in acid doped ice XIII it starts at about 105 K due to acceleration of reorientation of water molecules. KOH doping does not lead to formation of hydrogen ordered ice XIII, a result which is consistent with our powder neutron diffraction study (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758). We further conjecture whether or not ice XIII has a stable region in

  12. Structure of Water Ice in the Solar System

    NASA Technical Reports Server (NTRS)

    Blake, David; Jenniskens, Peter; Chang, Sherwood (Technical Monitor)

    1996-01-01

    Nearly all of the properties of solar system ices (chemical reaction rates, volatile retention and release, vaporization behavior, thermal conductivity, infrared spectral characteristics and the like) are a direct consequence of ice structure. However, the characterization of astrophysical ices and their laboratory analogs has typically utilized indirect measurements which yield phenomenological interpretations. When water ice is vapor-deposited at 14 K and warmed until it volatilizes in moderate vacuum, the ice undergoes a series of amorphous to amorphous and amorphous to crystalline structural transitions which we have characterized by diffraction methods. These structural transitions correlate with and underlie many phenomena observed in laboratory infrared and gas release experiments. The elucidation of the dynamic structural changes which occur in vapor-deposited water ice as a function of time, temperature and radiation history allows for the more complete interpretation of remote observations of astrophysical ices and their laboratory analogs.

  13. Coercivity of domain wall motion in thin films of amorphous rare earth-transition metal alloys

    NASA Technical Reports Server (NTRS)

    Mansuripur, M.; Giles, R. C.; Patterson, G.

    1991-01-01

    Computer simulations of a two dimensional lattice of magnetic dipoles are performed on the Connection Machine. The lattice is a discrete model for thin films of amorphous rare-earth transition metal alloys, which have application as the storage media in erasable optical data storage systems. In these simulations, the dipoles follow the dynamic Landau-Lifshitz-Gilbert equation under the influence of an effective field arising from local anisotropy, near-neighbor exchange, classical dipole-dipole interactions, and an externally applied field. Various sources of coercivity, such as defects and/or inhomogeneities in the lattice, are introduced and the subsequent motion of domain walls in response to external fields is investigated.

  14. Scaling description of the yielding transition in soft amorphous solids at zero temperature

    PubMed Central

    Lin, Jie; Lerner, Edan; Rosso, Alberto; Wyart, Matthieu

    2014-01-01

    Yield stress materials flow if a sufficiently large shear stress is applied. Although such materials are ubiquitous and relevant for industry, there is no accepted microscopic description of how they yield, even in the simplest situations in which temperature is negligible and in which flow inhomogeneities such as shear bands or fractures are absent. Here we propose a scaling description of the yielding transition in amorphous solids made of soft particles at zero temperature. Our description makes a connection between the Herschel–Bulkley exponent characterizing the singularity of the flow curve near the yield stress Σc, the extension and duration of the avalanches of plasticity observed at threshold, and the density P(x) of soft spots, or shear transformation zones, as a function of the stress increment x beyond which they yield. We argue that the critical exponents of the yielding transition may be expressed in terms of three independent exponents, θ, df, and z, characterizing, respectively, the density of soft spots, the fractal dimension of the avalanches, and their duration. Our description shares some similarity with the depinning transition that occurs when an elastic manifold is driven through a random potential, but also presents some striking differences. We test our arguments in an elasto-plastic model, an automaton model similar to those used in depinning, but with a different interaction kernel, and find satisfying agreement with our predictions in both two and three dimensions. PMID:25246567

  15. Superionic-Superionic Phase Transitions in Body-Centered Cubic H2O Ice

    NASA Astrophysics Data System (ADS)

    Hernandez, Jean-Alexis; Caracas, Razvan

    2016-09-01

    From first-principles molecular dynamics, we investigate the relation between the superionic proton conduction and the behavior of the O - H ⋯O bond (ice VII' to ice X transition) in body-centered-cubic (bcc) H2O ice between 1300 and 2000 K and up to 300 GPa. We bring evidence that there are three distinct phases in the superionic bcc stability field. A first superionic phase characterized by extremely fast diffusion of highly delocalized protons (denoted VII'' hereinafter) is stable at low pressures. A first-order transition separates this phase from a superionic VII' , characterized by a finite degree of localization of protons along the nonsymmetric O - H ⋯O bonds. The transition is identified in structural, energetic, and elastic analysis. Upon further compression a second-order phase transition leads to the superionic ice X with symmetric O - H - O bonds.

  16. Ice Phase Transitions by Atmospheric Aerosol Particles of Varied Composition

    NASA Astrophysics Data System (ADS)

    DeMott, P. J.; Prenni, A. J.; Archuleta, C. A.; Kreidenweis, S. M.; Cziczo, D. J.; Murphy, D. M.; Thomson, D. S.

    2001-12-01

    This paper describes laboratory and field study measurements of water uptake and ice nucleation by surrogate and real atmospheric aerosol particles. Laboratory measurements of water uptake are made using a humidified tandem differential mobility analyzer (HTDMA) and a cloud condensation nucleus (CCN) instrument operating at 20 to 30 \\deg C. Measurements of ice nucleation are made using a continuous flow ice-thermal diffusion chamber (CFDC) operated to -60 \\deg C for relevance toward understanding cirrus cloud formation. Extending earlier laboratory studies of single composition aerosols, we are investigating water uptake and ice nucleation rates and mechanisms by mixed aerosols of various types, including sulfate-nitrate, sulfate-organic, mineral oxide-sulfate and black carbon-sulfate types. Methodologies will be described and results will be summarized. Field measurements are planned to study heterogeneous and homogeneous ice nucleation by free tropospheric aerosols at a high altitude laboratory. The field study will include measurements of the compositions of aerosols that activate ice formation by homogeneous and heterogeneous ice nucleation mechanisms. This aspect of the study will be facilitated by interfacing the CFDC to the PALMS (Particle Analysis by Laser Mass Spectrometry) instrument. This combined instrument system was tested in the laboratory to quantify sampling efficiencies and validate specificity for sampling ice nucleus aerosol particles. Initial field data, if available at conference time, will be compared and contrasted with the results obtained for laboratory surrogate particles.

  17. IceCube simulation production and the transition to IceProd2

    NASA Astrophysics Data System (ADS)

    Schultz, David

    2016-04-01

    IceCube's simulation production relies largely on dynamic, heterogeneous resources spread around the world. Datasets consist of many thousands of job workflow subsets running in parallel as directed acyclic graphs (DAGs) and using varying resources. IceProd is a set of Python daemons which process job workflow and maintain configuration and status information on jobs before, during, and after processing. IceProd manages a complex workflow of DAGs to distribute jobs across all computing grids and optimize resource usage. IceProd2 is a new version of IceProd with substantial increases in security, reliability, scalability, and ease of use. It is undergoing testing and will be deployed this fall.

  18. Radiation-induced crystalline-to-amorphous transition in intermetallic compounds of the Cu-Ti alloy system

    SciTech Connect

    Lam, N.Q.; Okamoto, P.R.; Devanathan, R. ); Sabochick, M.J. . Computer Applications Div.)

    1992-02-01

    Recent progress in molecular-dynamics studies of radiation-induced crystalline-to-amorphous transition in the ordered intermetallic compounds of the Cu-Ti system is discussed. The effect of irradiation was simulated by the generation of Frenkel pairs,which resulted in both the formation of stable point defects and chemical disorder upon defect recombination. The thermodynamic, structural and mechanical responses of the compounds during irradiation were determined by monitoring changes in the system potential energy, volume expansion, pair correlation function, diffraction patterns, and elastic constants. It was found that the intermetallics Cu{sub 4}Ti{sub 3}, CuTi, and CuTi{sub 2} could be rendered amorphous by the creation of Frenkel pairs, but Cu{sub 4}Ti could not, consistent with experimental observations during electron irradiation. However, the simulations showed that Cu{sub 4}Ti did become amorphous when clusters of Frenkel pairs were introduced, indicating that this compound may be susceptible to amorphization by heavy-ion bombardment. A generalization of the Lindemann criterion was used to develop a thermodynamic description of solid-state amorphization as a disorder- induced melting process.

  19. The Medieval Warm/Little Ice Age Transition as Recorded by Ice Caps in East Greenland

    NASA Astrophysics Data System (ADS)

    Lowell, T. V.; Kelly, M. A.; Hall, B. L.; Bennike, O.; Honsaker, W. M.; Levy, L.; Lusas, A.

    2011-12-01

    The spatial-temporal distribution of late Holocene temperature changes over the last 2000 yr is still being defined. The high Arctic is often represented by the borehole tem-perature records from GISP and Dye 3. These both show a distinct, but different magni-tude, Medieval warm interval from ~500 to ~1200 AD, with two cold intervals after 1500 AD. However small glaciers in the high Arctic appear reflect a more complex late Holo-cene pattern. On the eastern coast of Greenland two ice caps record a warm interval from 400 AD to 600 AD but cooling after that. These ice caps, Istorvet ,on the coast beside the cold East Greenland Current, and Bregne ice cap, ~ 100 km inland, have yielded organic remains from > 50 sites. A preliminary interpretation is that the organic remains record the last time these ice caps were as small or smaller than the present configuration. Exposure ages show these ice caps reached their post glacial maximum extent within the last 1000 yr. The Istorvet ice cap is thought to show initial cooling at ~AD 884 and an advance to within 500 m of the Little Ice Age extent at AD 1022 and its fullest extent at 1125 AD. Core sediments suggest that extent was maintained until 1750 AD. Results from the inland site indicate a retracted ice cap from AD 1054 to 1393, followed by expansion. Although some of these events appear to have correlative events recorded in SST or sea ice near Iceland. Taken together they appear to have a different signature than lo-cations further south. This may indicate that temperature patterns at high latitudes are only partly coupled with those at lower latitudes.

  20. Effect of patch borders on coercivity in amorphous rare earth-transition metal thin films

    NASA Technical Reports Server (NTRS)

    Patterson, G.; Fu, H.; Giles, R. C.; Mansuripur, M.

    1991-01-01

    The coercivity at the micron scale is a very important property of magneto-optical media. It is a key factor that determines the magnetic domain wall movement and domain reversal. How the coercivity is influenced by a special type of patch borders is discussed. Patch formation is a general phenomenon in growth processes of amorphous rare earth transition metal thin films. Different patches may stem from different seeds and the patch borders are formed when they merge. Though little is known about the exact properties of the borders, we may expect that the exchange interaction at the patch border is weaker than that within a patch, since there is usually a spatial gap between two patches. Computer simulations were performed on a 2-D hexagonal lattice consisting of 37 complete patches with random shape and size. From the series of simulations we may conclude that the domain in the patch with borders of 30 percent exchange strength can expand most easily to the whole lattice, because the exchange strength can expand most easily to the whole lattice, because the exchange strength of the border is not too high to prevent the domain from growing within the patch and it is not too low to prevent the domain from expanding beyond the patch.

  1. Structural transition and amorphization in compressed α - Sb 2 O 3

    DOE PAGES

    Zhao, Zhao; Zeng, Qiaoshi; Zhang, Haijun; Wang, Shibing; Hirai, Shigeto; Zeng, Zhidan; Mao, Wendy L.

    2015-05-27

    Sb₂O₃-based materials are of broad interest in materials science and industry. High-pressure study using diamond anvil cells shows promise in obtaining new crystal and electronic structures different from their pristine states. Here, we conducted in situ angle dispersive synchrotron x-ray-diffraction and Raman spectroscopy experiments on α-Sb₂O₃ up to 50 GPa with neon as the pressure transmitting medium. A first-order structural transition was observed in between 15 and 20 GPa, where the cubic phase I gradually transformed into a layered tetragonal phase II through structural distortion and symmetry breaking. To explain the dramatic changes in sample color and transparency, we performedmore » first-principles calculations to track the evolution of its density of states and electronic structure under pressure. At higher pressure, a sluggish amorphization was observed. Our results highlight the structural connections among the sesquioxides, where the lone electron pair plays an important role in determining the local structures.« less

  2. Magnetic and Transport Properties of Amorphous GdGe Alloys near the Metal-Insulator Transition

    NASA Astrophysics Data System (ADS)

    Sinenian, Nareg; Smith, D. J.

    2005-03-01

    The temperature and field dependence of magnetization and conductivity of amorphous Ge doped with the rare earth Gd (a-GdxGe1-x) has been measured for a range of x near the metal-insulator transition 0.08 < x <0.25). As in previous work on a-Gd-Si, high field magnetization and low field susceptibility per Gd atom in the paramagnetic state above the spin glass freezing temperature are significantly suppressed below that of non-interacting Gd, indicative of strong antiferromagnetic interactions. However, unlike a-Gd-Si, the low field susceptibility does not fit a Curie-Weiss law, instead showing 1/T^α dependence. As in a-Gd-Si, Gd causes localization of charge carriers below a characteristic temperature T*, which is also an onset of significant negative magnetoresistance MR. Both T* and the magnitude of MR are however significantly less in a-Gd-Ge than in comparable a-Gd-Si alloys. It is suggested that the large effects of matrix (Ge vs Si) are due to differences in dielectric constant and bandgap, which cause changes in screening, thereby altering the effect of the magnetic moments of Gd on both localization of carriers and on the indirect mediated Gd-Gd exchange interactions. We thank the NSF for support.

  3. Structural transition in sputter-deposited amorphous germanium films by aging at ambient temperature

    NASA Astrophysics Data System (ADS)

    Okugawa, M.; Nakamura, R.; Ishimaru, M.; Watanabe, K.; Yasuda, H.; Numakura, H.

    2016-06-01

    The structure of amorphous Ge (a-Ge) films prepared by sputter-deposition and the effects of aging at ambient temperature and pressure were studied by pair-distribution-function (PDF) analysis from electron scattering and molecular dynamics simulations. The PDFs of the as-deposited and aged samples for 3-13 months showed that the major peaks for Ge-Ge bonds decrease in intensity and broaden with aging for up to 7 months. In the PDFs of a-Ge of molecular dynamics simulation obtained by quenching liquid at different rates, the major peak intensities of a slowly cooled model are higher than those of a rapidly cooled model. Analyses on short- and medium-range configurations show that the slowly cooled model includes a certain amount of medium-range ordered (MRO) clusters, while the rapidly cooled model includes liquid-like configurations rather than MRO clusters. The similarity between experimental and computational PDFs implies that as-deposited films are similar in structure to the slowly cooled model, whereas the fully aged films are similar to the rapidly cooled model. It is assumed that as they undergo room-temperature aging, the MRO clusters disintegrate and transform into liquid-like regions in the same matrix. This transition in local configurations is discussed in terms of instability and the non-equilibrium of nanoclusters produced by a vapor-deposition process.

  4. Bacterial communities in Arctic first-year drift ice during the winter/spring transition.

    PubMed

    Eronen-Rasimus, Eeva; Piiparinen, Jonna; Karkman, Antti; Lyra, Christina; Gerland, Sebastian; Kaartokallio, Hermanni

    2016-08-01

    Horizontal and vertical variability of first-year drift-ice bacterial communities was investigated along a North-South transect in the Fram Strait during the winter/spring transition. Two different developmental stages were captured along the transect based on the prevailing environmental conditions and the differences in bacterial community composition. The differences in the bacterial communities were likely driven by the changes in sea-ice algal biomass (2.6-5.6 fold differences in chl-a concentrations). Copiotrophic genera common in late spring/summer sea ice, such as Polaribacter, Octadecabacter and Glaciecola, dominated the bacterial communities, supporting the conclusion that the increase in the sea-ice algal biomass was possibly reflected in the sea-ice bacterial communities. Of the dominating bacterial genera, Polaribacter seemed to benefit the most from the increase in algal biomass, since they covered approximately 39% of the total community at the southernmost stations with higher (>6 μg l(-1) ) chl-a concentrations and only 9% at the northernmost station with lower chl-a concentrations (<6 μg l(-1) ). The sea-ice bacterial communities also varied between the ice horizons at all three stations and thus we recommend that for future studies multiple ice horizons be sampled to cover the variability in sea-ice bacterial communities in spring. PMID:27264318

  5. FORMATION OF COMPACT AMORPHOUS H{sub 2}O ICE BY CODEPOSITION OF HYDROGEN ATOMS WITH OXYGEN MOLECULES ON GRAIN SURFACES

    SciTech Connect

    Oba, Y.; Miyauchi, N.; Hidaka, H.; Chigai, T.; Watanabe, N.; Kouchi, A.

    2009-08-10

    Formation of H{sub 2}O molecules through the codeposition of oxygen molecules and hydrogen atoms is examined in situ using IR spectroscopy at 10-40 K under various O{sub 2} and H fluxes. It is found that H{sub 2}O and H{sub 2}O{sub 2} are continuously formed by reaction, even at 40 K. The H{sub 2}O ice formed is amorphous, but has a compact (not microporous) structure compared to vapor-deposited amorphous H{sub 2}O ice, because dangling OH bonds are not observed in the IR spectrum. This is consistent with astronomical observations in molecular clouds and theoretical predictions, which suggest that hydrogenation of O{sub 2} is one of the potential routes for reproducing these IR spectral characteristics. The composition of the ice formed by codeposition varies with the O{sub 2}/H ratio and temperature. Although no data are available at present for the H{sub 2}O/H{sub 2}O{sub 2} ratio of ice in molecular clouds, this study suggests that hydrogenation of O{sub 2} has a potential to yield a H{sub 2}O/H{sub 2}O{sub 2} ratio of 5 or more in molecular clouds.

  6. Dynamics enhanced by HCl doping triggers full Pauling entropy release at the ice XII–XIV transition

    PubMed Central

    Köster, K. W.; Fuentes-Landete, V.; Raidt, A.; Seidl, M.; Gainaru, C.; Loerting, T.; Böhmer, R.

    2015-01-01

    The pressure–temperature phase diagram of ice displays a perplexing variety of structurally distinct phases. In the century-long history of scientific research on ice, the proton-ordered ice phases numbered XIII through XV were discovered only recently. Despite considerable effort, none of the transitions leading from the low-temperature ordered ices VIII, IX, XI, XIII, XIV and XV to their high-temperature disordered counterparts were experimentally found to display the full Pauling entropy. Here we report calorimetric measurements on suitably high-pressure-treated, hydrogen chloride-doped ice XIV that demonstrate just this at the transition to ice XII. Dielectric spectroscopy on undoped and on variously doped ice XII crystals reveals that addition of hydrogen chloride, the agent triggering complete proton order in ice XIV, enhances the precursor dynamics strongest. These discoveries provide new insights into the puzzling observation that different dopants trigger the formation of different proton-ordered ice phases. PMID:26076946

  7. Magnetic phase transitions and monopole excitations in spin ice under uniaxial pressure: A Monte Carlo simulation

    SciTech Connect

    Xie, Y. L. Yan, Z. B.; Liu, J.-M.; Lin, L.

    2015-05-07

    In this work, we explore the spin ice model under uniaxial pressure using the Monte Carlo simulation method. For the known spin ices, the interaction correction (δ) introduced by the uniaxial pressure varies in quite a wide range from positive to negative. When δ is positive, the ground state characterized by the ferromagnetic spin chains is quite unstable, and in real materials it serves as intermediate state connecting the ice state and the long range ordered dipolar spin ice ground state. In the case of negative δ, the system relaxes from highly degenerate ice state to ordered ferromagnetic state via a first order phase transition. Furthermore, the domain walls in such ferromagnetic state are the hotbed of the excitations of magnetic monopoles, thus indicating that the uniaxial pressure can greatly increase the monopole density.

  8. Charging and Discharging of Amorphous Solid Water Ice: Effects of Porosity

    NASA Astrophysics Data System (ADS)

    Bu, Caixia; Baragiola, Raul A.

    2015-11-01

    Introduction: Amorphous solid water (ASW) is abundant on Saturn’s icy satellites and rings [1,2], where it is subject to bombardment of energetic ions, electrons, and photons; together with secondary electron and ion emission, this may leave the surfaces charged. Surface potential can affect the flux of incoming charged particles, altering surface evolution. We examined the role of porosity [3] on electrostatic charging and discharging of ASW films at 30-140 K.Experiment: Experiments were performed in ultra-high vacuum [4]. ASW films were deposited at 30 K onto a liquid-He-cooled quartz crystal microbalance (QCM). Film porosity was calculated from the areal mass via the QCM and thickness via a UV-visible interferometry. ASW films were charged at 30 K using 500 eV He+. Surface potentials (Vs) of the films were measured with a Kelvin probe, and infrared spectra were collected using a Fourier transform infrared spectrometer.Results: We measured Vs of the ASW film at 30 K as a function of ion fluence (F). The Vs(F) deviates from a straight line at low fluence, attributed to emitted secondary electrons due to the negative polarization voltage [5,6], and increases linearly when the Vs is positive. We also measured Vs as a function of annealing temperature. We prepared ASW films with various porosities by annealing the films to different temperatures (Ta) prior to irradiation or varying the vapor-beam incidence angle (θ). Upon heating, we observed sharp decreases of the Vs at temperatures that strongly depend on Ta and θ. Decreases of the infrared absorbance of the dangling OH bands of the charged film share similar trends as that of the Vs. We propose a model that includes porosity for electrostatic charging/discharging of ASW films at temperatures below 100 K. Results are applicable to the study of plasma-surface interactions of icy satellites and rings.References: [1] Jurac et al., J. Geophys. Res. 100, 14821 (1995); [2] A. L. Graps et al., Space Sci. Rev. 137, 435

  9. Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2004-01-01

    Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

  10. Surface Transition on Ice Induced by the Formation of a Grain Boundary

    PubMed Central

    Pedersen, Christian; Mihranyan, Albert; Strømme, Maria

    2011-01-01

    Interfaces between individual ice crystals, usually referred to as grain boundaries, play an important part in many processes in nature. Grain boundary properties are, for example, governing the sintering processes in snow and ice which transform a snowpack into a glacier. In the case of snow sintering, it has been assumed that there are no variations in surface roughness and surface melting, when considering the ice-air interface of an individual crystal. In contrast to that assumption, the present work suggests that there is an increased probability of molecular surface disorder in the vicinity of a grain boundary. The conclusion is based on the first detailed visualization of the formation of an ice grain boundary. The visualization is enabled by studying ice crystals growing into contact, at temperatures between −20°C and −15°C and pressures of 1–2 Torr, using Environmental Scanning Electron Microscopy. It is observed that the formation of a grain boundary induces a surface transition on the facets in contact. The transition does not propagate across facet edges. The surface transition is interpreted as the spreading of crystal dislocations away from the grain boundary. The observation constitutes a qualitatively new finding, and can potentially increase the understanding of specific processes in nature where ice grain boundaries are involved. PMID:21915317

  11. Dielectric properties of water ice, the ice Ih/XI phase transition, and an assessment of density functional theory.

    PubMed

    Schönherr, Mandes; Slater, Ben; Hutter, Jürg; VandeVondele, Joost

    2014-01-16

    The dielectric properties of the hydrogen disordered hexagonal phase (Ih) of water ice have been computed using density functional theory (DFT) based Monte Carlo simulations in the isobaric-isothermal ensemble. Temperature dependent data yield a fit for the Curie-Weiss law of the system and hence a prediction of the temperature of the phase transition from the Ih phase to the hydrogen ordered ice XI phase. Direct simulations around the phase transition temperature confirm and refine the predicted phase transition temperatures and provide data for further properties, such as the linear thermal expansion coefficient. Results have been obtained with both hybrid and semilocal density functionals, which yields insight in the performance of the electronic structure method. In particular, the hybrid functional yields significantly more realistic dielectric constants than the semilocal variant, namely ε ≈ 116 as opposed to ε ≈ 151 at 273 K (εexperiment = 95). This can be attributed to the tendency of semilocal functionals to be biased to configurations with a large dipole moment, and their overestimation of the dipole moments of these configurations. This is also reflected in the estimates of the Ih/XI transition temperature, which is 70-80 and 90-100 K for the hybrid and semilocal functional respectively. DFT based sampling of the millions of configurations necessary for this work has been enabled by a Tree Monte Carlo algorithm, designed for massively parallel computers. PMID:24392971

  12. An observation of amorphous-crystalline phase transitions at severe plastic deformation of the Ti50Ni25Cu25 alloy

    NASA Astrophysics Data System (ADS)

    Nosova, G. I.; Shalimova, A. V.; Sundeev, R. V.; Glezer, A. M.; Pankova, M. N.; Shelyakov, A. V.

    2009-11-01

    The features of structural and phase transitions during severe plastic deformation (in Bridgman anvils) of the amorphous Ti50Ni25Cu25 alloy have been studied by X-ray diffraction and transmission electron microscopy. Application of successively increasing deformation has revealed three cycles of successive phase transitions from amorphous to crystalline state and vice versa. The results obtained are explained in terms of the superposition of the different channels of elastic energy dissipation, which are activated during severe plastic deformation.

  13. Atomic-Level Simulations of Epitaxial Recrystallization and Amorphous-to-Crystalline Transition in 4H-SiC

    SciTech Connect

    Gao, Fei; Zhang, Yanwen; Posselt, Matthias; Weber, William J.

    2006-09-01

    The amorphous-to-crystalline (a-c) transition in 4H-SiC has been studied using molecular dynamics (MD) methods, with simulation times of up to a few hundred ns and at temperatures ranging from 1000 to 2000 K. Two nano-sized amorphous layers, one with the normal of a-c interfaces along the [ -12-10] direction and the other along the [ -1010] direction, were created within a crystalline cell to study expitaxial recrystallization and the formation of secondary phases. The recovery of bond defects at the interfaces is an important process driving the epitaxial recrystallization of the amorphous layers. The amorphous layer with the a-c interface normal along the [-12-10] direction can be completely recrystallized at the temperatures of 1500 and 2000 K, but the recrystallized region is defected with dislocations and stacking faults. On the other hand, the recrystallization process for the a-c interface normal along [-1010] direction is hindered by the nucleation of polycrystalline phases, and these secondary ordered phases are stable for longer simulation times. A general method to calculate activation energy spectra is employed to analyze the MD annealing simulations, and the recrystallization mechanism in SiC consists of multiple stages with activation energies ranging from 0.8 to 1.7 eV.

  14. Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI{sub 4}

    SciTech Connect

    Liu, H.; Tse, J. S.; Hu, M. Y.; Bi, W.; Zhao, J.; Alp, E. E.; Pasternak, M.; Taylor, R. D.; Lashley, J. C.

    2015-10-28

    The pressure-induced amorphization and subsequent recrystallization of SnI{sub 4} have been investigated using first principles molecular dynamics calculations together with high-pressure {sup 119}Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI{sub 4} under ambient conditions. Although high pressure structures of SnI{sub 4} were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.

  15. Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl4

    SciTech Connect

    Liu, Hanyu; Tse, John S.; Hu, Michael Y.; Bi, Wenli; Zhao, Jiyong; Alp, E. Ercan; Pasternak, Moshe; Taylor, R. Dean; Lashley, Jason C.

    2015-10-27

    The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.

  16. Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture.

    PubMed

    Zhao, Hai-Xia; Kong, Xiang-Jian; Li, Hui; Jin, Yi-Chang; Long, La-Sheng; Zeng, Xiao Cheng; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-03-01

    Ferroelectric materials are characterized by spontaneous electric polarization that can be reversed by inverting an external electric field. Owing to their unique properties, ferroelectric materials have found broad applications in microelectronics, computers, and transducers. Water molecules are dipolar and thus ferroelectric alignment of water molecules is conceivable when water freezes into special forms of ice. Although the ferroelectric ice XI has been proposed to exist on Uranus, Neptune, or Pluto, evidence of a fully proton-ordered ferroelectric ice is still elusive. To date, existence of ferroelectric ice with partial ferroelectric alignment has been demonstrated only in thin films of ice grown on platinum surfaces or within microdomains of alkali-hydroxide doped ice I. Here we report a unique structure of quasi-one-dimensional (H(2)O)(12n) wire confined to a 3D supramolecular architecture of H(4)CDTA, trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid; 4,4'-bpy, 4,4'-bipyridine). In stark contrast to the bulk, this 1D water wire not only exhibits enormous dielectric anomalies at approximately 175 and 277 K, respectively, but also undergoes a spontaneous transition between "1D liquid" and "1D ferroelectric ice" at approximately 277 K. Hitherto unrevealed properties of the 1D water wire will be valuable to the understanding of anomalous properties of water and synthesis of novel ferroelectric materials.

  17. Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture.

    PubMed

    Zhao, Hai-Xia; Kong, Xiang-Jian; Li, Hui; Jin, Yi-Chang; Long, La-Sheng; Zeng, Xiao Cheng; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-03-01

    Ferroelectric materials are characterized by spontaneous electric polarization that can be reversed by inverting an external electric field. Owing to their unique properties, ferroelectric materials have found broad applications in microelectronics, computers, and transducers. Water molecules are dipolar and thus ferroelectric alignment of water molecules is conceivable when water freezes into special forms of ice. Although the ferroelectric ice XI has been proposed to exist on Uranus, Neptune, or Pluto, evidence of a fully proton-ordered ferroelectric ice is still elusive. To date, existence of ferroelectric ice with partial ferroelectric alignment has been demonstrated only in thin films of ice grown on platinum surfaces or within microdomains of alkali-hydroxide doped ice I. Here we report a unique structure of quasi-one-dimensional (H(2)O)(12n) wire confined to a 3D supramolecular architecture of H(4)CDTA, trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid; 4,4'-bpy, 4,4'-bipyridine). In stark contrast to the bulk, this 1D water wire not only exhibits enormous dielectric anomalies at approximately 175 and 277 K, respectively, but also undergoes a spontaneous transition between "1D liquid" and "1D ferroelectric ice" at approximately 277 K. Hitherto unrevealed properties of the 1D water wire will be valuable to the understanding of anomalous properties of water and synthesis of novel ferroelectric materials. PMID:21321232

  18. Water in Inhomogeneous Nanoconfinement: Coexistence of Multilayered Liquid and Transition to Ice Nanoribbons.

    PubMed

    Qiu, Hu; Zeng, Xiao Cheng; Guo, Wanlin

    2015-10-27

    Phase behavior and the associated phase transition of water within inhomogeneous nanoconfinement are investigated using molecular dynamics simulations. The nanoconfinement is constructed by a flat bottom plate and a convex top plate. At 300 K, the confined water can be viewed as a coexistence of monolayer, bilayer, and trilayer liquid domains to accommodate the inhomogeneous confinement. With increasing liquid density, the confined water with uneven layers transforms separately into two-dimensional ice crystals with unchanged layer number and rhombic in-plane symmetry for oxygen atoms. The monolayer water undergoes the transition first into a puckered ice nanoribbon, and the bilayer water transforms into a rhombic ice nanoribbon next, followed by the transition of trilayer water into a trilayer ice nanoribbon. The sequential localized liquid-to-solid transition within the inhomogeneous confinement can also be achieved by gradually decreasing the temperature at low liquid densities. These findings of phase behaviors of water under the inhomogeneous nanoconfinement not only extend the phase diagram of confined water but also have implications for realistic nanofluidic systems and microporous materials.

  19. Evidence from Ice-Rafted Debris and Sediment Provenance for a Dynamic East Antarctic Ice Sheet During the Mid-Miocene Climate Transition

    NASA Astrophysics Data System (ADS)

    Williams, T.; Pierce, E. L.; van de Flierdt, T.; Hemming, S. R.; Cook, C. P.; Passchier, S.; Sangiorgi, F.; Bijl, P.

    2015-12-01

    The Antarctic ice sheets underwent a major expansion during the Mid-Miocene Climate Transition, around 14 Ma, lowering eustatic sea level by perhaps 50m, based on evidence from benthic oxygen isotope records and sea level indicators. However, direct evidence of changes in the ice sheet is limited to sites in or close to the Transantarctic Mountains. Here we present evidence for ice sheet change from two widely separated sites offshore of East Antarctica, IODP Site U1356, Wilkes Land, and ODP Site 1165, Prydz Bay. Between 14.1 and 13.8 Ma at these sites, episodic pulses of ice-rafted debris (IRD), including dropstones, were deposited in concentrations exceeding those in the rest of the Miocene. These repeated pulses of IRD-bearing icebergs indicate large and repeated advances and retreats of the ice sheet during the course of the transition to a larger and relatively more stable ice sheet. We conducted provenance analyses on the mid-Miocene IRD and sediments. At Site U1356, 40Ar/39Ar ages of ice-rafted hornblende grains show that a major ice drainage was situated along the inland part of the Mertz Shear Zone and its southward extension along the west side of the Wilkes Subglacial Basin, while Nd isotope data from the terrigenous fine fraction show that the ice margin periodically expanded from high ground well into the Wilkes Subglacial Basin during periods of ice growth. At Site 1165, 40Ar/39Ar on dropstones indicate provenance from both the Lambert Glacier region and the part of Wilkes Land that contains the Aurora Subglacial Basin. The two sites provide a direct record of repeated collapse and re-growth of ice in at least two of East Antarctica's main drainage basins during the mid-Miocene climate transition. We will set our ice-rafted debris and provenance evidence for cryosphere change in the context of mid-Miocene climate records.

  20. Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture

    PubMed Central

    Zhao, Hai-Xia; Kong, Xiang-Jian; Li, Hui; Jin, Yi-Chang; Long, La-Sheng; Zeng, Xiao Cheng; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-01-01

    Ferroelectric materials are characterized by spontaneous electric polarization that can be reversed by inverting an external electric field. Owing to their unique properties, ferroelectric materials have found broad applications in microelectronics, computers, and transducers. Water molecules are dipolar and thus ferroelectric alignment of water molecules is conceivable when water freezes into special forms of ice. Although the ferroelectric ice XI has been proposed to exist on Uranus, Neptune, or Pluto, evidence of a fully proton-ordered ferroelectric ice is still elusive. To date, existence of ferroelectric ice with partial ferroelectric alignment has been demonstrated only in thin films of ice grown on platinum surfaces or within microdomains of alkali-hydroxide doped ice I. Here we report a unique structure of quasi-one-dimensional (H2O)12n wire confined to a 3D supramolecular architecture of H4CDTA, trans-1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid; 4,4′-bpy, 4,4′-bipyridine). In stark contrast to the bulk, this 1D water wire not only exhibits enormous dielectric anomalies at approximately 175 and 277 K, respectively, but also undergoes a spontaneous transition between “1D liquid” and “1D ferroelectric ice” at approximately 277 K. Hitherto unrevealed properties of the 1D water wire will be valuable to the understanding of anomalous properties of water and synthesis of novel ferroelectric materials. PMID:21321232

  1. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    PubMed

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

    2014-11-26

    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

  2. Evolution of ocean temperature and ice volume through the mid-Pleistocene climate transition.

    PubMed

    Elderfield, H; Ferretti, P; Greaves, M; Crowhurst, S; McCave, I N; Hodell, D; Piotrowski, A M

    2012-08-10

    Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the mid-Pleistocene transition (MPT), when the dominant periodicity of climate cycles changed from 41 thousand to 100 thousand years in the absence of substantial change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep-ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume 900 thousand years ago. We see no evidence of a pattern of gradual cooling, but near-freezing temperatures occur at every glacial maximum. PMID:22879512

  3. Thermal phase transition in artificial spin ice systems induces the formation and migration of monopole-like magnetic excitations

    NASA Astrophysics Data System (ADS)

    León, Alejandro

    2016-11-01

    Artificial spin ice systems exhibit monopole-like magnetic excitations. We develop here a theoretical study of the thermal phase transition of an artificial spin ice system, and we elucidate the role of the monopole excitations in the transition temperature. The dynamics of the spin ice is described by an efficient model based on cellular automata, which considers both thermal effects and dipolar interactions. We have established the critical temperature of the phase transition as function of the magnetic moment and the energy barrier of reversion. In addition, we predict that thermal gradients in the system induce the motion of elementary excitations, which could permit to manipulate monopole-like states.

  4. The peculiar behavior of the glass transition temperature of amorphous drug-polymer films coated on inert sugar spheres.

    PubMed

    Dereymaker, Aswin; Van Den Mooter, Guy

    2015-05-01

    Fluid bed coating has been proposed in the past as an alternative technology for manufacturing of drug-polymer amorphous solid dispersions, or so-called glass solutions. It has the advantage of being a one-step process, and thus omitting separate drying steps, addition of excipients, or manipulation of the dosage form. In search of an adequate sample preparation method for modulated differential scanning calorimetry analysis of beads coated with glass solutions, glass transition broadening and decrease of the glass transition temperature (Tg ) were observed with increasing particle size of crushed coated beads and crushed isolated films of indomethacin (INDO) and polyvinylpyrrolidone (PVP). Substituting INDO with naproxen gave comparable results. When ketoconazole was probed or the solvent in INDO-PVP films was switched to dichloromethane (DCM) or a methanol-DCM mixture, two distinct Tg regions were observed. Small particle sizes had a glass transition in the high Tg region, and large particle sizes had a glass transition in the low Tg region. This particle size-dependent glass transition was ascribed to different residual solvent amounts in the bulk and at the surface of the particles. A correlation was observed between the deviation of the Tg from that calculated from the Gordon-Taylor equation and the amount of residual solvent at the Tg of particles with different sizes.

  5. Phase transitions and charge ordering in a square spin ice model with conserved monopole density

    NASA Astrophysics Data System (ADS)

    Xie, Yunlong; Zhou, Xiaohui; Liu, Jun-Ming

    2015-03-01

    Artificial spin ices represent a class of highly interested frustrated magnetic systems under intensive investigations for fascinating ground states and thermodynamics/dynamics of spin excitations in recent years. As one of these issues, magnetic charge ordering and the corresponding phase transitions in the two-dimensional system are emerging topics in condensed matter physics. In this work, we investigate all the monopole-ordered phases of the square spin ice model using the conserved monopole density algorithm. In low monopole density (ρ ~ 0), the Coulomb potential determines the monopoles' dynamics. We test the Coulomb's law in a two-dimension lattice and justify the monopole dimerization which is quite different from the three-dimensional pyrochlore spin ice. These monopole dimers are charge neutral, and the interactions between them have also been investigated using our algorithm. In the cases of high monopole density (ρ ~ 1), the system is similar to the dipolar kagome spin ice model, and our simulation results show that there exists an intermediate phase between the paramagnetic phase and the ordered magnetic phase. Such intermediate phase can be distinguished by the order of magnetic charges. In a cooling process, the system undergoes a two-stage magnetic phase transition before freezing to the long range magnetic ordered phase via a staggered charge ordering. Furthermore, a liquefaction process of monopole dimers can be justified upon the increasing effective internal pressure in the isothermal condition.

  6. Solubility of crystalline organic compounds in high and low molecular weight amorphous matrices above and below the glass transition by zero enthalpy extrapolation.

    PubMed

    Amharar, Youness; Curtin, Vincent; Gallagher, Kieran H; Healy, Anne Marie

    2014-09-10

    Pharmaceutical applications which require knowledge of the solubility of a crystalline compound in an amorphous matrix are abundant in the literature. Several methods that allow the determination of such data have been reported, but so far have only been applicable to amorphous polymers above the glass transition of the resulting composites. The current work presents, for the first time, a reliable method for the determination of the solubility of crystalline pharmaceutical compounds in high and low molecular weight amorphous matrices at the glass transition and at room temperature (i.e. below the glass transition temperature), respectively. The solubilities of mannitol and indomethacin in polyvinyl pyrrolidone (PVP) K15 and PVP K25, respectively were measured at different temperatures. Mixtures of undissolved crystalline solute and saturated amorphous phase were obtained by annealing at a given temperature. The solubility at this temperature was then obtained by measuring the melting enthalpy of the crystalline phase, plotting it as a function of composition and extrapolating to zero enthalpy. This new method yielded results in accordance with the predictions reported in the literature. The method was also adapted for the measurement of the solubility of crystalline low molecular weight excipients in amorphous active pharmaceutical ingredients (APIs). The solubility of mannitol, glutaric acid and adipic acid in both indomethacin and sulfadimidine was experimentally determined and successfully compared with the difference between their respective calculated Hildebrand solubility parameters. As expected from the calculations, the dicarboxylic acids exhibited a high solubility in both amorphous indomethacin and sulfadimidine, whereas mannitol was almost insoluble in the same amorphous phases at room temperature. This work constitutes the first report of the methodology for determining an experimentally measured solubility for a low molecular weight crystalline solute

  7. Magnetic-charge ordering and phase transitions in monopole-conserved square spin ice.

    PubMed

    Xie, Y-L; Du, Z-Z; Yan, Z-B; Liu, J-M

    2015-01-01

    Magnetic-charge ordering and corresponding magnetic/monopole phase transitions in spin ices are the emergent topics of condensed matter physics. In this work, we investigate a series of magnetic-charge (monopole) phase transitions in artificial square spin ice model using the conserved monopole density algorithm. It is revealed that the dynamics of low monopole density lattices is controlled by the effective Coulomb interaction and the Dirac string tension, leading to the monopole dimerization which is quite different from the dynamics of three-dimensional pyrochlore spin ice. The condensation of the monopole dimers into monopole crystals with staggered magnetic-charge order can be predicted clearly. For the high monopole density cases, the lattice undergoes two consecutive phase transitions from high-temperature paramagnetic/charge-disordered phase into staggered charge-ordered phase before eventually toward the long-range magnetically-ordered phase as the ground state which is of staggered charge order too. A phase diagram over the whole temperature-monopole density space, which exhibits a series of emergent spin and monopole ordered states, is presented. PMID:26511870

  8. Magnetic-charge ordering and phase transitions in monopole-conserved square spin ice

    PubMed Central

    Xie, Y.-L.; Du, Z.-Z.; Yan, Z.-B.; Liu, J.-M.

    2015-01-01

    Magnetic-charge ordering and corresponding magnetic/monopole phase transitions in spin ices are the emergent topics of condensed matter physics. In this work, we investigate a series of magnetic-charge (monopole) phase transitions in artificial square spin ice model using the conserved monopole density algorithm. It is revealed that the dynamics of low monopole density lattices is controlled by the effective Coulomb interaction and the Dirac string tension, leading to the monopole dimerization which is quite different from the dynamics of three-dimensional pyrochlore spin ice. The condensation of the monopole dimers into monopole crystals with staggered magnetic-charge order can be predicted clearly. For the high monopole density cases, the lattice undergoes two consecutive phase transitions from high-temperature paramagnetic/charge-disordered phase into staggered charge-ordered phase before eventually toward the long-range magnetically-ordered phase as the ground state which is of staggered charge order too. A phase diagram over the whole temperature-monopole density space, which exhibits a series of emergent spin and monopole ordered states, is presented. PMID:26511870

  9. An observation of amorphous-crystalline phase transitions at severe plastic deformation of the Ti{sub 50}Ni{sub 25}Cu{sub 25} alloy

    SciTech Connect

    Nosova, G. I.; Shalimova, A. V.; Sundeev, R. V.; Glezer, A. M. Pankova, M. N.; Shelyakov, A. V.

    2009-11-15

    The features of structural and phase transitions during severe plastic deformation (in Bridgman anvils) of the amorphous Ti{sub 50}Ni{sub 25}Cu{sub 25} alloy have been studied by X-ray diffraction and transmission electron microscopy. Application of successively increasing deformation has revealed three cycles of successive phase transitions from amorphous to crystalline state and vice versa. The results obtained are explained in terms of the superposition of the different channels of elastic energy dissipation, which are activated during severe plastic deformation.

  10. Deep Ocean Circulation Changes During the Transition to the Last Ice Age

    NASA Astrophysics Data System (ADS)

    Zylberberg, D. R.; Piotrowski, A. M.; Goldstein, S. L.; Hemming, S. R.

    2003-12-01

    The transition between marine isotope stages (MIS) 5a and 4 appears in the stacked benthic foraminferal δ 18O SPECMAP record as a gradual increase in ice volume. In contrast, the transition occurs in the Greenland ice core δ 18O records with two well-developed interstadial events (I19 and I20), which are the first Dansgaard-Oescheger events of the last ice age. The MIS 5b/5a transition appears as a much more rapid warming in both the Greenland ice and benthic δ 18O records. Recent work (Lehmann et al. 2002, Chapman et al. 1999) indicates that climate variability in MIS 5 as indicated in the Greenland ice record was closely interconnected with iceberg discharges, surface temperature changes, and deep ocean circulation in the North Atlantic. In order to determine the response of deep ocean circulation to climate changes from late in MIS 5 to full glacial MIS 4, we have measured Nd isotope ratios from the Fe-Mn portion of core TNO57-21 from the Cape Basin in the South Atlantic. Nd isotopes, unlike nutrient water mass proxies, are not affected by biological fractionation, and reflect the strength of the North Atlantic Deep Water (NADW) signal in the seawater above the core site. Results from cores TNO57-21 and RC11-83 (also from the Cape Basin) indicate that the NADW export to the Southern Ocean has varied on time scales reflecting glacial-interglacial cycles through MIS 4 (Rutberg et al. 2000) and during interstadial events through MIS 3 (Piotrowski et al. Fall AGU), and was stronger and weaker during warmer and colder Northern Hemisphere climate intervals, respectively. The extension of the Nd isotope record to MIS 5a and 5b indicates an increased NADW signal during MIS 5, therefore the long-term pattern of strong and weak NADW export during warm and cold periods persists beyond the last ice age. The Nd isotope pattern during MIS 4 through 5b generally corresponds to the benthic foraminferal δ 13C record from Cape Basin cores (Ninnemann et al. 1999), indicating

  11. Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water.

    PubMed

    Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

    2015-10-27

    Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, T(g) . Here we report a universal water-content, X(aqu) , dependence of T(g) for aqueous solutions. Solutions with X(aqu)>X(cr)(aqu)vitrify/devitrify at a constant temperature, ~T(g) , referring to freeze-concentrated phase with X(aqu)left behind ice crystallization. Those solutions with X(aqu)ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of T(g) by annealing is attributable to freeze-concentrated phase of solutions instead of 'liquid II phase of water'. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution.

  12. Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water.

    PubMed

    Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

    2015-01-01

    Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, T(g) . Here we report a universal water-content, X(aqu) , dependence of T(g) for aqueous solutions. Solutions with X(aqu)>X(cr)(aqu)vitrify/devitrify at a constant temperature, ~T(g) , referring to freeze-concentrated phase with X(aqu)left behind ice crystallization. Those solutions with X(aqu)ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of T(g) by annealing is attributable to freeze-concentrated phase of solutions instead of 'liquid II phase of water'. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

  13. Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

    NASA Astrophysics Data System (ADS)

    Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

    2015-10-01

    Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution.

  14. Crystalline to amorphous phase transition of tin oxide nanocrystals induced by SHI at low temperature

    SciTech Connect

    Kumar, Vijay; Pratap, Deepti; Jain, Anshul; Agarwal, D. C.; Sulania, I.; Tripathi, A.; Chaudhary, R. J.; Chauhan, R. S.

    2012-06-05

    Tin oxide (SnO{sub 2}) thin films were deposited using pulsed laser deposition (PLD) technique on Si substrates. The as-deposited films were irradiated using 100 MeV Ag ions at different fluences ranging from 3x10{sup 13} to 3x10{sup 14} ions/cm{sup 2} at an incidence angle of 75 deg. with respect to surface normal at liquid nitrogen (LN2) temperature. The as-deposited and irradiated films have been characterized using X-ray diffraction (XRD) and atomic force microscopy (AFM) techniques to study the modifications in structural and surface morphological properties. Nanocrystalline film become completely amorphous and nanograins of tin oxide disappeared from the surface as indicated by XRD spectra and AFM micrographs respectively.

  15. Structural mechanisms of the Ih–II and II → Ic transitions between the crystalline phases of aqueous ice

    SciTech Connect

    Zheligovskaya, E. A.

    2015-09-15

    Structural mechanisms are proposed for experimentally observed phase transitions between crystalline modifications of aqueous ice, Ih and II, as well as II and Ic. It is known that the Ih–II transition occurs with the conservation of large structural units (hexagonal channels) common for these ices. It is shown that the Ih → II transition may occur with the conservation of 5/6 of all hydrogen bonds in crystal, including all hydrogen bonds in the retained channels (3/4 of the total number of bonds in crystal) and 1/3 of the bonds between these channels (1/12 of the total number). The transformation of other hydrogen bonds between the retained channels leads to the occurrence of proton order in ice II. A structural mechanism is proposed to explain the transformation of single crystals of ice Ih either into single crystals of ice II or into crystalline twins of ice II with c axes rotated by 180° with respect to each other, which is often observed at the Ih → II transition. It is established that up to 7/12 of all hydrogen bonds are retained at the irreversible cooperative II → Ic transition.

  16. The Structural Properties of Vapor Deposited Water Ice and Astrophysical Implications

    NASA Technical Reports Server (NTRS)

    Jenniskens, P.; Blake, D. F.; Chang, Sherwood (Technical Monitor)

    1996-01-01

    Films of vapor deposited water ice at low temperature (T<30 K) show a number of interesting structural changes during a gradual warmup. We would like to talk about the structure of the low temperature high density amorphous form of water ice, the process of crystallization, and some recent work on the morphological changes of water ice films at high temperature. The studies of the high density amorphous form are from in-situ electron microscopy as well as numerical simulations of molecular dynamics and have lead to new insights into the physical distinction between this high density amorphous form and the low density amorphous form. For the process of crystallization, we propose a model that describes the crystallization of water ice from the amorphous phase to cubic ice in terms of the nucleation of small domains in the ice. This model agrees well with the behavior of water ice in our electron microscopy studies and finds that pure water above the glass transition is a strong liquid. In more recent work, we have concentrated on temperatures above the crystallization temperature and we find interesting morphological changes related to the decrease in viscosity of the amorphous component in the cubic crystalline regime. Given enough time, we would like to put these results in an astrophysical context and discuss some observed features of the frost on interstellar grains and the bulk ice in comets.

  17. Sea ice melt onset associated with lead opening during the spring/summer transition near the North Pole

    NASA Astrophysics Data System (ADS)

    Vivier, Frédéric; Hutchings, Jennifer K.; Kawaguchi, Yusuke; Kikuchi, Takashi; Morison, James H.; Lourenço, Antonio; Noguchi, Tomohide

    2016-04-01

    In the central Arctic Ocean, autonomous observations of the ocean mixed layer and ice documented the transition from cold spring to early summer in 2011. Ice-motion measurements using GPS drifters captured three events of lead opening and ice ridge formation in May and June. Satellite sea ice concentration observations suggest that locally observed lead openings were part of a larger-scale pattern. We clarify how these ice deformation events are linked with the onset of basal sea ice melt, which preceded surface melt by 20 days. Observed basal melt and ocean warming are consistent with the available input of solar radiation into leads, once the advent of mild atmospheric conditions prevents lead refreezing. We use a one-dimensional numerical simulation incorporating a Local Turbulence Closure scheme to investigate the mechanisms controlling basal melt and upper ocean warming. According to the simulation, a combination of rapid ice motion and increased solar energy input at leads promotes basal ice melt, through enhanced mixing in the upper mixed layer, while slow ice motion during a large lead opening in mid-June produced a thin, low-density surface layer. This enhanced stratification near the surface facilitates storage of solar radiation within the thin layer, instead of exchange with deeper layers, leading to further basal ice melt preceding the upper surface melt.

  18. Deep water temperature, carbonate ion, and ice volume changes across the Eocene-Oligocene climate transition

    NASA Astrophysics Data System (ADS)

    Pusz, A. E.; Thunell, R. C.; Miller, K. G.

    2011-06-01

    Paired benthic foraminiferal stable isotope and Mg/Ca data are used to estimate bottom water temperature (BWT) and ice volume changes associated with the Eocene-Oligocene Transition (EOT), the largest global climate event of the past 50 Myr. We utilized ODP Sites 1090 and 1265 in the South Atlantic to assess seawater δ18O (δw), Antarctic ice volume, and sea level changes across the EOT (˜33.8-33.54 Ma). We also use benthic δ13C data to reconstruct the sources of the deep water masses in this region during the EOT. Our data, together with previously published records, indicate that a pulse of Northern Component Water influenced the South Atlantic immediately prior to and following the EOT. Benthic δ18O records show a 0.5‰ increase at ˜33.8 Ma (EOT-1) that represents a ˜2°C cooling and a small (˜10 m) eustatic fall that is followed by a 1.0‰ increase associated with Oi-1. The expected cooling of deep waters at Oi-1 (˜33.54 Ma) is not apparent in our Mg/Ca records. We suggest the cooling is masked by coeval changes in the carbonate saturation state (Δ[CO32-]) which affect the Mg/Ca data. To account for this, the BWT, ice volume, and δw estimates are corrected for a change in the Δ[CO32-] of deep waters on the basis of recently published work. Corrected BWT at Sites 1090 and 1265 show a ˜1.5°C cooling coincident with Oi-1 and an average δw increase of ˜0.75‰. The increase in ice volume during Oi-1 resulted in a ˜70 m drop in global sea level and the development of an Antarctic ice sheet that was near modern size or slightly larger.

  19. On the role of thermohaline advection and sea ice in glacial transitions

    NASA Astrophysics Data System (ADS)

    Kravtsov, S.; Dewar, W. K.

    2003-06-01

    A two-dimensional, one-basin thermohaline oceanic circulation (THC) model coupled to an atmospheric energy balance model (EBM) with land ice albedo effect and a thermodynamic sea ice model is used to study global climate on centennial, and longer, timescales. The model is interpreted to represent the effect of the global ocean, rather than the Atlantic, as is commonly done. It is forced by symmetric insolation and includes a diagnostic parameterization of the hydrologic cycle. Here the strength of the ocean's haline forcing is controlled by a parameter, which reflects the effect of river runoff. This parameter is varied in a set of experiments, which also differ by the magnitude of solar insolation. In wide ranges of the hydrologic cycle, multiple climatic equilibria exist, consisting of circulations with different degrees of asymmetry. More symmetric states have a higher global atmospheric temperature, characteristic of modern climate, whereas less symmetric states are colder and resemble glacial conditions. The maximum global atmospheric temperature difference between such states is consistent with proxy-data-derived temperature drop of about 4°C during the glacial, in contrast to EBM-only sensitivity of about 0.4°C. The mechanics of climate transitions in the model are due to amplification of the orbitally induced global heat budget changes by a major reorganization of the oceanic heat transport. In our model this reorganization is caused by the nonlinear dynamics of the ocean's THC, whose stability regime shifts subject to variable external forcing. Sea ice enhances model climate sensitivity by anchoring deep-ocean temperature to be near freezing [, 2000] and by affecting atmospheric temperature and land ice extent near the poles because of sea ice insulating properties.

  20. Nanocrystals in compression: unexpected structural phase transition and amorphization due to surface impurities

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Kong, Lingping; Yan, Jinyuan; Liu, Zhenxian; Zhang, Hengzhong; Lei, Pei; Xu, Tao; Mao, Ho-Kwang; Chen, Bin

    2016-06-01

    We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium-doped brookite amorphizes above 20 GPa. The abnormal structural evolution observed in yttrium-doped TiO2 does not agree with the reported phase stability of nano titania polymorphs, thus suggesting that the physical properties of the interior of nanocrystals can be controlled by the surface, providing an unconventional and new degree of freedom in search for nanocrystals with novel tunable properties that can trigger applications in multiple areas of industry and provoke more related basic science research.We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium

  1. Nanocrystals in compression: unexpected structural phase transition and amorphization due to surface impurities.

    PubMed

    Liu, Gang; Kong, Lingping; Yan, Jinyuan; Liu, Zhenxian; Zhang, Hengzhong; Lei, Pei; Xu, Tao; Mao, Ho-Kwang; Chen, Bin

    2016-06-01

    We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium-doped brookite amorphizes above 20 GPa. The abnormal structural evolution observed in yttrium-doped TiO2 does not agree with the reported phase stability of nano titania polymorphs, thus suggesting that the physical properties of the interior of nanocrystals can be controlled by the surface, providing an unconventional and new degree of freedom in search for nanocrystals with novel tunable properties that can trigger applications in multiple areas of industry and provoke more related basic science research. PMID:27280175

  2. Amorphous to crystalline phase transition: Onset of pattern formation during ion erosion of Si(001)

    NASA Astrophysics Data System (ADS)

    Engler, Martin; Michely, Thomas

    2016-02-01

    The morphological evolution of Si(001) is investigated for normal incidence 2 keV Kr+ion irradiation under ultra-high vacuum conditions as a function of temperature and ion fluence through scanning tunneling microscopy and low energy electron diffraction. Under the conditions chosen, the selvage of Si(001) amorphizes below the critical temperature Tc of 670 K, while above it remains crystalline. Below Tc the sample remains flat, irrespective of the ion fluence. Above Tc, the crystalline sample displays for fixed ion fluence and as a function of sample temperature a pronounced roughness maximum at 700 K. Around this temperature, with increasing ion fluence a strong increase of roughness as well as coarsening are observed. Pyramidal pits and mounds develop, with facets formed by Si steps and narrow reconstructed terraces. Most exciting, with increasing ion fluence the pattern reorients from pits and mounds with edges along the <110 > directions to ridges and valleys rotated ≈45 ∘ to the <110 > directions.

  3. Iceberg calving during transition from grounded to floating ice: Columbia Glacier, Alaska

    USGS Publications Warehouse

    Walter, Fabian; O'Neel, Shad; McNamara, Daniel; Pfeffer, W.T.; Bassis, Jeremy N.; Fricker, Helen Amanda

    2010-01-01

    The terminus of Columbia Glacier, Alaska, unexpectedly became ungrounded in 2007 during its prolonged retreat. Visual observations showed that calving changed from a steady release of low-volume bergs, to episodic flow-perpendicular rifting, propagation, and release of very large icebergs - a style reminiscent of calving from ice shelves. Here, we compare passive seismic and photographic observations through this transition to examine changes in calving. Mechanical changes accompany the visible changes in calving style post flotation: generation of seismic energy during calving is substantially reduced. We propose this is partly due to changes in source processes.

  4. Vibrational spectra and UV photochemistry of (CH 2) 2O thin films and (CH 2) 2O in amorphous water ice

    NASA Astrophysics Data System (ADS)

    Schriver, A.; Coanga, J. M.; Schriver-Mazzuoli, L.; Ehrenfreund, P.

    2004-08-01

    We use Fourier transform infrared (FTIR) reflection spectroscopy (incidence angle of 5°) to characterize thin films of ethylene oxide (EO) and water/EO mixtures (between 11 and 170 K under a pressure of 10 -7 mbar). The photochemistry of EO in matrices, in the solid phase and ice was also investigated at 11 K using a microwave excited hydrogen flow lamp. Solid EO has two solid phases: an amorphous phase which is obtained below 75 K and a crystalline phase observed below 110 K. EO begins to sublimate around 100 K with a binding energy of 20 ± 2 kJ mol -1. Gaseous mixtures of EO containing water traces deposited at 30 K lead to the condensation of small clusters (EO 2) m(H 2O) n. The vibrational spectrum of EO diluted in water ice remains nearly unchanged between 11 and 120 K. Between 120 and 130 K, a large part of EO is released and changes in the frequencies and in the profile of the EO absorptions are observed. In the water lattice the trapped EO is hydrogen-bonded to water molecules below 120 K. In the range 130-160 K, EO is primarily present as clathrate hydrate. UV photochemistry of EO showed to be rather independent on the matrix or solid it is embedded. In matrices, in the solid phase and in ice, three primary photoproducts are formed from two different channels: acetaldehyde, methane and carbon monoxide. Only in matrices, acetaldhehyde decomposes partially into ketene and into a acetylene/water complex.

  5. Nanocrystal dispersed amorphous alloys

    NASA Technical Reports Server (NTRS)

    Perepezko, John H. (Inventor); Allen, Donald R. (Inventor); Foley, James C. (Inventor)

    2001-01-01

    Compositions and methods for obtaining nanocrystal dispersed amorphous alloys are described. A composition includes an amorphous matrix forming element (e.g., Al or Fe); at least one transition metal element; and at least one crystallizing agent that is insoluble in the resulting amorphous matrix. During devitrification, the crystallizing agent causes the formation of a high density nanocrystal dispersion. The compositions and methods provide advantages in that materials with superior properties are provided.

  6. Zooplankton abundance and biomass size spectra in the East Antarctic sea-ice zone during the winter-spring transition

    NASA Astrophysics Data System (ADS)

    Wallis, Jake R.; Swadling, Kerrie M.; Everett, Jason D.; Suthers, Iain M.; Jones, Hugh J.; Buchanan, Pearse J.; Crawford, Christine M.; James, Lainey C.; Johnson, Robert; Meiners, Klaus M.; Virtue, Patti; Westwood, Karen; Kawaguchi, So

    2016-09-01

    Sea ice is an influential feature in Southern Ocean-Antarctic marine environments creating a 2-phase vertical ecosystem. The lack of information on how this system influences community structure during the winter-spring transition, however, is largely lacking. Zooplankton form the link that bridges these environments, with the meiofaunal and algal communities within sea ice directly influencing the epipelagic zooplankton community at the ice-water interface. A combination of methods including sea-ice coring, umbrella net sampling and Laser Optical Plankton Counter were used to describe the vertical structure of zooplankton and meiofaunal communities. The distribution of meiofauna and chlorophyll a both played important roles in structuring the zooplankton community within this dynamic region. Many dominant taxa, including Calanus propinquus and Oithona similis, directly responded to the high availability of algae present within the bottom strata of sea ice. The sea-ice associated species Stephos longipes represented a strong link between this 2-phase ecosystem. Observations of the vertical distribution of biomass obtained from the LOPC suggests that the responses of these species to the sea ice directly influences the vertical structure of zooplankton during the winter-spring transition.

  7. A SAXS-WAXS study of the endothermic transitions in amorphous or supercooled liquid itraconazole

    DOE PAGES

    Benmore, C. J.; Mou, Q.; Benmore, K. J.; Robinson, D. S.; Neuefeind, J.; Ilavsky, J.; Byrn, S. R.; Yarger, J. L.

    2016-10-07

    Small and wide angle high energy x-ray scattering experiments were performed upon cooling itraconazole from the melt to investigate the structural origin of the two transitions at ~74 °C and ~90 °C observed in DSC measurements. Slight changes to the main WAXS peak at Q = 1.33 ± 0.01 Å–1 were observed at 90 °C and are found to be inter-molecular in nature, suggesting a liquid to isotropic transition. This finding was supported by complementary wide angle neutron scattering measurements. For temperatures at and below ~74 °C two strong rings appear in the 2D-SAXS pattern at Q = 0.24 ±more » 0.01 Å–1 and 0.43 ± 0.01 Å–1. The SAXS spectra were further deconvoluted into sharp and broad components. Lastly, a narrowing of the broad component is associated with only minor changes in the packing arrangements of the itraconazole molecules below ~90 °C, while the appearance of the sharp component below ~74 °C is attributed to the formation of a polydomain lamellar phase.« less

  8. Self-catalyzed growth of S layers via an amorphous-to-crystalline transition limited by folding kinetics

    PubMed Central

    Chung, Sungwook; Shin, Seong-Ho; Bertozzi, Carolyn R.; De Yoreo, James J.

    2010-01-01

    The importance of nonclassical, multistage crystallization pathways is increasingly evident from theoretical studies on colloidal systems and experimental investigations of proteins and biomineral phases. Although theoretical predictions suggest that proteins follow these pathways as a result of fluctuations that create unstable dense-liquid states, microscopic studies indicate these states are long-lived. Using in situ atomic force microscopy to follow 2D assembly of S-layer proteins on supported lipid bilayers, we have obtained a molecular-scale picture of multistage protein crystallization that reveals the importance of conformational transformations in directing the pathway of assembly. We find that monomers with an extended conformation first form a mobile adsorbed phase, from which they condense into amorphous clusters. These clusters undergo a phase transition through S-layer folding into crystalline clusters composed of compact tetramers. Growth then proceeds by formation of new tetramers exclusively at cluster edges, implying tetramer formation is autocatalytic. Analysis of the growth kinetics leads to a quantitative model in which tetramer creation is rate limiting. However, the estimated barrier is much smaller than expected for folding of isolated S-layer proteins, suggesting an energetic rationale for this multistage pathway. PMID:20823255

  9. Magnetic and transport properties of amorphous GdxGe1-x alloys near the metal-insulator transition

    NASA Astrophysics Data System (ADS)

    Helgren, E.; Hellman, F.; Zeng, Li; Sinenian, N.; Islam, R.; Smith, David J.

    2007-11-01

    The temperature and field dependence of magnetization and conductivity of amorphous Ge doped with Gd (a-GdxGe1-x) has been measured for a wide range of x (0.08transition. Magnetization and magnetic susceptibility measurements show strong magnetic interactions and a low temperature spin-glass freezing. High field magnetization and susceptibility per Gd atom in the paramagnetic state are significantly suppressed below that of noninteracting Gd, as observed previously for a-Gd-Si alloys. However, unlike a-Gd-Si , the low field susceptibility does not fit a Curie-Weiss law and shows no significant dependence on composition. Conductivity measurements show that Gd causes localization of charge carriers below a characteristic temperature T* , which also marks the onset of significant negative magnetoresistance. Both T* and the magnitude of the MR are significantly lower in a-Gd-Ge than in comparable a-Gd-Si alloys. It is proposed that the large effects of the host matrix (Ge vs Si) are due to differences in both the band gap and dielectric constant, which cause changes in screening, thereby altering the effect of Gd magnetic moments on the localization of carriers and on the indirect mediated Gd-Gd exchange interactions.

  10. Mechanism of Pressure-Induced Phase Transitions, Amorphization, and Absorption-Edge Shift in Photovoltaic Methylammonium Lead Iodide.

    PubMed

    Szafrański, Marek; Katrusiak, Andrzej

    2016-09-01

    Our single-crystal X-ray diffraction study of methylammonium lead triiodide, MAPbI3, provides the first comprehensive structural information on the tetragonal phase II in the pressure range to 0.35 GPa, on the cubic phase IV stable between 0.35 and 2.5 GPa, and on the isostructural cubic phase V observed above 2.5 GPa, which undergoes a gradual amorphization. The optical absorption study confirms that up to 0.35 GPa, the absorption edge of MAPbI3 is red-shifted, allowing an extension of spectral absorption. The transitions to phases IV and V are associated with the abrupt blue shifts of the absorption edge. The strong increase of the energy gap in phase V result in a spectacular color change of the crystal from black to red around 3.5 GPa. The optical changes have been correlated with the pressure-induced strain of the MAPbI3 inorganic framework and its frustration, triggered by methylammonium cations trapped at random orientations in the squeezed voids. PMID:27538989

  11. High-throughput exploration of thermoelectric and mechanical properties of amorphous NbO2 with transition metal additions

    NASA Astrophysics Data System (ADS)

    Music, Denis; Geyer, Richard W.; Hans, Marcus

    2016-07-01

    To increase the thermoelectric efficiency and reduce the thermal fatigue upon cyclic heat loading, alloying of amorphous NbO2 with all 3d and 5d transition metals has systematically been investigated using density functional theory. It was found that Ta fulfills the key design criteria, namely, enhancement of the Seebeck coefficient and positive Cauchy pressure (ductility gauge). These quantum mechanical predictions were validated by assessing the thermoelectric and elastic properties on combinatorial thin films, which is a high-throughput approach. The maximum power factor is 2813 μW m-1 K-2 for the Ta/Nb ratio of 0.25, which is a hundredfold increment compared to pure NbO2 and exceeds many oxide thermoelectrics. Based on the elasticity measurements, the consistency between theory and experiment for the Cauchy pressure was attained within 2%. On the basis of the electronic structure analysis, these configurations can be perceived as metallic, which is consistent with low electrical resistivity and ductile behavior. Furthermore, a pronounced quantum confinement effect occurs, which is identified as the physical origin for the Seebeck coefficient enhancement.

  12. Simulating the last glacial-interglacial transition with a coupled atmosphere-ocean-ice sheet model

    NASA Astrophysics Data System (ADS)

    Mikolajewicz, Uwe; Ziemen, Florian

    2015-04-01

    One of the major challenges in climate modeling is the simulation of glacial-interglacial transitions. A few models of intermediate complexity have been successful in simulating the last termination. Complex atmosphere-ocean general circulation models have been shown to be able to yield realistic climate changes with prescribed ice sheets. Here we presents results from a first attempt to simulate a substantial part of the last glacial cycle with an AOGCM coupled interactively with a state-of-the-art ice sheet model. The ECHAM5/MPIOM AOGCM has been interactively coupled to the dynamical ice sheet model PISM. The latter is run for most of the northern hemisphere with a horizontal resolution of 20 km. An earlier version of this model ( Ziemen et al. 2014) has been applied to a steady state simulation of the last glacial maximum (LGM). The model was integrated from the late Glacial into the Holocene using insolation and greenhouse gas concentrations as transient forcing. Land sea mask and ocean topography are fixed at LGM conditions, river routing and surface elevation for the atmospheric model component are calculated interactively depending on the simulated ice sheets. To make these long simulations feasible, the atmosphere is accelerated by a factor of 10 relative to the other model components using a periodically-synchronous coupling technique. A mini-ensemble with different initial conditions has been run. In all simulation the northern hemispheric deglaciation starts between 18 and 17 kyr BP, consistent with the onset of global warming. The model produces Heinrich event like variability as part of its internal variability. These rapid ice discharge events have a strong impact on the North Atlantic meridional overturning circulation (NAMOC). During the peak deglaciation the NAMOC is collapsed (with a few short interruptions) for several thousand years, which is longer than the estimates from reconstructions. This seems to be an artifact due to keeping ocean

  13. Nucleation of Ice

    NASA Astrophysics Data System (ADS)

    Molinero, Valeria

    2009-03-01

    The freezing of water into ice is a ubiquitous transformation in nature, yet the microscopic mechanism of homogeneous nucleation of ice has not yet been elucidated. One of the reasons is that nucleation happens in time scales that are too fast for an experimental characterization and two slow for a systematic study with atomistic simulations. In this work we use coarse-grained molecular dynamics simulations with the monatomic model of water mW[1] to shed light into the mechanism of homogeneous nucleation of ice and its relationship to the thermodynamics of supercooled water. Cooling of bulk water produces either crystalline ice or low- density amorphous ice (LDA) depending on the quenching rate. We find that ice crystallization occurs faster at temperatures close to the liquid-liquid transition, defined as the point of maximum inflection of the density with respect to the temperature. At the liquid-liquid transition, the time scale of nucleation becomes comparable to the time scale of relaxation within the liquid phase, determining --effectively- the end of the metastable liquid state. Our results imply that no ultraviscous liquid water can exist at temperatures just above the much disputed glass transition of water. We discuss how the scenario is changed when water is in confinement, and the relationship of the mechanism of ice nucleation to that of other liquids that present the same phase behavior, silicon [2] and germanium [3]. [4pt] [1] Molinero, V. & Moore, E. B. Water modeled as an intermediate element between carbon and silicon. Journal of Physical Chemistry B (2008). Online at http://pubs.acs.org/cgi- bin/abstract.cgi/jpcbfk/asap/abs/jp805227c.html [0pt] [2] Molinero, V., Sastry, S. & Angell, C. A. Tuning of tetrahedrality in a silicon potential yields a series of monatomic (metal-like) glass formers of very high fragility. Physical Review Letters 97, 075701 (2006).

  14. Influence of the torsional potential on the glass transition temperature and the structure of amorphous polyethylene.

    PubMed

    Canales, Manel

    2009-05-01

    The effect of the torsional potential on several thermodynamic and structural properties of a system of polyethylene chains has been analyzed. To this end, molecular dynamics simulations of a coarse-grained model, whose sites interact through a force field with bending, torsional, and nonbonded terms, have been considered. The torsional potential has three stable configurations: gauche-, trans, and gauche+ . It has been modeled using a simple functional form with only two parameters: the trans-gauche and the gauche-gauche energy barriers. In order to analyze the influence of these parameters on the properties considered in this work, five models with different values of the torsional barriers have been considered. We have observed that the glass transition temperature, the intrachain radial distribution function, the radius of gyration, and the end to end distribution functions are very sensitive to the changes in the trans-gauche torsional barrier. Moreover, at low temperatures, the interchain radial distribution function, the orientational correlation function, and the volume distribution functions of the Voronoi polyhedra, that surround every site of the polymeric chains, also depend on the trans-gauche torsional barrier. On the contrary, the gauche-gauche energy barrier has a minor influence in the properties considered in this work.

  15. Water's second glass transition.

    PubMed

    Amann-Winkel, Katrin; Gainaru, Catalin; Handle, Philip H; Seidl, Markus; Nelson, Helge; Böhmer, Roland; Loerting, Thomas

    2013-10-29

    The glassy states of water are of common interest as the majority of H2O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water's calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This "double Tg scenario" is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at Tg,2 about five times as large as at Tg,1. By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate-dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20-25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known ("superstrong"), and also high-density liquid is classified as a strong liquid. PMID:24101518

  16. Problems in obtaining perfect images by single-particle electron cryomicroscopy of biological structures in amorphous ice.

    PubMed

    Henderson, Richard; McMullan, Greg

    2013-02-01

    Theoretical considerations together with simulations of single-particle electron cryomicroscopy images of biological assemblies in ice demonstrate that atomic structures should be obtainable from images of a few thousand asymmetric units, provided the molecular weight of the whole assembly being studied is greater than the minimum needed for accurate position and orientation determination. However, with present methods of specimen preparation and current microscope and detector technologies, many more particles are needed, and the alignment of smaller assemblies is difficult or impossible. Only larger structures, with enough signal to allow good orientation determination and with enough images to allow averaging of many hundreds of thousands or even millions of asymmetric units, have successfully produced high-resolution maps. In this review, we compare the contrast of experimental electron cryomicroscopy images of two smaller molecular assemblies, namely apoferritin and beta-galactosidase, with that expected from perfect simulated images calculated from their known X-ray structures. We show that the contrast and signal-to-noise ratio of experimental images still require significant improvement before it will be possible to realize the full potential of single-particle electron cryomicroscopy. In particular, although reasonably good orientations can be obtained for beta-galactosidase, we have been unable to obtain reliable orientation determination from experimental images of apoferritin. Simulations suggest that at least 2-fold improvement of the contrast in experimental images at ~10 Å resolution is needed and should be possible.

  17. Phonon renormalization and Raman spectral evolution through amorphous to crystalline transitions in Sb{sub 2}Te{sub 3} thin films

    SciTech Connect

    Secor, Jeff; Zhao, Lukas; Krusin-Elbaum, Lia; Harris, Matt A.; Deng, Haiming; Raoux, Simone

    2014-06-02

    A symmetry specific phonon mode renormalization is observed across an amorphous to crystalline phase transformation in thin films of the topological material Sb{sub 2}Te{sub 3} using Raman spectroscopy. We present evidence for local crystalline symmetry in the amorphous state, eventhough, the q = 0 Raman selection rule is broken due to strong structural disorder. At crystallization, the in-plane polarized (E{sub g}{sup 2}) mode abruptly sharpens while the out-of-plane polarized (A{sub 1g}) modes are only weakly effected. This effect unique to the E{sub g} symmetry is exceptional considering that polarized spectra and comparison of the single phonon density of states between the amorphous and crystalline phases suggest that short range order of the amorphous phase is, on the average, similar to that of the crystalline material while electrical transport measurements reveal a sharp insulator-to-metal transition. Our findings point to the important role of anisotropic disorder affecting potential applications of topological and phase-change based electronics.

  18. Ultrafast crystalline-to-amorphous phase transition in Ge{sub 2}Sb{sub 2}Te{sub 5} chalcogenide alloy thin film using single-shot imaging spectroscopy

    SciTech Connect

    Takeda, Jun Oba, Wataru; Minami, Yasuo; Katayama, Ikufumi; Saiki, Toshiharu

    2014-06-30

    We have observed an irreversible ultrafast crystalline-to-amorphous phase transition in Ge{sub 2}Sb{sub 2}Te{sub 5} chalcogenide alloy thin film using broadband single-shot imaging spectroscopy. The absorbance change that accompanied the ultrafast amorphization was measured via single-shot detection even for laser fluences above the critical value, where a permanent amorphized mark was formed. The observed rise time to reach the amorphization was found to be ∼130–200 fs, which was in good agreement with the half period of the A{sub 1} phonon frequency in the octahedral GeTe{sub 6} structure. This result strongly suggests that the ultrafast amorphization can be attributed to the rearrangement of Ge atoms from an octahedral structure to a tetrahedral structure. Finally, based on the dependence of the absorbance change on the laser fluence, the stability of the photoinduced amorphous phase is discussed.

  19. DMSP and DMS cycling within Antarctic sea ice during the winter-spring transition

    NASA Astrophysics Data System (ADS)

    Damm, E.; Nomura, D.; Martin, A.; Dieckmann, G. S.; Meiners, K. M.

    2016-09-01

    This study describes within-ice concentrations of dimethylsulfoniopropionate (DMSP), its degradation product dimethylsulphide (DMS), as well as nutrients and chlorophyll a, that were sampled during the Sea Ice Physics and Ecosystems eXperiment-2 (SIPEX-2) in 2012. DMSP is a methylated substrate produced in large amounts annually by ice-associated microalgae, while DMS plays a significant role in carbon and sulphur cycling in the Southern Ocean. In the East Antarctic study area between 115-125°E and 64-66°S, ice and slush cores, brine, under-ice seawater and zooplankton (Antarctic krill) samples were collected at 6 ice stations. The pack-ice was characterised by high snow loading which initiated flooding events and triggered nutrient supply to the sea-ice surface, while variation in ice conditions influenced sea-ice permeability. This ranged from impermeable surface and middle sections of the sea ice, to completely permeable ice cores at some stations. Chlorophyll a maxima shifted from the sea-ice surface horizon at the first station to the sea ice bottom layer at the last station. Highest DMSP concentrations were detected in brine samples at the sea-ice surface, reflecting a mismatch with respect to the distribution of chlorophyll a. Our data suggest enhanced DMSP production by sea-ice surface algal communities and its release into brine during freezing and melting, which in turn is coupled to flooding events early in the season. A time-cycle of DMS production by DMSP degradation and DMS efflux is evident at the sea ice-snow interface when slush is formed during melt. Seawater under the ice contained only low concentrations of DMSP and DMS, even when brine drainage was evident and the sea ice became permeable. We postulate that in situ grazing by zooplankton may act as sink for the DMSP produced early in the season.

  20. Observed microphysical changes in Arctic mixed-phase clouds when transitioning from sea-ice to open ocean

    NASA Astrophysics Data System (ADS)

    Young, Gillian; Jones, Hazel M.; Crosier, Jonathan; Bower, Keith N.; Darbyshire, Eoghan; Taylor, Jonathan W.; Liu, Dantong; Allan, James D.; Williams, Paul I.; Gallagher, Martin W.; Choularton, Thomas W.

    2016-04-01

    The Arctic sea-ice is intricately coupled to the atmosphere[1]. The decreasing sea-ice extent with the changing climate raises questions about how Arctic cloud structure will respond. Any effort to answer these questions is hindered by the scarcity of atmospheric observations in this region. Comprehensive cloud and aerosol measurements could allow for an improved understanding of the relationship between surface conditions and cloud structure; knowledge which could be key in validating weather model forecasts. Previous studies[2] have shown via remote sensing that cloudiness increases over the marginal ice zone (MIZ) and ocean with comparison to the sea-ice; however, to our knowledge, detailed in-situ data of this transition have not been previously presented. In 2013, the Aerosol-Cloud Coupling and Climate Interactions in the Arctic (ACCACIA) campaign was carried out in the vicinity of Svalbard, Norway to collect in-situ observations of the Arctic atmosphere and investigate this issue. Fitted with a suite of remote sensing, cloud and aerosol instrumentation, the FAAM BAe-146 aircraft was used during the spring segment of the campaign (Mar-Apr 2013). One case study (23rd Mar 2013) produced excellent coverage of the atmospheric changes when transitioning from sea-ice, through the MIZ, to the open ocean. Clear microphysical changes were observed, with the cloud liquid-water content increasing by almost four times over the transition. Cloud base, depth and droplet number also increased, whilst ice number concentrations decreased slightly. The surface warmed by ~13 K from sea-ice to ocean, with minor differences in aerosol particle number (of sizes corresponding to Cloud Condensation Nuclei or Ice Nucleating Particles) observed, suggesting that the primary driver of these microphysical changes was the increased heat fluxes and induced turbulence from the warm ocean surface as expected. References: [1] Kapsch, M.L., Graversen, R.G. and Tjernström, M. Springtime

  1. Chronology and dynamics of the Amundsen Gulf Ice Stream in Arctic Canada during the last glacial-interglacial transition

    NASA Astrophysics Data System (ADS)

    Lakeman, T. R.; MacLean, B.; Blasco, S.; Bennett, R.; Hughes Clarke, J. E.

    2012-04-01

    influence of the Mackenzie and other fluvial sediment discharge on the seabed over the last 13,000 cal yr BP. The deglacial history of Amundsen Gulf under ameliorating climate conditions of the last ~19,000 cal yr BP provides important constraints on the variables that occasioned the demise of the northwest Laurentide Ice Sheet, such as sea level change, paleoclimate, and regional ice sheet dynamics. Understanding the complex interplay among these variables during the last deglaciation will bear on current model projections of the dynamics of the Greenland and Antarctic ice sheets. In addition, quantifying past iceberg fluxes to the Arctic Ocean has implications for assessing the origin of deep ice scours in the Arctic Ocean Basin and the nature of rapid climate changes at the last glacial-interglacial transition.

  2. Effect of Si additions on thermal stability and the phase transition sequence of sputtered amorphous alumina thin films

    SciTech Connect

    Bolvardi, H.; Baben, M. to; Nahif, F.; Music, D. Schnabel, V.; Shaha, K. P.; Mráz, S.; Schneider, J. M.; Bednarcik, J.; Michalikova, J.

    2015-01-14

    Si-alloyed amorphous alumina coatings having a silicon concentration of 0 to 2.7 at. % were deposited by combinatorial reactive pulsed DC magnetron sputtering of Al and Al-Si (90-10 at. %) split segments in Ar/O{sub 2} atmosphere. The effect of Si alloying on thermal stability of the as-deposited amorphous alumina thin films and the phase formation sequence was evaluated by using differential scanning calorimetry and X-ray diffraction. The thermal stability window of the amorphous phase containing 2.7 at. % of Si was increased by more than 100 °C compared to that of the unalloyed phase. A similar retarding effect of Si alloying was also observed for the α-Al{sub 2}O{sub 3} formation temperature, which increased by more than 120 °C. While for the latter retardation, the evidence for the presence of SiO{sub 2} at the grain boundaries was presented previously, this obviously cannot explain the stability enhancement reported here for the amorphous phase. Based on density functional theory molecular dynamics simulations and synchrotron X-ray diffraction experiments for amorphous Al{sub 2}O{sub 3} with and without Si incorporation, we suggest that the experimentally identified enhanced thermal stability of amorphous alumina with addition of Si is due to the formation of shorter and stronger Si–O bonds as compared to Al–O bonds.

  3. 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.

  4. 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.

  5. 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. PMID:23277941

  6. Automatic Detection of the Holocene Transition in Radio-Echo Sounding Data from the Greenland Ice Sheet

    NASA Astrophysics Data System (ADS)

    Karlsson, N. B.; Dahl-Jensen, D.; Gogineni, S. P.; Paden, J.; Hvidberg, C. S.

    2012-04-01

    Radio-echo sounding has provided important insights into the subsurface properties of the Greenland Ice-Sheet. Recent years have seen increasing interest in englacial radio reflectors (or internal layers) because their stratigraphy reflects both mass balance rates and flow dynamics. Thus patterns of internal layers contain information about the past behaviour of an ice mass. Unfortunately retrieving this information often relies on a large amount of user interaction and can be very time consuming. As the amount of radio-echo sounding data increases, the development of quantitative techniques for digitising internal layers in radar data is a logical step forward. In this study we present an automated method for estimating the elevation of the Holocene transition in radio-echo sounding data from Greenland. The data was collected by the Center for Remote Sensing of Ice Sheets (CReSIS), University of Kansas. The automated method is based on the observation that the CReSIS radio-echo data often display a characteristic appearance: the upper half of the radio-echo data contains numerous internal layering and appears much darker than the lower, older part, where only a few visible layers can be seen. Compared to the depth-age relationship from the NorthGRIP ice core this change in the radar-echo data coincides with the transition to the Holocene period. The method obtains a good match with manually traced data and also returns an estimate of the confidence in its output. The depth of the Holocene transition will provide insight into the large-scale variation of mass balance and basal melt rate over the Greenland Ice Sheet and will assist in efforts to model the past evolution of the ice sheet.

  7. Crystallization of amorphous solid films

    NASA Astrophysics Data System (ADS)

    Safarik, Douglas Joseph

    2003-06-01

    Below ˜130 K, H2O can exist for prolonged periods in a thermodynamically unstable, non-crystalline solid form known as amorphous solid water (ASW). When warmed to above 135 K, ASW crystallizes to the thermodynamically favored state, cubic ice I, on a laboratory time scale. Despite the relevance of ASW crystallization to a variety of scientific problems ranging from astrophysical phenomena to cryopreservation, the kinetics of this transformation are largely uncharacterized, and its mechanism is not fully understood. In the present work, the crystallization kinetics of vapor-deposited, nonporous ASW films less than one micron thick are investigated experimentally near 140 K. The amorphous to crystalline transition is characterized using a probe molecule, chlorodifluoromethane (CHF2Cl), whose adsorbed states and hence desorption kinetics are sensitive to the crystallinity of solid water surfaces. The transformation kinetics of very thick ASW films are found to be both independent of specimen size and consistent with simultaneous homogeneous nucleation and isotropic growth of crystalline ice grains. As the ASW film thickness is reduced from 385 nm to 55 nm, however, the rate of surface crystallization decelerates, in apparent conflict with a homogeneous nucleation and growth mechanism. In an attempt to explain this behavior, a geometrical model of phase transition kinetics at the surface of solids, with special consideration of finite specimen size in one dimension, is constructed. For materials in which nucleation occurs spatially randomly, phase change is predicted to decelerate when film thickness is reduced below the mean crystal grain size. This phenomenon originates from a reduction in the number of crystallites available to transform the surface as the sample becomes thinner. Good quantitative agreement between this simple model and the experimental data is attained using a minimum of kinetic parameters, suggesting it captures the essential physics of ASW

  8. An amorphous-to-crystalline phase transition within thin silicon films grown by ultra-high-vacuum evaporation and its impact on the optical response

    NASA Astrophysics Data System (ADS)

    Orapunt, Farida; Tay, Li-Lin; Lockwood, David J.; Baribeau, Jean-Marc; Noël, Mario; Zwinkels, Joanne C.; O'Leary, Stephen K.

    2016-02-01

    A number of thin silicon films are deposited on crystalline silicon, native oxidized crystalline silicon, and optical quality fused quartz substrates through the use of ultra-high-vacuum evaporation at growth temperatures ranging from 98 to 572 °C. An analysis of their grazing incidence X-ray diffraction and Raman spectra indicates that a phase transition, from amorphous-to-crystalline, occurs as the growth temperature is increased. Through a peak decomposition process, applied to the Raman spectroscopy results, the crystalline volume fractions associated with these samples are plotted as a function of the growth temperature for the different substrates considered. It is noted that the samples grown on the crystalline silicon substrates have the lowest crystallanity onset temperature, whereas those grown on the optical quality fused quartz substrates have the highest crystallanity onset temperature; the samples grown on the native oxidized crystalline silicon substrates have a crystallanity onset temperature between these two limits. These resultant dependencies on the growth temperature provide a quantitative means of characterizing the amorphous-to-crystalline phase transition within these thin silicon films. It is noted that the thin silicon film grown on an optical quality fused quartz substrate at 572 °C, possessing an 83% crystalline volume fraction, exhibits an optical absorption spectrum which is quite distinct from that associated with the other thin silicon films. We suggest that this is due to the onset of sufficient long-range order in the film for wave-vector conservation to apply, at least partially. Finally, we use a semi-classical optical absorption analysis to study how this phase transition, from amorphous-to-crystalline, impacts the spectral dependence of the optical absorption coefficient.

  9. Protist diversity in a permanently ice-covered Antarctic lake during the polar night transition.

    PubMed

    Bielewicz, Scott; Bell, Elanor; Kong, Weidong; Friedberg, Iddo; Priscu, John C; Morgan-Kiss, Rachael M

    2011-09-01

    The McMurdo Dry Valleys of Antarctica harbor numerous permanently ice-covered lakes, which provide a year-round oasis for microbial life. Microbial eukaryotes in these lakes occupy a variety of trophic levels within the simple aquatic food web ranging from primary producers to tertiary predators. Here, we report the first molecular study to describe the vertical distribution of the eukaryotic community residing in the photic zone of the east lobe (ELB) and west lobe (WLB) of the chemically stratified Lake Bonney. The 18S ribosomal RNA (rRNA) libraries revealed vertically stratified populations dominated by photosynthetic protists, with a cryptophyte dominating shallow populations (ELB-6 m; WLB-10 m), a haptophyte occupying mid-depths (both lobes 13 m) and chlorophytes residing in the deepest layers (ELB-18 and 20 m; WLB-15 and 20 m) of the photic zone. A previously undetected stramenopile occurred throughout the water column of both lobes. Temporal variation in the eukaryotic populations was examined during the transition from Antarctic summer (24-h sunlight) to polar night (complete dark). Protist diversity was similar between the two lobes of Lake Bonney due to exchange between the photic zones of the two basins via a narrow bedrock sill. However, vertical and temporal variation in protist distribution occurred, indicating the influence of the unique water chemistry on the biology of the two dry valley watersheds.

  10. Protist diversity in a permanently ice-covered Antarctic lake during the polar night transition.

    PubMed

    Bielewicz, Scott; Bell, Elanor; Kong, Weidong; Friedberg, Iddo; Priscu, John C; Morgan-Kiss, Rachael M

    2011-09-01

    The McMurdo Dry Valleys of Antarctica harbor numerous permanently ice-covered lakes, which provide a year-round oasis for microbial life. Microbial eukaryotes in these lakes occupy a variety of trophic levels within the simple aquatic food web ranging from primary producers to tertiary predators. Here, we report the first molecular study to describe the vertical distribution of the eukaryotic community residing in the photic zone of the east lobe (ELB) and west lobe (WLB) of the chemically stratified Lake Bonney. The 18S ribosomal RNA (rRNA) libraries revealed vertically stratified populations dominated by photosynthetic protists, with a cryptophyte dominating shallow populations (ELB-6 m; WLB-10 m), a haptophyte occupying mid-depths (both lobes 13 m) and chlorophytes residing in the deepest layers (ELB-18 and 20 m; WLB-15 and 20 m) of the photic zone. A previously undetected stramenopile occurred throughout the water column of both lobes. Temporal variation in the eukaryotic populations was examined during the transition from Antarctic summer (24-h sunlight) to polar night (complete dark). Protist diversity was similar between the two lobes of Lake Bonney due to exchange between the photic zones of the two basins via a narrow bedrock sill. However, vertical and temporal variation in protist distribution occurred, indicating the influence of the unique water chemistry on the biology of the two dry valley watersheds. PMID:21390078

  11. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts.

    PubMed

    Zimnyakov, D A; Sevrugin, A V; Yuvchenko, S A; Fedorov, F S; Tretyachenko, E V; Vikulova, M A; Kovaleva, D S; Krugova, E Y; Gorokhovsky, A V

    2016-06-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka-Munk function reveals a presence of local maxima in the regions 0.5-1.5 eV and 1.6-3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  12. Ice Age Reboot: Thermohaline Circulation Crisis during the Mid-Pleistocene Transition

    NASA Astrophysics Data System (ADS)

    Pena, L.; Goldstein, S. L.

    2014-12-01

    The mid-Pleistocene transition (MPT) marked a fundamental change in glacial-interglacial periodicity, when it increased from ~41- to 100-kyr cycles and developed higher amplitude climate variability. Because it took place without significant changes in the Milankovitch forcing, this fundamental change must reflect either non-linear responses of the climate system to these external forcings, or internal changes in the ocean-atmosphere-cryosphere system that led to longer periodicities and more intense glacial periods. We document using Nd isotopes a major disruption of the ocean thermohaline circulation (THC) system during the MPT between MIS 25-21 at ~950-860 ka, which effectively marks the first 100-kyr cycle, including an exceptional weakening through critical interglacial MIS 23 at ~900 ka. The data are from ODP Sites 1088 (41°8.163'S, 13°33.77'E, 2082m) and 1090 (42°54.82'S, 8°53.98E', 3702m) in the SE Atlantic Subantarctic Zone, near the upper and lower boundaries of NADW and Circumpolar Deep Water (CDW). Given evidence for nearly stable NADW and North Pacific Water (NPW) ɛNd-values over the last 2 Ma, we interpret the ɛNd variations to reflect changes in the NADW:NPW mixing fractions. During the studied pre-MPT 41-kyr world (MIS 31-25, 1,100-950 ka), at both sites the differences in glacial and interglacial ɛNd-values are small, indicating strong glacial as well as interglacial export of NADW. A major weakening of NADW export occurred during MIS 24-22, including MIS 23, which is unique as the only known interglacial in which the THC did not strengthen, and thus can be considered as a 'trans-glacial' period. The recovery into the post-MPT 100-kyr world is characterized by continued weak glacial THC. We conclude that the MPT ocean circulation crisis 'rebooted' the pacing and intensity of ice ages and facilitated the coeval drawdown of atmospheric CO2 and high latitude ice sheet growth, generating the conditions that stabilized 100-kyr cycles.

  13. Trehalose amorphization and recrystallization.

    PubMed

    Sussich, Fabiana; Cesàro, Attilio

    2008-10-13

    The stability of the amorphous trehalose prepared by using several procedures is presented and discussed. Amorphization is shown to occur by melting (T(m)=215 degrees C) or milling (room temperature) the crystalline anhydrous form TRE-beta. Fast dehydration of the di-hydrate crystalline polymorph, TRE-h, also produces an amorphous phase. Other dehydration procedures of TRE-h, such as microwave treatment, supercritical extraction or gentle heating at low scan rates, give variable fractions of the polymorph TRE-alpha, that undergo amorphization upon melting (at lower temperature, T(m)=130 degrees C). Additional procedures for amorphization, such as freeze-drying, spray-drying or evaporation of trehalose solutions, are discussed. All these procedures are classified depending on the capability of the undercooled liquid phase to undergo cold crystallization upon heating the glassy state at temperatures above the glass transition temperature (T(g)=120 degrees C). The recrystallizable amorphous phase is invariably obtained by the melt of the polymorph TRE-alpha, while other procedures always give an amorphous phase that is unable to crystallize above T(g). The existence of two different categories is analyzed in terms of the transformation paths and the hypothesis that the systems may exhibit different molecular mobilities.

  14. Characteristics and primary productivity of East Antarctic pack ice during the winter-spring transition

    NASA Astrophysics Data System (ADS)

    Ugalde, Sarah C.; Westwood, Karen J.; van den Enden, Rick; McMinn, Andrew; Meiners, Klaus M.

    2016-09-01

    Microbial communities have evolved mechanisms to allow them to survive within the challenging and changing pack ice environment. One such mechanism may be the exudation of photosynthetically-derived organic carbon into various extracellular pools. During the 2nd Sea Ice Physics and Ecosystems eXperiment (SIPEX-2), East Antarctic pack ice productivity and subsequent carbon allocation were quantified, together with physico-biogeochemical characteristics (29 September-28 October, 2012). Mean ice thickness ranged between 0.80 and 2.16 m, and typically exhibited a warm ice interior with weak temperature gradients. All stations, with one exception, were layered with granular (mean: 78%), columnar (mean: 15%), and mixed granular/columnar (mean: 4%) ice. Highest ice brine-volume fractions were at the ice-water interface, but all ice had high brine-volume fractions conducive for brine percolation (mean: 15%). Dissolved inorganic nutrient concentrations in the brine were scattered around theoretical dilution lines (TDLs), with some values of nitrate and nitrite, ammonium and silicic acid falling below TDLs, indicating nutrient depletion. Bulk ice dissolved organic carbon was low (mean: 64 μmol kg-1), but most samples showed enrichment in relation to TDLs. Microbial biomass (bacterial and algal) was low, and generally showed maxima in the sea-ice interior. Bottom ice algal communities were dominated by pennate diatom species (mean: 86% of total cell abundance). 14C-total primary productivity (14C-TPP) ranged from <0.01 to 2.22 mg C (mg chl a)-1 d-1 (<0.01 to 3.03 mg C m-2 d-1). The relative contribution of 14C-total extracellular organic carbon (14C-TEOC) to 14C-TPP decreased over the observational period (range: 44-21%), with the remaining proportion being 14C-particulate organic carbon. 14C-TEOC composition was dominated by low molecular weight 14C-extracellular dissolved organic carbon (mean: 61%), with the remaining proportion allocated to 14C-colloidal organic carbon

  15. THz time-domain spectroscopy of mixed CO2-CH3OH interstellar ice analogs.

    PubMed

    McGuire, Brett A; Ioppolo, Sergio; Allodi, Marco A; Blake, Geoffrey A

    2016-07-27

    The icy mantles of interstellar dust grains are the birthplaces of the primordial prebiotic molecular inventory that may eventually seed nascent solar systems and the planets and planetesimals that form therein. Here, we present a study of two of the most abundant species in these ices after water: carbon dioxide (CO2) and methanol (CH3OH), using TeraHertz (THz) time-domain spectroscopy and mid-infrared spectroscopy. We study pure and mixed-ices of these species, and demonstrate the power of the THz region of the spectrum to elucidate the long-range structure (i.e. crystalline versus amorphous) of the ice, the degree of segregation of these species within the ice, and the thermal history of the species within the ice. Finally, we comment on the utility of the THz transitions arising from these ices for use in astronomical observations of interstellar ices.

  16. On the origin of Gaussian network theory in the thermo/chemo-responsive shape memory effect of amorphous polymers undergoing photo-elastic transition

    NASA Astrophysics Data System (ADS)

    Lu, Haibao; Huang, Wei Min; Leng, Jinsong

    2016-06-01

    Amorphous polymers are normally isotropic in their physical properties, however, upon stress their structural randomness is disturbed and they become anisotropic. There is a close connection between the optical anisotropy and the elastic (or mechanical) anisotropy, since both are related to the type of symmetry exhibited by the molecular structure. On the origin of Gaussian network theory, a phenomenological constitutive framework was proposed to study the photo-elastic transition and working mechanism of the thermo-/chemo-responsive shape-memory effect (SME) in amorphous shape memory polymers (SMPs). Optically refractive index was initially employed to couple the stress, strain and the anisotropy of the random link in macromolecule chain. Based on the Arrhenius law, a constitutive framework was then applied for the temperature dependence of optical (or elastic or mechanical) anisotropy according to the fictive temperature parameter. Finally, the phenomenological photo-elastic model was proposed to quantitatively identify the influential factors behind the thermo-/chemo-responsive SME in SMPs, of which the shape recovery behavior is predicted and verified by the available experimental data reported in the literature.

  17. Understanding the amorphous-to-microcrystalline silicon transition in SiF{sub 4}/H{sub 2}/Ar gas mixtures

    SciTech Connect

    Dornstetter, Jean-Christophe; Bruneau, Bastien; Bulkin, Pavel; Johnson, Erik V.; Roca i Cabarrocas, Pere

    2014-06-21

    We report on the growth of microcrystalline silicon films from the dissociation of SiF{sub 4}/H{sub 2}/Ar gas mixtures. For this growth chemistry, the formation of HF molecules provides a clear signature of the amorphous to microcrystalline growth transition. Depositing films from silicon tetrafluoride requires the removal of F produced by SiF{sub 4} dissociation, and this removal is promoted by the addition of H{sub 2} which strongly reacts with F to form HF molecules. At low H{sub 2} flow rates, the films grow amorphous as all the available hydrogen is consumed to form HF. Above a critical flow rate, corresponding to the full removal of F, microcrystalline films are produced as there is an excess of atomic hydrogen in the plasma. A simple yet accurate phenomenological model is proposed to explain the SiF{sub 4}/H{sub 2} plasma chemistry in accordance with experimental data. This model provides some rules of thumb to achieve high deposition rates for microcrystalline silicon, namely, that increased RF power must be balanced by an increased H{sub 2} flow rate.

  18. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice.

    PubMed

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-11-20

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures.

  19. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

    PubMed Central

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-01-01

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

  20. Exploring controls on ice stream destabilisation during the LGM/Holocene transition in West Greenland

    NASA Astrophysics Data System (ADS)

    Roberts, David H.; Rea, Brice R.; Lane, Tim P.; Jamieson, Stewart S. R.; Cofaigh, Colm Ó.; Vieli, Andreas

    2014-05-01

    Newly emerging onshore and offshore deglacial chronologies from West Greenland enable investigation of the role of both climate and topography in controlling ice stream dynamics The Uummannaq ice stream system (UIS) now has a comprehensive deglacial chronology (eg. Lane et al; 2013; Ó Cofaigh et al., 2013; Roberts et al., 2013) which includes four dimensional control i.e. location and geometry of the ice margin and ice stream trunk and rates of thinning and retreat. This provides a framework for interpreting the main drivers and controls on ice stream dynamics under changing climatic conditions. Deglaciation of the UIS began on the outer shelf at ~14.8 ka, with Ubekendt Ejland becoming ice free at ~12.4 ka. Staircases of lateral moraines on the southern flanks of Ubekendt point to step-wise thinning of the UIS as ice retreated from the shelf edge. This period of retreat coincided with a rise in air temperature between 16 -14.5 ka, increasing JJA solar radiation as well sea-level rise. The wide, mid-shelf trough (> 30km; which harboured the main UIS trunk zone) also had few constrictions which facilitated grounding line retreat. The UIS then withdrew rapidly with 80 - 100 km of retreat by ~11.4 ka - 10.8 ka as the northern and southern feeder zones unzipped. This coincided with increasing insolation and peak sea-level, but topography and bathymetry were also influential on margin retreat (i.e. reverse slope over-deepening and fjord widening). This retreat occurred despite Younger Dryas air temperature cooling. Along the southern arm of the UIS the grounding line retreated towards Store Gletscher becoming topographically pinned at ~11.4 - 11.0 ka, but from 9.3 ka onwards retreat rates increased with the ice reaching the present Store Gletscher margin by 8.7 ka. This coincided with increased air temperatures and peak summer insolation at the start of the Holocene. The northern arm of the UIS also deglaciated quickly from Ubekendt, calving northward into Karrat

  1. Data on energy-band-gap characteristics of composite nanoparticles obtained by modification of the amorphous potassium polytitanate in aqueous solutions of transition metal salts

    PubMed Central

    Zimnyakov, D.A.; Sevrugin, A.V.; Yuvchenko, S.A.; Fedorov, F.S.; Tretyachenko, E.V.; Vikulova, M.A.; Kovaleva, D.S.; Krugova, E.Y.; Gorokhovsky, A.V.

    2016-01-01

    Here we present the data on the energy-band-gap characteristics of composite nanoparticles produced by modification of the amorphous potassium polytitanate in aqueous solutions of different transition metal salts. Band gap characteristics are investigated using diffuse reflection spectra of the obtained powders. Calculated logarithmic derivative quantity of the Kubelka–Munk function reveals a presence of local maxima in the regions 0.5–1.5 eV and 1.6–3.0 eV which correspond to band gap values of the investigated materials. The values might be related to the constituents of the composite nanoparticles and intermediate products of their chemical interaction. PMID:27158654

  2. Antarctic Ice Sheet variability across the Eocene-Oligocene boundary climate transition.

    PubMed

    Galeotti, Simone; DeConto, Robert; Naish, Timothy; Stocchi, Paolo; Florindo, Fabio; Pagani, Mark; Barrett, Peter; Bohaty, Steven M; Lanci, Luca; Pollard, David; Sandroni, Sonia; Talarico, Franco M; Zachos, James C

    2016-04-01

    About 34 million years ago, Earth's climate cooled and an ice sheet formed on Antarctica as atmospheric carbon dioxide (CO2) fell below ~750 parts per million (ppm). Sedimentary cycles from a drill core in the western Ross Sea provide direct evidence of orbitally controlled glacial cycles between 34 million and 31 million years ago. Initially, under atmospheric CO2 levels of ≥600 ppm, a smaller Antarctic Ice Sheet (AIS), restricted to the terrestrial continent, was highly responsive to local insolation forcing. A more stable, continental-scale ice sheet calving at the coastline did not form until ~32.8 million years ago, coincident with the earliest time that atmospheric CO2 levels fell below ~600 ppm. Our results provide insight into the potential of the AIS for threshold behavior and have implications for its sensitivity to atmospheric CO2 concentrations above present-day levels. PMID:27034370

  3. Antarctic Ice Sheet variability across the Eocene-Oligocene boundary climate transition.

    PubMed

    Galeotti, Simone; DeConto, Robert; Naish, Timothy; Stocchi, Paolo; Florindo, Fabio; Pagani, Mark; Barrett, Peter; Bohaty, Steven M; Lanci, Luca; Pollard, David; Sandroni, Sonia; Talarico, Franco M; Zachos, James C

    2016-04-01

    About 34 million years ago, Earth's climate cooled and an ice sheet formed on Antarctica as atmospheric carbon dioxide (CO2) fell below ~750 parts per million (ppm). Sedimentary cycles from a drill core in the western Ross Sea provide direct evidence of orbitally controlled glacial cycles between 34 million and 31 million years ago. Initially, under atmospheric CO2 levels of ≥600 ppm, a smaller Antarctic Ice Sheet (AIS), restricted to the terrestrial continent, was highly responsive to local insolation forcing. A more stable, continental-scale ice sheet calving at the coastline did not form until ~32.8 million years ago, coincident with the earliest time that atmospheric CO2 levels fell below ~600 ppm. Our results provide insight into the potential of the AIS for threshold behavior and have implications for its sensitivity to atmospheric CO2 concentrations above present-day levels.

  4. Antarctic Ice Sheet variability across the Eocene-Oligocene boundary climate transition

    NASA Astrophysics Data System (ADS)

    Galeotti, Simone; DeConto, Robert; Naish, Timothy; Stocchi, Paolo; Florindo, Fabio; Pagani, Mark; Barrett, Peter; Bohaty, Steven M.; Lanci, Luca; Pollard, David; Sandroni, Sonia; Talarico, Franco M.; Zachos, James C.

    2016-04-01

    About 34 million years ago, Earth’s climate cooled and an ice sheet formed on Antarctica as atmospheric carbon dioxide (CO2) fell below ~750 parts per million (ppm). Sedimentary cycles from a drillcore in the western Ross Sea provide direct evidence of orbitally controlled glacial cycles between 34 million and 31 million years ago. Initially, under atmospheric CO2 levels of ≥600 ppm, a smaller Antarctic Ice Sheet (AIS), restricted to the terrestrial continent, was highly responsive to local insolation forcing. A more stable, continental-scale ice sheet calving at the coastline did not form until ~32.8 million years ago, coincident with the earliest time that atmospheric CO2 levels fell below ~600 ppm. Our results provide insight into the potential of the AIS for threshold behavior and have implications for its sensitivity to atmospheric CO2 concentrations above present-day levels.

  5. Exploring controls on ice stream destabilisation during the LGM/Holocene transition in West Greenland

    NASA Astrophysics Data System (ADS)

    Roberts, D. H.; Lane, T. P.; Rea, B. R.; Ó Cofaigh, C.; Jamieson, S.; Vieli, A.

    2015-12-01

    Deglacial chronologies from West Greenland enable investigation of the role of climate and topography in controlling ice stream dynamics. The Uummannaq ice stream system (UIS) in particular has a comprehensive deglacial chronology which, when coupled with geometry, provides a framework for exploring controls on ice stream dynamics under changing climatic conditions. Here, we use a 2D numerical model to simulate grounding line-retreat behaviour and surface thinning in order explore the principal drivers of linear and non-linear ice stream behaviour during the end of the last glacial cycle. Deglaciation of the UIS began on the outer shelf at ~14.8 ka with ice retreat eastward to Ubekendt Ejland by ~12.4 ka. This initial retreat coincided with increasing air temperature, increasing solar radiation and sea-level rise. Awide, mid-shelf, trough also facilitated rapid retreat. The UIS then withdrew eastward ~ 100 km by ~11.4 ka - 10.8 ka as the northern and southern feeder zones unzipped. This coincided with increasing insolation and peak sea-level, but bathymetric over-deepening and fjord widening were also influential. Staircases of lateral moraines throughout the region point to step-wise thinning as ice retreated between 14.8 - 11.0 ka. By 8.7 ka the southern arm of the UIS had reached Store Gletscher and thereafter it retreated beyond the present day grounding line. This coincided with increased air/ocean temperatures and peak summer insolation. In contrast, the northern arm of the UIS stabilised until ~6.5 ka and became unresponsive to both atmospheric and ocean forcing due to topographic pinning. New research has adopted a 2D model approach to establish and quantify the relative importance of various mechanisms in governing UIS dynamics. These model results indicate that the non-linear retreat of the UIS is strongly influenced by vertical and lateral constrictions in the marine trough system which regulates grounding line stability. In turn, grounding line

  6. Heterogeneous ice nucleation: Exploring the transition from stochastic to singular freezing behavior

    NASA Astrophysics Data System (ADS)

    Stratmann, F.; Niedermeier, D.; Hartmann, S.; Shaw, R. A.; Clauss, T.; Wex, H.

    2011-12-01

    Heterogeneous ice nucleation directly influences cloud physical processes, precipitation formation, global radiation balances, and therefore Earth's climate (Cantrell and Heymsfield, 2005 and references therein). It is important to understand the heterogeneous freezing process at a fundamental level in order to describe this process in a physically-based way that will behave robustly in weather and climate models. There is longstanding debate as to whether heterogeneous ice nucleation is a stochastic process (e.g., Carte, 1956) or whether it exhibits singular behaviour (e.g., Langham and Mason, 1958). Fundamentally, the stochastic ice nucleation behavior implies ice nucleation being time dependent, while singular behavior is characterized by ice nucleation taking place on specific particle surface sites at a certain temperature and being time independent (Vali and Stansbury, 1966). We addressed this issue using both experimental and theoretical methods. Experiments focused on immersion freezing of Arizona Test Dust (ATD) were carried out using the Leipzig Aerosol Cloud Interaction Simulator (LACIS), a seven meter long laminar flow diffusion chamber. Both, temperature and time dependencies of ATD-particle induced immersion freezing were investigated. It was found, that ATD-particle induced immersion freezing took place over a wide temperature range and exhibited no detectable time dependence within the range investigated. The theoretical investigations were carried out using a Classical Nucleation Theory (CNT) based, i.e., purely stochastic, numerical model. This idealized model treats statistically similar particles as being covered with surface sites (patches of finite area) characterized by different nucleation barriers, but with each surface site following the stochastic nature of ice embryo formation. The model provides a phenomenological explanation for seemingly contradictory experimental results obtained in the past. Based on CNT alone, a population of

  7. Impact of suborbital climate changes in the North Atlantic on ice sheet dynamics at the Mid-Pleistocene Transition

    NASA Astrophysics Data System (ADS)

    HernáNdez-Almeida, I.; Sierro, F. J.; Cacho, I.; Flores, J. A.

    2012-09-01

    Early and Mid-Pleistocene climate, ocean hydrography and ice sheet dynamics have been reconstructed using a high-resolution data set (planktonic and benthicδ18O time series, faunal-based sea surface temperature (SST) reconstructions and ice-rafted debris (IRD)) record from a high-deposition-rate sedimentary succession recovered at the Gardar Drift formation in the subpolar North Atlantic (Integrated Ocean Drilling Program Leg 306, Site U1314). Our sedimentary record spans from late in Marine Isotope Stage (MIS) 31 to MIS 19 (1069-779 ka). Different trends of the benthic and planktonic oxygen isotopes, SST and IRD records before and after MIS 25 (˜940 ka) evidence the large increase in Northern Hemisphere ice-volume, linked to the cyclicity change from the 41-kyr to the 100-kyr that occurred during the Mid-Pleistocene Transition (MPT). Beside longer glacial-interglacial (G-IG) variability, millennial-scale fluctuations were a pervasive feature across our study. Negative excursions in the benthicδ18O time series observed at the times of IRD events may be related to glacio-eustatic changes due to ice sheets retreats and/or to changes in deep hydrography. Time series analysis on surface water proxies (IRD, SST and planktonicδ18O) of the interval between MIS 31 to MIS 26 shows that the timing of these millennial-scale climate changes are related to half-precessional (10 kyr) components of the insolation forcing, which are interpreted as cross-equatorial heat transport toward high latitudes during both equinox insolation maxima at the equator.

  8. Subsurface Thermal Erosion Of Ice-Wedge Polygon Terrains: Implications For Arctic Geosystem In Transition

    NASA Astrophysics Data System (ADS)

    Fortier, D.; Godin, E.; Lévesque, E.; Veillette, A.

    2014-12-01

    Subsurface thermal erosion is triggered by convective heat transfers between flowing water and permafrost. For inland ice-wedge polygon terrains, heat advection due to infiltration of run-off in the massive ice wedges and the ice-rich upper portion of permafrost creates sink holes and networks of interconnected tunnels in the permafrost. Mass movements such as collapse of tunnel's roof, retrogressive thaw-slumping along exposed permafrost and active layer detachment slides lead to the development of extensive gully networks in the landscape. These gullies drastically change the hydrology of ice-wedge polygon terrains and the fluxes of heat, water, sediment and carbon within the permafrost geosystem. Exportation of sediments by fluvial processes within gullies are positive mechanical feed-back effects that keep gully channels active over decades. Along gully margins, drainage of disturbed polygons and ponds, slope drainage, soil consolidation, plant colonization of disturbed gully slopes and wet to mesic plant succession of drained polygons change the thermal properties of the active layer and create negative feedback effects that stabilize active erosion processes and promote permafrost recovery in gully slopes and adjacent disturbed polygons. On Bylot Island (Nunavut), over 40 gullies were mapped and monitored to characterize gully geomorphology, thermal and mechanical processes of gully erosion, rates of gully erosion over time within different sedimentary deposits, total volume of eroded permafrost at the landscape scale and gully hydrology. We conducted field and laboratory experiments to quantify heat convection processes and speed of ice wedge ablation in order to derive empirical equations to develop a numerical, fully-coupled, heat and mass (water) transfer model of ice-wedge thermal erosion. We used data collected over 10 years of geomorphological gully monitoring, regional climate scenarios, our physics-based numerical thermal erosion model and our field

  9. Observation of a novel relaxation process associated with electronic transitions from deep (D) defects in hydrogenated amorphous silicon

    NASA Astrophysics Data System (ADS)

    Cohen, J. David; Leen, Thomas M.; Rasmussen, Randall J.

    1992-12-01

    Junction capacitance transient measurements were employed to study the thermal emission of electrons trapped in deep (D) defects in lightly n-doped a-Si:H samples. We conclude that a novel defect relaxation process occurs upon a change of change state of the defect such that an electron's thermal release rate is inversely proportional to its residence time in the defect. Supplemental spin transient measurements indicate that both D-/D0 and D0/D+ transitions must be involved. A good fit to our data is obtained if we assume a non-Markovian process for the D0/D+ transition.

  10. Bottom Fixed Platform Dynamics Models Assessing Surface Ice Interactions for Transitional Depth Structures in the Great Lakes: FAST8 – IceDyn

    SciTech Connect

    Karr, Dale G.; Yu, Bingbin; Sirnivas, Senu

    2015-04-01

    To create long-term solutions for offshore wind turbines in a variety of environmental conditions, CAE tools are needed to model the design-driving loads that interact with an offshore wind turbine system during operation. This report describes our efforts in augmenting existing CAE tools used for offshore wind turbine analysis with a new module that can provide simulation capabilities for ice loading on the system. This augmentation was accomplished by creating an ice-loading module coupled to FAST8, the CAE tool maintained by the NREL for simulating land-based and offshore wind turbine dynamics. The new module includes both static and dynamic ice loading that can be applied during a dynamic simulation of the response of an offshore wind turbine. The ice forces can be prescribed, or influenced by the structure’s compliant response, or by the dynamics of both the structure and the ice floe. The new module covers ice failure modes of spalling, buckling, crushing, splitting, and bending. The supporting structure of wind turbines can be modeled as a vertical or sloping form at the waterline. The Inward Battered Guide Structure (IBGS) foundation designed by Keystone Engineering for the Great Lakes was used to study the ice models coupled to FAST8. The IBGS foundation ice loading simulations in FAST8 were compared to the baseline simulation case without ice loading. The ice conditions reflecting those from Lake Huron at Port Huron and Lake Michigan at North Manitou were studied under near rated wind speed of 12 m/s for the NREL 5-MW reference turbine. Simulations were performed on ice loading models 1 through 4 and ice model 6 with their respective sub-models. The purpose of ice model 5 is to investigate ice loading on sloping structures such as ice-cones on a monopile and is not suitable for multi-membered jacketed structures like the IBGS foundation. The key response parameters from the simulations, shear forces and moments from the tower base and IBGS foundation

  11. Semiconductor to metallic transition in bulk accumulated amorphous indium-gallium-zinc-oxide dual gate thin-film transistor

    SciTech Connect

    Chun, Minkyu; Chowdhury, Md Delwar Hossain; Jang, Jin

    2015-05-15

    We investigated the effects of top gate voltage (V{sub TG}) and temperature (in the range of 25 to 70 {sup o}C) on dual-gate (DG) back-channel-etched (BCE) amorphous-indium-gallium-zinc-oxide (a-IGZO) thin film transistors (TFTs) characteristics. The increment of V{sub TG} from -20V to +20V, decreases the threshold voltage (V{sub TH}) from 19.6V to 3.8V and increases the electron density to 8.8 x 10{sup 18}cm{sup −3}. Temperature dependent field-effect mobility in saturation regime, extracted from bottom gate sweep, show a critical dependency on V{sub TG}. At V{sub TG} of 20V, the mobility decreases from 19.1 to 15.4 cm{sup 2}/V ⋅ s with increasing temperature, showing a metallic conduction. On the other hand, at V{sub TG} of - 20V, the mobility increases from 6.4 to 7.5cm{sup 2}/V ⋅ s with increasing temperature. Since the top gate bias controls the position of Fermi level, the temperature dependent mobility shows metallic conduction when the Fermi level is above the conduction band edge, by applying high positive bias to the top gate.

  12. Water’s second glass transition

    PubMed Central

    Amann-Winkel, Katrin; Gainaru, Catalin; Handle, Philip H.; Seidl, Markus; Nelson, Helge; Böhmer, Roland

    2013-01-01

    The glassy states of water are of common interest as the majority of H2O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water’s calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This “double Tg scenario” is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at Tg,2 about five times as large as at Tg,1. By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate–dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20–25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known (“superstrong”), and also high-density liquid is classified as a strong liquid. PMID:24101518

  13. Permafrost landscapes in transition - towards modeling interactions, thresholds and feedbacks related to ice-rich ground

    NASA Astrophysics Data System (ADS)

    Westermann, Sebastian; Langer, Moritz; Lee, Hanna; Berntsen, Terje; Boike, Julia; Krinner, Gerhard; Aalstad, Kristoffer; Schanke Aas, Kjetil; Peter, Maria; Heikenfeld, Max; Etzelmüller, Bernd

    2016-04-01

    Thawing of permafrost is governed by a complex interplay of different processes, of which only conductive heat transfer is taken into account in most model studies. However, heat conduction alone can not account for the dynamical evolution of many permafrost landscapes, e.g. in areas rich in ground ice shaped by thermokarst ponds and lakes. Novel process parameterizations are required to include such phenomena in future projections of permafrost thaw and hereby triggered climatic feedbacks. Recently, we have demonstrated a physically-based parameterization for thaw process in ice-rich ground in the permafrost model CryoGrid 3, which can reproduce the formation of thermokarst ponds and subsidence of the ground following thawing of ice-rich subsurface layers. Long-term simulations for different subsurface stratigraphies in the Lena River Delta, Siberia, demonstrate that the hydrological regime can both accelerate and delay permafrost thawing. If meltwater from thawed ice-rich layers can drain, the ground subsides while at the same time the formation of a talik is delayed. If the meltwater pools at the surface, a pond is formed which enhances heat transfer in the ground and leads to the formation of a talik. The PERMANOR project funded by the Norwegian Research Council until 2019 will extend this work by integrating such small-scale processes in larger-scale Earth System Models (ESMs). For this purpose, the project will explore and develop statistical approaches, in particular tiling, to represent permafrost landscape dynamics on subgrid scale. Ultimately, PERMANOR will conceptualize process understanding from in-situ studies to develop new model algorithms and pursue their implementation in a coupled ESM framework.

  14. A direct evidence of vibrationally delocalized response at ice surface

    SciTech Connect

    Ishiyama, Tatsuya; Morita, Akihiro

    2014-11-14

    Surface-specific vibrational spectroscopic responses at isotope diluted ice and amorphous ice are investigated by molecular dynamics (MD) simulations combined with quantum mechanics/molecular mechanics calculations. The intense response specific to the ordinary crystal ice surface is predicted to be significantly suppressed in the isotopically diluted and amorphous ices, demonstrating the vibrational delocalization at the ordinary ice surface. The collective vibration at the ice surface is also analyzed with varying temperature by the MD simulation.

  15. A review of the slow relaxation processes in the glass-rubber transition region of amorphous polymers

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; He, Xianru; Huang, Guangsu

    2015-09-01

    This article is a review that introduces several articles about slow relaxation processes, also known as slower segmental dynamics. According to the literature, the coupling effect and free volume holes are two important elements for slower micro-dynamics. In addition, the slower processes of many-body systems (blend and diluted systems) are summarised. A good numerical method for detecting multiple modes in the glass-rubber transition region is introduced.

  16. Modular community structure suggests metabolic plasticity during the transition to polar night in ice-covered Antarctic lakes.

    PubMed

    Vick-Majors, Trista J; Priscu, John C; Amaral-Zettler, Linda A

    2014-04-01

    High-latitude environments, such as the Antarctic McMurdo Dry Valley lakes, are subject to seasonally segregated light-dark cycles, which have important consequences for microbial diversity and function on an annual basis. Owing largely to the logistical difficulties of sampling polar environments during the darkness of winter, little is known about planktonic microbial community responses to the cessation of photosynthetic primary production during the austral sunset, which lingers from approximately February to April. Here, we hypothesized that changes in bacterial, archaeal and eukaryotic community structure, particularly shifts in favor of chemolithotrophs and mixotrophs, would manifest during the transition to polar night. Our work represents the first concurrent molecular characterization, using 454 pyrosequencing of hypervariable regions of the small-subunit ribosomal RNA gene, of bacterial, archaeal and eukaryotic communities in permanently ice-covered lakes Fryxell and Bonney, before and during the polar night transition. We found vertically stratified populations that varied at the community and/or operational taxonomic unit-level between lakes and seasons. Network analysis based on operational taxonomic unit level interactions revealed nonrandomly structured microbial communities organized into modules (groups of taxa) containing key metabolic potential capacities, including photoheterotrophy, mixotrophy and chemolithotrophy, which are likely to be differentially favored during the transition to polar night.

  17. Magnetic monopole condensation transition out of quantum spin ice: application to Pr2 Ir2 O7 and Yb2 Ti2 O7

    NASA Astrophysics Data System (ADS)

    Chen, Gang

    We study the proximate magnetic orders and the related quantum phase transition out of quantum spin ice (QSI). We apply the electromagnetic duality of the compact quantum electrodynamics to analyze the condensation of the magnetic monopoles for QSI. The monopole condensation transition represents a unconventional quantum criticality with unusual scaling laws. The magnetic monopole condensation leads to the magnetic states that belong to the ``2-in 2-out'' spin ice manifold and generically have an enlarged magnetic unit cell. We demonstrate that the antiferromagnetic state with the ordering wavevector Q = 2p(001) is proximate to QSI while the ferromagnetic state with the ordering wavevector Q = (000) is not proximate to QSI. This implies that if there exists a direct transition from QSI to the ferromagnetic state, the transition must be strongly first order. We apply the theory to the puzzling experiments on two pyrochlore systems Pr2Ir2O7 and Yb2Ti2O7. chggst@gmail.com.

  18. Magneto-optical measurement of anisotropy energy constant(s) for amorphous rare earth, transition metal alloys

    SciTech Connect

    Uber, R.E.; Mansuripur, M.

    1988-11-01

    Optical investigation of magneto-optical films is complementary to conventional torque and VSM magnetometry. In the authors' laboratory, they are now measuring anisotropy energy constants of RE-TM thin films at temperatures from ambient to 150/sup 0/C. An in-plane magnetic field (up to 16.5 KOe) is applied to a saturated sample with perpendicular magnetization. The movement away from the perpendicular direction is monitored using the polar Kerr effect. At the HeNe wavelength, the Kerr effect is principally due to the top 500 angstroms of the transition metal subnetwork in the films.

  19. Processing of amorphous PEEK and amorphous PEEK based composites

    SciTech Connect

    Kenny, J.; D'amore, A.; Nicolais, L.; Iannone, M.; Scatteia, B.; Aeritalia, S.p.A., Naples )

    1989-08-01

    An analysis of the crystallization behavior of amorphous PEEK, its carbon fiber composite, and its relationships with dynamic-mechanical properties of the system measured during and after processing is presented. The effect of the processing conditions, time and temperature, on the quality and on the amount of the crystallinity developed during cold crystallization has been investigated in order to evaluate the processability window of amorphous PEEK and amorphous PEEK based composite above the glass transition temperature and below the melting point. Also, the anomalous behavior of the amorphous matrix, crystallized at low temperatures, has been studied. Multiple melting peaks and changes of the glass transition during crystallization are explained in terms of crystalline morphology and molecular mobility. 20 refs.

  20. Amorphous effect on the advancing of wide-range absorption and structural-phase transition in γ-In2Se3 polycrystalline layers

    PubMed Central

    Ho, Ching-Hwa

    2014-01-01

    The exploitation of potential functions in material is crucial in materials research. In this study, we demonstrate a III-VI chalcogenide, polycrystalline γ-In2Se3, which simultaneously possesses the capabilities of thickness-dependent optical gaps and wide-energy-range absorption existed in the polycrystalline layers of γ-In2Se3. Transmission electron microscopy and Raman measurement show a lot of γ-phase nanocrystals contained in the disordered and polycrystalline state of the chalcogenide with medium-range order (MRO). The MRO effects on the γ-In2Se3 layers show thickness-dependent absorption-edge shift and thickness-dependent resistivities. The amorphous effect of MRO also renders a structural-phase transition of γ → α occurred inside the γ-In2Se3 layer with a heat treatment of about 700°C. Photo-voltage-current (Photo V-I) measurements of different-thickness γ-In2Se3 layers propose a wide-energy-range photoelectric conversion unit ranging from visible to ultraviolet (UV) may be achieved by stacking γ-In2Se3 layers in a staircase form containing dissimilar optical gaps. PMID:24755902

  1. Amorphous effect on the advancing of wide-range absorption and structural-phase transition in γ-In2Se3 polycrystalline layers.

    PubMed

    Ho, Ching-Hwa

    2014-04-23

    The exploitation of potential functions in material is crucial in materials research. In this study, we demonstrate a III-VI chalcogenide, polycrystalline γ-In2Se3, which simultaneously possesses the capabilities of thickness-dependent optical gaps and wide-energy-range absorption existed in the polycrystalline layers of γ-In2Se3. Transmission electron microscopy and Raman measurement show a lot of γ-phase nanocrystals contained in the disordered and polycrystalline state of the chalcogenide with medium-range order (MRO). The MRO effects on the γ-In2Se3 layers show thickness-dependent absorption-edge shift and thickness-dependent resistivities. The amorphous effect of MRO also renders a structural-phase transition of γ → α occurred inside the γ-In2Se3 layer with a heat treatment of about 700 °C. Photo-voltage-current (Photo V-I) measurements of different-thickness γ-In2Se3 layers propose a wide-energy-range photoelectric conversion unit ranging from visible to ultraviolet (UV) may be achieved by stacking γ-In2Se3 layers in a staircase form containing dissimilar optical gaps.

  2. Seasonally asymmetric transition of the Asian monsoon in response to ice age boundary conditions

    NASA Astrophysics Data System (ADS)

    Ueda, Hiroaki; Kuroki, Harumitsu; Ohba, Masamichi; Kamae, Youichi

    2011-12-01

    Modulation of a monsoon under glacial forcing is examined using an atmosphere-ocean coupled general circulation model (AOGCM) following the specifications established by Paleoclimate Modelling Intercomparison Project phase 2 (PMIP2) to understand the air-sea-land interaction under different climate forcing. Several sensitivity experiments are performed in response to individual changes in the continental ice sheet, orbital parameters, and sea surface temperature (SST) in the Last Glacial Maximum (LGM: 21 ka) to evaluate the driving mechanisms for the anomalous seasonal evolution of the monsoon. Comparison of the model results in the LGM with the pre-industrial (PI) simulation shows that the Arabian Sea and Bay of Bengal are characterized by enhancement of pre-monsoon convection despite a drop in the SST encompassing the globe, while the rainfall is considerably suppressed in the subsequent monsoon period. In the LGM winter relative to the PI, anomalies in the meridional temperature gradient (MTG) between the Asian continents minus the tropical oceans become positive and are consistent with the intensified pre-monsoon circulation. The enhanced MTG anomalies can be explained by a decrease in the condensation heating relevant to the suppressed tropical convection as well as positive insolation anomalies in the higher latitude, showing an opposing view to a warmer future climate. It is also evident that a latitudinal gradient in the SST across the equator plays an important role in the enhancement of pre-monsoon rainfall. As for the summer, the sensitivity experiments imply that two ice sheets over the northern hemisphere cools the air temperature over the Asian continent, which is consistent with the reduction of MTG involved in the attenuated monsoon. The surplus pre-monsoon convection causes a decrease in the SST through increased heat loss from the ocean surface; in other words, negative ocean feedback is also responsible for the subsequent weakening of summer

  3. Photometric Measurements of H2O Ice Crystallinity on Trans-Neptunian Objects

    NASA Astrophysics Data System (ADS)

    Terai, Tsuyoshi; Itoh, Yoichi; Oasa, Yumiko; Furusho, Reiko; Watanabe, Junichi

    2016-08-01

    We present a measurement of H2O ice crystallinity on the surface of trans-neptunian objects with near-infrared narrow-band imaging. The newly developed photometric technique allows us to efficiently determine the strength of a 1.65 μm absorption feature in crystalline H2O ice. Our data for three large objects—Haumea, Quaoar, and Orcus—which are known to contain crystalline H2O ice on the surfaces, show a reasonable result with high fractions of the crystalline phase. It can also be pointed out that if the grain size of H2O ice is larger than ˜20 μm, the crystallinities of these objects are obviously below 1.0, which suggests the presence of the amorphous phase. In particular, Orcus exhibits a high abundance of amorphous H2O ice compared to Haumea and Quaoar, possibly indicating a correlation between the bulk density of the bodies and the degree of surface crystallization. We also found the presence of crystalline H2O ice on Typhon and 2008 AP129, both of which are smaller than the minimum size limit for inducing cryovolcanism as well as a transition from amorphous to crystalline phase through thermal evolution due to the decay of long-lived isotopes. Based on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan (NAOJ).

  4. Critical speeding-up in the magnetoelectric response of spin-ice near its monopole liquid-gas transition.

    PubMed

    Grams, Christoph P; Valldor, Martin; Garst, Markus; Hemberger, Joachim

    2014-01-01

    Competing interactions in the so-called spin-ice compounds stabilize a frustrated ground state with finite zero-point entropy and, interestingly, emergent magnetic monopole excitations. The properties of these monopoles are at the focus of recent research with particular emphasis on their quantum dynamics. It is predicted that each monopole also possesses an electric dipole moment, which allows to investigate their dynamics via the dielectric function ε(ν). Here we report on broadband spectroscopic measurements of ε(ν) in Dy2Ti2O7 down to temperatures of 200 mK with a specific focus on the critical end point present for a magnetic field along the crystallographic [111] direction. Clear critical signatures are revealed in the dielectric response when, similarly as in the liquid-gas transition, the density of monopoles changes in a critical manner. The dielectric relaxation time τ exhibits a critical speeding-up with a significant enhancement of 1/τ as the temperature is lowered towards the critical temperature. Besides demonstrating the magnetoelectric character of the emergent monopole excitations, our results corroborate the unique critical dynamics near the monopole condensation transition. PMID:25188290

  5. Critical speeding-up in the magnetoelectric response of spin-ice near its monopole liquid-gas transition.

    PubMed

    Grams, Christoph P; Valldor, Martin; Garst, Markus; Hemberger, Joachim

    2014-09-04

    Competing interactions in the so-called spin-ice compounds stabilize a frustrated ground state with finite zero-point entropy and, interestingly, emergent magnetic monopole excitations. The properties of these monopoles are at the focus of recent research with particular emphasis on their quantum dynamics. It is predicted that each monopole also possesses an electric dipole moment, which allows to investigate their dynamics via the dielectric function ε(ν). Here we report on broadband spectroscopic measurements of ε(ν) in Dy2Ti2O7 down to temperatures of 200 mK with a specific focus on the critical end point present for a magnetic field along the crystallographic [111] direction. Clear critical signatures are revealed in the dielectric response when, similarly as in the liquid-gas transition, the density of monopoles changes in a critical manner. The dielectric relaxation time τ exhibits a critical speeding-up with a significant enhancement of 1/τ as the temperature is lowered towards the critical temperature. Besides demonstrating the magnetoelectric character of the emergent monopole excitations, our results corroborate the unique critical dynamics near the monopole condensation transition.

  6. 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.

  7. Disordered electronic systems: Concentration dependence of the dc conductivity in amorphous transition-metal-metalloid alloys (metallic regime)

    NASA Astrophysics Data System (ADS)

    Sonntag, Joachim

    1989-08-01

    In the metallic regime of several a-N1-xMx and a-T1-xMx alloys, the concentration dependence of the electrical resistivity ρ can be approximated by dlnρ=α*dξ, where α* is constant for a given alloy and ξ=x/(1-x). $N- and -T- stand for a transition metal with completely and incompletely occupied d bands, respectively, and M stands for a metalloid element. If, in the alloy, phase separation is realized, there is electron redistribution between the two phases A and B. For a-N1-xMx alloys this can be described by -dn=βndζ with ζ=XB/XA, where n is the electron density in the conduction band (CB) formed by the A phase. XA and XB are the fractions of the A and B phases having the average concentrations xA and xB, respectively. β depends on the average potential difference between the A and B phases. B is the phase with the deeper average potential. Part of the electrons in the B phase occupies the valence band (VB) formed by the B phase. Another part occupies trap states (as far as available below EF), leading to electron localization. The electron redistribution leads to long-range electron-density fluctuations expressed by δn=(1+ζ-1)(n0-n) n0 is the total s and p valence-electron concentration. Under certain conditions both CB and VB can contribute to the electronic transport. -dn=βn dζ is expected to apply also to a-T1-xMx alloys, where the electron redistribution can enclose part of the d electrons as well. Positive Hall coefficients are expected, when both the VB has ``hole'' conductivity, and this contribution dominates compared with those of the CB. Activation of electrons from the B to the A phase with increasing temperature can lead to a negative temperature coefficient of ρ.

  8. Mineral dust archive in Taylor Dome ice core as evidence for shifting coastal east Antarctic climate during the LGM-Holocene transition

    NASA Astrophysics Data System (ADS)

    Aarons, S. M.; Aciego, S.; Gabrielli, P.; Delmonte, B.; Koornneef, J.; Bouman, C.; Wegner, A.

    2014-12-01

    Ice cores from ice sheets in Antarctica provide valuable records of past climates encompassing hundreds of thousands of years. Chemical and mineralogical characterization of aerosol mineral particles (dust) transported through the atmosphere and deposited on ice sheets and glaciers provide insight into the regional and global climate conditions during a time period. Elemental and isotopic analysis of dust entrapped in ice aids in determining provenance, with variations signifying changes in dust production, sources and transport pathways, indicating an evolving local and/or global climate. We present radiogenic isotope and elemental compositions of insoluble dust entrained in a coastal Antarctic ice core during the transition from the Last Glacial Maximum (LGM) to the Holocene. A series of 15 samples from the Taylor Dome ice core, 113-391 m in depth covering a time period of 1.8-31.5 ka were analyzed using traditional Thermal Ionization Mass Spectrometry (TIMS) equipped with 10-11 Ohm resistors (87Sr/86Sr) and 10-13 Ohm resistors (143Nd/144Nd). We determined trace (TE) and rare earth element (REE) concentrations by Inductively Coupled Plasma Sector Field Mass Spectrometry (ICP-SFMS) and dust concentration and size distribution by Coulter Counter. The radiogenic isotopic compositions of glacial dust agrees with previously measured Antarctic dust: 87Sr/86Sr= 0.7052 - 0.7124 and ɛNd= -0.9 - -4.7, whereas Holocene dust displays a broader range from 87Sr/86Sr= 0.7054 - 0.7163 and ɛNd= -0.9 - -7.1, suggesting a shift from globally transported dust to more variable local input following the LGM to Holocene transition. The REE and TE concentrations display typical East Antarctic ice core dust patterns. The average dust particle diameter increases from ~1.8 to ~3 μm with decreasing depositional age, supporting the alteration in dust transport mechanism hypothesis. Our results display dust concentrations of >500 and <15 ppb during glacial and interglacial periods

  9. Infrared spectra of crystalline phase ices condensed on silicate smokes at T less than 20 K

    NASA Astrophysics Data System (ADS)

    Moore, Marla H.; Ferrante, Robert F.; Hudson, Reggie L.; Nuth, Joseph A., III; Donn, Bertram

    1994-06-01

    Infrared spectra of H2O, CH3OH, and NH3 condensed at T less than 20 K on amorphous silicate smokes reveal that predominantly crystalline phase ice forms directly on deposit. Spectra of these molecules condensed on aluminum substrates at T less than 20 K indicate that amorphous phase ice forms. On aluminum, crystalline phase H2O and CH3OH are formed by annealing amorphous deposits to 155 K and 130 K, respectively (or by direct deposit at these temperatures); crystalline NH3 is formed by direct deposit at 88 K. Silicate smokes are deposited onto aluminum substrates by evaporation of SiO solid or by combustion of SiH4 with O2 in flowing H2 followed by vapor phase nucleation and growth. Silicate smokes which are oxygen-deficient may contain active surface sites which facilitate the amorphous-to-crystalline phase transition during condensation. Detailed experiments to understand the mechanism are currently in progress. The assumption that amorphous phase ice forms routinely on grains at T less than 80 K is often used in models describing the volatile content of comets or in interpretations of interstellar cloud temperatures. This assumption needs to be reexamined in view of these results.

  10. Infrared spectra of crystalline phase ices condensed on silicate smokes at T less than 20 K

    NASA Technical Reports Server (NTRS)

    Moore, Marla H.; Ferrante, Robert F.; Hudson, Reggie L.; Nuth, Joseph A., III; Donn, Bertram

    1994-01-01

    Infrared spectra of H2O, CH3OH, and NH3 condensed at T less than 20 K on amorphous silicate smokes reveal that predominantly crystalline phase ice forms directly on deposit. Spectra of these molecules condensed on aluminum substrates at T less than 20 K indicate that amorphous phase ice forms. On aluminum, crystalline phase H2O and CH3OH are formed by annealing amorphous deposits to 155 K and 130 K, respectively (or by direct deposit at these temperatures); crystalline NH3 is formed by direct deposit at 88 K. Silicate smokes are deposited onto aluminum substrates by evaporation of SiO solid or by combustion of SiH4 with O2 in flowing H2 followed by vapor phase nucleation and growth. Silicate smokes which are oxygen-deficient may contain active surface sites which facilitate the amorphous-to-crystalline phase transition during condensation. Detailed experiments to understand the mechanism are currently in progress. The assumption that amorphous phase ice forms routinely on grains at T less than 80 K is often used in models describing the volatile content of comets or in interpretations of interstellar cloud temperatures. This assumption needs to be reexamined in view of these results.

  11. Liquid water in the domain of cubic crystalline ice Ic

    NASA Astrophysics Data System (ADS)

    Jenniskens, P.; Banham, S. F.; Blake, D. F.; McCoustra, M. R. S.

    1997-07-01

    Vapor-deposited amorphous water ice, when warmed above the glass transition temperature (120-140 K), is a viscous liquid which exhibits a viscosity vs temperature relationship different from that of liquid water at room temperature. New studies of thin water ice films now demonstrate that viscous liquid water persists in the temperature range 140-210 K, where it coexists with cubic crystalline ice. The liquid character of amorphous water above the glass transition is demonstrated by (1) changes in the morphology of water ice films on a nonwetting surface observed in transmission electron microscopy (TEM) at around 175 K during slow warming, (2) changes in the binding energy of water molecules measured in temperature programmed desorption (TPD) studies, and (3) changes in the shape of the 3.07 μm absorption band observed in grazing angle reflection-absorption infrared spectroscopy (RAIRS) during annealing at high temperature, whereby the decreased roughness of the water surface is thought to cause changes in the selection rules for the excitation of O-H stretch vibrations. Because it is present over such a wide range of temperatures, we propose that this form of liquid water is a common material in nature, where it is expected to exist in the subsurface layers of comets and on the surfaces of some planets and satellites.

  12. Amorphic complexity

    NASA Astrophysics Data System (ADS)

    Fuhrmann, G.; Gröger, M.; Jäger, T.

    2016-02-01

    We introduce amorphic complexity as a new topological invariant that measures the complexity of dynamical systems in the regime of zero entropy. Its main purpose is to detect the very onset of disorder in the asymptotic behaviour. For instance, it gives positive value to Denjoy examples on the circle and Sturmian subshifts, while being zero for all isometries and Morse-Smale systems. After discussing basic properties and examples, we show that amorphic complexity and the underlying asymptotic separation numbers can be used to distinguish almost automorphic minimal systems from equicontinuous ones. For symbolic systems, amorphic complexity equals the box dimension of the associated Besicovitch space. In this context, we concentrate on regular Toeplitz flows and give a detailed description of the relation to the scaling behaviour of the densities of the p-skeletons. Finally, we take a look at strange non-chaotic attractors appearing in so-called pinched skew product systems. Continuous-time systems, more general group actions and the application to cut and project quasicrystals will be treated in subsequent work.

  13. 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.

  14. 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. PMID:27468430

  15. Quelccaya Ice Cap extents during the last glacial-interglacial transition: evidence for rapid climate changes in the southern tropics during Younger Dryas time

    NASA Astrophysics Data System (ADS)

    Kelly, M. A.; Lowell, T. V.; Applegate, P. J.; Smith, C.; Phillips, F. M.; Hudson, A. M.

    2011-12-01

    Paleoglacial data from the Peruvian Andes shed light on the mechanisms which influenced rapid climate changes during late glacial time. Here, we present a radiocarbon-based chronology of Quelccaya Ice Cap (QIC) fluctuations during the last glacial-interglacial transition that registers paleoclimatic conditions at high altitude (~5000 m asl) in the southern tropics (~14°S, 70°W). Subsequent to the last glacial maximum, major recession of QIC was underway by ~17.2 ka. The timing of this recession is prior to the warming registered by Greenland ice cores, but similar to the timing of mountain glacier recession in both Northern and Southern hemispheres, likely influenced by rising atmospheric CO2 concentrations. At ~12.6 ka, QIC underwent the most significant readvance during the last glacial-interglacial transition, reaching a position ~4-5 km from the modern ice cap margin and depositing a prominent set of moraines that is nearly continuous on the western side of the ice cap. Recession from this rapid readvance was underway by ~12.3 ka, and QIC was within its Little Ice Age extent (~1-2 km from the modern ice margin) by ~11.2 ka. The readvance of QIC occurred early in the Younger Dryas cold interval (12.9-11.7 ka) and ice cap recession was underway while Greenland ice cores registered continuously cold conditions. Whereas QIC receded by at least 3-4 km between 12.3 and 11.2 ka, paleo-lake levels and other indicators of moisture on the Bolivian Altiplano, document wet conditions in the southern tropics until the end of the Younger Dryas. Thus, we suggest that QIC recession at ~12.3 ka was associated with warming in the tropics that occurred during middle Younger Dryas time. Warming at this time is also registered by climate proxy records from the Cariaco Basion, in the northern tropical Atlantic region, and in the eastern tropical Pacific Ocean. Recent modeling studies suggest that a southerly position of the Intertropical Convergence Zone (ITCZ) associated with

  16. Recurrent transitional group charnockites in the east Amery Ice Shelf coast (East Antarctica): Petrogenesis and implications on tectonic evolution

    NASA Astrophysics Data System (ADS)

    Mikhalsky, E. V.; Kamenev, I. A.

    2013-08-01

    We present new geochemical and isotopic Sm-Nd data on two transitional group charnockite generations which were emplaced within the same crustal block in the east Amery Ice Shelf coast in East Antarctica at ca. 980 Ma (Reinbolt charnockite) and ca. 500 Ma (Jennings charnockite). Thus it is the only known area in Antarctica where recurrent charnockite emplacements occurred providing a basis to trace the secular changes in charnockite composition and to put additional constraints on their nature and tectonic settings. Our data show that in spite of a prolonged time gap between the two charnockite generations their chemical and Sm-Nd isotopic compositions resemble very closely. Both generations comprise low-silica and relatively high-Fe* rocks with high TiO2, and other HFSEs. We suppose that both generations originated by partial melting of low crustal to sub-crustal mafic sources at high pressures and temperatures. However, the Cambrian Jennings charnockite has consistently higher TiO2, P2O5 and LaN/YbN arguing for their derivation from a garnet-bearing source under higher temperature conditions. The Sm-Nd data show that all charnockites irrespective of their age have very similar isotopic compositions suggestive of derivation from the same or very similar source(s), which precludes significant Sm-Nd fractionation before or during the Cambrian episode. We also present new U-Pb zircon (SHRIMP) age of ca. 980 Ma obtained for apparently undeformed charnockite from Gillock Island, which argues for essentially thermal rather than deformational nature of the subsequent (the Cambrian) episode. We conclude that at ca. 550-500 Ma this part of East Antarctica experienced thermal reworking from hypothetical mafic underplating at the base of the crust.

  17. Wind and wave influences on sea ice floe size and leads in the Beaufort and Chukchi Seas during the summer-fall transition 2014

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Holt, Benjamin; Erick Rogers, W.; Thomson, Jim; Shen, Hayley H.

    2016-02-01

    Sea ice floe size distribution and lead properties in the Beaufort and Chukchi Seas are studied in the summer-fall transition 2014 to examine the impact on the sea ice cover from storms and surface waves. Floe size distributions are analyzed from MEDEA, Landsat8, and RADARSAT-2 imagery, with a resolution span of 1-100 m. Landsat8 imagery is also used to identify the orientation and spacing of leads. The study period centers around three large wave events during August-September 2014 identified by SWIFT buoys and WAVEWATCH III® model data. The range of floe sizes from different resolutions provides the overall distribution across a wide range of ice properties and estimated thickness. All cumulative floe size distribution curves show a gradual bending toward shallower slopes for smaller floe sizes. The overall slopes in the cumulative floe size distribution curves from Landsat8 images are lower than, while those from RADARSAT-2 are similar to, previously reported results in the same region and seasonal period. The MEDEA floe size distributions appeared to be sensitive to the passage of storms. Lead orientations, regardless of length, correlate slightly better with the peak wave direction than with the mean wave direction. Their correlation with the geostrophic wind is stronger than with the surface wind. The spacing between shorter leads correlates well with the local incoming surface wavelengths, obtained from the model peak wave frequency. The information derived shows promise for a coordinated multisensor study of storm effects in the Arctic marginal ice zone.

  18. Radiation damage and associated phase change effect on photodesorption rates from ices—Lyα studies of the surface behavior of CO{sub 2}(ice)

    SciTech Connect

    Yuan, Chunqing; Yates, John T. Jr.

    2014-01-01

    Photodesorption from a crystalline film of CO{sub 2}(ice) at 75 K has been studied using Lyα (10.2 eV) radiation. We combine quantitative mass spectrometric studies of gases evolved and transmission IR studies of species trapped in the ice. Direct CO desorption is observed from the primary CO{sub 2} photodissociation process, which occurs promptly for CO{sub 2} molecules located on the outermost surface of the ice (Process I). As the fluence of Lyα radiation increases to ∼5.5 × 10{sup 17} photons cm{sup –2}, extensive damage to the crystalline ice occurs and photo-produced CO molecules from deeper regions (Process II) are found to desorb at a rapidly increasing rate, which becomes two orders of magnitude greater than Process I. It is postulated that deep radiation damage to produce an extensive amorphous phase of CO{sub 2} occurs in the 50 nm ice film and that CO (and CO{sub 2}) diffusive transport is strongly enhanced in the amorphous phase. Photodesorption in Process II is a combination of electronic and thermally activated processes. Radiation damage in crystalline CO{sub 2} ice has been monitored by its effects on the vibrational line shapes of CO{sub 2}(ice). Here the crystalline-to-amorphous phase transition has been correlated with the occurrence of efficient molecular transport over long distances through the amorphous phase of CO{sub 2}(ice). Future studies of the composition of the interstellar region, generated by photodesorption from ice layers on grains, will have to consider the significant effects of radiation damage on photodesorption rates.

  19. Pressure induced crystallization in amorphous silicon

    NASA Astrophysics Data System (ADS)

    Pandey, K. K.; Garg, Nandini; Shanavas, K. V.; Sharma, Surinder M.; Sikka, S. K.

    2011-06-01

    We have investigated the high pressure behavior of amorphous silicon (a-Si) using x-ray diffraction and Raman scattering techniques. Our experiments show that a-Si undergoes a polyamorphous transition from the low density amorphous to the high density amorphous phase, followed by pressure induced crystallization to the primitive hexagonal (ph) phase. On the release path, the sequence of observed phase transitions depends on whether the pressure is reduced slowly or rapidly. Using the results of our first principles calculations, pressure induced preferential crystallization to the ph phase is explained in terms of a thermodynamic model based on phenomenological random nucleation and the growth process.

  20. Development of a novel ultra cryo-milling technique for a poorly water-soluble drug using dry ice beads and liquid nitrogen.

    PubMed

    Sugimoto, Shohei; Niwa, Toshiyuki; Nakanishi, Yasuo; Danjo, Kazumi

    2012-04-15

    A novel ultra cryo-milling micronization technique has been established using dry ice beads and liquid nitrogen (LN2). Drug particles were co-suspended with dry ice beads in LN2 and ground by stirring. Dry ice beads were prepared by storing dry ice pellets in LN2. A poorly water-soluble drug, phenytoin, was micronized more efficiently using either dry ice beads or zirconia beads compared to jet milling. Dry ice beads retained their granular shape without pulverizing and sublimating in LN2 as the milling operation progressed. Longer milling times produced smaller-sized phenytoin particles. The agitation speed for milling was optimized. Analysis of the glass transition temperature revealed that phenytoin particles co-ground with polyvinylpyrrolidone (PVP) by dry ice milling were crystalline, whereas a planetary ball-milled mixtures process with zirconia beads contained the amorphous form. The dissolution rate of phenytoin milled with PVP using dry ice beads or zirconia beads was significantly improved compared to jet-milled phenytoin or the physical mixture. Dry ice beads together with LN2 were spontaneously sublimated at ambient condition after milling. Thus, the yield was significantly improved by dry ice beads compared to zirconia beads since the loss arisen from adhering to the surface of dry ice beads could be completely avoided, resulting in about 85-90% of recovery. In addition, compounds milled using dry ice beads are free from abraded contaminating material originating from the beads and internal vessel wall. PMID:22266538

  1. Development of a novel ultra cryo-milling technique for a poorly water-soluble drug using dry ice beads and liquid nitrogen.

    PubMed

    Sugimoto, Shohei; Niwa, Toshiyuki; Nakanishi, Yasuo; Danjo, Kazumi

    2012-04-15

    A novel ultra cryo-milling micronization technique has been established using dry ice beads and liquid nitrogen (LN2). Drug particles were co-suspended with dry ice beads in LN2 and ground by stirring. Dry ice beads were prepared by storing dry ice pellets in LN2. A poorly water-soluble drug, phenytoin, was micronized more efficiently using either dry ice beads or zirconia beads compared to jet milling. Dry ice beads retained their granular shape without pulverizing and sublimating in LN2 as the milling operation progressed. Longer milling times produced smaller-sized phenytoin particles. The agitation speed for milling was optimized. Analysis of the glass transition temperature revealed that phenytoin particles co-ground with polyvinylpyrrolidone (PVP) by dry ice milling were crystalline, whereas a planetary ball-milled mixtures process with zirconia beads contained the amorphous form. The dissolution rate of phenytoin milled with PVP using dry ice beads or zirconia beads was significantly improved compared to jet-milled phenytoin or the physical mixture. Dry ice beads together with LN2 were spontaneously sublimated at ambient condition after milling. Thus, the yield was significantly improved by dry ice beads compared to zirconia beads since the loss arisen from adhering to the surface of dry ice beads could be completely avoided, resulting in about 85-90% of recovery. In addition, compounds milled using dry ice beads are free from abraded contaminating material originating from the beads and internal vessel wall.

  2. Evidence of Complex Ice-Volcano Interactions in the Transition Zone Between Elysium Rise and Utopia Basin

    NASA Astrophysics Data System (ADS)

    Pedersen, G. B. M.; Head, J. W.

    2012-03-01

    We report on morphologic evidence of a complex succession of ice-volcano interactions in the Galaxias region, Mars, and reconsider the emplacement properties of volcanoclastic outflow deposit under martian conditions.

  3. Vibrational dynamics of ice in reverse micelles.

    PubMed

    Dokter, Adriaan M; Petersen, Christian; Woutersen, Sander; Bakker, Huib J

    2008-01-28

    The ultrafast vibrational dynamics of HDO:D(2)O ice at 180 K in anionic reverse micelles is studied by midinfrared femtosecond pump-probe spectroscopy. Solutions containing reverse micelles are cooled to low temperatures by a fast-freezing procedure. The heating dynamics of the micellar solutions is studied to characterize the micellar structure. Small reverse micelles with a water content up to approximately 150 water molecules contain an amorphous form of ice that shows remarkably different vibrational dynamics compared to bulk hexagonal ice. The micellar amorphous ice has a much longer vibrational lifetime than bulk hexagonal ice and micellar liquid water. The vibrational lifetime is observed to increase linearly from 0.7 to 4 ps with the resonance frequency ranging from 3100 to 3500 cm(-1). From the pump dependence of the vibrational relaxation the homogeneous linewidth of the amorphous ice is determined (55+/-5 cm(-1)).

  4. Relation between the High Density Phase and the Very-High Density Phase of Amorphous Solid Water

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas; Stanley, H. Eugene; Sciortino, Francesco

    2005-03-01

    It has been suggested that high-density amorphous (HDA) ice is a structurally arrested form of high-density liquid (HDL) water, while low-density amorphous ice is a structurally arrested form of low-density liquid (LDL) water. Recent experiments and simulations have been interpreted to support the possibility of a second distinct high-density structural state, named very high-density amorphous (VHDA) ice, questioning the LDL-HDL hypothesis. We test this interpretation using extensive computer simulations and find that VHDA is a more stable form of HDA and that, in fact, VHDA should be considered as the amorphous ice of the quenched HDL.

  5. Ion-beam amorphization of semiconductors: A physical model based on the amorphous pocket population

    SciTech Connect

    Mok, K.R.C.; Jaraiz, M.; Martin-Bragado, I.; Rubio, J.E.; Castrillo, P.; Pinacho, R.; Barbolla, J.; Srinivasan, M.P.

    2005-08-15

    We introduce a model for damage accumulation up to amorphization, based on the ion-implant damage structures commonly known as amorphous pockets. The model is able to reproduce the silicon amorphous-crystalline transition temperature for C, Si, and Ge ion implants. Its use as an analysis tool reveals an unexpected bimodal distribution of the defect population around a characteristic size, which is larger for heavier ions. The defect population is split in both size and composition, with small, pure interstitial and vacancy clusters below the characteristic size, and amorphous pockets with a balanced mixture of interstitials and vacancies beyond that size.

  6. An ice lithography instrument

    NASA Astrophysics Data System (ADS)

    Han, Anpan; Chervinsky, John; Branton, Daniel; Golovchenko, J. A.

    2011-06-01

    We describe the design of an instrument that can fully implement a new nanopatterning method called ice lithography, where ice is used as the resist. Water vapor is introduced into a scanning electron microscope (SEM) vacuum chamber above a sample cooled down to 110 K. The vapor condenses, covering the sample with an amorphous layer of ice. To form a lift-off mask, ice is removed by the SEM electron beam (e-beam) guided by an e-beam lithography system. Without breaking vacuum, the sample with the ice mask is then transferred into a metal deposition chamber where metals are deposited by sputtering. The cold sample is then unloaded from the vacuum system and immersed in isopropanol at room temperature. As the ice melts, metal deposited on the ice disperses while the metals deposited on the sample where the ice had been removed by the e-beam remains. The instrument combines a high beam-current thermal field emission SEM fitted with an e-beam lithography system, cryogenic systems, and a high vacuum metal deposition system in a design that optimizes ice lithography for high throughput nanodevice fabrication. The nanoscale capability of the instrument is demonstrated with the fabrication of nanoscale metal lines.

  7. Amorphous metal composites

    DOEpatents

    Byrne, Martin A.; Lupinski, John H.

    1984-01-01

    An improved amorphous metal composite and process of making the composite. The amorphous metal composite comprises amorphous metal (e.g. iron) and a low molecular weight thermosetting polymer binder. The process comprises placing an amorphous metal in particulate form and a thermosetting polymer binder powder into a container, mixing these materials, and applying heat and pressure to convert the mixture into an amorphous metal composite.

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

    PubMed

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

    2015-09-22

    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

  9. 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

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

    PubMed

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

    2015-09-22

    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.

  11. Exploring the coupling between surface crystallinity and surface hydrophilicity in heterogeneous ice nucleation

    NASA Astrophysics Data System (ADS)

    Bi, Yuanfei; Cabriolu, Raffaela; Li, Tianshu

    Heterogeneous ice nucleation has significant influence in a variety of fields ranging from global climate change to intracellular freezing. Although its prevalence can be explained quantitatively by the classical nucleation theory, there is a lack of molecular level understanding of the key factors governing ice nucleation at the interface between water and ice nucleator. Here, by employing advanced molecular simulation, we show that heterogeneous ice nucleation on graphitic surface is controlled by the coupling of surface crystallinity and surface hydrophilicity. Molecular level analysis shows that the crystalline graphitic surface with an appropriate hydrophilicity templates ice basal plane forming in the contact layer, thus significantly enhances its ice nucleation efficiency. Remarkably, the templating effect is found to transit from within the first contact layer of water to the second as the hydrophilicity increases, yielding an oscillating distinction between the crystalline and amorphous graphitic surfaces in their ice nucleation efficiencies. Our study sheds new light on the long-standing question of what constitutes a good ice nucleator.

  12. Structure, thermodynamics, and crystallization of amorphous hafnia

    SciTech Connect

    Luo, Xuhui; Demkov, Alexander A.

    2015-09-28

    We investigate theoretically amorphous hafnia using the first principles melt and quench method. We identify two types of amorphous structures of hafnia. Type I and type II are related to tetragonal and monoclinic hafnia, respectively. We find type II structure to show stronger disorder than type I. Using the phonon density of states, we calculate the specific heat capacity for type II amorphous hafnia. Using the nudged elastic band method, we show that the averaged transition barrier between the type II amorphous hafnia and monoclinic phase is approximately 0.09 eV/HfO{sub 2}. The crystallization temperature is estimated to be 421 K. The calculations suggest an explanation for the low thermal stability of amorphous hafnia.

  13. Transitions.

    ERIC Educational Resources Information Center

    Field, David; And Others

    1992-01-01

    Includes four articles: "Career Aspirations" (Field); "Making the Transition to a New Curriculum" (Baker, Householder); "How about a 'Work to School' Transition?" (Glasberg); and "Technological Improvisation: Bringing CNC to Woodworking" (Charles, McDuffie). (SK)

  14. Amorphous Computing

    NASA Astrophysics Data System (ADS)

    Sussman, Gerald

    2002-03-01

    agents constructed by engineered cells, but we have few ideas for programming them effectively: How can one engineer prespecified, coherent behavior from the cooperation of immense numbers of unreliable parts that are interconnected in unknown, irregular, and time-varying ways? This is the challenge of Amorphous Computing.

  15. Grain sizes, surface areas, and porosities of vapor-deposited H2O ices used to simulate planetary icy surfaces.

    PubMed

    Boxe, C S; Bodsgard, B R; Smythe, W; Leu, M T

    2007-05-15

    Mean grain sizes and specific surface areas (SSAs) of ice substrates formed by vapor deposition at low temperatures are of importance in simulating external surfaces of icy satellites in the solar system. Environmental scanning electron microscopy (ESEM) was used to obtain granule sizes and to observe the phase of ice granules prepared on borosilicate, silicon, and metallic plates. Ices prepared at a temperature lower than 140 K appear to be amorphous, and their granule sizes are typically submicrometer. At slightly warmer temperatures, near 180-200 K, ice films are composed of either hexagonal or cubic granules with sizes up to a few micrometers. When briefly annealed to even warmer temperatures, ice granule sizes approach approximately 10 microm. SSAs of ice substrates were determined from BET (Brunauer, Emmett, and Teller) analysis of gas adsorption isotherms in the temperature range from 83.5 to 261 K. SSAs decrease drastically from 102 m2/g at 83.5 K to 0.87 m2/g at 150 K and further decrease slowly to 0.22 m2/g at 261 K, suggesting that the transition from amorphous to crystalline forms occurs at approximately 150 K. The overall decrease in SSAs is primarily due to metamorphism and sintering. These results are comparable to recent field and laboratory measurements. Possible implications for theoretical models of icy satellites of outer planets using remote sensing techniques are also discussed. PMID:17306289

  16. Transits

    NASA Astrophysics Data System (ADS)

    Gilliland, Ronald L.

    Transits of the planets Mercury and especially Venus have been exciting events in the development of astronomy over the past few hundred years. Just two years ago the first transiting extra-solar planet, HD 209458b, was discovered, and subsequent studies during transit have contributed fundamental new knowledge. From the photometric light curve during transit one obtains a basic confirmation that the radial velocity detected object is indeed a planet by allowing precise determination of its mass and radius relative to these stellar quantities. From study of spectroscopic changes during transit it has been possible to probe for individual components of the transiting planets atmosphere. Planet transits are likely to become a primary tool for detection of new planets, especially other Earth-like planets with the Kepler Discovery Mission. Looking ahead, the additional aperture of the James Webb Space Space Telescope promises to allow the first possibility of studying the atmosphere of extra-solar Earth-analogue planets, perhaps even providing the first evidence of direct relevance to the search for signs of life on other planets.

  17. Naled ice growth

    NASA Astrophysics Data System (ADS)

    Schohl, G. A.; Ettema, R.

    1986-02-01

    Based on theoretical formulation and dimensional analysis, supported by the results of laboratory experiments, a theory and a detailed description of naled ice growth are presented. The theory, concepts, and data should be of interest to engineers concerned with the effects of naleds (also referred to as aufeis or icings) on engineering works. The growth of a two dimensional, or laterally confined (flume), naled is shown to depend primarily on seven, independent, dimensionless parameters. The early, two dimensional, phase of growth, a naled consists of a mixture of ice and water, or ice-water slush, forming on a frigid base. The influence of two of the three remaining parameters is not felt until after a transition time has passed. The continuing, cyclic process by which slush layers form and eventually freeze results in the ice laminations that are a feature of naled ice.

  18. 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

  19. 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

  20. Amorphous Solid Water (ASW): Macroscale Environmentally-Neutral Application for Remediation of Hazardous Pollutants using Condensed-Phase Cryogenic Fluids

    NASA Astrophysics Data System (ADS)

    de Strulle, Ronald; Rheinhart, Maximilian

    2012-03-01

    We report macroscale environmentally-neutral use of cryogenic fluids to induce phase transitions from crystalline water-ices to amorphous solid water (ASW). New IP and uses in remediation of oil-spills and hazardous immiscibles from aquatic environments. We display high-resolution images of the transitions from hexagonal to cubic crystalline water-ice, then to hydrophobic ASW. Accretion and encapsulation of viscous pollutants within crystalline water-ice, and sequestration of condensed volatiles (PAH, methane) and low viscosity fluids within the interstitial cavities of ASW are shown and differentiated for: crude oils, diesel (heating) and blended oils, petroleum byproducts, vegetable and mineral oils, lipids, and light immiscible fluids. The effects of PdV work and thermal energy transfers during phase changes are shown, along with the sequestration efficiencies for hexagonal and cubic ice lattices vs. non-crystalline ASW, for a range of pollutant substances. The viability of ASW as a medium for study of quantum criticality phases is also proposed. The process is environmentally-neutral in that only substantially condensed-phase air liquefaction products, e.g. nitrogen in >90% liquid phase are employed as an active agent. The applications are also presented in terms of the scale-up of experiments performed at the nanoscale.

  1. 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

  2. Canted spin structure and the first order magnetic transition in CoFe2O4 nanoparticles coated by amorphous silica

    NASA Astrophysics Data System (ADS)

    Lyubutin, I. S.; Starchikov, S. S.; Gervits, N. E.; Korotkov, N. Yu.; Dmitrieva, T. V.; Lin, Chun-Rong; Tseng, Yaw-Teng; Shih, Kun-Yauh; Lee, Jiann-Shing; Wang, Cheng-Chien

    2016-10-01

    The functional polymer (PMA-co-MAA) latex microspheres were used as a core template to prepare magnetic hollow spheres consisting of CoFe2O4/SiO2 composites. The spinel type crystal structure of CoFe2O4 ferrite is formed under annealing, whereas the polymer cores are completely removed after annealing at 450 °C. Magnetic and Mössbauer spectroscopy measurements reveal very interesting magnetic properties of the CoFe2O4/SiO2 hollow spheres strongly dependent on the particle size which can be tuned by the annealing temperature. In the ground state of low temperatures, the CoFe2O4 nanoparticles are in antiferromagnetic state due to the canted magnetic structure. Under heating in the applied field, the magnetic structure gradually transforms from canted to collinear, which increases the magnetization. The Mössbauer data revealed that the small size CoFe2O4/SiO2 particles (2.2-4.3 nm) do not show superparamagnetic behavior but transit from the magnetic to the paramagnetic state by a jump-like magnetic transition of the first order This effect is a specific property of the magnetic nanoparticles isolated by inert material, and can be initiated by internal pressure creating at the particle surface. The suggested method of synthesis can be modified with various bio-ligands on the silane surface, and such materials can find many applications in diagnostics and bio-separation.

  3. K/Ar Dating of Fine Grained Sediments Near Prydz Bay, Antarctica: East Antarctic Ice Sheet Behavior During the Middle-Miocene Climate Transition

    NASA Astrophysics Data System (ADS)

    Duchesne, A. E.; Pierce, E. L.; Williams, T.; Hemming, S. R.; Johnson, D. L.; May, T.; Gombiner, J.; Torfstein, A.

    2012-12-01

    ¶ The Middle Miocene Climate Transition (MMCT) (~14 Ma) represents a time of major East Antarctic Ice-Sheet (EAIS) expansion, with research suggesting major global sea level fall on the order of ~60 meters (John et al., 2011, EPSL). Ocean Drilling Program (ODP) core data from Site 1165B near Prydz Bay shows an influx of cobbles deposited ~13.8-13.5 Ma, representing a sudden burst of ice-rafted detritus (IRD) during the MMCT. Based on 40Ar/39Ar dating of hornblendes and/or biotite grains, 5 of 6 dated pebbles from a companion study show Wilkes Land origins, indicating transport from over 1500 kilometers away. However, samples throughout this time interval have an anomalously low abundance of sand, thus we seek to understand the sedimentary processes that led to the deposition of these isolated dropstones in a fine matrix through provenance studies of the core's terrigenous fine fraction. Geochemical provenance studies of the terrigenous fraction of marine sediments can aid in identifying past dynamic EAIS behavior; the few outcrops available on the continent provide specific rock characterizations and age constraints from which cored marine sediments can then be matched to using established radiogenic isotope techniques. Here we apply the K/Ar dating method as a provenance tool for identifying the source area(s) of fine-grained terrigenous sediments (<63 μm) deposited during the MMCT. ¶ After source area characterization, we find that the fine-grained sediments from the mid-Miocene show a mixture of both local Prydz Bay sourcing (~400 Ma signature) and Wilkes Land provenance (~900 Ma signature). While locally-derived Prydz Bay sediments are likely to have been delivered via meltwater from ice and deposited as hemipelagic sediments (with some possible bottom current modification, as this is a drift site), sediments sourced from Wilkes Land required transport via large icebergs. Future work will involve further provenance determination on both the fine

  4. Nuclear Quantum Effects in Ice Phases and Water from First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Pamuk, Betul

    Despite the simplicity of the molecule, condensed phases of water show many physical anomalies, some of which are still unexplained to date. This thesis focuses on one striking anomaly that has been largely neglected and never explained. When hydrogen (1H) is replaced by deuterium (2 D), zero point fluctuations of the heavy isotope causes ice to expand, whereas in normal isotope effect, heavy isotope causes volume contraction. Furthermore, in a normal isotope effect, the shift in volume should decrease with increasing temperature, while, in ice, the volume shift increases with increasing temperature and persists up to the melting temperature and also exists in liquid water. In this dissertation, nuclear quantum effects on structural and cohesive properties of different ice polymorphs are investigated. We show that the anomalous isotope effect is well described by first principles density functional theory with van der Waals (vdW-DF) functionals within the quasi-harmonic approximation. Our theoretical modeling explains how the competition between the intra- and inter-molecular bonding of ice leads to an anomalous isotope effect in the volume and bulk modulus of ice. In addition, we predict a normal isotope effect when 16O is replaced by 18O, which is experimentally confirmed. Furthermore, the transition from proton disordered hexagonal phase, ice Ih to proton ordered hexagonal phase, ice XI occurs with a temperature difference between 1H and 2D of 6K, in good agreement with experimental value of 4K. We explain, for first time for that this temperature difference is entirely due to the zero point energy. In the second half of this thesis, we expand our study to the other ice phases: ice Ic, ice IX, ice II, ice VIII, clathrate hydrates, and low and high density amorphous ices. We employ the methodology that we have developed to investigate the isotope effect in structures with different configurations. We show that there is a transition from anomalous isotope effect

  5. Nuclear Zero Point Effects as a Function of Density in Ice-like Structures and Liquid Water from vdW-DF Ab Initio Calculations

    NASA Astrophysics Data System (ADS)

    Pamuk, Betül; Allen, Philip B.; Soler, Jose M.; Fernández-Serra, Marivi

    2014-03-01

    The contributions of nuclear zero point vibrations to the structures of liquid water and ice are not negligible. Recently, we have explained the source of an anomalous isotope shift in hexagonal ice, representing itself as an increase in the lattice volume when H is replaced by D, by calculating free energy within the quasiharmonic approximation, with ab initio density functional theory. In this work, we extend our studies to analyze the zero point effect in other ice-like structures under different densities: clathrate hydrates, LDL and HDL-like amorphous ices with different densities, and a highly dense ice phase, ice VIII. We show that there is a transition from anomalous isotope effect to normal isotope effect as the density increases. We also analyze nuclear zero point effects in liquid water using different vdW-DFs and make connections to this anomalous-normal isotope effect transition in ice. This work is supported by DOE Early Career Award No. DE-SC0003871.

  6. HCl adsorption and ionization on amorphous and crystalline H2O films below 50 K.

    PubMed

    Ayotte, Patrick; Marchand, Patrick; Daschbach, John L; Smith, R Scott; Kay, Bruce D

    2011-06-16

    Molecular beams were used to grow amorphous and crystalline H(2)O films and to dose HCl upon their surface. The adsorption state of HCl on the ice films was probed with infrared spectroscopy. A Zundel continuum is clearly observed for exposures up to the saturation HCl coverage on ice upon which features centered near 2530, 2120, 1760, and 1220 cm(-1) are superimposed. The band centered near 2530 cm(-1) is observed only when the HCl adlayer is in direct contact with amorphous solid water or crystalline ice films at temperatures as low as 20 K. The spectral signature of solid HCl (amorphous or crystalline) was identified only after saturation of the adsorption sites in the first layer or when HCl was deposited onto a rare gas spacer layer between the HCl and ice film. These observations strongly support conclusions from recent electron spectroscopy work that reported ionic dissociation of the first layer HCl adsorbed onto the ice surface is spontaneous.

  7. Pressure-induced transformations in amorphous silicon: A computational study

    SciTech Connect

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

    2014-02-14

    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.

  8. Layered kagome spin ice

    NASA Astrophysics Data System (ADS)

    Hamp, James; Dutton, Sian; Mourigal, Martin; Mukherjee, Paromita; Paddison, Joseph; Ong, Harapan; Castelnovo, Claudio

    Spin ice materials provide a rare instance of emergent gauge symmetry and fractionalisation in three dimensions: the effective degrees of freedom of the system are emergent magnetic monopoles, and the extensively many `ice rule' ground states are those devoid of monopole excitations. Two-dimensional (kagome) analogues of spin ice have also been shown to display a similarly rich behaviour. In kagome ice however the ground-state `ice rule' condition implies the presence everywhere of magnetic charges. As temperature is lowered, an Ising transition occurs to a charge-ordered state, which can be mapped to a dimer covering of the dual honeycomb lattice. A second transition, of Kosterlitz-Thouless or three-state Potts type, occurs to a spin-ordered state at yet lower temperatures, due to small residual energy differences between charge-ordered states. Inspired by recent experimental capabilities in growing spin ice samples with selective (layered) substitution of non-magnetic ions, in this work we investigate the fate of the two ordering transitions when individual kagome layers are brought together to form a three-dimensional pyrochlore structure coupled by long range dipolar interactions. We also consider the response to substitutional disorder and applied magnetic fields.

  9. Structures and Low-Energy Excitations of Amorphous Gas Hydrates

    NASA Astrophysics Data System (ADS)

    Kikuchi, Tatsuya; Inamura, Yasuhiro; Onoda-Yamamuro, Noriko; Yamamuro, Osamu

    2012-09-01

    We have prepared amorphous clathrate hydrates of Ar, CD4, Xe, and SF6 by depositing mixed vapors of water and guest molecules on a substrate at ca. 10 K. The structure and vibrational density of states were investigated by neutron diffraction and inelastic scattering techniques, respectively. The radial distribution functions of the amorphous hydrates are larger than that of pure amorphous ice in the region around 4 Å (the center-edge distance of the 12-hedral cage), indicating that a local cagelike structure is maintained even in the amorphous solids. The incorporation of the guest molecules decreases the intensity of the phonon excitation below 7 meV, which is known as a low-energy excitation characteristic of amorphous ice. This may be due to the effect that the disorder, defects and distortion producing the low-energy excitation are reduced by a hydrophobic hydration between the guest and water molecules and the resultant hydrogen-bond formation. A similar effect was also observed in the libration mode of water molecules at about 60 meV. The present work has revealed the relation among the local cage formation, hydrogen bonds, and low energy excitations in amorphous hydrates that is the simplest hydrophobic hydration system (H2O--gas mixture).

  10. Reversibility and criticality in amorphous solids

    PubMed Central

    Regev, Ido; Weber, John; Reichhardt, Charles; Dahmen, Karin A.; Lookman, Turab

    2015-01-01

    The physical processes governing the onset of yield, where a material changes its shape permanently under external deformation, are not yet understood for amorphous solids that are intrinsically disordered. Here, using molecular dynamics simulations and mean-field theory, we show that at a critical strain amplitude the sizes of clusters of atoms undergoing cooperative rearrangements of displacements (avalanches) diverges. We compare this non-equilibrium critical behaviour to the prevailing concept of a ‘front depinning' transition that has been used to describe steady-state avalanche behaviour in different materials. We explain why a depinning-like process can result in a transition from periodic to chaotic behaviour and why chaotic motion is not possible in pinned systems. These findings suggest that, at least for highly jammed amorphous systems, the irreversibility transition may be a side effect of depinning that occurs in systems where the disorder is not quenched. PMID:26564783

  11. Reversibility and criticality in amorphous solids

    DOE PAGES

    Regev, Ido; Weber, John; Reichhardt, Charles; Dahmen, Karin A.; Lookman, Turab

    2015-11-13

    The physical processes governing the onset of yield, where a material changes its shape permanently under external deformation, are not yet understood for amorphous solids that are intrinsically disordered. Here, using molecular dynamics simulations and mean-field theory, we show that at a critical strain amplitude the sizes of clusters of atoms undergoing cooperative rearrangements of displacements (avalanches) diverges. We compare this non-equilibrium critical behaviour to the prevailing concept of a ‘front depinning’ transition that has been used to describe steady-state avalanche behaviour in different materials. We explain why a depinning-like process can result in a transition from periodic to chaoticmore » behaviour and why chaotic motion is not possible in pinned systems. As a result, these findings suggest that, at least for highly jammed amorphous systems, the irreversibility transition may be a side effect of depinning that occurs in systems where the disorder is not quenched.« less

  12. Reversibility and criticality in amorphous solids

    SciTech Connect

    Regev, Ido; Weber, John; Reichhardt, Charles; Dahmen, Karin A.; Lookman, Turab

    2015-11-13

    The physical processes governing the onset of yield, where a material changes its shape permanently under external deformation, are not yet understood for amorphous solids that are intrinsically disordered. Here, using molecular dynamics simulations and mean-field theory, we show that at a critical strain amplitude the sizes of clusters of atoms undergoing cooperative rearrangements of displacements (avalanches) diverges. We compare this non-equilibrium critical behaviour to the prevailing concept of a ‘front depinning’ transition that has been used to describe steady-state avalanche behaviour in different materials. We explain why a depinning-like process can result in a transition from periodic to chaotic behaviour and why chaotic motion is not possible in pinned systems. As a result, these findings suggest that, at least for highly jammed amorphous systems, the irreversibility transition may be a side effect of depinning that occurs in systems where the disorder is not quenched.

  13. Reversibility and criticality in amorphous solids.

    PubMed

    Regev, Ido; Weber, John; Reichhardt, Charles; Dahmen, Karin A; Lookman, Turab

    2015-01-01

    The physical processes governing the onset of yield, where a material changes its shape permanently under external deformation, are not yet understood for amorphous solids that are intrinsically disordered. Here, using molecular dynamics simulations and mean-field theory, we show that at a critical strain amplitude the sizes of clusters of atoms undergoing cooperative rearrangements of displacements (avalanches) diverges. We compare this non-equilibrium critical behaviour to the prevailing concept of a 'front depinning' transition that has been used to describe steady-state avalanche behaviour in different materials. We explain why a depinning-like process can result in a transition from periodic to chaotic behaviour and why chaotic motion is not possible in pinned systems. These findings suggest that, at least for highly jammed amorphous systems, the irreversibility transition may be a side effect of depinning that occurs in systems where the disorder is not quenched. PMID:26564783

  14. Hydrogen in amorphous silicon

    SciTech Connect

    Peercy, P. S.

    1980-01-01

    The structural aspects of amorphous silicon and the role of hydrogen in this structure are reviewed with emphasis on ion implantation studies. In amorphous silicon produced by Si ion implantation of crystalline silicon, the material reconstructs into a metastable amorphous structure which has optical and electrical properties qualitatively similar to the corresponding properties in high-purity evaporated amorphous silicon. Hydrogen studies further indicate that these structures will accomodate less than or equal to 5 at.% hydrogen and this hydrogen is bonded predominantly in a monohydride (SiH/sub 1/) site. Larger hydrogen concentrations than this can be achieved under certain conditions, but the excess hydrogen may be attributed to defects and voids in the material. Similarly, glow discharge or sputter deposited amorphous silicon has more desirable electrical and optical properties when the material is prepared with low hydrogen concentration and monohydride bonding. Results of structural studies and hydrogen incorporation in amorphous silicon were discussed relative to the different models proposed for amorphous silicon.

  15. Fire beneath the ice

    SciTech Connect

    Monastersky, R.

    1993-02-13

    A volcano discovered six years ago by researchers Blankenship and Bell under Antarctica poses questions about a potential climatic catastrophe. The researchers claim that the volcano is still active, erupting occasionally and growing. A circular depression on the surface of the ice sheet has ice flowing into it and is used to provide a portrait of the heat source. The volcano is on a critical transition zone within West Antarctica with fast flowing ice streams directly downhill. Work by Blankenship shows that a soft layer of water-logged sediments called till provide the lubricating layer on the underside of the ice streams. Volcanos may provide the source of this till. The ice streams buffer the thick interior ice from the ocean and no one know what will happen if the ice streams continue to shorten. These researchers believe their results indicate that the stability of West Antarctica ultimately depends less on the current climate than on the location of heat and sediments under the ice and the legacy of past climatic changes.

  16. Water Freezing and Ice Melting.

    PubMed

    Małolepsza, Edyta; Keyes, Tom

    2015-12-01

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to the freezing of liquid water and the melting of hexagonal and cubic ice. It is confirmed that coexisting states are well-sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice ↔ liquid and cubic ice ↔ liquid with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. Pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.

  17. Water Freezing and Ice Melting.

    PubMed

    Małolepsza, Edyta; Keyes, Tom

    2015-12-01

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to the freezing of liquid water and the melting of hexagonal and cubic ice. It is confirmed that coexisting states are well-sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice ↔ liquid and cubic ice ↔ liquid with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. Pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice. PMID:26642983

  18. Impact craters: An ice study on Rhea

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    The goal of this project is to study the properties of H2O ice in the environment of the Saturn satellites and in particular to measure the relative amounts of crystalline and amorphous H2O ice in and around two craters on Rhea. The craters are remnants of cataclysmic events that, by raising the local temperature, melted the ice, which subsequently crystallized. Based on laboratory experiments it is expected that, when exposed to ion bombardment at the temperatures typical of the Saturn satellites, the crystalline structure of the ice will be broken, resulting in the disordered, amorphous phase. We therefore expect the ice in and around the craters to be partially crystalline and partially amorphous. We have designed a technique that estimates the relative amounts of crystalline and amorphous H2O ice based on measurements of the distortion of the 2-μm spectral absorption band. The technique is best suited for planetary surfaces that are predominantly icy, but works also for surfaces slightly contaminated with other ices and non-ice components. We apply the tool to two areas around the Inktomi and the Obatala craters. The first is a young impact crater on the leading hemisphere of Rhea, the second is an older one on the trailing hemisphere. For each crater we obtain maps of the fraction of crystalline ice, which were overlain onto Imaging Science Subsystem (ISS) images of the satellite searching for correlations between crystallinity and geography. For both craters the largest fractions of crystalline ice are in the center, as would be intuitively expected since the 'ground zero' areas should be most affected by the effects of the impact. The overall distribution of the crystalline ice fraction maps the shape of the crater and, in the case of Inktomi, of the rays. The Inktomi crater ranges between a maximum fraction of 67% crystalline ice to a minimum of 39%. The Obatala crater varies between a maximum of 51% and a minimum of 33%. Based on simplifying assumptions

  19. Evolution of first-year and second-year snow properties on sea ice in the Weddell Sea during spring-summer transition

    NASA Astrophysics Data System (ADS)

    Nicolaus, Marcel; Haas, Christian; Willmes, Sascha

    2009-09-01

    Observations of snow properties, superimposed ice, and atmospheric heat fluxes have been performed on first-year and second-year sea ice in the western Weddell Sea, Antarctica. Snow in this region is particular as it does usually survive summer ablation. Measurements were performed during Ice Station Polarstern (ISPOL), a 5-week drift station of the German icebreaker RV Polarstern. Net heat flux to the snowpack was 8 W m-2, causing only 0.1 to 0.2 m of thinning of both snow cover types, thinner first-year and thicker second-year snow. Snow thinning was dominated by compaction and evaporation, whereas melt was of minor importance and occurred only internally at or close to the surface. Characteristic differences between snow on first-year and second-year ice were found in snow thickness, temperature, and stratigraphy. Snow on second-year ice was thicker, colder, denser, and more layered than on first-year ice. Metamorphism and ablation, and thus mass balance, were similar between both regimes, because they depend more on surface heat fluxes and less on underground properties. Ice freeboard was mostly negative, but flooding occurred mainly on first-year ice. Snow and ice interface temperature did not reach the melting point during the observation period. Nevertheless, formation of discontinuous superimposed ice was observed. Color tracer experiments suggest considerable meltwater percolation within the snow, despite below-melting temperatures of lower layers. Strong meridional gradients of snow and sea-ice properties were found in this region. They suggest similar gradients in atmospheric and oceanographic conditions and implicate their importance for melt processes and the location of the summer ice edge.

  20. Amorphous diamond films

    DOEpatents

    Falabella, S.

    1998-06-09

    Amorphous diamond films having a significant reduction in intrinsic stress are prepared by biasing a substrate to be coated and depositing carbon ions thereon under controlled temperature conditions. 1 fig.

  1. Investigation of the amorphous to crystalline phase transition of chemical solution deposited Pb(Zr30Ti70)O3 thin films by soft x-ray absorption and soft x-ray emission spectroscopy

    SciTech Connect

    Schneller, T.; Schneller, T.; Kohlstedt, H.; Petraru, A.; Waser, R.; Guo, J.; Denlinger, J.; Learmonth, T.; Glans, Per-Andres; Smith, K. E.

    2008-08-01

    Chemical solution deposited (CSD) complex oxide thin films attract considerable interest in various emerging fields as for example, fuel cells, ferroelectric random access memories or coated conductors. In the present paper the results of soft-x-ray spectroscopy between 100 eV and 500 eV on the amorphous to crystalline phase transition of ferroelectric PbZr{sub 0.3}Ti{sub 0.7}O{sub 3} (PZT) thin films are presented. Five CSD samples derived from the same wafer coated with a PZT film pyrolyzed at 350 C were heat treated at different temperatures between 400 C and 700 C. At first the sample were morphologically and electrically characterized. Subsequently the soft-x-ray absorption and emission experiments were performed at the undulator beamline 8.0 of the Advanced Light Source of the Lawrence Berkeley National Laboratory. Soft-x-ray absorption spectra were acquired for the Ti L{sub 2,3-}, O K-, and C K-edge thresholds by using simultaneously the total electron yield (TEY) and total fluorescence yield (TFY) detection methods. For two samples, annealed at 400 C and 700 C, respectively, the resonant inelastic soft-x-ray spectroscopy (RIXS) was applied for various excitation energies near the Ti L-, O K-edges. We observed clear evidence of a rutile phase at untypically low temperatures. This rutile phase transforms into the perovskite phase upon increasing annealing temperature. These results are discussed in the framework of current microscopic models of the PZT (111) texture selection.

  2. Amorphous metal alloy

    DOEpatents

    Wang, R.; Merz, M.D.

    1980-04-09

    Amorphous metal alloys of the iron-chromium and nickel-chromium type have excellent corrosion resistance and high temperature stability and are suitable for use as a protective coating on less corrosion resistant substrates. The alloys are stabilized in the amorphous state by one or more elements of titanium, zirconium, hafnium, niobium, tantalum, molybdenum, and tungsten. The alloy is preferably prepared by sputter deposition.

  3. Amorphous molybdenum silicon superconducting thin films

    SciTech Connect

    Bosworth, D. Sahonta, S.-L.; Barber, Z. H.; Hadfield, R. H.

    2015-08-15

    Amorphous superconductors have become attractive candidate materials for superconducting nanowire single-photon detectors due to their ease of growth, homogeneity and competitive superconducting properties. To date the majority of devices have been fabricated using W{sub x}Si{sub 1−x}, though other amorphous superconductors such as molybdenum silicide (Mo{sub x}Si{sub 1−x}) offer increased transition temperature. This study focuses on the properties of MoSi thin films grown by magnetron sputtering. We examine how the composition and growth conditions affect film properties. For 100 nm film thickness, we report that the superconducting transition temperature (Tc) reaches a maximum of 7.6 K at a composition of Mo{sub 83}Si{sub 17}. The transition temperature and amorphous character can be improved by cooling of the substrate during growth which inhibits formation of a crystalline phase. X-ray diffraction and transmission electron microscopy studies confirm the absence of long range order. We observe that for a range of 6 common substrates (silicon, thermally oxidized silicon, R- and C-plane sapphire, x-plane lithium niobate and quartz), there is no variation in superconducting transition temperature, making MoSi an excellent candidate material for SNSPDs.

  4. Amorphous molybdenum silicon superconducting thin films

    NASA Astrophysics Data System (ADS)

    Bosworth, D.; Sahonta, S.-L.; Hadfield, R. H.; Barber, Z. H.

    2015-08-01

    Amorphous superconductors have become attractive candidate materials for superconducting nanowire single-photon detectors due to their ease of growth, homogeneity and competitive superconducting properties. To date the majority of devices have been fabricated using WxSi1-x, though other amorphous superconductors such as molybdenum silicide (MoxSi1-x) offer increased transition temperature. This study focuses on the properties of MoSi thin films grown by magnetron sputtering. We examine how the composition and growth conditions affect film properties. For 100 nm film thickness, we report that the superconducting transition temperature (Tc) reaches a maximum of 7.6 K at a composition of Mo83Si17. The transition temperature and amorphous character can be improved by cooling of the substrate during growth which inhibits formation of a crystalline phase. X-ray diffraction and transmission electron microscopy studies confirm the absence of long range order. We observe that for a range of 6 common substrates (silicon, thermally oxidized silicon, R- and C-plane sapphire, x-plane lithium niobate and quartz), there is no variation in superconducting transition temperature, making MoSi an excellent candidate material for SNSPDs.

  5. Upper ocean stratification and sea ice growth rates during the summer-fall transition, as revealed by Elephant seal foraging in the Adélie Depression, East Antarctica

    NASA Astrophysics Data System (ADS)

    Williams, G. D.; Hindell, M.; Houssais, M.-N.; Tamura, T.; Field, I. C.

    2010-11-01

    Southern elephant seals (Mirounga leonina), fitted with Conductivity-Temperature-Depth sensors at Macquarie Island in January 2005 and 2010, collected unique oceanographic observations of the Adélie and George V Land continental shelf (140-148° E) during the summer-fall transition (late February through April). This is a key region of dense shelf water formation from enhanced sea ice growth/brine-rejection in the local coastal polynyas. In 2005 two seals occupied the continental shelf break near the grounded icebergs at the northern end of the Mertz Glacier Tongue for nearly two weeks at the onset of sea ice growth. One of the seals migrated north thereafter and the other headed west, possibly utilising the Antarctic Slope Front current near the continental shelf break. In 2010, after that years calving of the Mertz Glacier Tongue, two seals migrated to the same region but penetrated much further southwest across the Adélie Depression and occupied the Commonwealth Bay polynya from March through April. Here we present unique observations of the regional oceanography during the summer-fall transition, in particular (a) the zonal distribution of modified Circumpolar Deep Water exchange across the shelf break, (b) the upper ocean stratification across the Adélie Depression, including alongside iceberg C-28 that calved from the Mertz Glacier and (c) the convective overturning of the deep remnant seasonal mixed layer in Commonwealth Bay from sea ice growth (7.5-12.5 cm s-1). Heat and freshwater budgets to 200-300 m are used to estimate the ocean heat content, heat flux and sea ice growth rates. We speculate that the continuous foraging by the seals within Commonwealth Bay during the summer-fall transition was due to favorable feeding conditions resulting from the convective overturning of the deep seasonal mixed layer and chlorophyll maximum that is a reported feature of this location.

  6. Diversity and Expression of RubisCO Genes in a Perennially Ice-Covered Antarctic Lake during the Polar Night Transition

    PubMed Central

    Kong, Weidong; Ream, David C.; Priscu, John C.

    2012-01-01

    The autotrophic communities in the lakes of the McMurdo Dry Valleys, Antarctica, have generated interest since the early 1960s owing to low light transmission through the permanent ice covers, a strongly bimodal seasonal light cycle, constant cold water temperatures, and geographical isolation. Previous work has shown that autotrophic carbon fixation in these lakes provides an important source of organic matter to this polar desert. Lake Bonney has two lobes separated by a shallow sill and is one of several chemically stratified lakes in the dry valleys that support year-round biological activity. As part of an International Polar Year initiative, we monitored the diversity and abundance of major isoforms of RubisCO in Lake Bonney by using a combined sequencing and quantitative PCR approach during the transition from summer to polar winter. Form ID RubisCO genes related to a stramenopile, a haptophyte, and a cryptophyte were identified, while primers specific for form IA/B RubisCO detected a diverse autotrophic community of chlorophytes, cyanobacteria, and chemoautotrophic proteobacteria. Form ID RubisCO dominated phytoplankton communities in both lobes of the lake and closely matched depth profiles for photosynthesis and chlorophyll. Our results indicate a coupling between light availability, photosynthesis, and rbcL mRNA levels in deep phytoplankton populations. Regulatory control of rbcL in phytoplankton living in nutrient-deprived shallow depths does not appear to be solely light dependent. The distinct water chemistries of the east and west lobes have resulted in depth- and lobe-dependent variability in RubisCO diversity, which plays a role in transcriptional activity of the key gene responsible for carbon fixation. PMID:22492447

  7. Moringa coagulant as a stabilizer for amorphous solids: Part I.

    PubMed

    Bhende, Santosh; Jadhav, Namdeo

    2012-06-01

    Stabilization of amorphous state is a focal area for formulators to reap benefits related with solubility and consequently bioavailability of poorly soluble drugs. In the present work, an attempt has been made to explore the potential of moringa coagulant as an amorphous state stabilizer by investigating its role in stabilization of spray-dried (amorphous) ibuprofen, meloxicam and felodipine. Thermal studies like glass forming ability, glass transition temperature, hot stage microscopy and DSC were carried out for understanding thermodynamic stabilization of drugs. PXRD and dissolution studies were performed to support contribution of moringa coagulant. Studies showed that hydrogen bonding and electrostatic interactions between drug and moringa coagulant are responsible for amorphous state stabilization as explored by ATR-FTIR and molecular docking. Especially, H-bonding was found to be predominant mechanism for drug stabilization. Therein, arginine (basic amino acid in coagulant) exhibited various interactions and played important role in stabilization of aforesaid amorphous drugs. PMID:22359158

  8. Sea Ice

    NASA Technical Reports Server (NTRS)

    Parkinson, Claire L.; Cavalieri, Donald J.

    2005-01-01

    Sea ice covers vast areas of the polar oceans, with ice extent in the Northern Hemisphere ranging from approximately 7 x 10(exp 6) sq km in September to approximately 15 x 10(exp 6) sq km in March and ice extent in the Southern Hemisphere ranging from approximately 3 x 10(exp 6) sq km in February to approximately 18 x 10(exp 6) sq km in September. These ice covers have major impacts on the atmosphere, oceans, and ecosystems of the polar regions, and so as changes occur in them there are potential widespread consequences. Satellite data reveal considerable interannual variability in both polar sea ice covers, and many studies suggest possible connections between the ice and various oscillations within the climate system, such as the Arctic Oscillation, North Atlantic Oscillation, and Antarctic Oscillation, or Southern Annular Mode. Nonetheless, statistically significant long-term trends are also apparent, including overall trends of decreased ice coverage in the Arctic and increased ice coverage in the Antarctic from late 1978 through the end of 2003, with the Antarctic ice increases following marked decreases in the Antarctic ice during the 1970s. For a detailed picture of the seasonally varying ice cover at the start of the 21st century, this chapter includes ice concentration maps for each month of 2001 for both the Arctic and the Antarctic, as well as an overview of what the satellite record has revealed about the two polar ice covers from the 1970s through 2003.

  9. The Mesoscale Morphologies of Ice Films: Porous and Biomorphic Forms of Ice under Astrophysical Conditions

    NASA Astrophysics Data System (ADS)

    Cartwright, Julyan H. E.; Escribano, Bruno; Sainz-Diaz, C. Ignacio

    2008-11-01

    We present the results of experiments in which we grow submicrometer- to millimeter-thick ice films at temperatures of 6-220 K at low pressures in situ in a cryo environmental scanning electron microscope. We find that ice films show pronounced morphologies at the mesoscale similar to those previously described in films of ceramics, semiconductors, and metals; materials with quite different material properties to ice. Our experiments are aimed at revealing the mesoscale morphologies of amorphous and crystalline ice with regard to astrophysical environments, as the conditions in which the ice films grow in our experiments are those under which exists most extraterrestrial ice. The porosity on the mesoscale of many of the morphologies is notable in this regard; a further intriguing finding is that these ice films can emulate biological forms.

  10. 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.

  11. Over Ice

    NASA Video Gallery

    All about NASA's IceBridge P-3B plane and its IceBridge retrofit. Upgraded with 21st century "special modifications", the aircraft is less a cold war relic and more like the Space Agency's Millenni...

  12. Ices in space

    NASA Astrophysics Data System (ADS)

    Greenberg, J. Mayo; van de Bult, C. E. P. M.; Allamandola, Louis J.

    The chemical and physical properties of ice grains in interstellar space have been studied in the laboratory and theoretically modeled to compare with astronomical spectra between 2700 and 3700/cm. The observed polarization of starlight in this region clearly indicates that elongated particles are involved. Absorption characteristics for various shaped grains whose radii vary from approximately 0.1 to 1.0 micrometer, containing either pure amorphous H20 or amorphous mixtures of H20 with NH3, have been calculated with the aim of narrowing the range of acceptable grain parameters. By comparing the band shapes for spherical, spheroidal, and cylindrical grains with astronomical spectra we show that elongated particles whose radii are approximately equal to 0.15 micrometer produce an acceptable match and that both spherical and elongated particles whose radii are greater than or equal to 0.5 micrometer are definitely not consistent with observations. Details of the band shape are shown to depend on particle size, shape, and composition. Similar profiles can be produced by using different combinations of particle shape and composition. For example, the NH3 signature at 2.97 micrometer, which is prominent in a spherical grain, is greatly suppressed when in an elongated grain. This is exactly equivalent to reducing the concentration of NH3 in a spherical grain. A morphological grain model is used to explain the large variations in the observed strength of the 3.07 micrometer ice band from one region of space to another.

  13. Formation of amorphous materials

    DOEpatents

    Johnson, William L.; Schwarz, Ricardo B.

    1986-01-01

    Metastable amorphous or fine crystalline materials are formed by solid state reactions by diffusion of a metallic component into a solid compound or by diffusion of a gas into an intermetallic compound. The invention can be practiced on layers of metals deposited on an amorphous substrate or by intermixing powders with nucleating seed granules. All that is required is that the diffusion of the first component into the second component be much faster than the self-diffusion of the first component. The method is practiced at a temperature below the temperature at which the amorphous phase transforms into one or more crystalline phases and near or below the temperature at which the ratio of the rate of diffusion of the first component to the rate of self-diffusion is at least 10.sup.4. This anomalous diffusion criteria is found in many binary, tertiary and higher ordered systems of alloys and appears to be found in all alloy systems that form amorphous materials by rapid quenching. The method of the invention can totally convert much larger dimensional materials to amorphous materials in practical periods of several hours or less.

  14. Predicting Crystallization of Amorphous Drugs with Terahertz Spectroscopy.

    PubMed

    Sibik, Juraj; Löbmann, Korbinian; Rades, Thomas; Zeitler, J Axel

    2015-08-01

    There is a controversy about the extent to which the primary and secondary dielectric relaxations influence the crystallization of amorphous organic compounds below the glass transition temperature. Recent studies also point to the importance of fast molecular dynamics on picosecond-to-nanosecond time scales with respect to the glass stability. In the present study we provide terahertz spectroscopy evidence on the crystallization of amorphous naproxen well below its glass transition temperature and confirm the direct role of Johari-Goldstein (JG) secondary relaxation as a facilitator of the crystallization. We determine the onset temperature Tβ above which the JG relaxation contributes to the fast molecular dynamics and analytically quantify the level of this contribution. We then show there is a strong correlation between the increase in the fast molecular dynamics and onset of crystallization in several chosen amorphous drugs. We believe that this technique has immediate applications to quantify the stability of amorphous drug materials.

  15. Synthesis of new amorphous metallic spin glasses

    DOEpatents

    Haushalter, R.C.

    1985-02-11

    Disclosed are: amorphous metallic precipitates having the formula (M/sub 1/)/sub a/(M/sub 2/)/sub b/ wherein M/sub 1/ is at least one transition metal, M/sub 2/ is at least one main group metal and the integers ''a'' and ''b'' provide stoichiometric balance; the precipitates having a degree of local order characteristic of chemical compounds from the precipitation process and useful electrical and mechanical properties.

  16. Synthesis of new amorphous metallic spin glasses

    DOEpatents

    Haushalter, Robert C.

    1988-01-01

    Amorphous metallic precipitates having the formula (M.sub.1).sub.a (M.sub.2).sub.b wherein M.sub.1 is at least one transition metal, M.sub.2 is at least one main group metal and the integers "a" and "b" provide stoichiometric balance; the precipitates having a degree of local order characteristic of chemical compounds from the precipitation process and useful electrical and mechanical properties.

  17. Synthesis of new amorphous metallic spin glasses

    DOEpatents

    Haushalter, Robert C.

    1986-01-01

    Amorphous metallic precipitates having the formula (M.sub.1).sub.a (M.sub.2).sub.b wherein M.sub.1 is at least one transition metal, M.sub.2 is at least one main group metal and the integers "a" and "b" provide stoichiometric balance; the precipitates having a degree of local order characteristic of chemical compounds from the precipitation process and useful electrical and mechanical properties.

  18. The Nature of the Medieval Warm Period - Little Ice Ace Transition in an Annually Resolved Speleothem Record from Voli Voli Cave, Fiji

    NASA Astrophysics Data System (ADS)

    Mattey, D.; Stephens, M.; Garcia-Anton, E.; Hoffmann, D.; Dredge, J. A.; Fisher, R. E.; Lowry, D.

    2011-12-01

    The modern tropical Fiji climate is characterised by seasonal rainfall controlled by the position of the South Pacific Convergance Zone, which is closest to the islands during the wet summer season and weakens when migrating north during the drier winter season. Annual rainfall is strongly modulated on decadal timescales by ENSO with higher rainfall associated with La Nina events with dry spells sometimes leading to drought conditions during El Nino events. A laminated speleothem from Voli Voli cave Fiji spans a 1500 year interval across the transition from the Medieval Warm Period into the Little Ice Age. Fabrics change from calcite with thin clay layers at the base to white laminated calcite and the older record is characterised by elevated δ13C values then a rapid decrease in δ13C, dated at 1200-1300 AD, coinciding with the onset of clean calcite deposition. δ18O values define a simpler trend that monotonically decreases by ≈1% across the transition but high resolution micromilling at 100 micron resolution reveals smooth oscillations in δ18O and a key question is whether these cycles are annual or multi-annual features. To understand relationships between local cave processes and seasonal weather patterns, a program of cave monitoring has been underway since 2009. Voli Voli cave is a descending passage that terminates near a fissured cliff facing the SE trade winds; these are more persistent during the winter and weaken during the summer and cave monitoring shows that high cave air CO2 levels decline near the cave termination as a result of weak incoming ventilation by atmosphere driven by wind strength or chimney ventilation. The high resolution δ13C record shows regular peaks that are correlated with cycles in P and Sr and are interpreted as annual markers driven by rainfall and seasonal ventilation. The smooth δ18O cycles are quasi-decadal features possessing a similar frequency to ENSO with an amplitude of 2-3% equivalent to an amount-effect related

  19. The 'depletion layer' of amorphous p-n junctions

    NASA Technical Reports Server (NTRS)

    Von Roos, O.

    1981-01-01

    It is shown that within reasonable approximations for the density of state distribution within the mobility gap of a:Si, a one-to-one correspondence exists between the electric field distribution in the transition region of an amorphous p-n junction and that in the depletion layer of a crystalline p-n junction. Thus it is inferred that the depletion layer approximation which leads to a parabolic potential distribution within the depletion layer of crystalline junctions also constitutes a fair approximation in the case of amorphous junctions. This fact greatly simplifies an analysis of solid-state electronic devices based on amorphous material (i.e., solar cells).

  20. Depressurization amorphization of single-crystal boron carbide.

    PubMed

    Yan, X Q; Tang, Z; Zhang, L; Guo, J J; Jin, C Q; Zhang, Y; Goto, T; McCauley, J W; Chen, M W

    2009-02-20

    We report depressurization amorphization of single-crystal boron carbide (B4C) investigated by in situ high-pressure Raman spectroscopy. It was found that localized amorphization of B4C takes place during unloading from high pressures, and nonhydrostatic stresses play a critical role in the high-pressure phase transition. First-principles molecular dynamics simulations reveal that the depressurization amorphization results from pressure-induced irreversible bending of C-B-C atomic chains cross-linking 12 atom icosahedra at the rhombohedral vertices.

  1. Structural Amorphous Steels

    NASA Astrophysics Data System (ADS)

    Lu, Z. P.; Liu, C. T.; Thompson, J. R.; Porter, W. D.

    2004-06-01

    Recent advancement in bulk metallic glasses, whose properties are usually superior to their crystalline counterparts, has stimulated great interest in fabricating bulk amorphous steels. While a great deal of effort has been devoted to this field, the fabrication of structural amorphous steels with large cross sections has remained an alchemist’s dream because of the limited glass-forming ability (GFA) of these materials. Here we report the discovery of structural amorphous steels that can be cast into glasses with large cross-section sizes using conventional drop-casting methods. These new steels showed interesting physical, magnetic, and mechanical properties, along with high thermal stability. The underlying mechanisms for the superior GFA of these materials are discussed.

  2. Growth Induced Magnetic Anisotropy in Crystalline and Amorphous Thin Films

    SciTech Connect

    Hellman, Frances

    1998-10-03

    OAK B204 Growth Induced Magnetic Anisotropy in Crystalline and Amorphous Thin Films. The work in the past 6 months has involved three areas of magnetic thin films: (1) amorphous rare earth-transition metal alloys, (2) epitaxial Co-Pt and hTi-Pt alloy thin films, and (3) collaborative work on heat capacity measurements of magnetic thin films, including nanoparticles and CMR materials.

  3. Crystallization Behaviour of Amorphous Al-Ni-Nd Alloy

    SciTech Connect

    Goegebakan, Musa; Guendes, Alaaddin

    2007-04-23

    In this study, crystallization behaviour of rapidly solidified Al85Ni5Nd10 alloy has been investigated by differential scanning calorimetry (DSC). Continuous heating DSC trace of amorphous Al85Ni5Nd10 alloy consisted of three exothermic peaks. This indicated that; crystallization of amorphous Al85Ni5Nd10 alloy during continous heating takes places in three stages. Before the first exothermic peak, a glass transition temperature was observed.

  4. Swift heavy ion irradiation of water ice from MeV to GeV energies. Approaching true cosmic ray compaction

    NASA Astrophysics Data System (ADS)

    Dartois, E.; Ding, J. J.; de Barros, A. L. F.; Boduch, P.; Brunetto, R.; Chabot, M.; Domaracka, A.; Godard, M.; Lv, X. Y.; Mejía Guamán, C. F.; Pino, T.; Rothard, H.; da Silveira, E. F.; Thomas, J. C.

    2013-09-01

    Context. Cosmic ray ion irradiation affects the chemical composition of and triggers physical changes in interstellar ice mantles in space. One of the primary structural changes induced is the loss of porosity, and the mantles evolve toward a more compact amorphous state. Previously, ice compaction was monitored at low to moderate ion energies. The existence of a compaction threshold in stopping power has been suggested. Aims: In this article we experimentally study the effect of heavy ion irradiation at energies closer to true cosmic rays. This minimises extrapolation and allows a regime where electronic interaction always dominates to be explored, providing the ice compaction cross section over a wide range of electronic stopping power. Methods: High-energy ion irradiations provided by the GANIL accelerator, from the MeV up to the GeV range, are combined with in-situ infrared spectroscopy monitoring of ice mantles. We follow the IR spectral evolution of the ice as a function of increasing fluence (induced compaction of the initial microporous amorphous ice into a more compact amorphous phase). We use the number of OH dangling bonds of the water molecule, i.e. pending OH bonds not engaged in a hydrogen bond in the initially porous ice structure as a probe of the phase transition. These high-energy experiments are combined with lower energy experiments using light ions (H, He) from other facilities in Catania, Italy, and Washington, USA. Results: We evaluated the cross section for the disappearance of OH dangling bonds as a function of electronic stopping power. A cross-section law in a large energy range that includes data from different ice deposition setups is established. The relevant phase structuring time scale for the ice network is compared to interstellar chemical time scales using an astrophysical model. Conclusions: The presence of a threshold in compaction at low stopping power suggested in some previous works seems not to be confirmed for the high

  5. Excess electrons in ice: a density functional theory study.

    PubMed

    Bhattacharya, Somesh Kr; Inam, Fakharul; Scandolo, Sandro

    2014-02-21

    We present a density functional theory study of the localization of excess electrons in the bulk and on the surface of crystalline and amorphous water ice. We analyze the initial stages of electron solvation in crystalline and amorphous ice. In the case of crystalline ice we find that excess electrons favor surface states over bulk states, even when the latter are localized at defect sites. In contrast, in amorphous ice excess electrons find it equally favorable to localize in bulk and in surface states which we attribute to the preexisting precursor states in the disordered structure. In all cases excess electrons are found to occupy the vacuum regions of the molecular network. The electron localization in the bulk of amorphous ice is assisted by its distorted hydrogen bonding network as opposed to the crystalline phase. Although qualitative, our results provide a simple interpretation of the large differences observed in the dynamics and localization of excess electrons in crystalline and amorphous ice films on metals.

  6. Only Amorphous Ethanethiol Exists in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Sivaraman, Bhalamurugan; Mason, Nigel; Chakrabarti, Sandip Kumar; Das, Ankan; Gorai, Prasanta; Rajan, Rabin; Pradeep, T.; Sundararajan, Pavithraa; Cheng, Bing-Ming

    2016-07-01

    In the ISM, it is now recognised that many molecular species are synthesised on the surface of dust grains which remain within the icy mantles on these grains until desorbed or sputtered (e.g., during star or planetary formation processes). Spitzer has revealed the presence of molecular ices in the dense clouds of the ISM but it is the advent of ALMA and then JWST that is expected to reveal the chemical complexity of such ices. Since the detection of methanol (CH_3OH) in Sgr A and Sgr B2 and hydrogen sulphide (H_2S) in Sgr B2, and other sources, it was long expected that a molecule containing thiol group could the synthesized in the complex chemical regions of the ISM. In 1979, first detection of methanethiol in Sgr B2 was reported. However, the first report on the detection of the higher order thiol, ethanethiol, has only been made recently in Orion KL, 30 years after the first observations of methanethiol, although the necessary precursors were detected earlier, ethylene in IRC +10216, ethanol in Sgr B2 and hydrogen sulfide. In the laboratory for experimental astrochemistry facility in PRL, thiol ices on cold dust grains are simulated and are probed by the FTIR for the first time. Ethanethiol ices were formed on zinc selenide substrate cooled to 10 K in an ultrahigh vacuum chamber. An infrared spectrum recorded after forming the ethanethiol ice at 10K revealed the ice formed to be amorphous in nature. Ices thus formed are then gradually warmed to higher temperatures with subsequent recording of infrared spectra. From the spectrum recorded at 180K, ethanethiol molecules from the ice phase were found to sublime. Until sublimation, which is typical indication for molecules turning from amorphous to crystalline phase, significant change in the infrared spectra, was not observed. Therefore we conclude that ethanethiol exists only in amorphous phase in the icy mantles of the cold dust grains. It is also the first known largest molecule to be present only in the

  7. Crystallization of CO2 ice at astronomical conditions

    NASA Astrophysics Data System (ADS)

    Escribano, R. M.; Munoz-Caro, G.; Cruz-Diaz, G.; Mate, B.; Rodriguez-Lazcano, Y.

    2013-12-01

    Carbon dioxide is, after water and comparable to carbon monoxide, one of the most abundant frozen molecular species observed in the lines of sight towards many astrophysical media. We present here an experimental and theoretical investigation on carbon dioxide ices, generated in the lab in a range of temperature, density, amorphicity, and growing conditions (1), and simulated via high level theoretical calculations. Amorphous CO2 ice was generated at CAB by deposition onto a CsI substrate at 8 K under ultrahigh vacuum conditions in the 10-11 mbar range. The pressure increase used for the deposition of CO2 was very low, 10-9 mbar, to enable the formation of highly amorphous CO2 ice, at very low deposition rate. The transmittance infrared spectra, collected at several stages of sample growth, from 20 to 360 monolayers, are shown in the Figure. In a different set of experiments performed at IEM, the morphology of the amorphous CO2 ice has been studied using reflexion-absorption infrared (RAIR) spectroscopy. Calculated spectra of amorphous CO2 ice are obtained using the SIESTA code (2). In a first step, crystalline structures are processed by molecular dynamics to generate amorphous samples, which are subsequently relaxed until an equilibrium configuration is reached. The vibrational spectra of the amorphous solids are then calculated. The spectra of amorphous ice can change significantly depending on the density of the sample. An IR band, red-shifted with respect to ν3, has been identified as a witness of pure and amorphous CO2 ice. It vanishes when the sample becomes crystalline, either by temperature increase or by accumulation of increasing number of layers. The absence of this band in the observed spectra of solid CO2 is an indication that there is no pure and amorphous CO2 ice in inter- and circumstellar mantles References 1. Escribano, R., Muñoz Caro, G., Cruz-Díaz, G.A. Rodríguez-Lazcano, Y. and Maté, B., PNAS, accepted for publication, July 2013.. 2

  8. Upper ocean stratification and sea ice growth rates during the summer-fall transition, as revealed by Elephant seal foraging in the Adélie Depression, East Antarctica

    NASA Astrophysics Data System (ADS)

    Williams, G. D.; Hindell, M.; Houssais, M.-N.; Tamura, T.; Field, I. C.

    2011-03-01

    Southern elephant seals (Mirounga leonina), fitted with Conductivity-Temperature-Depth sensors at Macquarie Island in January 2005 and 2010, collected unique oceanographic observations of the Adélie and George V Land continental shelf (140-148° E) during the summer-fall transition (late February through April). This is a key region of dense shelf water formation from enhanced sea ice growth/brine rejection in the local coastal polynyas. In 2005, two seals occupied the continental shelf break near the grounded icebergs at the northern end of the Mertz Glacier Tongue for several weeks from the end of February. One of the seals migrated west to the Dibble Ice Tongue, apparently utilising the Antarctic Slope Front current near the continental shelf break. In 2010, immediately after that year's calving of the Mertz Glacier Tongue, two seals migrated to the same region but penetrated much further southwest across the Adélie Depression and sampled the Commonwealth Bay polynya from March through April. Here we present observations of the regional oceanography during the summer-fall transition, in particular (i) the zonal distribution of modified Circumpolar Deep Water exchange across the shelf break, (ii) the upper ocean stratification across the Adélie Depression, including alongside iceberg C-28 that calved from the Mertz Glacier and (iii) the convective overturning of the deep remnant seasonal mixed layer in Commonwealth Bay from sea ice growth. Heat and freshwater budgets to 200-300 m are used to estimate the ocean heat content (400→50 MJ m-2), flux (50-200 W m-2 loss) and sea ice growth rates (maximum of 7.5-12.5 cm day-1). Mean seal-derived sea ice growth rates were within the range of satellite-derived estimates from 1992-2007 using ERA-Interim data. We speculate that the continuous foraging by the seals within Commonwealth Bay during the summer/fall transition was due to favorable feeding conditions resulting from the convective overturning of the deep

  9. The role of ice stream dynamics in deglaciation

    NASA Astrophysics Data System (ADS)

    Robel, Alexander A.; Tziperman, Eli

    2016-08-01

    Since the mid-Pleistocene transition, deglaciation has occurred only after ice sheets have grown large while experiencing several precession and obliquity cycles, indicating that large ice sheets are more sensitive to Milankovitch forcing than small ice sheets are. Observations and model simulations suggest that the development of ice streams in the Laurentide Ice Sheet played an as yet unknown role in deglaciations. In this study, we propose a mechanism by which ice streams may enhance deglaciation and render large ice sheets more sensitive to Milankovitch forcing. We use an idealized configuration of the Parallel Ice Sheet Model that permits the formation of ice streams. When the ice sheet is large and ice streams are sufficiently developed, an upward shift in equilibrium line altitude, commensurate with Milankovitch forcing, results in rapid deglaciation, while the same shift applied to an ice sheet without fully formed ice streams results in continued ice sheet growth or slower deglaciation. Rapid deglaciation in ice sheets with significant streaming behavior is caused by ice stream acceleration and the attendant enhancement of calving and surface melting at low elevations. Ice stream acceleration is ultimately the result of steepening of the ice surface and increased driving stresses in ice stream onset zones, which come about due to the dependence of surface mass balance on elevation. These ice sheet simulations match the broad features of geomorphological observations and add ice stream dynamics that are missing from previous model studies of deglaciation.

  10. Thermal and nonthermal physiochemical processes in nanoscale films of amorphous solid water.

    PubMed

    Smith, R Scott; Petrik, Nikolay G; Kimmel, Greg A; Kay, Bruce D

    2012-01-17

    Amorphous solid water (ASW) is a disordered version of ice created by vapor deposition onto a cold substrate (typically less than 130 K). It has a higher free energy than the crystalline phase of ice, and when heated above its glass transition temperature, it transforms into a metastable supercooled liquid. This unusual form of water exists on earth only in laboratories, after preparation with highly specialized equipment. It is thus fair to ask why there is any interest in studying such an esoteric material. Much of the scientific interest results from the ability to use ASW as a model system for exploring the physical and reactive properties of liquid water and aqueous solutions. ASW is also thought to be the predominant form of water in the extremely cold temperatures of many interstellar and planetary environments. In addition, ASW is a convenient model system for studying the stability of amorphous and glassy materials as well as the properties of highly porous materials. A fundamental understanding of such properties is invaluable in a diverse range of applications, including cryobiology, food science, pharmaceuticals, astrophysics, and nuclear waste storage, among others. Over the past 15 years, we have used molecular beams and surface science techniques to probe the thermal and nonthermal properties of nanoscale films of ASW. In this Account, we present a survey of our research on the properties of ASW using this approach. We use molecular beams to precisely control the deposition conditions (flux, incident energy, and incident angle) and create compositionally tailored, nanoscale films of ASW at low temperatures. To study the transport properties (viscosity and diffusivity), we heat the amorphous films above their glass transition temperature, T(g), at which they transform into deeply supercooled liquids prior to crystallization. The advantage of this approach is that at temperatures near T(g), the viscosity is approximately 15 orders of magnitude larger

  11. Amorphous semiconductor solar cell

    DOEpatents

    Dalal, Vikram L.

    1981-01-01

    A solar cell comprising a back electrical contact, amorphous silicon semiconductor base and junction layers and a top electrical contact includes in its manufacture the step of heat treating the physical junction between the base layer and junction layer to diffuse the dopant species at the physical junction into the base layer.

  12. Amorphous silicon photovoltaic devices

    DOEpatents

    Carlson, David E.; Lin, Guang H.; Ganguly, Gautam

    2004-08-31

    This invention is a photovoltaic device comprising an intrinsic or i-layer of amorphous silicon and where the photovoltaic device is more efficient at converting light energy to electric energy at high operating temperatures than at low operating temperatures. The photovoltaic devices of this invention are suitable for use in high temperature operating environments.

  13. Dissolved iron and iron(II) distributions beneath the pack ice in the East Antarctic (120°E) during the winter/spring transition

    NASA Astrophysics Data System (ADS)

    Schallenberg, Christina; van der Merwe, Pier; Chever, Fanny; Cullen, Jay T.; Lannuzel, Delphine; Bowie, Andrew R.

    2016-09-01

    Distributions of dissolved iron (dFe) and its reduced form, Fe(II), to a depth of 1000 m were investigated under the seasonal pack ice off East Antarctica during the Sea Ice Physics and Ecosystem experiment (SIPEX-2) sea-ice voyage in September-October 2012. Concentrations of dFe were elevated up to five-fold relative to Southern Ocean background concentrations and were spatially variable. The mean dFe concentration was 0.44±0.4 nM, with a range from 0.09 to 3.05 nM. Profiles of dFe were more variable within and among stations than were macronutrients, suggesting that coupling between these biologically-essential elements was weak at the time of the study. Brine rejection and drainage from sea ice are estimated to be the dominant contributors to elevated dFe concentrations in the mixed layer, but mass budget considerations indicate that estimated dFe fluxes from brine input alone are insufficient to account for all observed dFe. Melting icebergs and shelf sediments are suspected to provide the additional dFe. Fe(II) was mostly below the detection limit but elevated at depth near the continental shelf, implying that benthic processes are a source of reduced Fe in bottom waters. The data indicate that dFe builds up under the seasonal sea-ice cover during winter and that reduction of Fe may be hampered in early spring by several factors such as lack of electron donors, low biological productivity and inadequate light below the sea ice. The accumulated dFe pool in the mixed layer is expected to contribute to the formation of the spring bloom as the ice retreats.

  14. Electric-field-induced phase transition of confined water nanofilms between two graphene sheets.

    PubMed

    Qian, Zhenyu; Wei, Guanghong

    2014-10-01

    A recent study reported that confined water nanofilms may freeze continuously or discontinuously depending on their densities. In this study, we report results from molecular dynamics simulations of the structures and the phase transition of water confined between two graphene sheets with a separation of 1.0 nm under the influence of an electric (E) field applied along the direction parallel to the sheets. We find that confined water can form three kinds of ice phases at atmospheric pressure: amorphous, hexagonal, or rhombic bilayer ice, depending on the E-field strength (0-1.5 V/nm). As the E-field strength changes, these ice configurations can transform into each other through a first-order phase transition. These E-field-induced water phases are different from those induced by high pressure (under high density). In addition, we find that all of the three ice nanofilms melt through a first-order transition. The heating and cooling processes are accompanied by a hysteresis loop between the solid and liquid phases. A phase diagram of confined water between two graphene sheets is given in the temperature-E-field plane. PMID:24831927

  15. Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

    NASA Technical Reports Server (NTRS)

    Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.

    1993-01-01

    Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

  16. 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.

  17. The influence of ice accretion physics on the forecasting of aircraft icing conditions

    NASA Technical Reports Server (NTRS)

    Hansman, R. John, Jr.

    1990-01-01

    The physics which control aircraft ice accretion are reviewed in the context of identifying and forecasting hazardous icing conditions. The severity of aircraft icing is found to be extremely sensitive to temperature, liquid water content and droplet size distribution particularly near the transition between rime and mixed icing. The difficulty in measurement and the variability of these factors with altitude, position and time coupled with variable aircraft sensitivity make forecasting and identifying icing conditions difficult. Automated Pilot Reports (PIREPS) are suggested as one mechanism for improving the data base necessary to forecast icing conditions.

  18. Sea Ice

    NASA Technical Reports Server (NTRS)

    Perovich, D.; Gerland, S.; Hendricks, S.; Meier, Walter N.; Nicolaus, M.; Richter-Menge, J.; Tschudi, M.

    2013-01-01

    During 2013, Arctic sea ice extent remained well below normal, but the September 2013 minimum extent was substantially higher than the record-breaking minimum in 2012. Nonetheless, the minimum was still much lower than normal and the long-term trend Arctic September extent is -13.7 per decade relative to the 1981-2010 average. The less extreme conditions this year compared to 2012 were due to cooler temperatures and wind patterns that favored retention of ice through the summer. Sea ice thickness and volume remained near record-low levels, though indications are of slightly thicker ice compared to the record low of 2012.

  19. Orientational disorder: A mechanism of amorphization at high pressure

    NASA Astrophysics Data System (ADS)

    Sakuntala, T.; Arora, A. K.; Shekar, N. V. Chandra; Sahu, P. Ch.

    1998-12-01

    Amorphization generally arises due to chemical disorder, high defect density or kinetic hindrances of equilibrium phase transitions. In this paper, we report that it can also be driven by orientational disorder of polyatomic ions or units. In potash alum, some of the sulphate ions are misoriented with their S-O bonds pointing towards potassium rather than towards aluminum, leading to an "orientational disorder" which ranges from 10 to 24%. Raman spectroscopic and X-ray diffraction studies reveal that samples with high initial orientational disorder exhibit a "reversible" amorphization at pressure around 60 kbar whereas those with low initial disorder exhibit an "irreversible" structural transition to a disorder-free crystalline phase.

  20. Variable-amplitude oscillatory shear response of amorphous materials

    NASA Astrophysics Data System (ADS)

    Perchikov, Nathan; Bouchbinder, Eran

    2014-06-01

    Variable-amplitude oscillatory shear tests are emerging as powerful tools to investigate and quantify the nonlinear rheology of amorphous solids, complex fluids, and biological materials. Quite a few recent experimental and atomistic simulation studies demonstrated that at low shear amplitudes, an amorphous solid settles into an amplitude- and initial-conditions-dependent dissipative limit cycle, in which back-and-forth localized particle rearrangements periodically bring the system to the same state. At sufficiently large shear amplitudes, the amorphous system loses memory of the initial conditions, exhibits chaotic particle motions accompanied by diffusive behavior, and settles into a stochastic steady state. The two regimes are separated by a transition amplitude, possibly characterized by some critical-like features. Here we argue that these observations support some of the physical assumptions embodied in the nonequilibrium thermodynamic, internal-variables based, shear-transformation-zone model of amorphous viscoplasticity; most notably that "flow defects" in amorphous solids are characterized by internal states between which they can make transitions, and that structural evolution is driven by dissipation associated with plastic deformation. We present a rather extensive theoretical analysis of the thermodynamic shear-transformation-zone model for a variable-amplitude oscillatory shear protocol, highlighting its success in accounting for various experimental and simulational observations, as well as its limitations. Our results offer a continuum-level theoretical framework for interpreting the variable-amplitude oscillatory shear response of amorphous solids and may promote additional developments.

  1. Hugoniot of water ice

    SciTech Connect

    Gaffney, E.S.

    1984-01-19

    Hugoniot data for water ice are available for pressures ranging from about 150 MPa to about 50 GPa from initial states near 260 K. Limited data on porous ice (snow) at the same initial temperatures are available from 3.5 to 38 GPa and initial densities of 600 and 350 Mg/m/sup 3/. Above about 5 GPa, the data are fairly well-fit by a linear relation between shock and particle velocity: D(km/s) = 1.79 + 1.42u. However, a quadratic form fits the data better: D(km/s) = 1.32 + 1.68u - 0.035u/sup 2/. At lower stresses the velocity is a very complicated function of particle velocity due to elastic propagation, yielding and several possible phase changes. The Hugoniot elastic limit (HEL) of ice at these temperatures is about 180 +- 20 MPa with the elastic waves travelling at about 3900 m/s. The mean stress at the HEL is 115 +- 14 MPa. Comparison with strength measurements at lower strain rate indicates that failure at the HEL probably involves fracture and is almost independent of both temperature and strain rate. Ice V has been reported at about 600 MPa, and ice VI at 1.9 GPa and possibly at 3.7 GPa. Transition to ice III probably commences at the HEL at 200 MPa. Relations between volume, enthalpy and internal energy indicate that states below about 1 GPa maintain their shear strength even after undergoing complete transition to a high pressure phase. Time-resolved stress measurements indicate that equilibrium is achieved in about three microseconds for a 695 MPa shock. Melting is definitely complete below 10 GPa.

  2. Amorphous silicon radiation detectors

    DOEpatents

    Street, R.A.; Perez-Mendez, V.; Kaplan, S.N.

    1992-11-17

    Hydrogenated amorphous silicon radiation detector devices having enhanced signal are disclosed. Specifically provided are transversely oriented electrode layers and layered detector configurations of amorphous silicon, the structure of which allow high electric fields upon application of a bias thereby beneficially resulting in a reduction in noise from contact injection and an increase in signal including avalanche multiplication and gain of the signal produced by incoming high energy radiation. These enhanced radiation sensitive devices can be used as measuring and detection means for visible light, low energy photons and high energy ionizing particles such as electrons, x-rays, alpha particles, beta particles and gamma radiation. Particular utility of the device is disclosed for precision powder crystallography and biological identification. 13 figs.

  3. Amorphous silicon radiation detectors

    DOEpatents

    Street, Robert A.; Perez-Mendez, Victor; Kaplan, Selig N.

    1992-01-01

    Hydrogenated amorphous silicon radiation detector devices having enhanced signal are disclosed. Specifically provided are transversely oriented electrode layers and layered detector configurations of amorphous silicon, the structure of which allow high electric fields upon application of a bias thereby beneficially resulting in a reduction in noise from contact injection and an increase in signal including avalanche multiplication and gain of the signal produced by incoming high energy radiation. These enhanced radiation sensitive devices can be used as measuring and detection means for visible light, low energy photons and high energy ionizing particles such as electrons, x-rays, alpha particles, beta particles and gamma radiation. Particular utility of the device is disclosed for precision powder crystallography and biological identification.

  4. THE PHASES OF WATER ICE IN THE SOLAR NEBULA

    SciTech Connect

    Ciesla, Fred J.

    2014-03-20

    Understanding the phases of water ice that were present in the solar nebula has implications for understanding cometary and planetary compositions as well as the internal evolution of these bodies. Here we show that amorphous ice formed more readily than previously recognized, with formation at temperatures <70 K being possible under protoplanetary disk conditions. We further argue that photodesorption and freeze-out of water molecules near the surface layers of the solar nebula would have provided the conditions needed for amorphous ice to form. This processing would be a natural consequence of ice dynamics and would allow for the trapping of noble gases and other volatiles in water ice in the outer solar nebula.

  5. East Antarctic Ice Sheet fluctuations during the Middle Miocene Climatic Transition inferred from faunal and biogeochemical data on planktonic foraminifera (ODP Hole 747A, Kerguelen Plateau)

    USGS Publications Warehouse

    Verducci, M.; Foresi, L.M.; Scott, G.H.; ,; Sprovieri, M.; Lirer, F.

    2007-01-01

    This research focuses on a detailed study of faunal and biogeochemical changes that occurred at ODP Hole 747A in the Kerguelen Plateau region of the Southern Ocean during the middle Miocene (14.8-11.8 Ma). Abundance fluctuations of several planktonic foraminiferal taxa, stable oxygen isotope and Mg/Ca ratios have been integrated as a multi-proxy approach to reach a better understanding of the growth modality and fluctuations of the East Antarctic Ice Sheet (EAIS) during this period. A 7°C decrease in Sea Surface Temperature (SST), an abrupt turnover in the planktonic foraminiferal assemblage, a 1.5‰ shift towards heavier δ18O values (Mi3 event) and a related shift towards heavier seawater δ118O values between 13.9 and 13.7 Ma, are interpreted to reflect rapid surface water cooling and EAIS expansion. Hole 747A data suggest a major change in the variability of the climate system fostered by EAIS expansion between 13.9 and 13.7 Ma. Ice sheet fluctuations were greater during the interval 14.8-13.9 Ma compared with those from 13.7 to 11.8 Ma, whereas the latter interval was characterized by a more stable EAIS. In our opinion, the middle Miocene ice sheet expansion in Antarctica represents a first step towards the development of the modern permanent ice sheet

  6. Observation of viscosity transition in α-pinene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Järvinen, Emma; Ignatius, Karoliina; Nichman, Leonid; Kristensen, Thomas B.; Fuchs, Claudia; Hoyle, Christopher R.; Höppel, Niko; Corbin, Joel C.; Craven, Jill; Duplissy, Jonathan; Ehrhart, Sebastian; El Haddad, Imad; Frege, Carla; Gordon, Hamish; Jokinen, Tuija; Kallinger, Peter; Kirkby, Jasper; Kiselev, Alexei; Naumann, Karl-Heinz; Petäjä, Tuukka; Pinterich, Tamara; Prevot, Andre S. H.; Saathoff, Harald; Schiebel, Thea; Sengupta, Kamalika; Simon, Mario; Slowik, Jay G.; Tröstl, Jasmin; Virtanen, Annele; Vochezer, Paul; Vogt, Steffen; Wagner, Andrea C.; Wagner, Robert; Williamson, Christina; Winkler, Paul M.; Yan, Chao; Baltensperger, Urs; Donahue, Neil M.; Flagan, Rick C.; Gallagher, Martin; Hansel, Armin; Kulmala, Markku; Stratmann, Frank; Worsnop, Douglas R.; Möhler, Ottmar; Leisner, Thomas; Schnaiter, Martin

    2016-04-01

    Under certain conditions, secondary organic aerosol (SOA) particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH) range for SOA to exist in these states. In the Cosmics Leaving Outdoor Droplets (CLOUD) experiment at The European Organisation for Nuclear Research (CERN), we deployed a new in situ optical method to detect the viscous state of α-pinene SOA particles and measured their transition from the amorphous highly viscous state to states of lower viscosity. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical particles at relative humidities near the deliquescence point. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to a spherical shape was observed as the RH was increased to between 35 % at -10 °C and 80 % at -38 °C, confirming previous calculations of the viscosity-transition conditions. Consequently, α-pinene SOA particles exist in a viscous state over a wide range of ambient conditions, including the cirrus region of the free troposphere. This has implications for the physical, chemical, and ice-nucleation properties of SOA and SOA-coated particles in the atmosphere.

  7. Effect of counterions on the properties of amorphous atorvastatin salts.

    PubMed

    Sonje, Vishal M; Kumar, Lokesh; Puri, Vibha; Kohli, Gunjan; Kaushal, Aditya M; Bansal, Arvind K

    2011-11-20

    Amorphous systems have gained importance as a tool for addressing delivery challenges of poorly water soluble drugs. A careful assessment of thermodynamic and kinetic behavior of amorphous form is necessary for successful use of amorphous form in drug delivery. The present study was undertaken to evaluate effect of monovalent sodium (Na(+); ATV Na), and bivalent calcium (Ca(2+); ATV Ca) and magnesium (Mg(2+); ATV Mg) counterions on properties of amorphous salts of atorvastatin (ATV) model drug. Amorphous form was generated from crystalline salts of ATV by spray drying, and characterized for glass transition temperature (T(g)), fragility and devitrification tendency. In addition, chemical stability of the amorphous salt forms was evaluated. Fragility was studied by calculating activation enthalpy for structural relaxation at T(g), from heating rate dependency of T(g). Density functional theory and relative pK(a)'s of counterions were evaluated to substantiate trend in glass transition temperature. T(g) of salts followed order: ATV Ca>ATV Mg>ATV Na. All salts were fragile to moderately fragile, with D value ranging between 9 and 16. Ease of devitrification followed the order: ATV Na∼ATV Mg≫ATV Ca, using isothermal crystallization and reduced crystallization temperature method. Chemical stability at 80°C showed higher degradation of amorphous ATV Ca (∼5%), while ATV Na and ATV Mg showed degradation of 1-2%. Overall, ATV Ca was better in terms of glass forming ability, higher T(g) and physical stability. The study has importance in selection of a suitable amorphous form, during early drug development phase. PMID:21907794

  8. The determination of ice composition with instruments on cometary landers.

    PubMed

    Boynton, W V; D'Uston, L C; Young, D T; Lunine, J I; Waite, J H; Bailey, S H; Berthelier, J J; Bertaux, J L; Borrel, V; Burke, M F; Cohen, B A; McComas, D H; Nordholt, J E; Evans, L G; Trombka, J I

    1997-05-01

    The determination of the composition of materials that make up comets is essential in trying to understand the origin of these primitive objects. The ices especially could be made in several different astrophysical settings including the solar nebula, protosatellite nebulae of the giant planets, and giant molecular clouds that predate the formation of the solar system. Each of these environments makes different ices with different composition. In order to understand the origin of comets, one needs to determine the composition of each of the ice phases. For example, it is of interest to know that comets contain carbon monoxide, CO, but it is much more important to know how much of it is a pure solid phase, is trapped in clathrate hydrates, or is adsorbed on amorphous water ice. In addition, knowledge of the isotopic composition of the constituents will help determine the process that formed the compounds. Finally, it is important to understand the bulk elemental composition of the nucleus. When these data are compared with solar abundances, they put strong constraints on the macro-scale processes that formed the comet. A differential scanning calorimeter (DSC) and an evolved gas analyzer (EGA) will make the necessary association between molecular constituents and their host phases. This combination of instruments takes a small (tens of mg) sample of the comet and slowly heats it in a sealed oven. As the temperature is raised, the DSC precisely measures the heat required, and delivers the gases to the EGA. Changes in the heat required to raise the temperature at a controlled rate are used to identify phase transitions, e.g., crystallization of amorphous ice or melting of hexagonal ice, and the EGA correlates the gases released with the phase transition. The EGA consists of two mass spectrometers run in tandem. The first mass spectrometer is a magnetic-sector ion-momentum analyzer (MAG), and the second is an electrostatic time-of-flight analyzer (TOF). The TOF acts as

  9. The determination of ice composition with instruments on cometary landers.

    PubMed

    Boynton, W V; D'Uston, L C; Young, D T; Lunine, J I; Waite, J H; Bailey, S H; Berthelier, J J; Bertaux, J L; Borrel, V; Burke, M F; Cohen, B A; McComas, D H; Nordholt, J E; Evans, L G; Trombka, J I

    1997-05-01

    The determination of the composition of materials that make up comets is essential in trying to understand the origin of these primitive objects. The ices especially could be made in several different astrophysical settings including the solar nebula, protosatellite nebulae of the giant planets, and giant molecular clouds that predate the formation of the solar system. Each of these environments makes different ices with different composition. In order to understand the origin of comets, one needs to determine the composition of each of the ice phases. For example, it is of interest to know that comets contain carbon monoxide, CO, but it is much more important to know how much of it is a pure solid phase, is trapped in clathrate hydrates, or is adsorbed on amorphous water ice. In addition, knowledge of the isotopic composition of the constituents will help determine the process that formed the compounds. Finally, it is important to understand the bulk elemental composition of the nucleus. When these data are compared with solar abundances, they put strong constraints on the macro-scale processes that formed the comet. A differential scanning calorimeter (DSC) and an evolved gas analyzer (EGA) will make the necessary association between molecular constituents and their host phases. This combination of instruments takes a small (tens of mg) sample of the comet and slowly heats it in a sealed oven. As the temperature is raised, the DSC precisely measures the heat required, and delivers the gases to the EGA. Changes in the heat required to raise the temperature at a controlled rate are used to identify phase transitions, e.g., crystallization of amorphous ice or melting of hexagonal ice, and the EGA correlates the gases released with the phase transition. The EGA consists of two mass spectrometers run in tandem. The first mass spectrometer is a magnetic-sector ion-momentum analyzer (MAG), and the second is an electrostatic time-of-flight analyzer (TOF). The TOF acts as

  10. DETECTIONS OF TRANS-NEPTUNIAN ICE IN PROTOPLANETARY DISKS

    SciTech Connect

    McClure, M. K.; Calvet, N.; Bergin, E.; Cleeves, L. I.; Espaillat, C.; D'Alessio, P.; Watson, D. M.; Manoj, P.; Sargent, B. E-mail: ncalvet@umich.edu E-mail: cleeves@umich.edu E-mail: p.dalessio@crya.unam.mx E-mail: manoj.puravankara@tifr.res.in

    2015-02-01

    We present Herschel Space Observatory PACS spectra of T Tauri stars, in which we detect amorphous and crystalline water ice features. Using irradiated accretion disk models, we determine the disk structure and ice abundance in each of the systems. Combining a model-independent comparison of the ice feature strength and disk size with a detailed analysis of the model ice location, we estimate that the ice emitting region is at disk radii >30 AU, consistent with a proto-Kuiper belt. Vertically, the ice emits most below the photodesorption zone, consistent with Herschel observations of cold water vapor. The presence of crystallized water ice at a disk location (1) colder than its crystallization temperature and (2) where it should have been re-amorphized in ∼1 Myr suggests that localized generation is occurring; the most likely cause appears to be micrometeorite impact or planetesimal collisions. Based on simple tests with UV models and different ice distributions, we suggest that the SED shape from 20 to 50 μm may probe the location of the water ice snowline in the disk upper layers. This project represents one of the first extra-solar probes of the spatial structure of the cometary ice reservoir thought to deliver water to terrestrial planets.

  11. Ice Thickness in the Northwest Passage

    NASA Astrophysics Data System (ADS)

    Haas, C.; Howell, S.

    2015-12-01

    Recently the feasibility of commercial shipping in the ice-prone Northwest Passage has attracted a lot of attention. However, very little ice thickness information actually exists. We present results of the first-ever airborne electromagnetic ice thickness surveys over the NWP carried out in April and May 2011 and 2015 over first-year and multiyear ice. Results show modal thicknesses between 1.8 and 2.0 m in all regions. Mean thicknesses over 3 m and thick, deformed ice were observed over some multiyear ice regimes shown to originate from the Arctic Ocean. Thick ice features more than 100 m wide and thicker than 4 m occurred frequently. There are few other data to compare with to evaluate if the ice of the Northwest Passage has transitioned as other parts of the Arctic have. Although likely thinner than some 20 or more years ago, ice conditions must still be considered severe, and the Canadian Arctic Archipelao may well be considered the last ice refuge of the Arctic. These results have important implications for the prediction of ice break-up and summer ice conditions, and the assessment of sea ice hazards during the summer shipping season.

  12. 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.

  13. 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. PMID:25810206

  14. Water freezing and ice melting

    SciTech Connect

    Malolepsza, Edyta; Keyes, Tom

    2015-10-12

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubic ice↔liquid, with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.

  15. Water freezing and ice melting

    DOE PAGES

    Malolepsza, Edyta; Keyes, Tom

    2015-10-12

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubic ice↔liquid,more » with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.« less

  16. Temperature, shape, and phase of mesospheric ice from Solar Occultation for Ice Experiment observations

    NASA Astrophysics Data System (ADS)

    Hervig, Mark E.; Gordley, Larry L.

    2010-08-01

    The temperature and shape of ice particles in polar mesospheric clouds (PMCs) were determined using observations near 3 μm wavelength from the Solar Occultation for Ice Experiment (SOFIE). The resulting ice temperatures are 5-20 K colder than the current SOFIE temperatures retrieved from CO2 transmission measurements. Particle shape is described using oblate spheroids, and the axial ratios determined in this study are slightly more spherical than previous results obtained using SOFIE observations assuming constant temperature (1.9 at the altitude of peak mass density compared to 2.3 previously). Using ice temperatures in an equilibrium PMC model results in ice mass densities that are much higher than observed. SOFIE observations indicate that the amount of H2O that can enter the ice phase is related to ice concentration, suggesting that ice nucleation plays an important role in determining PMC formation and variability. This result may also imply that the neglect of transient phenomena in the equilibrium PMC model may be a large source of error. SOFIE observations do not support the existence of amorphous ice particles near the summer mesopause but rather indicate that cubic ice is ubiquitous.

  17. Multidisciplinary study of sediments deposited in the Ross Sea (Antarctica) during the last 50 ka: information on changes of ice extent during the glacial-interglacial transition

    NASA Astrophysics Data System (ADS)

    Del Carlo, Paola; Baneschi, Ilaria; Bertagnini, Antonella; Boschi, Chiara; Cascella, Antonio; Colizza, Ester; Di Roberto, Alessio; Di Vincenzo, Gianfranco; Finocchiaro, Furio; Landi, Patrizia; Lirer, Fabrizio; Pompilio, Massimo; Sagnotti, Leonardo; Sangiorgi, Francesca; Sprovieri, Mario; Wrinkler, Aldo

    2013-04-01

    In the Ross Sea (Antarctica), sedimentation is controlled by the dynamics of the ice shelves, fluctuations of the ice sheets extensions (Eastern and Western) and volcanic activity from several volcanic complex of the Victoria Land. Marine sediments consisting of alternated glacigenic, biogenic and volcanic deposits can be interpreted in terms of changes in paleoclimate and paleoenvironment conditions. In this project we present a multidisciplinary study (comprising tephrostratigraphy, petrology, paleomagnetism, rock magnetism, TIC/TOC geochemistry, Ar/Ar dating, palinology and integrated biostratigraphy of forams and calcareous nannoplankton) of the sediments recovered in selected cores from Ross Sea during 1999 and 2000 cruises and stored in the Italian archive at Museo Nazionale dell'Antartide (Trieste). Results provide new data on local and/or global changes of paleoclimate and paleoenvironmental conditions over the past 50 Ka. Furthermore, the study of the recovered volcanic deposits adds new information about the poorly known, recent volcanic activity in the Victoria Land area.

  18. Study of thermal conductivity of ice clusters after impact deposition on the silica surfaces using the ReaxFF reactive force field.

    PubMed

    Rahnamoun, A; van Duin, A C T

    2016-01-21

    During aircraft or spacecraft missions, ice accumulates on different parts of their surface elements. An important parameter affecting the ability to remove this ice from the surface is the heat transfer characteristics of the accumulated ice. The ice heat transfer is related to the process of ice formation and its density and internal structure. In this study we investigate the effects of the ice and silica structure and the ice cluster attachment mechanism to the silica surface on the thermal conductivity (TC) of the attached ice cluster using the ReaxFF reactive force field. The purpose of this study is to investigate the thermal transport in amorphous and crystalline ice after high-velocity deposition on the silica surfaces. A dual thermostat method has been applied for the calculation of TC values. The validity of this method has been verified by comparing the calculated values of TC for crystal and amorphous ice with available experimental values. Our calculations show that the TC values of both crystal and amorphous ice drop after deposition on the silica surfaces. This decrease in the TC is more significant for the ice deposition on suboxide silica surfaces. Furthermore, crystal ice shows higher TC values than amorphous ice after accumulation. However, when crystal ice impacts on the silica surface at 1 km s(-1) impact speed, the crystalline shape of the ice cluster is lost to a considerable level and the TC values obtained for the ice clusters in such cases are closer to amorphous ice TC values. We observed a decrease in the TC values when ionic species are added inside the ice clusters.

  19. Neutron diffraction study of the interaction of iron with amorphous fullerite

    NASA Astrophysics Data System (ADS)

    Borisova, P. A.; Agafonov, S. S.; Blanter, M. S.; Somenkov, V. A.

    2014-01-01

    The amorphous fullerite C60 has been prepared by mechanical activation (grinding in a ball mill), and its interaction with iron during sintering of powders with 0-95 at % Fe has been studied. After sintering in the range 800-1200°C under a pressure of 70 MPa, the samples have nonequilibrium structures different from the structures of both annealed and quenched steels. In this case, the carbon phase, i.e., amorphous fullerite, undergoes a polyamorphous transition to amorphous graphite. It has also been shown that the interaction of amorphous fullerite with iron is weaker compared to crystalline fullerite or crystalline graphite.

  20. Growth induced magnetic anisotropy in crystalline and amorphous thin films

    SciTech Connect

    Hellman, F.

    1998-07-20

    The work in the past 6 months has involved three areas of magnetic thin films: (1) amorphous rare earth-transition metal alloys, (2) epitaxial Co-Pt and Ni-Pt alloy thin films, and (3) collaborative work on heat capacity measurements of magnetic thin films, including nanoparticles and CMR materials. A brief summary of work done in each area is given.

  1. Environment at the Grounding Zone of the Whillans Ice Stream-Ross Ice Shelf, West Antarctica

    NASA Astrophysics Data System (ADS)

    Hodson, T. O.; Powell, R. D.; Mikucki, J.; Scherer, R. P.; Tulaczyk, S. M.; Coenen, J. J.; Puttkammer, R.; Branecky, C.

    2015-12-01

    Grounding zones where grounded ice sheets transition to floating ice shelves, are the primary gateways through which the Antarctic Ice Sheet loses mass to the ocean. In these environments, ice, ocean, meltwater and sediment meet and interact, influencing both the ice sheet and ocean circulation beneath the ice shelf. Here, we report on conditions near the grounding zone of the Whillans Ice Stream, which feeds into the Ross Ice Shelf. Cameras and instruments lowered through an access borehole to the ocean cavity beneath the ice shelf found a 10m-thick water column comprising an upper layer of colder ice shelf water formed from mixing between meltwater with the lower layer of warmer higher salinity shelf water. This style of stratification is typical of large ice shelves, but it was uncertain whether it existed so near the grounding zone, where stronger tidal currents and/or strong subglacial stream discharges could mix the water column. Salinity and temperature of the water suggest it formed from sea ice production in the Western Ross Sea, with minimal modification beneath the ice shelf. This source region is distinct from waters previously observed at the nearby J-9 borehole, illustrating the importance of the sub-ice shelf bathymetry in steering circulation between the ocean and the grounding zone. Preliminary data suggest an active exchange of heat and nutrients between the grounding zone and the open ocean, despite being separated by 600km. Thus life found near the grounding line is probably not an isolated oasis, but may instead be part of a much broader ecosystem that spans the ice shelf. Although sea ice formation presently maintains water in the sub-ice shelf cavity near the surface freezing point, buffering many larger ice shelves from gradual ocean warming, these findings suggest that even grounding zones of extensive ice shelves may respond quickly to abrupt changes in ocean circulation, such as that observed in the Amundsen Sea.

  2. Stabilization of amorphous structure in silicon thin film by adding germanium

    SciTech Connect

    Makino, Nobuaki; Shigeta, Yukichi

    2015-06-21

    The stabilization of the amorphous structure in amorphous silicon film by adding Ge atoms was studied using Raman spectroscopy. Amorphous Si{sub 1−x}Ge{sub x} (x = 0.0, 0.03, 0.14, and 0.27) films were deposited on glass substrates from electron beam evaporation sources and annealed in N{sub 2} atmosphere. The change in the amorphous states and the phase transition from amorphous to crystalline were characterized using the TO, LO, and LA phonons in the Raman spectra. The temperature of the transition from the amorphous phase to the crystalline phase was higher for the a-Si{sub 1−x}Ge{sub x} (x = 0.03, 0.14) films, and the crystallization was hindered. The reason why the addition of a suitable quantity of Ge atoms into the three-dimensional amorphous silicon network stabilizes its amorphous structure is discussed based on the changes in the Raman signals of the TO, LO, and LA phonons during annealing. The characteristic bond length of the Ge atoms allows them to stabilize the random network of the amorphous Si composed of quasi-tetrahedral Si units, and obstruct its rearrangement.

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

    SciTech Connect

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

    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 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 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.

  4. 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.

  5. Pharmaceutical micro-particles give amorphous sucrose higher physical stability.

    PubMed

    Hellrup, Joel; Mahlin, Denny

    2011-05-16

    The aim of this study was to explore how pharmaceutical micro-sized filler particles affect the amorphous stability of sucrose in sucrose/filler particle composites produced by freeze-drying. Focus was put on the filler particles' properties crystallinity, hygroscopicity, hydrophobicity, and surface area, and their influence on physical stability of the amorphous phase. The micro-sized filler particles were examined with Blaine permeametry, gas adsorption, pycnometry, gravimetric vapour sorption, X-ray diffraction, and light microscopy before composites of sucrose and micro-sized filler particles were prepared by freeze-drying. The stability of the composites was examined with X-ray diffraction, differential scanning calorimetry (DSC), and microcalorimetry. All composites were amorphous and showed higher stability compared to pure amorphous sucrose, which was evident from a delay in heat and moisture-induced crystallization. However, calcium carbonate and oxazepam micro-sized filler particles lost their ability to stabilize the amorphous sucrose when exposed to humidity. The dry glass transition temperature (T(g)) was higher for the composites, indicating the stabilization was mediated by a reduced molecular mobility of the amorphous phase. PMID:21356288

  6. Effect of different "states" of sorbed water on amorphous celecoxib.

    PubMed

    Shete, Ganesh; Kuncham, Swathi; Puri, Vibha; Gangwal, Rahul P; Sangamwar, Abhay T; Bansal, Arvind Kumar

    2014-07-01

    Glass transition temperature (Tg) of an amorphous drug is a vital physical phenomenon that influences its visco-elastic properties, physical, and chemical stability. Water acts as a plasticizer for amorphous drugs thus increasing their recrystallization kinetics. This reduces the solubility advantage of an amorphous drug. Hence, there is an interest in understanding the relationship between water content and Tg of amorphous drug. We have studied the effect of "state" of sorbed water on Tg of amorphous celecoxib (ACLB). ACLB was allowed to sorb water at relative humidity of 33%, 53%, 75%, and 93%. ALCB showed biphasic sorption of water designated as "bound" and "solvent-like" state of water associated with ACLB. Molecular modeling studies provided deeper insights into the interaction of water with ACLB. A distinct co-relationship between the state of water and its plasticization capacity was observed. Bound state of water had a very profound effect on the fall in experimentally observed Tg (T(g-exp)) value. Solvent-like state of water had little impact on T(g-exp) value. Tg of ACLB-water mixture was predicted by Gordon-Taylor equation (T(g-pre)). The deviations in T(g-exp) and Tg-pre were correlated to volume non-additivity and non-ideal mixing. This study has implications on the development of formulations based on amorphous forms. PMID:24801826

  7. Reversible Avalanches and Criticality in Amorphous Solids

    NASA Astrophysics Data System (ADS)

    Reichhardt, Charles

    2015-03-01

    Despite its importance for basic science and industry, the physical process that causes a solid to change its shape permanently under external deformation is still not well understood. In this paper we use molecular dynamics simulations of amorphous solids under oscillatory shear to study this phenomenon, and show that at a critical strain amplitude, the size of the cooperative atomic motion that allows for a permanent deformation diverges. We compare this non-equilibrium critical behavior to that of a ``front depinning'' transition. This viewpoint, based on fluctuations and statistics, is complementary to the dynamical ``transition to chaos'' which was previously identified at the same strain amplitude. Below this irreversibile-depinning transition, we observe large avalanches which are completely repetitive with each shear strain cycle. This suggests that while avalanches on their own do not cause irreversible deformation, it is likely that the irreversibility transition and the ``depinning-like'' transition are two aspects of the same phenomena. One implication is that the transition could be detected before the onset of irreversible flow by an analysis of the power spectra of avalanches. Work done in collaboration with Ido Regev, Karin Dahmen, John Weber, and Turab Lookman.

  8. Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

    NASA Astrophysics Data System (ADS)

    Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

    2016-04-01

    Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

  9. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, Robert A.; Mendez, Victor P.; Kaplan, Selig N.

    1988-01-01

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation.

  10. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, R.A.; Mendez, V.P.; Kaplan, S.N.

    1988-11-15

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation. 15 figs.

  11. Relating C-band Microwave and Optical Satellite Observations as A Function of Snow Thickness on First-Year Sea Ice during the Winter to Summer Transition

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Yackel, J.

    2015-12-01

    The Arctic sea ice and its snow cover have a direct impact on both the Arctic and global climate system through their ability to moderate heat exchange across the ocean-sea ice-atmosphere (OSA) interface. Snow cover plays a key role in the OSA interface radiation and energy exchange, as it controls the growth and decay of first-year sea ice (FYI). However, meteoric accumulation and redistribution of snow on FYI is highly stochastic over space and time, which makes it poorly understood. Previous studies have estimated local-scale snow thickness distributions using in-situ technique and modelling but it is spatially limited and challenging due to logistic difficulties. Moreover, snow albedo is also critical for determining the surface energy balance of the OSA during the critical summer ablation season. Even then, due to persistent and widespread cloud cover in the Arctic at various spatio-temporal scales, it is difficult and unreliable to remotely measure albedo of snow cover on FYI in the optical spectrum. Previous studies demonstrate that only large-scale sea ice albedo was successfully estimated using optical-satellite sensors. However, space-borne microwave sensors, with their capability of all-weather and 24-hour imaging, can provide enhanced information about snow cover on FYI. Daily spaceborne C-band scatterometer data (ASCAT) and MODIS data are used to investigate the the seasonal co-evolution of the microwave backscatter coefficient and optical albedo as a function of snow thickness on smooth FYI. The research focuses on snow-covered FYI near Cambridge Bay, Nunavut (Fig.1) during the winter to advanced-melt period (April-June, 2014). The ACSAT time series (Fig.2) show distinct increase in scattering at melt onset indicating the first occurrence of melt water in the snow cover. The corresponding albedo exhibits no decrease at this stage. We show how the standard deviation of ASCAT backscatter on FYI during winter can be used as a proxy for surface roughness

  12. Ancient ice streams and their megalineated beds

    NASA Astrophysics Data System (ADS)

    Eyles, Nick; Ross, Martin

    2016-06-01

    Ice streams are corridors of fast-flowing (~ 800 m yr- 1) ice inset within otherwise sluggish-moving ice sheets. According to reported estimates, as much as 90% of the total discharge of the Antarctic Ice Sheet, for example, occurs through such corridors. Recognition of ice stream records in paleo-ice sheet research has profoundly changed the discipline of glacial geology. The key has been identification of the distinctive corrugated or 'megalineated' geomorphology of their beds, consisting of elongate ridges that are parallel to ice flow direction and often transitional to drumlins. Access to new satellite imagery has enabled mapping of megascale glacial lineations (MSGLs) over large swaths of terrain and the recognition of regional-scale ice stream flow paths and origins. At the peak of the last ice age, just after 20,000 years ago, there were more than 100 ice streams within the Laurentide Ice Sheet. Only now are we beginning to fully appreciate the fundamental role that such streams (which have been called the 'arteries' of ice sheets) have had on glaciated landscapes, by moving enormous volumes of sediment and releasing armadas of floating ice to the Arctic and Atlantic oceans. There is also a growing awareness of the erosional role of ice streams in overdeepening of lakes, fiords and other troughs along coastlines. Much remains to be learnt and new discoveries surely await. The picture of past ice sheets, like the Laurentide and Fennoscandian Ice Sheets, that is emerging today is very different from that of 20 years ago.

  13. Structure and Properties of Amorphous Transparent Conducting Oxides

    NASA Astrophysics Data System (ADS)

    Medvedeva, Julia

    Driven by technological appeal, the research area of amorphous oxide semiconductors has grown tremendously since the first demonstration of the unique properties of amorphous indium oxide more than a decade ago. Today, amorphous oxides, such as a-ITO, a-IZO, a-IGZO, or a-ZITO, exhibit the optical, electrical, thermal, and mechanical properties that are comparable or even superior to those possessed by their crystalline counterparts, pushing the latter out of the market. Large-area uniformity, low-cost low-temperature deposition, high carrier mobility, optical transparency, and mechanical flexibility make these materials appealing for next-generation thin-film electronics. Yet, the structural variations associated with crystalline-to-amorphous transition as well as their role in carrier generation and transport properties of these oxides are far from being understood. Although amorphous oxides lack grain boundaries, factors like (i) size and distribution of nanocrystalline inclusions; (ii) spatial distribution and clustering of incorporated cations in multicomponent oxides; (iii) formation of trap defects; and (iv) piezoelectric effects associated with internal strains, will contribute to electron scattering. In this work, ab-initio molecular dynamics (MD) and accurate density-functional approaches are employed to understand how the properties of amorphous ternary and quaternary oxides depend on quench rates, cation compositions, and oxygen stoichiometries. The MD results, combined with thorough experimental characterization, reveal that interplay between the local and long-range structural preferences of the constituent oxides gives rise to a complex composition-dependent structural behavior in the amorphous oxides. The proposed network models of metal-oxygen polyhedra help explain the observed intriguing electrical and optical properties in In-based oxides and suggest ways to broaden the phase space of amorphous oxide semiconductors with tunable properties. The

  14. 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. PMID:19827849

  15. 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.

  16. Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds.

    PubMed

    Klotz, S; Komatsu, K; Pietrucci, F; Kagi, H; Ludl, A-A; Machida, S; Hattori, T; Sano-Furukawa, A; Bove, L E

    2016-01-01

    It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random. PMID:27562476

  17. Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds

    PubMed Central

    Klotz, S.; Komatsu, K.; Pietrucci, F.; Kagi, H.; Ludl, A.-A.; Machida, S.; Hattori, T.; Sano-Furukawa, A.; Bove, L. E.

    2016-01-01

    It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random. PMID:27562476

  18. Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds

    NASA Astrophysics Data System (ADS)

    Klotz, S.; Komatsu, K.; Pietrucci, F.; Kagi, H.; Ludl, A.-A.; Machida, S.; Hattori, T.; Sano-Furukawa, A.; Bove, L. E.

    2016-08-01

    It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl•RH2O and LiBr•RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random.

  19. New Fluid Prevents Railway Ice

    NASA Technical Reports Server (NTRS)

    2001-01-01

    Through a licensing agreement between NASA's Ames Research Center and Midwest Industrial Supply, Inc. (MIS), two MIS products have been enhanced with NASA's anti-icing fluid technology. MIS offers the new fluid in two commercial products, the Zero Gravity(TM) Third Rail Anti-Icer/Deicer and the Ice Free Switch(R). Using NASA's fluid technology, these products form a protective-coating barrier that prevents the buildup of ice and snow. Applying the fluid to the railway components prior to ice or snowstorm works as an anti-icing fluid, remaining in place to melt precipitation as it hits the surface. It also functions as a deicing fluid. If applied to an already frozen switch or rail, it will quickly melt the ice, free the frozen parts, and then remain in place to prevent refreezing. Additional benefits include the ability to cling to vertical rail surfaces and resist the effects of rain and wind. With the Ice Free Switch, it takes only five minutes to treat the switch by spraying, brushing, or pouring on the product. Ice Free Switch requires as little as one gallon per switch whereas other deicing fluids require five to ten gallons of liquid to effectively melt ice. Zero Gravity serves the same anti-icing/deicing purposes but applies fluid to the third rail through a system that is easily installed onto mass transit cars. A tank of fluid and a dispensing system are placed underneath the train car and the fluid is applied as the train runs its route.

  20. Investigation of the Rigid Amorphous Fraction in Nylon-6

    SciTech Connect

    Chen,H.; Cebe, P.

    2007-01-01

    A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (X{sub c}, X{sub MA}, X{sub rA}, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110 C, then briefly heated to 136 C, then re-annealed at 110 C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow the devitrification of the rigid amorphous fraction to be examined. We observe a lower endotherm, termed the 'annealing' peak in the non-reversing heat flow after annealing at 110 C. By brief heating above this lower endotherm and immediately quenching in LN{sub 2}-cooled glass beads, the glass transition temperature and X{sub RA} decrease substantially, X{sub MA} increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110 C causes the glass transition and X{sub RA} to increase, and X{sub MA} to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid amorphous fraction. Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show the homogeneous stack model is the correct one for Nylon-6. The cooperativity length ({var_epsilon}{sub A}) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of some of the RAF leads to the broadening of the glass transition region and shift of T{sub g}.

  1. Analysis and Application of the Amorphous Properties in Freeze-Dried Foods

    NASA Astrophysics Data System (ADS)

    Kawai, Kiyoshi

    The dynamic properties of amorphous materials drastically change by the phase transition between glassy state and rubber state. Furthermore, the dynamic properties of amorphous materials in glassy state are affected by the thermal history such as processing and/or storage conditions. In this paper, effect of the glass transition of freeze-dried food systems on the storage stability was summarized. Moreover, analytical approaches of the amorphous properties for glassy products with enthalpy relaxation measurements by using differential scanning calorimetry were presented and its application to food industry was proposed.

  2. Evidence for middle Eocene Arctic sea ice from diatoms and ice-rafted debris.

    PubMed

    Stickley, Catherine E; St John, Kristen; Koç, Nalân; Jordan, Richard W; Passchier, Sandra; Pearce, Richard B; Kearns, Lance E

    2009-07-16

    Oceanic sediments from long cores drilled on the Lomonosov ridge, in the central Arctic, contain ice-rafted debris (IRD) back to the middle Eocene epoch, prompting recent suggestions that ice appeared in the Arctic about 46 million years (Myr) ago. However, because IRD can be transported by icebergs (derived from land-based ice) and also by sea ice, IRD records are restricted to providing a history of general ice-rafting only. It is critical to differentiate sea ice from glacial (land-based) ice as climate feedback mechanisms vary and global impacts differ between these systems: sea ice directly affects ocean-atmosphere exchanges, whereas land-based ice affects sea level and consequently ocean acidity. An earlier report assumed that sea ice was prevalent in the middle Eocene Arctic on the basis of IRD, and although somewhat preliminary supportive evidence exists, these data are neither comprehensive nor quantified. Here we show the presence of middle Eocene Arctic sea ice from an extraordinary abundance of a group of sea-ice-dependent fossil diatoms (Synedropsis spp.). Analysis of quartz grain textural characteristics further supports sea ice as the dominant transporter of IRD at this time. Together with new information on cosmopolitan diatoms and existing IRD records, our data strongly suggest a two-phase establishment of sea ice: initial episodic formation in marginal shelf areas approximately 47.5 Myr ago, followed approximately 0.5 Myr later by the onset of seasonally paced sea-ice formation in offshore areas of the central Arctic. Our data establish a 2-Myr record of sea ice, documenting the transition from a warm, ice-free environment to one dominated by winter sea ice at the start of the middle Eocene climatic cooling phase.

  3. Bulk amorphous materials

    SciTech Connect

    Schwarz, R.B.; Archuleta, J.I.; Sickafus, K.E.

    1998-12-01

    This is the final report for a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of this work was to develop the competency for the synthesis of novel bulk amorphous alloys. The authors researched their synthesis methods and alloy properties, including thermal stability, mechanical, and transport properties. The project also addressed the development of vanadium-spinel alloys for structural applications in hostile environments, the measurement of elastic constants and thermal expansion in single-crystal TiAl from 300 to 750 K, the measurement of elastic constants in gallium nitride, and a study of the shock-induced martensitic transformations in NiTi alloys.

  4. Structural transition and amorphization in compressed α - Sb 2 O 3

    SciTech Connect

    Zhao, Zhao; Zeng, Qiaoshi; Zhang, Haijun; Wang, Shibing; Hirai, Shigeto; Zeng, Zhidan; Mao, Wendy L.

    2015-05-27

    Sb₂O₃-based materials are of broad interest in materials science and industry. High-pressure study using diamond anvil cells shows promise in obtaining new crystal and electronic structures different from their pristine states. Here, we conducted in situ angle dispersive synchrotron x-ray-diffraction and Raman spectroscopy experiments on α-Sb₂O₃ up to 50 GPa with neon as the pressure transmitting medium. A first-order structural transition was observed in between 15 and 20 GPa, where the cubic phase I gradually transformed into a layered tetragonal phase II through structural distortion and symmetry breaking. To explain the dramatic changes in sample color and transparency, we performed first-principles calculations to track the evolution of its density of states and electronic structure under pressure. At higher pressure, a sluggish amorphization was observed. Our results highlight the structural connections among the sesquioxides, where the lone electron pair plays an important role in determining the local structures.

  5. ICE AND DUST IN THE PRESTELLAR DARK CLOUD LYNDS 183: PREPLANETARY MATTER AT THE LOWEST TEMPERATURES

    SciTech Connect

    Whittet, D. C. B.; Poteet, C. A.; Bajaj, V. M.; Horne, D.; Chiar, J. E.; Pagani, L.; Shenoy, S. S.; Adamson, A. J.

    2013-09-10

    Dust grains are nucleation centers and catalysts for the growth of icy mantles in quiescent interstellar clouds, the products of which may accumulate into preplanetary matter when new stars and solar systems form within the clouds. In this paper, we present the first spectroscopic detections of silicate dust and the molecular ices H{sub 2}O, CO, and CO{sub 2} in the vicinity of the prestellar core L183 (L134N). An infrared photometric survey of the cloud was used to identify reddened background stars, and we present spectra covering solid-state absorption features in the wavelength range 2-20 {mu}m for nine of them. The mean composition of the ices in the best-studied line of sight (toward J15542044-0254073) is H{sub 2}O:CO:CO{sub 2} Almost-Equal-To 100:40:24. The ices are amorphous in structure, indicating that they have been maintained at low temperature ({approx}< 15 K) since formation. The ice column density N(H{sub 2}O) correlates with reddening by dust, exhibiting a threshold effect that corresponds to the transition from unmantled grains in the outer layers of the cloud to ice-mantled grains within, analogous to that observed in other dark clouds. A comparison of results for L183 and the Taurus and IC 5146 dark clouds suggests common behavior, with mantles first appearing in each case at a dust column corresponding to a peak optical depth {tau}{sub 9.7} = 0.15 {+-} 0.03 in the silicate feature. Our results support a previous conclusion that the color excess E{sub J-K} does not obey a simple linear correlation with the total dust column in lines of sight that intercept dense clouds. The most likely explanation is a systematic change in the optical properties of the dust as the density increases.

  6. Ice and Dust in the Prestellar Dark Cloud Lynds 183: Preplanetary Matter at the Lowest Temperatures

    NASA Astrophysics Data System (ADS)

    Whittet, D. C. B.; Poteet, C. A.; Chiar, J. E.; Pagani, L.; Bajaj, V. M.; Horne, D.; Shenoy, S. S.; Adamson, A. J.

    2013-09-01

    Dust grains are nucleation centers and catalysts for the growth of icy mantles in quiescent interstellar clouds, the products of which may accumulate into preplanetary matter when new stars and solar systems form within the clouds. In this paper, we present the first spectroscopic detections of silicate dust and the molecular ices H2O, CO, and CO2 in the vicinity of the prestellar core L183 (L134N). An infrared photometric survey of the cloud was used to identify reddened background stars, and we present spectra covering solid-state absorption features in the wavelength range 2-20 μm for nine of them. The mean composition of the ices in the best-studied line of sight (toward J15542044-0254073) is H2O:CO:CO2 ≈ 100:40:24. The ices are amorphous in structure, indicating that they have been maintained at low temperature (lsim 15 K) since formation. The ice column density N(H2O) correlates with reddening by dust, exhibiting a threshold effect that corresponds to the transition from unmantled grains in the outer layers of the cloud to ice-mantled grains within, analogous to that observed in other dark clouds. A comparison of results for L183 and the Taurus and IC 5146 dark clouds suggests common behavior, with mantles first appearing in each case at a dust column corresponding to a peak optical depth τ9.7 = 0.15 ± 0.03 in the silicate feature. Our results support a previous conclusion that the color excess E J - K does not obey a simple linear correlation with the total dust column in lines of sight that intercept dense clouds. The most likely explanation is a systematic change in the optical properties of the dust as the density increases.

  7. 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).

  8. Operation IceBridge: Sea Ice Interlude

    NASA Video Gallery

    Sea ice comes in an array of shapes and sizes and has its own ephemeral beauty. Operation IceBridge studies sea ice at both poles, and also runs across interesting formations en route to other targ...

  9. Controls on Arctic sea ice from first-year and multi-year survival rates

    SciTech Connect

    Hunke, Jes

    2009-01-01

    The recent decrease in Arctic sea ice cover has transpired with a significant loss of multi year ice. The transition to an Arctic that is populated by thinner first year sea ice has important implications for future trends in area and volume. Here we develop a reduced model for Arctic sea ice with which we investigate how the survivability of first year and multi year ice control the mean state, variability, and trends in ice area and volume.

  10. Interstellar ice analogs: band strengths of H2O, CO2, CH3OH, and NH3 in the far-infrared region

    NASA Astrophysics Data System (ADS)

    Giuliano, B. M.; Escribano, R. M.; Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

    2014-05-01

    Context. Whereas observational astronomy now routinely extends to the far-infrared region of the spectrum, systematic laboratory studies are sparse. In particular, experiments on laboratory analogs performed through the years have provided information mainly about the band positions and shapes, while information about the band strengths are scarce and derivable principally from the optical constants. Aims: We measure the band strengths in the far-infrared region of interstellar ice analogs of astrophysically relevant species, such as H2O, CO2, CH3OH, and NH3, deposited at low temperature (8-10 K), followed by warm-up, to induce amorphous-crystalline phase transitions when relevant. Methods: The spectra of pure H2O, NH3, and CH3OH ices have been measured in the near-, mid- and far-infrared spectroscopic regions using the Interstellar Astrochemistry Chamber (ISAC) ultra-high-vacuum setup. In addition, far-infrared spectra of NH3 and CO2 were measured using a different set-up equipped with a bolometer detector. Band strengths in the far-infrared region were estimated using the corresponding near- and mid-infrared values as a reference. We also performed theoretical calculations of the amorphous and crystalline structures of these molecules using solid state computational programs at density functional theory (DFT) level. Vibrational assignment and mode intensities for these ices were predicted. Results: Infrared band strengths in the 25-500 μm range have been determined for the considered ice samples by direct comparison in the near- and mid-infrared regions. Our values were compared to those we calculated from the literature complex index of refraction. We found differences of a factor of two between the two sets of values. Conclusions: The calculated far-infrared band strengths provide a benchmark for interpreting the observational data from future space telescope missions, allowing the estimation of the ice column densities.

  11. Breakup of Pack Ice, Antarctic Ice Shelf

    NASA Technical Reports Server (NTRS)

    1991-01-01

    Breakup of Pack Ice along the periphery of the Antarctic Ice Shelf (53.5S, 3.0E) produced this mosaic of ice floes off the Antarctic Ice Shelf. Strong offshore winds, probably associated with strong katabatic downdrafts from the interior of the continent, are seen peeling off the edges of the ice shelf into long filamets of sea ice, icebergs, bergy bits and growlers to flow northward into the South Atlantic Ocean. 53.5S, 3.0E

  12. Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

    DOE PAGES

    Xiao, Haiyan Y.; Weber, William J.; Zhang, Yanwen; Zu, X. T.; Li, Sean

    2015-02-09

    In this study, the response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser,more » electron and ion irradiations.« less

  13. Controls on Arctic sea ice from first-year and multi-year ice survival rates

    NASA Astrophysics Data System (ADS)

    Armour, K.; Bitz, C. M.; Hunke, E. C.; Thompson, L.

    2009-12-01

    The recent decrease in Arctic sea ice cover has transpired with a significant loss of multi-year (MY) ice. The transition to an Arctic that is populated by thinner first-year (FY) sea ice has important implications for future trends in area and volume. We develop a reduced model for Arctic sea ice with which we investigate how the survivability of FY and MY ice control various aspects of the sea-ice system. We demonstrate that Arctic sea-ice area and volume behave approximately as first-order autoregressive processes, which allows for a simple interpretation of September sea-ice in which its mean state, variability, and sensitivity to climate forcing can be described naturally in terms of the average survival rates of FY and MY ice. This model, used in concert with a sea-ice simulation that traces FY and MY ice areas to estimate the survival rates, reveals that small trends in the ice survival rates explain the decline in total Arctic ice area, and the relatively larger loss of MY ice area, over the period 1979-2006. Additionally, our model allows for a calculation of the persistence time scales of September area and volume anomalies. A relatively short memory time scale for ice area (~ 1 year) implies that Arctic ice area is nearly in equilibrium with long-term climate forcing at all times, and therefore observed trends in area are a clear indication of a changing climate. A longer memory time scale for ice volume (~ 5 years) suggests that volume can be out of equilibrium with climate forcing for long periods of time, and therefore trends in ice volume are difficult to distinguish from its natural variability. With our reduced model, we demonstrate the connection between memory time scale and sensitivity to climate forcing, and discuss the implications that a changing memory time scale has on the trajectory of ice area and volume in a warming climate. Our findings indicate that it is unlikely that a “tipping point” in September ice area and volume will be

  14. Crystalline and amorphous H2O on Charon

    NASA Astrophysics Data System (ADS)

    Dalle Ore, Cristina M.; Cruikshank, Dale P.; Grundy, Will M.; Ennico, Kimberly; Olkin, Catherine B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.

    2015-11-01

    Charon, the largest satellite of Pluto, is a gray-colored icy world covered mostly in H2O ice, with spectral evidence for NH3, as previously reported (Cook et al. 2007, Astrophys. J. 663, 1406-1419 Merlin, et al. 2010, Icarus, 210, 930; Cook, et al. 2014, AAS/Division for Planetary Sciences Meeting Abstracts, 46, #401.04). Images from the New Horizons spacecraft reveal a surface with terrains of widely different ages and a moderate degree of localized coloration. The presence of H2O ice in its crystalline form (Brown & Calvin 2000 Science 287, 107-109; Buie & Grundy 2000 Icarus 148, 324-339; Merlin et al, 2010) along with NH3 is consistent with a fresh surface.The phase of H2O ice is a key tracer of variations in temperature and physical conditions on the surface of outer Solar System objects. At Charon’s surface temperature H2O is expected to be amorphous, but ground-based observations (e.g., Merlin et al. 2010) show a clearly crystalline signature. From laboratory experiments it is known that amorphous H2O ice becomes crystalline at temperatures of ~130 K. Other mechanisms that can change the phase of the ice from amorphous to crystalline include micro-meteoritic bombardment (Porter et al. 2010, Icarus, 208, 492) or resurfacing processes such as cryovolcanism.New Horizons observed Charon with the LEISA imaging spectrometer, part of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Science Reviews, 140, 129). Making use of high spatial resolution (better than 10 km/px) and spectral resolving power of 240 in the wavelength range 1.25-2.5 µm, and 560 in the range 2.1-2.25 µm, we report on an analysis of the phase of H2O ice on parts of Charon’s surface with a view to investigate the recent history and evolution of this small but intriguing object.This work was supported by NASA’s New Horizons project.

  15. Connecting Local Yield Stresses with Plastic Activity in Amorphous Solids

    NASA Astrophysics Data System (ADS)

    Patinet, Sylvain; Vandembroucq, Damien; Falk, Michael L.

    2016-07-01

    In model amorphous solids produced via differing quench protocols, a strong correlation is established between local yield stress measured by direct local probing of shear stress thresholds and the plastic rearrangements observed during remote loading in shear. This purely local measure shows a higher predictive power for identifying sites of plastic activity when compared with more conventional structural properties. Most importantly, the sites of low local yield stress, thus defined, are shown to be persistent, remaining predictive of deformation events even after fifty or more such plastic rearrangements. This direct and nonperturbative approach gives access to relevant transition pathways that control the stability of amorphous solids. Our results reinforce the relevance of modeling plasticity in amorphous solids based on a gradually evolving population of discrete and local zones preexisting in the structure.

  16. Connecting Local Yield Stresses with Plastic Activity in Amorphous Solids.

    PubMed

    Patinet, Sylvain; Vandembroucq, Damien; Falk, Michael L

    2016-07-22

    In model amorphous solids produced via differing quench protocols, a strong correlation is established between local yield stress measured by direct local probing of shear stress thresholds and the plastic rearrangements observed during remote loading in shear. This purely local measure shows a higher predictive power for identifying sites of plastic activity when compared with more conventional structural properties. Most importantly, the sites of low local yield stress, thus defined, are shown to be persistent, remaining predictive of deformation events even after fifty or more such plastic rearrangements. This direct and nonperturbative approach gives access to relevant transition pathways that control the stability of amorphous solids. Our results reinforce the relevance of modeling plasticity in amorphous solids based on a gradually evolving population of discrete and local zones preexisting in the structure. PMID:27494480

  17. Amorphous copper tungsten oxide with tunable band gaps

    SciTech Connect

    Chen Le; Shet, Sudhakar; Tang Houwen; Wang Heli; Yan Yanfa; Turner, John; Al-Jassim, Mowafak; Ahn, Kwang-soon

    2010-08-15

    We report on the synthesis of amorphous copper tungsten oxide thin films with tunable band gaps. The thin films are synthesized by the magnetron cosputtering method. We find that due to the amorphous nature, the Cu-to-W ratio in the films can be varied without the limit of the solubility (or phase separation) under appropriate conditions. As a result, the band gap and conductivity type of the films can be tuned by controlling the film composition. Unfortunately, the amorphous copper tungsten oxides are not stable in aqueous solution and are not suitable for the application of photoelectrochemical splitting of water. Nonetheless, it provides an alternative approach to search for transition metal oxides with tunable band gaps.

  18. Connecting Local Yield Stresses with Plastic Activity in Amorphous Solids.

    PubMed

    Patinet, Sylvain; Vandembroucq, Damien; Falk, Michael L

    2016-07-22

    In model amorphous solids produced via differing quench protocols, a strong correlation is established between local yield stress measured by direct local probing of shear stress thresholds and the plastic rearrangements observed during remote loading in shear. This purely local measure shows a higher predictive power for identifying sites of plastic activity when compared with more conventional structural properties. Most importantly, the sites of low local yield stress, thus defined, are shown to be persistent, remaining predictive of deformation events even after fifty or more such plastic rearrangements. This direct and nonperturbative approach gives access to relevant transition pathways that control the stability of amorphous solids. Our results reinforce the relevance of modeling plasticity in amorphous solids based on a gradually evolving population of discrete and local zones preexisting in the structure.

  19. Flexible Protocrystalline Silicon Solar Cells with Amorphous Buffer Layer

    NASA Astrophysics Data System (ADS)

    Ishikawa, Yasuaki; Schubert, Markus B.

    2006-09-01

    A low deposition temperature of 110 °C is mandatory for directly growing amorphous-silicon-based solar cells on plastic foil. The optimum absorber material at this low temperature is protocrystalline, i.e., right at the transition between amorphous and crystalline silicon. Polyethylene terephtalate foil of 50 μm thickness form the substrate of our flexible p-i-n single-junction cells. We discuss three peculiar processing techniques for achieving the maximum photovoltaic conversion efficiency of flexible low-temperature solar cells. First, we employ an optimized microcrystalline silicon p-type window layer; second, we use protocrystalline silicon for the i-layer; third, we insert an undoped amorphous silicon buffer layer at the p/i interface. The best flexible cells attain power conversion efficiencies of up to 4.9%.

  20. Apatite Formation from Amorphous Calcium Phosphate and Mixed Amorphous Calcium Phosphate/Amorphous Calcium Carbonate.

    PubMed

    Ibsen, Casper J S; Chernyshov, Dmitry; Birkedal, Henrik

    2016-08-22

    Crystallization from amorphous phases is an emerging pathway for making advanced materials. Biology has made use of amorphous precursor phases for eons and used them to produce structures with remarkable properties. Herein, we show how the design of the amorphous phase greatly influences the nanocrystals formed therefrom. We investigate the transformation of mixed amorphous calcium phosphate/amorphous calcium carbonate phases into bone-like nanocrystalline apatite using in situ synchrotron X-ray diffraction and IR spectroscopy. The speciation of phosphate was controlled by pH to favor HPO4 (2-) . In a carbonate free system, the reaction produces anisotropic apatite crystallites with large aspect ratios. The first formed crystallites are highly calcium deficient and hydrogen phosphate rich, consistent with thin octacalcium phosphate (OCP)-like needles. During growth, the crystallites become increasingly stoichiometric, which indicates that the crystallites grow through addition of near-stoichiometric apatite to the OCP-like initial crystals through a process that involves either crystallite fusion/aggregation or Ostwald ripening. The mixed amorphous phases were found to be more stable against phase transformations, hence, the crystallization was inhibited. The resulting crystallites were smaller and less anisotropic. This is rationalized by the idea that a local phosphate-depletion zone formed around the growing crystal until it was surrounded by amorphous calcium carbonate, which stopped the crystallization. PMID:27460160

  1. Fabrication of amorphous diamond films

    DOEpatents

    Falabella, S.

    1995-12-12

    Amorphous diamond films having a significant reduction in intrinsic stress are prepared by biasing a substrate to be coated and depositing carbon ions thereon under controlled temperature conditions. 1 fig.

  2. Ice friction: Role of non-uniform frictional heating and ice premelting.

    PubMed

    Persson, B N J

    2015-12-14

    The low friction of ice is usually attributed to the formation of a thin water film due to melting of ice by frictional heating. Melting of ice is a first order phase transition where physical quantities like mass density, the elastic modulus or the shear strength changes abruptly at the transition temperature. Thus, one may expect the friction coefficient to change abruptly at some characteristic sliding speed, when the melt water film is produced. We show that taking into account that, due to non-uniform frictional heating, melting does not occur simultaneously in all the ice contact regions, the transition is not abrupt but still more rapid (as a function of sliding speed) than observed experimentally. The slower than expected drop in the friction with increasing sliding speed may be a consequence of the following paradoxical phenomena: before the melt-water film is formed, the friction of ice is high and a large frictional heating occur which may result in the melting of the ice. If a thin (nanometer) water film would form, the friction becomes low which results in small frictional heating and the freezing of the water film. This suggests a region in sliding speed where a thin (nanometer) surface layer of the ice may be in a mixed state with small ice-like and water-like domains, which fluctuate rapidly in space and time. Alternatively, and more likely, heat-softening of the ice may occur resulting in a thin, statistically homogeneous (in the lateral direction) layer of disordered ice, with a shear strength which decreases continuously as the ice surface temperature approaches the bulk melting temperature. This layer could be related to surface premelting of ice. Using a phenomenological expression for the frictional shear stress, I show that the calculated ice friction is in good agreement with experimental observations.

  3. Unveiling the complex electronic structure of amorphous metal oxides

    PubMed Central

    Århammar, C.; Pietzsch, Annette; Bock, Nicolas; Holmström, Erik; Araujo, C. Moyses; Gråsjö, Johan; Zhao, Shuxi; Green, Sara; Peery, T.; Hennies, Franz; Amerioun, Shahrad; Föhlisch, Alexander; Schlappa, Justine; Schmitt, Thorsten; Strocov, Vladimir N.; Niklasson, Gunnar A.; Wallace, Duane C.; Rubensson, Jan-Erik; Johansson, Börje; Ahuja, Rajeev

    2011-01-01

    Amorphous materials represent a large and important emerging area of material’s science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today’s integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5–10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides.

  4. Molecular mobility in amorphous state: Implications on physical stability

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Sunny Piyush

    Amorphous pharmaceuticals are desirable in drug development due to their advantageous biopharmaceutical properties of higher apparent aqueous solubility and dissolution rate. The main obstacle in their widespread use, however, is their higher physicochemical instability than their crystalline counterparts. The goal of the present research project was to investigate correlations between the molecular mobility and physical stability in model amorphous compounds. The objective was to identify the specific mobility which is responsible for the physical instability in each case. This will potentially enable the development of effective strategies for the stabilization of amorphous pharmaceuticals. Moreover, these correlations can be used to develop predictive models for the stability at the pharmaceutically relevant storage conditions. Subtraction of dc conductivity enabled the comprehensive characterization of molecular mobility in amorphous trehalose. This was followed by investigation of correlation between crystallization behavior and different relaxations. Global mobility was found to be strongly coupled to both crystallization onset time and rate. Different preparation methods imparted different mobility states to amorphous trehalose which was postulated to be the reason for the significant physical stability differences. Predictive models were developed and a good agreement was found between the predicted and the experimental crystallization onset times at temperatures around and below the glass transition temperature (Tg). Effect of annealing was investigated on water sorption, enthalpic recovery and dielectric relaxation times in amorphous trehalose. Global mobility was found to be linearly correlated to the water sorption potential which enabled the development of predictive models. Global mobility was also found to be strongly correlated to physical instability in amorphous itraconazole. Effect of polymer (PVP and HPMCAS) on itraconazole mobility and

  5. In situ observation of shear-driven amorphization in silicon crystals

    NASA Astrophysics Data System (ADS)

    He, Yang; Zhong, Li; Fan, Feifei; Wang, Chongmin; Zhu, Ting; Mao, Scott X.

    2016-10-01

    Amorphous materials are used for both structural and functional applications. An amorphous solid usually forms under driven conditions such as melt quenching, irradiation, shock loading or severe mechanical deformation. Such extreme conditions impose significant challenges on the direct observation of the amorphization process. Various experimental techniques have been used to detect how the amorphous phases form, including synchrotron X-ray diffraction, transmission electron microscopy (TEM) and Raman spectroscopy, but a dynamic, atomistic characterization has remained elusive. Here, by using in situ high-resolution TEM (HRTEM), we show the dynamic amorphization process in silicon nanocrystals during mechanical straining on the atomic scale. We find that shear-driven amorphization occurs in a dominant shear band starting with the diamond-cubic (dc) to diamond-hexagonal (dh) phase transition and then proceeds by dislocation nucleation and accumulation in the newly formed dh-Si phase. This process leads to the formation of an amorphous Si (a-Si) band, embedded with dh-Si nanodomains. The amorphization of dc-Si via an intermediate dh-Si phase is a previously unknown pathway of solid-state amorphization.

  6. Large-Scale Surveys of Snow Depth on Arctic Sea Ice from Operation IceBridge

    NASA Technical Reports Server (NTRS)

    Kurtz, Nathan T.; Farrell, Sinead L.

    2011-01-01

    We show the first results of a large ]scale survey of snow depth on Arctic sea ice from NASA fs Operation IceBridge snow radar system for the 2009 season and compare the data to climatological snow depth values established over the 1954.1991 time period. For multiyear ice, the mean radar derived snow depth is 33.1 cm and the corresponding mean climatological snow depth is 33.4 cm. The small mean difference suggests consistency between contemporary estimates of snow depth with the historical climatology for the multiyear ice region of the Arctic. A 16.5 cm mean difference (climatology minus radar) is observed for first year ice areas suggesting that the increasingly seasonal sea ice cover of the Arctic Ocean has led to an overall loss of snow as the region has transitioned away from a dominantly multiyear ice cover.

  7. Amorphous metal alloy and composite

    DOEpatents

    Wang, Rong; Merz, Martin D.

    1985-01-01

    Amorphous metal alloys of the iron-chromium and nickel-chromium type have excellent corrosion resistance and high temperature stability and are suitable for use as a protective coating on less corrosion resistant substrates. The alloys are stabilized in the amorphous state by one or more elements of titanium, zirconium, hafnium, niobium, tantalum, molybdenum, and tungsten. The alloy is preferably prepared by sputter deposition.

  8. Amorphization of hard crystalline materials by electrosprayed nanodroplet impact

    SciTech Connect

    Gamero-Castaño, Manuel Torrents, Anna; Borrajo-Pelaez, Rafael; Zheng, Jian-Guo

    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 transmission 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.

  9. Radiation effects in water ice: A near-edge x-ray absorption fine structure study

    NASA Astrophysics Data System (ADS)

    Laffon, C.; Lacombe, S.; Bournel, F.; Parent, Ph.

    2006-11-01

    The changes in the structure and composition of vapor-deposited ice films irradiated at 20K with soft x-ray photons (3-900eV) and their subsequent evolution with temperatures between 20 and 150K have been investigated by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K edge. We observe the hydroxyl OH, the atomic oxygen O, and the hydroperoxyl HO2 radicals, as well as the oxygen O2 and hydrogen peroxide H2O2 molecules in irradiated porous amorphous solid water (p-ASW) and crystalline (Icryst) ice films. The evolution of their concentrations with the temperature indicates that HO2, O2, and H2O2 result from a simple step reaction fuelled by OH, where O2 is a product of HO2 and HO2 a product of H2O2. The local order of ice is also modified, whatever the initial structure is. The crystalline ice Icryst becomes amorphous. The high-density amorphous phase (Iah ) of ice is observed after irradiation of the p-ASW film, whose initial structure is the normal low-density form of the amorphous ice (Ial). The phase Iah is thus peculiar to irradiated ice and does not exist in the as-deposited ice films. A new "very high density" amorphous phase—we call Iavh—is obtained after warming at 50K the irradiated p-ASW ice. This phase is stable up to 90K and partially transforms into crystalline ice at 150K.

  10. 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,

  11. Superconducting Metallic Glass Transition-Edge-Sensors

    NASA Technical Reports Server (NTRS)

    Hays, Charles C. (Inventor)

    2013-01-01

    A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

  12. 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.

  13. 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.

  14. Sudden switchover between the polyamorphic phase separation and the glass-to-liquid transition in glassy LiCl aqueous solutions.

    PubMed

    Suzuki, Yoshiharu; Mishima, Osamu

    2013-02-28

    Lithium chloride aqueous solutions (LiClaq solutions) below 10 mol.% are vitrified by cooling from room temperature to 77 K at 0.3 GPa. We examine the solvent state of the glassy sample and its transformation by heating at 1 atm using low-temperature differential scanning calorimetry and Raman spectroscopy. This experimental study suggests strongly that the solvent state of the glassy LiClaq solution closely relates to the state of high-density amorphous ice. Moreover, we reconfirm that the separation into the low-density amorphous ice and the glassy highly concentrated LiClaq solution occurs in the glassy dilute LiClaq solution at ∼130 K, not the glass-to-liquid transition which is commonly observed in the glassy LiClaq solution above ∼10 mol.%. In order to interpret the sudden switchover between the glass-to-liquid transition and the phase separation at ∼10 mol.%, we propose a state diagram of LiClaq solution which connects with a polyamorphic state diagram of pure water and discuss a possibility that the electric field induces a polyamorphic transition of water. PMID:23464160

  15. Glassy aerosols heterogeneously nucleate cirrus ice particles

    NASA Astrophysics Data System (ADS)

    Wilson, Theodore W.; Murray, Benjamin J.; Dobbie, Steven; Cui, Zhiqiang; Al-Jumur, Sardar M. R. K.; Möhler, Ottmar; Schnaiter, Martin; Wagner, Robert; Benz, Stefan; Niemand, Monika; Saathoff, Harald; Ebert, Volker; Wagner, Steven; Kärcher, Bernd

    2010-05-01

    Ice clouds in the tropical tropopause layer (TTL, ~12-18 km, ~180-200 K) play a key role in dehydrating air entering the stratosphere. However, in-situ measurements show that air within these clouds is unexpectedly supersaturated(1); normally the growth of ice crystals rapidly quenches any supersaturation. A number of explanations for high in-cloud humidity have been put forward, but recent research suggests high humidity may be related to the low numbers of ice crystals found within these clouds(1). Low ice number densities can be produced through selective nucleation by a small subset of aerosol particles. This is inconsistent with homogeneous nucleation of ice in liquid aerosols. However, droplets rich in organic material, ubiquitous in the TTL, are known to become glassy (amorphous, non-crystalline solid) under TTL conditions(2,3). Here we show, using a large cloud simulation chamber, that glassy solution droplets nucleate ice heterogeneously at low supersaturations. Using a one-dimensional cirrus model we also show that nucleation by glassy aerosol in the TTL may explain low TTL ice number densities and high in-cloud humidity. Recent measurements of the composition of TTL cirrus residues are consistent with our findings(4). (1) Krämer, M. et al. Ice supersaturations and cirrus cloud crystal numbers. Atm. Chem. Phys. 9, 3505-3522 (2009). (2) Murray, B. J. Inhibition of ice crystallisation in highly viscous aqueous organic acid droplets. Atm. Chem. Phys. 8, 5423-5433 (2008). (3) Zobrist, B., Marcolli, C., Pedernera, D. A. & Koop, T. Do atmospheric aerosols form glasses? Atm. Chem. Phys. 8, 5221-5244 (2008). (4) Froyd, K. D., Murphy, D. M., Lawson, P., Baumgardner, D. & Herman, R. L. Aerosols that form subvisible cirrus at the tropical tropopause. Atmos. Chem. Phys. 10, 209-218 (2010).

  16. Amorphous phase formation in mechanically alloyed iron-based systems

    NASA Astrophysics Data System (ADS)

    Sharma, Satyajeet

    Bulk metallic glasses have interesting combination of physical, chemical, mechanical, and magnetic properties which make them attractive for a variety of applications. Consequently there has been a lot of interest in understanding the structure and properties of these materials. More varied applications can be sought if one understands the reasons for glass formation and the methods to control them. The glass-forming ability (GFA) of alloys can be substantially increased by a proper selection of alloying elements and the chemical composition of the alloy. High GFA will enable in obtaining large section thickness of amorphous alloys. Ability to produce glassy alloys in larger section thicknesses enables exploitation of these advanced materials for a variety of different applications. The technique of mechanical alloying (MA) is a powerful non-equilibrium processing technique and is known to produce glassy (or amorphous) alloys in several alloy systems. Metallic amorphous alloys have been produced by MA starting from either blended elemental metal powders or pre-alloyed powders. Subsequently, these amorphous alloy powders could be consolidated to full density in the temperature range between the glass transition and crystallization temperatures, where the amorphous phase has a very low viscosity. This Dissertation focuses on identifying the various Fe-based multicomponent alloy systems that can be amorphized using the MA technique, studying the GFA of alloys with emphasis on improving it, and also on analyzing the effect of extended milling time on the constitution of the amorphous alloy powder produced at earlier times. The Dissertation contains seven chapters, where the lead chapter deals with the background, history and introduction to bulk metallic glasses. The following four chapters are the published/to be published work, where the criterion for predicting glass formation, effect of Niobium addition on glass-forming ability (GFA), lattice contraction on

  17. Structural Characterization of Crystalline Ice Nanoclusters

    NASA Technical Reports Server (NTRS)

    Blake, David

    2000-01-01

    Water ice nanoclusters are useful analogs for studying a variety of processes that occur within icy grains in the extraterrestrial environment. The surface of ice nanoclusters prepared in the laboratory is similar to the surface of interstellar ice grains. In cold molecular clouds, the silicate cores of interstellar grains are typically approx. 100 nm in diameter and have a coating of impure amorphous water ice. Depositional, thermal and radiolytic processes leave the surface and subsurface molecules in a disordered state. In this state, structural defects become mobile and reactions of trapped gases and small molecules can occur. The large surface area of nanocluster deposits relative to their bulk allows for routine observation of such surface-mediated processes. Furthermore, the disordered surface and subsurface layers in nanocluster deposits mimic the structure of amorphous ice rinds found on interstellar dust grains. Transmission Electron Microscopy (TEM has been used tn characterize the crystallinity, growth mechanism, and size distribution of nanoclusters formed from a mixture of water vapor with an inert carrier gas that has been rapidly cooled to 77K. E M imaging reveals a Gaussian size distribution around a modal diameter that increases from approx. 15 to 30 nm as the percentage of water vapor within the mixture increases from 0.5 to 2.007, respectively . TEM bright and dark field imaging also reveals the crystalline nature of the clusters. h4any of the clusters show a mosaic structure in which crystalline domains originate at the center Other images show mirror planes that are separated by approx. 10 nm. Electron diffraction patterns of these clusters show that the clusters are composed of cubic ice with only a small hexagonal component. Further, the crystalline domain size is approximately the same as the modal diameter suggesting that the clusters are single crystals.

  18. Solar radiation interactions with seasonal sea ice

    NASA Astrophysics Data System (ADS)

    Ehn, Jens Kristian

    Presently, the Arctic Ocean is undergoing an escalating reduction in sea ice and a transition towards a seasonal sea ice environment. This warrants detailed investigations into improving our understanding of the seasonal evolution of sea ice and snow covers, and their representation in climate models. The interaction of solar radiation with sea ice is an important process influencing the energy balance and biological activity in polar seas, and consequently plays a key role in the earth's climate system. This thesis focuses on characterization of the optical properties---and the underlying physical properties that determine them---of seasonal sea ice during the fall freeze-up and the spring melt periods. Both periods display high spatial heterogeneity and rapid temporal changes in sea ice properties, and are therefore poorly understood. Field data were collected in Amundsen Gulf/Franklin Bay (FB), southern-eastern Beaufort Sea, in Oct.-Nov. 2003 and Apr. 2004 and in Button Bay (BB), western Hudson Bay, in Mar.-May 2005 to address (1) the temporal and spatial evolution of surface albedo and transmittance, (2) how radiative transfer in sea ice is controlled by its physical nature, and (3) the characteristics of the bottom ice algae community and its effect on the optical properties. The fall study showed the importance of surface features such as dry or slushy bare ice, frost flowers and snow cover in determining the surface albedo. Ice thickness was also important, however, mostly because surface features were associated with thickness. For example, nilas (<10 cm thick) was typically not covered by a snow layer as snow grains were dissolved or merged with the salty and warm brine skim layer on the surface, while surface conditions on thicker ice types were cold and dry enough to support a snow cover. In general, the surface albedo increased exponentially with an ice thickness increase, however, variability within ice thickness types were very large. It is apparent

  19. Topographically mediated ice stream subglacial drainage networks

    NASA Astrophysics Data System (ADS)

    Hiester, J.; Sergienko, O. V.; Hulbe, C. L.

    2016-02-01

    Satellite laser altimetry reveals short timescale changes in Antarctic ice sheet surface elevation that are suggested to be driven by subglacial water transport and storage. Here details of the interaction between the dynamics of ice stream flow, subglacial water system, and bed elevation relief are examined in the context of idealized, heterogeneous bed geometries. Using a two-way coupled model of ice and subglacial water flow, we show that basal topography controls the temporal and spatial variability of the sub-ice stream hydraulic system. The orientation and characteristic dimensions of the topographic undulations determine the morphology (connected subglacial ponds or channel-like subglacial water features) and timescales of the sub-ice stream drainage system. The short-term (several years to decades) variability of the simulated coupled ice stream/subglacial water system suggests that the short-term surface variations detected in remote sensing observations may be indicative of a rapidly evolving subglacial water system. Our simulations also show that interaction between ice flow and the highly dynamic subglacial water system has a strong effect on effective stress in the ice. Large effective stress magnitudes arise over areas where the basal traction is characterized by strong spatial gradients, that is, transitions from high to low basal traction or vise versa. These transitions migrate on multiyear timescales and thus cause large effective stress variability on the same temporal scales.

  20. Growing timescales and lengthscales characterizing vibrations of amorphous solids.

    PubMed

    Berthier, Ludovic; Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Seoane, Beatriz; Zamponi, Francesco

    2016-07-26

    Low-temperature properties of crystalline solids can be understood using harmonic perturbations around a perfect lattice, as in Debye's theory. Low-temperature properties of amorphous solids, however, strongly depart from such descriptions, displaying enhanced transport, activated slow dynamics across energy barriers, excess vibrational modes with respect to Debye's theory (i.e., a boson peak), and complex irreversible responses to small mechanical deformations. These experimental observations indirectly suggest that the dynamics of amorphous solids becomes anomalous at low temperatures. Here, we present direct numerical evidence that vibrations change nature at a well-defined location deep inside the glass phase of a simple glass former. We provide a real-space description of this transition and of the rapidly growing time- and lengthscales that accompany it. Our results provide the seed for a universal understanding of low-temperature glass anomalies within the theoretical framework of the recently discovered Gardner phase transition.

  1. Growing timescales and lengthscales characterizing vibrations of amorphous solids.

    PubMed

    Berthier, Ludovic; Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Seoane, Beatriz; Zamponi, Francesco

    2016-07-26

    Low-temperature properties of crystalline solids can be understood using harmonic perturbations around a perfect lattice, as in Debye's theory. Low-temperature properties of amorphous solids, however, strongly depart from such descriptions, displaying enhanced transport, activated slow dynamics across energy barriers, excess vibrational modes with respect to Debye's theory (i.e., a boson peak), and complex irreversible responses to small mechanical deformations. These experimental observations indirectly suggest that the dynamics of amorphous solids becomes anomalous at low temperatures. Here, we present direct numerical evidence that vibrations change nature at a well-defined location deep inside the glass phase of a simple glass former. We provide a real-space description of this transition and of the rapidly growing time- and lengthscales that accompany it. Our results provide the seed for a universal understanding of low-temperature glass anomalies within the theoretical framework of the recently discovered Gardner phase transition. PMID:27402768

  2. Preparation of an amorphous sodium furosemide salt improves solubility and dissolution rate and leads to a faster Tmax after oral dosing to rats.

    PubMed

    Nielsen, Line Hagner; Gordon, Sarah; Holm, René; Selen, Arzu; Rades, Thomas; Müllertz, Anette

    2013-11-01

    Amorphous forms of furosemide sodium salt and furosemide free acid were prepared by spray drying. For the preparation of the amorphous free acid, methanol was utilised as the solvent, whereas the amorphous sodium salt was formed from a sodium hydroxide-containing aqueous solvent in equimolar amounts of NaOH and furosemide. Information about the structural differences between the two amorphous forms was obtained by Fourier Transform Infrared Spectroscopy (FTIR), and glass transition temperature (Tg) was determined using Differential Scanning Calorimetry (DSC). The stability and devitrification tendency of the two amorphous forms were investigated by X-ray Powder Diffraction (XRPD). The apparent solubility of the two amorphous forms and the crystalline free acid form of furosemide in various gastric and intestinal stimulated media was determined. Moreover, the dissolution characteristics of the two amorphous forms and of crystalline free acid were investigated. FTIR confirmed molecular differences between the amorphous free acid and salt. The amorphous salt showed a Tg of 101.2 °C, whereas the Tg for the amorphous free acid was found to be 61.8 °C. The amorphous free acid was physically stable for 4 days at 22 °C and 33% relative humidity (RH), while the amorphous salt exhibited physical stability for 291 days at the same storage conditions. When storing the amorphous forms at 40 °C and 75% RH both forms converted to crystalline forms after 2 days. The apparent solubility of the amorphous salt form was higher than that of both amorphous and crystalline free acid in all media studied. All three forms of furosemide exhibited a greater solubility in the presence of biorelevant media as compared to buffer, however, an overall trend for a further increase in solubility in relation to an increase in media surfactant concentration was not seen. The amorphous salt demonstrated an 8- and 20-fold higher intrinsic dissolution rate (IDR) when compared to amorphous and

  3. 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.

  4. 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.

  5. Formation of amorphous metal alloys by chemical vapor deposition

    DOEpatents

    Mullendore, Arthur W.

    1990-01-01

    Amorphous alloys are deposited by a process of thermal dissociation of mixtures or organometallic compounds and metalloid hydrides, e.g., transition metal carbonyl such as nickel carbonyl, and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit.

  6. Formation of amorphous metal alloys by chemical vapor deposition

    DOEpatents

    Mullendore, A.W.

    1988-03-18

    Amorphous alloys are deposited by a process of thermal dissociation of mixtures of organometallic compounds and metalloid hydrides,e.g., transition metal carbonyl, such as nickel carbonyl and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit. 1 fig.

  7. Nonlinear threshold behavior during the loss of Arctic sea ice.

    PubMed

    Eisenman, I; Wettlaufer, J S

    2009-01-01

    In light of the rapid recent retreat of Arctic sea ice, a number of studies have discussed the possibility of a critical threshold (or "tipping point") beyond which the ice-albedo feedback causes the ice cover to melt away in an irreversible process. The focus has typically been centered on the annual minimum (September) ice cover, which is often seen as particularly susceptible to destabilization by the ice-albedo feedback. Here, we examine the central physical processes associated with the transition from ice-covered to ice-free Arctic Ocean conditions. We show that although the ice-albedo feedback promotes the existence of multiple ice-cover states, the stabilizing thermodynamic effects of sea ice mitigate this when the Arctic Ocean is ice covered during a sufficiently large fraction of the year. These results suggest that critical threshold behavior is unlikely during the approach from current perennial sea-ice conditions to seasonally ice-free conditions. In a further warmed climate, however, we find that a critical threshold associated with the sudden loss of the remaining wintertime-only sea ice cover may be likely.

  8. Ice cloud processing of ultra-viscous/glassy aerosol particles leads to enhanced ice nucleation ability

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Skrotzki, J.; Leisner, T.; Wilson, T. W.; Malkin, T. L.; Murray, B. J.

    2012-04-01

    The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA), levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition) before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosols that have re-vitrified in contact with the

  9. Ice cloud processing of ultra-viscous/glassy aerosol particles leads to enhanced ice nucleation ability

    NASA Astrophysics Data System (ADS)

    Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Skrotzki, J.; Leisner, T.; Wilson, T. W.; Malkin, T. L.; Murray, B. J.

    2012-09-01

    The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA), levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition) before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosol particles that have re-vitrified in contact

  10. Process induced disorder in crystalline materials: differentiating defective crystals from the amorphous form of griseofulvin.

    PubMed

    Feng, Tao; Pinal, Rodolfo; Carvajal, M Teresa

    2008-08-01

    This research investigates milling induced disorder in crystalline griseofulvin. Griseofulvin was subjected to cryogenic milling for various lengths of time. For comparison, the amorphous form of griseofulvin was also prepared by the quench melt method. Different analytical techniques were used to study the differences between the cryomilled, amorphous and crystalline forms of the drug. Cryogenic milling of griseofulvin progressively reduces the crystallinity of the drug by inducing crystal defects, rather than amorphous materials. Raman analysis provides evidence of structural differences between the two. The differences between the defective crystals produced by milling and the amorphous form are significant enough as to be measurable in their bulk thermal properties. Defective crystals show significant decrease in the heat of fusion as a function of milling time but do not exhibit a glass transition nor recrystallization from the amorphous form. Crystal defects undergo recrystallization upon heating at temperatures well below the glass transition temperature (T(g)) in a process that is separate and completely independent from the crystallization of the amorphous griseofulvin, observed above T(g). Physical mixtures of defective crystals and amorphous drug demonstrate that the thermal events associated with each form persist in the mixtures, unaffected by the presence of the other form.

  11. Nanostructures having crystalline and amorphous phases

    DOEpatents

    Mao, Samuel S; Chen, Xiaobo

    2015-04-28

    The present invention includes a nanostructure, a method of making thereof, and a method of photocatalysis. In one embodiment, the nanostructure includes a crystalline phase and an amorphous phase in contact with the crystalline phase. Each of the crystalline and amorphous phases has at least one dimension on a nanometer scale. In another embodiment, the nanostructure includes a nanoparticle comprising a crystalline phase and an amorphous phase. The amorphous phase is in a selected amount. In another embodiment, the nanostructure includes crystalline titanium dioxide and amorphous titanium dioxide in contact with the crystalline titanium dioxide. Each of the crystalline and amorphous titanium dioxide has at least one dimension on a nanometer scale.

  12. Amorphous-diamond electron emitter

    DOEpatents

    Falabella, Steven

    2001-01-01

    An electron emitter comprising a textured silicon wafer overcoated with a thin (200 .ANG.) layer of nitrogen-doped, amorphous-diamond (a:D-N), which lowers the field below 20 volts/micrometer have been demonstrated using this emitter compared to uncoated or diamond coated emitters wherein the emission is at fields of nearly 60 volts/micrometer. The silicon/nitrogen-doped, amorphous-diamond (Si/a:D-N) emitter may be produced by overcoating a textured silicon wafer with amorphous-diamond (a:D) in a nitrogen atmosphere using a filtered cathodic-arc system. The enhanced performance of the Si/a:D-N emitter lowers the voltages required to the point where field-emission displays are practical. Thus, this emitter can be used, for example, in flat-panel emission displays (FEDs), and cold-cathode vacuum electronics.

  13. Stochastic approach to plasticity and yield in amorphous solids

    NASA Astrophysics Data System (ADS)

    Hentschel, H. G. E.; Jaiswal, Prabhat K.; Procaccia, Itamar; Sastry, Srikanth

    2015-12-01

    We focus on the probability distribution function (PDF) P (Δ γ ;γ ) where Δ γ are the measured strain intervals between plastic events in a athermal strained amorphous solids, and γ measures the accumulated strain. The tail of this distribution as Δ γ →0 (in the thermodynamic limit) scales like Δ γη . The exponent η is related via scaling relations to the tail of the PDF of the eigenvalues of the plastic modes of the Hessian matrix P (λ ) which scales like λθ, η =(θ -1 )/2 . The numerical values of η or θ can be determined easily in the unstrained material and in the yielded state of plastic flow. Special care is called for in the determination of these exponents between these states as γ increases. Determining the γ dependence of the PDF P (Δ γ ;γ ) can shed important light on plasticity and yield. We conclude that the PDF's of both Δ γ and λ are not continuous functions of γ . In slowly quenched amorphous solids they undergo two discontinuous transitions, first at γ =0+ and then at the yield point γ =γ Y to plastic flow. In quickly quenched amorphous solids the second transition is smeared out due to the nonexisting stress peak before yield. The nature of these transitions and scaling relations with the system size dependence of <Δ γ > are discussed.

  14. Stochastic approach to plasticity and yield in amorphous solids.

    PubMed

    Hentschel, H G E; Jaiswal, Prabhat K; Procaccia, Itamar; Sastry, Srikanth

    2015-12-01

    We focus on the probability distribution function (PDF) P(Δγ;γ) where Δγ are the measured strain intervals between plastic events in a athermal strained amorphous solids, and γ measures the accumulated strain. The tail of this distribution as Δγ→0 (in the thermodynamic limit) scales like Δγ(η). The exponent η is related via scaling relations to the tail of the PDF of the eigenvalues of the plastic modes of the Hessian matrix P(λ) which scales like λ(θ), η=(θ-1)/2. The numerical values of η or θ can be determined easily in the unstrained material and in the yielded state of plastic flow. Special care is called for in the determination of these exponents between these states as γ increases. Determining the γ dependence of the PDF P(Δγ;γ) can shed important light on plasticity and yield. We conclude that the PDF's of both Δγ and λ are not continuous functions of γ. In slowly quenched amorphous solids they undergo two discontinuous transitions, first at γ=0(+) and then at the yield point γ=γ(Y) to plastic flow. In quickly quenched amorphous solids the second transition is smeared out due to the nonexisting stress peak before yield. The nature of these transitions and scaling relations with the system size dependence of 〈Δγ〉 are discussed.

  15. Amorphous Alloy Membranes for High Temperature Hydrogen Separation

    SciTech Connect

    Coulter, K

    2013-09-30

    At the beginning of this project, thin film amorphous alloy membranes were considered a nascent but promising new technology for industrial-scale hydrogen gas separations from coal- derived syngas. This project used a combination of theoretical modeling, advanced physical vapor deposition fabricating, and laboratory and gasifier testing to develop amorphous alloy membranes that had the potential to meet Department of Energy (DOE) targets in the testing strategies outlined in the NETL Membrane Test Protocol. The project is complete with Southwest Research Institute® (SwRI®), Georgia Institute of Technology (GT), and Western Research Institute (WRI) having all operated independently and concurrently. GT studied the hydrogen transport properties of several amorphous alloys and found that ZrCu and ZrCuTi were the most promising candidates. GT also evaluated the hydrogen transport properties of V, Nb and Ta membranes coated with different transition-metal carbides (TMCs) (TM = Ti, Hf, Zr) catalytic layers by employing first-principles calculations together with statistical mechanics methods and determined that TiC was the most promising material to provide catalytic hydrogen dissociation. SwRI developed magnetron coating techniques to deposit a range of amorphous alloys onto both porous discs and tubular substrates. Unfortunately none of the amorphous alloys could be deposited without pinhole defects that undermined the selectivity of the membranes. WRI tested the thermal properties of the ZrCu and ZrNi alloys and found that under reducing environments the upper temperature limit of operation without recrystallization is ~250 °C. There were four publications generated from this project with two additional manuscripts in progress and six presentations were made at national and international technical conferences. The combination of the pinhole defects and the lack of high temperature stability make the theoretically identified most promising candidate amorphous alloys

  16. Partially ordered state of ice XV

    PubMed Central

    Komatsu, K.; Noritake, F.; Machida, S.; Sano-Furukawa, A.; Hattori, T.; Yamane, R.; Kagi, H.

    2016-01-01

    Most ice polymorphs have order–disorder “pairs” in terms of hydrogen positions, which contributes to the rich variety of ice polymorphs; in fact, three recently discovered polymorphs— ices XIII, XIV, and XV—are ordered counter forms to already identified disordered phases. Despite the considerable effort to understand order–disorder transition in ice crystals, there is an inconsistency among the various experiments and calculations for ice XV, the ordered counter form of ice VI, i.e., neutron diffraction observations suggest antiferroelectrically ordered structures, which disagree with dielectric measurement and theoretical studies, implying ferroelectrically ordered structures. Here we investigate in-situ neutron diffraction measurements and density functional theory calculations to revisit the structure and stability of ice XV. We find that none of the completely ordered configurations are particular favored; instead, partially ordered states are established as a mixture of ordered domains in disordered ice VI. This scenario in which several kinds of ordered configuration coexist dispels the contradictions in previous studies. It means that the order–disorder pairs in ice polymorphs are not one-to-one correspondent pairs but rather have one-to-n correspondence, where there are n possible configurations at finite temperature. PMID:27375120

  17. Partially ordered state of ice XV

    NASA Astrophysics Data System (ADS)

    Komatsu, K.; Noritake, F.; Machida, S.; Sano-Furukawa, A.; Hattori, T.; Yamane, R.; Kagi, H.

    2016-07-01

    Most ice polymorphs have order–disorder “pairs” in terms of hydrogen positions, which contributes to the rich variety of ice polymorphs; in fact, three recently discovered polymorphs— ices XIII, XIV, and XV—are ordered counter forms to already identified disordered phases. Despite the considerable effort to understand order–disorder transition in ice crystals, there is an inconsistency among the various experiments and calculations for ice XV, the ordered counter form of ice VI, i.e., neutron diffraction observations suggest antiferroelectrically ordered structures, which disagree with dielectric measurement and theoretical studies, implying ferroelectrically ordered structures. Here we investigate in-situ neutron diffraction measurements and density functional theory calculations to revisit the structure and stability of ice XV. We find that none of the completely ordered configurations are particular favored; instead, partially ordered states are established as a mixture of ordered domains in disordered ice VI. This scenario in which several kinds of ordered configuration coexist dispels the contradictions in previous studies. It means that the order–disorder pairs in ice polymorphs are not one-to-one correspondent pairs but rather have one-to-n correspondence, where there are n possible configurations at finite temperature.

  18. Annealing studies of amorphous alloys

    SciTech Connect

    Wiley, J.D.; Perepezko, J.H.; Nordman, J.E.

    1983-04-01

    Amorphous films of the alloys Ni-Nb, Ni-Mo, Mo-Si, and W-Si were sputter deposited on single-crystal semiconductor substrates. One-hour crystallization temperatures of the films were determined to within +-25/sup 0/C by annealing and x-ray diffraction measurements. Interdiffusion between Au or Cu overlayers and the amorphous films were studied by annealing combined with Auger Electron Spectroscopy (AES) profiling, and by Rutherford Backscatter (RBS) analysis. Supplementary measurements used to study structural relaxation and crystallization included resistivity as a function of temperature; DTA and DSC; and electron microscopy.

  19. Icing Simulation

    NASA Technical Reports Server (NTRS)

    Bidwell, Colin

    2009-01-01

    A grid block transformation scheme which allows the input of grids in arbitrary reference frames, the use of mirror planes, and grids with relative velocities has been developed. A simple ice crystal and sand particle bouncing scheme has been included.. Added an SLD splashing model based on that developed by William Wright for the LEWICE 3.2.2 software. A new area based collection efficiency algorithm will be incorporated which calculates trajectories from inflow block boundaries to outflow block boundaries. This method will be used for calculating and passing collection efficiency data between blade rows for turbo-machinery calculations.

  20. Ice Observatory

    NASA Astrophysics Data System (ADS)

    blugerman, n.

    2015-10-01

    My project is to make ice observatories to perceive astral movements as well as light phenomena in the shape of cosmic rays and heat, for example.I find the idea of creating an observation point in space, that in time will change shape and eventually disappear, in consonance with the way we humans have been approaching the exploration of the universe since we started doing it. The transformation in the elements we use to understand big and small transformations, within the universe elements.

  1. Heat transfer on accreting ice surfaces

    NASA Technical Reports Server (NTRS)

    Yamaguchi, Keiko; Hansman, R. John, Jr.

    1993-01-01

    Based on previous observations of glaze ice accretion on aircraft surfaces, a multizone model with distinct zones of different surface roughness is demonstrated. The use of surface roughness in the LEWICE ice accretion prediction code is examined. It was found that roughness is used in two ways: (1) to determine the laminar to turbulent boundary-layer transition location; and (2) to calculate the convective turbulent heat-transfer coefficient. A two-zone version of the multizone model is implemented in the LEWICE code, and compared with experimental convective heat-transfer coefficient and ice accretion results. The analysis of the boundary-layer transition, surface roughness, and viscous flowfield effects significantly increased the accuracy in predicting heat-transfer coefficients. The multizone model was found to significantly improve the ice accretion prediction for the cases compared.

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

    PubMed

    Hudait, Arpa; Molinero, Valeria

    2014-06-01

    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

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

    PubMed

    Hudait, Arpa; Molinero, Valeria

    2014-06-01

    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

  4. Fluid and electromagnetic transport in sea ice

    NASA Astrophysics Data System (ADS)

    Gully, Adam Spence

    Covering 7-10% of the Earth's ocean surface, sea ice is both an indicator and agent of climate change. The sea ice cover controls the exchange of heat, momentum, and gases between the ocean and atmosphere. As a material, sea ice is a polycrystalline composite consisting of a pure ice host containing brine, air, and solid salt inclusions. This dissertation examines sea ice processes that are important to climate studies. In particular, we investigate the fluid transport properties of sea ice, which mediate melt pond evolution and ice pack reflectance, snow-ice formation, nutrient replenishment for microbial communities, and the evolution of salinity profiles. We also examine the electromagnetic monitoring of these processes, which rely on some knowledge of the effective electrical properties of sea ice. Columnar sea ice is effectively impermeable to fluid flow below a 5% brine volume fraction, yet is permeable for brine volume fractions above this threshold value. In two different experiments conducted in the Arctic and Antarctic, we have found that this critical transition in fluid flow at the brine connectivity threshold displays a strong electrical signature. The sea ice conductivity data are accurately explained by percolation theory with a universal critical exponent of 2. The data also indicate marked changes in the conductivity profile with the onset of surface ponding. Further, resistance data from classical four-probe Wenner arrays on the surfaces of ice floes in Antarctica were used to indirectly reconstruct the conductivity profiles with depth, involving both the horizontal and vertical components. We note the close agreement with the actual data for some models and the inadequacy of others. Additionally, a network model for the electrical conductivity of sea ice is developed, which incorporates statistical measurements of the brine microstructure. The numerical simulations are in close agreement with direct measurements we made in Antarctica on the

  5. Colloidal assembly by ice templating.

    PubMed

    Kumaraswamy, Guruswamy; Biswas, Bipul; Choudhury, Chandan Kumar

    2016-01-01

    We investigate ice templating of aqueous dispersions of polymer coated colloids and crosslinkers, at particle concentrations far below that required to form percolated monoliths. Freezing the aqueous dispersions forces the particles into close proximity to form clusters, that are held together as the polymer chains coating the particles are crosslinked. We observe that, with an increase in the particle concentration from about 10(6) to 10(8) particles per ml, there is a transition from isolated single particles to increasingly larger clusters. In this concentration range, most of the colloidal clusters formed are linear or sheet like particle aggregates. Remarkably, the cluster size distribution for clusters smaller than about 30 particles, as well as the size distribution of linear clusters, is only weakly dependent on the dispersion concentration in the range that we investigate. We demonstrate that the main features of cluster formation are captured by kinetic simulations that do not consider hydrodynamics or instabilities at the growing ice front due to particle concentration gradients. Thus, clustering of colloidal particles by ice templating dilute dispersions appears to be governed only by particle exclusion by the growing ice crystals that leads to their accumulation at ice crystal boundaries.

  6. Critical behavior of transport in sea ice

    NASA Astrophysics Data System (ADS)

    Golden, K. M.

    2003-10-01

    Geophysical materials such as sea ice, rocks, soils, snow, and glacial ice are composite media with complex, random microstructures. The effective fluid, gas, thermal, and electromagnetic transport properties of these materials play an important role in the large-scale dynamics and behavior of many geophysical systems. A striking feature of such media is that subtle changes in microstructural characteristics can induce changes over many orders of magnitude in the transport properties of the materials, which in turn can have significant large-scale geophysical effects. For example, sea ice, which mediates energy transfer between the ocean and atmosphere, plays a key role in global climate, and serves as an indicator of climatic change, is a porous composite of ice, brine and gases. Relevant length scales range from microns and millimeters for individual brine structures, to centimeters and meters for connected brine channels across floes, to hundreds of kilometers across an ice pack. Sea ice is distinguished from many other porous composites, such as sandstones or bone, in that its microstructure and bulk material properties can vary dramatically over a relatively small temperature range. The fluid permeability of sea ice ranges over six orders of magnitude for temperatures between 0°C and -25°C. Moreover, small changes in brine volume fraction around a threshold value of about 5%, corresponding to variations in temperature around a critical point of about -5°C, control an important transition between low and high fluid permeability regimes. Below this critical temperature, the sea ice is effectively impermeable, while for higher temperatures the brine phase becomes connected over macroscopic scales, allowing fluid transport through the ice. This transition has been observed to impact a wide range of phenomena such as surface flooding and snow-ice formation, enhancement of heat transfer due to fluid motion, mixing in the upper ocean, melt pool persistence

  7. Imprinting bulk amorphous alloy at room temperature

    PubMed Central

    Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; Lograsso, Thomas A.; Huh, Moo-Young; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

    2015-01-01

    We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the ability of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. Our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment. PMID:26563908

  8. Imprinting bulk amorphous alloy at room temperature.

    PubMed

    Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T; Lograsso, Thomas A; Huh, Moo-Young; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

    2015-01-01

    We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the ability of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. Our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment. PMID:26563908

  9. Imprinting bulk amorphous alloy at room temperature

    NASA Astrophysics Data System (ADS)

    Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; Lograsso, Thomas A.; Huh, Moo-Young; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

    2015-11-01

    We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the ability of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. Our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment.

  10. Imprinting bulk amorphous alloy at room temperature

    SciTech Connect

    Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; Lograsso, Thomas A.; Huh, Moo-Young; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

    2015-11-13

    We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the ability of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. In conclusion, our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment.

  11. Friction of ice on ice

    NASA Astrophysics Data System (ADS)

    Schulson, Erland M.; Fortt, Andrew L.

    2012-12-01

    New measurements have been made of the friction coefficient of freshwater polycrystalline ice sliding slowly (5 × 10-8 to 1 × 10-3 m s-1) upon itself at temperatures from 98 to 263 K under low normal stresses (≤98 kPa). Sliding obeys Coulomb's law: the shear stress is directly proportional to the normal stress across the interface, while cohesion offers little contribution to frictional resistance. The coefficient of kinetic friction of smooth surfaces varies from μk = 0.15 to 0.76 and, at elevated temperatures (≥223 K), exhibits both velocity strengthening at lower velocities (<10-5 to 10-4 m s-1) and velocity weakening at higher velocities. Strengthening and weakening are attributed to creep deformation of asperities and localized melting, respectively. At intermediate temperatures of 173 and 133 K, the kinetic coefficient appears to not exhibit significant dependence upon velocity. However, at the low temperature of 98 K the coefficient of kinetic friction exhibits moderate velocity strengthening at both the lowest and the highest velocities but velocity independence over the range of intermediate velocities. No effect was detected of either grain size or texture. Over the range of roughness 0.4 × 10-6 m ≤ Ra ≤ 12 × 10-6 m, a moderate effect was detected, where μk ∝ Ra0.08. Slide-hold-slide experiments revealed that the coefficient of static friction increases by an amount that scales logarithmically with holding time. Implications of the results are discussed in relation to shearing across "tiger stripe" faults within the icy crust of Saturn's Enceladus, sliding of the arctic sea ice cover and brittle compressive failure of cold ice.

  12. Amorphous rare earth magnet powders

    SciTech Connect

    Sellers, C.H.; Branagan, D.J.; Hyde, T.A.; Lewis, L.H.; Panchanathan, V.

    1996-08-01

    Gas atomization (GA) processing does not generally have a high enough cooling rate to produce the initial amorphous microstructure needed to obtain optimal magnetic properties in RE{sub 2}Fe{sub 14}B alloys. Phase separation and an underquenched microstructure result from detrimental {alpha}-Fe precipitation, and the resulting magnetic domain structure is very coarse. Additionally, there is a dramatic dependence of the magnetic properties on the cooling rate (and therefore the particle size) and the powders can be sensitive to environmental degradation. Alloy compositions designed just for GA (as opposed to melt spinning) are necessary to produce an amorphous structure that can be crystallized to result in a fine structure with magnetic properties which are independent of particle size. The addition of titanium and carbon to the melt has been found to change the solidification process sufficiently to result in an ``overquenched`` state in which most of the powder size fractions have an amorphous component. Crystallization with a brief heat treatment produces a structure which has improved magnetic properties, in part due to the ability to use compositions with higher Fe contents without {alpha}-Fe precipitation. Results from magnetometry, magnetic force microscopy, and x-ray analyses will be used to contrast the microstructure, domain structure, and magnetic properties of this new generation of amorphous powders with their multiphase predecessors.

  13. Amorphous titanium-oxide supercapacitors

    PubMed Central

    Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko

    2016-01-01

    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. PMID:27767103

  14. Radiation-induced amorphization of rare-earth titanate pyrochlores

    NASA Astrophysics Data System (ADS)

    Lian, Jie; Chen, Jian; Wang, L. M.; Ewing, Rodney C.; Farmer, J. Matt; Boatner, Lynn A.; Helean, K. B.

    2003-10-01

    Single crystals of the entire series of A2Ti2O7 (A=Sm to Lu, and Y) pyrochlore compounds were irradiated by 1-MeV Kr+ ions at temperatures from 293 to 1073 K, and the microstructure evolution, as a function of increasing radiation fluence, was characterized using in situ transmission electron microscopy (TEM). The critical amorphization temperature, Tc, generally increases from ˜480 to ˜1120 K with increasing A-site cation size (e.g., 0.977 Å for Lu3+ to 1.079 Å for Sm3+). An abnormally high susceptibility to ion beam damage was found for Gd2Ti2O7 (with the highest Tc of ˜1120 K). Factors influencing the response of titanate pyrochlores to ion irradiation-induced amorphization are discussed in terms of cation radius ratio, defect formation, and the tendency to undergo an order-disorder transition to the defect-fluorite structure. The resistance of the pyrochlore structure to ion beam-induced amorphization is not only affected by the relative sizes of the A- and B-site cations, but also the cation electronic configuration and the structural disorder. Pyrochlore compositions that have larger structural deviations from the ideal fluorite structure, as evidenced by the smaller 48f oxygen positional parameter, x, are more sensitive to ion beam-induced amorphization.

  15. Formation of hydroxylamine (NH2OH) in electron-irradiated ammonia-water ices.

    PubMed

    Zheng, Weijun; Kaiser, Ralf I

    2010-04-29

    We investigated chemical and physical processes in electron-irradiated ammonia-water ices at temperatures of 10 and 50 K. Chemically speaking, the formation of hydroxylamine (NH(2)OH) was observed in electron-irradiated ammonia-water ices. The synthesis of molecular hydrogen (H(2)), molecular nitrogen (N(2)), molecular oxygen (O(2)), hydrazine (N(2)H(4)), and hydrogen peroxide (H(2)O(2)), which was also monitored in previous irradiation of pure ammonia and water ices, was also evident. These newly formed species were trapped inside of the ices and were released into the gas phase during the warm-up phase of the sample after the irradiation. A quantitative analysis of the data showed that the production rates of the newly formed species at 10 K are higher compared to those at 50 K. Our studies also suggest that hydroxylamine is likely formed by the recombination of amino (NH(2)) with hydroxyl (OH) radicals inside of the ices. Considering the physical effects on the ice sampled during the irradiation, the experiments provided compelling evidence that the crystalline ammonia-water ice samples can be partially converted to amorphous ices during the electron irradiation; similar to the chemical processes, the irradiation-induced amorphization of the ices is faster at 10 K than that at 50 K--a finding which is similar to electron-irradiated crystalline water ices under identical conditions. However, the amorphization of water in water-ammonia ices was found to be faster than that in pure water ices at identical temperatures.

  16. Atomic-scale simulations of atomic and molecular mobility in models of interstellar ice

    NASA Astrophysics Data System (ADS)

    Andersson, Stefan

    The mobility of atoms and molecular radicals at ice-covered dust particles controls the surprisingly rich chemistry of circumstellar and interstellar environments, where a large number of different organic molecules have been observed. Both thermal and non-thermal processes, for instance caused by UV radiation, have been inferred to play important roles in this chemistry. A growing number of experimental studies support previously suggested mechanisms and add to the understanding of possible astrochemical processes. Simulations, of both experiments and astrophysical environments, aid in interpreting experiments and suggesting important mechanisms. Still, the exact mechanisms behind the mobility of species in interstellar ice are far from fully understood. We have performed calculations at the molecular level on the mobility of H atoms and OH radicals at water ice surfaces of varying morphology. Calculations of binding energies and diffusion barriers of H atoms at crystalline and amorphous ice surfaces show that the experimentally observed slower diffusion at amorphous ice is due to considerably stronger binding energies and higher diffusion barriers than at crystalline ice. These results are in excellent agreement with recent experiments. It was also found that quantum tunneling is important for H atom mobility below 10 K. The binding energies and diffusion barriers of OH radicals at crystalline ice have been studied using the ONIOM(QM:AMOEBA) approach. Results indicate that OH diffusion over crystalline ice, contrary to the case of H atoms, might be slower at crystalline ice than at amorphous ice, due to a higher surface density of stronger binding sites at crystalline ice. We have also performed molecular dynamics simulations of the photoexcitation of vapor-deposited water at a range of surface temperatures. These results support that the experimentally observed desorption of H atoms following UV excitation is best explained by release of H atoms from

  17. Tandem junction amorphous silicon solar cells

    DOEpatents

    Hanak, Joseph J.

    1981-01-01

    An amorphous silicon solar cell has an active body with two or a series of layers of hydrogenated amorphous silicon arranged in a tandem stacked configuration with one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon arranged in tandem configuration can have the same bandgap or differing bandgaps.

  18. Changes on the ice plain of Ice Stream B and Ross Ice Shelf

    NASA Technical Reports Server (NTRS)

    Shabtaie, Sion

    1993-01-01

    During the 1970's and 1980's, nearly 200 stations from which accurate, three dimensional position fixes have been obtained from TRANSIT satellites were occupied throughout the Ross Ice Shelf. We have transformed the elevations obtained by satellite altimetry to the same geodetic datum, and then applied a second transformation to reduce the geodetic heights to elevations above mean sea level using the GEM-10C geoidal height. On the IGY Ross Ice Shelf traverse between Oct. 1957 and Feb. 1958, an accurate method of barometric altimetry was used on a loop around the ice shelf that was directly tied to the sea at both ends of the travel route, thus providing absolute elevations. Comparisons of the two sets of data at 32 station pairs on floating ice show a mean difference of 0 +/- 1 m. The elevation data were also compared with theoretical values of elevations for a hydrostatically floating ice shelf. The mean difference between theoretical and measured values of elevations is -2 +/- 1 m.

  19. Scrambled Ice

    NASA Technical Reports Server (NTRS)

    1998-01-01

    This complex area on the side of Europa which faces away from Jupiter shows several types of features which are formed by disruptions of Europa's icy crust. North is to the top of the image, taken by NASA's Galileo spacecraft, and the Sun illuminates the surface from the left. The prominent wide, dark bands are up to 20 kilometers (12 miles) wide and over 50 kilometers (30 miles) long. They are believed to have formed when Europa's icy crust fractured, separated and filled in with darker, 'dirtier' ice or slush from below. A relatively rare type of feature on Europa is the 15-kilometer-diameter (9.3-mile) impact crater in the lower left corner. The small number of impact craters on Europa's surface is an indication of its relatively young age. A region of chaotic terrain south of this impact crater contains crustal plates which have broken apart and rafted into new positions. Some of these 'ice rafts' are nearly 1 kilometer (about half a mile) across. Other regions of chaotic terrain are visible and indicate heating and disruption of Europa's icy crust from below. The youngest features in this scene are the long, narrow cracks in the ice which cut across all other features. One of these cracks is about 30 kilometers (18 miles) to the right of the impact crater and extends for hundreds of miles from the top to the bottom of the image.

    The image, centered near 23 degrees south latitude and 179 degrees longitude, covers an area about 240 by 215 kilometers (150 by 130 miles) across. The finest details that can be discerned in this picture are about 460 meters (500 yards) across. The image was taken as Galileo flew by Europa on March 29, 1998. The image was taken by the onboard solid state imaging system camera from an altitude of 23,000 kilometers (14,000 miles).

    The Jet Propulsion Laboratory, Pasadena, CA manages the Galileo mission for NASA's Office of Space Science, Washington, DC. JPL is an operating division of California Institute of Technology (Caltech

  20. 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.

  1. Milling induces disorder in crystalline griseofulvin and order in its amorphous counterpart

    SciTech Connect

    Otte, Andrew; Zhang, Yan; Carvajal, M. Teresa; Pinal, Rodolfo

    2012-04-02

    This study investigates two apparently similar thermal signatures, shaped as bimodal exotherms, observed when either the crystalline or the amorphous from of the drug are subjected to milling. Crystalline griseofulvin was cryomilled and the (quenched-melt) amorphous form was subjected to either cryomilling or grinding. The thermal and surface properties of the resulting samples were analyzed using differential scanning calorimetry (DSC) and surface energy analysis. After milling, both the crystalline and the amorphous material revealed visually similar bimodal exothermic events when the heating rate was 20 C min{sup -1}. Under different heating rates, the pair of DSC peaks for the bimodal exotherm of each material behaved entirely different from each other. The two peaks of the bimodal event, as well as the glass transition, can be kinetically resolved for the ground amorphous form using standard mode DSC. In contrast, similar analysis was unable to resolve the bimodal exotherm or a glass transition in the case of the cryomilled crystals. Furthermore, cryomilled crystals do not exhibit a glass transition even when analyzed using modulated DSC. Synchrotron sourced X-ray analysis revealed that grinding the amorphous material results in the nucleation and growth of the crystalline form. Milling thus induces disorder in the crystals of griseofulvin but induces order in the amorphous form of the drug. The surface of the two milled systems consistently exhibited different energetics under a wide range of relative humidity conditions. These findings suggest that cryomilling induces both bulk and surface disorder, specifically, a certain level of dislocations on the crystal. In contrast, grinding the amorphous material lowers the activation energy for crystal formation, inducing nuclei formation and growth throughout the amorphous matrix.

  2. Physiological and ecological significance of biological ice nucleators.

    PubMed Central

    Lundheim, Rolv

    2002-01-01

    When a pure water sample is cooled it can remain in the liquid state at temperatures well below its melting point (0 degrees C). The initiation of the transition from the liquid state to ice is called nucleation. Substances that facilitate this transition so that it takes place at a relatively high sub-zero temperature are called ice nucleators. Many living organisms produce ice nucleators. In some cases, plausible reasons for their production have been suggested. In bacteria, they could induce frost damage to their hosts, giving the bacteria access to nutrients. In freeze-tolerant animals, it has been suggested that ice nucleators help to control the ice formation so that it is tolerable to the animal. Such ice nucleators can be called adaptive ice nucleators. There are, however, also examples of ice nucleators in living organisms where the adaptive value is difficult to understand. These ice nucleators might be structures with functions other than facilitating ice formation. These structures might be called incidental ice nucleators. PMID:12171657

  3. Intermediate range chemical ordering in amorphous and liquid water, Si, and Ge

    SciTech Connect

    Benmore, C.J.; Hart, R.T.; Mei, Q.; Price, D.L.; Yarger, J.; Tulk, C.A.; Klug, D.D.

    2005-10-01

    Neutron and x-ray diffraction data for low, high, and very high density amorphous ice and liquid water, silicon, and germanium have been compared in terms of the first sharp diffraction peak in the structure factor and at the radial distribution function level. The low and high density forms of H{sub 2}O, Si, and Ge are shown to have very similar structures if the contributions from the hydrogen correlations in water are neglected. The very high density amorphous ice form is shown to be structurally analogous to recently reported high pressure liquid forms of Si and Ge, although there are slight differences in the way interstitial atoms or molecules are pushed into the first coordination shell.

  4. High pressure ices

    PubMed Central

    Hermann, Andreas; Ashcroft, N. W.; Hoffmann, Roald

    2012-01-01

    H2O will be more resistant to metallization than previously thought. From computational evolutionary structure searches, we find a sequence of new stable and meta-stable structures for the ground state of ice in the 1–5 TPa (10 to 50 Mbar) regime, in the static approximation. The previously proposed Pbcm structure is superseded by a Pmc21 phase at p = 930 GPa, followed by a predicted transition to a P21 crystal structure at p = 1.3 TPa. This phase, featuring higher coordination at O and H, is stable over a wide pressure range, reaching 4.8 TPa. We analyze carefully the geometrical changes in the calculated structures, especially the buckling at the H in O-H-O motifs. All structures are insulating—chemistry burns a deep and (with pressure increase) lasting hole in the density of states near the highest occupied electronic levels of what might be component metallic lattices. Metallization of ice in our calculations occurs only near 4.8 TPa, where the metallic C2/m phase becomes most stable. In this regime, zero-point energies much larger than typical enthalpy differences suggest possible melting of the H sublattice, or even the entire crystal. PMID:22207625

  5. Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

    SciTech Connect

    Xiao, Haiyan Y.; Weber, William J.; Zhang, Yanwen; Zu, X. T.; Li, Sean

    2015-02-09

    In this study, the response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations.

  6. Transpolar observations of the morphological properties of Arctic sea ice

    NASA Astrophysics Data System (ADS)

    Perovich, Donald K.; Grenfell, Thomas C.; Light, Bonnie; Elder, Bruce C.; Harbeck, Jeremy; Polashenski, Christopher; Tucker, Walter B.; Stelmach, Casey

    2009-01-01

    During the 5 August to 30 September 2005 Healy Oden Trans-Arctic Expedition a trans-Arctic survey of the physical properties of the polar ice pack was conducted. The observational program consisted of four broad classes of snow and ice characterization activities: observations made while the ship was in transit, ice station measurements, helicopter survey flights, and the deployment of autonomous ice mass balance buoys. Ice conditions, including ice thicknesses, classes, and concentrations of primary, secondary, and tertiary categories were reported at 2-hour intervals. Pond fractions were large early in the cruise at the southern edge of the ice pack, reaching peak values of 0.5 and averaging 0.25. Ice concentrations ranged from 0.8 to 1.0 north of 79°N, save for an area between 88°30'N and 89°30'N, where polynyas and thin ice were observed. Surveys of snow depth, ice thickness, and ice properties were conducted at ice stations. Thickness observations suggest a general latitudinal trend of increasing ice thickness moving northward, with considerable variability from floe to floe and within a single floe. Average floe thicknesses varied from 1.0 to >2.8 m, and the standard deviation of thickness on an individual floe was as large as 1 m. Ice crystallography showed a large amount of granular ice. The average optical-equivalent soot content was 4 ng C g-1 for new snow, 8 ng C g-1 for the surface granular layer of multiyear ice, and 18 ng C g-1 for the interior of multiyear ice, indicating a tendency of the particulates to concentrate at the surface with melting.

  7. Icing: Accretion, Detection, Protection

    NASA Technical Reports Server (NTRS)

    Reinmann, John J.

    1994-01-01

    The global aircraft industry and its regulatory agencies are currently involved in three major icing efforts: ground icing; advanced technologies for in-flight icing; and tailplane icing. These three major icing topics correspondingly support the three major segments of any aircraft flight profile: takeoff; cruise and hold; and approach and land. This lecture addressess these three topics in the same sequence as they appear in flight, starting with ground deicing, followed by advanced technologies for in-flight ice protection, and ending with tailplane icing.

  8. Electrical and optical properties of sputtered amorphous vanadium oxide thin films

    SciTech Connect

    Podraza, N. J.; Gauntt, B. D.; Motyka, M. A.; Horn, M. W.; Dickey, E. C.

    2012-04-01

    Amorphous vanadium oxide (VO{sub x}) is a component found in composite nanocrystalline VO{sub x} thin films. These types of composite films are used as thermistors in pulsed biased uncooled infrared imaging devices when containing face centered cubic vanadium monoxide phase crystallites, and substantial fractions of amorphous material in the composite are necessary to optimize device electrical properties. Similarly, optoelectronic devices exploiting the metal-to-semiconductor transition contain the room-temperature monoclinic or high-temperature (>68 deg. C) rutile vanadium dioxide phase. Thin films of VO{sub x} exhibiting the metal-to-semiconductor transition are typically polycrystalline or nanocrystalline, implying that significant amounts of disordered, amorphous material is present at grain boundaries or surrounding the crystallites and can impact the overall optical or electronic properties of the film. The performance of thin film material for either application depends on both the nature of the crystalline and amorphous components, and in this work we seek to isolate and study amorphous VO{sub x}. VO{sub x} thin films were deposited by pulsed dc reactive magnetron sputtering to produce amorphous materials with oxygen contents {>=}2, which were characterized electrically by temperature dependent current-voltage measurements and optically characterized by spectroscopic ellipsometry. Film resistivity, thermal activation energy, and complex dielectric function spectra from 0.75 to 6.0 eV were used to identify the impact of microstructural variations including composition and density.

  9. West Antarctic Ice Sheet formed earlier than thought

    NASA Astrophysics Data System (ADS)

    Balcerak, Ernie

    2013-10-01

    About 34 million years ago, Earth transitioned from a warm "greenhouse" climate to a cold "icehouse" climate, marking the transition between the Eocene and Oligocene epochs. This transition has been associated with the formation of a large ice sheet on Antarctica.

  10. Planetary ice and planetary oceans

    NASA Astrophysics Data System (ADS)

    Stevenson, D. J.

    2003-04-01

    Water is the most abundant condensate in the universe and the most common constituent of many bodies in the outer solar system. There are other cryogenic condensibles of interest, notably ammonia, methane, carbon monoxide, carbon dioxide, and nitrogen. An understanding of the physical and chemical properties of these ices is needed to interpret the nature of these bodies as we see them. There are three important aspects: (i) Thermochemistry and phase equilibria (melting, sublimation): We need to understand which constituents are likely, whether they can condense as planetary bodies form, and their melting curves (including multicomponent systems). Recent evidence for oceans in the satellites Europa, Ganymede and Callisto will be discussed and understood in light of expected phase diagrams, especially the unusual (negative) dependence of H2O melting point on pressure. Even Triton and Pluto may have oceans because of the melting point depression arising from significant amounts of ammonia in the ice. (ii) Equation of state including solid-solid phase transitions. In order to interpret the expected composition deep within a body such as Ganymede or Titan, we need to know which phases are present. An example of recent interest is the possible presence of high pressure modifications of methane clathrate, which may influence the outgassing ("volcanism") and hydrocarbon "aquifer" of Titan. (iii) Rheological properties of ice. We need to know how ice flows and fractures. Ice viscosity is a central parameter in estimating internal thermal structure since it relates temperature to heat flow. Moreover, the interpretation of surface features depends on knowing ice deformation properties. This is the least well understood aspect. Examples of morphologies exhibited in Galileo images of Europa and Ganymede will be discussed. The possible exciting new results for the upcoming Cassini mission at Titan will also be discussed.

  11. Ice phases under ambient and high pressure: Insights from density functional theory

    NASA Astrophysics Data System (ADS)

    Fang, Yuan; Xiao, Bing; Tao, Jianmin; Sun, Jianwei; Perdew, John P.

    2013-06-01

    Water is common and plays a crucial role in biological, chemical, and physical processes, but its crystalline or ice state has a complicated structure. In this work, we study the lattice mismatch challenge for ice nucleation on silver iodide, the sublimation energy for different ice phases, and the structural phase-transition pressures of ice, with various density functionals. Our calculations show that the recently developed meta-generalized gradient approximation made simple (MGGA_MS) yields a lattice mismatch (3%) of hexagonal ice (ice Ih) with β-AgI in good agreement with experiment (2%), significantly better than the Perdew-Burke-Ernzerhof (PBE) GGA mismatch (6%). MGGA_MS is a computationally efficient semilocal functional that incorporates intermediate-range van der Waals (vdW) interaction, which, overall, performs well for ice and may be expected to improve upon PBE for liquid water. While MGGA_MS predicts the most realistic volumes and volume changes in the phase transitions of ice Ih to trigonal ice (ice II) and tetragonal ice (ice VIII), a more accurate description of some other properties of the higher-pressure phases (ice II and ice VIII) is provided by some functionals that include long-range vdW corrections (e.g., revised Tao-Perdew-Staroverov-Scuseria+vdW for sublimation energy and optB88-vdW for transition pressure).

  12. Atomic Structure of an Amorphous/Crystal Interface

    SciTech Connect

    Shibata, Naoya; Painter, Gayle S; Becher, Paul F; Pennycook, Stephen J

    2006-01-01

    In this study, the authors report atomic-resolution images that illustrate the transition from a crystalline Si{sub 3}N{sub 4} grain across the interface into an amorphous Lu-Si-Mg-N-O glassy phase. The interface is not atomically abrupt, but is comprised of sub-nanometer-scale ordered regions that resemble a LuN-like structure. These ordered clusters bind to the prismatic surface of the Si{sub 3}N{sub 4} grains at specific low energy positions for Lu adsorption as predicted by first-principles calculations. The ordered regions are filamentary in nature, extending for at least two atomic layers into the amorphous pockets at multigrain junctions before disappearing.

  13. Breakdown of nonlinear elasticity in amorphous solids at finite temperatures

    NASA Astrophysics Data System (ADS)

    Procaccia, Itamar; Rainone, Corrado; Shor, Carmel A. B. Z.; Singh, Murari

    2016-06-01

    It is known [H. G. E. Hentschel et al., Phys. Rev. E 83, 061101 (2011), 10.1103/PhysRevE.83.061101] that amorphous solids at zero temperature do not possess a nonlinear elasticity theory: besides the shear modulus, which exists, none of the higher order coefficients exist in the thermodynamic limit. Here we show that the same phenomenon persists up to temperatures comparable to that of the glass transition. The zero-temperature mechanism due to the prevalence of dangerous plastic modes of the Hessian matrix is replaced by anomalous stress fluctuations that lead to the divergence of the variances of the higher order elastic coefficients. The conclusion is that in amorphous solids elasticity can never be decoupled from plasticity: the nonlinear response is very substantially plastic.

  14. Protocol-dependent shear modulus of amorphous solids

    NASA Astrophysics Data System (ADS)

    Nakayama, Daijyu; Yoshino, Hajime; Zamponi, Francesco

    2016-10-01

    We investigate the linear elastic response of amorphous solids to a shear strain at zero temperature. We find that the response is characterized by at least two distinct shear moduli. The first one, {μ\\text{ZFC}} , is associated with the linear response of a single energy minimum. The second, {μ\\text{FC}} , is related to sampling, through plastic events, an ensemble of distinct energy minima. We provide examples of protocols that allow one to measure both shear moduli. In agreement with a theoretical prediction based on the exact solution in infinite spatial dimensions, the ratio {μ\\text{FC}}/{μ\\text{ZFC}} is found to vanish proportionally to the square root of pressure at the jamming transition. Our results establish that amorphous solids are characterized by a rugged energy landscape, which has a deep impact on their elastic response, as suggested by the infinite-dimensional solution.

  15. Polymeric Amorphous Solid Dispersions: A Review of Amorphization, Crystallization, Stabilization, Solid-State Characterization, and Aqueous Solubilization of Biopharmaceutical Classification System Class II Drugs.

    PubMed

    Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

    2016-09-01

    Poor water solubility of many drugs has emerged as one of the major challenges in the pharmaceutical world. Polymer-based amorphous solid dispersions have been considered as the major advancement in overcoming limited aqueous solubility and oral absorption issues. The principle drawback of this approach is that they can lack necessary stability and revert to the crystalline form on storage. Significant upfront development is, therefore, required to generate stable amorphous formulations. A thorough understanding of the processes occurring at a molecular level is imperative for the rational design of amorphous solid dispersion products. This review attempts to address the critical molecular and thermodynamic aspects governing the physicochemical properties of such systems. A brief introduction to Biopharmaceutical Classification System, solid dispersions, glass transition, and solubility advantage of amorphous drugs is provided. The objective of this review is to weigh the current understanding of solid dispersion chemistry and to critically review the theoretical, technical, and molecular aspects of solid dispersions (amorphization and crystallization) and potential advantage of polymers (stabilization and solubilization) as inert, hydrophilic, pharmaceutical carrier matrices. In addition, different preformulation tools for the rational selection of polymers, state-of-the-art techniques for preparation and characterization of polymeric amorphous solid dispersions, and drug supersaturation in gastric media are also discussed.

  16. Uranium incorporation into amorphous silica.

    PubMed

    Massey, Michael S; Lezama-Pacheco, Juan S; Nelson, Joey M; Fendorf, Scott; Maher, Kate

    2014-01-01

    High concentrations of uranium are commonly observed in naturally occurring amorphous silica (including opal) deposits, suggesting that incorporation of U into amorphous silica may represent a natural attenuation mechanism and promising strategy for U remediation. However, the stability of uranium in opaline silicates, determined in part by the binding mechanism for U, is an important factor in its long-term fate. U may bind directly to the opaline silicate matrix, or to materials such as iron (hydr)oxides that are subsequently occluded within the opal. Here, we examine the coordination environment of U within opaline silica to elucidate incorporation mechanisms. Precipitates (with and without ferrihydrite inclusions) were synthesized from U-bearing sodium metasilicate solutions, buffered at pH ∼ 5.6. Natural and synthetic solids were analyzed with X-ray absorption spectroscopy and a suite of other techniques. In synthetic amorphous silica, U was coordinated by silicate in a double corner-sharing coordination geometry (Si at ∼ 3.8-3.9 Å) and a small amount of uranyl and silicate in a bidentate, mononuclear (edge-sharing) coordination (Si at ∼ 3.1-3.2 Å, U at ∼ 3.8-3.9 Å). In iron-bearing synthetic solids, U was adsorbed to iron (hydr)oxide, but the coordination environment also contained silicate in both edge-sharing and corner-sharing coordination. Uranium local coordination in synthetic solids is similar to that of natural U-bearing opals that retain U for millions of years. The stability and extent of U incorporation into opaline and amorphous silica represents a long-term repository for U that may provide an alternative strategy for remediation of U contamination. PMID:24984107

  17. Stability study of amorphous valdecoxib.

    PubMed

    Ambike, Anshuman A; Mahadik, K R; Paradkar, Anant

    2004-09-10

    Formulation of poorly water-soluble drugs in the most stable dosage form for oral delivery perhaps presents the greatest challenge to pharmaceutical industry. Physical transformation of drug substance into its more soluble but metastable amorphous form is one of the approaches for improving dissolution rate of such drugs. The present study utilizes technique of spray drying for preparation of solid dispersions (SDs) and includes stability study of the same. Valdecoxib (VLD), a prototype of poorly water-soluble drugs, has been the drug of choice. The hydrophilic carriers selected were polyvinylpyrrolidone K30 (PVP) and hydroxypropylcellulose (HPC). SDs and pure VLD in the form of spray dried powder (SDVLD) in comparison with pure drug and corresponding physical mixtures (PMs) were initially characterized and then subjected to stability testing at ambient temperature and relative humidity up to 3 months. During initial characterization, increase in saturation solubility and dissolution rate was observed in all samples. DSC and XRPD studies of SDVLD and SDs suggested generation of amorphous form of drug. IR spectroscopy revealed presence of hydrogen bonding in SDs. During stability testing, there was gradual decrease in saturation solubility and dissolution rate of SDs, over the period of 3 months. While, saturation solubility of SDVLD dropped drastically within 15 days and was almost comparable with pure VLD. SD PVP retained the amorphous form of drug throughout stability period, whereas SD HPC and SDVLD presented incidence of crystallinity after 1 month and 15 days, respectively. This was justified by enthalpy relaxation studies in which, amorphous VLD showed considerable relaxation of enthalpy at Tg, while it was totally suppressed in SD PVP and partly in SD HPC. The study thus definitely reveals tremendous potential of solid dispersions of valdecoxib with PVP, from stability point of view.

  18. Pressure-induced amorphizations of silica analogues: A probe of the relationship between order and disorder

    SciTech Connect

    Hammack, W.S.

    1993-02-01

    Purpose of these of high pressure investigations is to determine the relationship between order and disorder in amorphous materials using high pressure techniques were used. High pressure x-ray diffraction, electron transmission microscopy, and Raman scattering. Cornell High Energy Synchrotron Source (CHESS) at Ithaca was used to measure x-ray diffraction patterns using Energy-Dispersive X-ray Diffraction. It was shown that the structural ordering in pressure-amorphized solids can be described as defects in curved-space. High-resolution transmissions electron microscopy showed that pressure-amorphized alpha-quartz lacks periodicity at the atomic level. Study of a silicate mineral shows that pressure-induced amorphizations occur because of an impeded phase transition.

  19. 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.

  20. THE COMPOSITION OF INTERSTELLAR GRAINS TOWARD ζ OPHIUCHI: CONSTRAINING THE ELEMENTAL BUDGET NEAR THE DIFFUSE-DENSE CLOUD TRANSITION

    SciTech Connect

    Poteet, Charles A.; Whittet, Douglas C. B.; Draine, Bruce T.

    2015-03-10

    We investigate the composition of interstellar grains along the line of sight toward ζ Ophiuchi, a well-studied environment near the diffuse-dense cloud transition. A spectral decomposition analysis of the solid-state absorbers is performed using archival spectroscopic observations from the Spitzer Space Telescope and Infrared Space Observatory. We find strong evidence for the presence of sub-micron-sized amorphous silicate grains, principally comprised of olivine-like composition, with no convincing evidence of H{sub 2}O ice mantles. However, tentative evidence for thick H{sub 2}O ice mantles on large (a ≈ 2.8 μm) grains is presented. Solid-state abundances of elemental Mg, Si, Fe, and O are inferred from our analysis and compared to standard reference abundances. We find that nearly all of the Mg and Si atoms along the line of sight reside in amorphous silicate grains, while a substantial fraction of the elemental Fe resides in compounds other than silicates. Moreover, we find that the total abundance of elemental O is largely inconsistent with the adopted reference abundances, indicating that as much as ∼156 ppm of interstellar O is missing along the line of sight. After taking into account additional limits on the abundance of elemental O in other O-bearing solids, we conclude that any missing reservoir of elemental O must reside on large grains that are nearly opaque to infrared radiation.

  1. Arctic ice islands

    SciTech Connect

    Sackinger, W.M.; Jeffries, M.O.; Lu, M.C.; Li, F.C.

    1988-01-01

    The development of offshore oil and gas resources in the Arctic waters of Alaska requires offshore structures which successfully resist the lateral forces due to moving, drifting ice. Ice islands are floating, a tabular icebergs, up to 60 meters thick, of solid ice throughout their thickness. The ice islands are thus regarded as the strongest ice features in the Arctic; fixed offshore structures which can directly withstand the impact of ice islands are possible but in some locations may be so expensive as to make oilfield development uneconomic. The resolution of the ice island problem requires two research steps: (1) calculation of the probability of interaction between an ice island and an offshore structure in a given region; and (2) if the probability if sufficiently large, then the study of possible interactions between ice island and structure, to discover mitigative measures to deal with the moving ice island. The ice island research conducted during the 1983-1988 interval, which is summarized in this report, was concerned with the first step. Monte Carlo simulations of ice island generation and movement suggest that ice island lifetimes range from 0 to 70 years, and that 85% of the lifetimes are less then 35 years. The simulation shows a mean value of 18 ice islands present at any time in the Arctic Ocean, with a 90% probability of less than 30 ice islands. At this time, approximately 34 ice islands are known, from observations, to exist in the Arctic Ocean, not including the 10-meter thick class of ice islands. Return interval plots from the simulation show that coastal zones of the Beaufort and Chukchi Seas, already leased for oil development, have ice island recurrences of 10 to 100 years. This implies that the ice island hazard must be considered thoroughly, and appropriate safety measures adopted, when offshore oil production plans are formulated for the Alaskan Arctic offshore. 132 refs., 161 figs., 17 tabs.

  2. Ice Nucleation from Ship Emissions

    NASA Astrophysics Data System (ADS)

    Thomson, E. S.; Weber, D.; Tuomi, J.; Pettersson, J.; Bingemer, H. G.

    2015-12-01

    Atmospheric ice particles play a significant role in many atmospheric processes and are central to the role of clouds in determining the global radiative balance. Atmospheric ice originates when Ice Nucleating Particles (INP) lower the free energy barrier to phase transformation. The Earth's polar regions are well isolated from the middle and lower latitudes and thus have limited access to INP, and therefore small changes in terms of regional sources or large scale transport of particulate may have significant impacts on polar ice cloud formation. Here we describe field measurements of INP collected in the Port of Gothenburg, Gothenburg, Sweden. The port is the largest Scandinavian seaport and thus has heavy and diverse ocean vessel traffic. Unique to this study was the ability to isolate the INP contribution directly from the ship traffic by utilizing a sampling method that nearly simultaneously captured transiting ship plumes and the background aerosol. A small but potentially significant increase in IN from marine vessels was observed over two consecutive years. The results have implications for Arctic and global climate in the context of growing global commerce and trans-polar transport.

  3. Effects of Ice Accretion on Aircraft Aerodynamics

    NASA Technical Reports Server (NTRS)

    Bragg, Michael B.

    1998-01-01

    The primary objective of this research was to support the development of a new ice accretion model by improving our physical understanding of the ice accretion process through experimental measurements. The focus was on the effect of the initial ice roughness (smooth/rough boundary) on the accretion process. This includes understanding the boundary-layer development over the roughness and especially its effect on the heat transfer which is fundamental to the ice accretion process. The research focused on acquiring the experimental data needed to formulate a new ice accretion physical model. Research was conducted to analyze boundary-layer data taken on a NACA 0012 airfoil with roughness to simulate the smooth/rough boundary. The effect of isolated roughness on boundary-layer transition was studied experimentally to determine if the classical critical roughness Reynolds number criteria could be applied to transition in the airfoil leading-edge area. The effect of simulated smooth/rough boundary roughness on convective heat transfer was studied to complete the study. During the course of this research the effect of free-stream wind tunnel turbulence on the boundary layer was measured. Since this quantity was not well known, research to accurately measure the wind tunnel turbulence in an icing cloud was undertaken. Preliminary results were attained and the final data were acquired, reduced and presented under a subsequent grant.

  4. Sea Ice Ecosystems

    NASA Astrophysics Data System (ADS)

    Arrigo, Kevin R.

    2014-01-01

    Polar sea ice is one of the largest ecosystems on Earth. The liquid brine fraction of the ice matrix is home to a diverse array of organisms, ranging from tiny archaea to larger fish and invertebrates. These organisms can tolerate high brine salinity and low temperature but do best when conditions are milder. Thriving ice algal communities, generally dominated by diatoms, live at the ice/water interface and in recently flooded surface and interior layers, especially during spring, when temperatures begin to rise. Although protists dominate the sea ice biomass, heterotrophic bacteria are also abundant. The sea ice ecosystem provides food for a host of animals, with crustaceans being the most conspicuous. Uneaten organic matter from the ice sinks through the water column and feeds benthic ecosystems. As sea ice extent declines, ice algae likely contribute a shrinking fraction of the total amount of organic matter produced in polar waters.

  5. Stochastic ice stream dynamics

    NASA Astrophysics Data System (ADS)

    Mantelli, Elisa; Bertagni, Matteo Bernard; Ridolfi, Luca

    2016-08-01

    Ice streams are narrow corridors of fast-flowing ice that constitute the arterial drainage network of ice sheets. Therefore, changes in ice stream flow are key to understanding paleoclimate, sea level changes, and rapid disintegration of ice sheets during deglaciation. The dynamics of ice flow are tightly coupled to the climate system through atmospheric temperature and snow recharge, which are known exhibit stochastic variability. Here we focus on the interplay between stochastic climate forcing and ice stream temporal dynamics. Our work demonstrates that realistic climate fluctuations are able to (i) induce the coexistence of dynamic behaviors that would be incompatible in a purely deterministic system and (ii) drive ice stream flow away from the regime expected in a steady climate. We conclude that environmental noise appears to be crucial to interpreting the past behavior of ice sheets, as well as to predicting their future evolution.

  6. Sea ice ecosystems.

    PubMed

    Arrigo, Kevin R

    2014-01-01

    Polar sea ice is one of the largest ecosystems on Earth. The liquid brine fraction of the ice matrix is home to a diverse array of organisms, ranging from tiny archaea to larger fish and invertebrates. These organisms can tolerate high brine salinity and low temperature but do best when conditions are milder. Thriving ice algal communities, generally dominated by diatoms, live at the ice/water interface and in recently flooded surface and interior layers, especially during spring, when temperatures begin to rise. Although protists dominate the sea ice biomass, heterotrophic bacteria are also abundant. The sea ice ecosystem provides food for a host of animals, with crustaceans being the most conspicuous. Uneaten organic matter from the ice sinks through the water column and feeds benthic ecosystems. As sea ice extent declines, ice algae likely contribute a shrinking fraction of the total amount of organic matter produced in polar waters.

  7. Stochastic ice stream dynamics.

    PubMed

    Mantelli, Elisa; Bertagni, Matteo Bernard; Ridolfi, Luca

    2016-08-01

    Ice streams are narrow corridors of fast-flowing ice that constitute the arterial drainage network of ice sheets. Therefore, changes in ice stream flow are key to understanding paleoclimate, sea level changes, and rapid disintegration of ice sheets during deglaciation. The dynamics of ice flow are tightly coupled to the climate system through atmospheric temperature and snow recharge, which are known exhibit stochastic variability. Here we focus on the interplay between stochastic climate forcing and ice stream temporal dynamics. Our work demonstrates that realistic climate fluctuations are able to (i) induce the coexistence of dynamic behaviors that would be incompatible in a purely deterministic system and (ii) drive ice stream flow away from the regime expected in a steady climate. We conclude that environmental noise appears to be crucial to interpreting the past behavior of ice sheets, as well as to predicting their future evolution. PMID:27457960

  8. Top Sounder Ice Penetration

    NASA Astrophysics Data System (ADS)

    Porter, D. L.; Goemmer, S. A.; Sweeney, J. H.

    2014-12-01

    Ice draft measurements are made as part of normal operations for all US Navy submarines operating in the Arctic Ocean. The submarine ice draft data are unique in providing high resolution measurements over long transects of the ice covered ocean. The data has been used to document a multidecadal drop in ice thickness, and for validating and improving numerical sea-ice models. A submarine upward-looking sonar draft measurement is made by a sonar transducer mounted in the sail or deck of the submarine. An acoustic beam is transmitted upward through the water column, reflecting off the bottom of the sea ice and returning to the transducer. Ice thickness is estimated as the difference between the ship's depth (measured by pressure) and the acoustic range to the bottom of the ice estimated from the travel time of the sonar pulse. Digital recording systems can provide the return off the water-ice interface as well as returns that have penetrated the ice. Typically, only the first return from the ice hull is analyzed. Information regarding ice flow interstitial layers provides ice age information and may possibly be derived with the entire return signal. The approach being investigated is similar to that used in measuring bottom sediment layers and will involve measuring the echo level from the first interface, solving the reflection loss from that transmission, and employing reflection loss versus impedance mismatch to ascertain ice structure information.

  9. Phytoplankton spring bloom beneath heavily snow-covered arctic sea ice during the N-ICE2015 cruise

    NASA Astrophysics Data System (ADS)

    Assmy, Philipp; Fernández-Méndez, Mar; Olsen, Lasse M.; Kauko, Hanna; Duarte, Pedro; Mundy, Christopher J.; Hop, Haakon; Fransson, Agneta; Chierici, Melissa; Gerland, Sebastian; Granskog, Mats A.; Hudson, Stephen R.; Roesel, Anja; Meyer, Amelie; Hughes, Nick; Steen, Harald

    2016-04-01

    The arctic icescape is rapidly transforming from a thick multi-year ice cover to a thinner and largely seasonal first-year ice cover with significant consequences for Arctic primary production. Recent studies have reported extensive phytoplankton blooms beneath ponded sea ice during summer, indicating that satellite-based arctic net primary production estimates may be significantly underestimated. We studied phytoplankton seasonal dynamics under changing sea-ice and snow conditions in the drifting pack-ice north of Svalbard from 11 January to 24 June 2015 during the Norwegian Young Sea ICE cruise (N-ICE2015). N-ICE2015 provided a unique time-series of under-ice bloom dynamics during the winter-spring transition in the high Arctic pack-ice ecosystem. Phytoplankton productivity stayed low throughout winter and early spring. By late May a large under-ice bloom (>300 mg Chl a m-2) dominated by Phaeocystis pouchetii developed over the Yermak plateau underneath 1.1 - 1.3 m thick sea ice and 0.3 - 0.5 m thick snow cover. The circulation characteristics over the plateau indicate that the bloom developed in situ and was not advected. The high lead activity, characteristic for the area, apparently provided enough open or thin ice covered area for sufficient light to penetrate into the underlying water column and initiate and sustain the bloom, despite the thick snow cover. Our observation of a spring under-ice phytoplankton bloom extends the spatial and temporal scale of under-ice blooms and indicates that these phenomena might become increasingly important in the future Arctic under changing sea-ice but also snow dynamics.

  10. Ross Ice Shelf, Antarctic Ice and Clouds

    NASA Technical Reports Server (NTRS)

    1991-01-01

    In this view of Antarctic ice and clouds, (56.5S, 152.0W), the Ross Ice Shelf of Antarctica is almost totally clear, showing stress cracks in the ice surface caused by wind and tidal drift. Clouds on the eastern edge of the picture are associated with an Antarctic cyclone. Winds stirred up these storms have been known to reach hurricane force.

  11. Metastable Nitric Acid Trihydrate in Ice Clouds

    PubMed Central

    Weiss, Fabian; Kubel, Frank; Gálvez, Óscar; Hoelzel, Markus; Parker, Stewart F.; Baloh, Philipp; Iannarelli, Riccardo; Rossi, Michel J.

    2016-01-01

    Abstract The composition of high‐altitude ice clouds is still a matter of intense discussion. The constituents in question are ice and nitric acid hydrates, but the exact phase composition of clouds and its formation mechanisms are still unknown. In this work, conclusive evidence for a long‐predicted phase, alpha‐nitric acid trihydrate (alpha‐NAT), is presented. This phase was characterized by a combination of X‐ray and neutron diffraction experiments, allowing a convincing structure solution. Furthermore, vibrational spectra (infrared and inelastic neutron scattering) were recorded and compared with theoretical calculations. A strong interaction between water ice and alpha‐NAT was found, which explains the experimental spectra and the phase‐transition kinetics. On the basis of these results, we propose a new three‐step mechanism for NAT formation in high‐altitude ice clouds. PMID:26879259

  12. Metastable Nitric Acid Trihydrate in Ice Clouds.

    PubMed

    Weiss, Fabian; Kubel, Frank; Gálvez, Óscar; Hoelzel, Markus; Parker, Stewart F; Baloh, Philipp; Iannarelli, Riccardo; Rossi, Michel J; Grothe, Hinrich

    2016-03-01

    The composition of high-altitude ice clouds is still a matter of intense discussion. The constituents in question are ice and nitric acid hydrates, but the exact phase composition of clouds and its formation mechanisms are still unknown. In this work, conclusive evidence for a long-predicted phase, alpha-nitric acid trihydrate (alpha-NAT), is presented. This phase was characterized by a combination of X-ray and neutron diffraction experiments, allowing a convincing structure solution. Furthermore, vibrational spectra (infrared and inelastic neutron scattering) were recorded and compared with theoretical calculations. A strong interaction between water ice and alpha-NAT was found, which explains the experimental spectra and the phase-transition kinetics. On the basis of these results, we propose a new three-step mechanism for NAT formation in high-altitude ice clouds.

  13. Metastable Nitric Acid Trihydrate in Ice Clouds.

    PubMed

    Weiss, Fabian; Kubel, Frank; Gálvez, Óscar; Hoelzel, Markus; Parker, Stewart F; Baloh, Philipp; Iannarelli, Riccardo; Rossi, Michel J; Grothe, Hinrich

    2016-03-01

    The composition of high-altitude ice clouds is still a matter of intense discussion. The constituents in question are ice and nitric acid hydrates, but the exact phase composition of clouds and its formation mechanisms are still unknown. In this work, conclusive evidence for a long-predicted phase, alpha-nitric acid trihydrate (alpha-NAT), is presented. This phase was characterized by a combination of X-ray and neutron diffraction experiments, allowing a convincing structure solution. Furthermore, vibrational spectra (infrared and inelastic neutron scattering) were recorded and compared with theoretical calculations. A strong interaction between water ice and alpha-NAT was found, which explains the experimental spectra and the phase-transition kinetics. On the basis of these results, we propose a new three-step mechanism for NAT formation in high-altitude ice clouds. PMID:26879259

  14. National Ice Center Visiting Scientist Program

    NASA Technical Reports Server (NTRS)

    Austin, Meg

    2001-01-01

    The objectives of the work done by Dr. Kim Partington were to manage NASA's polar research program, including its strategic direction, research funding and interagency and international collaborations. The objectives of the UCAR Visiting Scientist Program at the National Ice Center (NIC) are to: (1) Manage a visiting scientist program for the NIC Science Center in support of the mission of the NIC; (2) Provide a pool of researchers who will share expertise with the NIC and the science community; (3) Facilitate communications between the research and operational communities for the purpose of identifying work ready for validation and transition to an operational environment; and (4) Act as a focus for interagency cooperation. The NIC mission is to provide worldwide operational sea ice analyses and forecasts for the armed forces of the US and allied nations, the Departments of Commerce and Transportation, and other US Government and international agencies, and the civil sector. The NIC produces these analyses and forecasts of Arctic, Antarctic, Great Lakes, and Chesapeake Bay ice conditions to support customers with global, regional, and tactical scale interests. The NIC regularly deploys Naval Ice Center NAVICECEN Ice Reconnaissance personnel to the Arctic and Antarctica in order to perform aerial ice observation and analysis in support of NIC customers. NIC ice data are a key part of the US contribution to international global climate and ocean observing systems.

  15. Narrow band gap amorphous silicon semiconductors

    DOEpatents

    Madan, A.; Mahan, A.H.

    1985-01-10

    Disclosed is a narrow band gap amorphous silicon semiconductor comprising an alloy of amorphous silicon and a band gap narrowing element selected from the group consisting of Sn, Ge, and Pb, with an electron donor dopant selected from the group consisting of P, As, Sb, Bi and N. The process for producing the narrow band gap amorphous silicon semiconductor comprises the steps of forming an alloy comprising amorphous silicon and at least one of the aforesaid band gap narrowing elements in amount sufficient to narrow the band gap of the silicon semiconductor alloy below that of amorphous silicon, and also utilizing sufficient amounts of the aforesaid electron donor dopant to maintain the amorphous silicon alloy as an n-type semiconductor.

  16. Atomic structure of nanometer-sized amorphous TiO2

    SciTech Connect

    Zhang, H.; Chen, B.; Banfield, J.F.; Waychunas, G.A.

    2008-10-15

    Amorphous titania (TiO{sub 2}) is an important precursor for synthesis of single-phase nanocrystalline anatase. We synthesized x-ray amorphous titania by hydrolysis of titanium ethoxide at the ice point. Transmission electron microscopy examination and nitrogen gas adsorption indicated the particle size of the synthesized titania is {approx} 2 nm. Synchrotron wide-angle x-ray scattering (WAXS) was used to probe the atomic correlations in this amorphous sample. Atomic pair-distribution function (PDF) derived from Fourier transform of the WAXS data was used for reverse Monte Carlo (RMC) simulations of the atomic structure of the amorphous TiO{sub 2} nanoparticles. Molecular dynamics simulations were used to generate input structures for the RMC. X-ray absorption spectroscopy (XAS) simulations were used to screen candidate structures obtained from the RMC by comparing with experimental XAS data. The structure model that best describes both the WAXS and XAS data shows that an amorphous TiO{sub 2} particle consists of a highly distorted shell and a small strained anatase-like crystalline core. The average coordination number of Ti is 5.3 and most Ti-O bonds are populated around 1.940 {angstrom}. Relative to bulk TiO{sub 2}, the reduction of the coordination number is primarily due to the truncation of the Ti-O octahedra at the amorphous nanoparticle surface and the shortening of the Ti-O bond length to the bond contraction in the distorted shell. The preexistence of the anatase-like core may be critical to the formation of single-phase nanocrystalline anatase in crystallization of amorphous TiO{sub 2} upon heating.

  17. Amorphous silicon solar cell allowing infrared transmission

    DOEpatents

    Carlson, David E.

    1979-01-01

    An amorphous silicon solar cell with a layer of high index of refraction material or a series of layers having high and low indices of refraction material deposited upon a transparent substrate to reflect light of energies greater than the bandgap energy of the amorphous silicon back into the solar cell and transmit solar radiation having an energy less than the bandgap energy of the amorphous silicon.

  18. FORMATION OF MOLECULAR OXYGEN AND OZONE ON AMORPHOUS SILICATES

    SciTech Connect

    Jing Dapeng; He Jiao; Vidali, Gianfranco; Brucato, John Robert; Tozzetti, Lorenzo; De Sio, Antonio

    2012-09-01

    Oxygen in the interstellar medium is seen in the gas phase, in ices (incorporated in H{sub 2}O, CO, and CO{sub 2}), and in grains such as (Mg{sub x} Fe{sub 1-x} )SiO{sub 3} or (Mg{sub x} Fe{sub 1-x} ){sub 2}SiO{sub 4}, 0 < x < 1. In this investigation, we study the diffusion of oxygen atoms and the formation of oxygen molecules and ozone on the surface of an amorphous silicate film. We find that ozone is formed at low temperature (<30 K), and molecular oxygen forms when the diffusion of oxygen atoms becomes significant, at around 60 K. This experiment, besides being the first determination of the diffusion energy barrier (1785 {+-} 35 K) for oxygen atoms on a silicate surface, suggests bare silicates as a possible storage place for oxygen atoms in low-A{sub v} environments.

  19. Compaction of microporous amorphous solid water by ion irradiation.

    PubMed

    Raut, U; Teolis, B D; Loeffler, M J; Vidal, R A; Famá, M; Baragiola, R A

    2007-06-28

    We have studied the compaction of vapor-deposited amorphous solid water by energetic ions at 40 K. The porosity was characterized by ultraviolet-visible spectroscopy, infrared spectroscopy, and methane adsorption/desorption. These three techniques provide different and complementary views of the structural changes in ice resulting from irradiation. We find that the decrease in internal surface area of the pores, signaled by infrared absorption by dangling bonds, precedes the decrease in the pore volume during irradiation. Our results imply that impacts from cosmic rays can cause compaction in the icy mantles of the interstellar grains, which can explain the absence of dangling bond features in the infrared spectrum of molecular clouds. PMID:17614568

  20. Compaction of microporous amorphous solid water by ion irradiation.

    PubMed

    Raut, U; Teolis, B D; Loeffler, M J; Vidal, R A; Famá, M; Baragiola, R A

    2007-06-28

    We have studied the compaction of vapor-deposited amorphous solid water by energetic ions at 40 K. The porosity was characterized by ultraviolet-visible spectroscopy, infrared spectroscopy, and methane adsorption/desorption. These three techniques provide different and complementary views of the structural changes in ice resulting from irradiation. We find that the decrease in internal surface area of the pores, signaled by infrared absorption by dangling bonds, precedes the decrease in the pore volume during irradiation. Our results imply that impacts from cosmic rays can cause compaction in the icy mantles of the interstellar grains, which can explain the absence of dangling bond features in the infrared spectrum of molecular clouds.

  1. Preparation of amorphous sulfide sieves

    DOEpatents

    Siadati, Mohammad H.; Alonso, Gabriel; Chianelli, Russell R.

    2006-11-07

    The present invention involves methods and compositions for synthesizing catalysts/porous materials. In some embodiments, the resulting materials are amorphous sulfide sieves that can be mass-produced for a variety of uses. In some embodiments, methods of the invention concern any suitable precursor (such as thiomolybdate salt) that is exposed to a high pressure pre-compaction, if need be. For instance, in some cases the final bulk shape (but highly porous) may be same as the original bulk shape. The compacted/uncompacted precursor is then subjected to an open-flow hot isostatic pressing, which causes the precursor to decompose and convert to a highly porous material/catalyst.

  2. 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.

  3. Amplification of European Little Ice Age by sea ice-ocean-atmosphere feedbacks

    NASA Astrophysics Data System (ADS)

    Lehner, Flavio; Born, Andreas; Raible, Christoph C.; Stocker, Thomas F.

    2013-04-01

    The transition from the Medieval Climate Anomaly (~950-1250 AD) to the Little Ice Age (~1400-1700 AD) is believed to have been driven by an interplay of external forcing and climate system-internal variability. While the hemispheric signal seems to have been dominated by solar irradiance and volcanic eruptions, the understanding of mechanisms shaping the climate on continental scale is less robust. Examining an ensemble of transient model simulations as well as a new type of sensitivity experiments with artificial sea ice growth, we identify a sea ice-ocean-atmosphere feedback mechanism that amplifies the Little Ice Age cooling in the North Atlantic-European region and produces the temperature pattern expected from reconstructions. Initiated by increasing negative forcing, the Arctic sea ice substantially expands at the beginning of the Little Ice Age. The excess of sea ice is exported to the subpolar North Atlantic, where it melts, thereby weakening convection of the ocean. As a consequence, northward ocean heat transport is reduced, reinforcing the expansion of the sea ice and the cooling of the Northern Hemisphere. In the Nordic Seas, sea surface height anomalies cause the oceanic recirculation to strengthen at the expense of the warm Barents Sea inflow, thereby further reinforcing sea ice growth in the Barents Sea. The absent ocean-atmosphere heat flux in the Barents Sea results in an amplified cooling over Northern Europe. The positive nature of this feedback mechanism enables sea ice to remain in an expanded state for decades to centuries and explain sustained cold periods over Europe such as the Little Ice Age. Support for the feedback mechanism comes from recent proxy reconstructions around the Nordic Seas.

  4. An amorphous solid state of biogenic secondary organic aerosol particles.

    PubMed

    Virtanen, Annele; Joutsensaari, Jorma; Koop, Thomas; Kannosto, Jonna; Yli-Pirilä, Pasi; Leskinen, Jani; Mäkelä, Jyrki M; Holopainen, Jarmo K; Pöschl, Ulrich; Kulmala, Markku; Worsnop, Douglas R; Laaksonen, Ari

    2010-10-14

    Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90 billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.

  5. An amorphous solid state of biogenic secondary organic aerosol particles.

    PubMed

    Virtanen, Annele; Joutsensaari, Jorma; Koop, Thomas; Kannosto, Jonna; Yli-Pirilä, Pasi; Leskinen, Jani; Mäkelä, Jyrki M; Holopainen, Jarmo K; Pöschl, Ulrich; Kulmala, Markku; Worsnop, Douglas R; Laaksonen, Ari

    2010-10-14

    Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90 billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate. PMID:20944744

  6. Triggers for the Collapse of Ice Shelves in Antarctica: Investigating Compressive Arch Failure with Numerical Models

    NASA Astrophysics Data System (ADS)

    Huth, A.; Smith, B. E.

    2015-12-01

    Antarctic ice shelves restrain, or buttress, grounded ice from flowing freely into the ocean by redistributing the force of the ice flow to pinning points (ice rises) at the ice front and shear margins at adjacent bay walls. This buttressing process typically defines a 'compressive arch' in the strain rate-field of the ice shelf, where the smallest principal component transitions from compressive inland of the arch to extensive seaward of the arch. If the compressive arch is breached due to iceberg calving at the ice front or thinning at the shear margins, the ice shelf will retreat irreversibly to a new stable configuration or collapse entirely. This retreat can compromise ice shelf buttressing, resulting in sea-level rise and ocean freshening as grounded ice flows unrestricted into the ocean. Here, we investigate the dynamics of compressive arch failure using Larsen C ice shelf as a test case for a larger study that will include several other ice shelves and projections for sea-level rise. We use satellite observations to develop a steady state model of Larsen C in Elmer/ICE, a finite element ice sheet/ice flow software package. We run calving and thinning simulations to determine the conditions needed to trigger ice shelf retreat via compressive arch failure and discuss the likelihood of these scenarios occurring in relation to extrapolations of current melt profiles and calving trends.

  7. Martian Ice Caves

    NASA Astrophysics Data System (ADS)

    Frederick, R. D.; Billings, T. L.; McGown, R. D.; Walden, B. E.

    2000-07-01

    Ice in Martian lava tube caves would have scientific and developmental value. These natural channels in rock may hold keys to Mars' past as well as potential resources for humanity's futures. Terrestrial lava tube caves are natural receptacles for accumulations of water. Often, due to lower temperatures coupled with the superior insulation properties of the surrounding rock, these accumulations are in the form of ice. Historically, ice was mined from some lava tube caves. Many of the lava tubes in the Central Oregon area sport such names as "Arnolds Ice Cave," "Surveyors Ice Cave," "South Ice Cave," etc. These caves are not caves in ice, but rather common lava tubes with seasonal, and sometimes perennial ice deposits. Locating and cataloging similar features on Mars, could be of value for the colonization of Mars and the search for life. Such features may also prove useful in helping to determine past climatic conditions on the Red Planet.

  8. Greenland Ice Flow

    NASA Video Gallery

    Greenland looks like a big pile of snow seen from space using a regular camera. But satellite radar interferometry helps us detect the motion of ice beneath the snow. Ice starts flowing from the fl...

  9. Origin of photoinduced metastable defects in amorphous chalcogenides

    NASA Astrophysics Data System (ADS)

    Shimakawa, K.; Inami, S.; Kato, T.; Elliott, S. R.

    1992-10-01

    Prolonged exposure to band-gap light decreases the photoconductivity of annealed films of amorphous chalcogenides (As2S3, As3S7, AsS, As2Se3, GeS2, GeSe2, and GeSe). This can be attributed to photoinduced metastable defects, which could act as additional trapping and/or recombination centers. These metastable centers are removed by annealing near the glass transition temperature. The kinetics of the temporal change of photocurrent during illumination are discussed in a model of defect-conserved bond switching.