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Sample records for powder hydration time

  1. Glass powder blended cement hydration modelling

    NASA Astrophysics Data System (ADS)

    Saeed, Huda

    The use of waste materials in construction is among the most attractive options to consume these materials without affecting the environment. Glass is among these types of potential waste materials. In this research, waste glass in powder form, i.e. glass powder (GP) is examined for potential use in enhancing the characteristics of concrete on the basis that it is a pozzolanic material. The experimental and the theoretical components of the work are carried out primarily to prove that glass powder belongs to the "family" of the pozzolanic materials. The chemical and physical properties of the hydrated activated glass powder and the hydrated glass powder cement on the microstructure level have been studied experimentally and theoretically. The work presented in this thesis consists of two main phases. The first phase contains experimental investigations of the reaction of glass powder with calcium hydroxide (CH) and water. In addition, it includes experiments that are aimed at determining the consumption of water and CH with time. The reactivity, degree of hydration, and nature of the pore solution of the glass powder-blended cement pastes and the effect of adding different ratios of glass powder on cement hydration is also investigated. The experiments proved that glass powder has a pozzolanic effect on cement hydration; hence it enhances the chemical and physical properties of cement paste. Based on the experimental test results, it is recommended to use a glass powder-to-cement ratio (GP/C) of 10% as an optimum ratio to achieve the best hydration and best properties of the paste. Two different chemical formulas for the produced GP C-S-H gel due to the pure GP and GP-CH pozzolanic reaction hydration are proposed. For the pure GP hydration, the produced GP C-S-H gel has a calcium-to-silica ratio (C/S) of 0.164, water-to-silica ratio (H/S) of 1.3 and sodium/silica ratio (N/S) of 0.18. However, for the GP-CH hydration, the produced GP C-S-H gel has a C/S ratio of 1

  2. Inelastic X-ray scattering studies of the short-time collective vibrational motions in hydrated lysozyme powders and their possible relation to enzymatic function.

    PubMed

    Wang, Zhe; Bertrand, Christopher E; Chiang, Wei-Shan; Fratini, Emiliano; Baglioni, Piero; Alatas, Ahmet; Alp, E Ercan; Chen, Sow-Hsin

    2013-01-31

    High-resolution inelastic X-ray scattering was used to investigate the collective vibrational excitations in hydrated lysozyme powders as a function of hydration level and temperature. It is found that the samples with strong enzymatic function are "soft", in the sense that they exhibit low frequency and large amplitude intraprotein collective vibrational motions on certain length scales. This is not the case for samples with weak or no enzymatic activity. Thus, we identify a possible correlation between the short-time intraprotein collective vibrational motions and the establishment of enzymatic function in hydrated lysozyme powders, and bring new insight to notions of protein "conformational flexibility" and "softness" in terms of these motions. PMID:23301848

  3. Hydration of blended cement pastes containing waste ceramic powder as a function of age

    NASA Astrophysics Data System (ADS)

    Scheinherrová, Lenka; Trník, Anton; Kulovaná, Tereza; Pavlík, Zbyšek; Rahhal, Viviana; Irassar, Edgardo F.; Černý, Robert

    2016-07-01

    The production of a cement binder generates a high amount of CO2 and has high energy consumption, resulting in a very adverse impact on the environment. Therefore, use of pozzolana active materials in the concrete production leads to a decrease of the consumption of cement binder and costs, especially when some type of industrial waste is used. In this paper, the hydration of blended cement pastes containing waste ceramic powder from the Czech Republic and Portland cement produced in Argentina is studied. A cement binder is partially replaced by 8 and 40 mass% of a ceramic powder. These materials are compared with an ordinary cement paste. All mixtures are prepared with a water/cement ratio of 0.5. Thermal characterization of the hydrated blended pastes is carried out in the time period from 2 to 360 days. Simultaneous DSC/TG analysis is performed in the temperature range from 25 °C to 1000 °C in an argon atmosphere. Using this thermal analysis, we identify the temperature, enthalpy and mass changes related to the liberation of physically bound water, calcium-silicate-hydrates gels dehydration, portlandite, vaterite and calcite decomposition and their changes during the curing time. Based on thermogravimetry results, we found out that the portlandite content slightly decreases with time for all blended cement pastes.

  4. Time-dependent water dynamics in hydrated uranyl fluoride

    DOE PAGESBeta

    Miskowiec, Andrew J.; Anderson, Brian B.; Herwig, Kenneth W.; Huq, Ashfia; Mamontov, Eugene; Rondinone, Adam; Trowbridge, Lee D.

    2015-09-15

    In this study, uranyl fluoride is a three-layer, hexagonal structure with significant stacking disorder in the c-direction. It supports a range of unsolved ‘thermodynamic’ hydrates with 0–2.5 water molecules per uranium atom, and perhaps more. However, the relationship between water, hydrate crystal structures, and thermodynamic results, collectively representing the chemical pathway through these hydrate structures, has not been sufficiently elucidated. We used high-resolution quasielastic neutron scattering to study the dynamics of water in partially hydrated uranyl fluoride powder over the course of 4 weeks under closed conditions. The spectra are composed of two quasielastic components: one is associated with translationalmore » diffusive motion of water that is approximately five to six times slower than bulk water, and the other is a slow (on the order of 2–300 ps), spatially bounded water motion. The translational component represents water diffusing between the weakly bonded layers in the crystal, while the bounded component may represent water trapped in subnanometre ‘pockets’ formed by the space between uranium-centred polymerisation units. Complementary neutron diffraction measurements do not show any significant structural changes, suggesting that a chemical conversion of the material does not occur in the thermodynamically isolated system on this timescale.« less

  5. Time-dependent water dynamics in hydrated uranyl fluoride

    SciTech Connect

    Miskowiec, Andrew J.; Anderson, Brian B.; Herwig, Kenneth W.; Huq, Ashfia; Mamontov, Eugene; Rondinone, Adam; Trowbridge, Lee D.

    2015-09-15

    In this study, uranyl fluoride is a three-layer, hexagonal structure with significant stacking disorder in the c-direction. It supports a range of unsolved ‘thermodynamic’ hydrates with 0–2.5 water molecules per uranium atom, and perhaps more. However, the relationship between water, hydrate crystal structures, and thermodynamic results, collectively representing the chemical pathway through these hydrate structures, has not been sufficiently elucidated. We used high-resolution quasielastic neutron scattering to study the dynamics of water in partially hydrated uranyl fluoride powder over the course of 4 weeks under closed conditions. The spectra are composed of two quasielastic components: one is associated with translational diffusive motion of water that is approximately five to six times slower than bulk water, and the other is a slow (on the order of 2–300 ps), spatially bounded water motion. The translational component represents water diffusing between the weakly bonded layers in the crystal, while the bounded component may represent water trapped in subnanometre ‘pockets’ formed by the space between uranium-centred polymerisation units. Complementary neutron diffraction measurements do not show any significant structural changes, suggesting that a chemical conversion of the material does not occur in the thermodynamically isolated system on this timescale.

  6. In situ neutron powder diffraction investigation of the hydration of tricalcium aluminate in the presence of gypsum

    SciTech Connect

    Hartman, M.R. . E-mail: michael.hartman@nist.gov; Berliner, R.

    2005-11-15

    The hydration of a 1:3 molar ratio of tricalcium aluminate, Ca{sub 3}Al{sub 2}O{sub 6}, to gypsum, CaSO{sub 4}.2D{sub 2}O, was investigated at temperatures of 25, 50, and 80 deg. C using time-of-flight powder neutron diffraction combined with multiphase Rietveld structural refinement. It was shown that ettringite, Ca{sub 6}[Al(OD){sub 6}]{sub 2}(SO{sub 4}){sub 3}.{approx}26D{sub 2}O, was the first and only hydration product of the system, in contrast to a prior investigation which suggested the occurrence of a precursor phase prior to the formation of ettringite. Kinetics data showed that the hydration reaction is very sensitive to temperature: hydration at 25 deg. C was characterized by a single kinetic regime while hydration at higher temperatures consisted of two distinct kinetic regimes. The presence of two kinetic regimes was attributed to a change in either the dimensionality of the growth process or a change in the rate controlling mechanism in the hydration reaction.

  7. Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

    SciTech Connect

    Everett, Susan M; Rawn, Claudia J; Keffer, David J.; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy Joe

    2013-01-01

    Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot. Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  8. Neutron powder diffraction studies as a function of temperature of structure II hydrate formed from propane

    USGS Publications Warehouse

    Rawn, C.J.; Rondinone, A.J.; Chakoumakos, B.C.; Circone, S.; Stern, L.A.; Kirby, S.H.; Ishii, Y.

    2003-01-01

    Neutron powder diffraction data confirm that hydrate samples synthesized with propane crystallize as structure type II hydrate. The structure has been modeled using rigid-body constraints to describe C3H8 molecules located in the eight larger polyhedral cavities of a deuterated host lattice. Data were collected at 12, 40, 100, 130, 160, 190, 220, and 250 K and used to calculate the thermal expansivity from the temperature dependence of the lattice parameters. The data collected allowed for full structural refinement of atomic coordinates and the atomic-displacement parameters.

  9. In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

    SciTech Connect

    Álvarez-Pinazo, G.; Cuesta, A.; García-Maté, M.; Santacruz, I.; Losilla, E.R.; Fauth, F.; Aranda, M.A.G.; De la Torre, A.G.

    2014-02-15

    Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (α ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.

  10. Quil A-lipid powder formulations releasing ISCOMs and related colloidal structures upon hydration.

    PubMed

    Demana, Patrick H; Davies, Nigel M; Hook, Sarah; Rades, Thomas

    2005-03-01

    The aim of the present study was to prepare solid Quil A-cholesterol-phospholipid formulations (as powder mixtures or compressed to pellets) by physical mixing or by freeze-drying of aqueous dispersions of these components in ratios that allow spontaneous formation of ISCOMs and other colloidal structures upon hydration. The effect of addition of excess cholesterol to the lipid mixtures on the release of a model antigen (PE-FITC-OVA) from the pellets was also investigated. Physical properties were evaluated by X-ray powder diffractometry (XPRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and polarized light microscopy (PLM). Characterization of aqueous colloidal dispersions was performed by negative staining transmission electron microscopy (TEM). Physically mixed powders (with or without PE-FITC-OVA) and pellets prepared from the same powders did not spontaneously form ISCOM matrices and related colloidal structures such as worm-like micelles, ring-like micelles, lipidic/layered structures and lamellae (hexagonal array of ring-like micelles) upon hydration as expected from the pseudo-ternary diagram for aqueous mixtures of Quil A, cholesterol and phospholipid. In contrast, spontaneous formation of the expected colloids was demonstrated for the freeze-dried lipid mixtures. Pellets prepared by compression of freeze-dried powders released PE-FITC-OVA slower than those prepared from physically mixed powders. TEM investigations revealed that the antigen was released in the form of colloidal particles (ISCOMs) from pellets prepared by compression of freeze-dried powders. The addition of excess cholesterol slowed down the release of antigen. The findings obtained in this study are important for the formulation of solid Quil A-containing lipid articles as controlled particulate adjuvant containing antigen delivery systems. PMID:15710499

  11. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

    PubMed

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

    2013-05-01

    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions. PMID:23557375

  12. Hydration mechanisms of ternary Portland cements containing limestone powder and fly ash

    SciTech Connect

    De Weerdt, K.; Haha, M. Ben; Le Saout, G.; Kjellsen, K.O.; Justnes, H.; Lothenbach, B.

    2011-03-15

    The effect of minor additions of limestone powder on the properties of fly ash blended cements was investigated in this study using isothermal calorimetry, thermogravimetry (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) techniques, and pore solution analysis. The presence of limestone powder led to the formation of hemi- and monocarbonate and to a stabilisation of ettringite compared to the limestone-free cements, where a part of the ettringite converted to monosulphate. Thus, the presence of 5% of limestone led to an increase of the volume of the hydrates, as visible in the increase in chemical shrinkage, and an increase in compressive strength. This effect was amplified for the fly ash/limestone blended cements due to the additional alumina provided by the fly ash reaction.

  13. Precondition of time required for the generation of methane hydrate

    NASA Astrophysics Data System (ADS)

    Rezničák, Štefan; Malcho, Milan; Siažik, Ján

    2016-06-01

    The paper deals with methane hydrates generated from natural gas. Methane hydrates in nature. Thermobaric conditions necessary for their generation from the natural gas, composition of december 2015 from the company SPP - distribúcia, a.s. It deals with the estimated time of their formation, at a constant pressures of 5, 10 and 15 MPa and at different subcooling temperature. Determination the temperature required for the generation of methane hydrates at these pressures and temperature range based on the equation from research by Kim et. al..

  14. A Circuit Model of Real Time Human Body Hydration.

    PubMed

    Asogwa, Clement Ogugua; Teshome, Assefa K; Collins, Stephen F; Lai, Daniel T H

    2016-06-01

    Changes in human body hydration leading to excess fluid losses or overload affects the body fluid's ability to provide the necessary support for healthy living. We propose a time-dependent circuit model of real-time human body hydration, which models the human body tissue as a signal transmission medium. The circuit model predicts the attenuation of a propagating electrical signal. Hydration rates are modeled by a time constant τ, which characterizes the individual specific metabolic function of the body part measured. We define a surrogate human body anthropometric parameter θ by the muscle-fat ratio and comparing it with the body mass index (BMI), we find theoretically, the rate of hydration varying from 1.73 dB/min, for high θ and low τ to 0.05 dB/min for low θ and high τ. We compare these theoretical values with empirical measurements and show that real-time changes in human body hydration can be observed by measuring signal attenuation. We took empirical measurements using a vector network analyzer and obtained different hydration rates for various BMI, ranging from 0.6 dB/min for 22.7 [Formula: see text] down to 0.04 dB/min for 41.2 [Formula: see text]. We conclude that the galvanic coupling circuit model can predict changes in the volume of the body fluid, which are essential in diagnosing and monitoring treatment of body fluid disorder. Individuals with high BMI would have higher time-dependent biological characteristic, lower metabolic rate, and lower rate of hydration. PMID:26485354

  15. Dynamics and structure of hydration water on rutile and cassiterite nano-powders studied by quasielastic neutron scattering and molecular dynamics simulations

    SciTech Connect

    Mamontov, Eugene

    2007-01-01

    Quasielastic neutron scattering (QENS) experiments carried out using time-of-flight and backscattering neutron spectrometers with widely different energy resolution and dynamic range revealed the diffusion dynamics of hydration water in nano-powder rutile (TiO2) and cassiterite (SnO2) that possess the rutile crystal structure with the (110) crystal face predominant on the surface. These isostructural oxides differ in their bulk dielectric constants, metal atom electronegativities, and lattice spacings, which may all contribute to differences in the structure and dynamics of sorbed water. When hydrated under ambient conditions, the nano-powders had similar levels of hydration: about 3.5 (OH/H2O) molecules per Ti2O4 surface structural unit of TiO2 and about 4.0 (OH/H2O) molecules per Sn2O4 surface unit of SnO2. Ab initio-optimized classical molecular dynamics (MD) simulations of the (110) surfaces in contact with SPC/E water at these levels of hydration indicate three structurally-distinct sorbed water layers L1, L2, and L3, where the L1 species are either associated water molecules or dissociated hydroxyl groups in direct contact with the surface, L2 water molecules are hydrogen bonded to L1 and structural oxygen atoms at the surface, and L3 water molecules are more weakly bound. At the hydration levels studied, L3 is incomplete compared with axial oxygen density profiles of bulk SPC/E water in contact with these surfaces, but the structure and dynamics of L1 "L3 species are remarkably similar at full and reduced water coverage. Three hydration water diffusion components, on the time scale of a picosecond, tens of picoseconds, and a nanosecond could be extracted from the QENS spectra of both oxides. However, the spectral weight of the faster components was significantly lower for SnO2 compared to TiO2. In TiO2 hydration water, the more strongly bound L2 water molecules exhibited slow (on the time scale of a nanosecond) dynamics characterized by super

  16. Early age hydration and pozzolanic reaction in natural zeolite blended cements: Reaction kinetics and products by in situ synchrotron X-ray powder diffraction

    SciTech Connect

    Snellings, R.; Mertens, G.; Cizer, O.; Elsen, J.

    2010-12-15

    The in situ early-age hydration and pozzolanic reaction in cements blended with natural zeolites were investigated by time-resolved synchrotron X-ray powder diffraction with Rietveld quantitative phase analysis. Chabazite and Na-, K-, and Ca-exchanged clinoptilolite materials were mixed with Portland cement in a 3:7 weight ratio and hydrated in situ at 40 {sup o}C. The evolution of phase contents showed that the addition of natural zeolites accelerates the onset of C{sub 3}S hydration and precipitation of CH and AFt. Kinetic analysis of the consumption of C{sub 3}S indicates that the enveloping C-S-H layer is thinner and/or less dense in the presence of alkali-exchanged clinoptilolite pozzolans. The zeolite pozzolanic activity is interpreted to depend on the zeolite exchangeable cation content and on the crystallinity. The addition of natural zeolites alters the structural evolution of the C-S-H product. Longer silicate chains and a lower C/S ratio are deduced from the evolution of the C-S-H b-cell parameter.

  17. Pre-exercise glycerol hydration improves cycling endurance time

    NASA Technical Reports Server (NTRS)

    Montner, P.; Stark, D. M.; Riedesel, M. L.; Murata, G.; Robergs, R.; Timms, M.; Chick, T. W.

    1996-01-01

    The effects of glycerol ingestion (GEH) on hydration and subsequent cycle ergometer submaximal load exercise were examined in well conditioned subjects. We hypothesized that GEH would reduce physiologic strain and increase endurance. The purpose of Study I (n = 11) was to determine if pre-exercise GEH (1.2 gm/kg glycerol in 26 ml/kg solution) compared to pre-exercise placebo hydration (PH) (26 ml/kg of aspartame flavored water) lowered heart rate (HR), lowered rectal temperature (Tc), and prolonged endurance time (ET) during submaximal load cycle ergometry. The purpose of Study II (n = 7) was to determine if the same pre-exercise regimen followed by carbohydrate oral replacement solution (ORS) during exercise also lowered HR, Tc, and prolonged ET. Both studies were double-blind, randomized, crossover trials, performed at an ambient temperature of 23.5-24.5 degrees C, and humidity of 25-27%. Mean HR was lower by 2.8 +/- 0.4 beats/min (p = 0.05) after GEH in Study I and by 4.4 +/- 1.1 beats/min (p = 0.01) in Study II. Endurance time was prolonged after GEH in Study I (93.8 +/- 14 min vs. 77.4 +/- 9 min, p = 0.049) and in Study II (123.4 +/- 17 min vs. 99.0 +/- 11 min, p = 0.03). Rectal temperature did not differ between hydration regimens in both Study I and Study II. Thus, pre-exercise glycerol-enhanced hyperhydration lowers HR and prolongs ET even when combined with ORS during exercise. The regimens tested in this study could potentially be adapted for endurance activities.

  18. Effect of Protein-Lipid-Salt Interactions on Sodium Availability in the Mouth and Consequent Perception of Saltiness: As Affected by Hydration in Powders.

    PubMed

    Yucel, Umut; Peterson, Devin G

    2015-09-01

    There is a broad need to reformulate lower sodium food products without affecting their original taste. The present study focuses on characterizing the role of protein-salt interactions on the salt release in low-moisture systems and saltiness perception during hydration. Sodium release from freeze-dried protein powders and emulsion powders formulated at different protein/lipid ratios (5:0 to 1:4) were characterized using a chromatography column modified with a porcine tongue. Emulsion systems with protein structured at the interface were found to have faster initial sodium release rates and faster hydration and were perceived to have a higher initial salt intensity with a lower salty aftertaste. In summary, exposure of the hydrophilic segments of the interface-structured proteins in emulsions was suggested to facilitate hydration and release of sodium during dissolution of low-moisture powder samples. PMID:26255668

  19. Terahertz time-lapse imaging of hydration in physiological tissues

    NASA Astrophysics Data System (ADS)

    Bennett, David B.; Taylor, Zachary D.; Bajwa, Neha; Tewari, Priyamvada; Maccabi, Ashkan; Sung, Shijun; Singh, Rahul S.; Culjat, Martin O.; Grundfest, Warren S.; Brown, Elliott R.

    2011-02-01

    This study describes terahertz (THz) imaging of hydration changes in physiological tissues with high water concentration sensitivity. A fast-scanning, pulsed THz imaging system (centered at 525 GHz; 125 GHz bandwidth) was utilized to acquire a 35 mm x 35 mm field-of-view with 0.5 mm x 0.5 mm pixels in less than two minutes. THz time-lapsed images were taken on three sample systems: (1) a simple binary system of water evaporating from a polypropylene towel, (2) the accumulation of fluid at the site of a sulfuric acid burn on ex vivo porcine skin, and (3) the evaporative dehydration of an ex vivo porcine cornea. The diffusion-regulating behavior of corneal tissue is elucidated, and the correlation of THz reflectivity with tissue hydration is measured using THz spectroscopy on four ex vivo corneas. We conclude that THz imaging can discern small differences in the distribution of water in physiological tissues and is a good candidate for burn and corneal imaging.

  20. [Comparative examination of preparation time in docetaxel hydrate formulation].

    PubMed

    Arii, Daisuke; Ikeno, Yohei; Narita, Kumi; Murooka, Kunihiko; Nojima, Michio; Kidokoro, Akio

    2012-12-01

    Docetaxel hydrate(DTX), a taxane anticancer drug, is known to be effective against a wide range of cancers, including breast cancer and non-small cell lung cancer. The DTX preparation Taxotere(2-vial DTX)has conventionally required dissolution in the attached solvent, while Onetaxotere(1-vial DTX), a newer product, is provided as a solution. This allows reduction of preparation time, so that improvement in operational efficiency can be expected. In this study, we measured the actual preparation time for 2-vial DTX and 1-vial DTX to compare their usefulness. The median preparation time for 2-vial DTX(n=84)and 1-vial DTX(n=84)was significantly different, with the respective values being 6. 52 minutes and 2. 67 minutes(p<0. 01). By switching to 1-vial DTXfrom 2-vial DTX, which requires preparation of a premix solution with the attached solvent, the preparation procedure in daily practice becomes more convenient. This is because of a shorter preparation time as well as a lower risk of contamination, suggesting the usefulness of 1-vial DTX. PMID:23235174

  1. Clathrate hydrates for ozone preservation.

    PubMed

    Muromachi, Sanehiro; Ohmura, Ryo; Takeya, Satoshi; Mori, Yasuhiko H

    2010-09-01

    We report the experimental evidence for the preservation of ozone (O(3)) encaged in a clathrate hydrate. Although ozone is an unstable substance and is apt to decay to oxygen (O(2)), it may be preserved for a prolonged time if it is encaged in hydrate cavities in the form of isolated molecules. This possibility was assessed using a hydrate formed from an ozone + oxygen gas mixture coexisting with carbon tetrachloride or xenon. Each hydrate sample was stored in an air-filled container at atmospheric pressure and a constant temperature in the range between -20 and 2 degrees C and was continually subjected to iodometric measurements of its fractional ozone content. Such chronological measurements and structure analysis using powder X-ray diffraction have revealed that ozone can be preserved in a hydrate-lattice structure for more than 20 days at a concentration on the order of 0.1% (hydrate-mass basis). PMID:20707330

  2. Relative Timing of Phyllosilicate and Hydrated Sulfate Deposition in Eastern Sinus Meridiani

    NASA Astrophysics Data System (ADS)

    Wiseman, S. M.; Beyer, R. A.

    2014-07-01

    Both Fe/Mg phyllosilicates and hydrated sulfates are associated with extensive indurated, layered deposits. We determine the relative timing of alteration. Phyllosilicates appear to be contained within a laterally continuous stratigraphic horizon.

  3. A combined solid-state NMR and synchrotron x-ray diffraction powder study on the structure of the antioxidant(+)-catechin 4.5 hydrate.

    SciTech Connect

    Harper, J. K.; Doebbler, J. A.; Jaccques, E.; Grant, D. M.; Von Dreele, R. B.; Univ. of Utah

    2010-03-10

    Analyses combining X-ray powder diffraction (XRD) and solid-state NMR (SSNMR) data can now provide crystal structures in challenging powders that are inaccessible by traditional methods. The flavonoid catechin is an ideal candidate for these methods, as it has eluded crystallographic characterization despite extensive study. Catechin was first described nearly two centuries ago, and its powders exhibit numerous levels of hydration. Here, synchrotron XRD data provide all heavy-atom positions in (+)-catechin 4.5-hydrate and establish the space group as C2. SSNMR data ({sup 13}C tensor and {sup 1}H/{sup 13}C correlation) complete the conformation by providing catechin's five OH hydrogen orientations. Since 1903, this phase has been erroneously identified as a 4.0 hydrate, but XRD and density data establish that this discrepancy is due to the facile loss of the water molecule located at a Wyckoff special position in the unit cell. A final improvement to heavy-atom positions is provided by a geometry optimization of bond lengths and valence angles with XRD torsion angles held constant. The structural enhancement in this final structure is confirmed by the significantly improved fit of computed {sup 13}C tensors to experimental data.

  4. Dissociation of Natural and Artificial Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Misyura, S. Y.

    2016-02-01

    Present work deals with natural and artificial methane hydrate dissociation. The heating of the powder produced due to the temperature difference between the external air and the powder. The dissociation rate was determined by gravimetric method. The range of the partial self-preservation for the natural hydrate is significantly longer than for the artificial one and moved to higher temperatures. The destruction of the natural sample is slower than the artificial one. The time-averaged dissociation rate for the artificial sample is equal to 1,25 %/s and for the natural hydrate corresponds to 0,59 %/s.

  5. Stochastic Approach to Determine CO2 Hydrate Induction Time in Clay Mineral Suspensions

    NASA Astrophysics Data System (ADS)

    Lee, K.; Lee, S.; Lee, W.

    2008-12-01

    A large number of induction time data for carbon dioxide hydrate formation were obtained from a batch reactor consisting of four independent reaction cells. Using resistance temperature detector(RTD)s and a digital microscope, we successfully monitored the whole process of hydrate formation (i.e., nucleation and crystal growth) and detected the induction time. The experiments were carried out in kaolinite and montmorillonite suspensions at temperatures between 274 and 277 K and pressures ranging from 3.0 to 4.0 MPa. Each set of data was analyzed beforehand whether to be treated by stochastic manner or not. Geochemical factors potentially influencing the hydrate induction time under different experimental conditions were investigated by stochastic analyses. We observed that clay mineral type, pressure, and temperature significantly affect the stochastic behavior of the induction times for CO2 hydrate formation in this study. The hydrate formation kinetics along with stochastic analyses can provide basic understanding for CO2 hydrate storage in deep-sea sediment and geologic formation, securing its stability under the environments.

  6. Diffusion Processes in Water on Oxide Surfaces: Quasielastic Neutron Scattering Study of Hydration Water in Rutile Nano-Powder

    SciTech Connect

    Chu, Xiang-Qiang; Ehlers, Georg; Mamontov, Eugene; Podlesnyak, Andrey A; Wang, Wei; Wesolowski, David J

    2011-01-01

    Quasielastic neutron scattering (QENS) was used to investigate the diffusion dynamics of hydration water on the surface of rutile (TiO{sub 2}) nanopowder. The dynamics measurements utilizing two inelastic instruments, a backscattering spectrometer and a disk chopper spectrometer, probed the fast, intermediate, and slow motions of the water molecules on the time scale of picoseconds to more than a nanosecond. We employed a model-independent analysis of the data collected at each value of the scattering momentum transfer to investigate the temperature dependence of several diffusion components. All of the probed components were present in the studied temperature range of 230-320 K, providing, at a first sight, no evidence of discontinuity in the hydration water dynamics. However, a qualitative change in the elastic scattering between 240 and 250 K suggested a surface freezing-melting transition, when the motions that were localized at lower temperatures became delocalized at higher temperatures. On the basis of our previous molecular dynamics simulations of this system, we argue that interpretation of QENS data from such a complex interfacial system requires at least qualitative input from simulations, particularly when comparing results from spectrometers with very different energy resolutions and dynamic ranges.

  7. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2016-05-01

    The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  8. Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

    PubMed

    Yamamoto, Yo-ichi; Suzuki, Yoshi-Ichi; Tomasello, Gaia; Horio, Takuya; Karashima, Shutaro; Mitríc, Roland; Suzuki, Toshinori

    2014-05-01

    We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and I- in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed. PMID:24856723

  9. Characterizing the secondary hydration shell on hydrated myoglobin, hemoglobin, and lysozyme powders by its vitrification behavior on cooling and its calorimetric glass-->liquid transition and crystallization behavior on reheating.

    PubMed Central

    Sartor, G; Hallbrucker, A; Mayer, E

    1995-01-01

    For hydrated metmyoglobin, methemoglobin, and lysozyme powders, the freezable water fraction of between approximately 0.3-0.4 g water/g protein up to approximately 0.7-0.8 g water/g protein has been fully vitrified by cooling at rates up to approximately 1500 K min-1 and the influence of cooling rate characterized by x-ray diffractograms. This vitreous but freezable water fraction started to crystallize at approximately 210 K to cubic ice and at approximately 240 K to hexagonal ice. Measurements by differential scanning calorimetry have shown that this vitreous but freezable water fraction undergoes, on reheating at a rate of 30 K min-1, a glass-->liquid transition with an onset temperature of between approximately 164 and approximately 174 K, with a width of between approximately 9 and approximately 16 degrees and an increase in heat capacity of between approximately 20 and approximately 40 J K-1 (mol of freezable water)-1 but that the glass transition disappears upon crystallization of the freezable water. These calorimetric features are similar to those of water imbibed in the pores of a synthetic hydrogel but very different from those of glassy bulk water. The difference to glassy bulk water's properties is attributed to hydrophilic interaction and H-bonding of the macromolecules' segments with the freezable water fraction, which thereby becomes dynamically modified. Abrupt increase in minimal or critical cooling rate necessary for complete vitrification is observed at approximately 0.7-0.8 g water/g protein, which is attributed to an abrupt increase of water's mobility, and it is remarkably close to the threshold value of water's mobility on a hydrated protein reported by Kimmich et al. (1990, Biophys. J. 58:1183). The hydration level of approximately 0.7-0.8 g water/g protein is approximately that necessary for completing the secondary hydration shell. PMID:8599674

  10. Feasibility of monitoring gas hydrate production with time-lapse VSP

    SciTech Connect

    Kowalsky, M.B.; Nakagawa, S.; Moridis, G.J.

    2009-11-01

    In this work we begin to examine the feasibility of using time-lapse seismic methods-specifically the vertical seismic profiling (VSP) method-for monitoring changes in hydrate accumulations that are predicted to occur during production of natural gas.

  11. Terahertz time domain spectroscopy (THz-TDS) of hydrated biomolecular polymers and monomers

    NASA Astrophysics Data System (ADS)

    Glancy, Paul Michael

    Terahertz Time Domain Spectroscopy (THz-TDS) was utilized to obtain the complex dielectric spectra of hydrated biomolecules, betwixt the frequency range of 50 GHz to 2 THz. Two biological systems are observed; nucleic acid and carbohydrates. Monomers and polymers will be of interest for both. Utilizing both the Debye relaxation model and the suspension model, we observed both the mobility of biomolecules in solution as well as the influence they have on their surrounding water. Nucleotides and glucose (monomers) were found to have a small part in the overall dynamics of the polymers. Hydrated nucleotides were shown to form transition materials. The pyrimidine nucleotides act much like an ion where they break up the original structure of water and set up a less complicated structure (smaller main relaxation times than water) than water. Purine nucleotides act more like a hydrogen bond building material they set up a more complex hydrogen bond network (larger main relaxation times than water) than water. These nucleotides were shown to have an influence in water out to four water layers. The concentration studies that were preformed on native DNA, shows that concentration in the hydrated state is an important factor in the dielectric response. In addition, it was found that impurities in our samples did not play an important role in the dielectric response of our DNA solutions. Native DNA was shown to have a reach of six hydration layers. The influence temperature has on DNA solutions was observed, temperature has a large influence on hydrated DNA. It was found that hydrated DNA is more susceptible to change in temperature then that of bulk water. The main relaxation time increases at a much larger proportion to that of water. Using two synthetic DNA molecules with the same structure but different compositions and two carbohydrates with different structures but the same composition we found that the structure of a biopolymer is the most domination factor, rather than

  12. X-ray CT Observations of Methane Hydrate Distribution Changes over Time in a Natural Sediment Core from the BPX-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well

    SciTech Connect

    Kneafsey, T.J.; Rees, E.V.L.

    2010-03-01

    When maintained under hydrate-stable conditions, methane hydrate in laboratory samples is often considered a stable and immobile solid material. Currently, there do not appear to be any studies in which the long-term redistribution of hydrates in sediments has been investigated in the laboratory. These observations are important because if the location of hydrate in a sample were to change over time (e.g. by dissociating at one location and reforming at another), the properties of the sample that depend on hydrate saturation and pore space occupancy would also change. Observations of hydrate redistribution under stable conditions are also important in understanding natural hydrate deposits, as these may also change over time. The processes by which solid hydrate can move include dissociation, hydrate-former and water migration in the gas and liquid phases, and hydrate formation. Chemical potential gradients induced by temperature, pressure, and pore water or host sediment chemistry can drive these processes. A series of tests were performed on a formerly natural methane-hydrate-bearing core sample from the BPX-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, in order to observe hydrate formation and morphology within this natural sediment, and changes over time using X-ray computed tomography (CT). Long-term observations (over several weeks) of methane hydrate in natural sediments were made to investigate spatial changes in hydrate saturation in the core. During the test sequence, mild buffered thermal and pressure oscillations occurred within the sample in response to laboratory temperature changes. These oscillations were small in magnitude, and conditions were maintained well within the hydrate stability zone.

  13. Dynamics of protein hydration water

    NASA Astrophysics Data System (ADS)

    Wolf, M.; Emmert, S.; Gulich, R.; Lunkenheimer, P.; Loidl, A.

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  14. Dynamics of protein hydration water.

    PubMed

    Wolf, M; Emmert, S; Gulich, R; Lunkenheimer, P; Loidl, A

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water. PMID:26465518

  15. An investigation on the influence of milling time and calcination temperature on the characterization of nano cerium oxide powder synthesized by mechanochemical route

    SciTech Connect

    Aminzare, M.; Amoozegar, Z.; Sadrnezhaad, S.K.

    2012-11-15

    Highlights: ► Synthesis of nanosized CeO{sub 2} was carried out using mechanochemical reactions plus sequential calcinations procedure. ► The effect of milling time and calcinations procedure on crystallite size and surface area of the as-synthesized powders was investigated. ► The extended milling times were exposed to result in the smaller crystallite size, and hence higher surface area for the as-synthesized powder. ► Higher calcinations temperatures, on the other hand, led to the as-synthesized powder with a larger crystallite size and therefore, lower surface area. ► Activation energy for nanocrystallite growth was calculated during the calcinations procedure and the aforementioned crystallite growth was found to be conducted in the light of interfacial reactions. -- Abstract: The synthesis of nano-sized CeO{sub 2} powder was investigated via mechanochemical reactions between hydrate cerium chloride and sodium hydroxide as the starting materials. The process was followed by a subsequent calcination procedure. Characterization of as-synthesized powder was performed using X-ray diffraction, FTIR spectroscopy, Brunner–Emmett–Teller (BET) nitrogen gas absorption, scanning electron microscopy (SEM) and particle size analyzer (PSA). The precursors were milled for different milling times and then were subjected to different heat treatment procedure at variable temperatures from 100 to 700 °C. According to the results, milling time and calcination temperatures induce paramountal effects on crystallite size and surface area of as-synthesized powders. In addition, the average activation energy for the growth of nanocrystals during calcination was determined to be about 12.53 kJ/mol, suggesting the influence of interfacial reactions on the crystallite growth during the calcination procedure.

  16. Effect of Powder Reuse Times on Additive Manufacturing of Ti-6Al-4V by Selective Electron Beam Melting

    NASA Astrophysics Data System (ADS)

    Tang, H. P.; Qian, M.; Liu, N.; Zhang, X. Z.; Yang, G. Y.; Wang, J.

    2015-03-01

    An advantage of the powder-bed-based metal additive manufacturing (AM) processes is that the powder can be reused. The powder reuse or recycling times directly affect the affordability of the additively manufactured parts, especially for the AM of titanium parts. This study examines the influence of powder reuse times on the characteristics of Ti-6Al-4V powder, including powder composition, particle size distribution (PSD), apparent density, tap density, flowability, and particle morphology. In addition, tensile samples were manufactured and evaluated with respect to powder reuse times and sample locations in the powder bed. The following findings were made from reusing the same batch of powder 21 times for AM by selective electron beam melting: (i) the oxygen (O) content increased progressively with increasing reuse times but both the Al content and the V content remained generally stable (a small decrease only); (ii) the powder became less spherical with increasing reuse times and some particles showed noticeable distortion and rough surfaces after being reused 16 times; (iii) the PSD became narrower and few satellite particles were observed after 11 times of reuse; (iv) reused powder showed improved flowability; and (v) reused powder showed no measurable undesired influence on the AM process and the samples exhibited highly consistent tensile properties, irrespective of their locations in the powder bed. The implications of these findings were discussed.

  17. Multi-rate time stepping schemes for hydro-geomechanical model for subsurface methane hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Gupta, Shubhangi; Wohlmuth, Barbara; Helmig, Rainer

    2016-05-01

    We present an extrapolation-based semi-implicit multi-rate time stepping (MRT) scheme and a compound-fast MRT scheme for a naturally partitioned, multi-time-scale hydro-geomechanical hydrate reservoir model. We evaluate the performance of the two MRT methods compared to an iteratively coupled solution scheme and discuss their advantages and disadvantages. The performance of the two MRT methods is evaluated in terms of speed-up and accuracy by comparison to an iteratively coupled solution scheme. We observe that the extrapolation-based semi-implicit method gives a higher speed-up but is strongly dependent on the relative time scales of the latent (slow) and active (fast) components. On the other hand, the compound-fast method is more robust and less sensitive to the relative time scales, but gives lower speed up as compared to the semi-implicit method, especially when the relative time scales of the active and latent components are comparable.

  18. Incident spectrum determination for time-of-flight neutron powder diffraction data analysis.

    SciTech Connect

    Hodges, J. P.

    1998-08-27

    Accurate characterization of the incident neutron spectrum is an important requirement for precise Rietveld analysis of time-of-flight powder neutron diffraction data. Without an accurate incident spectrum the calculated model for the measured relative intensities of individual Bragg reflections will possess systematic errors. We describe a method for obtaining an accurate numerical incident spectrum using data from a transmitted beam monitor.

  19. Proceedings of the 1986 workshop on advanced time-of-flight neutron powder diffraction

    SciTech Connect

    Lawson, A.C.; Smith, K.

    1986-09-01

    This report contains abstracts of talks and summaries of discussions from a small workshop held to discuss the future of time-of-flight neutron powder diffraction and its implementation at the Los Alamos Neutron Scattering Center. 47 refs., 3 figs.

  20. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-01-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  1. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-06-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  2. A Study of Concrete Hydration and Dielectric Relaxation Mechanism Using Ground Penetrating Radar and Short-Time Fourier Transform

    NASA Astrophysics Data System (ADS)

    Lai, W. L.; Kind, T.; Wiggenhauser, H.

    2010-12-01

    Ground penetrating radar (GPR) was used to characterize the frequency-dependent dielectric relaxation phenomena in ordinary Portland cement (OPC) hydration in concrete changing from fresh to hardened state. The study was experimented by measuring the changes of GPR A-scan waveforms over a period of 90 days, and processed the waveforms with short-time Fourier transform (STFT) in joint time-frequency analysis (JTFA) domain rather than a conventional time or frequency domain alone. The signals of the direct wave traveled at the concrete surface and the reflected wave from an embedded steel bar were transformed with STFT, in which the changes of peak frequency over ages were tracked. The peak frequencies were found to increase with ages and the patterns were found to match closely with primarily the well-known OPC hydration process and secondarily, the evaporation effect. The close match is contributed to the simultaneous effects converting free to bound water over time, on both conventional OPC hydration and dielectric relaxation mechanisms.

  3. Time-series measurements of bubble plume variability and water column methane distribution above Southern Hydrate Ridge, Oregon

    NASA Astrophysics Data System (ADS)

    Philip, Brendan T.; Denny, Alden R.; Solomon, Evan A.; Kelley, Deborah S.

    2016-03-01

    An estimated 500-2500 gigatons of methane carbon is sequestered in gas hydrate at continental margins and some of these deposits are associated with overlying methane seeps. To constrain the impact that seeps have on methane concentrations in overlying ocean waters and to characterize the bubble plumes that transport methane vertically into the ocean, water samples and time-series acoustic images were collected above Southern Hydrate Ridge (SHR), a well-studied hydrate-bearing seep site ˜90 km west of Newport, Oregon. These data were coregistered with robotic vehicle observations to determine the origin of the seeps, the plume rise heights above the seafloor, and the temporal variability in bubble emissions. Results show that the locations of seep activity and bubble release remained unchanged over the 3 year time-series investigation, however, the magnitude of gas release was highly variable on hourly time scales. Bubble plumes were detected to depths of 320-620 m below sea level (mbsl), in several cases exceeding the upper limit of hydrate stability by ˜190 m. For the first time, sustained gas release was imaged at the Pinnacle site and in-between the Pinnacle and the Summit area of venting, indicating that the subseafloor transport of fluid and gas is not restricted to the Summit at SHR, requiring a revision of fluid-flow models. Dissolved methane concentrations above background levels from 100 to 300 mbsl are consistent with long-term seep gas transport into the upper water column, which may lead to the build-up of seep-derived carbon in regional subsurface waters and to increases in associated biological activity.

  4. Effect of time and temperature on the hydration process of barley grains

    NASA Astrophysics Data System (ADS)

    Montanuci, Flávia Daiana; Jorge, Luiz Mario Matos; Jorge, Regina Maria Matos

    2015-03-01

    The barley behavior during hydration regarding to water absorption, density, volume variation, and solids loss is identified, as well as employ mathematical models such as diffusional, Peleg, Weibull distribution function and first order kinetics, in order to verify the effect of temperature on the process. Hydration was carried out over 32 h at six different temperatures: 35, 30, 25, 20, 15 and 10 °C. The hydration isotherms were divided into two phases, the first one comprising the first 8 h, with a high hydration rate, and the second one in which the moisture content increases slowly until it reaches the equilibrium moisture content. During the first hour of process, the solids loss at 35 °C was 3.95 % higher than at 10 °C. The effective diffusion coefficients ranged from 5.14 to 10.8 × 10-12 m2/s. The model of Peleg and the first order kinetics model best described the water absorption characteristics at the temperatures investigated.

  5. Understanding gas hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Lapham, Laura; Chanton, Jeffrey; MacDonald, Ian; Martens, Christopher

    2010-05-01

    In order to understand the role gas hydrates play in climate change or their potential as an energy source, we must first understand their basic behaviors. One such behavior not well understood is their dissolution and the factors that control it. Theoretically, hydrates are stable in areas of high pressure, low temperature, moderate salt concentrations, and saturated methane. Yet in nature, we observe hydrate to outcrop seafloor sediments into overlying water that is under-saturated with respect to methane. How do these hydrates not dissolve away? To address this question, we combine both field and laboratory experiments. In the field, we have collected pore-waters directly surrounding gas hydrate outcrops and measured for in situ methane concentrations. This gives us an understanding of the concentration gradients, and thus methane flux, directly from the hydrate to the surrounding environment. From these samples, we found that methane concentrations decreased further from hydrate yet are always under-saturated with respect to methane hydrate. The resulting low methane gradients were then used to calculate low dissolution rates. This result suggests that hydrates are meta-stable in the environment. What controls their apparent meta-stability? We hypothesize that surrounding oils or microbial slimes help protect the hydrate and slow down their dissolution. To test this hypothesis, we conducted a series of laboratory experiments where hydrate was formed at in situ pressure and temperature and the source gas removed; first with no oils, then with oils. Dissolved methane concentrations were then measured in surrounding fluids over time and dissolution rates calculated. To date, both methane and mixed gas hydrate (methane, ethane, and propane) have similar dissolution rates of 0.12 mM/hr. Future experiments will add oils to determine how different hydrate dissolves with such contaminants. This study will further our understanding of factors that control hydrate

  6. Time-Dependent Properties of Multimodal Polyoxymethylene Based Binder for Powder Injection Molding

    NASA Astrophysics Data System (ADS)

    Gonzalez-Gutierrez, Joamin; Stringari, Gustavo Beulke; Zupancic, Barbara; Kubyshkina, Galina; Bernstorff, Bernd Von; Emri, Igor

    Powder injection molding (PIM) is one of the most versatile methods for the manufacturing of small complex shaped components from metal, ceramic or cemented carbide powders for the use in many applications. PIM consists of mixing the powder and a polymeric binder, injecting this mixture in a mold, debinding and then sintering. Catalytic debinding of polyoxymethylene (POM) is attractive since it shows high debinding rates and low risk of cracking. This work examines the possibility of using POM with bimodal molecular mass distribution as the main component of the binding agent by studying its time-dependent properties and comparing them to monomodal POM. Furthermore, possible optimization of the binder formulation was investigated by the addition of shorter polymeric chains (wax) to bimodal POM, as to create a multimodal material. It was observed that the magnitude of the complex viscosity for the commercial bimodal material was more than 2 times lower than for the chemically identical monomodal POM within the investigated frequency range and temperature. Viscosity values were observed to drop as the content of wax was increased, without compromising the binders mechanical properties in solid state. A new formulation of bimodal POM plus 8 wt.% of added wax provided the most appropriate results from investigated combinations. This work has shown how the addition of short polymeric chains in POM influences its time-dependent properties in solid and molten state, which can be an important tool for the optimization of binders designed to be used in PIM technology.

  7. Temporal Characterization of Hydrates System Dynamics beneath Seafloor Mounds. Integrating Time-Lapse Electrical Resistivity Methods and In Situ Observations of Multiple Oceanographic Parameters

    SciTech Connect

    Lutken, Carol; Macelloni, Leonardo; D'Emidio, Marco; Dunbar, John; Higley, Paul

    2015-01-31

    detect short-term changes within the hydrates system, identify relationships/impacts of local oceanographic parameters on the hydrates system, and improve our understanding of how seafloor instability is affected by hydrates-driven changes. A 2009 DCR survey of MC118 demonstrated that we could image resistivity anomalies to a depth of 75m below the seafloor in water depths of 1km. We reconfigured this system to operate autonomously on the seafloor in a pre-programmed mode, for periods of months. We designed and built a novel seafloor lander and deployment capability that would allow us to investigate the seafloor at potential deployment sites and deploy instruments only when conditions met our criteria. This lander held the DCR system, controlling computers, and battery power supply, as well as instruments to record oceanographic parameters. During the first of two cruises to the study site, we conducted resistivity surveying, selected a monitoring site, and deployed the instrumented lander and DCR, centered on what appeared to be the most active locations within the site, programmed to collect a DCR profile, weekly. After a 4.5-month residence on the seafloor, the team recovered all equipment. Unfortunately, several equipment failures occurred prior to recovery of the instrument packages. Prior to the failures, however, two resistivity profiles were collected together with oceanographic data. Results show, unequivocally, that significant changes can occur in both hydrate volume and distribution during time periods as brief as one week. Occurrences appear to be controlled by both deep and near-surface structure. Results have been integrated with seismic data from the area and show correspondence in space of hydrate and structures, including faults and gas chimneys.

  8. Time-Dependent Electrical Properties of Human Nail Upon Hydration In Vivo

    PubMed Central

    HAO, JINSONG; SMITH, KELLY A.; LI, S. KEVIN

    2009-01-01

    The objectives of this study were to investigate the effects of hydration and solution ion concentration on the electrical properties of human nail in vivo and compare these in vivo results with those in vitro. In vivo electrical resistance measurements on the nail were conducted with a three-electrode system in phosphate buffered saline of 0.01–0.6 M. The effect of electric current on nail resistance and possible adverse effects were studied under 1.5- and 9-V iontophoresis in vivo. The electrical resistance of the nail plate was measured in vitro in side-by-side diffusion cells under the same conditions and compared with those in vivo. The in vivo electrical resistance decreased significantly upon 2-h nail hydration and then slowly decreased to a constant value, showing the same pattern as that in vitro. No significant effect of the applied voltage upon the nail electrical resistance was observed. Higher current densities caused moderate sensation and slight changes in nail appearance after iontophoresis. The observed decrease in nail resistance demonstrates the significance of nail hydration in transungual iontophoresis. The in vitro and in vivo correlation suggests that the in vitro nail plate can be a model in the research and development of transungual iontophoretic delivery. PMID:19462425

  9. Hydration of anhydrite of gypsum (CaSO{sub 4}.II) in a ball mill

    SciTech Connect

    Sievert, T.; Wolter, A.; Singh, N.B

    2005-04-01

    The hydration of an anhydrite of gypsum (CaSO{sub 4}.II) in a ball mill was studied as a function of time and temperature. The amount of gypsum formed at different intervals of time was determined by weight loss method and powder X-ray diffraction technique. Specific surface area at different time intervals was determined by LASER granulometric method. The results showed that the maximum rate of formation of gypsum was at a longer time than the time for the development of maximum specific surface area. In the presence of activators, the time for maximum rate of gypsum formation and maximum specific surface area shifted towards lower hydration time. Morphological changes during the course of hydration have been studied by the scanning electron microscopic (SEM) technique. A mechanism of hydration has been proposed.

  10. Chloral Hydrate

    MedlinePlus

    Chloral hydrate, a sedative, is used in the short-term treatment of insomnia (to help you fall asleep and ... Chloral hydrate comes as a capsule and liquid to take by mouth and as a suppository to insert rectally. ...

  11. Absorption spectroscopy of powdered materials using time-resolved diffuse optical methods.

    PubMed

    D'Andrea, Cosimo; Obraztsova, Ekaterina A; Farina, Andrea; Taroni, Paola; Lanzani, Guglielmo; Pifferi, Antonio

    2012-11-10

    In this paper a novel method, based on time-resolved diffuse optical spectroscopy, is proposed to measure the absorption of small amounts of nanostructured powder materials independent of scattering. Experimental validation, in the visible and near-infrared spectral range, has been carried out on India Inkparticles. The effectiveness of the technique to measure scattering-free absorption is demonstrated on carbon nanotubes. The comparison between the absorption spectra acquired by the proposed method and conventional measurements performed with a commercial spectrophotometer is discussed. PMID:23142900

  12. Hydration kinetics of cements by Time-Domain Nuclear Magnetic Resonance: Application to Portland-cement-derived endodontic pastes

    SciTech Connect

    Bortolotti, Villiam; Fantazzini, Paola; Sauro, Salvatore; Zanna, Silvano

    2012-03-15

    Time-Domain Nuclear Magnetic Resonance (TD-NMR) of {sup 1}H nuclei is used to monitor the maturation up to 30 days of three different endodontic cement pastes. The 'Solid-liquid' separation of the NMR signals and quasi-continuous distributions of relaxation times allow one to follow the formation of chemical compounds and the build-up of the nano- and subnano-structured C-S-H gel. {sup 1}H populations, distinguished by their different mobilities, can be identified and assigned to water confined within the pores of the C-S-H gel, to crystallization water and Portlandite, and to hydroxyl groups. Changes of the TD-NMR parameters during hydration are in agreement with the expected effects of the different additives, which, as it is known, can substantially modify the rate of reactions and the properties of cementitious pastes. Endodontic cements are suitable systems to check the ability of this non-destructive technique to give insight into the complex hydration process of real cement pastes.

  13. Determination of Dicyandiamide in Powdered Milk Using Direct Analysis in Real Time Quadrupole Time-of-Flight Tandem Mass Spectrometry.

    PubMed

    Zhang, Liya; Yong, Wei; Liu, Jiahui; Wang, Sai; Chen, Qilong; Guo, Tianyang; Zhang, Jichuan; Tan, Tianwei; Su, Haijia; Dong, Yiyang

    2015-08-01

    The direct analysis in real time (DART) ionization source coupled with quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) system has the capability to desorb analytes directly from samples without sample cleanup or chromatographic separation. In this work, a method based on DART/Q-TOF MS/MS has been developed for rapid identification of dicyandiamide (DCD) present in powdered milk. Simple sample extraction procedure employing acetonitrile-water (80:20, v/v) mixture was followed by direct, high-throughput determination of sample extracts spread on a steel mesh of the transmission module by mass spectrometry under ambient conditions. The method has been evaluated for both qualitative and quantitative analysis of DCD in powdered milk. Variables including experimental apparatus, DART gas heater temperature, sample presentation speed, and vacuum pressure were investigated. The quantitative method was validated with respect to linearity, sensitivity, repeatability, precision, and accuracy by using external standards. After optimization of these parameters, a limit of detection (LOD) of 100 μg kg(-1) was obtained for DCD with a linear working range from 100 to 10000 μg kg(-1) and a satisfactory correlation coefficient (R(2)) of 0.9997. Good recovery (80.08%-106.47%) and repeatability (RSD = 3.0%-5.4%) were achieved for DCD. The DART/Q-TOF MS/MS-based method provides a rapid, efficient, and powerful scheme to analyze DCD in powdered milk with limited sample preparation, thus reducing time and complexity of quality control. PMID:25930094

  14. Determination of Dicyandiamide in Powdered Milk Using Direct Analysis in Real Time Quadrupole Time-of-Flight Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Liya; Yong, Wei; Liu, Jiahui; Wang, Sai; Chen, Qilong; Guo, Tianyang; Zhang, Jichuan; Tan, Tianwei; Su, Haijia; Dong, Yiyang

    2015-08-01

    The direct analysis in real time (DART) ionization source coupled with quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) system has the capability to desorb analytes directly from samples without sample cleanup or chromatographic separation. In this work, a method based on DART/Q-TOF MS/MS has been developed for rapid identification of dicyandiamide (DCD) present in powdered milk. Simple sample extraction procedure employing acetonitrile-water (80:20, v/v) mixture was followed by direct, high-throughput determination of sample extracts spread on a steel mesh of the transmission module by mass spectrometry under ambient conditions. The method has been evaluated for both qualitative and quantitative analysis of DCD in powdered milk. Variables including experimental apparatus, DART gas heater temperature, sample presentation speed, and vacuum pressure were investigated. The quantitative method was validated with respect to linearity, sensitivity, repeatability, precision, and accuracy by using external standards. After optimization of these parameters, a limit of detection (LOD) of 100 μg kg-1 was obtained for DCD with a linear working range from 100 to 10000 μg kg-1 and a satisfactory correlation coefficient (R2) of 0.9997. Good recovery (80.08%-106.47%) and repeatability (RSD = 3.0%-5.4%) were achieved for DCD. The DART/Q-TOF MS/MS-based method provides a rapid, efficient, and powerful scheme to analyze DCD in powdered milk with limited sample preparation, thus reducing time and complexity of quality control.

  15. Spectral and Hydration Dependence of Protein Dynamical Transition

    NASA Astrophysics Data System (ADS)

    Lipps, Ferdinand; Knab, J. R.; Chen, Jing Yin; He, Yunfen; Markelz, A. G.

    2008-03-01

    The protein dynamical transition, a rapid increase in flexibility at ˜ 200K, is hydration dependent suggesting that the transition may in fact be due to a transition in the surrounding water. Previously we have shown that the terahertz dielectric response is sensitive to the dynamical transition using terahertz time domain spectroscopy [1]. The broadband technique allows the determination of what motions are affected by the transition, that is whether long time scale motions such as side chain rotations, or faster vibrational motions. Here we examine both the frequency and hydration dependence of the protein dynamical transition for hydrated myoglobin powder for the 0.2 -- 2.0 THz and 80-295 K ranges. The transition is observed in both the real and imaginary parts of the dielectric response. Our earlier measurements of solutions did not show a transition in the real part of the permittivity, likely due to bulk solvent dominating the index. There is a strong frequency dependence with hydration. While a slight transition is observed at frequencies higher than 1 THz which is nearly hydration independent, for frequencies below 1 THz the strength of the transition rapidly increases with hydration. [1] A. G. Markelz, J. R. Knab, Jing Yin Chen, Yunfen He, Chem. Phys. Lett. 442, 413 (2007).

  16. Rietveld refinement with time-of-flight powder diffraction data from pulsed neutron sources

    SciTech Connect

    David, W.I.F. ); Jorgensen, J.D. )

    1990-10-01

    The recent development of accelerator-based pulsed neutron sources has led to the widespread use of the time-of-flight technique for neutron powder diffraction. The properties of the pulsed source make possible unusually high resolution over a wide range of d spacings, high count rates, and the ability to collect complete data at fixed scattering angles. The peak shape and other instrument characteristics can be accurately modelled, which make Rietveld refinement possible for complex structures. In this paper we briefly review the development of the Rietveld method for time-of-flight diffraction data from pulsed neutron sources and discuss the latest developments in high resolution instrumentation and advanced Rietveld analysis methods. 50 refs., 12 figs., 14 tabs.

  17. Neutron powder diffraction study of the layer organic-inorganic hybrid iron(II) methylphosphonate-hydrate, Fe[(CD 3PO 3)(D 2O)

    NASA Astrophysics Data System (ADS)

    Léone, Philippe; Bellitto, Carlo; Bauer, Elvira M.; Righini, Guido; André, Gilles; Bourée, Françoise

    2008-11-01

    The crystal and magnetic structures of the hybrid organic-inorganic layer compound Fe[(CD 3PO 3)(D 2O)] have been studied by neutron powder diffraction as a function of temperature down to 1.5 K. The neutron diffraction pattern recorded at 200 K shows that the fully deuterated compound crystallizes in one of the two known forms of the undeuterated Fe[(CH 3PO 3)(H 2O)]. The crystal structure is orthorhombic, space group Pmn2 1, with the following unit-cell parameters: a=5.7095(1) Å, b=8.8053(3) Å and c=4.7987(1) Å; Z=2. The crystal structure remains unchanged on cooling from 200 to 1.5 K. Moreover, at low temperature, Fe[(CD 3PO 3)(D 2O)] shows a commensurate magnetic structure ( k=(0,0,0)). As revealed by bulk susceptibility measurements on Fe[(CH 3PO 3)(H 2O)], the magnetic structure corresponds to a canted antiferromagnet with a critical temperature TN=25 K. Neutron powder diffraction reveals that below TN=23.5 K the iron magnetic moments in Fe[(CD 3PO 3)(D 2O)] are antiferromagnetically coupled and oriented along the b-axis, perpendicular to the inorganic layers. No ferromagnetic component is observable in the neutron powder diffraction experiment, due to its too small value (<0.1 μB).

  18. Time-resolved quasielastic neutron scattering study of the hydration of tricalcium silicate: Effects of CaCl 2 and sucrose

    NASA Astrophysics Data System (ADS)

    Peterson, Vanessa K.; Garci Juenger, Maria C.

    2006-11-01

    Time-resolved quasielastic neutron scattering coupled with hydration modeling enabled the interpretation of the hydration processes in a triclinic form of tricalcium silicate when calcium chloride and sucrose were added. Calcium chloride increases the rate of product formation and causes a less dense product to form. Sucrose was investigated at two concentrations. With increasing amount of sucrose, the retardation time and the length of the nucleation and growth period increase, and the product density decreases. The rate of nucleation and growth of products is not linearly dependent on the amount of sucrose added, a result attributed to complexation with Ca 2+ at higher concentrations.

  19. In-situ time resolved synchrotron powder diffraction studies of synthesis and chemical reactions

    SciTech Connect

    Norby, P.

    1995-09-01

    Equipment for time and temperature dependent powder diffraction has been developed, especially in order to be able to study hydrothermal syntheses of zeolites. The system is very versatile and has so far been used to study e.g. hydrothermal syntheses of zeolites and aluminophosphates, syntheses of layered phosphates, formation of Sorel cements, dehydration and phase transformations of zeolites, solid state synthesis of lanthanum manganites, ion exchange of zeolites using molten salt, and oxidation/reduction of lanthanum manganites at high temperatures. The sample is contained in quartz capillaries and is heated using a stream of hot air. External pressure can be applied allowing hydrothermal syntheses at temperatures up to 200 C to be performed. Controlled atmosphere is obtained by flowing gas or a mixture of gases through the capillary.

  20. Ocean temperature variability for the past 60 years on the Norwegian-Svalbard margin influences gas hydrate stability on human time scales

    NASA Astrophysics Data System (ADS)

    Ferré, BéNéDicte; Mienert, Jürgen; Feseker, Tomas

    2012-10-01

    The potential impact of future climate change on methane release from oceanic gas hydrates is the subject of much debate. We analyzed World Ocean Database quality controlled data on the Norwegian-Svalbard continental margin from the past 60 years to evaluate the potential effect of ocean temperature variations on continental margin gas hydrate reservoirs. Bottom water temperatures in the Norwegian-Svalbard margin were subject to significant cooling until 1980 (by ˜2°C offshore NW-Svalbard and in the Barents Sea) followed by a general bottom water temperature increase until 2010 (˜0.3°C in deep-water areas offshore NW-Svalbard and mid-Norwegian margin and ˜2°C in the shallow areas of the Barents Sea and Prins Karls Forland). Bottom water warming in the shallow outer shelf areas triggered the Gas Hydrate Stability Zone (GHSZ) retreat toward upper continental slope areas, potentially increasing methane release due to gas hydrate dissociation. GHSZ responses to temperature changes on human time scales occur exclusively in shallow water and only if near-surface gas hydrates exist. The responses are associated with a short time lag of less than 1 year. Temperatures in the bottom water column seem to be partly regulated by the North Atlantic Oscillation (NAO), with positive NAO associated with warm phases. However, cooling events in the surface water offshore NW-Svalbard might be associated with El Niño events of 1976-1977, 1986-1987 and 1997-1998 in the Pacific. Such ocean cooling, if long enough, may delay ocean temperature driven gas hydrate dissociation and potential releases of methane to the ocean.

  1. The relationship between drug concentration, mixing time, blending order and ternary dry powder inhalation performance.

    PubMed

    Jones, Matthew D; Santo, João G F; Yakub, Bilal; Dennison, Mansa; Master, Husein; Buckton, Graham

    2010-05-31

    Some studies have shown that the mixing order of drug, fines and coarse carrier in a ternary dry powder inhaler (DPI) formulation affects fine particle delivery; others have seen no difference. This was investigated by examining the influence of salbutamol sulphate concentration (0.5-4.5%(w)/(w)), mixing time and blending order (drug and lactose carrier first, then lactose fines; versus fines and carrier first, then drug) on formulation in vitro fine particle delivery. With 15 min of mixing, there was no effect of drug concentration or blending order on fine particle fraction (FPF). With 30 min of mixing, lower drug concentrations produced larger FPFs with the fines and carrier first blending order. Higher drug concentrations resulted in equal performance between the blending orders. With 60 min of mixing, the drug and carrier first blending order resulted in larger a FPF at 0.5%(w)/(w) salbutamol sulphate. The previous conflicting studies used a mixing time of 30 min; these results suggest that their conflicting results may have been due to the use of different drug concentrations. The complexity in the whole dataset suggests that blending order studies are of limited use for the investigation of the mechanism behind the effects of fines. PMID:20211715

  2. Nanosecond Relaxation Dynamics of Hydrated Proteins: Water versus protein contributions

    SciTech Connect

    Khodadadi, S; Curtis, J. E.; Sokolov, Alexei P

    2011-01-01

    We have studied picosecond to nanosecond dynamics of hydrated protein powders using dielectric spectroscopy and molecular dynamics (MD) simulations. Our analysis of hydrogen-atom single particle dynamics from MD simulations focused on main ( main tens of picoseconds) and slow ( slow nanosecond) relaxation processes that were observed in dielectric spectra of similar hydrated protein samples. Traditionally, the interpretation of these processes observed in dielectric spectra has been ascribed to the relaxation behavior of hydration water tightly bounded to a protein and not to protein atoms. Detailed analysis of the MD simulations and comparison to dielectric data indicate that the observed relaxation process in the nanosecond time range of hydrated protein spectra is mainly due to protein atoms. The relaxation processes involve the entire structure of protein including atoms in the protein backbone, side chains, and turns. Both surface and buried protein atoms contribute to the slow processes; however, surface atoms demonstrate slightly faster relaxation dynamics. Analysis of the water molecule residence and dipolar relaxation correlation behavior indicates that the hydration water relaxes at much shorter time scales.

  3. Methane Hydrates: Chapter 8

    USGS Publications Warehouse

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

    2008-01-01

    produced through exploratory drilling programs; (2) the tools for gas hydrate detection and characterisation from remote sensing data; (3) the details of gas hydrate reservoir production behaviour through additional, well-monitored and longer duration field tests and (4) the understanding of the potential environmental impacts of gas hydrate resource development. The results of future production tests, in the context of varying market and energy supply conditions around the globe, will be the key to determine the ultimate timing and scale of the commercial production of natural gas from gas hydrates.

  4. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding

  5. Partially Hydrated Electrons at the Air/Water Interface Observed by UV-Excited Time-Resolved Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

    PubMed

    Matsuzaki, Korenobu; Kusaka, Ryoji; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Nagata, Takashi; Tahara, Tahei

    2016-06-22

    Hydrated electrons are the most fundamental anion species, consisting only of electrons and surrounding water molecules. Although hydrated electrons have been extensively studied in the bulk aqueous solutions, even their existence is still controversial at the water surface. Here, we report the observation and characterization of hydrated electrons at the air/water interface using new time-resolved interface-selective nonlinear vibrational spectroscopy. With the generation of electrons at the air/water interface by ultraviolet photoirradiation, we observed the appearance of a strong transient band in the OH stretch region by heterodyne-detected vibrational sum-frequency generation. Through the comparison with the time-resolved spectra at the air/indole solution interface, the transient band was assigned to the vibration of water molecules that solvate electrons at the interface. The analysis of the frequency and decay of the observed transient band indicated that the electrons are only partially hydrated at the water surface, and that they escape into the bulk within 100 ps. PMID:27281547

  6. Time-resolved x-ray diffraction and Raman studies of the phase transition mechanisms of methane hydrate

    SciTech Connect

    Hirai, Hisako Kadobayashi, Hirokazu; Hirao, Naohisa; Ohishi, Yasuo; Ohtake, Michika; Yamamoto, Yoshitaka; Nakano, Satoshi

    2015-01-14

    The mechanisms by which methane hydrate transforms from an sI to sH structure and from an sH to filled-ice Ih structure were examined using time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device camera observation under fixed pressure conditions. The XRD data obtained for the sI–sH transition at 0.8 GPa revealed an inverse correlation between sI and sH, suggesting that the sI structure is replaced by sH. Meanwhile, the Raman analysis demonstrated that although the 12-hedra of sI are retained, the 14-hedra are replaced sequentially by additional 12-hedra, modified 12-hedra, and 20-hedra cages of sH. With the sH to filled-ice Ih transition at 1.8 GPa, both the XRD and Raman data showed that this occurs through a sudden collapse of the sH structure and subsequent release of solid and fluid methane that is gradually incorporated into the filled-ice Ih to complete its structure. This therefore represents a typical reconstructive transition mechanism.

  7. Hydration-dependent dynamic crossover phenomenon in protein hydration water

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Fratini, Emiliano; Li, Mingda; Le, Peisi; Mamontov, Eugene; Baglioni, Piero; Chen, Sow-Hsin

    2014-10-01

    The characteristic relaxation time τ of protein hydration water exhibits a strong hydration level h dependence. The dynamic crossover is observed when h is higher than the monolayer hydration level hc=0.2-0.25 and becomes more visible as h increases. When h is lower than hc, τ only exhibits Arrhenius behavior in the measured temperature range. The activation energy of the Arrhenius behavior is insensitive to h, indicating a local-like motion. Moreover, the h dependence of the crossover temperature shows that the protein dynamic transition is not directly or solely induced by the dynamic crossover in the hydration water.

  8. Hydration kinetics and physical properties of split chickpea as affected by soaking temperature and time.

    PubMed

    Johnny, Saeed; Razavi, Seyed M A; Khodaei, Diako

    2015-12-01

    In this study, some physical properties (principal dimensions, mean diameters, sphericity, area, density and electrical conductivity) of split chickpea were measured as function of soaking time (up to 360 min) and temperature (25-65 °C). Initially, the water absorption rate was high and then it showed a progressive decrease at all temperatures, whereas solid loss exhibited a power function of temperature (P < 0.05). The Peleg model was predicted well the kinetic of split chickpea soaking. No significant difference (P < 0.05) was observed in Peleg rate constant (K1) and Peleg capacity constant (K2) at all temperatures except for K1 at 25 °C. The discrepancy for K1 was in relation to permeability characteristics of split chickpea at temperature of 25 °C. As temperature increased from 25 to 65 °C, the K1 value decreased from 0.04620 to 0.00945 g h(-1), whereas the K2 value increased from 0.08597 to 0.11320 g(-1). Plot for K1 exhibited a slope changes around 45 °C corresponding to gelatinization temperature of split chickpeas. The effect of temperature and time on physical properties of split chickpea during soaking was monitored by regression equations. It was concluded that physical properties of split chickpea affected by its water absorption especially at higher temperatures. PMID:26604418

  9. Powder diffraction from a continuous microjet of submicrometer protein crystals.

    PubMed

    Shapiro, D A; Chapman, H N; Deponte, D; Doak, R B; Fromme, P; Hembree, G; Hunter, M; Marchesini, S; Schmidt, K; Spence, J; Starodub, D; Weierstall, U

    2008-11-01

    Atomic-resolution structures from small proteins have recently been determined from high-quality powder diffraction patterns using a combination of stereochemical restraints and Rietveld refinement [Von Dreele (2007), J. Appl. Cryst. 40, 133-143; Margiolaki et al. (2007), J. Am. Chem. Soc. 129, 11865-11871]. While powder diffraction data have been obtained from batch samples of small crystal-suspensions, which are exposed to X-rays for long periods of time and undergo significant radiation damage, the proof-of-concept that protein powder diffraction data from nanocrystals of a membrane protein can be obtained using a continuous microjet is shown. This flow-focusing aerojet has been developed to deliver a solution of hydrated protein nanocrystals to an X-ray beam for diffraction analysis. This method requires neither the crushing of larger polycrystalline samples nor any techniques to avoid radiation damage such as cryocooling. Apparatus to record protein powder diffraction in this manner has been commissioned, and in this paper the first powder diffraction patterns from a membrane protein, photosystem I, with crystallite sizes of less than 500 nm are presented. These preliminary patterns show the lowest-order reflections, which agree quantitatively with theoretical calculations of the powder profile. The results also serve to test our aerojet injector system, with future application to femtosecond diffraction in free-electron X-ray laser schemes, and for serial crystallography using a single-file beam of aligned hydrated molecules. PMID:18955765

  10. Rapid gas hydrate formation process

    SciTech Connect

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  11. LOW TEMPERATURE X-RAY DIFFRACTION STUDIES OF NATURAL GAS HYDRATE SAMPLES FROM THE GULF OF MEXICO

    SciTech Connect

    Rawn, Claudia J; Sassen, Roger; Ulrich, Shannon M; Phelps, Tommy Joe; Chakoumakos, Bryan C; Payzant, E Andrew

    2008-01-01

    Clathrate hydrates of methane and other small alkanes occur widespread terrestrially in marine sediments of the continental margins and in permafrost sediments of the arctic. Quantitative study of natural clathrate hydrates is hampered by the difficulty in obtaining pristine samples, particularly from submarine environments. Bringing samples of clathrate hydrate from the seafloor at depths without compromising their integrity is not trivial. Most physical property measurements are based on studies of laboratory-synthesized samples. Here we report X-ray powder diffraction measurements of a natural gas hydrate sample from the Green Canyon, Gulf of Mexico. The first data were collected in 2002 and revealed ice and structure II gas hydrate. In the subsequent time the sample has been stored in liquid nitrogen. More recent X-ray powder diffraction data have been collected as functions of temperature and time. This new data indicates that the larger sample is heterogeneous in ice content and shows that the amount of sII hydrate decreases with increasing temperature and time as expected. However, the dissociation rate is higher at lower temperatures and earlier in the experiment.

  12. Gas hydrate measurements at Hydrate Ridge using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Hester, K. C.; Dunk, R. M.; White, S. N.; Brewer, P. G.; Peltzer, E. T.; Sloan, E. D.

    2007-06-01

    Oceanic gas hydrates have been measured near the seafloor for the first time using a seagoing Raman spectrometer at Hydrate Ridge, Oregon, where extensive layers of hydrates have been found to occur near the seafloor. All of the hydrates analyzed were liberated from the upper meter of the sediment column near active gas venting sites in water depths of 770-780 m. Hydrate properties, such as structure and composition, were measured with significantly less disturbance to the sample than would be realized with core recovery. The natural hydrates measured were sI, with methane as the predominant guest component, and minor/trace amounts of hydrogen sulfide present in three of the twelve samples measured. Methane large-to-small cage occupancy ratios of the hydrates varied from 1.01 to 1.30, in good agreement with measurements of laboratory synthesized and recovered natural hydrates. Although the samples visually appeared to be solid, varying quantities of free methane gas were detected, indicating the possible presence of occluded gas in a hydrate bubble fabric.

  13. The search for negative amplitude components in quasi-continuous distributions of relaxation times: the example of 1H magnetization exchange in articular cartilage and hydrated collagen

    NASA Astrophysics Data System (ADS)

    Fantazzini, Paola; Galassi, Francesca; Bortolotti, Villiam; Brown, Robert J. S.; Vittur, Franco

    2011-06-01

    When inverting nuclear magnetic resonance relaxation data in order to obtain quasi-continuous distributions of relaxation times for fluids in porous media, it is common practice to impose a non-negative (NN) constraint on the distributions. While this approach can be useful in reducing the effects of data distortion and/or preventing wild oscillations in the distributions, it may give misleading results in the presence of real negative amplitude components. Here, some examples of valid negative components for articular cartilage and hydrated collagen are given. Articular cartilage is a connective tissue, consisting mainly of collagen, proteoglycans and water, which can be considered, in many aspects, as a porous medium. Separate T1 relaxation data are obtained for low-mobility ('solid') macromolecular 1H and for higher-mobility ('liquid') 1H by the separation of these components in free induction decays, with α denoting the solid/liquid 1H ratio. When quasi-continuous distributions of relaxation times (T1) of the solid and liquid signal components of cartilage or collagen are computed from experimental relaxation data without imposing the usual NN constraint, valid negative peaks may appear. The features of the distributions, in particular negative peaks, and the fact that peaks at longer times for macromolecular and water protons are at essentially the same T1, are interpreted as the result of a magnetization exchange between these two spin pools. For the only-slightly-hydrated collagen samples, with α>1, the exchange leads to small negative peaks at short T1 times for the macromolecular component. However, for the cartilage, with substantial hydration or for a strongly hydrated collagen sample, both with αLt1, the behavior is reversed, with a negative peak for water at short times. The validity of a negative peak may be accepted (dismissed) by a high (low) cost of NN in error of fit. Computed distributions for simulated data using observed signal

  14. Estimation of Time-Temperature-Transformation Diagrams of Mold Powder Slags from Thermo-analysis of Non-isothermal Crystallization

    NASA Astrophysics Data System (ADS)

    Maldonado, Yadira G.; Barraza de la P., Claudia; Rodríguez A., Sergio; Castillejos E., A. Humberto; Thomas, Brian G.

    2014-09-01

    The temperature range across the mold powder slag in the interfacial gap between the continuous casting mold and strand leads through different transformation behavior into crystalline phases. The transformation rates play a key role in determining the proportion of glassy and crystalline phases present, and thus greatly influence mold heat transfer and lubrication. Although thermal analysis has held great promise to quantify the crystallization of mold slags, so far the information it has provided is scarce. This work shows how differential scanning calorimetry, DSC, data allow evaluation of Time-Temperature-Transformation, TTT, diagrams of mold powder slags, when analyzed with the induction period and the Kissinger methods. The data required for estimating this important tool for the analysis and design of mold powders are onset temperature, T i, peak maximum temperature, T m, shape index, S, and conversion at peak maximum, x m, of the crystallization peaks appearing on thermograms obtained at various heating and cooling rates, ϕ or -ϕ, respectively. Industrial mold powders for casting low- and medium-carbon steels were analyzed to obtain TTT diagrams which correctly portray their different crystallization behavior. The diagrams reveal the start and end curves of the crystalline phases forming at each DSC crystallization peak. The estimated TTT curves present a correct picture of the degree of transformation observed in glass disks (~3 mm thick) treated isothermally for specified time intervals, quenched and examined with a scanning electron microscope. Additionally, the procedure developed for DSC-based TTT diagram calculation is supported by the good agreement between expected transformations and qualitative or quantitative X-ray diffraction results obtained from mold glass-powdered samples treated isothermally in a muffle furnace.

  15. Estimation of Time-Temperature-Transformation Diagrams of Mold Powder Slags from Thermo-analysis of Non-isothermal Crystallization

    NASA Astrophysics Data System (ADS)

    Maldonado, Yadira G.; Barraza de la P., Claudia; Rodríguez A., Sergio; Castillejos E., A. Humberto; Thomas, Brian G.

    2015-02-01

    The temperature range across the mold powder slag in the interfacial gap between the continuous casting mold and strand leads through different transformation behavior into crystalline phases. The transformation rates play a key role in determining the proportion of glassy and crystalline phases present, and thus greatly influence mold heat transfer and lubrication. Although thermal analysis has held great promise to quantify the crystallization of mold slags, so far the information it has provided is scarce. This work shows how differential scanning calorimetry, DSC, data allow evaluation of Time-Temperature-Transformation, TTT, diagrams of mold powder slags, when analyzed with the induction period and the Kissinger methods. The data required for estimating this important tool for the analysis and design of mold powders are onset temperature, T i, peak maximum temperature, T m, shape index, S, and conversion at peak maximum, x m, of the crystallization peaks appearing on thermograms obtained at various heating and cooling rates, ϕ or - ϕ, respectively. Industrial mold powders for casting low- and medium-carbon steels were analyzed to obtain TTT diagrams which correctly portray their different crystallization behavior. The diagrams reveal the start and end curves of the crystalline phases forming at each DSC crystallization peak. The estimated TTT curves present a correct picture of the degree of transformation observed in glass disks (~3 mm thick) treated isothermally for specified time intervals, quenched and examined with a scanning electron microscope. Additionally, the procedure developed for DSC-based TTT diagram calculation is supported by the good agreement between expected transformations and qualitative or quantitative X-ray diffraction results obtained from mold glass-powdered samples treated isothermally in a muffle furnace.

  16. Molecular-dynamics modelling and neutron diffraction study of the site disorder in air clathrate hydrates

    SciTech Connect

    Chazallon, Bertrand; Klapproth, Alice; Kuhs, Werner F.

    1999-06-15

    We present the results of MD-simulation runs with subsequent quenches for clathrate hydrates using SPC water in order to model properly the crystallographic site disorder of the guest molecules in the water cages. A procedure is described to transform the results of the quench (symmetry P1) into the proper space-time averaged space group (Fd3-bar m) of the clathrate hydrate. The resulting disorder models are compared with the outcome of crystallographic structure refinements (R-factors, Fourier maps) from our neutron powder diffraction data. A correct description of the disorder is important for a reliable determination of the pressure-dependent cage filling.

  17. Chloral hydrate

    Integrated Risk Information System (IRIS)

    Chloral hydrate ; CASRN 302 - 17 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  18. Hydration water dynamics and instigation of protein structuralrelaxation

    SciTech Connect

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-09-01

    Until a critical hydration level is reached, proteins do not function. This critical level of hydration is analogous to a similar lack of protein function observed for temperatures below a dynamical temperature range of 180-220K that also is connected to the dynamics of protein surface water. Restoration of some enzymatic activity is observed in partially hydrated protein powders, sometimes corresponding to less than a single hydration layer on the protein surface, which indicates that the dynamical and structural properties of the surface water is intimately connected to protein stability and function. Many elegant studies using both experiment and simulation have contributed important information about protein hydration structure and timescales. The molecular mechanism of the solvent motion that is required to instigate the protein structural relaxation above a critical hydration level or transition temperature has yet to be determined. In this work we use experimental quasi-elastic neutron scattering (QENS) and molecular dynamics simulation to investigate hydration water dynamics near a greatly simplified protein system. We consider the hydration water dynamics near the completely deuterated N-acetyl-leucine-methylamide (NALMA) solute, a hydrophobic amino acid side chain attached to a polar blocked polypeptide backbone, as a function of concentration between 0.5M-2.0M under ambient conditions. We note that roughly 50-60% of a folded protein's surface is equally distributed between hydrophobic and hydrophilic domains, domains whose lengths are on the order of a few water diameters, that justify our study of hydration dynamics of this simple model protein system. The QENS experiment was performed at the NIST Center for Neutron Research, using the disk chopper time of flight spectrometer (DCS). In order to separate the translational and rotational components in the spectra, two sets of experiments were carried out using different incident neutron wavelengths of 7

  19. Formation of porous gas hydrates: Diffraction experiments and multi-stage model

    NASA Astrophysics Data System (ADS)

    Staykova, D. K.; Genov, G.; Goreshnik, E.; Salamatin, A. N.; Kuhs, W. F.

    2003-04-01

    Laboratory-grown gas hydrates were examined by cryo scanning electron microscopy and found to have a sub-micron porous structure. This microstructure is undistinguishable from the one observed in natural gas hydrates suggesting similar formation processes. In-situ observations of the formation of synthetic porous methane and carbon dioxide hydrates starting from ice Ih powders with known surfaces areas were made using time-resolved neutron diffraction on the high-flux diffractometer D20 (ILL, Grenoble) at different pressures and temperatures. Some runs were also made going through the ice melting point into liquid water. At similar reduced fugacities, the reaction of carbon dioxide was distinctly faster than that of methane. The transient formation of carbon dioxide hydrate crystal structure II was observed in coexistence with the usual type-I hydrate reaching a maximum of 5% after 5 h of the reaction at 272 K. At lower temperatures a temporary inhibition of formation was observed in the case of carbon dioxide. The rate of methane hydrate growth showed little pressure sensitivity in our experiments at low temperatures ~230 K in contrast to the situation at higher temperatures. A phenomenological model for the kinetics of the gas hydrate formation from ice powders is developed with special account of sample consolidation effects. It describes the initial stage (I) of hydrate film spreading over the ice surface and the two subsequent stages which are limited (II) by the clathration reaction at the ice-hydrate interface and (III) by the gas and water transport (diffusion) through the hydrate shells surrounding the shrinking ice cores. Comparable activation energies of the CH4-hydrate formation are found in deuterated and hydrogenated systems for the reaction-limited process (stage II) to be 8.1 and 9.5 kcal/mol, respectively. In the case of a diffusion-limited clathration (stage III) the activation energy can be estimated as 14.3 kcal/mol. The relevance of our

  20. Effect of Time and storage temperature on anthocyanin decay and antioxidant activity in wild blueberry ( Vaccinium angustifolium ) powder.

    PubMed

    Fracassetti, Daniela; Del Bo', Cristian; Simonetti, Paolo; Gardana, Claudio; Klimis-Zacas, Dorothy; Ciappellano, Salvatore

    2013-03-27

    This study evaluated the effects of storage on total and single anthocyanin (ACN) content, and total antioxidant activity (TAA) of freeze-dried wild blueberry (WB) powder maintained at 25, 42, 60, and 80 °C for 49 days. Storage reduced single and total ACN content at all of the temperatures; it was slower at 25 °C (-3% after 2 weeks), whereas it was faster at 60 °C (-60%) and at 80 °C (-85%) after 3 days. The values of half-life time (t1/2) were found to be 139, 39, and 12 days at 25, 42, and 60 °C, respectively, utilizing the Arrhenius equation. No significant effects were detected on TAA by temperature increase. In conclusion, this study provides important information on the stability of WB powder at 25 °C; this is interesting scientific research for the food industry. PMID:23489164

  1. Time- and Space-Resolved SAXS Experiments Inform on Phase Transition Kinetics in Hydrated, Liquid-Crystalline Films of Polyion-Surfactant Ion "Complex Salts".

    PubMed

    Li, Joaquim; Gustavsson, Charlotte; Piculell, Lennart

    2016-05-24

    Detailed time- and space-resolved SAXS experiments show the variation with hydration of liquid crystalline structures in ethanol-cast 5-80 μm thick films of polyion-surfactant ion "complex salts" (CS). The CS were dodecyl- (C12) or hexadecyl- (C16) trimethylammonium surfactants with polyacrylate (DP 25 or 6000) counter-polyions. The experiments were carried out on vertical films in humid air above a movable water bath, so that gradients of hydration were generated, which could rapidly be altered. Scans over different positions along a film, kept fixed relative to the bath, showed that the surfactant aggregates of the various liquid-crystalline CS structures grow in cross-sectional area with decreasing hydration. This behavior is attributed to the low water content. Studies of films undergoing rapid dehydration, made possible by the original experimental setup, gave strong evidence that some of the investigated systems remain kinetically trapped for minutes in a nonequilibrium Pm3n micellar cubic phase before switching to the equilibrium P6mm 2D hexagonal phase. Both the length of the polyion and the length of the surfactant hydrocarbon "tail" affect the kinetics of the phase transition. The slowness of the cubic-to-hexagonal structural transition is attributed to the fact that it requires major rearrangements of the polyions and surfactant ions relative to each other. By contrast, other structure changes, such as between the hexagonal and rectangular phases, were observed to occur much more rapidly. PMID:27153140

  2. Thermal decomposition of HfCl{sub 4} as a function of its hydration state

    SciTech Connect

    Barraud, E.; Begin-Colin, S. . E-mail: begin@ipcms.u-strasbg.fr; Le Caer, G.; Villieras, F.; Barres, O.

    2006-06-15

    The thermogravimetric behavior of HfCl{sub 4} powders with different hydration states has been compared. Strongly hydrated powders consist of HfOCl{sub 2}.nH{sub 2}O with n>4. Partially hydrated powders consist of particles with a HfCl{sub 4} core and a hydrated outerlayer of HfOCl{sub 2}.nH{sub 2}O with n in the range of 0-8. Hydrated powders decomposed at temperature lower than 200 deg. C whereas the decomposition of partially hydrated powders was completed at a temperature of around 450 deg. C. The observed differences in decomposition temperature is related to the structure of HfOCl{sub 2}.nH{sub 2}O, which is different if n is higher or smaller than 4 and leads to intermediate compounds, which decompose at different temperatures.

  3. Effects of Preculturing Conditions on Lag Time and Specific Growth Rate of Enterobacter sakazakii in Reconstituted Powdered Infant Formula

    PubMed Central

    Kandhai, M. C.; Reij, M. W.; Grognou, C.; van Schothorst, M.; Gorris, L. G. M.; Zwietering, M. H.

    2006-01-01

    Enterobacter sakazakii can be present, although in low levels, in dry powdered infant formulae, and it has been linked to cases of meningitis in neonates, especially those born prematurely. In order to prevent illness, product contamination at manufacture and during preparation, as well as growth after reconstitution, must be minimized by appropriate control measures. In this publication, several determinants of the growth of E. sakazakii in reconstituted infant formula are reported. The following key growth parameters were determined: lag time, specific growth rate, and maximum population density. Cells were harvested at different phases of growth and spiked into powdered infant formula. After reconstitution in sterile water, E. sakazakii was able to grow at temperatures between 8 and 47°C. The estimated optimal growth temperature was 39.4°C, whereas the optimal specific growth rate was 2.31 h−1. The effect of temperature on the specific growth rate was described with two secondary growth models. The resulting minimum and maximum temperatures estimated with the secondary Rosso equation were 3.6°C and 47.6°C, respectively. The estimated lag time varied from 83.3 ± 18.7 h at 10°C to 1.73 ± 0.43 h at 37°C and could be described with the hyperbolic model and reciprocal square root relation. Cells harvested at different phases of growth did not exhibit significant differences in either specific growth rate or lag time. Strains did not have different lag times, and lag times were short given that the cells had spent several (3 to 10) days in dry powdered infant formula. The growth rates and lag times at various temperatures obtained in this study may help in calculations of the period for which reconstituted infant formula can be stored at a specific temperature without detrimental impact on health. PMID:16597976

  4. Bubble migration during hydrate formation

    NASA Astrophysics Data System (ADS)

    Shagapov, V. Sh.; Chiglintseva, A. S.; Rusinov, A. A.

    2015-03-01

    A model of the process of migration of methane bubbles in water under thermobaric conditions of hydrate formation is proposed. The peculiarities of the temperature field evolution, migration rate, and changes in the radius and volume fraction of gas hydrate bubbles are studied. It is shown that, with a constant mass flow of gas from the reservoir bottom, for all parameters of the surfacing gas hydrate disperse system, there is a quasistationary pattern in the form of a "step"-like wave. Depending on the relationship of the initial gas bubble density with the average gas density in the hydrate composition determined by the depth from which bubbles rise to the surface, the final radius of hydrate particles may be larger or smaller than the initial gas bubble radii. It is established that the speed at which gas hydrate inclusions rise to the surface decreases by several times due to an increase in their weight during hydrate formation. The influence of the depth of the water reservoir whose bottom is a gas flow source on the dynamics of hydrate formation is studied.

  5. Ductile flow of methane hydrate

    USGS Publications Warehouse

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

    2003-01-01

    Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

  6. Dry stress and survival time of Enterobacter sakazakii and other Enterobacteriaceae in dehydrated powdered infant formula.

    PubMed

    Barron, Juncal Caubilla; Forsythe, Stephen J

    2007-09-01

    Powdered infant formula is not a sterile product, and opportunistic pathogens could multiply in the reconstituted product, resulting in neonatal infections. In this study, the generation of sublethally injured Enterobacteriaceae during desiccation and their persistence in dehydrated powdered infant formula was assessed during a 2.5-year period. The study included 27 strains of Enterobacter sakazakii, Enterobacter cloacae, Salmonella Enteritidis, Citrobacter koseri, Citrobacter freundii, Escherichia coli, Escherichia vulneris, Pantoea spp., Klebsiella oxytoca, and Klebsiella pneumoniae. The number of sublethally injured cells generated during desiccation was lower for K. oxytoca, Pantoea spp., Salmonella Enteritidis, and capsulated strains of E. sakazakii than for the other Enterobacteriaceae. The Enterobacteriaceae could be divided into three groups with respect to their long-term survival in the desiccated state. C. freundii, C. koseri, and E. cloacae were no longer recoverable after 6 months, and Salmonella Enteritidis, K. pneumoniae, and E. coli could not be recovered after 15 months. Pantoea spp., K. oxytoca, and E. vulneris persisted over 2 years, and some capsulated strains of E. sakazakii were still recoverable after 2.5 years. PMID:17900090

  7. Evidence that the crystalline cores of uplifts adjacent to the Powder River Basin were breached during Paleocene time

    SciTech Connect

    Merin, I.S.; Lindholm, R.C.

    1986-10-01

    Sandstones in the upper part of the Paleocene Tongue River Member of the Fort Union Formation in the Powder River basin are dominantly sublitharenite. These rocks contain abundant rock fragments of non-ferroan calcite, dolomite, chert, and foliated fine-grained metamorphic rock (phyllite). The carbonate and chert rock fragments were probably eroded from paleozoic carbonate sequences flanking the Bighorn Mountains or the Black Hills. The phyllitic rock fragments indicate that the crystalline cores of these uplifts were exposed during Paleocene time, which is earlier during the Laramide Orogeny than has been previously demonstrated.

  8. Antiatherosclerotic and Cardioprotective Effects of Time-Released Garlic Powder Pills.

    PubMed

    Karagodin, Vasily P; Sobenin, Igor A; Orekhov, Alexander N

    2016-01-01

    Garlic is believed to produce beneficial changes in different cardiovascular risk factors, thus possessing antiatherosclerotic properties. The hypotensive and cholesterol-lowering effects were investigated in two studies in men with mild arterial hypertension and in men with mild hypercholesterolemia. Eight-week treatment resulted in the reduction of both systolic and diastolic blood pressure by 5.2% (P=0.008) and 4.0% (P=0.014), respectively. In hypolipidemic study, the 12-week treatment resulted in a decrease in LDL cholesterol by 11.8% (P=0.002), while HDL cholesterol increased by 11.5% (P=0.013). In men with cerebral atherosclerosis it has been demonstrated that 14-days treatment inhibited ADP-induced platelet aggregation by 25.4% (P<0.05) and increased plasma fibrinolytic activity by 22.4% (P<0.05). One more study was performed in high-risk patients to evaluate the changes of prognostic cardiovascular risk that was calculated using algorithms derived from Framingham and Muenster Studies. Twelve-months treatment lowered 10-years prognostic risk of CHD by 13.2% in men (P=0.005), and by 7.1% in women (P=0.040). Ten-year prognostic risk of acute myocardial infarction and sudden coronary death was lowered by 26.1% in men (P=0.025). The Atherosclerosis Monitoring and Atherogenicity Reduction Study (AMAR) was designed to estimate the effect of two-year treatment with garlic powder pills on the progression of carotid atherosclerosis in asymptomatic men. A significant correlation has been revealed between the changes in blood serum atherogenicity and the changes in carotid intima-media thickness (r=0.144, P=0.045). Evidence obtained from these studies as well as series of double-blinded placebo-controlled clinical trials indicates that garlic powder pills are effective for prevention of cardiovascular disorders. PMID:26561055

  9. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    Whoever said there is nothing new under the sun did not delve deeply enough to the bottom of the ocean. There in the Gulf of Mexico, about 150 miles south of New Orleans, scientists have just discovered what could be a new species of centipede—like worms living on or within gas hydrates— mounds of methane ice— rising from the ocean floor.Scientists have previously recognized an association between some bacteria and these hydrates. However, this is the first discovery of a higher life form there.

  10. Diffusion of CO2 During Hydrate Formation and Dissolution

    SciTech Connect

    Franklin M. Orr, Jr.

    2002-08-20

    Experiments were performed to measure the rate of diffusion of CO2 through hydrate films. Hydrate films were created in a capillary tube, and the growth of the hydrate film was measured. Difficulties were encountered in creating hydrate repeatedly, and some non-uniform growth of the films was observed. Sufficient observations were obtained to demonstrate that hydrate growth occurs preferentially on the hydrate/water side of the interface, rather than at the hydrate/CO2 interface. Diffusion coefficients were estimated from observations of the rate of growth of the hydrate film along with estimates of the solubility of CO2 in water and of the concentration gradient across the hydrate layer. The experimental observations indicate that hydrate formation occurs much more rapidly at the hydrate water interface than at the hydrate/CO2 interface. Any growth of hydrate at the CO2/hydrate interface was too slow to be observed at the time scale of the experiments. That observation is consistent with the idea that CO2 can move more easily through the hydrate, presumably by hopping between hydrate cages, than water can move through the hydrate, presumably by lattice hopping. Estimated diffusion coefficients were in the range 1-3E-06 cm2/sec. Those values are about an order of magnitude lower than the diffusion coefficient for CO2 in liquid water, but four orders of magnitude larger than the value for diffusion of CO2 in a solid. The rate of diffusion through the hydrate controls both the creation of new hydrate at the hydrate/water interface and the rate at which CO2 dissolves in the liquid water and diffuses away from the hydrate layer. Formation of a hydrate layer reduces the rate at which CO2 dissolves in liquid water.

  11. Method for classifying ceramic powder

    NASA Technical Reports Server (NTRS)

    Takabe, K.

    1983-01-01

    Under the invented method, powder A of particles of less than 10 microns, and carrier powder B, whose average particle diameter is more than five times that of powder A, are premixed so that the powder is less than 40 wt.% of the total mixture, before classifying.

  12. Obsidian Hydration: A New Paleothermometer

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Riciputi, Lee R; Cole, David R; Fayek, Mostafa; Elam, J. Michael

    2006-01-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  13. Direct correlation of structure changes and thermal events in hydrated lipid established by simultaneous calorimetry and time-resolved x-ray diffraction.

    PubMed Central

    Chung, H; Caffrey, M

    1992-01-01

    In many lipid systems, polymorphic and mesomorphic behavior depends on sample thermal history. To establish unequivocally the structural origin of endothermic and exothermic events in such systems, we have performed simultaneous calorimetry and time-resolved x-ray diffraction (SCALTRD). To this end, aluminum calorimetry crucibles were used to contain the hydrated lipid sample, and the calorimeter was mounted with the base of the crucible oriented perpendicular to a synchrotron-derived focused monochromatic x-ray beam for SCALTRD data collection. Measurements were made with hydrated monoelaidin and 1,2-dielaidoyl-sn-glycero-3-phosphoethanolamine (DEPE) contained in hermetically sealed crucibles. Time-resolved x-ray diffraction (TRXRD) data were collected using an x-ray image intensifier/video system and a streak camera containing an x-ray sensitive image plate and/or film. SCALTRD analysis of the lamellar gel to lamellar liquid crystalline phase transition in hydrated monoelaidin gives identical progress curves by calorimetry and TRXRD at a scan rate of 1 degree C/min. At faster rates, calorimetry shows a broader phase transition that starts at a lower and ends at a higher temperature than is observed by TRXRD. The disparity arises in part because the x-ray beam used in TRXRD interrogates only a small portion of the sample, whereas the calorimeter responds to the entire sample volume. Because data collection times are relatively long, radiation damage is an important potential problem for SCALTRD measurements. Such an effect was observed with DEPE/water in that TRXRD shows the lamellar gel to lamellar liquid crystalline phase transition occurring at a lower temperature than observed by calorimetry. We speculate that the sample accumulates impurities locally as a result of radiation damage that has the effect of lowering the phase transition temperature at the site of interrogation by the x-ray beam. This "methods-in-combination" SCALTRD approach facilitates the

  14. A robotic DNA purification protocol and real-time PCR for the detection of Enterobacter sakazakii in powdered infant formulae

    PubMed Central

    Derzelle, Sylviane; Dilasser, Françoise

    2006-01-01

    Background Enterobacter sakazakii is the causative agent of rare but severe food-borne infections associated with meningitis, necrotizing enterocolitis and sepsis in infants. Rehydrated powdered infant formulae have been implicated as the source of infection in several outbreaks and sporadic cases. In this work, a real time fluorescence resonance energy transfer PCR assay incorporating an internal amplification control (IAC) was developed for the specific detection of E. sakazakii in foods. Performance of the assay, coupled to an automated DNA extraction system and the E. sakazakii ISO-IDF (TS 22964/RM 210) enrichment procedure, was evaluated on infant formulae and samples from production environment. Results The real-time PCR assay had 100% specificity as assessed using 35 E. sakazakii and 184 non-E. sakazakii strains. According to the E. sakazakii strains tested, the detection limits ranged from 5 to 25 genomic copies. Assays on pure cultures (including real-time PCR and DNA extraction) gave a sensitivity of about 102 to 103 CFU/ml. Out of 41 naturally contaminated infant formulae and environmental samples analysed for the presence of E. sakazakii, 23 were positive by real-time PCR and 22 by the conventional culture method, giving 97.5% concordance with the ISO-IDF reference method. Conclusion This method, combining specific real-time PCR, automated DNA extraction and ISO-IDF standard enrichments, provides a useful tool for rapid screening of E. sakazakii in food and environmental matrices. PMID:17166252

  15. Hydrate control in deepwater drilling

    SciTech Connect

    1997-09-01

    Gas-hydrate formation during deepwater offshore drilling and production is a well-recognized operational hazard. In water depths greater than 1,000 ft, seabed conditions of pressure and temperature become conducive to gas-hydrate formation. In a well-control situation, although the kick fluid leaves the formation at a high temperature, it can cool to seabed temperature with an extended shut-in period. With high enough hydrostatic pressure at the mudline, hydrates could form in the blowout-preventer (BOP) stack and choke and kill lines, as has been observed in field operations. The current practice in deepwater drilling is to suppress the hydrate-formation temperature by use of highly saline drilling fluids formulated from NaCl or other salts. This solution is applicable for the Gulf of Mexico but insufficient for the conditions encountered in Norwegian deep waters. At extreme water depths or extremely low mudline temperatures, this thermodynamic inhibition alone may not be sufficient to prevent hydrate formation. Instead, the use of kinetic inhibitors or crystal modifiers, in conjunction with thermodynamic inhibitors, may allow successful operations in such an environment. The definition of kinetic inhibitors (to distinguish them from the classic thermodynamic inhibitors, such as polar compounds and electrolytes) comes from the effect of the chemicals on the nucleation and growth of natural gas hydrates, both of which are time-dependent, stochastic processes. The paper describes deepwater drilling fluids, polar and surface-active additives, kinetic inhibition and crystal modifiers, laboratory measurements, and test results.

  16. Fundamentals and applications of gas hydrates.

    PubMed

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties. PMID:22432618

  17. Hydration characteristics of alpha-tricalcium phosphates: Comparison of preparation routes.

    PubMed

    Camire', C L; Jegou Saint-Jean, S; Hansen, S; McCarthy, I; Lidgren, L

    2005-01-01

    Alpha tricalcium phosphate ( á -TCP) cement powders were obtained by solid state reaction and milling (M1) and by precipitation from aqueous solution followed by heating (M2). The materials were hydrated to form calcium-deficient hydroxyapatite (CDHA) with a 2.5 wt% solution of Na2 HPO4 (liquid to powder ratio = 0.34 ml/g, temperature = 37.5 degrees C) and subjected to isothermal calorimetry, mechanical compression tests, X-ray powder diffraction, at various times during hydration, as well as scanning electron microscopy (SEM), laser diffraction and gas adsorption. The particle characteristics of the two powders were similar, but M2 exhibited two reaction events in the thermal power curve, while M1 showed a single event. Both reaction events were attributed to á -TCP dissolution and CDHA recipitation. The minimum in the reaction rate response of M2 was probably due to the formation of a passivating product layer. No such layer was formed on the milled M1 due to its rougher surfaces. Both preparations reached a compressive strength of 30-40 MPa after 24 hr. PMID:20799230

  18. A Rietveld refinement method for angular- and wavelength-dispersive neutron time-of-flight powder diffraction data

    PubMed Central

    Jacobs, Philipp; Houben, Andreas; Schweika, Werner; Tchougréeff, Andrei L.; Dronskowski, Richard

    2015-01-01

    This paper introduces a two-dimensional extension of the well established Rietveld refinement method for modeling neutron time-of-flight powder diffraction data. The novel approach takes into account the variation of two parameters, diffraction angle 2θ and wavelength λ, to optimally adapt to the varying resolution function in diffraction experiments. By doing so, the refinement against angular- and wavelength-dispersive data gets rid of common data-reduction steps and also avoids the loss of high-resolution information typically introduced by integration. In a case study using a numerically simulated diffraction pattern of Rh0.81Fe3.19N taking into account the layout of the future POWTEX instrument, the profile function as parameterized in 2θ and λ is extracted. As a proof-of-concept, the resulting instrument parameterization is then utilized to perform a typical refinement of the angular- and wavelength-dispersive diffraction pattern of CuNCN, yielding excellent residuals within feasible computational efforts. Another proof-of-concept is carried out by applying the same approach to a real neutron diffraction data set of CuNCN obtained from the POWGEN instrument at the Spallation Neutron Source in Oak Ridge. The paper highlights the general importance of the novel approach for data analysis at neutron time-of-flight diffractometers and its possible inclusion within existing Rietveld software packages. PMID:26664340

  19. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    NASA Astrophysics Data System (ADS)

    Max, M. D.; Osegovic, J. P.

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  20. The effects of time-released garlic powder tablets on multifunctional cardiovascular risk in patients with coronary artery disease

    PubMed Central

    2010-01-01

    The double-blinded placebo-controlled randomized study has been performed in 51 coronary heart disease (CHD) patients to estimate the effects of time-released garlic powder tablets Allicor on the values of 10-year prognostic risk of acute myocardial infarction (fatal and non-fatal) and sudden death, with the respect of secondary CHD prevention. It has been demonstrated that 12-month treatment with Allicor results in the significant decrease of cardiovascular risk by 1.5-fold in men (p < 0.05), and by 1.3-fold in women. The above results were equitable also in terms of relative risks. The main effect that played a role in cardiovascular risk reduction was the decrease in LDL cholesterol by 32.9 mg/dl in men (p < 0.05), and by 27.3 mg/dl in women. Thus, the most significant effects were observed in men, while in women the decrease of cardiovascular risk appeared as a trend that might be due presumably to the insufficient sample size. Since Allicor is the remedy of natural origin, it is safe with the respect to adverse effects and allows even perpetual administration that may be crucial for the secondary prevention of atherosclerotic diseases in CHD patients. PMID:20958974

  1. Fast Water Diffusion and Long-Term Polymer Reorganization during Nafion Membrane Hydration Evidenced by Time-Resolved Small-Angle Neutron Scattering.

    PubMed

    Fumagalli, M; Lyonnard, S; Prajapati, G; Berrod, Q; Porcar, L; Guillermo, A; Gebel, G

    2015-06-11

    We report a small-angle neutron scattering study of liquid water sorption in Nafion membranes. The swelling of hydrophilic domains was measured on the nanoscale by combining in situ time-resolved and long-term static experiments, yielding kinetic curves recorded over an unprecedented time scale, from hundreds of milliseconds to several years. At low water content, typically below 5 water molecules per ionic group, a limited subdiffusive regime was observed and ascribed to nanoconfinement and local interactions between charged species and water molecules. Further ultrafast and thermally activated swelling due to massive liquid water sorption was observed and analyzed by using Fick's equation. The extracted mutual water diffusion coefficients are in good agreement with pulsed field gradient NMR self-diffusion coefficient values, evidencing a water diffusion-driven process due to concentration gradients within the Nafion membrane. Finally, after completion of the ultrafast regime, the kinetic swelling curves exhibit a remarkable long-term behavior scaling as the logarithm of time, showing that the polymer membrane can continuously accommodate additional water molecules upon hydration stress. The present nanoscale kinetics results provide insights into the vapor-versus-liquid sorption mechanisms, the nanostructure of Nafion, and the role of polymer reorganization modes, highlighting that the membrane can never reach a steady state. PMID:25971732

  2. Development of hydrate risk quantification in oil and gas production

    NASA Astrophysics Data System (ADS)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  3. An X-ray diffraction analysis of crystallised whey and whey-permeate powders.

    PubMed

    Nijdam, Justin; Ibach, Alexander; Eichhorn, Klaus; Kind, Matthias

    2007-11-26

    Amorphous whey, whey-permeate and lactose powders have been crystallised at various air temperatures and humidities, and these crystallised powders have been examined using X-ray diffraction. The most stable lactose crystal under normal storage conditions, alpha-lactose monohydrate, forms preferentially in whey and whey-permeate powders at 50 degrees C, provided sufficient moisture is available, whereas anhydrous beta-lactose and mixed anhydrous lactose crystals, which are unstable under normal storage conditions, form preferentially at 90 degrees C. Thus, faster crystallisation at higher temperatures is offset by the formation of lactose-crystal forms that are less stable under normal storage conditions. Very little alpha-lactose monohydrate crystallised in the pure lactose powders over the range of temperatures and humidities tested, because the crystallisation of alpha- and beta-lactose is considerably more rapid than the mutarotation of beta- to alpha-lactose in the amorphous phase and the hydration of alpha-lactose during crystallisation. Protein and salts hinder the crystallisation process, which provides more time for mutarotation and crystal hydration in the whey and whey-permeate powders. PMID:17719020

  4. Hydrothermal Transformation of the Calcium Aluminum Oxide Hydrates CaAl2O4 . 10H2O and Ca2Al2O. 8H2O to Ca3Al2(OH)12 Investigated by In Situ Synchrotron X-ray Powder Diffraction

    SciTech Connect

    Jensen,T.; Christensen, A.; Hanson, J.

    2005-01-01

    The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl{sub 2}O{sub 4}{center_dot}10H{sub 2}O converted to Ca{sub 3}Al{sub 2}(OH){sub 12} and amorphous aluminum hydroxide. Ca{sub 2}Al{sub 2}O{sub 5}{center_dot}8H{sub 2}O transformed via the intermediate phase Ca{sub 4}Al{sub 2}O{sub 7}{center_dot}13H{sub 2}O to Ca{sub 3}Al{sub 2}(OH){sub 12} and gibbsite, Al(OH){sub 3}. The phase Ca{sub 4}Al{sub 2}O{sub 7}{center_dot}19H{sub 2}O reacted via the same intermediate phase to Ca{sub 3}Al{sub 2}(OH){sub 12} and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.

  5. Increasing Gas Hydrate Formation Temperature for Desalination of High Salinity Produced Water with Secondary Guests

    SciTech Connect

    Cha, Jong-Ho; Seol, Yongkoo

    2013-10-07

    We suggest a new gas hydrate-based desalination process using water-immiscible hydrate formers; cyclopentane (CP) and cyclohexane (CH) as secondary hydrate guests to alleviate temperature requirements for hydrate formation. The hydrate formation reactions were carried out in an isobaric condition of 3.1 MPa to find the upper temperature limit of CO2 hydrate formation. Simulated produced water (8.95 wt % salinity) mixed with the hydrate formers shows an increased upper temperature limit from -2 °C for simple CO2 hydrate to 16 and 7 °C for double (CO2 + CP) and (CO2 + CH) hydrates, respectively. The resulting conversion rate to double hydrate turned out to be similar to that with simple CO2 hydrate at the upper temperature limit. Hydrate formation rates (Rf) for the double hydrates with CP and CH are shown to be 22 and 16 times higher, respectively, than that of the simple CO2 hydrate at the upper temperature limit. Such mild hydrate formation temperature and fast formation kinetics indicate increased energy efficiency of the double hydrate system for the desalination process. Dissociated water from the hydrates shows greater than 90% salt removal efficiency for the hydrates with the secondary guests, which is also improved from about 70% salt removal efficiency for the simple hydrates.

  6. Coupling of the hydration water dynamics and the internal dynamics of actin detected by quasielastic neutron scattering

    SciTech Connect

    Fujiwara, Satoru; Plazanet, Marie; Oda, Toshiro

    2013-02-15

    Highlights: ► Quasielastic neutron scattering spectra of F-actin and G-actin were measured. ► Analysis of the samples in D{sub 2}O and H{sub 2}O provided the spectra of hydration water. ► The first layer hydration water around F-actin is less mobile than around G-actin. ► This difference in hydration water is in concert with the internal dynamics of actin. ► Water outside the first layer behaves bulk-like but influenced by the first layer. -- Abstract: In order to characterize dynamics of water molecules around F-actin and G-actin, quasielastic neutron scattering experiments were performed on powder samples of F-actin and G-actin, hydrated either with D{sub 2}O or H{sub 2}O, at hydration ratios of 0.4 and 1.0. By combined analysis of the quasielastic neutron scattering spectra, the parameter values characterizing the dynamics of the water molecules in the first hydration layer and those of the water molecules outside of the first layer were obtained. The translational diffusion coefficients (D{sub T}) of the hydration water in the first layer were found to be 1.2 × 10{sup −5} cm{sup 2}/s and 1.7 × 10{sup −5} cm{sup 2}/s for F-actin and G-actin, respectively, while that for bulk water was 2.8 × 10{sup −5} cm{sup 2}/s. The residence times were 6.6 ps and 5.0 ps for F-actin and G-actin, respectively, while that for bulk water was 0.62 ps. These differences between F-actin and G-actin, indicating that the hydration water around G-actin is more mobile than that around F-actin, are in concert with the results of the internal dynamics of F-actin and G-actin, showing that G-actin fluctuates more rapidly than F-actin. This implies that the dynamics of the hydration water is coupled to the internal dynamics of the actin molecules. The D{sub T} values of the water molecules outside of the first hydration layer were found to be similar to that of bulk water though the residence times are strongly affected by the first hydration layer. This supports the

  7. Gas hydrate and humans

    USGS Publications Warehouse

    Kvenvolden, K.A.

    2000-01-01

    The potential effects of naturally occurring gas hydrate on humans are not understood with certainty, but enough information has been acquired over the past 30 years to make preliminary assessments possible. Three major issues are gas hydrate as (1) a potential energy resource, (2) a factor in global climate change, and (3) a submarine geohazard. The methane content is estimated to be between 1015 to 1017 m3 at STP and the worldwide distribution in outer continental margins of oceans and in polar regions are significant features of gas hydrate. However, its immediate development as an energy resource is not likely because there are various geological constraints and difficult technological problems that must be solved before economic recovery of methane from hydrate can be achieved. The role of gas hydrate in global climate change is uncertain. For hydrate methane to be an effective greenhouse gas, it must reach the atmosphere. Yet there are many obstacles to the transfer of methane from hydrate to the atmosphere. Rates of gas hydrate dissociation and the integrated rates of release and destruction of the methane in the geo/hydro/atmosphere are not adequately understood. Gas hydrate as a submarine geohazard, however, is of immediate and increasing importance to humans as our industrial society moves to exploit seabed resources at ever-greater depths in the waters of our coastal oceans. Human activities and installations in regions of gas-hydrate occurrence must take into account the presence of gas hydrate and deal with the consequences of its presence.

  8. DSC and TG Analysis of a Blended Binder Based on Waste Ceramic Powder and Portland Cement

    NASA Astrophysics Data System (ADS)

    Pavlík, Zbyšek; Trník, Anton; Kulovaná, Tereza; Scheinherrová, Lenka; Rahhal, Viviana; Irassar, Edgardo; Černý, Robert

    2016-03-01

    Cement industry belongs to the business sectors characteristic by high energy consumption and high {CO}2 generation. Therefore, any replacement of cement in concrete by waste materials can lead to immediate environmental benefits. In this paper, a possible use of waste ceramic powder in blended binders is studied. At first, the chemical composition of Portland cement and ceramic powder is analyzed using the X-ray fluorescence method. Then, thermal and mechanical characterization of hydrated blended binders containing up to 24 % ceramic is carried out within the time period of 2 days to 28 days. The differential scanning calorimetry and thermogravimetry measurements are performed in the temperature range of 25°C to 1000°C in an argon atmosphere. The measurement of compressive strength is done according to the European standards for cement mortars. The thermal analysis results in the identification of temperature and quantification of enthalpy and mass changes related to the liberation of physically bound water, calcium-silicate-hydrates dehydration and portlandite, vaterite and calcite decomposition. The portlandite content is found to decrease with time for all blends which provides the evidence of the pozzolanic activity of ceramic powder even within the limited monitoring time of 28 days. Taking into account the favorable results obtained in the measurement of compressive strength, it can be concluded that the applied waste ceramic powder can be successfully used as a supplementary cementing material to Portland cement in an amount of up to 24 mass%.

  9. Crystal structures of deuterated sodium molybdate dihydrate and sodium tungstate dihydrate from time-of-flight neutron powder diffraction.

    PubMed

    Fortes, A Dominic

    2015-07-01

    Time-of-flight neutron powder diffraction data have been measured from ∼90 mol% deuterated isotopologues of Na2MoO4·2H2O and Na2WO4·2H2O at 295 K to a resolution of sin (θ)/λ = 0.77 Å(-1). The use of neutrons has allowed refinement of structural parameters with a precision that varies by a factor of two from the heaviest to the lightest atoms; this contrasts with the X-ray based refinements where precision may be > 20× poorer for O atoms in the presence of atoms such as Mo and W. The accuracy and precision of inter-atomic distances and angles are in excellent agreement with recent X-ray single-crystal structure refinements whilst also completing our view of the hydrogen-bond geometry to the same degree of statistical certainty. The two structures are isotypic, space-group Pbca, with all atoms occupying general positions, being comprised of edge- and corner-sharing NaO5 and NaO6 polyhedra that form layers parallel with (010) inter-leaved with planes of XO4 (X = Mo, W) tetra-hedra that are linked by chains of water mol-ecules along [100] and [001]. The complete structure is identical with the previously described molybdate [Capitelli et al. (2006 ▸). Asian J. Chem. 18, 2856-2860] but shows that the purported three-centred inter-action involving one of the water mol-ecules in the tungstate [Farrugia (2007 ▸). Acta Cryst. E63, i142] is in fact an ordinary two-centred 'linear' hydrogen bond. PMID:26279871

  10. Crystal structures of deuterated sodium molybdate dihydrate and sodium tungstate dihydrate from time-of-flight neutron powder diffraction

    PubMed Central

    Fortes, A. Dominic

    2015-01-01

    Time-of-flight neutron powder diffraction data have been measured from ∼90 mol% deuterated isotopologues of Na2MoO4·2H2O and Na2WO4·2H2O at 295 K to a resolution of sin (θ)/λ = 0.77 Å−1. The use of neutrons has allowed refinement of structural parameters with a precision that varies by a factor of two from the heaviest to the lightest atoms; this contrasts with the X-ray based refinements where precision may be > 20× poorer for O atoms in the presence of atoms such as Mo and W. The accuracy and precision of inter­atomic distances and angles are in excellent agreement with recent X-ray single-crystal structure refinements whilst also completing our view of the hydrogen-bond geometry to the same degree of statistical certainty. The two structures are isotypic, space-group Pbca, with all atoms occupying general positions, being comprised of edge- and corner-sharing NaO5 and NaO6 polyhedra that form layers parallel with (010) inter­leaved with planes of XO4 (X = Mo, W) tetra­hedra that are linked by chains of water mol­ecules along [100] and [001]. The complete structure is identical with the previously described molybdate [Capitelli et al. (2006 ▸). Asian J. Chem. 18, 2856–2860] but shows that the purported three-centred inter­action involving one of the water mol­ecules in the tungstate [Farrugia (2007 ▸). Acta Cryst. E63, i142] is in fact an ordinary two-centred ‘linear’ hydrogen bond. PMID:26279871

  11. Methane hydrate formation in confined nanospace can surpass nature.

    PubMed

    Casco, Mirian E; Silvestre-Albero, Joaquín; Ramírez-Cuesta, Anibal J; Rey, Fernando; Jordá, Jose L; Bansode, Atul; Urakawa, Atsushi; Peral, Inma; Martínez-Escandell, Manuel; Kaneko, Katsumi; Rodríguez-Reinoso, Francisco

    2015-01-01

    Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. Here we report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 °C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. The formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. These findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation). PMID:25728378

  12. In vivo measurement of tissue oxygenation by time-resolved luminescence spectroscopy: advantageous properties of dichlorotris(1, 10-phenanthroline)-ruthenium(II) hydrate

    NASA Astrophysics Data System (ADS)

    Huntosova, Veronika; Gay, Sandrine; Nowak-Sliwinska, Patrycja; Rajendran, Senthil Kumar; Zellweger, Matthieu; van den Bergh, Hubert; Wagnières, Georges

    2014-07-01

    Measuring tissue oxygenation in vivo is of interest in fundamental biological as well as medical applications. One minimally invasive approach to assess the oxygen partial pressure in tissue (pO2) is to measure the oxygen-dependent luminescence lifetime of molecular probes. The relation between tissue pO and the probes' luminescence lifetime is governed by the Stern-Volmer equation. Unfortunately, virtually all oxygen-sensitive probes based on this principle induce some degree of phototoxicity. For that reason, we studied the oxygen sensitivity and phototoxicity of dichlorotris(1, 10-phenanthroline)-ruthenium(II) hydrate [Ru(Phen)] using a dedicated optical fiber-based, time-resolved spectrometer in the chicken embryo chorioallantoic membrane. We demonstrated that, after intravenous injection, Ru(Phen)'s luminescence lifetime presents an easily detectable pO dependence at a low drug dose (1 mg/kg) and low fluence (120 mJ/cm2 at 470 nm). The phototoxic threshold was found to be at 10 J/cm2 with the same wavelength and drug dose, i.e., about two orders of magnitude larger than the fluence necessary to perform a pO measurement. Finally, an illustrative application of this pO measurement approach in a hypoxic tumor environment is presented.

  13. Methane hydrates in nature - Current knowledge and challenges

    USGS Publications Warehouse

    Collett, Timothy S.

    2014-01-01

    Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

  14. Hydration-dependent dynamics of human telomeric oligonucleotides in the picosecond timescale: A neutron scattering study

    SciTech Connect

    Sebastiani, F.; Comez, L.; Sacchetti, F.; Orecchini, A.; Petrillo, C.; Paciaroni, A.; De Francesco, A.; Teixeira, S. C. M.

    2015-07-07

    The dynamics of the human oligonucleotide AG{sub 3}(T{sub 2}AG{sub 3}){sub 3} has been investigated by incoherent neutron scattering in the sub-nanosecond timescale. A hydration-dependent dynamical activation of thermal fluctuations in weakly hydrated samples was found, similar to that of protein powders. The amplitudes of such thermal fluctuations were evaluated in two different exchanged wave-vector ranges, so as to single out the different contributions from intra- and inter-nucleotide dynamics. The activation energy was calculated from the temperature-dependent characteristic times of the corresponding dynamical processes. The trends of both amplitudes and activation energies support a picture where oligonucleotides possess a larger conformational flexibility than long DNA sequences. This additional flexibility, which likely results from a significant relative chain-end contribution to the average chain dynamics, could be related to the strong structural polymorphism of the investigated oligonucleotides.

  15. Superfine powdered activated carbon (S-PAC) coatings on microfiltration membranes: Effects of milling time on contaminant removal and flux.

    PubMed

    Amaral, Pauline; Partlan, Erin; Li, Mengfei; Lapolli, Flavio; Mefford, O Thompson; Karanfil, Tanju; Ladner, David A

    2016-09-01

    In microfiltration processes for drinking water treatment, one method of removing trace contaminants is to add powdered activated carbon (PAC). Recently, a version of PAC called superfine PAC (S-PAC) has been under development. S-PAC has a smaller particle size and thus faster adsorption kinetics than conventionally sized PAC. Membrane coating performance of various S-PAC samples was evaluated by measuring adsorption of atrazine, a model micropollutant. S-PACs were created in-house from PACs of three different materials: coal, wood, and coconut shell. Milling time was varied to produce S-PACs pulverized with different amounts of energy. These had different particles sizes, but other properties (e.g. oxygen content), also differed. In pure water the coal based S-PACs showed superior atrazine adsorption; all milled carbons had over 90% removal while the PAC had only 45% removal. With addition of calcium and/or NOM, removal rates decreased, but milled carbons still removed more atrazine than PAC. Oxygen content and specific external surface area (both of which increased with longer milling times) were the most significant predictors of atrazine removal. S-PAC coatings resulted in loss of filtration flux compared to an uncoated membrane and smaller particles caused more flux decline than larger particles; however, the data suggest that NOM fouling is still more of a concern than S-PAC fouling. The addition of calcium improved the flux, especially for the longer-milled carbons. Overall the data show that when milling S-PAC with different levels of energy there is a tradeoff: smaller particles adsorb contaminants better, but cause greater flux decline. Fortunately, an acceptable balance may be possible; for example, in these experiments the coal-based S-PAC after 30 min of milling achieved a fairly high atrazine removal (overall 80%) with a fairly low flux reduction (under 30%) even in the presence of NOM. This suggests that relatively short duration (low energy

  16. Neutron powder diffraction study of the layer organic-inorganic hybrid iron(II) methylphosphonate-hydrate, Fe[(CD{sub 3}PO{sub 3})(D{sub 2}O)

    SciTech Connect

    Leone, Philippe Bellitto, Carlo; Bauer, Elvira M.; Righini, Guido; Andre, Gilles; Bouree, Francoise

    2008-11-15

    The crystal and magnetic structures of the hybrid organic-inorganic layer compound Fe[(CD{sub 3}PO{sub 3})(D{sub 2}O)] have been studied by neutron powder diffraction as a function of temperature down to 1.5 K. The neutron diffraction pattern recorded at 200 K shows that the fully deuterated compound crystallizes in one of the two known forms of the undeuterated Fe[(CH{sub 3}PO{sub 3})(H{sub 2}O)]. The crystal structure is orthorhombic, space group Pmn2{sub 1}, with the following unit-cell parameters: a=5.7095(1) A, b=8.8053(3) A and c=4.7987(1) A; Z=2. The crystal structure remains unchanged on cooling from 200 to 1.5 K. Moreover, at low temperature, Fe[(CD{sub 3}PO{sub 3})(D{sub 2}O)] shows a commensurate magnetic structure (k=(0,0,0)). As revealed by bulk susceptibility measurements on Fe[(CH{sub 3}PO{sub 3})(H{sub 2}O)], the magnetic structure corresponds to a canted antiferromagnet with a critical temperature T{sub N}=25 K. Neutron powder diffraction reveals that below T{sub N}=23.5 K the iron magnetic moments in Fe[(CD{sub 3}PO{sub 3})(D{sub 2}O)] are antiferromagnetically coupled and oriented along the b-axis, perpendicular to the inorganic layers. No ferromagnetic component is observable in the neutron powder diffraction experiment, due to its too small value (<0.1{mu}{sub B}). - Graphical abstract: Crystal structure and magnetic structure of Fe[(CD{sub 3}PO{sub 3})(D{sub 2}O)].

  17. Origins of hydration lubrication

    NASA Astrophysics Data System (ADS)

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-01

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

  18. Methane Hydrate Field Program

    SciTech Connect

    2013-12-31

    This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report. • Historical Methane Hydrate Project Review Report • Methane Hydrate Workshop Report • Topical Report: Marine Methane Hydrate Field Research Plan • Final Scientific/Technical Report

  19. Origins of hydration lubrication.

    PubMed

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-01

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication. PMID:25585501

  20. Natural Gas Hydrates: Occurrence, Distribution, and Detection

    NASA Astrophysics Data System (ADS)

    Paull, Charles K.; Dillon, William P.

    We publish this volume at a time when there is a growing interest in gas hydrates and major expansion in international research efforts. The first recognition of natural gas hydrate on land in Arctic conditions was in the mid-1960s (by I. Makogon) and in the seabed environment only in the early 1970s, after natural seafloor gas hydrate was drilled on the Blake Ridge during Deep Sea Drilling Project Leg 11. Initial scientific investigations were slow to develop because the study of natural gas hydrates is unusually challenging. Gas hydrate exists in nature in conditions of temperature and pressure where human beings cannot survive, and if gas hydrate is transported from its region of stability to normal Earth-surface conditions, it dissociates. Thus, in contrast to most minerals, we cannot depend on drilled samples to provide accurate estimates of the amount of gas hydrate present. Even the heat and changes in chemistry (methane saturation, salinity, etc.) introduced by the drilling process affect the gas hydrate, independent of the changes brought about by moving a sample to the surface. Gas hydrate has been identified in nature generally by inference from indirect evidence in drilling data or by using remotely sensed indications, mostly from seismic data. Obviously, the established techniques ofgeologic analysis, which require direct observation and sampling, do not apply to gas hydrate studies, and controversy has surrounded many interpretations. Pressure/temperature conditions appropriate for the existence of gas hydrate occur over the greater part of the shallow subsurface of the Earth beneath the ocean at water depths exceeding about 500 m (shallower beneath colder Arctic seas) and on land beneath high-latitude permafrost. Gas hydrate actually will be present in such conditions, however, only where methane is present at high concentrations. In the Arctic, these methane concentrations are often associated with petroleum deposits, whereas at continental margins

  1. Gas Hydrate Storage of Natural Gas

    SciTech Connect

    Rudy Rogers; John Etheridge

    2006-03-31

    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  2. Sintering titanium powders

    SciTech Connect

    Gerdemann, Stephen J.; Alman, David E.

    2005-09-01

    Recently, there has been renewed interest in low-cost titanium. Near-net-shape powder metallurgy offers the potential of manufacturing titanium articles without costly and difficult forming and machining operations; hence, processing methods such as conventional press-and-sinter, powder forging and powder injection molding are of interest. The sintering behavior of a variety of commercial and experimental titanium powders was studied. Commercial powders were acquired that were produced different routes: (i) sponge fines from the primary titanium processing; (ii) via the hydride-dehydride process; and (iii) gas atomization. The influence of vacuum sintering time (0.5 to 32 hrs) and temperature (1200, 1275 or 1350°C) on the microstructure (porosity present) of cold pressed powders was studied. The results are discussed in terms of the difference in powder characteristics, with the aim of identify the characteristics required for full density via press-and-sinter processing. Near-net-shape tensile bars were consolidated via cold pressed and sintered. After sintering, a sub-set of the tensile bars was hot-isostatic pressed (HIPed). The microstructure and properties of the bars were compared in the sintered and HIPed conditions.

  3. Devitrification of Mechanically Alloyed Zr-Ti-Nb-Cu-Ni-Al Glassy Powders Studied by Time-Resolved X-ray Diffraction

    SciTech Connect

    Scudino, S.; Sordelet, D.J.; Eckert, J.

    2009-04-13

    The crystallization of mechanically alloyed Zr{sub 67}Ti{sub 6.14}Nb{sub 1.92}Cu{sub 10.67}Ni{sub 8.52}Al{sub 5.75} glassy powder is investigated by time-resolved X-ray diffraction. The powder displays a multi-step crystallization behavior characterized by the formation of a metastable nanoscale quasicrystalline phase during the first stage of the crystallization process. At higher temperatures, coinciding with the second crystallization event, the amorphous-to-quasicrystalline transformation is followed by the precipitation of the tetragonal Zr{sub 2}Cu phase (space group I4/mmm) and the tetragonal Zr{sub 2}Ni phase (space group I4/mcm). The transformations are gradual and the quasicrystals and the subsequent phases coexist over a temperature interval of about 25K.

  4. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    PubMed

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method. PMID:23383955

  5. TOUGH-Fx/Hydrate

    Energy Science and Technology Software Center (ESTSC)

    2005-02-01

    TOUGH-Fx/HYORATL can model the non-isothermal gas release. phase behavior and flow of fluids and heat in complex geologic media. The code can simulate production from natural gas hydrate deposits in the subsurtace (i.e., in the permafrost and in deep ocean sediments), as well as laboratory experiments of hydrate dissociation/formation in porous/fractured media. T006H-Fx/HYDRATE vi .0 includes both an equilibrium and a kinetic model of hydrate Ibmiation and dissociation. The model accounts for heat and upmore » to four mass components-- i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dIssociation or formation, phase changes, and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects, and inhibItor-Induced effects.« less

  6. Rapid gas hydrate formation processes: Will they work?

    DOE PAGESBeta

    Brown, Thomas D.; Taylor, Charles E.; Bernardo, Mark P.

    2010-06-07

    Researchers at DOE’s National Energy Technology Laboratory (NETL) have been investigating the formation of synthetic gas hydrates, with an emphasis on rapid and continuous hydrate formation techniques. The investigations focused on unconventional methods to reduce dissolution, induction, nucleation and crystallization times associated with natural and synthetic hydrates studies conducted in the laboratory. Numerous experiments were conducted with various high-pressure cells equipped with instrumentation to study rapid and continuous hydrate formation. The cells ranged in size from 100 mL for screening studies to proof-of-concept studies with NETL’s 15-Liter Hydrate Cell. The results from this work demonstrate that the rapid and continuousmore » formation of methane hydrate is possible at predetermined temperatures and pressures within the stability zone of a Methane Hydrate Stability Curve.« less

  7. Rapid gas hydrate formation processes: Will they work?

    SciTech Connect

    Brown, Thomas D.; Taylor, Charles E.; Bernardo, Mark P.

    2010-06-07

    Researchers at DOE’s National Energy Technology Laboratory (NETL) have been investigating the formation of synthetic gas hydrates, with an emphasis on rapid and continuous hydrate formation techniques. The investigations focused on unconventional methods to reduce dissolution, induction, nucleation and crystallization times associated with natural and synthetic hydrates studies conducted in the laboratory. Numerous experiments were conducted with various high-pressure cells equipped with instrumentation to study rapid and continuous hydrate formation. The cells ranged in size from 100 mL for screening studies to proof-of-concept studies with NETL’s 15-Liter Hydrate Cell. The results from this work demonstrate that the rapid and continuous formation of methane hydrate is possible at predetermined temperatures and pressures within the stability zone of a Methane Hydrate Stability Curve.

  8. Effects of drying methods on the physicochemical and compressional characteristics of Okra powder and the release properties of its metronidazole tablet formulation.

    PubMed

    Bakre, L G; Jaiyeoba, K T

    2009-02-01

    A study has been made of the effects of sun and oven drying methods on the physicochemical characteristics and compressibility of Okra powder and the release properties of its metronidazole tablet formulation. Corn starch was used as the reference standard. The mechanical properties of the tablets were evaluated using crushing strength and friability, while the release properties were determined using the disintegration times and dissolution rates. The results obtained showed that sun-dried Okra powder had smaller particle size, exhibited good flow and possessed higher hydration and swelling capacities compared to the oven dried samples. The compressibility of Okra powders assessed by the indices of plasticity from Heckel (Py) and Kawakita plots (Pk) showed that sun dried Okra powders had higher Py but lower Pk values than the oven-dried Okra powder. Metronidazole tablets formulated with oven dried Okra powder formed stronger tablets than tablets containing sun dried Okra powder. Generally, tablets containing sun dried Okra powders had faster disintegration and dissolution than tablets formulated with oven-dried powder. The results suggest that the choice of drying method during the processing of pharmaceutical raw materials is critical to its physicochemical properties and the release properties of its tablet formulations. PMID:19280157

  9. Hydration rate of obsidian.

    PubMed

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years. PMID:17782901

  10. Characteristics of hydrate-bound gases from the Eastern Nankai Trough

    NASA Astrophysics Data System (ADS)

    Kida, M.; Jin, Y.; Watanabe, M.; Konno, Y.; Yoneda, J.; Egawa, K.; Ito, T.; Nakatsuka, Y.; Suzuki, K.; Nagao, J.

    2013-12-01

    Natural gas hydrates are crystalline clathrate compounds that encage a large amount of natural gas, are stable under high pressure and low temperature conditions such as deep marine environments. Hydrate-bound natural gas compositions are related to a thermodynamically stable condition, crystallographic structure, or origin of natural gas hydrates, which are important to characterize natural gas hydrate reservoirs. The hydrate-bearing sediments were recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation, aboard the RV CHIKYU. In this study, the molecular and isotopic compositions of the gases released from the hydrate-bearing sediments were characterized. In addition, the powder X-ray diffraction (PXRD) profiles of the hydrate-bearing sediments were obtained using a cryo-system to characterize the crystallographic structure of gas hydrate. The gases released from the hydrate-bearing sediments contained methane as a main hydrocarbon component. The carbon isotope ratios (δ13C) of methane were approximately -65‰ (vs. VPDB). The molecular and isotopic compositions suggest a microbial origin for the hydrate-bound gas. The hydrate-bound gas contained small amounts of ethane and heavier hydrocarbons (less than 400 ppm). The concentrations of the minor hydrocarbon components tended to decrease at upper levels of the sediment core recovered, implying a compositional fractionation of natural gas during the migration of fluid from deeper level. The PXRD profiles of the hydrate-bearing sediments showed that the natural gas hydrates in the sediments is of structure I. The crystallographic character of the natural gas hydrates is supported by the fact that pure methane forms a structure I hydrate. This work was supported by funding from the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by METI.

  11. Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

    SciTech Connect

    Kirchheim,, A. P.; Dal Molin, D.C.; Emwas, Abdul-Hamid; Provis, J.L.; Fischer, P.; Monteiro, P.J.M.

    2010-12-01

    This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C{sub 3}A or 3CaO {center_dot} Al{sub 2}O{sub 3}) and Na-doped tricalcium aluminate (orthorhombic C{sub 3}A or Na{sub 2}Ca{sub 8}Al{sub 6}O{sub 18}), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the early phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by {sup 27}Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C{sub 3}A hydration during the early stages. There are differences in the hydration mechanism between the two types of C{sub 3}A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C{sub 3}A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C{sub 3}A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping.

  12. Multipoint near-infrared spectrometry for real-time monitoring of protein conformational stability in powdered infant formula.

    PubMed

    Pabari, Ritesh M; Togashi, Denisio; Cama-Moncunill, Raquel; El Arnaout, Toufic; Rifai, Hicham; Cruise, Paul; Cullen, Patrick J; Sullivan, Carl

    2015-01-01

    Powdered infant formula (PIF) can be the sole source of nutrition for babies and infants. Monitoring conformational changes in protein during manufacture of PIF is critical in order to maintain its nutritional value. This study presents the development of a calibration model for monitoring conformational changes in PIF protein by applying a novel multipoint near-infrared (NIR) spectrometry. NIR spectra were collected for PIF and PIF proteins, casein and whey protein isolate, before and after heat treatment. Results show that principal component analysis showed discrimination between native protein at room temperature and protein conformational changes caused at elevated temperature. Partial least squares regression analysis showed good calibration models with correlation coefficients ranging between 87% and 99% for the prediction of protein quality. This novel multipoint NIR spectrometry could serve as a simple in-line tool to rapidly monitor protein quality during processing stages, contributing to product nutritional value. PMID:26176650

  13. Withdrawing Nutrition, Hydration

    Cancer.gov

    Module eleven of the EPEC-O Self-Study Original Version discusses the general aspects of withholding or withdrawing of life-sustaining therapies, and presents a specific application to artificial nutrition and hydration.

  14. Transformations in methane hydrates

    PubMed Central

    Chou, I-Ming; Sharma, Anurag; Burruss, Robert C.; Shu, Jinfu; Mao, Ho-kwang; Hemley, Russell J.; Goncharov, Alexander F.; Stern, Laura A.; Kirby, Stephen H.

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) Å and volume V = 5051.3(13) Å3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) Å, c = 9.992(3) Å, and V = 1241.9(5) Å3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins. PMID:11087836

  15. Hydrate morphology: Physical properties of sands with patchy hydrate saturation

    USGS Publications Warehouse

    Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.

    2012-01-01

    The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

  16. Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.

    PubMed

    Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-10-15

    In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples. PMID:24054645

  17. Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

    NASA Astrophysics Data System (ADS)

    Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

    2014-05-01

    The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase

  18. If not water then what? - The possible role of CO2 hydrates in terraforming processes on Mars

    NASA Astrophysics Data System (ADS)

    Falenty, A.; Kuhs, W. F.

    The presence of water on Mars is a subject of a hot debate for over hundred years since the discovery famous channels by Giovanni Schiaparelli. With advance in technology more and more observational facts for the existence of liquids on Mars, at least in the past, have been found. It is accepted that in the distant past water played an active role in shaping Martian landscape. The problems arise for the recent past. In this period Mars is no longer wet but cold and dry. In spite of this fact, fresh, few million years old, features like gullies, chaotic terrains or pancake domes have been observed. Their origin was ascribed to water, brines, liquid CO2 or CO2 hydrates [1]. Presently liquid water is not stable at the surface and close to it. Even under high salinity it is not able to stand the harsh Martian climate for a long time. Clathrates do not have this disadvantage and can stay in meta-stable form for geologically long periods ("anomalous or self-preservation"). This makes hydrates an excellent reservoir of water ice and gases like CO2 or CH4 . The meta-stable state may be easily destroyed by e.g. climate changes, meteorite impacts or earthquakes. In this way clathrates could replenish periodically or gradually the atmosphere in trapped gases. To provide a better basis for these ideas a number of experiments for CO2 hydrate formation and decomposition were performed in our laboratory mimicking Martian surface and sub-surface conditions [2], [3], [4]. Up to now self-preservation of gas hydrates was known to exist only above 240K, which limited the applicability of this phenomenon to Martian issues. Recent investigation on anomalous preservation reviled another previously unknown aspect. In a certain pressure range outside the stability field and below 240K, hydrates unexpectedly enter the self-preservation state. Although, the mechanism, which controls this phenomenon, seems to be different from the one already reported by Kuhs et al [5], the effect is quite

  19. Exploitation of subsea gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

    2016-04-01

    Natural gas hydrates are considered to be a potential energy resource in the future. They occur in permafrost areas as well as in subsea sediments and are stable at high pressure and low temperature conditions. According to estimations the amount of carbon bonded in natural gas hydrates worldwide is two times larger than in all known conventional fossil fuels. Besides technical challenges that have to be overcome climate and safety issues have to be considered before a commercial exploitation of such unconventional reservoirs. The potential of producing natural gas from subsea gas hydrate deposits by various means (e.g. depressurization and/or injection of carbon dioxide) is numerically studied in the frame of the German research project »SUGAR«. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into a numerical model. The physics of the process leads to strong non-linear couplings between hydraulic fluid flow, hydrate dissociation and formation, hydraulic properties of the sediment, partial pressures and seawater solution of components and the thermal budget of the system described by the heat equation. This paper is intended to provide an overview of the recent development regarding the production of natural gas from subsea gas hydrate reservoirs. It aims at giving a broad insight into natural gas hydrates and covering relevant aspects of the exploitation process. It is focused on the thermodynamic principles and technological approaches for the exploitation. The effects occurring during natural gas production within hydrate filled sediment layers are identified and discussed by means of numerical simulation results. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is described and compared for different strategies. The simulations are complemented by calculations for different safety relevant problems.

  20. Terahertz spectroscopy of concrete for evaluating the critical hydration level

    NASA Astrophysics Data System (ADS)

    Dash, Jyotirmayee; Ray, Shaumik; Nallappan, Kathirvel; Sasmal, Saptarshi; Pesala, Bala

    2014-03-01

    Concrete, a mixture of cement, coarse aggregate, sand and filler material (if any), is widely used in the construction industry. Cement, mainly composed of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) reacts readily with water, a process known as hydration. The hydration process forms a solid material known as hardened cement paste which is mainly composed of Calcium Silicate Hydrate (C-S-H), Calcium Hydroxide and Calcium Carbonate. To quantify the critical hydration level, an accurate and fast technique is highly desired. However, in conventional XRD technique, the peaks of the constituents of anhydrated and hydrated cement cannot be resolved properly, where as Mid-infrared (MIR) spectroscopy has low penetration depth and hence cannot be used to determine the hydration level of thicker concrete samples easily. Further, MIR spectroscopy cannot be used to effectively track the formation of Calcium Hydroxide, a key by-product during the hydration process. This paper describes a promising approach to quantify the hydration dynamics of cement using Terahertz (THz) spectroscopy. This technique has been employed to track the time dependent reaction mechanism of the key constituents of cement that react with water and form the products in the hydrated cement, viz., C-S-H, Calcium Hydroxide and Calcium Carbonate. This study helps in providing an improved understanding on the hydration kinetics of cement and also to optimise the physio-mechanical characteristics of concrete.

  1. Time for the 70°C water precautionary option in the home dilution of powdered infant formula.

    PubMed

    Silano, Marco; Paganin, Paola; Davanzo, Riccardo

    2016-01-01

    Powdered infant formulas (PIF) are usually not sterile and may frequently be contaminated by several bacteria strains. Among them, Cronobacter species, previously known as Enterobacter sakazakii, is one of the most harmful, since it might be the causative agent of sepsis and meningitis in newborns and preterm infants during the first weeks of life. The mortality rate of these infections is up to 80 %. Therefore, some precautions are required in the home handling and dilution of PIF. Whereas there is wide consensus about the need that a PIF should be used immediately after being diluted or, if not, stored at < "5 °C", still recently the optimal temperature of the water used to dilute PIF is controversial among scientific societies and health agencies. The current knowledge is reviewed in this paper and provides sufficient evidence to cautiously advise the use of hot water at a temperature of "70 °C" in the dilution of PIF in order to prevent the Cronobacter sp. contamination and growth. PMID:26895705

  2. Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form.

    PubMed

    Takeya, Satoshi; Fujihisa, Hiroshi; Yamawaki, Hiroshi; Gotoh, Yoshito; Ohmura, Ryo; Alavi, Saman; Ripmeester, John A

    2016-08-01

    The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH4 ) and propanol are reported from powder X-ray diffraction measurements. The deformation of host water cages at the cubic-tetragonal phase transition of 2-propanol+CH4 hydrate, but not 1-propanol+CH4 hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2-propanol+CH4 hydrate can be explained by the restriction of the motion of 2-propanol within the 5(12) 6(4) host water cages. This result provides a low-temperature structure due to a temperature-induced symmetry-lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition. PMID:27346760

  3. Dynamics of a globular protein and its hydration water studied by neutron scattering and MD simulations

    DOE PAGESBeta

    Chen, Sow-Hsin; Lagi, Marco; Chu, Xiang-qiang; Zhang, Yang; Kim, Chansoo; Faraone, Antonio; Fratini, Emiliano; Baglioni, Piero

    2010-01-01

    This review article describes our neutron scattering experiments made in the past four years for the understanding of the single-particle (hydrogen atom) dynamics of a protein and its hydration water and the strong coupling between them. We found that the key to this strong coupling is the existence of a fragile-to-strong dynamic crossover (FSC) phenomenon occurring at around T L = 225±5 K in the hydration water. On lowering of the temperature toward FSC, the structure of hydration water makes a transition from predominantly the high density form (HDL), a more fluid state, to predominantly the low density formmore » (LDL), a less fluid state, derived from the existence of a liquid–liquid critical point at an elevated pressure. We show experimentally that this sudden switch in the mobility of hydration water on Lysozyme, B-DNA and RNA triggers the dynamic transition, at a temperature T D = 220 K, for these biopolymers. In the glassy state, below T D , the biopolymers lose their vital conformational flexibility resulting in a substantial diminishing of their biological functions. We also performed molecular dynamics (MD) simulations on a realistic model of hydrated lysozyme powder, which confirms the existence of the FSC and the hydration level dependence of the FSC temperature. Furthermore, we show a striking feature in the short time relaxation ( β -relaxation) of protein dynamics, which is the logarithmic decay spanning 3 decades (from ps to ns). The long time α -relaxation shows instead a diffusive behavior, which supports the liquid-like motions of protein constituents. We then discuss our recent high-resolution X-ray inelastic scattering studies of globular proteins, Lysozyme and Bovine Serum Albumin. We were able to measure the dispersion relations of collective, intra-protein phonon-like excitations in these proteins for the first time. We found that the phonon energies show a marked softening and at the same time their population increases

  4. Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

    SciTech Connect

    Deschner, Florian; Lothenbach, Barbara; Winnefeld, Frank; Neubauer, Jürgen

    2013-10-15

    The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H.

  5. Face powder poisoning

    MedlinePlus

    Face powder poisoning occurs when someone swallows or breathes in this substance. This article is for information ... The ingredients in face powder that can be harmful are: Baking soda Talcum powder Many other types of powder

  6. Microscopic Origin of Strain Hardening in Methane Hydrate

    PubMed Central

    Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

    2016-01-01

    It has been reported for a long time that methane hydrate presents strain hardening, whereas the strength of normal ice weakens with increasing strain after an ultimate strength. However, the microscopic origin of these differences is not known. Here, we investigated the mechanical characteristics of methane hydrate and normal ice by compressive deformation test using molecular dynamics simulations. It is shown that methane hydrate exhibits strain hardening only if the hydrate is confined to a certain finite cross-sectional area that is normal to the compression direction. For normal ice, it does not present strain hardening under the same conditions. We show that hydrate guest methane molecules exhibit no long-distance diffusion when confined to a finite-size area. They appear to serve as non-deformable units that prevent hydrate structure failure, and thus are responsible for the strain-hardening phenomenon. PMID:27009239

  7. Microscopic Origin of Strain Hardening in Methane Hydrate.

    PubMed

    Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

    2016-01-01

    It has been reported for a long time that methane hydrate presents strain hardening, whereas the strength of normal ice weakens with increasing strain after an ultimate strength. However, the microscopic origin of these differences is not known. Here, we investigated the mechanical characteristics of methane hydrate and normal ice by compressive deformation test using molecular dynamics simulations. It is shown that methane hydrate exhibits strain hardening only if the hydrate is confined to a certain finite cross-sectional area that is normal to the compression direction. For normal ice, it does not present strain hardening under the same conditions. We show that hydrate guest methane molecules exhibit no long-distance diffusion when confined to a finite-size area. They appear to serve as non-deformable units that prevent hydrate structure failure, and thus are responsible for the strain-hardening phenomenon. PMID:27009239

  8. Pore scale distribution of gas hydrates in sediments by micro X-ray Computed Tomography (X-CT)

    NASA Astrophysics Data System (ADS)

    Hu, G.; Li, C.; Ye, Y.; Liu, C.; Best, A. I.

    2013-12-01

    A dedicated apparatus was developed to observe in-situ pore scale distribution of gas hydrate directly during hydrate formation in artificial cores. The high-resolution X-ray Computed Tomography (type: GE Sensing & Inspection Technologies GmbH Phoenix x-ray V/tomex/s) was used and the effective resolution for observing gas hydrate bearing sediments can up to about 18μm. Methane gas hydrate was formed in 0.425-0.85mm sands under a pressure of 6MPa and a temperature of 3°C. During the process, CT scanning was conducted if there's a pressure drop (the scanning time is 66 minutes each time), so that the hydrate morphology could be detected. As a result, five scanning CT images of the same section during gas hydrate formation (i.e. hydrate saturation at 3.9%, 24.6%, 35.0%, 51.4% and 97.0%) were obtained. The result shows that at each hydrate saturation level, hydrate morphology models are complicated. The occurrence of 'floating model' (i.e. hydrate floats in pore fluid), 'contact model' (i.e. hydrate contact with the sediment particle), and the 'cementing model' (i.e. hydrates cement the sediment particles) can be found at the same time (Fig. 1). However, it shows that at different hydrate formation stages, the dominant hydrate morphology are not the same. For instance, at the first stage of hydrate formation, although there are some hydrates floating in the pore fluid, most hydrates connect the sediment particles. Consequently, the hydrate morphology at this moment can be described as a cementing model. With this method, it can be obtained that at the higher level of saturation (e.g., hydrate saturation at 24.6% and 35.0%), hydrates are mainly grow as a floating model. As hydrate saturation is much higher (e.g. after hydrate saturation is more than 51.4%), however, the floating hydrates coalesce with each other and the hydrates cement the sediment particle again. The direct observed hydrate morphology presented here may have significant impact on investigating

  9. Hydrate pingoes at Nyegga: some characteristic features

    NASA Astrophysics Data System (ADS)

    Hovland, M.

    2009-04-01

    Hydrate pingoes were observed on the seafloor during two different remotely operated vehicle (ROV)-dives, conducted by Statoil at complex-pockmark G11, at Nyegga, off Mid-Norway. Confirmation that these structures actually represent hydrate ice-cored sediment mounds (pingoes), was done by other investigators (Ivanov et al., 2006). Because it is expected that hydrate pingoes represent relatively dynamic seafloor topographic structures and that their shape and size most probably will change over relatively short time, it is important to know how to recognise them visually. Hovland and Svensen (2006) highlighted five different characteristic aspects that define hydrate pingoes on the sea floor: 1) They are dome- or disc-shaped features, which may attain any size from ~0.5 m in height and upwards. Inside pockmark G11, they were up to 1 m high. 2) They are circular or oval in plan view and may attain lateral sizes on the seafloor ranging upwards from ~0.5 m. Inside G11 they had lengths of several metres and widths of up to 4 m. 3) They have dense communities of organisms growing on their surfaces. At G11, they were overgrown with small pogonophoran tube-worms. 4) They have patches of white or grey bacterial mats growing on their surface, indicating advection (seepage) of reduced pore-waters. 5) They have small pits and patches of fluidized sediments on their surface, indicating pit corrosion of the sub-surface gas hydrate. Because gas hydrates often form in high-porosity, near-surface sediments, where water is readily available, it is thought that they will build up at locations where gases are actively migrating upwards from depth. However, gas hydrates are not stable in the presence of ambient seawater, as seawater is deficient in guest molecule gases (normally methane). Therefore, they tend to build up below surface above conduits for gas flow from depth. But, the near-surface hydrate ice-lenses will continually be corroded by seawater circulating into the sediments

  10. A rapid method for chemical fingerprint analysis of Pan Panax notoginseng powders by ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry.

    PubMed

    Liu, Peng; Yu, He-Shuil; Zhang, Li-Juan; Song, Xin-Bo; Kang, Li-Ping; Liu, Jing-Yuan; Zhang, Jie; Cao, Man; Yu, Kate; Kang, Ting-Guo; Ma, Bai-Ping

    2015-06-01

    A method coupling ultra-performance liquid chromatography (UPLC) with quadrupole time-of-flight mass spectrometer (Qtof MS) using the electrospray ionization (ESI) source was developed for the identification of the major saponins from Panax notoginseng powder (PNP). Ten different PNP samples were analyzed and evaluated for their quality by similarity evaluation and principle component analysis (PCA). Based on the accurate mass, summarized characteristic fragmentation behaviors, retention times of different types of saponins, related botanical biogenesis, and reported chromatographic behavior of saponins, fifty-one common peaks were effectively separated and identified, including 28 protopanaxadiol saponins and 18 protopanaxatriol saponins. Simultaneously, 15 significant discrepancy compounds were identified from the disqualified PNP samples. The established UPLC/Qtof MS fingerprint method was successfully applied for profiling and identifying the major saponins of PNP, providing a fast quality evaluation tool for distinguishing the authentic PNP and the adulterated products. PMID:26073345

  11. Micromechanical cohesion force measurements to determine cyclopentane hydrate interfacial properties.

    PubMed

    Aman, Zachary M; Joshi, Sanjeev E; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

    2012-06-15

    Hydrate aggregation and deposition are critical factors in determining where and when hydrates may plug a deepwater flowline. We present the first direct measurement of structure II (cyclopentane) hydrate cohesive forces in the water, liquid hydrocarbon and gas bulk phases. For fully annealed hydrate particles, gas phase cohesive forces were approximately twice that obtained in a liquid hydrocarbon phase, and approximately six times that obtained in the water phase. Direct measurements show that hydrate cohesion force in a water-continuous bulk may be only the product of solid-solid cohesion. When excess water was present on the hydrate surface, gas phase cohesive forces increased by a factor of three, suggesting the importance of the liquid or quasi-liquid layer (QLL) in determining cohesive force. Hydrate-steel adhesion force measurements show that, when the steel surface is coated with hydrophobic wax, forces decrease up to 96%. As the micromechanical force technique is uniquely capable of measuring hydrate-surface forces with variable contact time, the present work contains significant implications for hydrate applications in flow assurance. PMID:22484169

  12. Phase field modeling of CH4 hydrate conversion into CO2 hydrate in the presence of liquid CO2.

    PubMed

    Tegze, G; Gránásy, L; Kvamme, B

    2007-06-28

    We present phase field simulations to estimate the conversion rate of CH(4) hydrate to CO(2) hydrate in the presence of liquid CO(2) under conditions typical for underwater gas hydrate reservoirs. In the computations, all model parameters are evaluated from physical properties taken from experiment or molecular dynamics simulations. It has been found that hydrate conversion is a diffusion controlled process, as after a short transient, the displacement of the conversion front scales with t(1/2). Assuming a diffusion coefficient of D(s) = 1.1 x 10(-11) m(2) s(-1) in the hydrate phase, the predicted time dependent conversion rate is in reasonable agreement with results from magnetic resonance imaging experiments. This value of the diffusion coefficient is higher than expected for the bulk hydrate phase, probably due to liquid inclusions remaining in the porous sample used in the experiment. PMID:17612734

  13. HYDRATE CORE DRILLING TESTS

    SciTech Connect

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

    2002-11-01

    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate formation comprised of coarse, large

  14. Ceramic Powders

    NASA Technical Reports Server (NTRS)

    1984-01-01

    In developing its product line of specialty ceramic powders and related products for government and industrial customers, including companies in the oil, automotive, electronics and nuclear industries, Advanced Refractory Technologies sought technical assistance from NERAC, Inc. in specific areas of ceramic materials and silicon technology, and for assistance in identifying possible applications of these materials in government programs and in the automotive and electronics industry. NERAC conducted a computerized search of several data bases and provided extensive information in the subject areas requested. NERAC's assistance resulted in transfer of technologies that helped ART staff develop a unique method for manufacture of ceramic materials to precise customer specifications.

  15. Energetic powder

    DOEpatents

    Jorgensen, Betty S.; Danen, Wayne C.

    2003-12-23

    Fluoroalkylsilane-coated metal particles. The particles have a central metal core, a buffer layer surrounding the core, and a fluoroalkylsilane layer attached to the buffer layer. The particles may be prepared by combining a chemically reactive fluoroalkylsilane compound with an oxide coated metal particle having a hydroxylated surface. The resulting fluoroalkylsilane layer that coats the particles provides them with excellent resistance to aging. The particles can be blended with oxidant particles to form energetic powder that releases chemical energy when the buffer layer is physically disrupted so that the reductant metal core can react with the oxidant.

  16. New Methods for Gas Hydrate Energy and Climate Studies

    NASA Astrophysics Data System (ADS)

    Ruppel, C. D.; Pohlman, J.; Waite, W. F.; Hunt, A. G.; Stern, L. A.; Casso, M.

    2015-12-01

    Over the past few years, the USGS Gas Hydrates Project has focused on advancements designed to enhance both energy resource and climate-hydrate interaction studies. On the energy side, the USGS now manages the Pressure Core Characterization Tools (PCCTs), which includes the Instrumented Pressure Testing Chamber (IPTC) that we have long maintained. These tools, originally built at Georgia Tech, are being used to analyze hydrate-bearing sediments recovered in pressure cores during gas hydrate drilling programs (e.g., Nankai 2012; India 2015). The USGS is now modifying the PCCTs for use on high-hydrate-saturation and sand-rich sediments and hopes to catalyze third-party tool development (e.g., visualization). The IPTC is also being used for experiments on sediments hosting synthetic methane hydrate, and our scanning electron microscope has recently been enhanced with a new cryo-stage for imaging hydrates. To support climate-hydrate interaction studies, the USGS has been re-assessing the amount of methane hydrate in permafrost-associated settings at high northern latitudes and examined the links between methane carbon emissions and gas hydrate dissociation. One approach relies on the noble gas signature of methane emissions. Hydrate dissociation uniquely releases noble gases partitioned by molecular weight, providing a potential fingerprint for hydrate-sourced methane emissions. In addition, we have linked a DOC analyzer with an IRMS at Woods Hole Oceanographic Institution, allowing rapid and precise measurement of DOC and DIC concentrations and carbon isotopic signatures. The USGS has also refined methods to measure real-time sea-air flux of methane and CO2 using cavity ring-down spectroscopy measurements coupled with other data. Acquiring ~8000 km of data on the Western Arctic, US Atlantic, and Svalbard margins, we have tested the Arctic methane catastrophe hypothesis and the link between seafloor methane emissions and sea-air methane flux.

  17. How Hydrate Saturation Anomalies are Diffusively Constructed and Advectively Smoothed

    NASA Astrophysics Data System (ADS)

    Rempel, A. W.; Irizarry, J. T.; VanderBeek, B. P.; Handwerger, A. L.

    2015-12-01

    The physical processes that control the bulk characteristics of hydrate reservoirs are captured reasonably well by long-established model formulations that are rooted in laboratory-verified phase equilibrium parameterizations and field-based estimates of in situ conditions. More detailed assessments of hydrate distribution, especially involving the occurrence of high-saturation hydrate anomalies have been more difficult to obtain. Spatial variations in sediment properties are of central importance for modifying the phase behavior and promoting focussed fluid flow. However, quantitative predictions of hydrate anomaly development cannot be made rigorously without also addressing the changes in phase behavior and mechanical balances that accompany changes in hydrate saturation level. We demonstrate how pore-scale geometrical controls on hydrate phase stability can be parameterized for incorporation in simulations of hydrate anomaly development along dipping coarse-grained layers embedded in a more fine-grained background that is less amenable to fluid transport. Model simulations demonstrate how hydrate anomaly growth along coarse-layer boundaries is promoted by diffusive gas transport from the adjacent fine-grained matrix, while advective transport favors more distributed growth within the coarse-grained material and so effectively limits the difference between saturation peaks and background levels. Further analysis demonstrates how sediment contacts are unloaded once hydrate saturation reaches sufficient levels to form a load-bearing skeleton that can evolve to produce segregated nodules and lenses. Decomposition of such growth forms poses a significant geohazard that is expected to be particularly sensitive to perturbations induced by gas extraction. The figure illustrates the predicted evolution of hydrate saturation Sh in a coarse-grained dipping layer showing how prominent bounding hydrate anomalies (spikes) supplied by diffusive gas transport at early times

  18. Controls on Gas Hydrate Formation and Dissociation

    SciTech Connect

    Miriam Kastner; Ian MacDonald

    2006-03-03

    up-flow and down-flow of fluid at rates that range between 0.5 to 214 cm/yr and 2-162 cm/yr, respectively. The fluid flow system at the mound and background sites are coupled having opposite polarities that oscillate episodically between 14 days to {approx}4 months. Stability calculations suggest that despite bottom water temperature fluctuations, of up to {approx}3 C, the Bush Hill gas hydrate mound is presently stable, as also corroborated by the time-lapse video camera images that did not detect change in the gas hydrate mound. As long as methane (and other hydrocarbon) continues advecting at the observed rates the mound would remain stable. The {_}{sup 13}C-DIC data suggest that crude oil instead of methane serves as the primary electron-donor and metabolic substrate for anaerobic sulfate reduction. The oil-dominated environment at Bush Hill shields some of the methane bubbles from being oxidized both anaerobically in the sediment and aerobically in the water column. Consequently, the methane flux across the seafloor is higher at Bush hill than at non-oil rich seafloor gas hydrate regions, such as at Hydrate Ridge, Cascadia. The methane flux across the ocean/atmosphere interface is as well higher. Modeling the methane flux across this interface at three bubble plumes provides values that range from 180-2000 {_}mol/m{sup 2} day; extrapolating it over the Gulf of Mexico basin utilizing satellite data is in progress.

  19. Pulsed neutron powder diffraction at high pressure by a capacity-increased sapphire anvil cell

    NASA Astrophysics Data System (ADS)

    Okuchi, Takuo; Yoshida, Masashi; Ohno, Yoshiki; Tomioka, Naotaka; Purevjav, Narangoo; Osakabe, Toyotaka; Harjo, Stefanus; Abe, Jun; Aizawa, Kazuya; Sasaki, Shigeo

    2013-12-01

    A new design of opposed anvil cell for time-of-flight neutron powder diffraction was prepared for use at advanced pulsed sources. A couple of single-crystal sapphire sphere anvils and a gasket of fully hardened Ti-Zr null alloy were combined to compress 35 mm3 of sample volume to 1 GPa and 11 mm3 to 2 GPa of pressures, respectively. A very high-quality powder diffraction pattern was obtained at Japan Proton Accelerator Research Complex for a controversial high pressure phase of methane hydrate. The counting statistics, resolution, absolute accuracy and d-value range of the pattern were all improved to be best suitable for precise structure refinement. The sample is optically accessible to be measured by Raman and fluorescence spectroscopy during and after compression. The current cell will be an alternative choice to study hydrogenous materials of complex structures that are stable at the described pressure regime.

  20. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  1. Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ

    PubMed Central

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-01-01

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles. PMID:25996055

  2. Dynamical Disorder in the DNA Hydration Shell.

    PubMed

    Duboué-Dijon, Elise; Fogarty, Aoife C; Hynes, James T; Laage, Damien

    2016-06-22

    The reorientation and hydrogen-bond dynamics of water molecules within the hydration shell of a B-DNA dodecamer, which are of interest for many of its biochemical functions, are investigated via molecular dynamics simulations and an analytic jump model, which provide valuable new molecular level insights into these dynamics. Different sources of heterogeneity in the hydration shell dynamics are determined. First, a pronounced spatial heterogeneity is found at the DNA interface and explained via the jump model by the diversity in local DNA interfacial topographies and DNA-water H-bond interactions. While most of the hydration shell is moderately retarded with respect to the bulk, some water molecules confined in the narrow minor groove exhibit very slow dynamics. An additional source of heterogeneity is found to be caused by the DNA conformational fluctuations, which modulate the water dynamics. The groove widening aids the approach of, and the jump to, a new water H-bond partner. This temporal heterogeneity is especially strong in the minor groove, where groove width fluctuations occur on the same time scale as the water H-bond rearrangements, leading to a strong dynamical disorder. The usual simplifying assumption that hydration shell dynamics is much faster than DNA dynamics is thus not valid; our results show that biomolecular conformational fluctuations are essential to facilitate the water motions and accelerate the hydration dynamics in confined groove sites. PMID:27240107

  3. Natural gas hydrates on the North Slope of Alaska

    SciTech Connect

    Collett, T.S.

    1991-01-01

    Gas hydrates are crystalline substances composed of water and gas, mainly methane, in which a solid-water lattice accommodates gas molecules in a cage-like structure, or clathrate. These substances often have been regarded as a potential (unconventional) source of natural gas. Significant quantities of naturally occurring gas hydrates have been detected in many regions of the Arctic including Siberia, the Mackenzie River Delta, and the North Slope of Alaska. On the North Slope, the methane-hydrate stability zone is areally extensive beneath most of the coastal plain province and has thicknesses as great as 1000 meters in the Prudhoe Bay area. Gas hydrates have been identified in 50 exploratory and production wells using well-log responses calibrated to the response of an interval in one well where gas hydrates were recovered in a core by ARCO Alaska and EXXON. Most of these gas hydrates occur in six laterally continuous Upper Cretaceous and lower Tertiary sandstone and conglomerate units; all these gas hydrates are geographically restricted to the area overlying the eastern part of the Kuparuk River Oil Field and the western part of the Prudhoe Bay Oil Field. The volume of gas within these gas hydrates is estimated to be about 1.0 {times} 10{sup 12} to 1.2 {times} 10{sup 12} cubic meters (37 to 44 trillion cubic feet), or about twice the volume of conventional gas in the Prudhoe Bay Field. Geochemical analyses of well samples suggest that the identified hydrates probably contain a mixture of deep-source thermogenic gas and shallow microbial gas that was either directly converted to gas hydrate or first concentrated in existing traps and later converted to gas hydrate. The thermogenic gas probably migrated from deeper reservoirs along the same faults thought to be migration pathways for the large volumes of shallow, heavy oil that occur in this area. 51 refs., 11 figs., 3 tabs.

  4. Relaxation mechanism of the hydrated electron.

    PubMed

    Elkins, Madeline H; Williams, Holly L; Shreve, Alexander T; Neumark, Daniel M

    2013-12-20

    The relaxation dynamics of the photoexcited hydrated electron have been subject to conflicting interpretations. Here, we report time-resolved photoelectron spectra of hydrated electrons in a liquid microjet with the aim of clarifying ambiguities from previous experiments. A sequence of three ultrashort laser pulses (~100 femtosecond duration) successively created hydrated electrons by charge-transfer-to-solvent excitation of dissolved anions, electronically excited these electrons via the s→p transition, and then ejected them into vacuum. Two distinct transient signals were observed. One was assigned to the initially excited p-state with a lifetime of ~75 femtoseconds, and the other, with a lifetime of ~400 femtoseconds, was attributed to s-state electrons just after internal conversion in a nonequilibrated solvent environment. These assignments support the nonadiabatic relaxation model. PMID:24357314

  5. Calorimetric studies of the kinetic unfreezing of molecular motions in hydrated lysozyme, hemoglobin, and myoglobin.

    PubMed Central

    Sartor, G; Mayer, E; Johari, G P

    1994-01-01

    Differential scanning calorimetric (DSC) studies of the glassy states of as-received and hydrated lysozyme, hemoglobin, and myoglobin powders, with water contents of < or = 0.25, < or = 0.30, and < or = 0.29 g/g of protein, show that their heat capacity slowly increases with increasing temperature, without showing an abrupt increase characteristic of glass-->liquid transition. Annealing (also referred to as physical aging) of the hydrated proteins causes their DSC scans to show an endothermic region, similar to an overshoot, immediately above the annealing temperature. This annealing effect appears at all temperatures between approximately 150 and 300 K. The area under these peaks increases with increasing annealing time at a fixed temperature. The effects are attributed to the presence of a large number of local structures in which macromolecular segments diffuse at different time scales over a broad range. The lowest time scale corresponds to the > N-H and -O-H group motions which become kinetically unfrozen at approximately 150-170 K on heating at a rate of 30 K min-1 and which have a relaxation time of 5-10 s in this temperature range. The annealing effects confirm that the individual glass transition of the relaxing local regions is spread over a temperature range up to the denaturation temperature region of the proteins. The interpretation is supported by simulation of DSC scans in which the distribution of relaxation times is assumed to be exceptionally broad and in which annealing done at several temperatures over a wide range produces endothermic effects (or regions of DSC scans) qualitatively similar to those observed for the hydrated proteins. PMID:8130342

  6. Mapping the hydration dynamics of ubiquitin.

    PubMed

    Nucci, Nathaniel V; Pometun, Maxim S; Wand, A Joshua

    2011-08-17

    The nature of water's interaction with biomolecules such as proteins has been difficult to examine in detail at atomic resolution. Solution NMR spectroscopy is potentially a powerful method for characterizing both the structural and temporal aspects of protein hydration but has been plagued by artifacts. Encapsulation of the protein of interest within the aqueous core of a reverse micelle particle results in a general slowing of water dynamics, significant reduction in hydrogen exchange chemistry and elimination of contributions from bulk water thereby enabling the use of nuclear Overhauser effects to quantify interactions between the protein surface and hydration water. Here we extend this approach to allow use of dipolar interactions between hydration water and hydrogens bonded to protein carbon atoms. By manipulating the molecular reorientation time of the reverse micelle particle through use of low viscosity liquid propane, the T(1ρ) relaxation time constants of (1)H bonded to (13)C were sufficiently lengthened to allow high quality rotating frame nuclear Overhauser effects to be obtained. These data supplement previous results obtained from dipolar interactions between the protein and hydrogens bonded to nitrogen and in aggregate cover the majority of the molecular surface of the protein. A wide range of hydration dynamics is observed. Clustering of hydration dynamics on the molecular surface is also seen. Regions of long-lived hydration water correspond with regions of the protein that participate in molecular recognition of binding partners suggesting that the contribution of the solvent entropy to the entropy of binding has been maximized through evolution. PMID:21761828

  7. Time-resolved X-ray powder diffraction on a three-way catalyst at the GILDA beamline.

    PubMed

    Martorana, A; Deganello, G; Longo, A; Deganello, F; Liotta, L; Macaluso, A; Pantaleo, G; Balerna, A; Meneghini, C; Mobilio, S

    2003-03-01

    Time-resolved X-ray diffraction experiments carried out at the beamline BM08-GILDA of ESRF allowed a study of the structural modifications taking place in a Pt/ceria-zirconia catalyst while the CO oxidation reaction was in progress. The capillary tube in which the sample is stored acts effectively as a chemical microreactor that ensures homogeneity of the sample treatments and minimization of diffusion effects. During the flowing of the reactant CO/He mixture, the investigated catalyst undergoes a fast Ce(IV)-Ce(III) partial reduction that involves the release of one O atom for every two reduced Ce cations. Because Ce(III) has a larger ionic radius than Ce(IV), the structural modification produces an increase of the lattice constant of the ceria-zirconia mixed oxide, and this increase is monitored by the translating imaging-plate device implemented at GILDA. The CO(2) resulting from the oxidation of the fluxed CO is monitored by a quadrupole mass spectrometer during the recording of the time-resolved X-ray diffraction pattern. The chemical and structural information was combined to show that the CO(2) yield is nearly constant until the catalytic system can provide oxygen for the reaction, while the structural rearrangement of the catalyst is delayed with respect to the switching on of the CO/He flux. After this induction time, during which CO(2) is produced with no structural modification of the catalyst, a fast increase of the lattice constant takes place. PMID:12606797

  8. Detailed analysis of methane hydrate concentrated zone of lobe type

    NASA Astrophysics Data System (ADS)

    Kobayashi, T.; Saeki, T.; Inamori, T.; Fujii, T.; Shimoda, N.

    2007-12-01

    Japan Oil, Gas and Metals National Corporation (hereinafter called JOGMEC), as a member of MH21 Research Consortium, takes charge of a study of the Research for Resources Assessment, and is pursuing a possibility that methane hydrate, which is presumed to be distributed around ocean area of Japan, will be energy resources. JOGMEC is currently conducting analysis of seismic data which was acquired by 3D seismic survey conducted from Tokai-Oki to Kumano-nada in the eastern Nankai Trough by METI (Ministry of Economy, Trade and Industry) in 2002 under the national program of assessment for methane hydrates as energy resources. It was understood that methane hydrate was correlated to high resistivity and high velocity based on the results of drilling surveys and velocity analysis, and that methane hydrate concentrated zones can be roughly classified into the channels and lobes in seismic geomorphology because they were characterized with reserves consisting turbidite sand bodies. In this study, the detailed analysis of the inner structure of the methane hydrate concentrated zone of lobe type was conducted to understand the occurrence configurations of methane hydrates. The reflected waves that construct the methane hydrate concentrated zones in the seismic data were extracted and those reflected waves were classified into some groups every one reflector. As the result, some reflectors that construct the methane hydrate concentrated zones were revealed. Those reflectors show the layers including methane hydrates, and the detailed distribution of the methane hydrates in those layers was revealed by the intensity distribution of the amplitude. This time, we introduce the example of the detailed analysis of the methane hydrate concentrated zone in the lobe of submarine fan.

  9. The efficient hemostatic effect of Antarctic krill chitosan is related to its hydration property.

    PubMed

    Wu, Shuai; Huang, Zhuoyao; Yue, Jianhui; Liu, Di; Wang, Ting; Ezanno, Pierre; Ruan, Changshun; Zhao, Xiaoli; Lu, William W; Pan, Haobo

    2015-11-01

    Antarctic krill chitosan (A-Chitosan) was first evaluated in its hemostatic effect in this study. The prepared A-Chitosan powder showed low level of crystallinity and significantly high water binding capacity as 1293% (w/w). By mice tail amputation model and blood coagulation timing experiment, it is showed that this chitosan accelerated the tail hemostasis by 55% and shortened the blood clotting time by 38%. This efficacy was better than two other commercial chitosans investigated and was corresponding to their water binding capacities. Through examining the effect of chitosan on blood components, it could be found that platelets adhesion was mainly affected by the water binding capacity, and red blood cells aggregation was dependent on their deacetylation degree. The physicochemical properties resulted in better hydration property of chitosan would improve its hemostatic effect. These results suggested that Antarctic krill chitosan is a good candidate for hemostatic application. PMID:26256352

  10. Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    USGS Publications Warehouse

    Stern, Laura A.; Lorenson, T.D.; Pinkston, John C.

    2011-01-01

    Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA–DOE–USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5 m to 760.1 m depth, and sections investigated here were retrieved from 619.9 m and 661.0 m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70–75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20–120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas.

  11. Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    USGS Publications Warehouse

    Stern, L.A.; Lorenson, T.D.; Pinkston, J.C.

    2011-01-01

    Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5. m to 760.1. m depth, and sections investigated here were retrieved from 619.9. m and 661.0. m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70-75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20-120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas. ?? 2009.

  12. Instant conversion of air to a clathrate hydrate: CO(2) hydrates directly from moist air and moist CO(2)(g).

    PubMed

    Devlin, J Paul; Monreal, I Abrrey

    2010-12-23

    The rapid conversion of vapor mixtures containing the gases CO(2), H(2)S, and HCN to clathrate hydrates was reported recently. The novel method is based on the pulsing of warm vapor mixtures, including a carrier gas, into a cold condensation chamber. With cooling, the vapors, which also include ∼1% water and either tetrahydrofuran or trimethylene oxide as a catalyst, nucleate aqueous solution nanodroplets that, on a millisecond time scale, crystallize as hydrate nanoparticles that consume 100% of the water. Humid air approximates the content of mixtures used successfully in the vapor-to-hydrate conversions. FTIR spectra are examined for gas hydrates formed directly from air and air enriched with CO(2), as well as hydrate particles for which CO(2)(g) serves as both guest and aerosol medium. In each instance all of the water in the condensed phase converts to a clathrate hydrate. The subsecond ether-catalyzed formation of the hydrates near 230 K requires only a few percent of the CO(2) pressure used in conventional processes that yield fractional amounts of gas hydrates on an hour time scale in the same temperature range. PMID:21105676

  13. Powder treatment process

    DOEpatents

    Weyand, J.D.

    1988-02-09

    Disclosed are: (1) a process comprising spray drying a powder-containing slurry, the slurry containing a powder constituent susceptible of oxidizing under the temperature conditions of the spray drying, while reducing the tendency for oxidation of the constituent by including as a liquid constituent of the slurry an organic liquid; (2) a process comprising spray drying a powder-containing slurry, the powder having been pretreated to reduce content of a powder constituent susceptible of oxidizing under the temperature conditions of the spray drying, the pretreating comprising heating the powder to react the constituent; and (3) a process comprising reacting ceramic powder, grinding the reacted powder, slurrying the ground powder, spray drying the slurried powder, and blending the dried powder with metal powder. 2 figs.

  14. Powder treatment process

    DOEpatents

    Weyand, John D.

    1988-01-01

    (1) A process comprising spray drying a powder-containing slurry, the slurry containing a powder constituent susceptible of oxidizing under the temperature conditions of the spray drying, while reducing the tendency for oxidation of the constituent by including as a liquid constituent of the slurry an organic liquid; (2) a process comprising spray drying a powder-containing slurry, the powder having been pretreated to reduce content of a powder constituent susceptible of oxidizing under the temperature conditions of the spray drying, the pretreating comprising heating the powder to react the constituent; and (3) a process comprising reacting ceramic powder, grinding the reacted powder, slurrying the ground powder, spray drying the slurried powder, and blending the dried powder with metal powder.

  15. Nondestructive evaluation of crystallized-particle size in lactose-powder by terahertz time-domain spectroscopy

    NASA Astrophysics Data System (ADS)

    Yamauchi, Satoshi; Hatakeyama, Sakura; Imai, Yoh; Tonouchi, Masayoshi

    2014-03-01

    Transmission-type terahertz time-domain spectroscopy is applied to evaluate crystallized lactose particle of size below 30 μm, which is far too small compared to the wavelength of incident terahertz (THz)-wave. The THz-absorption spectrum of lactose is successfully deconvoluted by Lorentzian to two spectra with peaks at 17.1 cm-1 (0.53 THz) and 45.6 cm-1 (1.37 THz) derived from α-lactose monohydrate, and a spectrum at 39.7 cm-1 (1.19 THz) from anhydrous β-lactose after removal of the broad-band spectrum by polynomial cubic function. Lactose is mainly crystallized into α-lactose monohydrate from the supersaturated solution at room temperature with a small amount of anhydrous β-lactose below 4%. The absorption feature is dependent on the crystallized particle size and the integrated intensity ratio of the two absorptions due to α-lactose monohydrate is correlated in linear for the size.

  16. Experimental Study of Gas Hydrate Dynamics

    NASA Astrophysics Data System (ADS)

    Fandino, O.; Ruffine, L.

    2011-12-01

    Important quantities of methane and other gases are trapped below the seafloor and in the permafrost by an ice-like solid, called gas hydrates or clathrate hydrates. The latter is formed when water is mixing with different gases at high pressures and low temperatures. Due to a their possible use as a source of energy [1] or the problematic related to flow assurance failure in pipelines [2] the understanding of their processes of formation/destabilisation of these structures becomes a goal for many laboratories research as well as industries. In this work we present an experimental study on the stochastic behaviour of hydrate formation from a bulk phase. The method used here for the experiments was to repeat several time the same hydrate formation procedure and to notice the different from one experiment to another. A variable-volume type high-pressure apparatus with two sapphire windows was used. This device, already presented by Ruffine et al.[3], allows us to perform both kinetics and phase equilibrium measurements. Three initial pressure conditions were considered here, 5.0 MPa, 7.5 MPa and 10.0 MPa. Hydrates have been formed, then allowed to dissociate by stepwise heating. The memory effect has also been investigated after complete dissociation. It turned out that, although the thermodynamics conditions of formation and/or destabilization were reproducible. An attempt to determine the influence of pressure on the nucleation induction time will be discussed. References 1. Sum, A. K.; Koh, C. A.; Sloan, E. D., Clathrate Hydrates: From Laboratory Science to Engineering Practice. Industrial & Engineering Chemistry Research 2009, 48, 7457-7465. 2. Sloan, E. D., A changing hydrate paradigm-from apprehension to avoidance to risk management. Fluid Phase Equilibria 2005, 228, 67-74. 3. Ruffine, L.; Donval, J. P.; Charlou, J. L.; Cremière, A.; Zehnder, B. H., Experimental study of gas hydrate formation and destabilisation using a novel high-pressure apparatus. Marine

  17. Arctic Gas hydrate, Environment and Climate

    NASA Astrophysics Data System (ADS)

    Mienert, Jurgen; Andreassen, Karin; Bünz, Stefan; Carroll, JoLynn; Ferre, Benedicte; Knies, Jochen; Panieri, Giuliana; Rasmussen, Tine; Myhre, Cathrine Lund

    2015-04-01

    Arctic methane hydrate exists on land beneath permafrost regions and offshore in shelf and continental margins sediments. Methane or gas hydrate, an ice-like substrate, consists mainly of light hydrocarbons (mostly methane from biogenic sources but also ethane and propane from thermogenic sources) entrapped by a rigid cage of water molecules. The pressure created by the overlying water and sediments offshore stabilizes the CH4 in continental margins at a temperature range well above freezing point; consequently CH4 exists as methane ice beneath the seabed. Though the accurate volume of Arctic methane hydrate and thus the methane stored in hydrates throughout the Quaternary is still unknown it must be enormous if one considers the vast regions of Arctic continental shelves and margins as well as permafrost areas offshore and on land. Today's subseabed methane hydrate reservoirs are the remnants from the last ice age and remain elusive targets for both unconventional energy and as a natural methane emitter influencing ocean environments and ecosystems. It is still contentious at what rate Arctic warming may govern hydrate melting, and whether the methane ascending from the ocean floor through the hydrosphere reaches the atmosphere. As indicated by Greenland ice core records, the atmospheric methane concentration rose rapidly from ca. 500 ppb to ca. 750 ppb over a short time period of just 150 years at the termination of the younger Dryas period ca. 11600 years ago, but the dissociation of large quantities of methane hydrates on the ocean floor have not been documented yet (Brook et al., 2014 and references within). But with the major projected warming and sea ice melting trend (Knies et al., 2014) one may ask, for how long will CH4 stay trapped in methane hydrates if surface and deep-ocean water masses will warm and permafrost continuous to melt (Portnov et al. 2014). How much of the Arctic methane will be consumed by the micro- and macrofauna, how much will

  18. Hydration dynamics near a model protein surface

    SciTech Connect

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-09-01

    The evolution of water dynamics from dilute to very high concentration solutions of a prototypical hydrophobic amino acid with its polar backbone, N-acetyl-leucine-methylamide (NALMA), is studied by quasi-elastic neutron scattering and molecular dynamics simulation for both the completely deuterated and completely hydrogenated leucine monomer. We observe several unexpected features in the dynamics of these biological solutions under ambient conditions. The NALMA dynamics shows evidence of de Gennes narrowing, an indication of coherent long timescale structural relaxation dynamics. The translational water dynamics are analyzed in a first approximation with a jump diffusion model. At the highest solute concentrations, the hydration water dynamics is significantly suppressed and characterized by a long residential time and a slow diffusion coefficient. The analysis of the more dilute concentration solutions takes into account the results of the 2.0M solution as a model of the first hydration shell. Subtracting the first hydration layer based on the 2.0M spectra, the translational diffusion dynamics is still suppressed, although the rotational relaxation time and residential time are converged to bulk-water values. Molecular dynamics analysis shows spatially heterogeneous dynamics at high concentration that becomes homogeneous at more dilute concentrations. We discuss the hydration dynamics results of this model protein system in the context of glassy systems, protein function, and protein-protein interfaces.

  19. Hydration of Portland cement with additions of calcium sulfoaluminates

    SciTech Connect

    Le Saout, Gwenn; Lothenbach, Barbara; Hori, Akihiro; Higuchi, Takayuki; Winnefeld, Frank

    2013-01-15

    The effect of mineral additions based on calcium aluminates on the hydration mechanism of ordinary Portland cement (OPC) was investigated using isothermal calorimetry, thermal analysis, X-ray diffraction, scanning electron microscopy, solid state nuclear magnetic resonance and pore solution analysis. Results show that the addition of a calcium sulfoaluminate cement (CSA) to the OPC does not affect the hydration mechanism of alite but controls the aluminate dissolution. In the second blend investigated, a rapid setting cement, the amorphous calcium aluminate reacts very fast to ettringite. The release of aluminum ions strongly retards the hydration of alite but the C-S-H has a similar composition as in OPC with no additional Al to Si substitution. As in CSA-OPC, the aluminate hydration is controlled by the availability of sulfates. The coupling of thermodynamic modeling with the kinetic equations predicts the amount of hydrates and pore solution compositions as a function of time and validates the model in these systems.

  20. Submarine gas hydrate estimation: Theoretical and empirical approaches

    SciTech Connect

    Ginsburg, G.D.; Soloviev, V.A.

    1995-12-01

    The published submarine gas hydrate resource estimates are based on the concepts of their continuous extent over large areas and depth intervals and/or the regionally high hydrate concentrations in sediments. The observational data are in conflict with these concepts. At present such estimates cannot be made to an accuracy better than an order of magnitude. The amount of methane in shallow subbottom (seepage associated) gas-hydrate accumulations is estimated at 10{sup 14} m{sup 3} STP, and in deep-seated hydrates at 10{sup 15} m{sup 3} according to observational data. From the genetic standpoint for the time being gas hydrate potential could be only assessed as far less than 10{sup 17} m{sup 3} because rates of related hydrogeological and geochemical processes have not been adequately studied.

  1. UV254 absorbance as real-time monitoring and control parameter for micropollutant removal in advanced wastewater treatment with powdered activated carbon.

    PubMed

    Altmann, Johannes; Massa, Lukas; Sperlich, Alexander; Gnirss, Regina; Jekel, Martin

    2016-05-01

    This study investigates the applicability of UV absorbance measurements at 254 nm (UVA254) to serve as a simple and reliable surrogate parameter to monitor and control the removal of organic micropollutants (OMPs) in advanced wastewater treatment applying powdered activated carbon (PAC). Correlations between OMP removal and corresponding UVA254 reduction were determined in lab-scale adsorption batch tests and successfully applied to a pilot-scale PAC treatment stage to predict OMP removals in aggregate samples with good accuracy. Real-time UVA254 measurements were utilized to evaluate adapted PAC dosing strategies and proved to be effective for online monitoring of OMP removal. Furthermore, active PAC dosing control according to differential UVA254 measurements was implemented and tested. While precise removal predictions based on real-time measurements were not accurate for all OMPs, UVA254-controlled dynamic PAC dosing was capable of achieving stable OMP removals. UVA254 can serve as an effective surrogate parameter for OMP removal in technical PAC applications. Even though the applicability as control parameter to adjust PAC dosing to water quality changes might be limited to applications with fast response between PAC adjustment and adsorptive removal (e.g. direct filtration), UVA254 measurements can also be used to monitor the adsorption efficiency in more complex PAC applications. PMID:26963606

  2. Oxidation and hydration of U3O8 materials following controlled exposure to temperature and humidity.

    PubMed

    Tamasi, Alison L; Boland, Kevin S; Czerwinski, Kenneth; Ellis, Jason K; Kozimor, Stosh A; Martin, Richard L; Pugmire, Alison L; Reilly, Dallas; Scott, Brian L; Sutton, Andrew D; Wagner, Gregory L; Walensky, Justin R; Wilkerson, Marianne P

    2015-04-21

    Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In this study, a high-purity α-U3O8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2-3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. Signatures measured from the α-U3O8 sample indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. The absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presence at the initial time of production. LA-UR-15-21495. PMID:25786096

  3. Dynamics of the gas hydrate system off Svalbard

    NASA Astrophysics Data System (ADS)

    Berndt, Christian; Feseker, Tomas; Treude, Tina; Krastel, Sebastian; Liebetrau, Volker; Niemann, Helge; Bertics, Victoria; Dumke, Ines; Dünnbier, Karolin; Ferre, Benedicte; Graves, Carolyn; Gross, Felix; Hissmann, Karen; Hühnerbach, Veit; Krause, Stefan; Lieser, Kathrin; Schauer, Jürgen; Steinle, Lea

    2013-04-01

    Marine methane hydrate is an ice-like substance stable at high-pressure and low temperature found frequently in continental margins. Since discovery of a large number of gas flares between 380 and 400 m water depth at the landward termination of the gas hydrate stability zone off Svalbard, there is concern that warming bottom waters have already started to melt large amounts of marine gas hydrate and may possibly accelerate global warming. The location of gas flares observed in PARASOUND data, geochemical anomalies in sediment cores, and anomalies in heat flow profiles suggest that hydrates play a role in the observed seepage of gas. However, the observation of thick carbonate crusts during manned submersible dives and their subsequent dating suggest that seepage off Svalbard has been ongoing for at least several hundred years and that decadal scale warming of the West Svalbard Current is at most of minor importance for the bulk of the observed seepage. Thus, the seeps off Svalbard do not necessarily represent the beginning of large-scale hydrate dissociation in the Arctic. Instead, it is likely that seasonal bottom water temperature fluctuations of 1-2°C cause periodic gas hydrate formation and dissociation, which focuses seepage at the observed gas flare depth. The results show that hydrate is highly sensitive to bottom water temperature changes and that bottom water warming will affect the stability of any large hydrate accumulations at the seabed on a short time scale.

  4. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  5. Structural stability of methane hydrate at high pressures

    USGS Publications Warehouse

    Shu, J.; Chen, X.; Chou, I.-Ming; Yang, W.; Hu, Jiawen; Hemley, R.J.; Mao, Ho-kwang

    2011-01-01

    The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII (Pn3m). The results highlight the role of guest (CH4)-host (H2O) interactions in the stabilization of the hydrate structures under pressure. ?? 2011, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. All rights reserved.

  6. New Simulator for Non-Equilibrium Modeling of Hydrate Reservoirs

    NASA Astrophysics Data System (ADS)

    Kvamme, B.; Qorbani Nashaqi, K.; Jemai, K.; Vafaei, M.

    2014-12-01

    Due to Gibbs phase rule and combination of first and second law of thermodynamics, hydrate in nature cannot be in equilibrium since they come from different parent phases. In this system hydrate formation and dissociation is affected by local variables such as pressure, temperature and composition with mass and energy transport restrictions. Available simulators have attempted to model hydrate phase transition as an equilibrium reaction. Although those which treated the processes of formation and dissociation as kinetics used model of Kim and Bishnoi based on laboratory PVT experiment, and consequently hard to accept up scaling to real reservoirs condition. Additionally, they merely check equilibrium in terms of pressure and temperature projections and disregard thermodynamic requirements for equilibrium especially along axes of concentrations in phases. Non-equilibrium analysis of hydrate involves putting aside all the phase transitions which are not possible and use kinetic evaluation to measure phase transitions progress in each grid block for each time step. This procedure is Similar to geochemical reservoir simulators logic. As a result RetrasoCodeBright has been chosen as hydrate reservoir simulator and our work involves extension of this code. RetrasoCodeBright (RCB) is able to handle competing processes of formation and dissociation of hydrates as pseudo reactions at each node and each time step according to the temperature, pressure and concentration. Hydrates can therefore be implemented into the structure as pseudo minerals, with appropriate kinetic models. In order to implement competing nature of phase transition kinetics of hydrate formation, we use classical nucleation theory based on Kvamme et al. as a simplified model inside RCB and use advanced theories to fit parameters for the model (PFT). Hydrate formation and dissociation can directly be observed through porosity changes in the specific areas of the porous media. In this work which is in

  7. Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

    NASA Astrophysics Data System (ADS)

    Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

    2016-04-01

    We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

  8. Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering.

    PubMed

    Yoshida, Koji; Baron, Alfred Q R; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

    2016-04-01

    We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure. PMID:27059578

  9. Kinetics of the barotropic ripple (P beta')/lamellar liquid crystal (L alpha) phase transition in fully hydrated dimyristoylphosphatidylcholine (DMPC) monitored by time-resolved x-ray diffraction.

    PubMed Central

    Caffrey, M; Hogan, J; Mencke, A

    1991-01-01

    We present here the first study of the use of a pressure-jump to induce the ripple (P beta')/lamellar liquid crystal (L alpha) phase transition in fully hydrated 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). The transition was monitored by using time-resolved x-ray diffraction (TRXRD). Applying a pressure-jump from atmospheric to 11.3 MPa (1640 psig, 111.6 atm) in 2.5 s induces the L alpha to P beta' phase transition which takes place in two stages. The lamellar repeat spacing initially increases from a value of 66.0 +/- 0.1 A (n = 4) to a maximum value of 70.3 +/- 0.8 A (n = 4) after 10 s and after a further 100-150 s decreases slightly to 68.5 +/- 0.3 A (n = 4). The reverse transition takes place following a pressure jump in 5.5 s from 11.3 MPa to atmospheric pressure. Again, the transition occurs in two stages with the repeat spacing steadily decreasing from an initial value of 68.5 +/- 0.3 A (n = 3) to a minimum value of 66.6 +/- 0.3 A (n = 3) after 50 s and then increasing by approximately 0.5 A over a period of 100 s. The transition temperature increases linearly with pressure up to 14.1 MPa in accordance with the Clapeyron relation, giving a dT/dP value of 0.285 degrees C/MPa (28.5 degrees C/kbar) and an associated volume change of 40 microliters/g. A dynamic compressibility of 0.13 +/- 0.01 A/MPa has been determined for the L alpha phase. This value is compared with the equilibrium compressibilities of bilayer and nonbilayer phases reported in the literature. The results suggest testable mechanisms for the pressure-induced transition involving changes in periodicity, phase hydration, chain order, and orientation. A more complete understanding of the transition mechanism will require improvement in detector spatial resolution and sensitivity, and data on the pressure sensitivity of phase hydration. PMID:1912281

  10. Simulation of subsea gas hydrate exploitation

    NASA Astrophysics Data System (ADS)

    Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

    2014-05-01

    The recovery of methane from gas hydrate layers that have been detected in several subsea sediments and permafrost regions around the world is a promising perspective to overcome future shortages in natural gas supply. Being aware that conventional natural gas resources are limited, research is going on to develop technologies for the production of natural gas from such new sources. Thus various research programs have started since the early 1990s in Japan, USA, Canada, India, and Germany to investigate hydrate deposits and develop required technologies. In recent years, intensive research has focussed on the capture and storage of CO2 from combustion processes to reduce climate impact. While different natural or man-made reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid CO2, the storage of CO2 as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in the form of hydrates. Regarding technological implementation many problems have to be overcome. Especially mixing, heat and mass transfer in the reservoir are limiting factors causing very long process times. Within the scope of the German research project »SUGAR« different technological approaches for the optimized exploitation of gas hydrate deposits are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical processes are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs. Simulations based on geological field data have been carried out. The studies focus on the potential of gas production from turbidites and their fitness for CO2 storage. The effects occurring during gas production and CO2 storage within

  11. Effects of sludge retention times on reactivity of effluent dissolved organic matter for trihalomethane formation in hybrid powdered activated carbon membrane bioreactors.

    PubMed

    Ma, Defang; Gao, Baoyu; Xia, Chufan; Wang, Yan; Yue, Qinyan; Li, Qian

    2014-08-01

    In this study, real municipal wastewater intended for reuse was treated by two identical hybrid PAC/MBRs (membrane bioreactors with powdered activated carbon addition), which were operated at sludge retention times (SRTs) of 30 and 180 days, respectively. In order to investigate the effects of SRT on trihalomethane (THM) formation in chlorinated PAC/MBR effluents, characteristics and THM formation reactivity of effluent dissolved organic matter (EfOM) at different SRTs were examined. PAC/MBR-180 had higher level of EfOM, which contained less simple aromatic proteins and exhibited lower specific UV absorbance. EfOM with molecular weight <5 kDa from PAC/MBR-30 (23%) was lower than PAC/MBR-180 (26%). About 50% of EfOM from PAC/MBR-30 was hydrophobic acids, which was higher than that from PAC/MBR-180 (about 36%). EfOM at SRT 180 days exhibited higher hydrophilicity. Prolonging SRT greatly reduced THM formation reactivity of EfOM, but increased the formation of bromine-containing species during chlorination of PAC/MBR effluents. PMID:24929809

  12. Gas hydrate cool storage system

    DOEpatents

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  13. Kinetics Characteristics of Nitrogen Hydrates Respond to Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Chen, Q.; Liu, C.; Ye, Y.; Gong, J.

    2012-12-01

    a function of time can be obtained by integrating the exothermic peaks. As a series of experiments were carried out using the same bulk phase, these curves represented a semi-quantitative result of hydrate crystal growth speed (see Figure 1). The slope of the energy curve reflected the growth speed at a certain time. The steeper the curve became, the faster the hydrates growth was. As could be expected, hydrate growth speed is extremely dependent of the sub-cooling.; Figure 1. Energy released of hydrates growth as a function of time

  14. High-pressure dynamics of hydrated protein in bioprotective trehalose environment

    SciTech Connect

    Diallo, S. O.; Zhang, Q.; O'Neill, H.; Mamontov, E.

    2014-10-30

    Here we present a pressure-dependence study of the dynamics of lysozyme protein powder immersed in deuterated , α-trehalose environment via quasielastic neutron scattering (QENS). The goal is to assess the baroprotective benefits of trehalose on biomolecules by comparing the findings with those of a trehalose-free reference study. While the mean-square displacement of the trehalose-free protein (hydrated to dD₂O ≃40 w%) as a whole, is reduced by increasing pressure, the actual observable relaxation dynamics in the picoseconds to nanoseconds time range remains largely unaffected by pressure up to the maximum investigated pressure of 2.78(2) Kbar. Our observation is independent of whether or not the protein is mixed with the deuterated sugar. This suggests that the hydrated protein s conformational states at atmospheric pressure remain unaltered by hydrostatic pressures, below 2.78 Kbar. We also found the QENS response to be totally recoverable after ambient pressure conditions are restored. Small-angle neutron diffraction measurements confirm that the protein-protein correlation remains undisturbed.We observe, however, a clear narrowing of the QENS response as the temperature is decreased from 290 to 230 K in both cases, which we parametrize using the Kohlrausch-Williams-Watts stretched exponential model. Finally, only the fraction of protons that are immobile on the accessible time window of the instrument, referred to as the elastic incoherent structure factor, is observably sensitive to pressure, increasing only marginally but systematically with increasing pressure.

  15. High pressure dynamics of hydrated protein in bio-protective trehalose environment

    DOE PAGESBeta

    Omar Diallo, Souleymane; Zhang, Qiu; O'Neill, Hugh Michael; Mamontov, Eugene

    2014-01-01

    We present a pressure-dependence study of the dynamics of lysozyme protein powder immersed in deuterated , -trehalose environment via quasielastic neutron scattering (QENS). The goal is to assess the baroprotective benefits of trehalose on biomolecules by comparing the findings with those of a trehalose-free reference study. While the mean-square displacement of the trehalose-free protein (hydrated to dD2O 40 w%) as a whole, is reduced by increasing pressure, the actual observable relaxation dynamics in the picoseconds to nanoseconds time range remains largely unaffected by pressure up to the maximum investigated pressure of 2.78(2) Kbar. Our observation is independent of whether ormore » not the protein is mixed with the deuterated sugar. This suggests that the hydrated protein s conformational states at atmospheric pressure remain unaltered by hydrostatic pressures, below 2.78 Kbar. We also found the QENS response to be totally recoverable after ambient pressure conditions are restored. Small-angle neutron diffraction measurements confirm that the protein-protein correlation remains undisturbed.We observe, however, a clear narrowing of the QENS response as the temperature is decreased from 290 to 230 K in both cases, which we parametrize using the Kohlrausch-Williams-Watts stretched exponential model. Only the fraction of protons that are immobile on the accessible time window of the instrument, referred to as the elastic incoherent structure factor, is observably sensitive to pressure, increasing only marginally but systematically with increasing pressure.« less

  16. High-pressure dynamics of hydrated protein in bioprotective trehalose environment

    NASA Astrophysics Data System (ADS)

    Diallo, S. O.; Zhang, Q.; O'Neill, H.; Mamontov, E.

    2014-10-01

    We present a pressure-dependence study of the dynamics of lysozyme protein powder immersed in deuterated α ,α -trehalose environment via quasielastic neutron scattering (QENS). The goal is to assess the baroprotective benefits of trehalose on biomolecules by comparing the findings with those of a trehalose-free reference study. While the mean-square displacement of the trehalose-free protein (hydrated to dD2O≃ 40 w%) as a whole, is reduced by increasing pressure, the actual observable relaxation dynamics in the picoseconds to nanoseconds time range remains largely unaffected by pressure—up to the maximum investigated pressure of 2.78(2) Kbar. Our observation is independent of whether or not the protein is mixed with the deuterated sugar. This suggests that the hydrated protein's conformational states at atmospheric pressure remain unaltered by hydrostatic pressures, below 2.78 Kbar. We also found the QENS response to be totally recoverable after ambient pressure conditions are restored. Small-angle neutron diffraction measurements confirm that the protein-protein correlation remains undisturbed. We observe, however, a clear narrowing of the QENS response as the temperature is decreased from 290 to 230 K in both cases, which we parametrize using the Kohlrausch-Williams-Watts stretched exponential model. Only the fraction of protons that are immobile on the accessible time window of the instrument, referred to as the elastic incoherent structure factor, is observably sensitive to pressure, increasing only marginally but systematically with increasing pressure.

  17. Geochemistry of a naturally occurring massive marine gas hydrate

    USGS Publications Warehouse

    Kvenvolden, K.A.; Claypool, G.E.; Threlkeld, C.N.; Dendy, Sloan E.

    1984-01-01

    During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4??C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ???0.2% ethane, and ???0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 permil(( 0 00), relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift. ?? 1984.

  18. Depressurization-induced gas production from Class 1 and Class 2hydrate deposits

    SciTech Connect

    Moridis, George J.; Kowalsky, Michael

    2006-05-12

    Class 1 hydrate deposits are characterized by a Hydrate-Bearing Layer (HBL) underlain by a two-phase zone involving mobile gas. Such deposits are further divided to Class 1W (involving water and hydrate in the HBL) and Class 1G (involving gas and hydrate in the HBL). In Class 2 deposits, a mobile water zone underlies the hydrate zone. Methane is the main hydrate-forming gas in natural accumulations. Using TOUGH-FX/HYDRATE to study the depressurization-induced gas production from such deposits, we determine that large volumes of gas could be readily produced at high rates for long times using conventional technology. Dissociation in Class 1W deposits proceeds in distinct stages, but is continuous in Class 1G deposits. Hydrates are shown to contribute significantly to the production rate (up to 65 percent and 75 percent in Class 1W and 1G, respectively) and to the cumulative volume of produced gas (up to 45 percent and 54 percent in Class 1W and 1G, respectively). Large volumes of hydrate-originating CH4 could be produced from Class 2 hydrates, but a relatively long lead time would be needed before gas production (which continuously increases over time) attains a substantial level. The permeability of the confining boundaries plays a significant role in gas production from Class 2 deposits. In general, long-term production is needed to realize the full potential of the very promising Class 1 and Class 2 hydrate deposits.

  19. Heat transfer and multiphase flow with hydrate formation in subsea pipelines

    NASA Astrophysics Data System (ADS)

    Odukoya, A.; Naterer, G. F.

    2015-07-01

    A new predictive model is developed to analyze hydrate formation with coupled heat and mass transfer in a pipe. The model tracks the particle velocity at each time step, while estimating the growth of the hydrate using the change in Biot number and dimensionless time. The numerical results are validated experimental results for R134a hydrates. The effects of change in heat transfer ratio, phase change number, superheating, and pipe diameter on hydrate formation are reported in this paper. The results indicate that higher heat transfer ratio between the internal and external fluids reduces the possibility of hydrates creating a blockage in the pipeline. The pipes with smaller diameters are also found to reduce the possibility of hydrate formation at a constant pipeline pressure. The results show that at temperatures below -10 °C, changing thermophysical properties have limited impact on the rate of hydrate formation in the pipe.

  20. Direct Observations of Three Dimensional Growth of Hydrates Hosted in Porous Media

    SciTech Connect

    Kerkar, P.; Jones, K; Kleinberg, R; Lindquist, W; Tomov, S; Feng, H; Mahajan, D

    2009-01-01

    The visualization of time-resolved three-dimensional growth of tetrahydrofuran hydrates with glass spheres of uniform size as porous media using synchrotron x-ray computed microtomography is presented. The images of hydrate patches, formed from excess tetrahydrofuran in aqueous solution, show random nucleation and growth concomitant with grain movement but independent of container-wall effect. Away from grain surfaces, hydrate surface curvature was convex showing that liquid, not hydrate, was the wetting phase, similar to ice growth in porous media. The extension of the observed behavior to methane hydrates could have implications in understanding their role in seafloor stability and climate change.

  1. Early hydration and setting of oil well cement

    SciTech Connect

    Zhang Jie; Weissinger, Emily A.; Peethamparan, Sulapha; Scherer, George W.

    2010-07-15

    A broad experimental study has been performed to characterize the early hydration and setting of cement pastes prepared with Class H oil well cement at water-to-cement ratios (w/c) from 0.25 to 0.40, cured at temperatures from 10 to 60 {sup o}C, and mixed with chemical additives. Chemical shrinkage during hydration was measured by a newly developed system, degree of hydration was determined by thermogravimetric analysis, and setting time was tested by Vicat and ultrasonic velocity measurements. A Boundary Nucleation and Growth model provides a good fit to the chemical shrinkage data. Temperature increase and accelerator additions expedite the rate of cement hydration by causing more rapid nucleation of hydration products, leading to earlier setting; conversely, retarder and viscosity modifying agents delay cement nucleation, causing later setting times. Lower w/c paste needs less hydration product to form a percolating solid network (i.e., to reach the initial setting point). However, for the systems evaluated, at a given w/c, the degree of hydration at setting is a constant, regardless of the effects of ambient temperature or the presence of additives.

  2. Preparation of metal diboride powders

    DOEpatents

    Brynestad, J.; Bamberger, C.E.

    Finely-divided titanium diboride or zirconium diboride powders are formed by reacting gaseous boron trichloride with a material selected from the group of consisting of titanium powder, zirconium powder, titanium dichloride powder, titanium trichloride powder, and gaseous titanium trichloride.

  3. Preparation of titanium diboride powder

    DOEpatents

    Brynestad, Jorulf; Bamberger, Carlos E.

    1985-01-01

    Finely-divided titanium diboride or zirconium diboride powders are formed by reacting gaseous boron trichloride with a material selected from the group consisting of titanium powder, zirconium powder, titanium dichloride powder, titanium trichloride powder, and gaseous titanium trichloride.

  4. Hydrated Minerals on Asteroids: The Astronomical Record

    NASA Technical Reports Server (NTRS)

    Rivkin, A. S.; Howell, E. S.; Vilas, F.; Lebofsky, L. A.

    2002-01-01

    Knowledge of the hydrated mineral inventory on the asteroids is important for deducing the origin of Earth's water, interpreting the meteorite record, and unraveling the processes occurring during the earliest times in solar system history. Reflectance spectroscopy shows absorption features in both the 0.6-0.8 and 2.5-3.5 micrometers regions, which are diagnostic of or associated with hydrated minerals. Observations in those regions show that hydrated minerals are common in the mid-asteroid belt, and can be found in unexpected spectral groupings, as well. Asteroid groups formerly associated with mineralogies assumed to have high temperature formation, such as M- and E-class asteroids, have been observed to have hydration features in their reflectance spectra. Some asteroids have apparently been heated to several hundred degrees Celsius, enough to destroy some fraction of their phyllosilicates. Others have rotational variation suggesting that heating was uneven. We summarize this work, and present the astronomical evidence for water- and hydroxyl-bearing minerals on asteroids.

  5. Hydrated Minerals on Asteroids: The Astronomical Record

    NASA Technical Reports Server (NTRS)

    Rivkin, A. S.; Howell, E. S.; Vilas, F.; Lebofsky, L. A.

    2003-01-01

    Knowledge of the hydrated mineral inventory on the asteroids is important for deducing the origin of Earth's water, interpreting the meteorite record, and unraveling the processes occurring during the earliest times in solar system history. Reflectance spectroscopy shows absorption features in both the 0.6-0.8 and 2.5-3.5-micron regions, which are diagnostic of or associated with hydrated minerals. Observations in those regions show that hydrated minerals are common in the mid-asteroid belt, and can be found in unexpected spectral groupings as well. Asteroid groups formerly associated with mineralogies assumed to have high-temperature formation, such as M- and E-class steroids, have been observed to have hydration features in their reflectance spectra. Some asteroids have apparently been heated to several hundred degrees Celsius, enough to destroy some fraction of their phyllosilicates. Others have rotational variation suggesting that heating was uneven. We summarize this work, and present the astronomical evidence for water- and Hydroxl-bearing minerals on asteroids.

  6. Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

    USGS Publications Warehouse

    Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

    2004-01-01

    To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

  7. Electronucleation for Rapid and Controlled Formation of Hydrates.

    PubMed

    Carpenter, Katherine; Bahadur, Vaibhav

    2016-07-01

    Nucleation of hydrates involves very long induction times (hours to days), which is a challenge for applications requiring rapid hydrate formation. This study introduces and analyzes the use of electric fields to accelerate and control hydrate nucleation. Experiments with tetrahydrofuran (THF) hydrates reveal that the induction time can be reduced by 100×, by applying an electrical potential across the precursor solution. The induction time rapidly decreases with increasing voltages and is on the order of a few minutes at 100 V. It is seen that voltage-induced current flow in the solution is responsible for electronucleation. Very low currents (microamperes) are sufficient for electronucleation. Nucleation promotion can be attributed to phenomena associated with bubble formation due to chemical reactions at the electrodes. Overall, this study lays the foundation for the control and promotion of nucleation by electric fields, and enables possibilities for instantaneous nucleation. PMID:27299519

  8. Computational investigation of dynamical transitions in Trp-cage miniprotein powders

    PubMed Central

    Kim, Sang Beom; Gupta, Devansh R.; Debenedetti, Pablo G.

    2016-01-01

    We investigate computationally the dynamical transitions in Trp-cage miniprotein powders, at three levels of hydration: 0.04, 0.26 and 0.4 g water/g protein. We identify two distinct temperatures where transitions in protein dynamics occur. Thermal motions are harmonic and independent of hydration level below Tlow ≈ 160 K, above which all powders exhibit harmonic behavior but with a different and enhanced temperature dependence. The second onset, which is often referred to as the protein dynamical transition, occurs at a higher temperature TD that decreases as the hydration level increases, and at the lowest hydration level investigated here (0.04 g/g) is absent in the temperature range we studied in this work (T ≤ 300 K). Protein motions become anharmonic at TD, and their amplitude increases with hydration level. Upon heating above TD, hydrophilic residues experience a pronounced enhancement in the amplitude of their characteristic motions in hydrated powders, whereas it is the hydrophobic residues that experience the more pronounced enhancement in the least hydrated system. The dynamical transition in Trp-cage is a collective phenomenon, with every residue experiencing a transition to anharmonic behavior at the same temperature. PMID:27151767

  9. Computational investigation of dynamical transitions in Trp-cage miniprotein powders

    NASA Astrophysics Data System (ADS)

    Kim, Sang Beom; Gupta, Devansh R.; Debenedetti, Pablo G.

    2016-05-01

    We investigate computationally the dynamical transitions in Trp-cage miniprotein powders, at three levels of hydration: 0.04, 0.26 and 0.4 g water/g protein. We identify two distinct temperatures where transitions in protein dynamics occur. Thermal motions are harmonic and independent of hydration level below Tlow ≈ 160 K, above which all powders exhibit harmonic behavior but with a different and enhanced temperature dependence. The second onset, which is often referred to as the protein dynamical transition, occurs at a higher temperature TD that decreases as the hydration level increases, and at the lowest hydration level investigated here (0.04 g/g) is absent in the temperature range we studied in this work (T ≤ 300 K). Protein motions become anharmonic at TD, and their amplitude increases with hydration level. Upon heating above TD, hydrophilic residues experience a pronounced enhancement in the amplitude of their characteristic motions in hydrated powders, whereas it is the hydrophobic residues that experience the more pronounced enhancement in the least hydrated system. The dynamical transition in Trp-cage is a collective phenomenon, with every residue experiencing a transition to anharmonic behavior at the same temperature.

  10. Computational investigation of dynamical transitions in Trp-cage miniprotein powders.

    PubMed

    Kim, Sang Beom; Gupta, Devansh R; Debenedetti, Pablo G

    2016-01-01

    We investigate computationally the dynamical transitions in Trp-cage miniprotein powders, at three levels of hydration: 0.04, 0.26 and 0.4 g water/g protein. We identify two distinct temperatures where transitions in protein dynamics occur. Thermal motions are harmonic and independent of hydration level below Tlow ≈ 160 K, above which all powders exhibit harmonic behavior but with a different and enhanced temperature dependence. The second onset, which is often referred to as the protein dynamical transition, occurs at a higher temperature TD that decreases as the hydration level increases, and at the lowest hydration level investigated here (0.04 g/g) is absent in the temperature range we studied in this work (T ≤ 300 K). Protein motions become anharmonic at TD, and their amplitude increases with hydration level. Upon heating above TD, hydrophilic residues experience a pronounced enhancement in the amplitude of their characteristic motions in hydrated powders, whereas it is the hydrophobic residues that experience the more pronounced enhancement in the least hydrated system. The dynamical transition in Trp-cage is a collective phenomenon, with every residue experiencing a transition to anharmonic behavior at the same temperature. PMID:27151767

  11. Handling, transport and dispersion of sorbent powder for in-furnace injection. Third year final report

    SciTech Connect

    Fan, Liang-Shih; Bavarian, F.; Lee, R.J.; Hsia, Chung-wei; Abou-Zeida, E.; Jiang, Peijun; Dastidar, A.G.; Mahuli, S.

    1993-09-01

    The purpose of this study is to explain, using fundamental theories of interparticle forces, the difference in transport and dispersion between various sorbents. This project is closely tied with 1.1 through the focus of maximum utilization of sorbent materials used in the LIMB process. Interparticle forces lead to agglomeration or removal to transport tube walls of the sorbent fine particles, reducing sulfur removal capabilities. In the first and second years, the pneumatic transport of sorbent powders was investigated for four typical sorbent materials, calcium carbonate, dolomite, dolomitic hydrate and hydrated lime. Results indicate that hydrated lime has the best dispersion and flowability. Studies in the third year involved investigating improving the performance of hydrated lime with additives. The addition of calcium liposulfonate to the water of hydration appears to improve both the dispersibility and reactivity of the resulting product hydrate. Increased reactivity is closely tied to available surface area for reaction, as expected. However, in applications where powder flowability becomes important, such as in the use of hydrate in flue-gas desulfurization, a balance between the flowability and surface area must be considered. If the powder has poor flowability, the added surface area may not be utilized. Powder dispersion and the high-temperature are used to determine the dispersibility of the modified and unmodified sorbents at room temperature and at typical furnace temperatures. Results verify that an increase in dispersibility is realized with the liposulfonate-modified hydrate. Phase 1 results show this increased dispersibility to be due to electrostatic repulsion between liposulfonate molecules on the surface of the dry powder.

  12. Calorimetric and X-ray studies of clathrate hydrates of tetraisoamylammonium polyacrylates.

    PubMed

    Terekhova, Irina S; Manakov, Andrey Yu; Soldatov, Dmitriy V; Suwinska, Kinga; Skiba, Sergey S; Stenin, Yuri G; Villevald, Galina V; Karpova, Tamara D; Yunoshev, Alexander S

    2009-04-30

    The structure of clathrate hydrates with tetraisoamylammonium polyacrylate salt incorporated as guest has been studied in this work. Also, quantitative studies on the stability changes of the clathrate hydrates with different degrees of cross-linking of the guest polymer (varied from 0 to 3%) have been conducted. A single crystal X-ray diffraction study of a crystal of the hydrate with linear (uncross-linked) tetraisoamylammonium polyacrylate as guest reveals a hexagonal structure (space group P6m2, a = 12.15 A, c =12.58 A at 100 K) with 39 host framework water molecules per one guest monomeric unit. Powder X-ray diffraction analyses confirm the identity of the above crystal structure of the hydrate with linear guest polymer and the crystal structure of the hydrates with cross-linked guest (hexagonal, a = 12.25 A, c =12.72 A at 276 K). In order to quantitatively determine the stability differences of the hydrates with the included guests having various degrees of cross-linking of the anionic chain, a series of differential scanning calorimetry measurements of the fusion enthalpy of the hydrate samples has been carried out. On the basis of the results obtained, a structural model describing the decrease in the stability of the clathrate hydrates with tetraisoamylammonium polyacrylate guest as a function of the degree of cross-linking of the guest polymer has been suggested. PMID:19344169

  13. Structural transformation and tuning behavior induced by the propylamine concentration in hydrogen clathrate hydrates.

    PubMed

    Park, Seongmin; Kang, Hyery; Shin, Kyuchul; Seo, Yutaek; Lee, Huen

    2015-01-21

    The structures and the guest-host distributions of iso-propylamine (i-PA) and n-propylamine (n-PA) hydrates with hydrogen as a secondary guest were identified by powder X-ray diffraction and Raman spectroscopic analysis. The structure of 11.1 mol% i-PA + H2 hydrate was identified to be hexagonal (space group P63/mmc) with a few unindexed diffraction peaks, while 5.6 mol% i-PA + H2 hydrate had a cubic structure (space group Fd3¯m). Similarly, the structure of 13.3 mol% n-PA + H2 hydrate was found to be monoclinic (space group P2(1)/n), while 5.6 mol% n-PA + H2 hydrate had a cubic structure (space group Fd3¯m). The 'tuning' phenomenon, multiple occupancy of hydrogen in the large cage at the pressure and temperature regions outside of pure hydrogen hydrate stability, was observed in the i-PA + H2 hydrate only when the amine concentration was lower than the stoichiometric value of structure II hydrate. The three-phase (H-L(w)-V) equilibria for alkylamine + H2 + water mixtures were also measured to investigate their thermodynamic stability. PMID:25475482

  14. A Study on the Chemical Compositions of the Yinqiaosan (Lonicerae and Forsythiae Powder) at Different Time of Later-decoction by Gas Chromatography Mass Spectrometry

    PubMed Central

    Shu, Yachun; Chen, Yajun; Qin, Kunming; Liu, Xiao; Cai, Baochang

    2016-01-01

    Background: Yinqiaosan (Lonicerae and Forsythiae Powder), as a famous prescription of Dr. Wu Jutong in Qing dynasty of China, has the effects of diaphoresis cooling, fire-purging, and detoxicaton. It is mainly used in the treatment of influenza, hand-foot-mouth disease, esophagitis, pneumonia, acute tonsillitis, mumps, and other viral infections. It is one of the widely used traditional Chinese medicine prescriptions with proven curative effects in clinical use. Objective: To research the material basis of Yinqiaosan decoction when decocting mint, herba schizonepetae in different length of later-decoction time, to find the influence on volatile components of Yinqiaosan decoction decocted later in different length of time, to lay the foundation to further clarify the after-decoction mechanism of Yinqiaosan, and the specification of Yinqiaosan decoction process. Materials and Methods: Gas chromatography mass spectrometry method is used to analyze the volatile components of Yinqiaosan decoction samples decocted for 0, 3, 5, 8, and 10 min. Results: Later-decocting mint and herba schizonepetae at different time when decocting Yinqiaosan had a significant influence on the volatile components of the solution. 54 different chemical components were identified: 25 were identified when later-decocting the sample for 3 min; 13 were identified when later-decocting the sample for 5 min; 11 were identified when later-decocting the sample for 8 min; 7 were identified when later-decocting the sample for 10 min; and 26 were identified when later-decocting the sample for 0 min. There were more volatile components in the sample after-decocted for 3 min. A total of 54 different chemical components were identified in different later-decocting solution samples. These components form the basis of the Yinqiaosan drug effect. Conclusions: The length of later-decoction time of mint and herba schizonepetae was confirmed to be 3 min when decocting Yinqiaosan. SUMMARY Later-decocting mint and

  15. The growth rate of gas hydrate from refrigerant R12

    SciTech Connect

    Kendoush, Abdullah Abbas; Jassim, Najim Abid; Joudi, Khalid A.

    2006-07-15

    Experimental and theoretical investigations were presented dealing with three phase direct-contact heat transfer by evaporation of refrigerant drops in an immiscible liquid. Refrigerant R12 was used as the dispersed phase, while water and brine were the immiscible continuous phase. A numerical solution is presented to predict the formation rate of gas hydrates in test column. The solution provided an acceptable agreement when compared with experimental results. The gas hydrate growth rate increased with time. It increased with increasing dispersed phase flow rate. The presence of surface-active sodium chloride in water had a strong inhibiting effect on the gas hydrate formation rate. (author)

  16. Quantifying Hydrate Formation in Gas-rich Environments Using the Method of Characteristics

    NASA Astrophysics Data System (ADS)

    You, K.; Flemings, P. B.; DiCarlo, D. A.

    2015-12-01

    Methane hydrates hold a vast amount of methane globally, and have huge energy potential. Methane hydrates in gas-rich environments are the most promising production targets. We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation in such environments (Figure 1). Our solution shows that hydrate saturation is constant with time and space in a homogeneous system. Hydrate saturation is controlled by the initial thermodynamic condition of the system, and changed by the gas fractional flow. Hydrate saturation increases with the initial distance from the hydrate phase boundary. Different gas fractional flows behind the hydrate solidification front lead to different gas saturations at the hydrate solidification front. The higher the gas saturation at the front, the less the volume available to be filled by hydrate, and hence the lower the hydrate saturation. The gas fractional flow depends on the relative permeability curves, and the forces that drive the flow. Viscous forces (the drive for flow induced from liquid pressure gradient) dominate the flow, and hydrate saturation is independent on the gas supply rates and the flow directions at high gas supply rates. Hydrate saturation can be estimated as one minus the ratio of the initial to equilibrium salinity. Gravity forces (the drive for flow induced from the gravity) dominate the flow, and hydrate saturation depends on the flow rates and the flow directions at low gas supply rates. Hydrate saturation is highest for upward flow, and lowest for downward flow. Hydrate saturation decreases with the flow rate for upward flow, and increases with the flow rate for downward flow. This analytical solution illuminates how hydrate is formed by gas (methane, CO2, ethane, propane) flowing into brine-saturated sediments at both the laboratory and geological scales (Figure 1). It provides an approach to generalize the understanding of hydrate solidification in gas

  17. Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

    SciTech Connect

    Rutkowski, Philip X; Michelini, Maria C.; Bray, Travis H.; Russo, Nino; Marcalo, Joaquim; Gibson, John K.

    2011-02-11

    Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX{sub 2}{sup +} and YbX(OH){sup +} (X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations - kinetics and extent of hydration - are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.

  18. Mechanical and electromagnetic properties of northern Gulf of Mexico sediments with and without THF hydrates

    USGS Publications Warehouse

    Lee, J.Y.; Santamarina, J.C.; Ruppel, C.

    2008-01-01

    Using an oedometer cell instrumented to measure the evolution of electromagnetic properties, small strain stiffness, and temperature, we conducted consolidation tests on sediments recovered during drilling in the northern Gulf of Mexico at the Atwater Valley and Keathley Canyon sites as part of the 2005 Chevron Joint Industry Project on Methane Hydrates. The tested specimens include both unremolded specimens (as recovered from the original core liner) and remolded sediments both without gas hydrate and with pore fluid exchanged to attain 100% synthetic (tetrahydrofuran) hydrate saturation at any stage of loading. Test results demonstrate the extent to which the electromagnetic and mechanical properties of hydrate-bearing marine sediments are governed by the vertical effective stress, stress history, porosity, hydrate saturation, fabric, ionic concentration of the pore fluid, and temperature. We also show how permittivity and electrical conductivity data can be used to estimate the evolution of hydrate volume fraction during formation. The gradual evolution of geophysical properties during hydrate formation probably reflects the slow increase in ionic concentration in the pore fluid due to ion exclusion in closed systems and the gradual decrease in average pore size in which the hydrate forms. During hydrate formation, the increase in S-wave velocity is delayed with respect to the decrease in permittivity, consistent with hydrate formation on mineral surfaces and subsequent crystal growth toward the pore space. No significant decementation/debonding occurred in 100% THF hydrate-saturated sediments during unloading, hence the probability of sampling hydrate-bearing sediments without disturbing the original sediment fabric is greatest for samples in which the gas hydrate is primarily responsible for maintaining the sediment fabric and for which the time between core retrieval and restoration of in situ effective stress in the laboratory is minimized. In evaluating the

  19. Some thermodynamical aspects of protein hydration water

    SciTech Connect

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene; Chen, Sow-Hsin

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  20. Growth Kinetics and Mechanics of Hydrate Films by Interfacial Rheology.

    PubMed

    Leopércio, Bruna C; de Souza Mendes, Paulo R; Fuller, Gerald G

    2016-05-01

    A new approach to study and understand the kinetics and mechanical properties of hydrates by interfacial rheology is presented. This is made possible using a "double wall ring" interfacial rheology cell that has been designed to provide the necessary temperature control. Cyclopentane and water are used to form hydrates, and this model system forms these structures at ambient pressures. Different temperature and water/hydrocarbon contact protocols are explored. Of particular interest is the importance of first contacting the hydrocarbon against ice crystals in order to initiate hydrate formation. Indeed, this is found to be the case, even though the hydrates may be created at temperatures above the melting point of ice. Once hydrates completely populate the hydrocarbon/water interface, strain sweeps of the interfacial elastic and viscous moduli are conducted to interrogate the mechanical response and fragility of the hydrate films. The dependence on temperature, Tf, by the kinetics of formation and the mechanical properties is reported, and the cyclopentane hydrate dissociation temperature was found to be between 6 and 7 °C. The formation time (measured from the moment when cyclopentane first contacts ice crystals) as well as the elastic modulus and the yield strain increase as Tf increases. PMID:27076092

  1. Effects of ensembles on methane hydrate nucleation kinetics.

    PubMed

    Zhang, Zhengcai; Liu, Chan-Juan; Walsh, Matthew R; Guo, Guang-Jun

    2016-06-21

    By performing molecular dynamics simulations to form a hydrate with a methane nano-bubble in liquid water at 250 K and 50 MPa, we report how different ensembles, such as the NPT, NVT, and NVE ensembles, affect the nucleation kinetics of the methane hydrate. The nucleation trajectories are monitored using the face-saturated incomplete cage analysis (FSICA) and the mutually coordinated guest (MCG) order parameter (OP). The nucleation rate and the critical nucleus are obtained using the mean first-passage time (MFPT) method based on the FS cages and the MCG-1 OPs, respectively. The fitting results of MFPT show that hydrate nucleation and growth are coupled together, consistent with the cage adsorption hypothesis which emphasizes that the cage adsorption of methane is a mechanism for both hydrate nucleation and growth. For the three different ensembles, the hydrate nucleation rate is quantitatively ordered as follows: NPT > NVT > NVE, while the sequence of hydrate crystallinity is exactly reversed. However, the largest size of the critical nucleus appears in the NVT ensemble, rather than in the NVE ensemble. These results are helpful for choosing a suitable ensemble when to study hydrate formation via computer simulations, and emphasize the importance of the order degree of the critical nucleus. PMID:27222203

  2. Dynamics of Hydration Water in Sugars and Peptides Solutions

    SciTech Connect

    Perticaroli, Stefania; Nakanishi, Masahiro; Pashkovski, Eugene; Sokolov, Alexei P

    2013-01-01

    We analyzed solute and solvent dynamics of sugars and peptides aqueous solutions using extended epolarized light scattering (EDLS) and broadband dielectric spectroscopies (BDS). Spectra measured with both techniques reveal the same mechanism of rotational diffusion of peptides molecules. In the case of sugars, this solute reorientational relaxation can be isolated by EDLS measurements, whereas its ontribution to the dielectric spectra is almost negligible. In the presented analysis, we characterize the hydration water in terms of hydration number and retardation ratio between relaxation times of hydration and bulk water. Both techniques provide similar estimates of . The retardation imposed on the hydration water by sugars is 3.3 1.3 and involves only water molecules hydrogen-bonded (HB) to solutes ( 3 water molecules per sugar OH-group). In contrast, polar peptides cause longer range erturbations beyond the first hydration shell, and between 2.8 and 8, increasing with the number of chemical groups engaged in HB formation. We demonstrate that chemical heterogeneity and specific HB interactions play a crucial role in hydration dynamics around polar solutes. The obtained results help to disentangle the role of excluded volume and enthalpic contributions in dynamics of hydration water at the interface with biological molecules.

  3. Physical modeling of the formation of clathrate hydrates of methane

    NASA Astrophysics Data System (ADS)

    Drobyshev, A.; Aldiyarov, A.; Kurnosov, V.; Katpaeva, K.; Korshikov, E.; Sokolov, D.; Shinbayeva, A.; Timchenko, A.

    2015-06-01

    Nowadays natural gas hydrates attract special attention as a possible source of fossil fuel. According to various estimates, the reserves of hydrocarbons in hydrates exceed considerably explored reserves of natural gas. Due to the clathrate structure the unit volume of the gas hydrate can contain up to 160-180 volumes of pure gas. In recent years interest to a problem of gas hydrates has considerably increased. Such changes are connected with the progress in searches of the alternative sources of hydrocarbonic raw materials in countries that do not possess the resources of energy carriers. Thus gas hydrates are nonconventional sources of the hydrocarbonic raw materials which can be developed in the near future. At the same time, mechanisms of methane clathrate hydrates formations have not reached an advanced level, their thermophysical and mechanical properties have not been investigated profoundly. Thereby our experimental modeling of the processes of formation of methane clathrate hydrates in water cryomatrix prepared by co-condensation from the gas phase onto a cooled substrate was carried out over the range of condensation temperatures 12-60 K and pressures 10-4-10-6 Torr. In our experiments the concentration of methane in water varied in the range of 5%-90%. The thickness deposited films was 30-60 μm. The vibrational spectra of two-component thin films of CH4 + H2O condensates were measured and analyzed.

  4. The connection between natural gas hydrate and bottom-simulating reflectors

    NASA Astrophysics Data System (ADS)

    Majumdar, Urmi; Cook, Ann E.; Shedd, William; Frye, Matthew

    2016-07-01

    Bottom-simulating reflectors (BSRs) on marine seismic data are commonly used to identify the presence of natural gas hydrate in marine sediments, although the exact relationship between gas hydrate and BSRs is undefined. To clarify this relationship we compile a data set of probable gas hydrate occurrence as appraised from well logs of 788 industry wells in the northern Gulf of Mexico. We combine the well log data set with a data set of BSR distribution in the same area identified from 3-D seismic data. We find that a BSR increases the chances of finding gas hydrate by 2.6 times as opposed to drilling outside a BSR and that the wells within a BSR also contain thicker and higher resistivity hydrate accumulations. Even so, over half of the wells drilled through BSRs have no detectable gas hydrate accumulations and gas hydrate occurrences and BSRs do not coincide in most cases.

  5. Gas Hydrate Petroleum System Analysis

    NASA Astrophysics Data System (ADS)

    Collett, T. S.

    2012-12-01

    In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is

  6. Promotion of Methane Hydrate Dissociation by Underwater Ultrasonic Wave

    NASA Astrophysics Data System (ADS)

    Miura, Hikaru; Takata, Makoto; Tajima, Daisuke; Tsuyuki, Kenichirou

    2006-05-01

    The methane hydrate that exists in the abyssal floor is receiving attention as a nonconventional type of natural gas resource. An efficient dissociation technology is necessary and indispensable to achieve a steady supply of methane from methane hydrate because it does not easily dissociate in a stable environment of high pressure and low temperature. We consider that underwater ultrasonic wave irradiation may be a method of promoting the dissociation of methane hydrate on the basis of the facilitator effect. We carried out a preliminary examination using dry ice at various pressures, water temperatures, and input electric power. Methane hydrate was similarly examined. As a result, it was clarified that the dissociation time was shorted by the ultrasonic wave, and the wave was effective when the water temperature was low at the time of dissociation.

  7. Detection and Appraisal of Gas Hydrates: Indian Scenario

    NASA Astrophysics Data System (ADS)

    Sain, K.

    2009-04-01

    Gas hydrates, found in shallow sediments of permafrost and outer continental margins, are crystalline form of methane and water. The carbon within global gas hydrates is estimated two times the carbon contained in world-wide fossil fuels. It is also predicted that 15% recovery of gas hydrates can meet the global energy requirement for the next 200 years. Several parameters like bathymetry, seafloor temperature, sediment thickness, rate of sedimentation and total organic carbon content indicate very good prospect of gas hydrates in the vast offshore regions of India. Methane stored in the form of gas hydrates within the Indian exclusive economic zone is estimated to be few hundred times the country's conventional gas reserve. India produces less than one-third of her oil requirement and gas hydrates provide great hopes as a viable source of energy in the 21st century. Thus identification and quantitative assessment of gas hydrates are very important. By scrutiny and reanalysis of available surface seismic data, signatures of gas hydrates have been found out in the Kerala-Konkan and Saurashtra basins in the western margin, and Krishna-Godavari, Mahanadi and Andaman regions in the eastern margin of India by mapping the bottom simulating reflector or BSR based on its characteristic features. In fact, the coring and drilling in 2006 by the Indian National Gas Hydrate Program have established the ground truth in the eastern margin. It has become all the more important now to identify further prospective regions with or without BSR; demarcate the lateral/areal extent of gas hydrate-bearing sediments and evaluate their resource potential in both margins of India. We have developed various approaches based on seismic traveltime tomography; waveform inversion; amplitude versus offset (AVO) modeling; AVO attributes; seismic attributes and rock physics modeling for the detection, delineation and quantification of gas-hydrates. The blanking, reflection strength, instantaneous

  8. Pectin as an Extraordinary Natural Kinetic Hydrate Inhibitor

    NASA Astrophysics Data System (ADS)

    Xu, Shurui; Fan, Shuanshi; Fang, Songtian; Lang, Xuemei; Wang, Yanhong; Chen, Jun

    2016-03-01

    Pectin as a novel natural kinetic hydrate inhibitor, expected to be eco-friendly and sufficiently biodegradable, was studied in this paper. The novel crystal growth inhibition (CGI) and standard induction time methods were used to evaluate its effect as hydrate inhibitor. It could successfully inhibit methane hydrate formation at subcooling temperature up to 12.5 °C and dramatically slowed the hydrate crystal growth. The dosage of pectin decreased by 66% and effective time extended 10 times than typical kinetic inhibitor. Besides, its maximum growth rate was no more than 2.0%/h, which was far less than 5.5%/h of growth rate for PVCap at the same dosage. The most prominent feature was that it totally inhibited methane hydrate crystal rapid growth when hydrate crystalline occurred. Moreover, in terms of typical natural inhibitors, the inhibition activity of pectin increased 10.0-fold in induction time and 2.5-fold in subcooling temperature. The extraordinary inhibition activity is closely related to its hydrogen bonding interaction with water molecules and the hydrophilic structure. Finally, the biodegradability and economical efficiency of pectin were also taken into consideration. The results showed the biodegradability improved 75.0% and the cost reduced by more than 73.3% compared to typical commercial kinetic inhibitors.

  9. Pectin as an Extraordinary Natural Kinetic Hydrate Inhibitor.

    PubMed

    Xu, Shurui; Fan, Shuanshi; Fang, Songtian; Lang, Xuemei; Wang, Yanhong; Chen, Jun

    2016-01-01

    Pectin as a novel natural kinetic hydrate inhibitor, expected to be eco-friendly and sufficiently biodegradable, was studied in this paper. The novel crystal growth inhibition (CGI) and standard induction time methods were used to evaluate its effect as hydrate inhibitor. It could successfully inhibit methane hydrate formation at subcooling temperature up to 12.5 °C and dramatically slowed the hydrate crystal growth. The dosage of pectin decreased by 66% and effective time extended 10 times than typical kinetic inhibitor. Besides, its maximum growth rate was no more than 2.0%/h, which was far less than 5.5%/h of growth rate for PVCap at the same dosage. The most prominent feature was that it totally inhibited methane hydrate crystal rapid growth when hydrate crystalline occurred. Moreover, in terms of typical natural inhibitors, the inhibition activity of pectin increased 10.0-fold in induction time and 2.5-fold in subcooling temperature. The extraordinary inhibition activity is closely related to its hydrogen bonding interaction with water molecules and the hydrophilic structure. Finally, the biodegradability and economical efficiency of pectin were also taken into consideration. The results showed the biodegradability improved 75.0% and the cost reduced by more than 73.3% compared to typical commercial kinetic inhibitors. PMID:26996773

  10. Pectin as an Extraordinary Natural Kinetic Hydrate Inhibitor

    PubMed Central

    Xu, Shurui; Fan, Shuanshi; Fang, Songtian; Lang, Xuemei; Wang, Yanhong; Chen, Jun

    2016-01-01

    Pectin as a novel natural kinetic hydrate inhibitor, expected to be eco-friendly and sufficiently biodegradable, was studied in this paper. The novel crystal growth inhibition (CGI) and standard induction time methods were used to evaluate its effect as hydrate inhibitor. It could successfully inhibit methane hydrate formation at subcooling temperature up to 12.5 °C and dramatically slowed the hydrate crystal growth. The dosage of pectin decreased by 66% and effective time extended 10 times than typical kinetic inhibitor. Besides, its maximum growth rate was no more than 2.0%/h, which was far less than 5.5%/h of growth rate for PVCap at the same dosage. The most prominent feature was that it totally inhibited methane hydrate crystal rapid growth when hydrate crystalline occurred. Moreover, in terms of typical natural inhibitors, the inhibition activity of pectin increased 10.0-fold in induction time and 2.5-fold in subcooling temperature. The extraordinary inhibition activity is closely related to its hydrogen bonding interaction with water molecules and the hydrophilic structure. Finally, the biodegradability and economical efficiency of pectin were also taken into consideration. The results showed the biodegradability improved 75.0% and the cost reduced by more than 73.3% compared to typical commercial kinetic inhibitors. PMID:26996773

  11. Method of making tungsten powder compacts

    SciTech Connect

    Peralta, R.E.

    1991-06-25

    This patent describes a process for forming a compact. It comprises essentially of pure tungsten metal powder by the steps of contacting a tungsten metal powder with and aqueous acid mixture at a sufficient concentration and for a sufficient period of time of etch the surface of the powder, the acid comprises a mixture of hydrofluoric acid and hydrochloric acid, and isostaticly pressuring the powder at an ambient temperature at a pressure of from about 18,000 to about 20,000 psi. for a sufficient period of time to form a compact.

  12. LARC powder prepreg system

    NASA Technical Reports Server (NTRS)

    Baucom, Robert M.; Marchello, Joseph M.

    1990-01-01

    Thermoplastic prepregs of LARC-TPI have been produced in a fluidized bed unit on spread continuous fiber tows. The powders are melted on the fibers by radiant heating to adhere the polymer to the fiber. This process produces tow prepreg uniformly without imposing severe stress on the fibers or requiring long high temperature residence times for the polymer. Unit design theory and operating correlations have been developed to provide the basis for scale up to commercial operation. Special features of the operation are the pneumatic tow spreader, fluidized bed and resin feed systems.

  13. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    PubMed Central

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  14. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

    PubMed

    Pustovgar, Elizaveta; Sangodkar, Rahul P; Andreev, Andrey S; Palacios, Marta; Chmelka, Bradley F; Flatt, Robert J; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of (29)Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  15. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    NASA Astrophysics Data System (ADS)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; D'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

  16. Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

    USGS Publications Warehouse

    Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

    2010-01-01

    Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

  17. The nurse's role in patient nutrition and hydration.

    PubMed

    Evans, Liz; Best, Carolyn

    Abstract Evans L, Best C (2015) Meeting patients' nutrition and hydration needs. The Nursing and Midwifery Council's new code was introduced in March 2015. For the first time, nutrition and hydration are mentioned specifically within the code. This article explores why this has become necessary and how nursing responsibility for the nutritional care of the patient has changed over the past 150 years. It also looks in more depth at how the nutritional care can meet the standards of the code. PMID:26477230

  18. Dynamics and hydration explain failed functional transformation in dehalogenase design.

    PubMed

    Sykora, Jan; Brezovsky, Jan; Koudelakova, Tana; Lahoda, Maryna; Fortova, Andrea; Chernovets, Tatsiana; Chaloupkova, Radka; Stepankova, Veronika; Prokop, Zbynek; Smatanova, Ivana Kuta; Hof, Martin; Damborsky, Jiri

    2014-06-01

    We emphasize the importance of dynamics and hydration for enzymatic catalysis and protein design by transplanting the active site from a haloalkane dehalogenase with high enantioselectivity to nonselective dehalogenase. Protein crystallography confirms that the active site geometry of the redesigned dehalogenase matches that of the target, but its enantioselectivity remains low. Time-dependent fluorescence shifts and computer simulations revealed that dynamics and hydration at the tunnel mouth differ substantially between the redesigned and target dehalogenase. PMID:24727901

  19. Micromechanical measurements of the effect of surfactants on cyclopentane hydrate shell properties.

    PubMed

    Brown, Erika P; Koh, Carolyn A

    2016-01-01

    Investigating the effect of surfactants on clathrate hydrate growth and morphology, especially particle shell strength and cohesion force, is critical to advancing new strategies to mitigate hydrate plug formation. In this study, dodecylbenzenesulfonic acid and polysorbate 80 surfactants were included during the growth of cyclopentane hydrates at several concentrations above and below the critical micelle concentration. A novel micromechanical method was applied to determine the force required to puncture the hydrate shell using a glass cantilever (with and without surfactants), with annealing times ranging from immediately after the hydrate nucleated to 90 minutes after formation. It was shown that the puncture force was decreased by the addition of both surfactants up to a maximum of 79%. Over the entire range of annealing times (0-90 minutes), the thickness of the hydrate shell was also measured. However, there was no clear change in shell thickness with the addition of surfactants. The growth rate of the hydrate shell was found to vary less than 15% with the addition of surfactants. The cohesive force between two hydrate particles was measured for each surfactant and found to be reduced by 28% to 78%. Interfacial tension measurements were also performed. Based on these results, microscopic changes to the hydrate shell morphology (due to the presence of surfactants) were proposed to cause the decrease in the force required to break the hydrate shell, since no macroscopic morphology changes were observed. Understanding the hydrate shell strength can be critical to reducing the capillary bridge interaction between hydrate particles or controlling the release of unconverted water from the interior of the hydrate particle, which can cause rapid hydrate conversion. PMID:26618773

  20. Kinetics of bread crumb hydration as related to porous microstructure.

    PubMed

    Mathieu, Vincent; Monnet, Anne-Flore; Jourdren, Solenne; Panouillé, Maud; Chappard, Christine; Souchon, Isabelle

    2016-08-10

    During oral processing and throughout the digestion process, hydration mechanisms have a key influence on the functional properties of food. This is the case with bread, for which hydration may affect the kinetics of starch hydrolysis as well as taste, aroma and texture perceptions. In this context, the aim of the present study is to understand how crumb porous micro-architecture impacts hydration kinetics. Four types of French baguettes were considered, varying in structure and/or compositions. An experimental set-up was developed for the real-time measurement of water uptake in crumb samples. Mathematical models were then fitted to extract quantitative parameters of use for the description and the understanding of experimental observations. Finally, bread crumb samples were analyzed before and after hydration through X-ray micro-computed tomography for the assessment of crumb micro-architectural properties. Distinct hydration behaviors were observed for the four types of bread. Higher hydration rates and capacities were reported for industrial baguettes (highest porosity) compared to denser semi-industrial, whole wheat and traditional baguettes. However, crumb porosity alone is not sufficient to predict hydration behavior. This study made it possible to point out the importance of capillary action in crumb hydration mechanisms, with a strong role of cells with diameters of 2 mm and below. The high density of these small cells generates high interconnection probabilities that may have an impact both on crumb hydration duration and capacity. As a consequence, accounting for microstructural features resulting from bread formulation may provide useful leverages for the control of functional properties. PMID:27466974

  1. Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

    NASA Astrophysics Data System (ADS)

    White, M. D.

    2011-12-01

    Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and

  2. Development of Multiplex Real-time PCR with Internal Amplification Control for Simultaneous Detection of Salmonella and Cronobacter sakazakii in Powdered Infant Formula.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Contamination of powdered infant formula (PIF) by the bacteria Cronobacter sakazakii and Salmonella enterica was deemed a matter of great concern by the World Health Organization and the Food and Agriculture Organization of the United Nations in 2004. Therefore, we developed a rapid and sensitive m...

  3. A novel microwave sensor for real-time online monitoring of roll compacts of pharmaceutical powders online--a comparative case study with NIR.

    PubMed

    Gupta, Anshu; Austin, John; Davis, Sierra; Harris, Michael; Reklaitis, Gintaras

    2015-05-01

    Control of particulate processes is hard to achieve because of the ease with which powders tend to segregate. Thus, proper sensing methods must be employed to ensure content uniformity during operation. The role of sensing schemes becomes even more critical while operating the process continuously as measurements are essential for implementation of feedback control (Austin et al. 2013. J Pharm Sci 102(6):1895-1904; Austin et al. 2014. Anal Chim Acta 819:82-93). A microwave sensor was developed and shown to be effective in online measurement of active pharmaceutical ingredient (API) concentration in a powder blend. During powder transport and hopper storage before processing, powder blends may segregate and cause quality deviations in the subsequent tableting operation. Therefore, it is critical to know the API concentration in the ribbons as the content uniformity is fixed once the ribbon is processed. In this study, a novel microwave sensor was developed that could provide measurement of a roller compacted ribbon's API concentration online, along with its density and moisture content. The results indicate that this microwave sensor is capable of increased accuracy compared with a commercially available near-IR probe for the determination of content uniformity and density in roller compacted ribbons online. PMID:25754185

  4. Hydration mechanisms of two polymorphs of synthetic ye'elimite

    SciTech Connect

    Cuesta, A.; Álvarez-Pinazo, G.; Peral, I.; Aranda, M.A.G.; De la Torre, A.G.

    2014-09-15

    Ye'elimite is the main phase in calcium sulfoaluminate cements and also a key phase in sulfobelite cements. However, its hydration mechanism is not well understood. Here we reported new data on the hydration behavior of ye'elimite using synchrotron and laboratory powder diffraction coupled to the Rietveld methodology. Both internal and external standard methodologies have been used to determine the overall amorphous contents. We have addressed the standard variables: water-to-ye'elimite ratio and additional sulfate sources of different solubilities. Moreover, we report a deep study of the role of the polymorphism of pure ye'elimites. The hydration behavior of orthorhombic stoichiometric and pseudo-cubic solid-solution ye'elimites is discussed. In the absence of additional sulfate sources, stoichiometric-ye'elimite reacts slower than solid-solution-ye'elimite, and AFm-type phases are the main hydrated crystalline phases, as expected. Moreover, solid-solution-ye'elimite produces higher amounts of ettringite than stoichiometric-ye'elimite. However, in the presence of additional sulfates, stoichiometric-ye'elimite reacts faster than solid-solution-ye'elimite.

  5. Water, Hydration and Health

    PubMed Central

    Popkin, Barry M.; D’Anci, Kristen E.; Rosenberg, Irwin H.

    2010-01-01

    This review attempts to provide some sense of our current knowledge of water including overall patterns of intake and some factors linked with intake, the complex mechanisms behind water homeostasis, the effects of variation in water intake on health and energy intake, weight, and human performance and functioning. Water represents a critical nutrient whose absence will be lethal within days. Water’s importance for prevention of nutrition-related noncommunicable diseases has emerged more recently because of the shift toward large proportions of fluids coming from caloric beverages. Nevertheless, there are major gaps in knowledge related to measurement of total fluid intake, hydration status at the population level, and few longer-term systematic interventions and no published random-controlled longer-term trials. We suggest some ways to examine water requirements as a means to encouraging more dialogue on this important topic. PMID:20646222

  6. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  7. Study on the hydration and microstructure of Portland cement containing diethanol-isopropanolamine

    SciTech Connect

    Ma, Suhua Li, Weifeng; Zhang, Shenbiao; Hu, Yueyang; Shen, Xiaodong

    2015-01-15

    Diethanol-isopropanolamine (DEIPA) is a tertiary alkanolamine used in the formulation of cement grinding-aid additives and concrete early-strength agents. In this research, isothermal calorimetry was used to study the hydration kinetics of Portland cement with DEIPA. A combination of X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC)–thermogravimetric (TG) analysis and micro-Raman spectroscopy was used to investigate the phase development in the process of hydration. Mercury intrusion porosimetry was used to study the pore size distribution and porosity. The results indicate that DEIPA promotes the formation of ettringite (AFt) and enhances the second hydration rate of the aluminate and ferrite phases, the transformation of AFt into monosulfoaluminate (AFm) and the formation of microcrystalline portlandite (CH) at early stages. At later stages, DEIPA accelerates the hydration of alite and reduces the pore size and porosity.

  8. A new hydrate form of diflunisal precipitated from a microemulsion system.

    PubMed

    Sung, Hsuan-Lei; Fan, Yueh-Lin; Yeh, Kimberly; Chen, Yen-Fu; Chen, Li-Jen

    2013-09-01

    Three microemulsion systems were applied as solvents for polymorph screening of seven active pharmaceutical ingredients (APIs): carbamazepine, piroxicam, sulfaguanidine, nitrofurantoin, theophylline, quercetin, and diflunisal. All the recrystallized compounds were examined by using powder X-ray diffractometry, differential scanning calorimetry, elemental analysis, Karl Fischer titration and dissolution rate. A new crystal form of diflunisal hydrate was discovered by the cooling method of recrystallization in a water-in-oil microemulsion system, composed of water, alkane and dioctyl sodium sulfosuccinate. The new hydrate form of diflunisal was characterized and confirmed to be a stoichiometry of diflunisal:water of 1:1. The other two microemulsion systems were able to convert the anhydrous diflunisal Form I to Form III. The dissolution rate of diflunisal hydrate is unexpectedly much higher than that of anhydrous ones (Forms I and III). All the other six APIs (carbamazepine, piroxicam, sulfaguanidine, nitrofurantoin, theophylline and quercetin) recrystallized from the microemulsion systems were all converted into hydrate form. PMID:23624616

  9. Face powder poisoning

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/002700.htm Face powder poisoning To use the sharing features on this page, please enable JavaScript. Face powder poisoning occurs when someone swallows or breathes ...

  10. Composite powder particles

    NASA Technical Reports Server (NTRS)

    Parker, Donald S. (Inventor); MacDowell, Louis G. (Inventor)

    2009-01-01

    A liquid coating composition including a coating vehicle and composite powder particles disposed within the coating vehicle. Each composite powder particle may include a magnesium component, a zinc component, and an indium component.

  11. Precision powder feeder

    DOEpatents

    Schlienger, M. Eric; Schmale, David T.; Oliver, Michael S.

    2001-07-10

    A new class of precision powder feeders is disclosed. These feeders provide a precision flow of a wide range of powdered materials, while remaining robust against jamming or damage. These feeders can be precisely controlled by feedback mechanisms.

  12. Aluminum powder metallurgy processing

    NASA Astrophysics Data System (ADS)

    Flumerfelt, Joel Fredrick

    In recent years, the aluminum powder industry has expanded into non-aerospace applications. However, the alumina and aluminum hydroxide in the surface oxide film on aluminum powder require high cost powder processing routes. A driving force for this research is to broaden the knowledge base about aluminum powder metallurgy to provide ideas for fabricating low cost aluminum powder components. The objective of this dissertation is to explore the hypothesis that there is a strong linkage between gas atomization processing conditions, as-atomized aluminum powder characteristics, and the consolidation methodology required to make components from aluminum powder. The hypothesis was tested with pure aluminum powders produced by commercial air atomization commercial inert gas atomization and gas atomization reaction synthesis (GARS). The commercial atomization methods are bench marks of current aluminum powder technology. The GARS process is a laboratory scale inert gas atomization facility. A benefit of using pure aluminum powders is an unambiguous interpretation of the results without considering the effects of alloy elements. A comparison of the GARS aluminum powders with the commercial aluminum powders showed the former to exhibit superior powder characteristics. The powders were compared in terms of size and shape, bulk chemistry, surface oxide chemistry and structure, and oxide film thickness. Minimum explosive concentration measurements assessed the dependence of explosibility hazard on surface area, oxide film thickness, and gas atomization processing conditions. The GARS aluminum powders were exposed to different relative humidity levels, demonstrating the effect of atmospheric conditions on post-atomization oxidation of aluminum powder. An Al-Ti-Y GARS alloy exposed in ambient air at different temperatures revealed the effect of reactive alloy elements on post-atomization powder oxidation. The pure aluminum powders were consolidated by two different routes, a

  13. Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

    NASA Technical Reports Server (NTRS)

    Loeffler, Mark J.; Hudson, Reggie L.

    2012-01-01

    In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

  14. Micromechanical adhesion force measurements between tetrahydrofuran hydrate particles.

    PubMed

    Taylor, Craig J; Dieker, Laura E; Miller, Kelly T; Koh, Carolyn A; Sloan, E Dendy

    2007-02-15

    Adhesion forces between tetrahydrofuran (THF) hydrate particles in n-decane were measured using an improved micromechanical technique. The experiments were performed at atmospheric pressure over the temperature range 261-275 K. The observed forces and trends were explained by a capillary bridge between the particles. The adhesion force of hydrates was directly proportional to the contact force and contact time. A scoping study examined the effects of temperature, anti-agglomerants, and interfacial energy on the particle adhesion forces. The adhesion force of hydrates was found to be directly proportional to interfacial energy of the surrounding liquid, and to increase with temperature. Both sorbitan monolaurate (Span20) and poly-N-vinyl caprolactam (PVCap) decreased the adhesion force between the hydrate particles. PMID:17126359

  15. Structural Transformations of sVI tert-Butylamine Hydrates to sII Binary Hydrates with Methane

    NASA Astrophysics Data System (ADS)

    Prasad, Pinnelli S. R.; Sugahara, Takeshi; Sloan, E. Dendy; Sum, Amadeu K.; Koh, Carolyn A.

    2009-09-01

    Binary clathrate hydrates with methane (CH4, 4.36 Å) and tert-butylamine (t-BuNH2, 6.72 Å) as guest molecules were synthesized at different molar concentrations of t-BuNH2 (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH2 hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to ˜6.86 wt % for 5.56 mol % > t-BuNH2 > 1.0 mol %.

  16. Aluminum powder metallurgy processing

    SciTech Connect

    Flumerfelt, J.F.

    1999-02-12

    The objective of this dissertation is to explore the hypothesis that there is a strong linkage between gas atomization processing conditions, as-atomized aluminum powder characteristics, and the consolidation methodology required to make components from aluminum powder. The hypothesis was tested with pure aluminum powders produced by commercial air atomization, commercial inert gas atomization, and gas atomization reaction synthesis (GARS). A comparison of the GARS aluminum powders with the commercial aluminum powders showed the former to exhibit superior powder characteristics. The powders were compared in terms of size and shape, bulk chemistry, surface oxide chemistry and structure, and oxide film thickness. Minimum explosive concentration measurements assessed the dependence of explosibility hazard on surface area, oxide film thickness, and gas atomization processing conditions. The GARS aluminum powders were exposed to different relative humidity levels, demonstrating the effect of atmospheric conditions on post-atomization processing conditions. The GARS aluminum powders were exposed to different relative humidity levels, demonstrating the effect of atmospheric conditions on post-atomization oxidation of aluminum powder. An Al-Ti-Y GARS alloy exposed in ambient air at different temperatures revealed the effect of reactive alloy elements on post-atomization powder oxidation. The pure aluminum powders were consolidated by two different routes, a conventional consolidation process for fabricating aerospace components with aluminum powder and a proposed alternative. The consolidation procedures were compared by evaluating the consolidated microstructures and the corresponding mechanical properties. A low temperature solid state sintering experiment demonstrated that tap densified GARS aluminum powders can form sintering necks between contacting powder particles, unlike the total resistance to sintering of commercial air atomization aluminum powder.

  17. Salt effects on the picosecond dynamics of lysozyme hydration water investigated by terahertz time-domain spectroscopy and an insight into the Hofmeister series for protein stability and solubility.

    PubMed

    Aoki, Katsuyoshi; Shiraki, Kentaro; Hattori, Toshiaki

    2016-06-01

    The addition of salts into protein aqueous solutions causes changes in protein solubility and stability, whose ability is known to be ordered in the Hofmeister series. We investigated the effects of Hofmeister salts on the picosecond dynamics of water around a lysozyme molecule using terahertz time-domain spectroscopy. The change in the absorption coefficient for 200 mg mL(-1) lysozyme aqueous solution by the addition of salts was found to depend on the salts used, whereas that for pure water was almost independent of salts. From the difference in the salt concentration dependence for various salts, it has been found that chaotropic anions make the dynamics of water around the lysozyme molecule slower, whereas kosmotropic anions make the dynamics faster. The ability of an anion to slow down the water dynamics was found to have the following order: SCN(-) > Cl(-) > H2PO4(-) > NO3(-) ≈ SO4(2-). This result indicates that the effects of anions on the dynamics of water around the lysozyme molecule are the opposite of those for bulk water. This finding agrees with a prediction from a molecular model proposed by Collins [K. D. Collins, Methods, 2004, 34, 300]. The results presented here are compared with the results from preferential interaction studies and the results from sum frequency generation spectroscopy. These discussions have led to the conclusion that the picosecond dynamics of protein hydration water strongly contributes to protein stability, whereas electrostatic interactions between protein molecules contribute to protein solubility. PMID:27193313

  18. Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

    NASA Astrophysics Data System (ADS)

    Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

    2012-12-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the

  19. 75 FR 9886 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-04

    ... Hydrate Advisory Committee AGENCY: Department of Energy, Office of Fossil Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  20. Online measured hydration heat for 32 meter span concrete box bridge girders during construction process

    NASA Astrophysics Data System (ADS)

    Hua, Yuan; Zhou, Taiquan

    2008-11-01

    The concrete stress induced by temperature change is regarded as one of the main causes of concrete box girder cracking. To understand the hydration heat distribution on the box girder transverse section, the concrete hydration heat temperature effect experiments were done according to the box girder construction condition, providing useful reference for box girder design and construction practice. The measured locations for concrete hydration heat were chosen as the middle span section and tip sections of box bridge girder. The temperature sensors were embedded in the concrete box girder at the top tray, bottom tray and web of the box girder during concrete pour construction. Then the time-history record for concrete hydration heat was recorded. According to the measured results for temperature, the time-history curve for concrete hydration heat process could be drawn. According to the 32 meter span concrete box girder hydration heat analysis result of Wuhan-Guangzhou railway express line, the common law of hydration heat during early concrete hydration heat process was obtained, including the basic laws of the concrete hydration temperature rise and heat drop, the temperature gradient of concrete and the relations between pumping temperature and thermal climax. Furthermore, the measured hydration heat temperature result provides useful information for preventing concrete cracks caused by temperature difference and temperature changing.

  1. Compressive strength and hydration processes of concrete with recycled aggregates

    SciTech Connect

    Koenders, Eduardus A.B.; Pepe, Marco; Martinelli, Enzo

    2014-02-15

    This paper deals with the correlation between the time evolution of the degree of hydration and the compressive strength of Recycled Aggregate Concrete (RAC) for different water to cement ratios and initial moisture conditions of the Recycled Concrete Aggregates (RCAs). Particularly, the influence of such moisture conditions is investigated by monitoring the hydration process and determining the compressive strength development of fully dry or fully saturated recycled aggregates in four RAC mixtures. Hydration processes are monitored via temperature measurements in hardening concrete samples and the time evolution of the degree of hydration is determined through a 1D hydration and heat flow model. The effect of the initial moisture condition of RCAs employed in the considered concrete mixtures clearly emerges from this study. In fact, a novel conceptual method is proposed to predict the compressive strength of RAC-systems, from the initial mixture parameters and the hardening conditions. -- Highlights: •The concrete industry is more and more concerned with sustainability issues. •The use of recycled aggregates is a promising solution to enhance sustainability. •Recycled aggregates affect both hydration processes and compressive strength. •A fundamental approach is proposed to unveil the influence of recycled aggregates. •Some experimental comparisons are presented to validate the proposed approach.

  2. Multiparameter Gas Hydrate Observations from NEPTUNE Canada's Seafloor Cable

    NASA Astrophysics Data System (ADS)

    Scherwath, M.; Heesemann, M.; Spence, G.; Zyla, T.; Riedel, M.; Thomsen, L.; University of Toronto Geophysics Group

    2012-04-01

    Cabled seafloor observatories can acquire long high-resolution time series of a large variety of data that provide us with a new look on the highly dynamic gas hydrate zones. At the northern Cascadia margin, over two years of continuous seafloor data have now been collected with NEPTUNE Canada, the North-East Pacific Time-series Undersea Networked Experiments, under the umbrella of Ocean Networks Canada of the University of Victoria. Two of NEPTUNE Canada's instrumented nodes are located atop the gas hydrate fields, one site called Barkley Hydrates near Barkley Canyon, and one site called ODP 889, also known as Bullseye Vent and Bubbly Gulch. From simple to complex data products, researchers around the world can access and download ocean observations from the many instrument types or conduct their experiments on the ocean floor via the internet. The diversity of available data ranges from simple instrumentations such as conductivity-temperature-pressure (CTD) meters, over current meters, to a CORK borehole, a controlled source electromagnetic (CSEM) system, a multibeam sonar that detects rising methane bubbles, or a seafloor crawler equipped with sediment profiler and methane sensor, among many others. Cameras and lights provide constant visual access to parts of the seafloor, and NEPTUNE Canada's infrastructure installation and maintenance cruises allow regular inspection of larger parts of the hydrated seafloor. We present some results on the observed gas plume activity, potential hydrate growth inferred from seafloor compliance, changes in bacterial communities, and some electromagnetic inferences on the deeper gas hydrate structures.

  3. THF water hydrate crystallization: an experimental investigation

    NASA Astrophysics Data System (ADS)

    Devarakonda, Surya; Groysman, Alexander; Myerson, Allan S.

    1999-08-01

    Supersaturated solutions of THF-water hydrate system were experimentally studied before and during crystallization, to examine the system's behavior in the metastable zone and observe any anomalies suggesting cluster formation. Nucleation induction time measurements, with and without additives, were performed to screen potential growth inhibitors. Shifts in the onset points of crystallization for water and THF-water mixtures with additives were measured using differential scanning calorimetry (DSC). Aspartame was among one of the few successfully screened inhibitors. Preliminary on-line crystal size distribution (CSD) measurements were performed on this system to monitor the crystal size during crystallization. The CSD data was also used to compute the hydrate crystal growth rates, which were found to be in the order of 145 μm/h.

  4. In vivo stratum corneum over-hydration and water diffusion coefficient measurements using opto-thermal radiometry and TEWL Instruments.

    PubMed

    Xiao, P; Wong, W; Cottenden, A M; Imhof, R E

    2012-08-01

    Skin over-hydration is a common problem that affects many people who wear incontinence pads or diapers. The aim of this study is to develop a new method for stratum corneum (SC) over-hydration and SC water diffusion coefficient measurements using opto-thermal transient emission radiometry (OTTER) and evaporimetry. With OTTER, we can measure the SC surface hydration and hydration gradient. With evaporimetry, we can measure the time-dependent evaporative drying curves of water vapour flux density (WVFD). The combination of hydration results and WVFD results can yield information on the SC water diffusion coefficient and how it depends on the SC surface hydration level. The results show that SC water diffusion coefficient is non-linearly proportional to the SC surface hydration level. The results also show strong correlations between evaporative drying flux measured using the Evaporimeter and surface hydration estimated from OTTER measurements. PMID:22515301

  5. Illuminating solid gas storage in confined spaces - methane hydrate formation in porous model carbons.

    PubMed

    Borchardt, Lars; Nickel, Winfried; Casco, Mirian; Senkovska, Irena; Bon, Volodymyr; Wallacher, Dirk; Grimm, Nico; Krause, Simon; Silvestre-Albero, Joaquín

    2016-07-27

    Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores. PMID:27412621

  6. Simultaneous study of mechanical property development and early hydration chemistry in Portland cement slurries using X-ray diffraction and ultrasound reflection

    SciTech Connect

    Jupe, Andrew C.; Wilkinson, Angus P.; Funkhouser, Gary P.

    2012-10-25

    A sample cell for the simultaneous measurement of synchrotron X-ray powder diffraction and ultrasound shear-wave reflection data from cement slurries is described. White cement slurries at 25 and 50 C with 0-3% bwoc CaCl{sub 2} were studied to illustrate the potential of the apparatus. The decrease in reflected S-wave amplitude, in dB, showed a linear correlation with C{sub 3}S hydration. CaCl{sub 2} retarded the development of G{prime} and G{double_prime} relative to the extent of C{sub 3}S hydration. At short times, there was a correlation between the time evolution of both G{prime} and G{double_prime}, and the amount of precipitated CH seen by diffraction, which was almost independent of CaCl{sub 2} concentration and temperature. CaCl{sub 2} addition resulted in a decrease in the amount of CH visible to X-rays, relative the degree of C{sub 3}S hydration. This may indicate a change in C-S-H gel C:S ratio or the presence of nanoscale CH that could not be seen by diffraction.

  7. Examination of Hydrate Formation Methods: Trying to Create Representative Samples

    SciTech Connect

    Kneafsey, T.J.; Rees, E.V.L.; Nakagawa, S.; Kwon, T.-H.

    2011-04-01

    Forming representative gas hydrate-bearing laboratory samples is important so that the properties of these materials may be measured, while controlling the composition and other variables. Natural samples are rare, and have often experienced pressure and temperature changes that may affect the property to be measured [Waite et al., 2008]. Forming methane hydrate samples in the laboratory has been done a number of ways, each having advantages and disadvantages. The ice-to-hydrate method [Stern et al., 1996], contacts melting ice with methane at the appropriate pressure to form hydrate. The hydrate can then be crushed and mixed with mineral grains under controlled conditions, and then compacted to create laboratory samples of methane hydrate in a mineral medium. The hydrate in these samples will be part of the load-bearing frame of the medium. In the excess gas method [Handa and Stupin, 1992], water is distributed throughout a mineral medium (e.g. packed moist sand, drained sand, moistened silica gel, other porous media) and the mixture is brought to hydrate-stable conditions (chilled and pressurized with gas), allowing hydrate to form. This method typically produces grain-cementing hydrate from pendular water in sand [Waite et al., 2004]. In the dissolved gas method [Tohidi et al., 2002], water with sufficient dissolved guest molecules is brought to hydrate-stable conditions where hydrate forms. In the laboratory, this is can be done by pre-dissolving the gas of interest in water and then introducing it to the sample under the appropriate conditions. With this method, it is easier to form hydrate from more soluble gases such as carbon dioxide. It is thought that this method more closely simulates the way most natural gas hydrate has formed. Laboratory implementation, however, is difficult, and sample formation is prohibitively time consuming [Minagawa et al., 2005; Spangenberg and Kulenkampff, 2005]. In another version of this technique, a specified quantity of gas

  8. Obsidian hydration dates glacial loading?

    PubMed

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow. PMID:17806883

  9. Obsidian hydration dates glacial loading?

    USGS Publications Warehouse

    Friedman, I.; Pierce, K.L.; Obradovich, J.D.; Long, W.D.

    1973-01-01

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming . The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  10. Molecular and dissociation studies of natural gas hydrates collected from different oceanic environments

    NASA Astrophysics Data System (ADS)

    Bourry, C.; Charlou, J.; Donval, J.; Focsa, C.; Chazallon, B.

    2007-12-01

    Natural gas hydrates occur globally in marine sediments or in permafrost regions when specific conditions of high pressure, low temperature and sufficiently methane concentration are combined to initiate their formation and stabilize their structure. As well as they appear attractive for gas industry, natural gas hydrates can have an important impact in continental slope stability or climate change. Therefore, it is important to focus our attention on structural evolution and thermodynamical stability of these natural minerals. For this, high-resolution powder X-ray synchrotron diffraction and Raman spectroscopy techniques are efficient and powerful tools to determine the hydrate structures. We performed a first physical characterization of two intact natural gas hydrates from the Congo-Angola and the Nigerian margin by X-ray synchrotron diffraction. The collected samples exhibit a preponderance of structure I (sI) (cubic lattice with space group Pm n). The Rietveld refinement of lattice parameters for the type I structure gives values intermediate between lattice constant of less pure methane specimens and pure artificial methane hydrates. This indicates that lattice constant can be affected by the presence of encaged CO2, H2S and other gas molecules, even in small amount. Thermal expansion is also presented for Congo-Angola hydrate in the temperature range 90-200 K and coefficients are comparable with values reported for synthetic hydrates at low temperature, whereas they tend to approach ice thermal expansion coefficient at higher temperature. In a second step, we performed a physical characterization by Raman spectroscopy of natural gas hydrates recovered from Haakon Mosby Mud Volcano (Norwegian Margin) during the Vicking cruise (HERMES project, 2006). These samples exhibit as well a preponderance of structure I (sI) embedded in ice originating from frozen pore water and hydrate dissociation during recovery. The dissociation temperature (Td) of these hydrates

  11. Large-scale and shape-controlled synthesis and characterization of nanorod-like nickel powders under microwave radiation

    SciTech Connect

    Guo, Yajie; Wang, Guangjian; Wang, Yuran; Huang, Yanhong; Wang, Fei

    2012-01-15

    Graphical abstract: The nanorod-like pure nickel were fabricated via hydrothermal liquid phase reduction route under microwave irradiation with hydrazine hydrate as a reducing agent as well as polyvinyl alcohol as a dispersant and/or structure directing agent. The materials were characterized by XRD, SEM, EDS, HRTEM, and selected-area electron diffraction, etc. The lattice expansion for Ni powders was explained in detail. As-prepared Ni sample was of obvious shape anisotropy with length diameter ratio of 5. Magnetic measurements shown that the magnetic properties of Ni nanorod-like (fcc) were quite different from those of hexagonal closed-packed (hcp) Ni nanoparticles. Highlights: Black-Right-Pointing-Pointer The synthesis of nanorod-like nickel under microwave irradiation. Black-Right-Pointing-Pointer Nitrogen generated in reaction as a shielding gas. Black-Right-Pointing-Pointer The lattice expansion for Ni powders was explained in detail. Black-Right-Pointing-Pointer Magnetic properties of Ni were quite different from those of Ni nanoparticles. -- Abstract: The nanorod-like nickel powders were fabricated via hydrothermal liquid phase reduction route under microwave irradiation with hydrazine hydrate as a reducing agent as well as polyvinyl alcohol as a dispersant and/or structure directing agent. The morphology and structure of as-prepared products could be easily tuned by adjusting process parameters such as pH value and microwave irradiation time. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscope, transmission electron microscopy and selected-area electron diffraction (SAED). The results demonstrated that pure nickel powders with face-centered cubic (fcc) structure were prepared at relatively mild condition and no characteristic peaks of nickel oxide in the XRD pattern were found. The phenomenon of lattice expansion for Ni powders was explained in details according to the XRD theory. As-prepared Ni sample was

  12. Antiviral activities of heated dolomite powder.

    PubMed

    Motoike, Koichi; Hirano, Shozo; Yamana, Hideaki; Onda, Tetsuhiko; Maeda, Takayoshi; Ito, Toshihiro; Hayakawa, Motozo

    2008-12-01

    The effect of the heating conditions of dolomite powder on its antiviral activity was studied against the H5N3 avian influenza virus. Calcium oxide (CaO) and magnesium oxide (MgO), obtained by the thermal decomposition of dolomite above 800 degrees C, were shown to have strong antiviral activity, but the effect was lessened when the heating temperature exceeded 1400 degrees C. Simultaneous measurement of the crystallite size suggested that the weakening of the activity was due to the considerable grain growth of the oxides. It was found that the presence of Mg in dolomite contributed to the deterrence of grain growth of the oxides during the heating process. Although both CaO and MgO exhibited strong antiviral activity, CaO had the stronger activity but quickly hydrated in the presence of water. On the other hand, the hydration of MgO took place gradually under the same conditions. Separate measurements using MgO and Mg(OH)2 revealed that MgO had a higher antiviral effect than Mg(OH)2. From the overall experiments, it was suggested that the strong antiviral activity of dolomite was related to the hydration reaction of CaO. PMID:19127652

  13. Precipitation of hydrated Mg carbonate with the aid of carbonic anhydrase for CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Power, I. M.; Harrison, A. L.; Dipple, G. M.

    2011-12-01

    and water was sampled for dissolved inorganic carbon (DIC) and magnesium concentrations. Final precipitates were collected for X-ray powder diffraction and determination of the percent carbon. The presence of BCA increases the concentration of DIC, thus accelerating the rate-limiting step. In alkaline Mg-rich solutions, disordered hydrated magnesium carbonate, resembling dypingite, rapidly precipitated within hours to form micron-wide flakes. At concentrations of 200 and 100 mg BCA/L, the rates of carbon uptake were ~7 and ~4.4 times that of the control system during the first 24 hours, respectively. BCA is able to catalyze the hydration of CO2 thereby increasing concentrations of DIC relatively rapidly and allowing for the sequestration of atmospheric CO2 as hydrated Mg carbonate minerals.

  14. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

    PubMed Central

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

  15. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

    NASA Astrophysics Data System (ADS)

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite.

  16. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste.

    PubMed

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

  17. The curious case of the hydrated proton.

    PubMed

    Knight, Chris; Voth, Gregory A

    2012-01-17

    Understanding the hydrated proton is a critically important problem that continues to engage the research efforts of chemists, physicists, and biologists because of its involvement in a wide array of phenomena. Only recently have several unique properties of the hydrated proton been unraveled through computer simulations. One such process is the detailed molecular mechanism by which protons hop between neighboring water molecules, thus giving rise to the anomalously high diffusion of protons relative to other simple cations. Termed Grotthuss shuttling, this process occurs over multiple time and length scales, presenting unique challenges for computer modeling and simulation. Because the hydrated proton is in reality a dynamical electronic charge defect that spans multiple water molecules, the simulation methodology must be able to dynamically readjust the chemical bonding topology. This reactive nature of the chemical process is automatically captured with ab initio molecular dynamics (AIMD) simulation methods, where the electronic degrees of freedom are treated explicitly. Unfortunately, these calculations can be prohibitively expensive for more complex proton solvation and transport phenomena in the condensed phase. These AIMD simulations remain extremely valuable, however, in validating empirical models, verifying results, and providing insight into molecular mechanisms. In this Account, we discuss recent progress in understanding the solvation and transport properties of the hydrated excess proton. The advances are based on results obtained from reactive molecular dynamics simulations using the multistate empirical valence bond (MS-EVB) methodology. This approach relies on a dynamic linear combination of chemical bond topologies to model charge delocalization and dynamic bonding environments. When parametrized via a variational force-matching algorithm from AIMD trajectories, the MS-EVB method can be viewed as a multiscale bridging of ab initio simulation

  18. Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

    DOE PAGESBeta

    Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk; Knott, Brandon C.; Beckham, Gregg T.; Yasuoka, Kenji; Wu, David T.; Amadeu K. Sum

    2015-01-06

    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP)more » methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.« less

  19. Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

    SciTech Connect

    Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk; Knott, Brandon C.; Beckham, Gregg T.; Yasuoka, Kenji; Wu, David T.; Amadeu K. Sum

    2015-01-06

    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP) methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.

  20. Determination of the Physical Properties of Sediments Depending on Hydrate Saturation Using a "Quick Look" Method

    NASA Astrophysics Data System (ADS)

    Strauch, B.; Schicks, J. M.; Spangenberg, E.; Seyberth, K.; Heeschen, K. U.; Priegnitz, M.

    2015-12-01

    Seismic and electromagnetic measurements are promising tools for the detection and quantification of gas hydrate occurrences in nature. The seismic wave velocity depends among others on the hydrate quantity and the quality (e.g. pore filling or cementing hydrate). For a proper interpretation of seismic data the knowledge of the dependency of physical properties as a function of hydrate saturation in a certain scenario is crucial. Within the SUGAR III project we determine such dependencies for various scenarios to support models for joint inversion of seismic and EM data e.g. for the shallow gas hydrate reservoirs in the Danube Delta. Since the formation of artificial lab samples containing pore filling hydrate from methane dissolved in water is a complex and time consuming procedure, we developed an easier alternative. Ice is very similar to hydrate in some of its physical properties. Therefore it might be used as analogous pore fill in a "quick look" experiment to determine the dependency of rock physical properties on hydrate content. We used the freezing point depression of a KCl solution to generate a dependency of ice saturation on temperature. The measured seismic wave velocity in dependence on ice saturation compares very well with data measured on a glass bead sediment sample with methane hydrate formed from methane dissolved in water. We could also observe that ice, formed from a salt solution in the pore space of sediment, behaves similar to methane hydrate as a non-cementing solid pore fill.

  1. Water-wetting surfaces as hydrate promoters during transport of carbon dioxide with impurities.

    PubMed

    Kuznetsova, Tatiana; Jensen, Bjørnar; Kvamme, Bjørn; Sjøblom, Sara

    2015-05-21

    Water condensing as liquid drops within the fluid bulk has traditionally been the only scenario accepted in the industrial analysis of hydrate risks. We have applied a combination of absolute thermodynamics and molecular dynamics modeling to analyze the five primary routes of hydrate formation in a rusty pipeline carrying dense carbon dioxide with methane, hydrogen sulfide, argon, and nitrogen as additional impurities. We have revised the risk analysis of all possible routes in accordance with the combination of the first and the second laws of thermodynamics to determine the highest permissible content of water. It was found that at concentrations lower than five percent, hydrogen sulfide will only support the formation of carbon dioxide-dominated hydrate from adsorbed water and hydrate formers from carbon dioxide phase rather than formation in the aqueous phase. Our results indicate that hydrogen sulfide leaving carbon dioxide for the aqueous phase will be able to create an additional hydrate phase in the aqueous region adjacent to the first adsorbed water layer. The growth of hydrate from different phases will decrease the induction time by substantially reducing the kinetically limiting mass transport across the hydrate films. Hydrate formation via adsorption of water on rusty walls will play the decisive role in hydrate formation risk, with the initial concentration of hydrogen sulfide being the critical factor. We concluded that the safest way to eliminate hydrate risks is to ensure that the water content of carbon dioxide is low enough to prevent water dropout via the adsorption mechanism. PMID:25903085

  2. Attenuation of seismic waves in methane gas hydrate-bearing sand

    NASA Astrophysics Data System (ADS)

    Priest, Jeffrey A.; Best, Angus I.; Clayton, Christopher R. I.

    2006-01-01

    Compressional wave (P wave) and shear wave (S wave) velocities (Vp and Vs, respectively) from remote seismic methods have been used to infer the distribution and volume of gas hydrate within marine sediments. Recent advances in seismic methods now allow compressional and shear wave attenuations (Q-1p and Q-1s, respectively) to be measured. However, the interpretation of these data is problematic due to our limited understanding of the effects of gas hydrate on physical properties. Therefore, a laboratory gas hydrate resonant column was developed to simulate pressure and temperature conditions suitable for methane gas hydrate formation in sand specimens and the subsequent measurement of both Q-1p and Q-1s at frequencies and strains relevant to marine seismic surveys. 13 dry (gas saturated) sand specimens were investigated with different amounts of methane gas hydrate evenly dispersed throughout each specimen. The results show that for these dry specimens both Q-1p and Q-1s are highly sensitive to hydrate saturation with unexpected peaks observed between 3 and 5 per cent hydrate saturation. It is thought that viscous squirt flow of absorbed water or free gas within the pore space is enhanced by hydrate cement at grain contacts and by the nanoporosity of the hydrate itself. These results show for the first time the dramatic effect methane gas hydrate can have on seismic wave attenuation in sand, and provide insight into wave propagation mechanisms. These results will aid the interpretation of elastic wave attenuation data obtained using marine seismic prospecting methods.

  3. Development of Sand Production Evaluation Apparatus for Methane Hydrate Development

    NASA Astrophysics Data System (ADS)

    Kakumoto, M.; Yoneda, J.; Tenma, N.; Katagiri, J.; Noda, S.

    2015-12-01

    As a part of a Japanese National hydrate research program (MH21, funded by METI), we performed a study on sand production mechanism during methane gas production. In 2013, the first methane hydrate offshore production test was conducted in Japan, and it was recognized in the production of about 20000m3/day of methane gas from methane hydrate bearing sand sediment in deep marine sediment. In methane hydrate development, depressurization method has been proposed for gas extraction. This method is a method to reduce the bottom hole pressure by submersible pump lowering water level in the production well, and gas and water is recovered by methane hydrate dissociation at the in situ. At that time, a phenomenon that sand flows into the wells is feared. In actually, sand production phenomenon occurred after 6 days from production start in offshore production test. A mechanism of sand production has not yet been resolved in case of methane hydrate development. Therefore, we developed large scale laboratory test apparatus for the purpose of elucidation of the mechanism of sand production phenomenon. In this presentation, we introduce basic performance of this apparatus, and usefulness is made mention by representative test results.

  4. Impact of Hydration Media on Ex Vivo Corneal Elasticity Measurements

    PubMed Central

    Dias, Janice; Ziebarth, Noël M.

    2014-01-01

    Objectives To determine the effect of hydration media on ex vivo corneal elasticity. Methods Experiments were conducted on forty porcine eyes retrieved from an abattoir (10 eyes each for PBS, BSS, Optisol, 15% Dextran). The epithelium was removed and the cornea was excised with an intact scleral rim and placed in 20% Dextran overnight to restore its physiological thickness. For each hydration media, corneas were evenly divided into two groups: one with an intact scleral rim and the other without. Corneas were mounted onto a custom chamber and immersed in a hydration medium for elasticity testing. While in each medium, corneal elasticity measurements were performed for 2 hours: at 5-minute intervals for the first 30 minutes and then 15-minute intervals for the remaining 90 minutes. Elasticity testing was performed using nanoindentation with spherical indenters and Young’s modulus was calculated using the Hertz model. Thickness measurements were taken before and after elasticity testing. Results The percentage change in corneal thickness and elasticity was calculated for each hydration media group. BSS, PBS, and Optisol showed an increase in thickness and Young’s moduli for corneas with and without an intact scleral rim. 15% Dextran exhibited a dehydrating effect on corneal thickness and provided stable maintenance of corneal elasticity for both groups. Conclusions Hydration media affects the stability of corneal thickness and elasticity measurements over time. 15% Dextran was most effective in maintaining corneal hydration and elasticity, followed by Optisol. PMID:25603443

  5. Wax and hydrate control with electrical power

    SciTech Connect

    1997-08-01

    Electrical heating of subsea flowlines is an effective way to prevent wax and hydrate information, especially for long transportation distances and in low-temperature deep water. Systems are available for use in conjunction with bundles, pipe-in-pipe, and wet-thermal-insulation systems. These systems provide environmentally friendly fluid-temperature control without chemicals or flaring for pipeline depressurizing. Enhanced production is achieved because no time is lost by unnecessary depressurizing, pigging, heating-medium circulation, or removal of hydrate and wax blockages. The seabed temperature at 100-m and greater water depths may range from 7 to {minus}1.5 C, causing a rapid cooling of the hot well streams being transported in subsea flowlines. Under these supercooling conditions, vulnerable crude oils and multiphase compositions will deposit wax and asphalts; also the gas/water phase may freeze solid with hydrate particles. The paper discusses thermal-insulated flowlines, heat-loss compensation with electrical power, electrical power consumption and operation, and subsea electrical-power distribution system.

  6. Ethical issues in artificial nutrition and hydration.

    PubMed

    Fine, Robert L

    2006-04-01

    From the time of Hippocrates, approximately 2500 years ago, medical ethics has been seen as an essential complement to medical science in pursuit of the healing art of medicine. This is no less true today, not only for physicians but also for other essential professionals involved in patient care, including clinical nutrition support practitioners. One aspect of medical ethics that the clinical nutritionist must face involves decisions to provide, withhold, or withdraw artificial nutrition and hydration. Such a decision is not only technical but often has a strong moral component as well. Although it is the physician who writes any such order, the clinical nutritionist as fellow professional should be a part not only of the scientific aspects of the order but of the moral discourse leading to such an order and may certainly be involved in counseling physicians, other healthcare providers, patients, and families alike. This paper is intended to give the clinical nutritionist a familiarity with the discipline of medical ethics and its proper relationship to medical science, politics, and law. This review will then offer a more specific analysis of the ethical aspects of decisions to initiate, withhold, or withdraw artificial nutrition and hydration (ANH) and offer particular commentary on the ethically significant pronouncements of Pope John Paul II in March of 2004 related to vegetative patients and artificial or "assisted" nutrition and hydration. PMID:16556921

  7. Early-age volume changes of extrudable reactive powder concrete

    NASA Astrophysics Data System (ADS)

    Cherkaoui, K.; Courtial, M.; Dunstetter, F.; Khelidj, A.; Mounanga, P.; de Noirfontaine, M. N.

    2010-06-01

    This article presents a study on the early-age autogenous deformations of Extrudable Reactive Powder Concretes (ERPCs), especially designed for the making of concrete pipes by extrusion. Different ERPC mixtures, with variable amounts of polycarboxylate superplasticizer (SP), have been investigated. Results on 28-day mechanical properties, early-age hydration rate, autogenous shrinkage and premature cracking risk are analyzed and discussed in relation with the ERPC mix parameters.

  8. Distribution and controls on gas hydrate in the ocean-floor environment

    SciTech Connect

    Dillon, W.P.

    1995-12-31

    Methane hydrate, a crystalline solid that is formed of water and gas molecules, is widespread in oceanic sediments. It occurs at water depths that exceed 300 to 500 m and in a zone that commonly extends from the sea floor, down several hundred meters - the base of the zone is limited by increased temperature. To determine factors that control gas hydrate concentration, we have mapped its distribution off the U.S. Atlantic coast using acoustic remote-sensing methods. Most natural gas hydrate is formed from biogenic methane, and therefore it is concentrated where there is a rapid accumulation of organic detritus and also where there is a rapid accumulation of sediments (which protect detritus from oxidation). When hydrate fills the pore space of sediment, it can reduce permeability and create a gas trap. Such trapping of gas beneath hydrate may cause the formation of the most concentrated hydrate deposits, perhaps because the gas that is held in the trap can slowly diffuse upwards or migrate through faults. Hydrate-sealed traps are formed by hills on the sea floor, by dipping strata, or by salt(?) domes. Off the southeastern United States, a small area (only 3000 km{sup 2}) beneath a ridge formed by rapidly-deposited sediments appears to contain a volume of methane in hydrate that is equivalent to {approximately}30 times the U.S. annual consumption of gas. The breakdown of hydrate can cause submarine landslides by converting the hydrate to gas plus water and generating a rise of pore pressure. Conversely, sea-floor landslides can cause breakdown of hydrate by reducing the pressure in sediments. These interacting processes may cause cascading slides, which would result in breakdown of hydrate and release of methane to the atmosphere. This addition of methane to the global greenhouse would significantly influence climate. Gas hydrate in sea-floor sediments is potentially significant to climate, energy resources, and sea-floor stability.

  9. Methane hydrate destabilization sensitivity to physical complexity and initial conditions in a numerical model

    NASA Astrophysics Data System (ADS)

    Darnell, K.; Flemings, P. B.; Bryant, S. L.

    2013-12-01

    We modify an existing dynamic, multiphase fluid flow model after Liu and Flemings (2007) to form methane hydrate and subsequently melt the hydrate in a marine, sedimentary environment. We then investigate the timing and evolution of hydrate melting when we include varying degrees of thermodynamic and chemical complexity. Our findings indicate that the incorporation of the latent heat of hydrate melting coupled with fresh water release retards the melting process. If the latent heat is neglected, the time required for the warming signal propagation to melt the hydrate completely is shorter by as much as a factor of two. Our basic model considers a one dimensional sedimentary column where the sediment is initially water saturated and supplied with a constant gas flux from below the hydrate stability zone, with the assumption that solid/gas/liquid phases are in equilibrium at the local pressure, temperature and salinity. We consider transport of water, methane, and salt over a 30 kyr interval to generate a modern hydrate deposit and corresponding salinity profile. Then, an instantaneous temperature increase is applied at the seafloor and held constant. This work suggests an alternative timing on the Gulf Stream shift that has been deduced from anomalous hydrate deposits by Phrampus and Hornbach (2012). Furthermore, we are able to show that current warming and relict warming from several hundreds years may be simultaneously convoluted in any current hydrate destabilization.

  10. Determination of Protein Surface Hydration by Systematic Charge Mutations

    NASA Astrophysics Data System (ADS)

    Yang, Jin; Jia, Menghui; Qin, Yangzhong; Wang, Dihao; Pan, Haifeng; Wang, Lijuan; Xu, Jianhua; Zhong, Dongping; Dongping Zhong Collaboration; Jianhua Xu Collaboration

    Protein surface hydration is critical to its structural stability, flexibility, dynamics and function. Recent observations of surface solvation on picosecond time scales have evoked debate on the origin of such relatively slow motions, from hydration water or protein charged sidechains, especially with molecular dynamics simulations. Here, we used a unique nuclease with a single tryptophan as a local probe and systematically mutated neighboring three charged residues to differentiate the contributions from hydration water and charged sidechains. By mutations of alternative one and two and all three charged residues, we observed slight increases in the total tryptophan Stokes shifts with less neighboring charged residue(s) and found insensitivity of charged sidechains to the relaxation patterns. The dynamics is correlated with hydration water relaxation with the slowest time in a dense charged environment and the fastest time at a hydrophobic site. On such picosecond time scales, the protein surface motion is restricted. The total Stokes shifts are dominantly from hydration water relaxation and the slow dynamics is from water-driven relaxation, coupled with local protein fluctuations.

  11. Development of ketoprofen loaded proliposomal powders for improved gastric absorption and gastric tolerance: in vitro and in situ evaluation.

    PubMed

    Gangishetty, Himabindu; Eedara, Basanth Babu; Bandari, Suresh

    2015-01-01

    The aim of the current investigation was to improve dissolution rate, gastric absorption and tolerance of a water insoluble non-steroidal anti-inflammatory drug ketoprofen by developing proliposomal powders. Ketoprofen proliposomal powders were prepared by solvent evaporation method with varying ratios of hydrogenated soyphosphatidyl choline (HSPC) and cholesterol. The prepared proliposomal powders were characterized for vesicle size, micromeritics, entrapment efficiency and in vitro dissolution behavior. Proliposomal powder (KPL3) composed of equimolar ratios of HSPC and cholesterol loaded on pearlitol SD 200 was selected as optimized formulation as it produced smaller liposomes (5.24 ± 1.35 μm) upon hydration with highest entrapment efficiency (53.16 ± 0.06%). All proliposomal powders showed improved dissolution characteristics than pure drug, however dissolution of drug from KPL3 was found to be highest (91.17 ± 6.3) and which is about 24 times higher than pure ketoprofen within 5 min. The transformation of crystalline ketoprofen to amorphous form was confirmed by solid state characterization. The absorption rate per hour for pure ketoprofen and proliposomal formulation (KPL3) was assessed in the stomach by conducting in situ gastric absorption studies in Wistar rats and was found to be 27 ± 1.22 and 36.98 ± 1.95%, respectively. In conclusion, enhanced dissolution and gastric absorption rate of ketoprofen from proliposomal powders suggest them as potential candidate for oral bioavailability improvement of ketoprofen. PMID:24820852

  12. Impacts of Hydrate Pore Habit on Physical Properties of Hydrate Bearing Sediments

    NASA Astrophysics Data System (ADS)

    Seol, Y.; Dai, S.; Choi, J. H.

    2014-12-01

    The physical properties of gas hydrate bearing sediments, to a large extent, are governed by the volume fraction and spatial distribution of the hydrate phase. For sediments containing the same amount of hydrates, their overall physical properties may vary several orders of magnitude depending on hydrate pore habit. We investigate the interplay among hydrate formation methods, hydrate pore habits, and fundamental physical properties of hydrate bearing sediments. We have developed a new method to synthesize noncementing hydrate in sands, a multi-properties characterization chamber to test the hydrate bearing sediments, and pore network models to simulate fluid flow processes in hydrate bearing sediments. We have found that (1) the growth pattern of hydrate crystal in the pore spaces of water saturated sediments is dominated by the relative magnitude of the capillary force (between hydrate crystal and pore fluid) and the skeleton force, which will result in pore-filling or grain-displacing type of hydrate pore character; (2) the existing capillary tube models of water permeability in hydrate bearing sediments are sensitive to pore geometry and hydrate pore habit; and (3) preliminary CT results suggest that hydrate nucleation in partially water saturated sands tends to agglomerate in patches, rather than in an uniformly-distributed contact-cementing morphology. Additional CT results with a small amount of fines (5wt%) and visualization via micro-CT of hydrate pore habits in sediments using different hydrate formation methods will be discussed.

  13. Energy resource potential of natural gas hydrates

    USGS Publications Warehouse

    Collett, T.S.

    2002-01-01

    The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

  14. Performance Characteristics of Waste Glass Powder Substituting Portland Cement in Mortar Mixtures

    NASA Astrophysics Data System (ADS)

    Kara, P.; Csetényi, L. J.; Borosnyói, A.

    2016-04-01

    In the present work, soda-lime glass cullet (flint, amber, green) and special glass cullet (soda-alkaline earth-silicate glass coming from low pressure mercury-discharge lamp cullet and incandescent light bulb borosilicate glass waste cullet) were ground into fine powders in a laboratory planetary ball mill for 30 minutes. CEM I 42.5N Portland cement was applied in mortar mixtures, substituted with waste glass powder at levels of 20% and 30%. Characterisation and testing of waste glass powders included fineness by laser diffraction particle size analysis, specific surface area by nitrogen adsorption technique, particle density by pycnometry and chemical analysis by X-ray fluorescence spectrophotometry. Compressive strength, early age shrinkage cracking and drying shrinkage tests, heat of hydration of mortars, temperature of hydration, X-ray diffraction analysis and volume stability tests were performed to observe the influence of waste glass powder substitution for Portland cement on physical and engineering properties of mortar mixtures.

  15. Acemetacin cocrystals and salts: structure solution from powder X-ray data and form selection of the piperazine salt

    PubMed Central

    Sanphui, Palash; Bolla, Geetha; Nangia, Ashwini; Chernyshev, Vladimir

    2014-01-01

    Acemetacin (ACM) is a non-steroidal anti-inflammatory drug (NSAID), which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM), isonicotinamide (INA), and picolinamide (PAM)], caprolactam (CPR), p-aminobenzoic acid (PABA), and piperazine (PPZ). The structures of an ACM–INA cocrystal and a binary adduct ACM–PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM–PAM and ACM–CPR, and the piperazine salt ACM–PPZ were solved from high-resolution powder X-ray diffraction data. The ACM–INA cocrystal is sustained by the acid⋯pyridine heterosynthon and N—H⋯O catemer hydrogen bonds involving the amide group. The acid⋯amide heterosynthon is present in the ACM–PAM cocrystal, while ACM–CPR contains carboxamide dimers of caprolactam along with acid–carbonyl (ACM) hydrogen bonds. The cocrystals ACM–INA, ACM–PAM and ACM–CPR are three-dimensional isostructural. The carboxyl⋯carboxyl synthon in ACM–PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM–PPZ salt and ACM–nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM–PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable piperazine

  16. Cell water dynamics on multiple time scales

    PubMed Central

    Persson, Erik; Halle, Bertil

    2008-01-01

    Water–biomolecule interactions have been extensively studied in dilute solutions, crystals, and rehydrated powders, but none of these model systems may capture the behavior of water in the highly organized intracellular milieu. Because of the experimental difficulty of selectively probing the structure and dynamics of water in intact cells, radically different views about the properties of cell water have proliferated. To resolve this long-standing controversy, we have measured the 2H spin relaxation rate in living bacteria cultured in D2O. The relaxation data, acquired in a wide magnetic field range (0.2 mT–12 T) and analyzed in a model-independent way, reveal water dynamics on a wide range of time scales. Contradicting the view that a substantial fraction of cell water is strongly perturbed, we find that ≈85% of cell water in Escherichia coli and in the extreme halophile Haloarcula marismortui has bulk-like dynamics. The remaining ≈15% of cell water interacts directly with biomolecular surfaces and is motionally retarded by a factor 15 ± 3 on average, corresponding to a rotational correlation time of 27 ps. This dynamic perturbation is three times larger than for small monomeric proteins in solution, a difference we attribute to secluded surface hydration sites in supramolecular assemblies. The relaxation data also show that a small fraction (≈0.1%) of cell water exchanges from buried hydration sites on the microsecond time scale, consistent with the current understanding of protein hydration in solutions and crystals. PMID:18436650

  17. Multiple feed powder splitter

    DOEpatents

    Lewis, Gary K.; Less, Richard M.

    2001-01-01

    A device for providing uniform powder flow to the nozzles when creating solid structures using a solid fabrication system such as the directed light fabrication (DLF) process. In the DLF process, gas entrained powders are passed through the focal point of a moving high-power laser light which fuses the particles in the powder to a surface being built up in layers. The invention is a device providing uniform flow of gas entrained powders to the nozzles of the DLF system. The device comprises a series of modular splitters which are slidably interconnected and contain an integral flow control mechanism. The device can take the gas entrained powder from between one to four hoppers and split the flow into eight tubular lines which feed the powder delivery nozzles of the DLF system.

  18. Granulation of fine powder

    DOEpatents

    Chen, Ching-Fong

    2016-08-09

    A mixture of fine powder including thorium oxide was converted to granulated powder by forming a first-green-body and heat treating the first-green-body at a high temperature to strengthen the first-green-body followed by granulation by crushing or milling the heat-treated first-green-body. The granulated powder was achieved by screening through a combination of sieves to achieve the desired granule size distribution. The granulated powder relies on the thermal bonding to maintain its shape and structure. The granulated powder contains no organic binder and can be stored in a radioactive or other extreme environment. The granulated powder was pressed and sintered to form a dense compact with a higher density and more uniform pore size distribution.

  19. Multiple feed powder splitter

    DOEpatents

    Lewis, Gary K.; Less, Richard M.

    2002-01-01

    A device for providing uniform powder flow to the nozzles when creating solid structures using a solid fabrication system such as the directed light fabrication (DLF) process. In the DLF process, gas entrained powders are passed through the focal point of a moving high-power laser light which fuses the particles in the powder to a surface being built up in layers. The invention is a device providing uniform flow of gas entrained powders to the nozzles of the DLF system. The device comprises a series of modular splitters which are slidably interconnected and contain an integral flow control mechanism. The device can take the gas entrained powder from between one to four hoppers and split the flow into eight tubular lines which feed the powder delivery nozzles of the DLF system.

  20. Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties

    USGS Publications Warehouse

    Lee, J.Y.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    2010-01-01

    The small-strain mechanical properties (e.g., seismic velocities) of hydrate-bearing sediments measured under laboratory conditions provide reference values for calibration of logging and seismic exploration results acquired in hydrate-bearing formations. Instrumented cells were designed for measuring the compressional (P) and shear (S) velocities of sand, silts, and clay with and without hydrate and subject to vertical effective stresses of 0.01 to 2 MPa. Tetrahydrofuran (THF), which is fully miscible in water, was used as the hydrate former to permit close control over the hydrate saturation Shyd and to produce hydrate from dissolved phase, as methane hydrate forms in most natural marine settings. The results demonstrate that laboratory hydrate formation technique controls the pattern of P and S velocity changes with increasing Shyd and that the small-strain properties of hydrate-bearing sediments are governed by effective stress, δ'v and sediment specific surface. The S velocity increases with hydrate saturation owing to an increase in skeletal shear stiffness, particularly when hydrate saturation exceeds Shyd≈ 0.4. At very high hydrate saturations, the small strain shear stiffness is determined by the presence of hydrates and becomes insensitive to changes in effective stress. The P velocity increases with hydrate saturation due to the increases in both the shear modulus of the skeleton and the bulk modulus of pore-filling phases during fluid-to-hydrate conversion. Small-strain Poisson's ratio varies from 0.5 in soft sediments lacking hydrates to 0.25 in stiff sediments (i.e., subject to high vertical effective stress or having high Shyd). At Shyd ≥ 0.5, hydrate hinders expansion and the loss of sediment stiffness during reduction of vertical effective stress, meaning that hydrate-rich natural sediments obtained through pressure coring should retain their in situ fabric for some time after core retrieval if the cores are maintained within the hydrate

  1. Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Francisca, F. M.; Santamarina, J. C.; Ruppel, C.

    2010-11-01

    The small-strain mechanical properties (e.g., seismic velocities) of hydrate-bearing sediments measured under laboratory conditions provide reference values for calibration of logging and seismic exploration results acquired in hydrate-bearing formations. Instrumented cells were designed for measuring the compressional (P) and shear (S) velocities of sand, silts, and clay with and without hydrate and subject to vertical effective stresses of 0.01 to 2 MPa. Tetrahydrofuran (THF), which is fully miscible in water, was used as the hydrate former to permit close control over the hydrate saturation Shyd and to produce hydrate from dissolved phase, as methane hydrate forms in most natural marine settings. The results demonstrate that laboratory hydrate formation technique controls the pattern of P and S velocity changes with increasing Shyd and that the small-strain properties of hydrate-bearing sediments are governed by effective stress, σ'v and sediment specific surface. The S velocity increases with hydrate saturation owing to an increase in skeletal shear stiffness, particularly when hydrate saturation exceeds Shyd≈ 0.4. At very high hydrate saturations, the small strain shear stiffness is determined by the presence of hydrates and becomes insensitive to changes in effective stress. The P velocity increases with hydrate saturation due to the increases in both the shear modulus of the skeleton and the bulk modulus of pore-filling phases during fluid-to-hydrate conversion. Small-strain Poisson's ratio varies from 0.5 in soft sediments lacking hydrates to 0.25 in stiff sediments (i.e., subject to high vertical effective stress or having high Shyd). At Shyd ≥ 0.5, hydrate hinders expansion and the loss of sediment stiffness during reduction of vertical effective stress, meaning that hydrate-rich natural sediments obtained through pressure coring should retain their in situ fabric for some time after core retrieval if the cores are maintained within the hydrate

  2. Fabrication of Ni-P/palygorskite core-shell linear powder via electroless deposition

    NASA Astrophysics Data System (ADS)

    Zhou, Sumin; Wang, Li; Shen, Shiming

    2011-09-01

    Palygorskite is a kind of hydrated magnesium aluminium silicate clay mineral. A novel linear core-shell structured Ni-P coated micro-fiber palygorskite (MFP) was fabricated via an electroless (EL) plating process in an alkaline bath. The composition, morphology and structure of the as-prepared products were characterized by the techniques such as powder X-ray diffraction (XRD), energy-dispersive X-ray spectrum (EDS), scanning electron microscopy (SEM) and transmission electron microscope (TEM). It was observed that the size and morphology of Ni-P coated MFPs were altered by depositing temperature and time. The as-prepared Ni-P coated MFPs showed good conductivity. To the best of our knowledge, the Ni-P coated MFPs have not been reported before. And this fabrication process might also apply in preparing other metal coated MFPs such as silver, copper and palladium.

  3. The effect of elevated methane pressure on methane hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

  4. CO2 + N2O mixture gas hydrate formation kinetics and effect of soil minerals on mixture-gas hydrate formation process

    NASA Astrophysics Data System (ADS)

    Enkh-Amgalan, T.; Kyung, D.; Lee, W.

    2012-12-01

    CO2 mitigation is one of the most pressing global scientific topics in last 30 years. Nitrous oxide (N2O) is one of the main greenhouse gases (GHGs) defined by the Kyoto Protocol and its global warming potential (GWP) of one metric ton is equivalent to 310 metric tons of CO2. They have similar physical and chemical properties and therefore, mixture-gas (50% CO2 + 50% N2O) hydrate formation process was studied experimentally and computationally. There were no significant research to reduce N20 gas and we tried to make hydrate to mitigate N20 and CO2 in same time. Mixture gas hydrate formation periods were approximately two times faster than pure N2O hydrate formation kinetic in general. The fastest induction time of mixture-gas hydrate formation observed in Illite and Quartz among various soil mineral suspensions. It was also observed that hydrate formation kinetic was faster with clay mineral suspensions such as Nontronite, Sphalerite and Montmorillonite. Temperature and pressure change were not significant on hydrate formation kinetic; however, induction time can be significantly affected by various chemical species forming under the different suspension pHs. The distribution of chemical species in each mineral suspension was estimated by a chemical equilibrium model, PHREEQC, and used for the identification of hydrate formation characteristics in the suspensions. With the experimental limitations, a study on the molecular scale modeling has a great importance for the prediction of phase behavior of the gas hydrates. We have also performed molecular dynamics computer simulations on N2O and CO2 hydrate structures to estimate the residual free energy of two-phase (hydrate cage and guest molecule) at three different temperature ranges of 260K, 273K, and 280K. The calculation result implies that N2O hydrates are thermodynamically stable at real-world gas hydrate existing condition within given temperature and pressure. This phenomenon proves that mixture-gas could be

  5. Hydration water in dynamics of a hydrated beta-lactoglobulin

    NASA Astrophysics Data System (ADS)

    Yoshida, K.; Yamaguchi, T.; Bellissent-Funel, M.-C.; Longeville, S.

    2007-02-01

    Incoherent spin-echo signals of a hydrated β-lactoglobulin protein were investigated, at 275 and 293 K. The intermediate scattering functions I(Q,t) were divided in two contributions from surface water and protein, respectively. On one hand, the dynamics of the surface water follows a KWW stretched exponential function (the exponent is ~0.5), on the other hand, that of the protein follows a single exponential. The present results are consistent with our previous results of hydrated C-phycocyanin combining elastic and quasielastic neutron scattering and by molecular dynamics simulation.

  6. Cow dung powder poisoning.

    PubMed

    Sherfudeen, Khaja Mohideen; Kaliannan, Senthil Kumar; Dammalapati, Pavan Kumar

    2015-11-01

    Cow dung, which has germicidal property, was used in ancient days to clean living premises in South India. Nowadays, people are using commercially available synthetic cow dung powder. It is locally known as "saani powder" in Tamil Nadu. It is freely available in homes and is sometimes accidentally consumed by children. It is available in two colors - yellow and green. Cow dung powder poisoning is common in districts of Tamil Nadu such as Coimbatore, Tirupur, and Erode. We report two cases of yellow cow dung powder poisoning from our hospital. PMID:26730123

  7. Effects of hydration on laser soldering

    NASA Astrophysics Data System (ADS)

    Chan, Eric K.; Brown, Dennis T.; Kovach, Ian S.; Welch, Ashley J.

    1997-05-01

    Laser welding with albumin-based tissue solder has been investigated as an alternative to surgical suturing. Many surgical procedures require the soldered tissues to be in a hydrated environment. We have studied the effects of hydration on laser soldered rat dermis and baboon articular cartilage in vitro. The solder is composed of human serum albumin, sodium hyaluronate and indocyanine green. We used a micro-pipette to deposit 2 (mu) l of solder on each tissue specimen. An 808 nm cw laser beam with irradiance of 27 W/cm2 was scanned 4 times over the same solder area at a constant speed of 0.84 mm/sec. After photo-coagulation, each tissue specimen was cut into two halves at the center of the solder, perpendicular to the direction of the scanning laser beam. One half was reserved as control while the other half was soaked in phosphate buffered saline for a designated hydration period. The hydration periods were 1 hr, 1, 2, and 7 days. All tissue specimens were fixed in glutaraldahyde, then prepared for scanning electron microcopy analysis. For most of the specimens, there was non-uniform coagulation across the thickness of the solder. Closer to the laser beam, the upper solder region formed a more dense coagulum. While the region closer to solder-tissue interface, the solder aggregated into small globules. This non-uniform coagulation was likely caused by non-uniform energy distribution during photocoagulation. The protein globules and coagulum seem to be responsible for the solder attachment from the specimen surface. However, we have noted that the solder detached from the cartilage substrate as early as after 1 hr of hydration. On the other hand, the solder attached to the dermis much better than to cartilage. This may be explained by the difference in surface roughness of the two tissue types. The dermal layer of the skin is composed of collagen matrix which may provide a better entrapment of the solder than the smooth surface of articular cartilage.

  8. Feedbacks of Rock Hydration on Hydrothermal Convection

    NASA Astrophysics Data System (ADS)

    Iyer, K.; Ruepke, L.

    2009-04-01

    Hydration of the oceanic lithosphere is an important process which alters both the chemical and physical properties of the affected lithologies. Although hydrothermal convection has been extensively researched, little work has been done on the effects of hydration reactions occurring during convection. One of the most important reactions occurring in the oceanic lithosphere is serpentinization of ultramafic rocks. We present a numerical solution for hydrothermal circulation which explores the feedbacks generated during serpentinization of mantle rocks. The model is two dimensional and uses the FEM approach. Three coupled, time-dependent equations are solved: the first equation is mass conserving and is based on Darcy flow. The second equation describes heat transport and accounts for advective and diffusive heat transfer as well as latent heat effects. The final equation describes the serpentinization rate of olivine in ultramafic rocks (Emmanuel and Berkowitz, 2006) and is derived from experimental results (Martin and Fyfe, 1970). Serpentinization is a fluid-consuming process and manifests itself as a sink term in the Darcy flow equation. The exothermic heat of reaction is added as a source term in the heat transport equation. Moreover, serpentinization is associated with a large positive volume change. This large volume change may decrease the porosity of the rock but can also increase permeability by deformation. The rate of serpentinization used in the model is, therefore, also coupled to the porosity and permeability. We investigate the role of hydration in a box model using thermodynamically constrained fluid properties where the lower part is composed of reactive mantle rocks. The effects of serpentinization on the temperatures of the venting fluids and variations in flow pathways are explored. Furthermore, the model is also used in a mid-ocean ridge setting and the amount and depth of serpentinization, in addition to the above mentioned effects, is also

  9. Hydration of polyethylene glycol-grafted liposomes.

    PubMed

    Tirosh, O; Barenholz, Y; Katzhendler, J; Priev, A

    1998-03-01

    This study aimed to characterize the effect of polyethylene glycol of 2000 molecular weight (PEG2000) attached to a dialkylphosphatidic acid (dihexadecylphosphatidyl (DHP)-PEG2000) on the hydration and thermodynamic stability of lipid assemblies. Differential scanning calorimetry, densitometry, and ultrasound velocity and absorption measurements were used for thermodynamic and hydrational characterization. Using a differential scanning calorimetry technique we showed that each molecule of PEG2000 binds 136 +/- 4 molecules of water. For PEG2000 covalently attached to the lipid molecules organized in micelles, the water binding increases to 210 +/- 6 water molecules. This demonstrates that the two different structural configurations of the PEG2000, a random coil in the case of the free PEG and a brush in the case of DHP-PEG2000 micelles, differ in their hydration level. Ultrasound absorption changes in liposomes reflect mainly the heterophase fluctuations and packing defects in the lipid bilayer. The PEG-induced excess ultrasound absorption of the lipid bilayer at 7.7 MHz for PEG-lipid concentrations over 5 mol % indicates the increase in the relaxation time of the headgroup rotation due to PEG-PEG interactions. The adiabatic compressibility (calculated from ultrasound velocity and density) of the lipid bilayer of the liposome increases monotonically with PEG-lipid concentration up to approximately 7 mol %, reflecting release of water from the lipid headgroup region. Elimination of this water, induced by grafted PEG, leads to a decrease in bilayer defects and enhanced lateral packing of the phospholipid acyl chains. We assume that the dehydration of the lipid headgroup region in conjunction with the increase of the hydration of the outer layer by grafting PEG in brush configuration are responsible for increasing thermodynamic stability of the liposomes at 5-7 mol % of PEG-lipid. At higher PEG-lipid concentrations, compressibility and partial volume of the lipid phase

  10. The impact of permafrost-associated microorganisms on hydrate formation kinetics

    NASA Astrophysics Data System (ADS)

    Luzi-Helbing, Manja; Liebner, Susanne; Spangenberg, Erik; Wagner, Dirk; Schicks, Judith M.

    2016-04-01

    The relationship between gas hydrates, microorganisms and the surrounding sediment is extremely complex: On the one hand, microorganisms producing methane provide the prerequisite for gas hydrate formation. As it is known most of the gas incorporated into natural gas hydrates originates from biogenic sources. On the other hand, as a result of microbial activity gas hydrates are surrounded by a great variety of organic compounds which are not incorporated into the hydrate structure but may influence the formation or degradation process. For gas hydrate samples from marine environments such as the Gulf of Mexico a direct association between microbes and gas hydrates was shown by Lanoil et al. 2001. It is further assumed that microorganisms living within the gas hydrate stability zone produce biosurfactants which were found to enhance the hydrate formation process significantly and act as nucleation centres (Roger et al. 2007). Another source of organic compounds is sediment organic matter (SOM) originating from plant material or animal remains which may also enhance hydrate growth. So far, the studies regarding this relationship were focused on a marine environment. The scope of this work is to extend the investigations to microbes originating from permafrost areas. To understand the influence of microbial activity in a permafrost environment on the methane hydrate formation process and the stability conditions of the resulting hydrate phase we will perform laboratory studies. Thereby, we mimic gas hydrate formation in the presence and absence of methanogenic archaea (e.g. Methanosarcina soligelidi) and other psychrophilic bacteria isolated from permafrost environments of the Arctic and Antarctic to investigate their impact on hydrate induction time and formation rates. Our results may contribute to understand and predict the occurrences and behaviour of potential gas hydrates within or adjacent to the permafrost. Lanoil BD, Sassen R, La Duc MT, Sweet ST, Nealson KH

  11. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  12. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence? Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  13. Complex gas hydrate from the Cascadia margin.

    PubMed

    Lu, Hailong; Seo, Yu-taek; Lee, Jong-won; Moudrakovski, Igor; Ripmeester, John A; Chapman, N Ross; Coffin, Richard B; Gardner, Graeme; Pohlman, John

    2007-01-18

    Natural gas hydrates are a potential source of energy and may play a role in climate change and geological hazards. Most natural gas hydrate appears to be in the form of 'structure I', with methane as the trapped guest molecule, although 'structure II' hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons. A third hydrate structure, 'structure H', which is capable of trapping larger guest molecules, has been produced in the laboratory, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure-temperature regime than can methane hydrate deposits. PMID:17230188

  14. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2003-08-05

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of ternary mixtures consisting of: Ni powder, Cu powder, and Al powder, Ni powder, Cr powder, and Al powder; Ni powder, W powder and Al powder; Ni powder, V powder, and Al powder; Ni powder, Mo powder, and Al powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  15. Comprehensive Study of Hydrated IDPs: X-Ray Diffraction, IR Spectroscopy and Electron Microscopic Analysis

    NASA Technical Reports Server (NTRS)

    Nakamura, K.; Keller, L. P.; Nakamura, T.; Noguchi, T.; Nozaki, W.; Tomeoka, K.

    2003-01-01

    Chondritic hydrated interplanetary dust particles (IDPs) comprise up to 50% of all IDPs collected in the stratosphere(1). Although much is known about the mineralogy, chemistry and carbon abundance of hydrated IDPs (2-4) controversies still exist regarding their formation, history, and relationship to other primitive solar system materials. Hydrated IDPs are generally believed to be derived from asteroidal sources that have undergone some degree of aqueous alteration. However, the high C contents of hydrated IDPs (by 2 to 6X CI levels (3,4) indicate that they are probably not derived from the same parent bodies sampled by the known chondritic meteorites. We report the comprehensive study of individual hydrated IDPs. The strong depletion in Ca (I) has been used as a diagnostic feature of hydrated IDPs. The particles are embedded in elemental sulfur or low viscosity epoxy and ultramicrotomed thin sections are observed using a transmission electron microscope (TEM) equipped with an energy-dispersive X-ray detector (EDX) followed by other measurements including: 1) FTIR microspectroscopy to understand the significant constraints on the organic functionality and the nature of the C-bearing phases and 2) powder X-ray difiaction using a synchrotron X-ray source to understand the bulk mineralogy of the particles.

  16. Active iron-rich belite sulfoaluminate cements: clinkering and hydration.

    PubMed

    Cuberos, Antonio J M; De la Torre, Angeles G; Alvarez-Pinazo, G; Martín-Sedeño, M Carmen; Schollbach, Katrin; Pöllmann, Herbert; Aranda, Miguel A G

    2010-09-01

    Ordinary Portland cement (OPC) is an environmentally contentious material, as for every ton of OPC produced, on average, 0.97 tons of CO2 are released. Conversely, belite sulfoaluminate (BSA) cements are promising eco-friendly building materials, as their production may deplete CO2 emissions up to 35% (compared to OPC). However, the hydration rate of belite is slow. Here, we report the clinkering of iron-rich BSA materials, their activation with B2O3, and establishing a methodology to measure their improved reactivities. Nonactivated BSA clinker contained only beta belite phase, 52 wt %. Meanwhile, BSA clinkers activated with 1 and 2 wt % of B2O3 contained 28 wt % of beta and 25 wt % of alpha'H; and 54 wt % of alpha'H phase, respectively. Therefore, activation of BSA has been proved as alpha'H-belite is stabilized. The hydration of the cements has been studied by laboratory and synchrotron X-ray powder diffraction (using Rietveld method and chemical constraints), calorimetry, and environmental scanning electron microscopy. Cement pastes have different hydration rates. For nonactivated BSA cement, 20 and 48% of the belite reacted after one and three months, respectively. Conversely, 37-49% after one month and 52-62% after three months of overall belite reactivities have been measured for BSA cements activated with B2O3. PMID:20701316

  17. Formation and Transformation Behavior of Sodium Dehydroacetate Hydrates.

    PubMed

    Zhang, Xia; Xie, Chuang; Huang, Yaohui; Hou, Baohong; Bao, Ying; Gong, Junbo; Yin, Qiuxiang; Rohani, Sohrab

    2016-01-01

    The effect of various controlling factors on the polymorphic outcome of sodium dehydroacetate crystallization was investigated in this study. Cooling crystallization experiments of sodium dehydroacetate in water were conducted at different concentrations. The results revealed that the rate of supersaturation generation played a key role in the formation of the hydrates. At a high supersaturation generation rate, a new sodium dehydroacetate dihydrate needle form was obtained; on the contrary, a sodium dehydroacetate plate monohydrate was formed at a low supersaturation generation rate. Furthermore, the characterization and transformation behavior of these two hydrated forms were investigated with the combined use of microscopy, powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and dynamic vapor sorption (DVS). It was found that the new needle crystals were dihydrated and hollow, and they eventually transformed into sodium dehydroacetate monohydrate. In addition, the mechanism of formation of sodium dehydroacetate hydrates was discussed, and a process growth model of hollow crystals in cooling crystallization was proposed. PMID:27058518

  18. Integrating Natural Gas Hydrates in the Global Carbon Cycle

    SciTech Connect

    David Archer; Bruce Buffett

    2011-12-31

    We produced a two-dimensional geological time- and basin-scale model of the sedimentary margin in passive and active settings, for the simulation of the deep sedimentary methane cycle including hydrate formation. Simulation of geochemical data required development of parameterizations for bubble transport in the sediment column, and for the impact of the heterogeneity in the sediment pore fluid flow field, which represent new directions in modeling methane hydrates. The model is somewhat less sensitive to changes in ocean temperature than our previous 1-D model, due to the different methane transport mechanisms in the two codes (pore fluid flow vs. bubble migration). The model is very sensitive to reasonable changes in organic carbon deposition through geologic time, and to details of how the bubbles migrate, in particular how efficiently they are trapped as they rise through undersaturated or oxidizing chemical conditions and the hydrate stability zone. The active margin configuration reproduces the elevated hydrate saturations observed in accretionary wedges such as the Cascadia Margin, but predicts a decrease in the methane inventory per meter of coastline relative to a comparable passive margin case, and a decrease in the hydrate inventory with an increase in the plate subduction rate.

  19. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

    Many efforts have been devoted to quantify excess pore pressures related to gas hydrate dissociation in marine sediments below the BSR using several approaches. Dissociation of gas hydrates in proximity of the BSR, in response to a change in the physical environment (i.e., temperature and/or pressure regime), can liberate excess gas incrising the local pore fluid pressure in the sediment, so decreasing the effective normal stress. So, gas hydrate dissociation may lead to excess pore pressure resulting in sediment deformation or failure, such as submarine landslides, sediment slumping, pockmarks and mud volcanoes, soft-sediment deformation and giant hummocks. Moreover, excess pore pressure may be the result of gas hydrate dissociation due to continuous sedimentation, tectonic uplift, sea level fall, heating or inhibitor injection. In order to detect the presence of the overpressure below the BSR, we propose two approachs. The fist approach models the BSR depth versus pore pressure; in fact, if the free gas below the BSR is in overpressure condition, the base of the gas hydrate stability is deeper with respect to the hydrostatic case. This effect causes a discrepancy between seismic and theoretical BSR depths. The second approach models the velocities versus gas hydrate and free gas concentrations and pore pressure, considering the approximation of the Biot theory in case of low frequency, i.e. seismic frequency. Knowing the P and S seismic velocity from seismic data analysis, it is possibile to jointly estimate the gas hydrate and free gas concentrations and the pore pressure regime. Alternatively, if the S-wave velocity is not availbale (due to lack of OBS/OBC data), an AVO analysis can be performed in order to extract information about Poisson ratio. Our modeling suggests that the areas characterized by shallow waters (i.e., areas in which human infrastructures, such as pipelines, are present) are significantly affected by the presence of overpressure condition

  20. Natural Gas Hydrates Update 1998-2000

    EIA Publications

    2001-01-01

    Significant events have transpired on the natural gas hydrate research and development front since "Future Supply Potential of Natural Gas Hydrates" appeared in Natural Gas 1998 Issues and Trends and in the Potential Gas Committee's 1998 biennial report.

  1. Compact apparatus for photogeneration of hydrated electrons

    NASA Technical Reports Server (NTRS)

    Hart, E.; Schmidt, K.

    1970-01-01

    Flash-photolysis instrument generates hydrated electrons and studies their reactions. It has a three-dimensional, multiple-reaction cell and the capacity to produce up to .1 micromole hydrated electron in a single 40 microsec light pulse.

  2. Permafrost-associated natural gas hydrate occurrences on the Alaska North Slope

    USGS Publications Warehouse

    Collett, T.S.; Lee, M.W.; Agena, W.F.; Miller, J.J.; Lewis, K.A.; Zyrianova, M.V.; Boswell, R.; Inks, T.L.

    2011-01-01

    In the 1960s Russian scientists made what was then a bold assertion that gas hydrates should occur in abundance in nature. Since this early start, the scientific foundation has been built for the realization that gas hydrates are a global phenomenon, occurring in permafrost regions of the arctic and in deep water portions of most continental margins worldwide. In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually become a producible energy resource, yet technical and economic hurdles have historically made gas hydrate development a distant goal. This view began to change in recent years with the realization that this unconventional resource could be developed with existing conventional oil and gas production technology. One of the most significant developments was the completion of the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope, which along with the Mallik project in Canada, have for the first time allowed the rational assessment of gas hydrate production technology and concepts. Almost 40 years of gas hydrate research in northern Alaska has confirmed the occurrence of at least two large gas hydrate accumulations on the North Slope. We have also seen in Alaska the first ever assessment of how much gas could be technically recovered from gas hydrates. However, significant technical concerns need to be further resolved in order to assess the ultimate impact of gas hydrate energy resource development in northern Alaska. ?? 2009 Elsevier Ltd.

  3. Methods to determine hydration states of minerals and cement hydrates

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  4. High-pressure dynamics of hydrated protein in bioprotective trehalose environment

    DOE PAGESBeta

    Diallo, S. O.; Zhang, Q.; O'Neill, H.; Mamontov, E.

    2014-10-30

    Here we present a pressure-dependence study of the dynamics of lysozyme protein powder immersed in deuterated , α-trehalose environment via quasielastic neutron scattering (QENS). The goal is to assess the baroprotective benefits of trehalose on biomolecules by comparing the findings with those of a trehalose-free reference study. While the mean-square displacement of the trehalose-free protein (hydrated to dD₂O ≃40 w%) as a whole, is reduced by increasing pressure, the actual observable relaxation dynamics in the picoseconds to nanoseconds time range remains largely unaffected by pressure up to the maximum investigated pressure of 2.78(2) Kbar. Our observation is independent of whethermore » or not the protein is mixed with the deuterated sugar. This suggests that the hydrated protein s conformational states at atmospheric pressure remain unaltered by hydrostatic pressures, below 2.78 Kbar. We also found the QENS response to be totally recoverable after ambient pressure conditions are restored. Small-angle neutron diffraction measurements confirm that the protein-protein correlation remains undisturbed.We observe, however, a clear narrowing of the QENS response as the temperature is decreased from 290 to 230 K in both cases, which we parametrize using the Kohlrausch-Williams-Watts stretched exponential model. Finally, only the fraction of protons that are immobile on the accessible time window of the instrument, referred to as the elastic incoherent structure factor, is observably sensitive to pressure, increasing only marginally but systematically with increasing pressure.« less

  5. Water of Hydration Dynamics in Minerals Gypsum and Bassanite: Ultrafast 2D IR Spectroscopy of Rocks.

    PubMed

    Yan, Chang; Nishida, Jun; Yuan, Rongfeng; Fayer, Michael D

    2016-08-01

    Water of hydration plays an important role in minerals, determining their crystal structures and physical properties. Here ultrafast nonlinear infrared (IR) techniques, two-dimensional infrared (2D IR) and polarization selective pump-probe (PSPP) spectroscopies, were used to measure the dynamics and disorder of water of hydration in two minerals, gypsum (CaSO4·2H2O) and bassanite (CaSO4·0.5H2O). 2D IR spectra revealed that water arrangement in freshly precipitated gypsum contained a small amount of inhomogeneity. Following annealing at 348 K, water molecules became highly ordered; the 2D IR spectrum became homogeneously broadened (motional narrowed). PSPP measurements observed only inertial orientational relaxation. In contrast, water in bassanite's tubular channels is dynamically disordered. 2D IR spectra showed a significant amount of inhomogeneous broadening caused by a range of water configurations. At 298 K, water dynamics cause spectral diffusion that sampled a portion of the inhomogeneous line width on the time scale of ∼30 ps, while the rest of inhomogeneity is static on the time scale of the measurements. At higher temperature, the dynamics become faster. Spectral diffusion accelerates, and a portion of the lower temperature spectral diffusion became motionally narrowed. At sufficiently high temperature, all of the dynamics that produced spectral diffusion at lower temperatures became motionally narrowed, and only homogeneous broadening and static inhomogeneity were observed. Water angular motions in bassanite exhibit temperature-dependent diffusive orientational relaxation in a restricted cone of angles. The experiments were made possible by eliminating the vast amount of scattered light produced by the granulated powder samples using phase cycling methods. PMID:27385320

  6. Detection of gas hydrate with downhole logs and assessment of gas hydrate concentrations (saturations) and gas volumes on the Blake Ridge with electrical resistivity log data

    USGS Publications Warehouse

    Collett, T.S.; Ladd, J.

    2000-01-01

    Let 164 of the Ocean Drilling Program was designed to investigate the occurrence of gas hydrate in the sedimentary section beneath the Blake Ridge on the southeastern continental margin of North America. Site 994, and 997 were drilled on the Blake Ridge to refine our understanding of the in situ characteristics of natural gas hydrate. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas hydrate-bearing sediments. Downhole logging tool strings deployed on Leg 164 included the Schlumberger quad-combination tool (NGT, LSS/SDT, DIT, CNT-G, HLDT), the Formation MicroScanner (FMS), and the Geochemical Combination Tool (GST). Electrical resistivity (DIT) and acoustic transit-time (LSS/SDT) downhole logs from Sites 994, 995, and 997 indicate the presence of gas hydrate in the depth interval between 185 and 450 mbsf on the Blake Ridge. Electrical resistivity log calculations suggest that the gas hydrate-bearing sedimentary section on the Blake Ridge may contain between 2 and 11 percent bulk volume (vol%) gas hydrate. We have determined that the log-inferred gas hydrates and underlying free-gas accumulations on the Blake Ridge may contain as much as 57 trillion m3 of gas.

  7. Collective dynamics of hydrated β-lactoglobulin by inelastic x-ray scattering.

    PubMed

    Yoshida, Koji; Hosokawa, Shinya; Baron, Alfred Q R; Yamaguchi, Toshio

    2010-10-01

    Inelastic x-ray scattering measurements of hydrated β-lactoglobulin (β-lg) were performed to investigate the collective dynamics of hydration water and hydrated protein on a picosecond time scale. Samples with different hydration levels h [=mass of water (g)/mass of protein (g)] of 0 (dry), 0.5, and 1.0 were measured at ambient temperature. The observed dynamical structure factor S(Q,ω)/S(Q) was analyzed by a model composed of a Lorentzian for the central peak and a damped harmonic oscillator (DHO) for the side peak. The dispersion relation between the excitation energy in the DHO model and the momentum transfer Q was obtained for the hydrated β-lg at both hydration levels, but no DHO excitation was found for the dry β-lg. The high-frequency sound velocity was similar to that previously observed in pure water. The ratio of the high-frequency sound velocity of hydrated β-lg to the adiabatic one of hydrated lysozyme (h=0.41) was estimated as ∼1.6 for h=0.5. The value is significantly smaller than that (∼2) of pure water that has the tetrahedral network structure. The present finding thus suggests that the tetrahedral network structure of water around the β-lg is partially disrupted by the perturbation from protein surface. These results are consistent with those reported from Brillouin neutron spectroscopy and molecular dynamics simulation studies of hydrated ribonuclease A. PMID:20942540

  8. High-Altitude Hydration System

    NASA Technical Reports Server (NTRS)

    Parazynski, Scott E.; Orndoff, Evelyne; Bue, Grant C.; Schaefbauer, Mark E.; Urban, Kase

    2010-01-01

    Three methods are being developed for keeping water from freezing during high-altitude climbs so that mountaineers can remain hydrated. Three strategies have been developed. At the time of this reporting two needed to be tested in the field and one was conceptual. The first method is Passive Thermal Control Using Aerogels. This involves mounting the fluid reservoir of the climber s canteen to an inner layer of clothing for better heat retention. For the field test, bottles were mounted to the inner fleece layer of clothing, and then aerogel insulation was placed on the outside of the bottle, and circumferentially around the drink straw. When climbers need to drink, they can pull up the insulated straw from underneath the down suit, take a sip, and then put it back into the relative warmth of the suit. For the field test, a data logger assessed the temperatures of the water reservoir, as well as near the tip of the drink straw. The second method is Passive Thermal Control with Copper-Shielded Drink Straw and Aerogels, also mounted to inner layers of clothing for better heat retention. Braided wire emanates from the inside of the fleece jacket layer, and continues up and around the drink straw in order to use body heat to keep the system-critical drink straw warm enough to keep water in the liquid state. For the field test, a data logger will be used to compare this with the above concept. The third, and still conceptual, method is Active Thermal Control with Microcontroller. If the above methods do not work, microcontrollers and tape heaters have been identified that could keep the drink straw warm even under extremely cold conditions. Power requirements are not yet determined because the thermal environment inside the down suit relative to the external environment has not been established. A data logger will be used to track both the external and internal temperatures of the suit on a summit day.

  9. 77 FR 40032 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice... Federal Officer; Welcome by the Chair of the Committee; Committee Business; Update on Prudhoe Bay Testing; FY 2012 Methane Hydrate Program Activities; Update on International Activity; Methane Hydrate...

  10. 76 FR 59667 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

    ... Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of Open Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

  11. 78 FR 37536 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-21

    ... Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  12. CO2 hydrate formation and dissociation in cooled porous media: a potential technology for CO2 capture and storage.

    PubMed

    Yang, Mingjun; Song, Yongchen; Jiang, Lanlan; Zhu, Ningjun; Liu, Yu; Zhao, Yuechao; Dou, Binlin; Li, Qingping

    2013-09-01

    The purpose of this study was to investigate the hydrate formation and dissociation with CO2 flowing through cooled porous media at different flow rates, pressures, temperatures, and flow directions. CO2 hydrate saturation was quantified using the mean intensity of water. The experimental results showed that the hydrate block appeared frequently, and it could be avoided by stopping CO2 flooding early. Hydrate formed rapidly as the temperature was set to 274.15 or 275.15 K, but the hydrate formation delayed when it was 276.15 K. The flow rate was an important parameter for hydrate formation; a too high or too low rate was not suitable for CO2 hydration formation. A low operating pressure was also unacceptable. The gravity made hydrate form easily in the vertically upward flow direction. The pore water of the second cycle converted to hydrate more completely than that of the first cycle, which was a proof of the hydrate "memory effect". When the pressure was equal to atmospheric pressure, hydrate did not dissociate rapidly and abundantly, and a long time or reduplicate depressurization should be used in industrial application. PMID:23915205

  13. Improved Small-Particle Powders for Plasma Spraying

    NASA Technical Reports Server (NTRS)

    Nguyen, QuynhGiao, N.; Miller, Robert A.; Leissler, George W.

    2005-01-01

    Improved small-particle powders and powder-processing conditions have been developed for use in plasma spray deposition of thermal-barrier and environmental barrier coatings. Heretofore, plasma-sprayed coatings have typically ranged in thickness from 125 to 1,800 micrometers. As explained below, the improved powders make it possible to ensure complete coverage of substrates at unprecedently small thicknesses of the order of 25 micrometers. Plasma spraying involves feeding a powder into a hot, high-velocity plasma jet. The individual powder particles melt in the plasma jet as they are propelled towards a substrate, upon which they splat to build up a coating. In some cases, multiple coating layers are required. The size range of the powder particles necessarily dictates the minimum thickness of a coating layer needed to obtain uniform or complete coverage. Heretofore, powder particle sizes have typically ranged from 40 to 70 micrometers; as a result, the minimum thickness of a coating layer for complete coverage has been about 75 micrometers. In some applications, thinner coatings or thinner coating layers are desirable. In principle, one can reduce the minimum complete-coverage thickness of a layer by using smaller powder particles. However, until now, when powder particle sizes have been reduced, the powders have exhibited a tendency to cake, clogging powder feeder mechanisms and feed lines. Hence, the main problem is one of synthesizing smaller-particle powders having desirable flow properties. The problem is solved by use of a process that begins with a spray-drying subprocess to produce spherical powder particles having diameters of less than 30 micrometers. (Spherical-particle powders have the best flow properties.) The powder is then passed several times through a commercial sifter with a mesh to separate particles having diameters less than 15 micrometers. The resulting fine, flowable powder is passed through a commercial fluidized bed powder feeder into a

  14. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago. PMID:17768978

  15. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  16. Attraction between hydrated hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.

    2014-08-01

    According to common knowledge, hydrophilic surfaces repel via hydration forces while hydrophobic surfaces attract, but mounting experimental evidence suggests that also hydrophilic surfaces can attract. Using all-atom molecular dynamics simulations at prescribed water chemical potential we study the crossover from hydration repulsion to hydrophobic attraction for planar polar surfaces of varying stiffness and hydrogen-bonding capability. Rescaling the partial charges of the polar surface groups, we cover the complete spectrum from very hydrophobic surfaces (characterized by contact angles θ ≃ 135°) to hydrophilic surfaces exhibiting complete wetting (θ = 0°). Indeed, for a finite range θadh < θ < 90°, we find a regime where hydrophilic surfaces attract at sub-nanometer separation and stably adhere without intervening water. The adhesive contact angle θadh depends on surface type and lies in the range 65° < θadh < 80°, in good agreement with experiments. Analysis of the total number of hydrogen bonds (HBs) formed by water and surface groups rationalizes this crossover between hydration repulsion and hydrophilic attraction in terms of a subtle balance: Highly polar surfaces repel because of strongly bound hydration water, less polar hydrophilic surfaces attract because water-water HBs are preferred over surface-water HBs. Such solvent reorganization forces presumably underlie also other important phenomena, such as selective ion adsorption to interfaces as well as ion pair formation.

  17. Neutron scattering studies of the hydration structure of Li+.

    PubMed

    Mason, P E; Ansell, S; Neilson, G W; Rempe, S B

    2015-02-01

    New results derived from the experimental method of neutron diffraction and isotopic substitution (NDIS) are presented for the hydration structure of the lithium cation (Li(+)) in aqueous solutions of lithium chloride in heavy water (D2O) at concentrations of 6, 3, and 1 m and at 1.5 m lithium sulfate. By introducing new and more-accurate data reduction procedures than in our earlier studies (I. Howell and G. W. Neilson, J. Phys: Condens. Matter, 1996, 8, 4455-4463), we find, in the first hydration shell of Li(+), ∼4.3(2) water molecules at 6 m, 4.9(3) at 3 m, 4.8(3) at 1 m in the LiCl solutions, and 5.0(3) water molecules in the case of Li2SO4 solution. The general form of the first hydration shell is similar in all four solutions, with the correlations for Li-O and Li-D sited at 1.96 (0.02) Å and 2.58 (0.02) Å, respectively. The results resemble those presented in 1996, in terms of ion-water distances and local coordination, but the hydration number is significantly lower for the case at 1 m than the 6.5 (1.0) given at that time. Thus, experimental and theoretical results now agree that lithium is hydrated by a small number of water molecules (4-5) in the nearest coordination shell. PMID:25559086

  18. Changes in the solid state of anhydrous and hydrated forms of sodium naproxen under different grinding and environmental conditions: Evidence of the formation of new hydrated forms.

    PubMed

    Censi, Roberta; Rascioni, Riccardo; Di Martino, Piera

    2015-05-01

    The aim of the present work was to investigate the solid state change of the anhydrous and hydrate solid forms of sodium naproxen under different grinding and environmental conditions. Grinding was carried out manually in a mortar under the following conditions: at room temperature under air atmosphere (Method A), in the presence of liquid nitrogen under air atmosphere (Method B), at room temperature under nitrogen atmosphere (Method C), and in the presence of liquid nitrogen under nitrogen atmosphere (Method D). Among the hydrates, the following forms were used: a dihydrate form (DSN) obtained by exposing the anhydrous form at 55% RH; a dihydrate form (CSN) obtained by crystallizing sodium naproxen from water; the tetrahydrate form (TSN) obtained by exposing the anhydrous form at 75% RH. The metastable monohydrate form (MSN), previously described in the literature, was not used because of its high physical instability. The chemical stability during grinding was firstly assessed and proven by HPLC. Modification of the particle size and shape, and changes in the solid state under different grinding methods were evaluated by scanning electron microscopy, and X-ray powder diffractometry and thermogravimetry, respectively. The study demonstrated the strong influence of starting form, grinding and environmental conditions on particle size, shape and solid state of recovered sodium naproxen forms. In particular, it was demonstrated that in the absence of liquid nitrogen (Methods A and C), either at air or at nitrogen atmosphere, the monohydrate form (MSN) was obtained from any hydrates, meaning that these grinding conditions favored the dehydration of superior hydrates. The grinding process carried out in the presence of liquid nitrogen (Method B) led to further hydration of the starting materials: new hydrate forms were identified as one pentahydrate form and one hexahydrate form. The hydration was caused by the condensation of the atmospheric water on sodium naproxen

  19. Physical activity, hydration and health.

    PubMed

    Marcos, Ascensión; Manonelles, Pedro; Palacios, Nieves; Wärnberg, Julia; Casajús, José A; Pérez, Margarita; Aznar, Susana; Benito, Pedro J; Martínez-Gomez, David; Ortega, Francisco B; Ortega, Eduardo; Urrialde, Rafael

    2014-01-01

    Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory disea ses and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences. PMID:24972459

  20. Mesoscale texture of cement hydrates.

    PubMed

    Ioannidou, Katerina; Krakowiak, Konrad J; Bauchy, Mathieu; Hoover, Christian G; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J-M; Del Gado, Emanuela

    2016-02-23

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium-silicate-hydrates (C-S-H) during cement hydration. Controlling structure and properties of the C-S-H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C-S-H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C-S-H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C-S-H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C-S-H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  1. Mesoscale texture of cement hydrates

    PubMed Central

    Ioannidou, Katerina; Krakowiak, Konrad J.; Bauchy, Mathieu; Hoover, Christian G.; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J.-M.; Del Gado, Emanuela

    2016-01-01

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  2. Compaction of Titanium Powders

    SciTech Connect

    Stephen J. Gerdemann; Paul D. Jablonski

    2010-11-01

    Accurate modeling of powder densification has been an area of active research for more than 60 years. The earliest efforts were focused on linearization of the data because computers were not readily available to assist with curve-fitting methods. In this work, eight different titanium powders (three different sizes of sponge fines <150 μm, <75 μm, and < 45 μm; two different sizes of a hydride-dehydride [HDH] <75 μm and < 45 μm; an atomized powder; a commercially pure [CP] Ti powder from International Titanium Powder [ITP]; and a Ti 6 4 alloy powder) were cold pressed in a single-acting die instrumented to collect stress and deformation data during compaction. From these data, the density of each compact was calculated and then plotted as a function of pressure. The results show that densification of all the powders, regardless of particle size, shape, or chemistry, can be modeled accurately as the sum of an initial density plus the sum of a rearrangement term and a work-hardening term. These last two terms are found to be a function of applied pressure and take the form of an exponential rise.

  3. Synthesis of nanocrystalline tungsten carbide (WC) powder

    NASA Astrophysics Data System (ADS)

    Singla, Gourav; Singh, K.; Pandey, O. P.

    2013-06-01

    Nanocrystalline tungsten carbide (WC) has been obtained from bulk WO3 by in situ reduction and carbonization reactions at low temperature (˜ 600 °C) by taking Mg as reductant and acetone C3H6O as carbon source. It was aimed to elucidate carburization behavior of WO3 powder and to establish optimal conditions for the synthesis of nanocrystalline WC. The role of reaction time on the synthesis of WC has been investigated and discussed. The synthesized powders were characterized by X-ray powder diffraction, differential thermal analyzer (DTA), thermo gravimetric analysis (TGA).

  4. Dynamical interaction between protein molecules and their hydration shell

    NASA Astrophysics Data System (ADS)

    Parak, Fritz G.

    2013-10-01

    The hydration shell of a protein molecule influences its functional important dynamics while the protein molecule influences the hydration shell. Neutron scattering experiments have been used to separate both effects. Neutron crystallography is used to determine the positions and the mean square displacements, , of the protons in met-myoglobin. Mean square displacements obtained by incoherent neutron scattering stem from motions occurring on a time scale faster than 100 ps. The combination of the two experimental results allows to separate three types of protein protons. The -values of lysine protons stem from motions faster than 100 ps. Half of the -values of methyl protons is caused by motions faster than 100 ps, the other halve comes from slower motions. The backbone protons move slower than 100 ps. Incoherent neutron scattering on a perdeuterated myoglobin with a 1H2O hydration shell allowed the study of the diffusion in this shell.

  5. Ceramic powder compaction

    SciTech Connect

    Glass, S.J.; Ewsuk, K.G.; Mahoney, F.M.

    1995-12-31

    With the objective of developing a predictive model for ceramic powder compaction we have investigated methods for characterizing density gradients in ceramic powder compacts, reviewed and compared existing compaction models, conducted compaction experiments on a spray dried alumina powder, and conducted mechanical tests and compaction experiments on model granular materials. Die filling and particle packing, and the behavior of individual granules play an important role in determining compaction behavior and should be incorporated into realistic compaction models. These results support the use of discrete element modeling techniques and statistical mechanics principals to develop a comprehensive model for compaction, something that should be achievable with computers with parallel processing capabilities.

  6. Handbook of gas hydrate properties and occurrence

    SciTech Connect

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  7. Monte-Carlo sorption and neutron diffraction study of the filling isotherm in clathrate hydrates

    SciTech Connect

    Klapproth, Alice; Kuhs, Werner F.; Chazallon, Bertrand

    1999-06-15

    We are interested in the thermodynamics of the gas filling of clathrate hydrates. In order to determine the pressure-dependent filling of the cages, neutron powder diffraction experiments on N{sub 2} and CO{sub 2} clathrates were performed. Interaction potentials were refined by comparing the experimentally determined fillings with those generated by MC-sorption calculations. Unsatisfactory agreement between experiment and simulation is observed when using the widely employed SPC water-water interaction potential.

  8. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    DOE PAGESBeta

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-05-21

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions.more » We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.« less

  9. Production of hydrocarbons from hydrates. [DOE patent application

    DOEpatents

    McGuire, P.L.

    1981-09-08

    An economical and safe method of producing hydrocarbons (or natural gas) from in situ hydrocarbon-containing hydrates is given. Once started, the method will be self-driven and will continue producing hydrocarbons over an extended period of time (i.e., many days).

  10. Obsidian hydration profile measurements using a nuclear reaction technique

    USGS Publications Warehouse

    Lee, R.R.; Leich, D.A.; Tombrello, T.A.; Ericson, J.E.; Friedman, I.

    1974-01-01

    AMBIENT water diffuses into the exposed surfaces of obsidian, forming a hydration layer which increases in thickness with time to a maximum depth of 20-40 ??m (ref. 1), this layer being the basic foundation of obsidian dating2,3. ?? 1974 Nature Publishing Group.

  11. Norwegian Research Strategies on gas Hydrates and Natural Seeps in the Nordic Seas Region (GANS)

    NASA Astrophysics Data System (ADS)

    Hjelstuen, B. O.; Sejrup, H. P.; Andreassen, K.; Boe, R.; Eldholm, O.; Hovland, M.; Knies, J.; Kvalstad, T.; Kvamme, B.; Mienert, J.; Pedersen, R. B.

    2004-12-01

    Continuous leakage of methane to the oceans from hydrate reservoirs that partially are exposed towards the seafloor is an increasing international concern, as the greenhouse gas methane is significantly more (c. 20 times) aggressive than CO2. In Norway we have research groups with interest and experience on natural seeps and gas hydrates. These features, and processes related to them, are challenging research targets which demands inputs from different fields if important research breakthroughs shall be made. In February 2004 deep sea researchers from the University of Tromso, Geological Survey of Norway, Norwegian Geotechnical Institute, Statoil and University of Bergen met to obtain an overview of the research effort in the fields of natural seeps and gas hydrates in Norway and to discuss national coordination, research strategies, research infrastructure and international co-operation. The following research strategies were agreed upon: i) Strengthen multidisciplinary research on deep sea systems, ii) develop a strategy for research on natural seeps and gas hydrates, iii) contribute in national coordination of research on natural seeps and gas hydrates, iv) Coordinate the use and development of research infrastructures important for research on natural seeps and gas hydrates, and v) contribute in the international evaluations of strategies for hydrate reservoir exploitation. Proposed research tasks for GANS include: i) Gas and gas hydrate formation processes and conditions for transport, accumulation, preservation and dissociation in sediments, ii) Effect of gas hydrate on physical properties of sediment, iii) Detection and quantification of in situ gas hydrate content and distribution pattern, iv) Effect of dissociation on soil properties, v) Gas hydrates as an energy resource, vi) Rapid methane release and climate change, and vii) Geohazard and environmental impact.

  12. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces. Copyright 2009 by the American Geophysical Union.

  13. Sintering of sponge and hydride-dehydride titanium powders

    SciTech Connect

    Alman, David E.; Gerdemann, Stephen J.

    2004-04-01

    The sintering behavior of compacts produced from sponge and hydride-dehydride (HDH) Ti powders was examined. Compacts were vacuum sintered at 1200 or 1300 deg C for 30, 60, 120, 240, 480 or 960 minutes. The porosity decreased with sintering time and/or temperature in compacts produced from the HDH powders. Compacts produced from these powders could be sintered to essentially full density. However, the sintering condition did not influence the amount of porosity present in compacts produced from the sponge powders. These samples could only be sintered to a density of 97% theoretical. The sintering behavior was attributed to the chemical impurities in the powders.

  14. Modeling pure methane hydrate dissociation using a numerical simulator from a novel combination of X-ray computed tomography and macroscopic data

    SciTech Connect

    Gupta, A.; Moridis, G.J.; Kneafsey, T.J.; Sloan, Jr., E.D.

    2009-08-15

    The numerical simulator TOUGH+HYDRATE (T+H) was used to predict the transient pure methane hydrate (no sediment) dissociation data. X-ray computed tomography (CT) was used to visualize the methane hydrate formation and dissociation processes. A methane hydrate sample was formed from granular ice in a cylindrical vessel, and slow depressurization combined with thermal stimulation was applied to dissociate the hydrate sample. CT images showed that the water produced from the hydrate dissociation accumulated at the bottom of the vessel and increased the hydrate dissociation rate there. CT images were obtained during hydrate dissociation to confirm the radial dissociation of the hydrate sample. This radial dissociation process has implications for dissociation of hydrates in pipelines, suggesting lower dissociation times than for longitudinal dissociation. These observations were also confirmed by the numerical simulator predictions, which were in good agreement with the measured thermal data during hydrate dissociation. System pressure and sample temperature measured at the sample center followed the CH{sub 4} hydrate L{sub w}+H+V equilibrium line during hydrate dissociation. The predicted cumulative methane gas production was within 5% of the measured data. Thus, this study validated our simulation approach and assumptions, which include stationary pure methane hydrate-skeleton, equilibrium hydrate-dissociation and heat- and mass-transfer in predicting hydrate dissociation in the absence of sediments. It should be noted that the application of T+H for the pure methane hydrate system (no sediment) is outside the general applicability limits of T+H.

  15. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions

    NASA Astrophysics Data System (ADS)

    Moudrakovski, Igor L.; Udachin, Konstantin A.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

    2015-02-01

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO2 and isobutane-CO2, that are predicted to enhance or to diminish guest-host hydrogen bonding interactions as compared to those in pure CO2 hydrate and we have studied guest dynamics in each using 13C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO2 sII hydrate using the combined single crystal X-ray diffraction and 13C NMR powder pattern data and have performed molecular dynamics-simulation of the CO2 dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO2 hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO2 molecules in the THF-CO2 hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A-host water-guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 106 than a published calculated value.

  16. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions

    SciTech Connect

    Moudrakovski, Igor L.; Udachin, Konstantin A.; Ratcliffe, Christopher I.; Alavi, Saman; Ripmeester, John A.

    2015-02-21

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO{sub 2} and isobutane-CO{sub 2}, that are predicted to enhance or to diminish guest–host hydrogen bonding interactions as compared to those in pure CO{sub 2} hydrate and we have studied guest dynamics in each using {sup 13}C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO{sub 2} sII hydrate using the combined single crystal X-ray diffraction and {sup 13}C NMR powder pattern data and have performed molecular dynamics-simulation of the CO{sub 2} dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO{sub 2} hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO{sub 2} molecules in the THF-CO{sub 2} hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A–host water–guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 10

  17. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions.

    PubMed

    Moudrakovski, Igor L; Udachin, Konstantin A; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

    2015-02-21

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO2 and isobutane-CO2, that are predicted to enhance or to diminish guest-host hydrogen bonding interactions as compared to those in pure CO2 hydrate and we have studied guest dynamics in each using (13)C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO2 sII hydrate using the combined single crystal X-ray diffraction and (13)C NMR powder pattern data and have performed molecular dynamics-simulation of the CO2 dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO2 hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO2 molecules in the THF-CO2 hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A-host water-guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 10(6) than a published calculated value. PMID:25702022

  18. The effect of hydrate saturation on water retention curves in hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Mahabadi, Nariman; Zheng, Xianglei; Jang, Jaewon

    2016-05-01

    The experimental measurement of water retention curve in hydrate-bearing sediments is critically important to understand the behavior of hydrate dissociation and gas production. In this study, tetrahydrofuran (THF) is selected as hydrate former. The pore habit of THF hydrates is investigated by visual observation in a transparent micromodel. It is confirmed that THF hydrates are not wetting phase on the quartz surface of the micromodel and occupy either an entire pore or part of pore space resulting in change in pore size distribution. And the measurement of water retention curves in THF hydrate-bearing sediments with hydrate saturation ranging from Sh = 0 to Sh = 0.7 is conducted for excess water condition. The experimental results show that the gas entry pressure and the capillary pressure increase with increasing hydrate saturation. Based on the experimental results, fitting parameters for van Genuchten equation are suggested for different hydrate saturation conditions.

  19. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunelé, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  20. Gelcasting superalloy powders

    SciTech Connect

    Janney, M.A.

    1995-12-31

    Gelcasting is a process for forming inorganic powders into complex shapes. It was originally developed for ceramic powders. A slurry of powder and a monomer solution is poured in to mold and polymerized in-situ to form gelled parts. Typically, only 2-4 wt % Polymer is used. The process has both aqueous and nonaqueous versions. Gelcasting is a generic process and has been used to produce ceramic parts from over a dozen different ceramic compositions ranging from alumina-based refractories to high-performance silicon nitride. Recently, gelcasting has been applied to forming superalloy powders into complex shapes. This application has posed several challenges not previously encountered in ceramics. In particular, problems were caused by the larger particle size and the higher density of the particles. Additional problems were encountered with binder removal. How these problems were overcome will be described.

  1. Magnetically responsive enzyme powders

    NASA Astrophysics Data System (ADS)

    Pospiskova, Kristyna; Safarik, Ivo

    2015-04-01

    Powdered enzymes were transformed into their insoluble magnetic derivatives retaining their catalytic activity. Enzyme powders (e.g., trypsin and lipase) were suspended in various liquid media not allowing their solubilization (e.g., saturated ammonium sulfate and highly concentrated polyethylene glycol solutions, ethanol, methanol, 2-propanol) and subsequently cross-linked with glutaraldehyde. Magnetic modification was successfully performed at low temperature in a freezer (-20 °C) using magnetic iron oxides nano- and microparticles prepared by microwave-assisted synthesis from ferrous sulfate. Magnetized cross-linked enzyme powders were stable at least for two months in water suspension without leakage of fixed magnetic particles. Operational stability of magnetically responsive enzymes during eight repeated reaction cycles was generally without loss of enzyme activity. Separation of magnetically modified cross-linked powdered enzymes from reaction mixtures was significantly simplified due to their magnetic properties.

  2. POWDER COAT APPLICATIONS

    EPA Science Inventory

    The report discusses an investigation of critical factors that affect the use of powder coatings on the environment, cost, quality, and production. The investigation involved a small business representative working with the National Defense Center for Environmental Excellence (ND...

  3. Pyrotechnic filled molding powder

    DOEpatents

    Hartzel, Lawrence W.; Kettling, George E.

    1978-01-01

    The disclosure relates to thermosetting molding compounds and more particularly to a pyrotechnic filled thermosetting compound comprising a blend of unfilled diallyl phthalate molding powder and a pyrotechnic mixture.

  4. Talcum powder poisoning

    MedlinePlus

    ... powder As a filler in street drugs, like heroin Other products may also contain talc. ... have developed serious lung damage and cancer. Injecting heroin that contains talc into a vein may lead ...

  5. The peculiarities of relict gas hydrate forms existence within permafrost layers

    NASA Astrophysics Data System (ADS)

    Chuvilin, E.

    2005-12-01

    It's well known that permafrost zone of the Earth is favorable for formation and existence of such ice-like compounds as gas (mainly methane) hydrates. Currently methane hydrate accumulations have identified either by direct evidences (hydrate-containing core sample) or indirect evidences in various permafrost regions of the world (Arctic coast of Canada, Alaska, the North of Siberia etc.). The special interest excites the fact that gas hydrate-shows (indirect evidences) are documented for shallow depths (down to 200-300 m) above the gas hydrate stability zone (GHSZ). The north-west part of Yamal ( West Siberia) is one of such areas (Chuvilin et al.,1998, Yakushev and Chuvilin, 2000). Special research, which included analysis of monitoring wells in cryolithozone, as well research of permafrost cores recovered during drilling, can be assumed that at least a part of gas in similar intrapermafrost accumulations exist in the form of metastable (relict) gas hydrates. They were formed in the past and exist now to the self-preservation effect. Some models of gas hydrate formation in shallow depths in permafrost are possible. They can associate with sea transgression, regional ice cover formation, freezing of gas saturated talik zones, permafrost sediments formation etc. After pressure reduction, hydrate passed through the self-preservation stage remained metastable for a long time. However, according to the shallow depth and metastable condition self reserved gas hydrate have tendency to dissociate due to the global climate warming, as well as to different technogenic effects such drilling and mining. Possibilities of formation metastable gas hydrate in permafrost confirm the special experimental investigation of gas hydrate accumulation in freezing sediments (Chuvilin and Kozlova, 2004). The experimental data shows, that the cooling of gas hydrate saturated sediments to negative temperature induced ice formation. Enclosing hydrate ice would originate from the remaining

  6. A Sea Floor Methane Hydrate Displacement Experiment Using N2 Gas

    NASA Astrophysics Data System (ADS)

    Brewer, P. G.; Peltzer, E. T.; Walz, P. M.; Zhang, X.; Hester, K.

    2009-12-01

    The production of free methane gas from solid methane hydrate accumulations presents a considerable challenge. The presently preferred procedure is pressure reduction whereby the relief of pressure to a condition outside the hydrate phase boundary creates a gas phase. The reaction is endothermic and thus a problematic water ice phase can form if the extraction of gas is too rapid, limiting the applicability of this procedure. Additionally, the removal of the formation water in contact with the hydrate phase is required before meaningful pressure reduction can be attained -- and this can take time. An alternate approach that has been suggested is the injection of liquid CO2 into the formation, thereby displacing the formation water. Formation of a solid CO2 hydrate is thermodynamically favored under these conditions. Competition between CH4 and CO2 for the hydrate host water molecules can occur displacing CH4 from the solid to the gas phase with formation of a solid CO2 hydrate. We have investigated another alternate approach with displacement of the surrounding bulk water phase by N2 gas, resulting in rapid release of CH4 gas and complete loss of the solid hydrate phase. Our experiment was carried out at the Southern Summit of Hydrate Ridge, offshore Oregon, at 780m depth. There we harvested hydrate fragments from surficial sediments using the robotic arm of the ROV Doc Ricketts. Specimens of the hydrate were collected about 1m above the sediment surface in an inverted funnel with a mesh covered neck as they floated upwards. The accumulated hydrate was transferred to an inverted glass cylinder, and N2 gas was carefully injected into this container. Displacement of the water phase occurred and when the floating hydrate material approached the lower rim the gas injection was stopped and the cylinder placed upon a flat metal plate effectively sealing the system. We returned to this site after 7 days to measure progress, and observed complete loss of the hydrate phase

  7. Simulation of submarine gas hydrate deposits as a sustainable energy source and CO2 storage

    NASA Astrophysics Data System (ADS)

    Janicki, G.; Hennig, T.; Schlüter, S.; Deerberg, G.

    2012-04-01

    Being aware that conventionally exploitable natural gas resources are limited, research concentrates on the development of new technologies for the extraction of methane from gas hydrate deposits in subsea sediments. The quantity of methane stored in hydrate form is considered to be a promising means to overcome future shortages in energy resources. In combination with storing carbon dioxide (CO2) as hydrates in the deposits chances for sustainable energy supply systems are given. The combustion of hydrate-based natural gas can contribute to the energy supply, but the coupled CO2 emissions cause climate change effects. At present, the possible options to capture and subsequently store CO2 (CCS-Technology) become of particular interest. To develop a sustainable hydrate-based energy supply system, the production of natural gas from hydrate deposits has to be coupled with the storage of CO2. Hence, the simultaneous storage of CO2 in hydrate deposits has to be developed. Decomposition of methane hydrate in combination with CO2 sequestration appears to be promising because CO2 hydrate is stable within a wider range of pressure and temperature than methane hydrate. As methane hydrate provides structural integrity and stability in its natural formation, incorporating CO2 hydrate as substitute for methane hydrate will help to preserve the natural sediments' stability. Regarding the technological implementation, many problems have to be overcome. Especially heat and mass transfer in the deposits are limiting factors causing very long process times. Within the scope of the German research project »SUGAR«, different technological approaches are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical effects are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs like

  8. Powder Diffraction: By Decades

    NASA Astrophysics Data System (ADS)

    David, William I. F.

    This introductory chapter reviews the first 100 years of powder diffraction, decade by decade, from the earliest X-ray powder diffraction measurements of the crystal structure of graphite through to the diversity and complexity of twenty-first century powder diffraction. Carbon features as an illustrative example throughout the discussion of these ten decades from graphite and the disorder of carbon black through to lonsdaleite, the elusive hexagonal polymorph of diamond, and C60, the most symmetrical of molecules. Electronics and computing have played a leading role in the development of powder diffraction, particularly over the past 60 years, and the Moore's Law decade-by-decade rise in computing power is clear in the increasing complexity of powder diffraction experiments and material systems that can be studied. The chapter concludes with a final discussion of decades - the four decades of length-scale from the ångstrom to the micron that not only represent the domain of powder diffraction but are also the distances that will dominate twenty-first century science and technology.

  9. Tantalum powder consolidation, modeling and properties

    SciTech Connect

    Bingert, S.R.; Vargas, V.D.; Sheinberg, H.C.

    1996-10-01

    A systematic approach was taken to investigate the consolidation of tantalum powders. The effects of sinter time, temperature and ramp rate; hot isostatic pressing (HIP) temperature and time; and powder oxygen content on consolidation density, kinetics, microstructure, crystallographic texture, and mechanical properties have been evaluated. In general, higher temperatures and longer hold times resulted in higher density compacts with larger grain sizes for both sintering and HIP`ing. HIP`ed compacts were consistently higher in density than sintered products. The higher oxygen content powders resulted in finer grained, higher density HIP`ed products than the low oxygen powders. Texture analysis showed that the isostatically processed powder products demonstrated a near random texture. This resulted in isotropic properties in the final product. Mechanical testing results showed that the HIP`ed powder products had consistently higher flow stresses than conventionally produced plates, and the sintered compacts were comparable to the plate material. A micromechanics model (Ashby HIP model) has been employed to predict the mechanisms active in the consolidation processes of cold isostatic pressing (CIP), HIP and sintering. This model also predicts the density of the end product and whether grain growth should be expected under the applied processing conditions.

  10. National workshop on gas hydrates

    NASA Astrophysics Data System (ADS)

    Max, Michael D.; Dillon, William P.; Malone, Rodney D.; Kvenvolden, Keith A.

    The range of present knowledge on the subject of gas hydrates and related federal research programs was the topic of discussion at the National Workshop on Gas Hydrates, April 23-24. The intention of the meeting was to provide the impetus for an expanded and broader-based national research program in both academia and government. Held at the U.S. Geological Survey National Center, Reston, Va., the workshop was organized by Michael D. Max, Naval Research Laboratory, Washington, D.C.; William P. Dillon, USGS, Woods Hole, Mass.; and Rodney D. Malone, U.S. Department of Energy, Morgantown Energy Technology Center, Morgantown, W.Va. The 33 attendees represented academia (33%), federal agencies (58%), and industry (9%).

  11. Dynamics of hydrated starch saccharides

    NASA Astrophysics Data System (ADS)

    Di Bari, M.; Deriu, A.; Albanese, G.; Cavatorta, F.

    2003-08-01

    We report here elastic neutron scattering data on glucose and on two of its polymeric forms: amylose and amylopectin. We have covered the hydration range from the dry state to about 0.6 g water/g dry saccharide. The data indicate, in all the analysed systems, the presence of a dynamic glass-like transition similar to that observed in hydrated proteins. The fact that this feature is observed also in a relatively small molecule like glucose confirms the hypothesis already put forward by other authors, that this transition in biomolecular species is essentially triggered and driven by the interaction of the macromolecule with the network of fluctuating H-bond of the solvent.

  12. Uranyl p-toluenesulphonate and its crystal hydrates. Synthesis and dehydration-hydration processes

    NASA Astrophysics Data System (ADS)

    Baluev, A. V.; Mityakhina, V. S.; Bogachev, S. V.; Suglobova, I. G.

    2003-01-01

    Lowest hydrates of uranyl p-toluenesulphonate (UPTS) and anhydrous salt were synthesised. The dehydration-hydration processes were studied by thermal gravimetric analysis. It has been established that the hydrate shell of UPTS has a layered structure. The IR spectra of UPTS and its hydrates were recorded. It was found that the IR spectra of UPTS crystal hydrates of the same composition, produced in dehydration-hydration, noticeably differ in the range of water vibrations and are the same in the range corresponding to vibrations of sulphonate groups.

  13. Methane hydrate behavior when exposed to a 23% carbon dioxide 77% nitrogen gas under conditions similar to the ConocoPhillips 2012 Ignik Sikumi Gas Hydrate Field Trial

    NASA Astrophysics Data System (ADS)

    Borglin, S. E.; Kneafsey, T. J.; Nakagawa, S.

    2013-12-01

    In-situ replacement of methane hydrate by carbon dioxide hydrate is considered to be a promising technique for producing natural gas, while simultaneously sequestering greenhouse gas in deep geological formations. For effective application of this technique in the field, kinetic models of gas exchange rates in hydrate under a variety of environmental conditions need to be established, and the impact of hydrate substitution on geophysical (seismic) properties has to be quantified in order to optimize monitoring techniques. We performed a series of laboratory tests in which we monitored changes in methane hydrate-bearing samples while a nitrogen/carbon dioxide gas mixture was flowed through. These experiments were conducted to gain insights into data obtained from a field test in which the same mixture of carbon dioxide and nitrogen was injected into a methane hydrate-bearing unit beneath the north slope of the Brooks Range in northern Alaska (ConocoPhillips 2012 Ignik Sikumi gas hydrate field trial). We have measured the kinetic gas exchange rate for a range of hydrate saturations and different test configurations, to provide an estimate for comparison to numerical model predictions. In our tests, the exchange rate decreased over time during the tests as methane was depleted from the system. Following the elution of residual gaseous methane, the exchange rate ranged from 3.8×10-7 moles methane/(mole water*s) to 5×10-8 moles methane/(mole water*s) (Note that in these rates, the moles of water refers to water originally held in the hydrate.). In addition to the gas exchange rate, we also monitored changes in permeability occurring due to the gas substitution. Further, we determined the seismic P and S wave velocities and attenuations using our Split Hopkinson Resonant Bar apparatus (e.g. Nakagawa, 2012, Rev. Sci. Instr.). In addition to providing geophysical signatures, changes in the seismic properties can also be related to changes in the mechanical strength of

  14. Proteorhodopsin Activation Is Modulated by Dynamic Changes in Internal Hydration.

    PubMed

    Feng, Jun; Mertz, Blake

    2015-12-01

    Proteorhodopsin, a member of the microbial rhodopsin family, is a seven-transmembrane α-helical protein that functions as a light-driven proton pump. Understanding the proton-pumping mechanism of proteorhodopsin requires intimate knowledge of the proton transfer pathway via complex hydrogen-bonding networks formed by amino acid residues and internal water molecules. Here we conducted a series of microsecond time scale molecular dynamics simulations on both the dark state and the initial photoactivated state of blue proteorhodopsin to reveal the structural basis for proton transfer with respect to protein internal hydration. A complex series of dynamic hydrogen-bonding networks involving water molecules exists, facilitated by water channels and hydration sites within proteorhodopsin. High levels of hydration were discovered at each proton transfer site-the retinal binding pocket and proton uptake and release sites-underscoring the critical participation of water molecules in the proton-pumping mechanism. Water-bridged interactions and local water channels were also observed and can potentially mediate long-distance proton transfer between each site. The most significant phenomenon is after isomerization of retinal, an increase in water flux occurs that connects the proton release group, a conserved arginine residue, and the retinal binding pocket. Our results provide a detailed description of the internal hydration of the early photointermediates in the proteorhodopsin photocycle under alkaline pH conditions. These results lay the fundamental groundwork for understanding the intimate role that hydration plays in the structure-function relationship underlying the proteorhodopsin proton-pumping mechanism, as well as providing context for the relationship of hydration in proteorhodopsin to other microbial retinal proteins. PMID:26562497

  15. Hydration properties determining the reactivity of nitrite in aqueous solution.

    PubMed

    Vchirawongkwin, Saowapak; Kritayakornupong, Chinapong; Tongraar, Anan; Vchirawongkwin, Viwat

    2014-08-28

    The knowledge of the hydration properties of the nitrite ion is key to understanding its reaction mechanism controlled by solvent effects. Here, ab initio quantum mechanical charge field molecular dynamics was performed to obtain the structural and dynamical properties of the hydration shell in an aqueous solution of nitrite ions, elucidated by data analysis using a molecular approach and an extended quantitative analysis of all superimposed trajectories with three-dimensional alignment (density map). The pattern of the power spectra corresponded to the experimental data, indicating the suitability of the Hartree-Fock method coupled with double-ζ plus polarization and diffuse functional basis sets to study this system. The density maps revealed the structure of the hydration shell, that presented a higher density in the N-O bond direction than in the axis vertical to the molecular plane, whereas the atomic and molecular radial distribution functions provided vague information. The number of actual contacts indicated 4.6 water molecules interacting with a nitrite ion, and 1.5 extra water molecules located in the molecular hydration shell, forming a H-bonding network with the bulk water. The mean residence times for the water ligands designated the strength of the hydration spheres for the oxygen sites, whilst the results for the nitrogen sites over-estimated the number of water molecules from other sites and indicated a weak structure. These results show the influence of the water molecules surrounding the nitrite ion creating an anisotropic hydration shell, suggesting that the reactive sites are situated above and below the molecular plane with a lower water density. PMID:24840033

  16. Separation of SF6 from gas mixtures using gas hydrate formation.

    PubMed

    Cha, Inuk; Lee, Seungmin; Lee, Ju Dong; Lee, Gang-woo; Seo, Yongwon

    2010-08-15

    This study aims to examine the thermodynamic feasibility of separating sulfur hexafluoride (SF(6)), which is widely used in various industrial fields and is one of the most potent greenhouse gases, from gas mixtures using gas hydrate formation. The key process variables of hydrate phase equilibria, pressure-composition diagram, formation kinetics, and structure identification of the mixed gas hydrates, were closely investigated to verify the overall concept of this hydrate-based SF(6) separation process. The three-phase equilibria of hydrate (H), liquid water (L(W)), and vapor (V) for the binary SF(6) + water mixture and for the ternary N(2) + SF(6) + water mixtures with various SF(6) vapor compositions (10, 30, 50, and 70%) were experimentally measured to determine the stability regions and formation conditions of pure and mixed hydrates. The pressure-composition diagram at two different temperatures of 276.15 and 281.15 K was obtained to investigate the actual SF(6) separation efficiency. The vapor phase composition change was monitored during gas hydrate formation to confirm the formation pattern and time needed to reach a state of equilibrium. Furthermore, the structure of the mixed N(2) + SF(6) hydrate was confirmed to be structure II via Raman spectroscopy. Through close examination of the overall experimental results, it was clearly verified that highly concentrated SF(6) can be separated from gas mixtures at mild temperatures and low pressure conditions. PMID:20704207

  17. Gas hydrate cool storage system

    DOEpatents

    Ternes, Mark P.; Kedl, Robert J.

    1985-01-01

    This invention is a process for formation of a gas hydrate to be used as a cool storage medium using a refrigerant in water. Mixing of the immiscible refrigerant and water is effected by addition of a surfactant and agitation. The difficult problem of subcooling during the process is overcome by using the surfactant and agitation and performance of the process significantly improves and approaches ideal.

  18. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, H.K. Jr.

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means for separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means. 7 figs.

  19. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, Jr., Harry K.

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means or separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means.

  20. The Development Path for Hydrate Natural Gas

    NASA Astrophysics Data System (ADS)

    Johnson, A. H.; Max, M. D.

    2008-12-01

    The question of when gas hydrate will become a commercially viable resource most concerns those nations with the most severe energy deficiencies. With the vast potential attributed to gas hydrate as a new gas play, the interest is understandable. Yet the resource potential of gas hydrate has persistently remained just over the horizon. While technical and economic hurdles have pushed back the timeline for development, considerable progress has been made in the past five years. An important lesson learned is that an analysis of the factors that control the formation of high grade hydrate deposits must be carried out so that both exploration and recovery scenarios can be modeled and engineered. Commercial hydrate development requires high concentrations of hydrate in porous, permeable reservoirs. It is only from such deposits that gas may be recovered in commercial quantities. While it is unrealistic to consider the global potential of gas hydrate to be in the hundreds of thousands of tcfs, there is a strong potential in the hundreds of tcfs or thousands of tcfs. Press releases from several national gas hydrate research programs have reported gas hydrate "discoveries". These are, in fact, hydrate shows that provide proof of the presence of hydrate where it may previously only have been predicted. Except in a few isolated areas, valid resource assessments remain to be accomplished through the identification of suitable hosts for hydrate concentrations such as sandstone reservoirs. A focused exploration effort based on geological and depositional characteristics is needed that addresses hydrate as part of a larger petroleum system. Simply drilling in areas that have identifiable bottom simulating reflectors (BSRs) is unlikely to be a viable exploration tool. It is very likely that with drilling on properly identified targets, commercial development could become a reality in less than a decade.

  1. Gas hydrates: Technology status report

    SciTech Connect

    Not Available

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  2. Micelle Structure and Hydrophobic Hydration.

    PubMed

    Long, Joshua A; Rankin, Blake M; Ben-Amotz, Dor

    2015-08-26

    Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized. PMID:26222042

  3. Energy landscape of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Desmedt, A.; Bedouret, L.; Pefoute, E.; Pouvreau, M.; Say-Liang-Fat, S.; Alvarez, M.

    2012-11-01

    Clathrate hydrates are nanoporous crystalline materials made of a network of hydrogen-bonded water molecules (forming host cages) that is stabilized by the presence of foreign (generally hydrophobic) guest molecules. The natural existence of large quantities of hydrocarbon hydrates in deep oceans and permafrost is certainly at the origin of numerous applications in the broad areas of energy and environmental sciences and technologies (e.g. gas storage). At a fundamental level, their nanostructuration confers on these materials specific properties (e.g. their "glass-like" thermal conductivity) for which the host-guest interactions play a key role. These interactions occur on broad timescale and thus require the use of multi-technique approach in which neutron scattering brings unvaluable information. This work reviews the dynamical properties of clathrate hydrates, ranging from intramolecular vibrations to Brownian relaxations; it illustrates the contribution of neutron scattering in the understanding of the underlying factors governing chemical-physics properties specific to these nanoporous systems.

  4. An Experimental Determination of Natural Clathrate Hydrate Dissolution Rates in the Deep Sea

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; Walz, P. M.; Brewer, P. G.; Dunk, R. M.; Hester, K.; Sloan, E. D.

    2006-12-01

    In August of 2006 we carried out a series of geochemical experiments on the massive Structure II hydrate mounds in Barkley Canyon using MBARI's ROV Tiburon deployed from the R/V Western Flyer. One of the primary questions regarding the fate of this hydrate exposure at 850m depth is the temporal persistence of un-sedimented surfaces exposed to steady currents of seawater undersaturated with methane. Previous work on the dissolution rate of laboratory prepared methane hydrate (Rehder et al., 2004) showed diameter reduction rates of ~3 m/year. These formations appeared largely unchanged from the earlier descriptions and photographs contained in media reports released in 2002 and later (Chapman et al., 2004; Lu et al., 2005) leading us to speculate that these hydrates are far slower to dissolve. In order to quantify their dissolution rates, samples of the outcropping hydrate, both a pure white hydrate and a much harder yellow, oil-stained hydrate, were collected using an ROV operated coring device and hydraulically expelled into an open mesh container for time-lapse photography over the course of the next 48 hours. By exposing these samples of natural hydrate to the flow of ambient seawater we hoped to observe the dissolution rate consistent with the local environmental conditions. Initial analysis of the time-lapse photographs obtained using a Nikon Cool-pix camera revealed an apparent diameter reduction rate for the yellow hydrate of approximately 0.040 μm/s, corresponding to a volume loss rate of 1.3×10-6cm3/cm2/s. The observed dissolution rate of the white hydrate was significantly faster, consistent with the observed large-scale undercutting of the exposed layered structures. Assuming that the yellow hydrate has a density of 0.93 g/cm3 and an average hydration number near 6, this yields a guest gas loss rate of about 9.4×10-9 mol/cm2/s. This is approximately one-fourth the rate that was observed for the dissolution of synthetic Structure I methane hydrates

  5. 3D monitoring of hydrate formation and dissociation using a cylindrical ERT

    NASA Astrophysics Data System (ADS)

    Priegnitz, Mike; Spangenberg, Erik; Thaler, Jan; Schicks, Judith M.; Reichardt, Alexander

    2013-04-01

    In the framework of the SUGAR-project (submarine gas hydrate reservoirs) innovative methods and approaches for the production of methane from hydrate-bearing reservoirs are studied. For this purpose a large reservoir simulator (LARS), allowing the formation and dissociation of gas hydrates under simulated in-situ conditions, was realized. Prior experiments within the LARS suggested higher hydrate formation rates in the boundary regions within the cylindrical reservoir, which is in agreement to the observed temperature distribution in the sediment sample. However, for improvement and validation of numerical reservoir modeling a sufficient quantitative understanding of the spatial distribution of hydrate formation and dissociation with respect to time is required. Since hydrate can be considered as an insulator, the resistivity in the reservoir will change with hydrate saturation. Thus, significant differences regarding the electrical properties within the investigated reservoir are expected and suggest the application of an electrical tomographic system. Tomographic measurements constitute a popular technique for high resolution imaging of various geometries. Therefore, a cylindrical electrical resistance tomography (ERT) composed of 25 electrode rings featuring 15 electrodes each, is implemented into the LARS. In advance, a number of numerical simulations has been carried out to optimize the electrode arrangement providing the best resolution for the resistivity tomography. As the present phases (sediment, liquid, hydrates, and gas) cover a wide range of electrical properties, the ERT allows the monitoring of the spatial distribution of the various phases during the experiments. These data serve as basis for numerical simulations of production scenarios in the LARS and the field. At a confining pressure of 12 - 15 MPa and a pore pressure of 8 - 11 MPa hydrate is formed at 278 K from methane-saturated water (no free gas phase) within the sediment sample until a

  6. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2003-08-19

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  7. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goval, Amit; Williams, Robert K.; Kroeger, Donald M.

    2005-06-07

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  8. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2003-07-29

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  9. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2004-09-14

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  10. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2005-05-10

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  11. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2003-08-26

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  12. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2004-09-28

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  13. Biaxially textured articles formed by powder metallurgy

    DOEpatents

    Goyal, Amit; Williams, Robert K.; Kroeger, Donald M.

    2005-01-25

    A biaxially textured alloy article having a magnetism less than pure Ni includes a rolled and annealed compacted and sintered powder-metallurgy preform article, the preform article having been formed from a powder mixture selected from the group of mixtures consisting of: at least 60 at % Ni powder and at least one of Cr powder, W powder, V powder, Mo powder, Cu powder, Al powder, Ce powder, YSZ powder, Y powder, Mg powder, and RE powder; the article having a fine and homogeneous grain structure; and having a dominant cube oriented {100}<100> orientation texture; and further having a Curie temperature less than that of pure Ni.

  14. An application of powder metallurgy to dentistry.

    PubMed

    Oda, Y; Ueno, S; Kudoh, Y

    1995-11-01

    Generally, the dental casting method is used to fabricate dental prostheses made with metal. The method of fabricating dental prostheses from sintered titanium alloy has certain advantages: the elimination of casting defects, a sintering temperature that is lower than the melting point, and a shorter processing time. By examining (1) the properties of green, sintered compacts of titanium powder, (2) the effects of adding aluminum powder on the properties of green, sintered compacts of Ti-Al compound, and (3) the effects of adding copper powder on the properties of green, sintered compacts of Ti-Al-Cu compound, the authors developed a sintered titanium alloy on a trial basis. Because the properties satisfied the requirements of dental restorations, a powder metallurgical method of making dental restorations from this sintered titanium alloy was devised. Applications of such sintered titanium alloys for the metal coping of metal-ceramic crowns and denture base plates were discussed. PMID:8689755

  15. Photoluminescence and photocatalytic activity of zinc tungstate powders

    NASA Astrophysics Data System (ADS)

    Gigorjeva, Larisa; Millers, Donats; Grabis, Jānis; Jankoviča, Dzidra

    2011-04-01

    ZnWO4 powders with grain size in range 20 nm-10 µm have been synthesized by a simple combustion method and subsequent calcinations. The photocatalytic activities of powders were tested by degradation of methylene blue solution under UV light. The luminescence spectra and luminescence decay kinetics were studied and luminescence decay time dependence on average powder-grain size was obtained. The correlation between self-trapped exciton luminescence decay time and photocatalytic activity of ZnWO4 powders was shown. A model explaining the excitonic luminescence decay time correlation with photocatalytic activity was proposed.

  16. Investigation of hydrate formation and transportability in multiphase flow systems

    NASA Astrophysics Data System (ADS)

    Grasso, Giovanny A.

    The oil and gas industry is moving towards offshore developments in more challenging environments, where evaluating hydrate plugging risks to avoid operational/safety hazards becomes more difficult (Sloan, 2005). Even though mechanistic models for hydrate plug formation have been developed, components for a full comprehensive model are still missing. Prior to this work, research efforts were focused on flowing hydrate particles with relatively little research on hydrate accumulation, leaving hydrate deposition in multiphase flow an unexplored subject. The focus of this thesis was to better understand hydrate deposition as a form of accumu- lation in pipelines. To incorporate the multiphase flow effect, hydrate formation experiments were carried out at varying water cut (WC) from 15 to 100 vol.%, liquid loading (LL) from 50 to 85 vol.%, mixture velocity (vmix) from 0.75 to 3 m/s, for three fluids systems (100 % WC, water in Conroe crude oil emulsions and King Ranch condensate + water) on the ExxonMobil flowloop (4 in. nominal size and 314 ft. long) at Friendswood, TX. For the 100 % WC flowloop tests, hydrate particle distribution transitions beyond a critical hydrate volume concentration, observed values were between 8.2 to 29.4 vol.%, causing a sudden increase in pressure drop (DP). A revised correlation of the transition as a function of Reynolds number and liquid loading was developed. For Conroe emulsions, DP starts increasing at higher hydrate concentrations than King Ranch condensate, many times at 10 vol.%. Experiments with King Ranch show higher relative DP (10 to 25) than Conroe (2 to 10) performed at the same vmix and LL. Cohesive force measurements between cyclopentane hydrate particles were reduced from a value of 3.32 mN/m to 1.26 mN/m when 6 wt.% Conroe was used and to 0.41 mN/m when 5 wt.% Caratinga crude oil was used; similar values were obtained when extracted asphaltenes were used. King Ranch condensate (11 wt.%) did not significantly change the

  17. Improvement of stability and absorbability of dry insulin powder for inhalation by powder-combination technique.

    PubMed

    Todo, Hiroaki; Okamoto, Hirokazu; Iida, Kotaro; Danjo, Kazumi

    2004-03-01

    The effect of pulmonary absorption enhancers on the stability of active ingredients is an important factor for successful inhalation therapy as well as the effect on pharmacological activity and safety. We examined the effect of pulmonary absorption enhancers on the stability of insulin in dry powders prepared by a spray-drying technique. Although the hypoglycemic effect was greatly improved when a dry insulin powder containing citric acid (MIC SD) was administered, insulin in the MIC SD was unstable compared with the other powders examined. Bacitracin and Span 85, which are potent pulmonary absorption enhancers of insulin formulated in solutions, showed no deteriorative effect on the stability of dry insulin powder. However, they did not improve the hypoglycemic effect of insulin in dry powders. We modified the insulin dosage form with citric acid to improve the insulin stability at room temperature without loss of hypoglycemic activity. MIC Mix was formulated as a combination of insulin powder (MI') and citric acid powder (MC). MIC Mix showed hypoglycemic activity comparable to MIC SD while the insulin stability was much better than that of MIC SD at a 60 degrees C/dry condition. However, moisture lowered the insulin stability and changed the particle morphology of MIC Mix with time at a 60 degrees C/75% relative humidity condition, suggesting that a package preventing moisture absorption was necessary for the MIC Mix powder. PMID:15129972

  18. Prolonging the hydration and active metabolism from light periods into nights substantially enhances lichen growth.

    PubMed

    Bidussi, Massimo; Gauslaa, Yngvar; Solhaug, Knut Asbjørn

    2013-05-01

    This study investigates how hydration during light and dark periods influences growth in two epiphytic old forest lichens, the green algal Lobaria pulmonaria and the cyanobacterial L. scrobiculata. The lichens were cultivated in growth chambers for 14 days (200 μmol m(-1) s(-2); 12 h photoperiod) at four temperature regimes (25/20 °C, 21/16 °C, 13/8 °C, and 6/1 °C; day/night temperatures) and two hydration regimes (12 h day-time hydration; 12 h day-time + 12 h night-time hydration). Growth was highly dynamic, showing that short-term growth experiments in growth cabinets have a high, but largely unexplored potential in functional lichen studies. The highest measured growth rates were not far from the maximal dry matter gain estimated from published net photosynthetic CO2 uptake data. For the entire data set, photobiont type, temperature, hydration regime and specific thallus mass accounted for 46.6 % of the variation in relative growth rate (RGR). Both species showed substantially higher relative growth rates based on both biomass (RGR) and thallus area (RTAGR) when they were hydrated day and night compared to hydration in light only. Chronic photoinhibition was substantial in thalli hydrated only during the day time and kept at the highest and lowest temperature regimes, resulting in exponential increases in RGR with increasing maximal PSII efficiency (F v/F m) in both species. However, the depression in F v/F m was stronger for the cyanolichen than for the cephalolichen at extreme temperatures. The growth-stimulating effect of night-time hydration suggests that nocturnal metabolic activity improves recovery of photoinhibition and/or enhances the conversion rate of photosynthates into thallus extension. PMID:23389675

  19. Hydroxyapatite ceramics from hydrothermally prepared powders

    SciTech Connect

    Lin, C.H.; Huang, C.W.; Chang, S.C.

    1994-12-31

    Hydroxyapatite (Ca{sub 5}(PO{sub 4}){sub 3}(OH)) is an effective material for artificial human bone production. Hydroxyapatite powders were hydrothermally produced in this work by reacting Ca(OH){sub 2} with Na{sub 3}PO{sub 4}{center_dot}12H{sub 2}O in an autoclave at various temperature and for various times. The particle size of hydroxyapatite was observed to be very fine, uniform, around 50 nm, as well as independent of reaction time. The hydroxyapatite powders were compacted and sintered at various temperatures for 2 hrs. The density, grain size, and hardness of the hydroxyapatite ceramics were measured and compared with those of the hydroxyapatite ceramics produced by the powders from the commercial source. The hydroxyapatite ceramics from the hydrothermal powders were found to have a higher density, smaller grain size, and higher hardness. After the hydroxyapatite ceramics were dipped in a simulated biological body liquid for 10 days, the density and hardness of the hydroxyapatite ceramics from the hydrothermal powders were less deteriorated than those of the hydroxyapatite ceramics from the commercial powder.

  20. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

  1. Fast X-Ray Fluorescence Microtomography of Hydrated Biological Samples

    PubMed Central

    Lombi, Enzo; de Jonge, Martin D.; Donner, Erica; Kopittke, Peter M.; Howard, Daryl L.; Kirkham, Robin; Ryan, Chris G.; Paterson, David

    2011-01-01

    Metals and metalloids play a key role in plant and other biological systems as some of them are essential to living organisms and all can be toxic at high concentrations. It is therefore important to understand how they are accumulated, complexed and transported within plants. In situ imaging of metal distribution at physiological relevant concentrations in highly hydrated biological systems is technically challenging. In the case of roots, this is mainly due to the possibility of artifacts arising during sample preparation such as cross sectioning. Synchrotron x-ray fluorescence microtomography has been used to obtain virtual cross sections of elemental distributions. However, traditionally this technique requires long data acquisition times. This has prohibited its application to highly hydrated biological samples which suffer both radiation damage and dehydration during extended analysis. However, recent advances in fast detectors coupled with powerful data acquisition approaches and suitable sample preparation methods can circumvent this problem. We demonstrate the heightened potential of this technique by imaging the distribution of nickel and zinc in hydrated plant roots. Although 3D tomography was still impeded by radiation damage, we successfully collected 2D tomograms of hydrated plant roots exposed to environmentally relevant metal concentrations for short periods of time. To our knowledge, this is the first published example of the possibilities offered by a new generation of fast fluorescence detectors to investigate metal and metalloid distribution in radiation-sensitive, biological samples. PMID:21674049

  2. Geomechanical Modeling of Gas Hydrate Bearing Sediments

    NASA Astrophysics Data System (ADS)

    Sanchez, M. J.; Gai, X., Sr.

    2015-12-01

    This contribution focuses on an advance geomechanical model for methane hydrate-bearing soils based on concepts of elasto-plasticity for strain hardening/softening soils and incorporates bonding and damage effects. The core of the proposed model includes: a hierarchical single surface critical state framework, sub-loading concepts for modeling the plastic strains generally observed inside the yield surface and a hydrate enhancement factor to account for the cementing effects provided by the presence of hydrates in sediments. The proposed framework has been validated against recently published experiments involving both, synthetic and natural hydrate soils, as well as different sediments types (i.e., different hydrate saturations, and different hydrates morphologies) and confinement conditions. The performance of the model in these different case studies was very satisfactory.

  3. Structural characteristics of hydration sites in lysozyme.

    PubMed

    Soda, Kunitsugu; Shimbo, Yudai; Seki, Yasutaka; Taiji, Makoto

    2011-06-01

    A new method is presented for determining the hydration site of proteins, where the effect of structural fluctuations in both protein and hydration water is explicitly considered by using molecular dynamics simulation (MDS). The whole hydration sites (HS) of lysozyme are composed of 195 single HSs and 38 clustered ones (CHS), and divided into 231 external HSs (EHS) and 2 internal ones (IHS). The largest CHSs, 'Hg' and 'Lβ', are the IHSs having 2.54 and 1.35 mean internal hydration waters respectively. The largest EHS, 'Clft', is located in the cleft region. The real hydration structure of a CHS is an ensemble of multiple structures. The transition between two structures occurs through recombinations of some H-bonds. The number of the experimental X-ray crystal waters is nearly the same as that of the estimated MDS hydration waters for 70% of the HSs, but significantly different for the rest of HSs. PMID:21435773

  4. Development of Alaskan gas hydrate resources

    SciTech Connect

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  5. Ultrafine hydrogen storage powders

    DOEpatents

    Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

    2000-06-13

    A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

  6. Aluminum-rich belite sulfoaluminate cements: Clinkering and early age hydration

    SciTech Connect

    Martin-Sedeno, M. Carmen; Cuberos, Antonio J.M.; De la Torre, Angeles G.; Alvarez-Pinazo, Gema; Ordonez, Luis M.; Gateshki, Milen; Aranda, Miguel A.G.

    2010-03-15

    Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO{sub 2} into the atmosphere when compared to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich BSA clinkers with nominal mineralogical compositions in the range C{sub 2}S (50-60%), C{sub 4}A{sub 3}$ (20-30%), CA (10%) and C{sub 12}A{sub 7} (10%). Using thermogravimetry, differential thermal analysis, high temperature microscopy, and X-ray powder diffraction with Rietveld quantitative phase analysis, we found that burning for 15 min at 1350 deg. C was the optimal procedure, in these experimental conditions, for obtaining the highest amount of C{sub 4}A{sub 3}$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt.% of C{sub 4}A{sub 3}$, had 19.6, 27.1 and 27.7 wt.%, C{sub 4}A{sub 3}$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the beta-C{sub 2}S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C{sub 4}A{sub 3}$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution.

  7. A molecular dynamics computer simulation study of the hydration of bis(methylsulphonyl)methane in water

    NASA Astrophysics Data System (ADS)

    Remerie, Klaas; van Gunsteren, Wilfred F.; Engberts, Jan B. F. N.

    The molecular dynamics computer simulation technique has been applied to study the hydration of bis(methylsulphonyl)methane (1) in water. This 1,3-disulphone has water-structure breaking properties as is deduced from both simulated time-averaged and time-dependent properties. The time-averaged properties of water molecules in the various atomic hydration shells can be directly related to the solute atom under consideration. Time-dependent properties show a mutual influencing of the hydration shells of neighbouring atoms. Moderate sulphonyl oxygen-water hydrogen bonding competes with water-water hydrogen bonding in the same hydration shell, while methylene hydrogen-water hydrogen bonding is stronger than water-water hydrogen bonding. These results are in accord with previous interpretations of 1H-N.M.R. chemical shift data for the central methylene moiety of (1) in mixtures of water with 1,4-dioxane, 1,3-dioxane, and 1,2-dimethoxyethane.

  8. In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Day, Sarah J.; Thompson, Stephen P.; Evans, Aneurin; Parker, Julia E.

    2015-02-01

    Context. Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites. However, the structural factors governing their formation and dissociation are poorly understood. Aims: We demonstrate the application of a high pressure gas cell, combined with variable temperature non-contact cooling and fast, time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Methods: Clathrates formed and processed within the sample cell are monitored in situ using time-resolved synchrotron X-ray powder diffraction and laser Raman spectroscopy. Results: X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000 cm-1 are present in the in situ Raman spectra that carry features characteristic of both ice and clathrate formation. Conclusions: This novel experimental arrangement is well suited to studying clathrate hydrates over a wide range of temperature (80 -500 K) and pressure (1-100 bar) conditions relevant to solar system bodies and can be used with a variety of different gases and starting aqueous compositions (e.g. saline solutions). We propose the increase in clathrate formation observed during thermal cycling may be due to the formation of a quasi liquid-like phase that forms at temperatures below the ice melting point, but which allows either easier formation of new clathrate cages, or the retention and delocalisation of previously formed clathrate structures, possibly as amorphous clathrate. The structural similarities between hexagonal ice, the quasi liquid-like phase, and crystalline CO2 hydrate mean that differences in the

  9. Gas hydrates of outer continental margins

    SciTech Connect

    Kvenvolden, K.A. )

    1990-05-01

    Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf of Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.

  10. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

    PubMed Central

    Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

    2013-01-01

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

  11. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

    PubMed

    Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

    2013-05-21

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

  12. Physical Properties of Gas Hydrates: A Review

    DOE PAGESBeta

    Gabitto, Jorge F.; Tsouris, Costas

    2010-01-01

    Memore » thane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 10 16   m 3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.« less

  13. Physical Properties of Gas Hydrates: A Review

    SciTech Connect

    Gabitto, Jorge; Tsouris, Costas

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

  14. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  15. Development of Carbon Sequestration Options by Studying Carbon Dioxide-Methane Exchange in Hydrates

    NASA Astrophysics Data System (ADS)

    Horvat, Kristine Nicole

    Gas hydrates form naturally at high pressures (>4 MPa) and low temperatures (<4 °C) when a set number of water molecules form a cage in which small gas molecules can be entrapped as guests. It is estimated that about 700,000 trillion cubic feet (tcf) of methane (CH4) exist naturally as hydrates in marine and permafrost environments, which is more than any other natural sources combined as CH4 hydrates contain about 14 wt% CH4. However, a vast amount of gas hydrates exist in marine environments, which makes gas extraction an environmental challenge, both for potential gas losses during extraction and the potential impact of CH4 extraction on seafloor stability. From the climate change point of view, a 100 ppm increase in atmospheric carbon dioxide (CO2) levels over the past century is of urgent concern. A potential solution to both of these issues is to simultaneously exchange CH4 with CO 2 in natural hydrate reserves by forming more stable CO2 hydrates. This approach would minimize disturbances to the host sediment matrix of the seafloor while sequestering CO2. Understanding hydrate growth over time is imperative to prepare for large scale CH4 extraction coupled with CO2 sequestration. In this study, we performed macroscale experiments in a 200 mL high-pressure Jerguson cell that mimicked the pressure-temperature conditions of the seafloor. A total of 13 runs were performed under varying conditions. These included the formation of CH4 hydrates, followed by a CO2 gas injection and CO2 hydrate formation followed by a CH4 gas injection. Results demonstrated that once gas hydrates formed, they show "memory effect" in subsequent charges, irrespective of the two gases injected. This was borne out by the induction time data for hydrate formation that reduced from 96 hours for CH4 and 24 hours for CO2 to instant hydrate formation in both cases upon injection of a secondary gas. During the study of CH4-CO2 exchange where CH4 hydrates were first formed and CO2 gas was

  16. Preparation and characterization of a novel strontium-containing calcium phosphate cement with the two-step hydration process.

    PubMed

    Yu, Tao; Ye, Jiandong; Wang, Yingjun

    2009-09-01

    A novel Sr-containing calcium phosphate cement (CPC) with excellent compressive strength, good radiopacity and suitable setting time was developed in this work. The two-step hydration reaction resulted in a high compressive strength, with a maximum of up to 74.9MPa. Sr was doped into the calcium-deficient hydroxyapatite as a hydrated product during the hydration reaction of the CPC. Because of the existence of Sr element and the compact microstructure after hydration, the Sr-containing CPC shows good radiopacity. It is expected to be used in orthopedic and maxillofacial surgery for bone defects repairing. PMID:19380262

  17. Coexistence of structure I and II gas hydrates in Lake Baikal suggesting gas sources from microbial and thermogenic origin

    NASA Astrophysics Data System (ADS)

    Kida, Masato; Khlystov, Oleg; Zemskaya, Tamara; Takahashi, Nobuo; Minami, Hirotsugu; Sakagami, Hirotoshi; Krylov, Alexey; Hachikubo, Akihiro; Yamashita, Satoshi; Shoji, Hitoshi; Poort, Jeffrey; Naudts, Lieven

    2006-12-01

    We report the field observation of hydrate deposits of different crystal structures in the same cores of a mud volcano in the Kukuy Canyon. We link those deposits to chemical fractionation during gas hydrate crystallization. Gas composition and crystallographic analyses of hydrate samples reveal involvement of two distinct gas source types in gas hydrate formation at present or in the past: microbial (methane) and thermogenic (methane and ethane) gas types. The clathrate structure II, observed for the first time in fresh water sediments, is believed to be formed by higher mixing of thermogenic gas.

  18. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  19. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    USGS Publications Warehouse

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

    2007-01-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  20. Iowa Powder Atomization Technologies

    SciTech Connect

    2012-01-01

    The same atomization effect seen in a fuel injector is being applied to titanium metal resulting in fine titanium powders that are less than half the width of a human hair. Titanium melts above 3,000°F and is highly corrosive therefore requiring specialized containers. The liquid titanium is poured through an Ames Laboratory - USDOE patented tube which is intended to increase the energy efficiency of the atomization process, which has the ability to dramatically decrease the cost of fine titanium powders. This novel process could open markets for green manufacturing of titanium components from jet engines to biomedical implants.

  1. Iowa Powder Atomization Technologies

    ScienceCinema

    None

    2013-03-01

    The same atomization effect seen in a fuel injector is being applied to titanium metal resulting in fine titanium powders that are less than half the width of a human hair. Titanium melts above 3,000°F and is highly corrosive therefore requiring specialized containers. The liquid titanium is poured through an Ames Laboratory - USDOE patented tube which is intended to increase the energy efficiency of the atomization process, which has the ability to dramatically decrease the cost of fine titanium powders. This novel process could open markets for green manufacturing of titanium components from jet engines to biomedical implants.

  2. Niclosamide methanol solvate and niclosamide hydrate: structure, solvent inclusion mode and implications for properties.

    PubMed

    Harriss, Bethany I; Wilson, Claire; Radosavljevic Evans, Ivana

    2014-08-01

    Structural studies have been carried out of two solid forms of niclosamide [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide, NCL], a widely used anthelmintic drug, namely niclosamide methanol monosolvate, C13H8Cl2N2O4·CH3OH or NCL·MeOH, and niclosamide monohydrate, denoted HA. The structure of the methanol solvate obtained from single-crystal X-ray diffraction is reported for the first time, elucidating the key host-guest hydrogen-bonding interactions which lead to solvate formation. The essentially planar NCL host molecules interact via π-stacking and pack in a herringbone-type arrangement, giving rise to channels along the crystallographic a axis in which the methanol guest molecules are located. The methanol and NCL molecules interact via short O-H...O hydrogen bonds. Laboratory powder X-ray diffraction (PXRD) measurements reveal that the initially phase-pure NCL·MeOH solvate readily transforms into NCL monohydrate within hours under ambient conditions. PXRD further suggests that the NCL monohydrate, HA, is isostructural with the NCL·MeOH solvate. This is consistent with the facile transformation of the methanol solvate into the hydrate when stored in air. The crystal packing and the topology of guest-molecule inclusion are compared with those of other NCL solvates for which the crystal structures are known, giving a consistent picture which correlates well with known experimentally observed desolvation properties. PMID:25093354

  3. Effect of mechanical denaturation on surface free energy of protein powders.

    PubMed

    Mohammad, Mohammad Amin; Grimsey, Ian M; Forbes, Robert T; Blagbrough, Ian S; Conway, Barbara R

    2016-10-01

    Globular proteins are important both as therapeutic agents and excipients. However, their fragile native conformations can be denatured during pharmaceutical processing, which leads to modification of the surface energy of their powders and hence their performance. Lyophilized powders of hen egg-white lysozyme and β-galactosidase from Aspergillus oryzae were used as models to study the effects of mechanical denaturation on the surface energies of basic and acidic protein powders, respectively. Their mechanical denaturation upon milling was confirmed by the absence of their thermal unfolding transition phases and by the changes in their secondary and tertiary structures. Inverse gas chromatography detected differences between both unprocessed protein powders and the changes induced by their mechanical denaturation. The surfaces of the acidic and basic protein powders were relatively basic, however the surface acidity of β-galactosidase was higher than that of lysozyme. Also, the surface of β-galactosidase powder had a higher dispersive energy compared to lysozyme. The mechanical denaturation decreased the dispersive energy and the basicity of the surfaces of both protein powders. The amino acid composition and molecular conformation of the proteins explained the surface energy data measured by inverse gas chromatography. The biological activity of mechanically denatured protein powders can either be reversible (lysozyme) or irreversible (β-galactosidase) upon hydration. Our surface data can be exploited to understand and predict the performance of protein powders within pharmaceutical dosage forms. PMID:27434157

  4. Time-resolved study on the reactions of organic selenides with hydroxyl and oxide radicals, hydrated electrons, and H-atoms in aqueous solution, and DFT calculations of transients in comparison with sulfur analogues.

    PubMed

    Tobien, Thomas; Bonifacić, Marija; Naumov, Sergej; Asmus, Klaus-Dieter

    2010-07-01

    A complementary experimental and quantum chemical study has been undertaken on the reactivity, formation and properties of transients generated in the reaction of selected organic selenides with hydroxyl radicals, oxide radical ions, hydrated electrons and hydrogen atoms in aqueous solution. A detailed study of the OH and O (-) reactions with Me(2)Se revealed the formation of the respective adduct-radicals as precursors of (Me(2)Se thereforeSeMe(2))(+) radical cations. In case of the neutral adduct radical Me(2)Se (OH) the conversion into the three-electron bonded dimer species proceeds, in part, via the molecular (Me(2)Se thereforeOH(2))(+) radical cation. Absolute rate constants have been determined for all the underlying processes. The respective reactions with hydrated electrons and hydrogen atoms indicate that selenides exhibit a higher reactivity towards redox-active species than sulfides. A most interesting finding is that the reaction of Me(2)Se with H atoms is faster (k = 4.1 x 10(9) M(-1) s(-1)) than the reduction by hydrated electrons (k = 2.1 x 10(8) M(-1) s(-1)), precluding an electron transfer as mechanistic background. The rationale is rather an effective dissociative attack of the hydrogen atom on the selenium. Both, the e(aq)(-)- and H -induced reductions of Me(2)Se and Me(2)S lead, under cleavage of CH(3) radicals, to the direct formation of selenol and thiol, respectively. Complementary quantum chemical studies, performed with Density Functional Theory (DFT) BHandHLYP methods, confirm this mechanism. They also reveal a generally higher thermodynamic stability of the Se-centered radicals relative to the S-centered ones, e.g., for the molecular radical anions (Me(2)Se) (-) (DeltaH-27 kJ mol(-1)) and (Me(2)S) (-) (DeltaH-16 kJ mol(-1)). Despite of these stabilization energies the calculations indicate an instantaneous Se/S-CH(3) bond lengthening in the respective molecular radical anions. The same applies for the reaction of Me(2)S and Me(2)Se with

  5. Sensitivity Analysis of Gas Production from Class 2 and Class 3 Hydrate Deposits

    SciTech Connect

    Reagan, Matthew; Moridis, George; Zhang, Keni

    2008-05-01

    Gas hydrates are solid crystalline compounds in which gas molecules are lodged within the lattices of an ice-like crystalline solid. The vast quantities of hydrocarbon gases trapped in hydrate formations in the permafrost and in deep ocean sediments may constitute a new and promising energy source. Class 2 hydrate deposits are characterized by a Hydrate-Bearing Layer (HBL) that is underlain by a saturated zone of mobile water. Class 3 hydrate deposits are characterized by an isolated Hydrate-Bearing Layer (HBL) that is not in contact with any hydrate-free zone of mobile fluids. Both classes of deposits have been shown to be good candidates for exploitation in earlier studies of gas production via vertical well designs - in this study we extend the analysis to include systems with varying porosity, anisotropy, well spacing, and the presence of permeable boundaries. For Class 2 deposits, the results show that production rate and efficiency depend strongly on formation porosity, have a mild dependence on formation anisotropy, and that tighter well spacing produces gas at higher rates over shorter time periods. For Class 3 deposits, production rates and efficiency also depend significantly on formation porosity, are impacted negatively by anisotropy, and production rates may be larger, over longer times, for well configurations that use a greater well spacing. Finally, we performed preliminary calculations to assess a worst-case scenario for permeable system boundaries, and found that the efficiency of depressurization-based production strategies are compromised by migration of fluids from outside the system.

  6. Formation of Structured Water and Gas Hydrate by the Use of Xenon Gas in Vegetable Tissue

    NASA Astrophysics Data System (ADS)

    Ando, Hiroko; Suzuki, Toru; Kawagoe, Yoshinori; Makino, Yoshio; Oshita, Seiichi

    Freezing is a valuable technique for food preservation. However, vegetables are known to be softening remarkably after freezing and thawing process. It is expected to find alternative technique instead of freezing. Recently, the application of structured water and/or gas hydrate had been attempted to prolong the preservation of vegetable. In this study, the formation process of structure water and/or gas hydrate in pure water and carrot tissue was investigated by using NMR relaxation times, T1 and T2, of which applying condition was up to 0.4MPa and 0.8MPa at 5oC. Under the pressure of 0.4MPa, no gas hydrate was appeared, however, at 0.8MPa, formation of gas hydrate was recognized in both water and carrot tissue. Once the gas hydrate formation process in carrot tissue started, T1 and T2 increased remarkably. After that, as the gas hydrate developed, then T1 and T2 turned to decrease. Since this phenomenon was not observed in pure water, it is suggested that behavior of NMR relaxation time just after the formation of gas hydrate in carrot tissue may be peculiar to compartment system such as inter and intracellular spaces.

  7. Volatile inventories in clathrate hydrates formed in the primordial nebula.

    PubMed

    Mousis, Olivier; Lunine, Jonathan I; Picaud, Sylvain; Cordier, Daniel

    2010-01-01

    The examination of ambient thermodynamic conditions suggests that clathrate hydrates could exist in the Martian permafrost, on the surface and in the interior of Titan, as well as in other icy satellites. Clathrate hydrates are probably formed in a significant fraction of planetesimals in the solar system. Thus, these crystalline solids may have been accreted in comets, in the forming giant planets and in their surrounding satellite systems. In this work, we use a statistical thermodynamic model to investigate the composition of clathrate hydrates that may have formed in the primordial nebula. In our approach, we consider the formation sequence of the different ices occurring during the cooling of the nebula, a reasonable idealization of the process by which volatiles are trapped in planetesimals. We then determine the fractional occupancies of guests in each clathrate hydrate formed at a given temperature. The major ingredient of our model is the description of the guest-clathrate hydrate interaction by a spherically averaged Kihara potential with a nominal set of parameters, most of which are fitted to experimental equilibrium data. Our model allows us to find that Kr, Ar and N2 can be efficiently encaged in clathrate hydrates formed at temperatures higher than approximately 48.5 K in the primitive nebula, instead of forming pure condensates below 30 K. However, we find at the same time that the determination of the relative abundances of guest species incorporated in these clathrate hydrates strongly depends on the choice of the parameters of the Kihara potential and also on the adopted size of cages. Indeed, by testing different potential parameters, we have noted that even minor dispersions between the different existing sets can lead to non-negligible variations in the determination of the volatiles trapped in clathrate hydrates formed in the primordial nebula. However, these variations are not found to be strong enough to reverse the relative abundances

  8. (U) Implementation and demonstration of a time-resolved pyrometry/spectroscopy capability in shock compression experiments on metal oxide powders

    SciTech Connect

    Goodwin, Peter Marvin; Lang, Jr., John Michael; Dattelbaum, Dana Mcgraw; Scharff, Robert Jason

    2015-04-08

    Temperature is notably the most difficult quantity to measure in shock compression experiments; however, it is critical for accurately constraining theoretical or tabular equations of state. Until now, the temperature achieved during the shock loading of porous materials could only be calculated. The technique presented in this report measures, for the first time, the shocked temperature of porous systems.

  9. Analysis of microporosity and setting of reactive powder concrete by proton nuclear relaxation.

    PubMed

    Philippot, S; Korb, J P; Petit, D; Zanni, H

    1998-01-01

    The proton spin-lattice relaxation measured at several frequencies leads to a resolved distribution of four Tli for reactive powder concrete (RPC). The typical Tli frequency dependences are quantitatively interpreted by a biphasic fast exchange model and a proton nuclear relaxation of hydrated paramagnetic ions at the surface of the pores. This leads to an estimation of the pore sizes. We present the first application of this nuclear relaxation method to follow in situ the kinetics of the hydration and setting of such material. PMID:9803900

  10. Uptake of chloride and carbonate ions by calcium monosulfoaluminate hydrate

    SciTech Connect

    Mesbah, Adel; Cau-dit-Coumes, Celine; Frizon, Fabien

    2012-08-15

    Decommissioning of old nuclear reactors may produce waste streams containing chlorides and carbonates, including radioactive {sup 36}Cl{sup -} and {sup 14}CO{sub 3}{sup 2-}. Their insolubilization by calcium monosulfoaluminate hydrate was investigated. Carbonates were readily depleted from the solution, giving at thermodynamic equilibrium monocarboaluminate, monocarboaluminate + calcite, or calcite only, depending on the initial ratio between the anion and calcium monosulfoaluminate hydrate. Chloride ions reacted more slowly and were precipitated as Kuzel's salt, Kuzel's and Friedel's salts, or Friedel's salt only. Rietveld refinement of X-Ray powder diffraction patterns was successfully used to quantify the phase distributions, which were compared to thermodynamic calculations. Moreover, analysing the lattice parameters of Kuzel's salt as a function of its chloride content showed the occurrence of a restricted solid solution towards the sulfate side with general formula 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}xCaCl{sub 2}{center_dot}(1 - x)CaSO{sub 4}{center_dot}(12 - 2x){center_dot}H{sub 2}O (0.36 {<=} x {<=} 0.50).

  11. Hydration studies of calcium sulfoaluminate cements blended with fly ash

    SciTech Connect

    García-Maté, M.; De la Torre, A.G.; León-Reina, L.; Aranda, M.A.G.; Santacruz, I.

    2013-12-15

    The main objective of this work is to study the hydration and properties of calcium sulfoaluminate cement pastes blended with fly ash (FA) and the corresponding mortars at different hydration ages. Laboratory X-ray powder diffraction, rheological studies, thermal analysis, porosimetry and compressive strength measurements were performed. The analysis of the diffraction data by Rietveld method allowed quantifying crystalline phases and overall amorphous contents. The studied parameters were: i) FA content, 0, 15 and 30 wt.%; and ii) water addition, water-to-CSA mass ratio (w/CSA = 0.50 and 0.65), and water-to-binder mass ratio (w/b = 0.50). Finally, compressive strengths after 6 months of 0 and 15 wt.% FA [w/CSA = 0.50] mortars were similar: 73 ± 2 and 72 ± 3 MPa, respectively. This is justified by the filler effect of the FA as no strong evidences of reactivity of FA with CSA were observed. These results support the partial substitution of CSA cements with FA with the economic and environmental benefits.

  12. Methane hydrate research at NETL: Research to make methane production from hydrates a reality

    SciTech Connect

    Taylor, C.E.; Link, D.D.; English, N.

    2007-03-01

    Research is underway at NETL to understand the physical properties of methane hydrates. Five key areas of research that need further investigation have been identified. These five areas, i.e. thermal properties of hydrates in sediments, kinetics of natural hydrate dissociation, hysteresis effects, permeability of sediments to gas flow and capillary pressures within sediments, and hydrate distribution at porous scale, are important to the production models that will be used for producing methane from hydrate deposits. NETL is using both laboratory experiments and computational modeling to address these five key areas. The laboratory and computational research reinforce each other by providing feedback. The laboratory results are used in the computational models and the results from the computational modeling is used to help direct future laboratory research. The data generated at NETL will be used to help fulfill The National Methane Hydrate R&D Program of a “long-term supply of natural gas by developing the knowledge and technology base to allow commercial production of methane from domestic hydrate deposits by the year 2015” as outlined on the NETL Website [NETL Website, 2005. http://www.netl.doe.gov/scngo/Natural%20Gas/hydrates/index.html]. Laboratory research is accomplished in one of the numerous high-pressure hydrate cells available ranging in size from 0.15 mL to 15 L in volume. A dedicated high-pressure view cell within the Raman spectrometer allows for monitoring the formation and dissociation of hydrates. Thermal conductivity of hydrates (synthetic and natural) at a certain temperature and pressure is performed in a NETL-designed cell. Computational modeling studies are investigating the kinetics of hydrate formation and dissociation, modeling methane hydrate reservoirs, molecular dynamics simulations of hydrate formation, dissociation, and thermal properties, and Monte Carlo simulations of hydrate formation and dissociation.

  13. {sup 1}H nuclear magnetic resonance study of hydrated water dynamics in perfluorosulfonic acid ionomer Nafion

    SciTech Connect

    Han, Jun Hee; Lee, Kyu Won; Jeon, G. W.; Lee, Cheol Eui; Park, W. K.; Choi, E. H.

    2015-01-12

    We have studied the dynamics of hydrated water molecules in the proton exchange membrane of Nafion by means of high-resolution {sup 1}H nuclear magnetic resonance (NMR) measurements. “Bound” and “free” states of hydrated water clusters as well as the exchange protons were identified from the NMR chemical shift measurements, and their activation energies were obtained from the temperature-dependent laboratory- and rotating-frame spin-lattice relaxation measurements. Besides, a peculiar motional transition in the ultralow frequency region was observed at 373 K for the “free” hydrated water from the rotating-frame NMR spin-lattice relaxation time measurements.

  14. Demystifying Mystery Powders.

    ERIC Educational Resources Information Center

    Kotar, Michael

    1989-01-01

    Describes science activities which use simple chemical tests to distinguish between materials and to determine some of their properties. Explains the water, iodine, heat, acid, baking soda, acid/base indicator, glucose, and sugar tests. Includes activities to enhance chemical testing and a list of suggested powders for use. (RT)

  15. Novelty shop 'itching powder'.

    PubMed

    Albert, M R

    1998-08-01

    To evaluate causes of itch, commercial 'itching powders' were sought for evaluation. Only one product, produced in Germany and consisting of ground rose hips, is currently sold in novelty shops in the Boston area. These plant fibres appear to provoke itch and prickle sensations by non-allergic mechanical stimulation, similar to the action of wool fibres. PMID:9737050

  16. Investigation of hydrate formation and transportability in multiphase flow systems

    NASA Astrophysics Data System (ADS)

    Grasso, Giovanny A.

    The oil and gas industry is moving towards offshore developments in more challenging environments, where evaluating hydrate plugging risks to avoid operational/safety hazards becomes more difficult (Sloan, 2005). Even though mechanistic models for hydrate plug formation have been developed, components for a full comprehensive model are still missing. Prior to this work, research efforts were focused on flowing hydrate particles with relatively little research on hydrate accumulation, leaving hydrate deposition in multiphase flow an unexplored subject. The focus of this thesis was to better understand hydrate deposition as a form of accumu- lation in pipelines. To incorporate the multiphase flow effect, hydrate formation experiments were carried out at varying water cut (WC) from 15 to 100 vol.%, liquid loading (LL) from 50 to 85 vol.%, mixture velocity (vmix) from 0.75 to 3 m/s, for three fluids systems (100 % WC, water in Conroe crude oil emulsions and King Ranch condensate + water) on the ExxonMobil flowloop (4 in. nominal size and 314 ft. long) at Friendswood, TX. For the 100 % WC flowloop tests, hydrate particle distribution transitions beyond a critical hydrate volume concentration, observed values were between 8.2 to 29.4 vol.%, causing a sudden increase in pressure drop (DP). A revised correlation of the transition as a function of Reynolds number and liquid loading was developed. For Conroe emulsions, DP starts increasing at higher hydrate concentrations than King Ranch condensate, many times at 10 vol.%. Experiments with King Ranch show higher relative DP (10 to 25) than Conroe (2 to 10) performed at the same vmix and LL. Cohesive force measurements between cyclopentane hydrate particles were reduced from a value of 3.32 mN/m to 1.26 mN/m when 6 wt.% Conroe was used and to 0.41 mN/m when 5 wt.% Caratinga crude oil was used; similar values were obtained when extracted asphaltenes were used. King Ranch condensate (11 wt.%) did not significantly change the

  17. Design and fabrication of a real-time measurement system for the capsaicinoid content of Korean red pepper (Capsicum annuum L.) powder by visible and near-infrared spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This research aims to design and fabricate a system to measure the capsaicinoid content of red pepper powder in a non-destructive and rapid method through visible and near infrared spectroscopy (VNIR). The developed system scans a well-leveled powder surface continuously to minimize the influence of...

  18. Pre-Practice Hydration Status and the Effects of Hydration Regimen on Collegiate Division III Male Athletes

    PubMed Central

    Magal, Meir; Cain, Rebekah J.; Long, Josh C.; Thomas, Kathleen S.

    2015-01-01

    Pre-practice euhydration is key in the prevention of heat related injuries. The pre-practice hydration status of male National Collegiate Athletic Association (NCAA)-Division III athletes and the effects of a direct hydration regimen have yet to be investigated therefore; the aim of the study was 1) to analyze the pre-practice hydration status of current NCAA-DIII male athletes and 2) assess the impact of a directed intervention on pre-practice hydration status. The study was divided into baseline, pre and post intervention phases. For baseline, hydration status through urine specific gravity (USG) and anthropometric indices were measured prior to morning practice. Following baseline, pre-intervention commenced and participants were assigned to either control (CON) or experimental (EXP) groups. The CON and EXP group participants were instructed to maintain normal hydration and diet schedules and record fluid intake for seven days leading to post-intervention. The EXP group participants were asked to consume an additional 23.9 fl oz (~ 750 ml) per day for one week (7 days) leading to post-intervention. After 7 days the same measures were taken. At baseline, the majority of the participants were hypohydrated. Following the intervention, the EXP group participants consumed significantly more fluids than the participants in the CON group (3277.91 ± 1360. 23 ml vs 1931.54 ± 881.81 ml; p < 0.05). A-two-way repeated measure ANOVA revealed a non-significant time or treatment effect for USG or body mass but did demonstrate a significant USG interaction. In addition, an independent t-test examining absolute changes in USG demonstrated a significant difference between groups in which the EXP group improved hydration status and the CON group did not (-0.02 ± 0.006 vs 0.001 ± 0.005 ml; p < 0.05). In addition, there was no significant (p >0.05) difference in the regression slopes or intercepts between the CON and EXP groups when expressed as daily fluid intake per kg body

  19. Pre-Practice Hydration Status and the Effects of Hydration Regimen on Collegiate Division III Male Athletes.

    PubMed

    Magal, Meir; Cain, Rebekah J; Long, Josh C; Thomas, Kathleen S

    2015-03-01

    Pre-practice euhydration is key in the prevention of heat related injuries. The pre-practice hydration status of male National Collegiate Athletic Association (NCAA)-Division III athletes and the effects of a direct hydration regimen have yet to be investigated therefore; the aim of the study was 1) to analyze the pre-practice hydration status of current NCAA-DIII male athletes and 2) assess the impact of a directed intervention on pre-practice hydration status. The study was divided into baseline, pre and post intervention phases. For baseline, hydration status through urine specific gravity (USG) and anthropometric indices were measured prior to morning practice. Following baseline, pre-intervention commenced and participants were assigned to either control (CON) or experimental (EXP) groups. The CON and EXP group participants were instructed to maintain normal hydration and diet schedules and record fluid intake for seven days leading to post-intervention. The EXP group participants were asked to consume an additional 23.9 fl oz (~ 750 ml) per day for one week (7 days) leading to post-intervention. After 7 days the same measures were taken. At baseline, the majority of the participants were hypohydrated. Following the intervention, the EXP group participants consumed significantly more fluids than the participants in the CON group (3277.91 ± 1360. 23 ml vs 1931.54 ± 881.81 ml; p < 0.05). A-two-way repeated measure ANOVA revealed a non-significant time or treatment effect for USG or body mass but did demonstrate a significant USG interaction. In addition, an independent t-test examining absolute changes in USG demonstrated a significant difference between groups in which the EXP group improved hydration status and the CON group did not (-0.02 ± 0.006 vs 0.001 ± 0.005 ml; p < 0.05). In addition, there was no significant (p >0.05) difference in the regression slopes or intercepts between the CON and EXP groups when expressed as daily fluid intake per kg body

  20. X-ray Scanner for ODP Leg 204: Drilling Gas Hydrates on Hydrate Ridge, Cascadia Continental Margin

    SciTech Connect

    Freifeld, Barry; Kneafsey, Tim; Pruess, Jacob; Reiter, Paul; Tomutsa, Liviu

    2002-08-08

    An x-ray scanner was designed and fabricated at Lawrence Berkeley National Laboratory to provide high speed acquisition of x-ray images of sediment cores collected on the Ocean Drilling Program (ODP) Leg 204: Drilling Gas Hydrates On Hydrate Ridge, Cascadia Continental Margin. This report discusses the design and fabrication of the instrument, detailing novel features that help reduce the weight and increase the portability of the instrument. Sample x-ray images are included. The x-ray scanner was transferred to scientific drilling vessel, the JOIDES Resolution, by the resupply ship Mauna Loa, out of Coos Bay, Oregon on July 25. ODP technicians were trained in the instruments operation. The availability of the x-ray scanner at the drilling site allows real-time imaging of cores containing methane hydrate immediately after retrieval. Thus, imaging experiments on cores can yield information on the distribution and quantity of methane hydrates. Performing these measurements at the location of core collection eliminates the need for high pressures or low temperature core handling while the cores are stored and transported to a remote imaging laboratory.

  1. Analysis of Moisture and CO(2) Uptake in Anhydrous CdCl(2) Powders Used for Vapor CdCl(2) Treatment of CdS/CdTe PV Devices

    SciTech Connect

    Mazur, T.; Gessert, T.; Martins, G.; Curtis, C.

    2000-01-01

    Water and CO(2) uptake in CdCl(2) powder precursors was investigated using thermogravimetric analysis/Fourier transform infrared spectroscopy (TGA/FTIR). Exposure of powders under ambient conditions shows that a steady-state hydration level near 9% (by weight) is achieved after brief exposure to room air.

  2. Vibrational lifetimes of hydrated phospholipids

    NASA Astrophysics Data System (ADS)

    Jadidi, Tayebeh; Anvari, Mehrnaz; Mashaghi, Alireza; Sahimi, Muhammad; Rahimi Tabar, M. Reza

    2013-04-01

    Large-scale ab initio molecular-dynamics simulations have been carried out to compute, at human-body temperature, the vibrational modes and lifetimes of pure and hydrated dipalmitoylphosphatidylcholine (DPPC) lipids. The projected atomic vibrations calculated from the spectral energy density are used to compute the vibrational modes and the lifetimes. All the normal modes of the pure and hydrated DPPC and their frequencies are identified. The computed lifetimes incorporate the full anharmonicity of the atomic interactions. The vibrational modes of the water molecules close to the head group of DPPC are active (possess large projected spectrum amplitudes) in the frequency range 0.5-55 THz, with a peak at 2.80 THz in the energy spectrum. The computed lifetimes for the high-frequency modes agree well with the recent data measured at room temperature where high-order phonon scattering is not negligible. The computed lifetimes of the low-frequency modes can be tested using the current experimental capabilities. Moreover, the approach may be applied to other lipids and biomolecules, in order to predict their vibrational dispersion relations, and to study the dynamics of vibrational energy transfer.

  3. Evaluation of Gas Production Potential of Hydrate Deposits in Alaska North Slope using Reservoir Simulations

    NASA Astrophysics Data System (ADS)

    Nandanwar, M.; Anderson, B. J.

    2015-12-01

    Over the past few decades, the recognition of the importance of gas hydrates as a potential energy resource has led to more and more exploration of gas hydrate as unconventional source of energy. In 2002, U.S. Geological Survey (USGS) started an assessment to conduct a geology-based analysis of the occurrences of gas hydrates within northern Alaska. As a result of this assessment, many potential gas hydrate prospects were identified in the eastern National Petroleum Reserve Alaska (NPRA) region of Alaska North Slope (ANS) with total gas in-place of about 2 trillion cubic feet. In absence of any field test, reservoir simulation is a powerful tool to predict the behavior of the hydrate reservoir and the amount of gas that can be technically recovered using best suitable gas recovery technique. This work focuses on the advanced evaluation of the gas production potential of hydrate accumulation in Sunlight Peak - one of the promising hydrate fields in eastern NPRA region using reservoir simulations approach, as a part of the USGS gas hydrate development Life Cycle Assessment program. The main objective of this work is to develop a field scale reservoir model that fully describes the production design and the response of hydrate field. Due to the insufficient data available for this field, the distribution of the reservoir properties (such as porosity, permeability and hydrate saturation) are approximated by correlating the data from Mount Elbert hydrate field to obtain a fully heterogeneous 3D reservoir model. CMG STARS is used as a simulation tool to model multiphase, multicomponent fluid flow and heat transfer in which an equilibrium model of hydrate dissociation was used. Production of the gas from the reservoir is carried out for a period of 30 years using depressurization gas recovery technique. The results in terms of gas and water rate profiles are obtained and the response of the reservoir to pressure and temperature changes due to depressurization and hydrate

  4. Influence of chemical and physical characteristics of cement kiln dusts (CKDs) on their hydration behavior and potential suitability for soil stabilization

    SciTech Connect

    Peethamparan, Sulapha Olek, Jan Lovell, Janet

    2008-06-15

    The interaction of CKDs with a given soil depends on the chemical and physical characteristics of the CKDs. Hence, the characterization of CKDs and their hydration products may lead to better understanding of their suitability as soil stabilizers. In the present article, four different CKD powders are characterized and their hydration products are evaluated. A detailed chemical (X-ray diffraction), thermogravimetric and morphological (scanning electron microscope) analyses of both the CKD powders and the hydrated CKD pastes are presented. In general, high free-lime content ({approx} 14-29%) CKDs, when reacted with water produced significant amounts of calcium hydroxide, ettringite and syngenite. These CKDs also developed higher unconfined compressive strength and higher temperature of hydration compared to CKDs with lower amounts of free-lime. An attempt was made to qualitatively correlate the performance of CKD pastes with the chemical and physical characteristics of the original CKD powders and to determine their potential suitability as soil stabilizers. To that effect a limited unconfined compressive strength testing of CKD-treated kaolinite clays was performed. The results of this study suggest that both the compressive strength and the temperature of hydration of the CKD paste can give early indications of the suitability of particular CKD for soil stabilization.

  5. Gas hydrates in the ocean environment

    USGS Publications Warehouse

    Dillon, William P.

    2002-01-01

    A GAS HYDRATE, also known as a gas clathrate, is a gas-bearing, icelike material. It occurs in abundance in marine sediments and stores immense amounts of methane, with major implications for future energy resources and global climate change. Furthermore, gas hydrate controls some of the physical properties of sedimentary deposits and thereby influences seafloor stability.

  6. Real-time near-infrared monitoring of content uniformity, moisture content, compact density, tensile strength, and Young's modulus of roller compacted powder blends.

    PubMed

    Gupta, Abhay; Peck, Garnet E; Miller, Ronald W; Morris, Kenneth R

    2005-07-01

    A method for real-time in-line near-infrared (NIR) monitoring of roller compaction is reported. Multivariate analysis using partial least square projections to latent structures (PLS) was used to relate the spectral data with key compact attributes: content uniformity, moisture content, relative density, tensile strength, and Young's modulus. NIR calibration curves were generated using the spectral data collected on simulated ribbons, that is, tablets prepared under uni-axial compression, and tested on the data collected on another set of simulated ribbons and by monitoring the ribbons as they exited the roller compactor. For all compact attributes, the NIR predicted values agreed well with the values measured using a reference method. PMID:15924348

  7. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the revolutionary and new

  8. Local and bulk hydration of zwitterionic glycine and its analogues through molecular simulations.

    PubMed

    White, Andrew; Jiang, Shaoyi

    2011-02-01

    Molecular dynamics simulations were used to characterize the differences in hydration between glycine and two of its zwitterionic analogues: N,N-dimethylglycine and N,N,N-trimethylglycine (glycine betaine). The hydration of dodecane and oligo(ethylene glycol) was studied for reference. Both structuring and dynamics of bulk and bound water were examined using a variety of properties and at multiple concentrations. Metrics, such as radial distribution functions and residence times, were used to characterize hydration. Also, we used more specialized metrics that can discriminate between subtle differences in hydration, such as condensed phase order parameters, Voronoi tessellations, and multidimensional pair-pair correlation functions. Trimethylglycine was found to have a unique hydration shell that extends across the entire molecule and has no specific interactions between solute molecules. Also, we found that dimethylglycine has a similar hydration structure to that of trimethylglycine despite its hydrogen-bond donor. Glycine was found to aggregate and have a more disjoint hydration shell. All three zwitterions were found to structurally affect water within 1.5-2.0 coordination shells. Lastly, trimethylglycine is disperse in solution even at very high concentrations, and water rapidly moves between trimethylglycine amine groups. This work has meaningful implications for protein stability where trimethylglycine is known to prevent protein aggregation and nonfouling interfaces where trimethylglycine prevents nonspecific protein adsorption. PMID:21174438

  9. The Meaning of Parenteral Hydration to Family Caregivers and Patients with Advanced Cancer Receiving Hospice Care

    PubMed Central

    Cohen, Marlene Z; Torres-Vigil, Isabel; Burbach, Beth E.; de Rosa, Allison; Bruera, Eduardo

    2012-01-01

    Context In the U.S., patients with advanced cancer who are dehydrated or have decreased oral intake virtually always receive parenteral hydration in acute care facilities but rarely in the hospice setting. Objectives To describe the meaning of hydration for terminally ill cancer patients in home hospice care and for their primary caregivers. Methods Phenomenological interviews were conducted at two time points with 85 patients and 84 caregivers enrolled in a randomized, double-blind, controlled trial examining the efficacy of parenteral hydration in patients with advanced cancer receiving hospice care in the southern U.S. Transcripts were analyzed hermeneutically by the interdisciplinary research team until consensus on the theme labels was reached. Results Patients and their family caregivers both saw hydration as meaning hope and comfort. Hope was the view that hydration might prolong a life of dignity and enhance quality of life by reducing symptoms such as fatigue and increasing patients’ alertness. Patients and caregivers also described hydration as improving patients’ comfort by reducing pain, enhancing the effectiveness of pain medication, and nourishing the body, mind and spirit. Conclusion These findings differ from traditional hospice beliefs that dehydration enhances patient comfort given that patients and their families in the study viewed fluids as enhancing comfort, dignity and quality of life. Discussion with patients and families about their preferences for hydration may help tailor care plans to meet specific patient needs. PMID:22459230

  10. Hydration forces at solid and fluid biointerfaces.

    PubMed

    Shrestha, Buddha Ratna; Banquy, Xavier

    2016-03-01

    The authors review the different molecular mechanisms giving rise to the repulsive hydration force between biologically relevant surfaces such as lipid bilayers and bioceramics. As the authors will show, the hydration force manifests itself in very different and subtle ways depending on the substrates. Soft, mobile surfaces such as lipid bilayers tend to exhibit monotonic, decaying hydration force, originated from the entropic constriction of the lipid head groups. Solid surfaces, on the other hand, tend to exhibit a periodic oscillatory hydration force, originated from the surface induced polarization of water molecules. In this review, the authors will describe both subtle faces of this important interaction by first describing the early experiments performed on solid surfaces and their interpretation by recent simulation studies. Then, the authors will describe the hydration force between fluid interfaces such as bilayers and explain how experimentally researchers have unraveled the dominant role of the lipid head groups' conformation. PMID:26795057

  11. Calorimetric study of crystal growth of ice in hydrated methemoglobin and of redistribution of the water clusters formed on melting the ice.

    PubMed Central

    Sartor, G; Mayer, E

    1994-01-01

    Calorimetric studies of the melting patterns of ice in hydrated methemoglobin powders containing between 0.43 and 0.58 (g water)/(g protein), and of their dependence on annealing at subzero temperatures and on isothermal treatment at ambient temperature are reported. Cooling rates were varied between approximately 1500 and 5 K min-1 and heating rate was 30 K min-1. Recrystallization of ice during annealing is observed at T > 228 K. The melting patterns of annealed samples are characteristically different from those of unannealed samples by the shifting of the melting temperature of the recrystallized ice fraction to higher temperatures toward the value of "bulk" ice. The "large" ice crystals formed during recrystallization melt on heating into "large" clusters of water whose redistribution and apparent equilibration is followed as a function of time and/or temperature by comparison with melting endotherms. We have also studied the effect of cooling rate on the melting pattern of ice with a methemoglobin sample containing 0.50 (g water)/(g protein), and we surmise that for this hydration cooling at rates of > or = approximately 150 K min-1 preserves on the whole the distribution of water molecules present at ambient temperature. PMID:7819504

  12. Method to blend separator powders

    DOEpatents

    Guidotti, Ronald A.; Andazola, Arthur H.; Reinhardt, Frederick W.

    2007-12-04

    A method for making a blended powder mixture, whereby two or more powders are mixed in a container with a liquid selected from nitrogen or short-chain alcohols, where at least one of the powders has an angle of repose greater than approximately 50 degrees. The method is useful in preparing blended powders of Li halides and MgO for use in the preparation of thermal battery separators.

  13. Method for synthesizing powder materials

    DOEpatents

    Buss, R.J.; Ho, P.

    1988-01-21

    A method for synthesizing ultrafine powder materials, for example, ceramic and metal powders, comprises admitting gaseous reactants from which the powder material is to be formed into a vacuum reaction chamber maintained at a pressure less than atmospheric and at a temperature less than about 400/degree/K (127/degree/C). The gaseous reactants are directed through a glow discharge provided in the vacuum reaction chamber to form the ultrafine powder material. 1 fig.

  14. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-07-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated and is

  16. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-06-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  17. Overview on Hydrate Coring, Handling and Analysis

    SciTech Connect

    Jon Burger; Deepak Gupta; Patrick Jacobs; John Shillinglaw

    2003-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Worldwide, gas hydrate is estimated to hold about 1016 kg of organic carbon in the form of methane (Kvenvolden et al., 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In June 2002, Westport Technology Center was requested by the Department of Energy (DOE) to prepare a ''Best Practices Manual on Gas Hydrate Coring, Handling and Analysis'' under Award No. DE-FC26-02NT41327. The scope of the task was specifically targeted for coring sediments with hydrates in Alaska, the Gulf of Mexico (GOM) and from the present Ocean Drilling Program (ODP) drillship. The specific subjects under this scope were defined in 3 stages as follows: Stage 1: Collect information on coring sediments with hydrates, core handling, core preservation, sample transportation, analysis of the core, and long term preservation. Stage 2: Provide copies of the first draft to a list of experts and stakeholders designated by DOE. Stage 3: Produce a second draft of the manual with benefit of input from external review for delivery. The manual provides an overview of existing information available in the published literature and reports on coring, analysis, preservation and transport of gas hydrates for laboratory analysis as of June 2003. The manual was delivered as draft version 3 to the DOE Project Manager for distribution in July 2003. This Final Report is provided for records purposes.

  18. FTIR spectroscopic study of the dynamics of conformational substates in hydrated carbonyl-myoglobin films via temperature dependence of the CO stretching band parameters.

    PubMed Central

    Mayer, E

    1994-01-01

    Two hydrated carbonyl myoglobin (MbCO) films, one containing (0.30 g water)/(g MbCO) from MbCO solution in water at pH 5.5 and the other (0.32 g water)/(gMbCO) from 0.1 M potassium phosphate buffer solution at pH 6.8, were studied by FTIR spectroscopy from 293 K to 78 K at selected temperatures on cooling and reheating. Above approximately 180 K the general trend in temperature dependence of half-bandwidths, peak maxima, and band area ratios of the A1 and A3 conformer bands is similar to those reported by Ansari et al. (1987. Biophys. J. 26:337) for MbCO in 75% glycerol/water solution, but abrupt changes in slopes at approximately 180-200 K and freezing-in of conformer populations, which could be taken as indicator for glass transition of the solvent or the protein, are absent for the hydrated MbCO films. This is interpreted in terms of an exceptionally broad distribution of relaxation times, and is in accord with conclusions from recent calorimetric annealing studies of hydrated protein powders (Sartor et al. 1994. Biophys. J. 66:249). Exchange between the three A conformers does not stop at approximately 180-200 K but occurs over the whole temperature region studied. These results are then discussed with respect to MbCO's behavior in the glass-->liquid transition region of glass-forming solvents, and it is concluded that, in analogy to the behavior of low-molecular-weight compounds with a distribution of rapidly interconverting conformers, freezing-in of MbCO's A conformer populations by the solvent should not be mistaken for a glass transition of MbCO. PMID:7948699

  19. Amorphous powders of Al-Hf prepared by mechanical alloying

    SciTech Connect

    Schwarz, R.B.; Hannigan, J.W.; Sheinberg, H.; Tiainen, T.

    1988-01-01

    We synthesized amorphous Al/sub 50/Hf/sub 50/ alloy powder by mechanically alloying an equimolar mixture of crystalline powders of Al and Hf using hexane as a dispersant. We characterized the powder as a function of mechanical-alloying time by scanning electron microscopy, x-ray diffraction, and differential scanning calorimetry. Amorphous Al/sub 50/Hf/sub 50/ powder heated at 10 K s/sup /minus/1/ crystallizes polymorphously at 1003 K into orthorhombic AlHf (CrB-type structure). During mechanical alloying, some hexane decomposes and hydrogen and carbon are incorporated into the amorphous alloy powder. The hydrogen can be removed by annealing the powder by hot pressing at a temperature approximately 30 K below the crystallization temperature. The amorphous compacts have a diamond pyramidal hardness of 1025 DPH. 24 refs., 7 figs., 1 tab.

  20. Ultrastructure of unstained, hydrated proteoglycan aggregates and monomer: a new method of imaging

    SciTech Connect

    Panessa, B J; Hoffman, P; Warren, J B; McCorkle, R A; Coleman, G

    1980-01-01

    The application of a new method for imaging delicate hydrated biological materials is reported, and the structure of isolated proteoglycan aggregates and monomer is demonstrated at better than 30 nm resolution. This new method for high resolution examination of labile hydrated biological materials, employing a wet cell and pulsed plasma x-ray source, permits short exposure times, minimal specimen damage, and sufficient radiation dosages for imaging. (ERB)

  1. Vacuum powder injector and method of impregnating fiber with powder

    NASA Technical Reports Server (NTRS)

    Working, Dennis C. (Inventor)

    1993-01-01

    A method and apparatus uniformly impregnate stranded material with dry powder such as low solubility, high melt flow polymer powder to produce, for example, composite prepregs. The stranded material is expanded in an impregnation chamber by an influx of air so that the powder, which may enter through the same inlet as the air, penetrates to the center of the stranded material. The stranded material then is contracted for holding the powder therein. The stranded material and powder may be pulled through the impregnation chamber in the same direction by vacuum. Larger particles of powder which do not fully penetrate the stranded material may be combed into the stranded material and powder which does not impregnate the stranded material may be collected and reused.

  2. Temperature dependence of polyhedral cage volumes in clathrate hydrates

    USGS Publications Warehouse

    Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Stern, L.A.; Circone, S.; Kirby, S.H.; Ishii, Y.; Jones, C.Y.; Toby, B.H.

    2003-01-01

    The polyhedral cage volumes of structure I (sI) (carbon dioxide, methane, trimethylene oxide) and structure II (sII) (methane-ethane, propane, tetrahydrofuran, trimethylene oxide) hydrates are computed from atomic positions determined from neutron powder-diffraction data. The ideal structural formulas for sI and sII are, respectively, S2L6 ?? 46H2O and S16L???8 ?? 136H2O, where S denotes a polyhedral cage with 20 vertices, L a 24-cage, and L??? a 28-cage. The space-filling polyhedral cages are defined by the oxygen atoms of the hydrogen-bonded network of water molecules. Collectively, the mean cage volume ratio is 1.91 : 1.43 : 1 for the 28-cage : 24-cage : 20-cage, which correspond to equivalent sphere radii of 4.18, 3.79, and 3.37 A??, respectively. At 100 K, mean polyhedral volumes are 303.8, 227.8, and 158.8 A??3 for the 28-cage, 24-cage, and 20-cage, respectively. In general, the 20-cage volume for a sII is larger than that of a sI, although trimethylene oxide is an exception. The temperature dependence of the cage volumes reveals differences between apparently similar cages with similar occupants. In the case of trimethylene oxide hydrate, which forms both sI and sII, the 20-cages common to both structures contract quite differently. From 220 K, the sII 20-cage exhibits a smooth monotonic reduction in size, whereas the sI 20-cage initially expands upon cooling to 160 K, then contracts more rapidly to 10 K, and overall the sI 20-cage is larger than the sII 20-cage. The volumes of the large cages in both structures contract monotonically with decreasing temperature. These differences reflect reoriented motion of the trimethyelene oxide molecule in the 24-cage of sI, consistent with previous spectroscopic and calorimetric studies. For the 20-cages in methane hydrate (sI) and a mixed methane-ethane hydrate (sII), both containing methane as the guest molecule, the temperature dependence of the 20-cage volume in sII is much less than that in sI, but sII is overall

  3. Processing polymeric powders

    NASA Technical Reports Server (NTRS)

    Throne, James L.

    1989-01-01

    The concept of uniformly and continuously depositing and sinter-fusing nominal 0.1 to 40 microns dimensioned electrostatically charged polymer powder particles onto essentially uniformly spread 5 to 20 micron grounded continuous fiber tow to produce a respoolable thermoplastic composite two-preg was formulated at NASA Langley. The process was reduced to practice under a NASA grant at the University of Akron this spring. The production of tow-preg is called phase 1. The production of ultrafine polymer powders from 5 to 10 percent (wt) polymer solids in solvent is considered. This is phase 0 and is discussed. The production of unitape from multi tow-pregs was also considered. This is phase 2 and is also discussed. And another approach to phase 1, also proposed last summer, was scoped. This is phase 1A and is also discussed.

  4. Advanced powder processing

    SciTech Connect

    Janney, M.A.

    1997-04-01

    Gelcasting is an advanced powder forming process. It is most commonly used to form ceramic or metal powders into complex, near-net shapes. Turbine rotors, gears, nozzles, and crucibles have been successfully gelcast in silicon nitride, alumina, nickel-based superalloy, and several steels. Gelcasting can also be used to make blanks that can be green machined to near-net shape and then high fired. Green machining has been successfully applied to both ceramic and metal gelcast blanks. Recently, the authors have used gelcasting to make tooling for metal casting applications. Most of the work has centered on H13 tool steel. They have demonstrated an ability to gelcast and sinter H13 to near net shape for metal casting tooling. Also, blanks of H13 have been cast, green machined into complex shape, and fired. Issues associated with forming, binder burnout, and sintering are addressed.

  5. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  6. Clathrate hydrate tuning for technological purposes

    NASA Astrophysics Data System (ADS)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

    2010-05-01

    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  7. Gravimetric method for in vitro calibration of skin hydration measurements.

    PubMed

    Martinsen, Ørjan G; Grimnes, Sverre; Nilsen, Jon K; Tronstad, Christian; Jang, Wooyoung; Kim, Hongsig; Shin, Kunsoo; Naderi, Majid; Thielmann, Frank

    2008-02-01

    A novel method for in vitro calibration of skin hydration measurements is presented. The method combines gravimetric and electrical measurements and reveals an exponential dependency of measured electrical susceptance to absolute water content in the epidermal stratum corneum. The results also show that absorption of water into the stratum corneum exhibits three different phases with significant differences in absorption time constant. These phases probably correspond to bound, loosely bound, and bulk water. PMID:18270010

  8. Dynamics in the methane hydrate system of the Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Mienert, Jurgen; Andreassen, Karin; Knies, Jochen; Carroll, JoLynn; Bünz, Stephan; Ferre, Benedicte; Rasmussen, Tine; Panieri, Giuliana; Myhre, Catherine Lund

    2014-05-01

    Methane hydrate formed in abundance in deep permafrost regions but little documentation exists about resource accumulation in shallow Arctic subsea areas and its evolution in time and space. Today's sub-seabed methane hydrate reservoirs remain elusive targets as a natural methane emitter that influences ocean environments and ecosystems. Rising Arctic Ocean temperatures are causing a destabilization of these reservoirs which in turn releases methane leading to geo-hazards, ocean acidification, and marine benthic reaction at unknown rates and response times. CAGE - Centre for Arctic Gas Hydrate, Environment, and Climate initiates a ten year interdisciplinary research and education program aimed at achieving a quantitative understanding of feedbacks between methane sub-seabed reservoirs, the seabed and the ocean. The Centre addresses how the coupled (reservoirs-seabed-ocean) system in the Arctic reacts and affects the future ocean, its environment and possibly the climate with focus on high resolution geophysics; seabed gas-emissions; environmental reactions; and benthic-response times. The project MOCA (Methane emissions from the Arctic Ocean to the Atmosphere) concentrates on the atmospheric component and present as well as future climate effects. Details on the CAGE research plan and organization will be presented to foster opportunities for cross-disciplinary collaboration. Based in Tromsø, at the world's northernmost University, CAGE establishes the intellectual and infrastructure resources for studying the amount of methane hydrate and magnitude of methane release in Arctic Ocean environments on time scales from the Neogene to the present (www.cage.uit.no). The Centre of Excellence is funded by the Norwegian Research Council ((grant No. 223259) over a period of ten years.

  9. Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

    USGS Publications Warehouse

    Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

    2013-01-01

    As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

  10. The Complexity of Hydration of Phloroglucinol: A Comprehensive Structural and Thermodynamic Characterization

    PubMed Central

    2012-01-01

    Hydrate formation is of great importance as the inclusion of water molecules affects many solid state properties and hence determines the required chemical processing, handling, and storage. Phloroglucinol is industrially important, and the observed differences in the morphology and diffuse scattering effects with growth conditions have been scientifically controversial. We have studied the anhydrate and dihydrate of phloroglucinol and their transformations by a unique combination of complementary experimental and computational techniques, namely, moisture sorption analysis, hot-stage microscopy, differential scanning calorimetry, thermogravimetry, isothermal calorimetry, single crystal and powder X-ray diffractometry, and crystal energy landscape calculations. The enthalpically stable dihydrate phase is unstable below 16% relative humidity (25 °C) and above 50 °C (ambient humidity), and the kinetics of hydration/dehydration are relatively rapid with a small hysteresis. A consistent atomistic picture of the thermodynamics of the hydrate/anhydrate transition was derived, consistent with the disordered single X-ray crystal structure and crystal energy landscape showing closely related low energy hydrate structures. These structures provide models for proton disorder and show stacking faults as intergrowth of different layers are possible. This indicates that the consequent variability in crystal surface features and diffuse scattering with growth conditions is not a practical concern. PMID:22390190

  11. X-ray synchrotron diffraction study of natural gas hydrates from African margin

    NASA Astrophysics Data System (ADS)

    Bourry, Christophe; Charlou, Jean-Luc; Donval, Jean-Pierre; Brunelli, Michela; Focsa, Cristian; Chazallon, Bertrand

    2007-11-01

    Natural gas hydrates recovered from the Congo-Angola basin and Nigerian margins are analyzed by synchrotron X-ray powder diffraction. Biogenic methane is the most abundant gas trapped in the samples and others minor components (CO2, H2S) are co-clathrated in a type I cubic lattice structure. The refinement for the type I structure gives lattice parameters of a = 11.8646 (39) Å and a = 11.8619 (23) Å for specimens from Congo-Angola and Nigerian margins respectively at 90 K. These values, intermediate between the lattice constant of less pure methane specimens and pure artificial methane hydrates, indicate that lattice constants can be affected by the presence of encaged CO2, H2S and other gas molecules, even in small amounts. Thermal expansion is also presented for Congo-Angola hydrate in the temperature range 90-200 K. The coefficients are comparable with values reported for synthetic hydrates at low temperature and tend to approach thermal expansion of ice at higher temperature.

  12. Detection and Production of Methane Hydrate

    SciTech Connect

    George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

    2011-12-31

    This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand processes

  13. Surface topography dependence of biomolecular hydrophobic hydration

    NASA Astrophysics Data System (ADS)

    Cheng, Yuen-Kit; Rossky, Peter J.

    1998-04-01

    Many biomolecules are characterized by surfaces containing extended nonpolar regions, and the aggregation and subsequent removal of such surfaces from water is believed to play a critical role in the biomolecular assembly in cells. A better understanding of the hydrophobic hydration of biomolecules may therefore yield new insights into intracellular assembly. Conventional views hold that the hydration shell of small hydrophobic solutes is clathrate-like, characterized by local cage-like hydrogen-bonding structures and a distinct loss in entropy. The hydration of extended nonpolar planar surfaces, however, appears to involve structures that are orientationally inverted relative to clathrate-like hydration shells,, with unsatisfied hydrogen bonds that are directed towards the hydrophobic surface. Here we present computer simulations of the interaction between the polypeptide melittin and water that demonstrate that the two different hydration structures also exist near a biomolecular surface. We find that the two structures are distinguished by a substantial difference in the water-water interaction enthalpy, and that their relative contributions depend strongly on the surface topography of the melittin molecule: clathrate-like structures dominate near convex surface patches, whereas the hydration shell near flat surfaces fluctuates between clathrate-like and less-ordered or inverted structures. The strong influence of surface topography on the structure and free energy of hydrophobic hydration is likely to hold in general, and will be particularly important for the many biomolecules whose surfaces contain convex patches, deep or shallow concave grooves and roughly planar areas.

  14. Gas Hydrates Research Programs: An International Review

    SciTech Connect

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  15. Electrical properties of methane hydrate + sediment mixtures

    USGS Publications Warehouse

    Du Frane, Wyatt L.; Stern, Laura A.; Weitemeyer, Karen A.; Constable, Steven; Roberts, Jeffery J.

    2011-01-01

    As part of our DOE-funded proposal to characterize gas hydrate in the Gulf of Mexico using marine electromagnetic methods, a collaboration between SIO, LLNL, and USGS with the goal of measuring the electrical properties of lab-created methane (CH4) hydrate and sediment mixtures was formed. We examined samples with known characteristics to better relate electrical properties measured in the field to specific gas hydrate concentration and distribution patterns. Here we discuss first-ever electrical conductivity (σ) measurements on unmixed CH4 hydrate (Du Frane et al., 2011): 6 x 10-5 S/m at 5 °C, which is ~5 orders of magnitude lower than seawater. This difference allows electromagnetic (EM) techniques to distinguish highly resistive gas hydrate deposits from conductive water saturated sediments in EM field surveys. More recently, we performed measurements on CH4 hydrate mixed with sediment and we also discuss those initial findings here. Our results on samples free of liquid water are important for predicting conductivity of sediments with pores highly saturated with gas hydrate, and are an essential starting point for comprehensive mixing models.

  16. Ab Initio Studies of Calcium Carbonate Hydration.

    PubMed

    Lopez-Berganza, Josue A; Diao, Yijue; Pamidighantam, Sudhakar; Espinosa-Marzal, Rosa M

    2015-11-25

    Ab initio simulations of large hydrated calcium carbonate clusters are challenging due to the existence of multiple local energy minima. Extensive conformational searches around hydrated calcium carbonate clusters (CaCO3·nH2O for n = 1-18) were performed to find low-energy hydration structures using an efficient combination of Monte Carlo searches, density-functional tight binding (DFTB+) method, and density-functional theory (DFT) at the B3LYP level, or Møller-Plesset perturbation theory at the MP2 level. This multilevel optimization yields several low-energy structures for hydrated calcium carbonate. Structural and energetics analysis of the hydration of these clusters revealed a first hydration shell composed of 12 water molecules. Bond-length and charge densities were also determined for different cluster sizes. The solvation of calcium carbonate in bulk water was investigated by placing the explicitly solvated CaCO3·nH2O clusters in a polarizable continuum model (PCM). The findings of this study provide new insights into the energetics and structure of hydrated calcium carbonate and contribute to the understanding of mechanisms where calcium carbonate formation or dissolution is of relevance. PMID:26505205

  17. Mechanisms for thermal conduction in hydrogen hydrate

    NASA Astrophysics Data System (ADS)

    English, Niall J.; Gorman, Paul D.; MacElroy, J. M. D.

    2012-01-01

    Extensive equilibrium molecular dynamics simulations have been performed to investigate thermal conduction mechanisms via the Green-Kubo approach for (type II) hydrogen hydrate, at 0.05 kbar and between 30 and 250 K, for both lightly filled H2 hydrates (1s4l) and for more densely filled H2 systems (2s4l), in which four H2 molecules are present in the large cavities, with respective single- and double-occupation of the small cages. The TIP4P water model was used in conjunction with a fully atomistic hydrogen potential along with long-range Ewald electrostatics. It was found that substantially less damping in guest-host energy transfer is present in hydrogen hydrate as is observed in common type I clathrates (e.g., methane hydrate), but more akin in to previous results for type II and H methane hydrate polymorphs. This gives rise to larger thermal conductivities relative to common type I hydrates, and also larger than type II and H methane hydrate polymorphs, and a more crystal-like temperature dependence of the thermal conductivity.

  18. Prospecting for marine gas hydrate resources

    USGS Publications Warehouse

    Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.

    2016-01-01

    As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.

  19. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, Raghunath

    1998-01-01

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

  20. Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Qorbani, Khadijeh; Kvamme, Bjørn

    2016-04-01

    Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated

  1. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2003-12-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the US have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by maurer Technology, noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R and D in the area of onshore hydrate deposition. They plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. They also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. They are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. They hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, the goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  2. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by Maurer Technology, Noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition. We plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. We also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. We are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. We hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, our goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  3. Electrical properties of methane hydrate + sediment mixtures

    NASA Astrophysics Data System (ADS)

    Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; Weitemeyer, Karen A.; Smith, Megan M.; Roberts, Jeffery J.

    2015-07-01

    Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. Toward this goal, we built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EM field surveys. Here we report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. These results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.

  4. Assessment of sorbent reactivation by water hydration for fluidized bed combustion application

    SciTech Connect

    Fabio Montagnaro; Piero Salatino; Fabrizio Scala; Yinghai Wu; Edward J. Anthony; Lufei Jia

    2006-06-15

    Disposal of fluidized bed combustion (FBC) solid residues currently represents one of the major issues in FBC design and operation, and contributes significantly to its operating cost. This issue has triggered research activities on the enhancement of sorbent utilization for in situ sulfur removal. The present study addresses the effectiveness of the reactivation by liquid water hydration of FB spent sorbents. Two materials are considered in the study, namely the bottom ash from the operation of a full-scale utility FB boiler and the raw commercial limestone used in the same boiler. Hydration-reactivation tests were carried out at temperatures of 40{sup o}C and 80{sup o}C and for curing times ranging from 15 minutes to 2d, depending on the sample. The influence of hydration conditions on the enhancement of sulfur utilization has been assessed. A combination of methods has been used to characterize the properties of liquid water-hydrated materials

  5. New insights into water bonding during early tricalcium silicate hydration with quasielastic neutron scattering

    SciTech Connect

    Gutberlet, T.; Hilbig, H.; Beddoe, R.E.; Lohstroh, W.

    2013-09-15

    New information on the water bonding during the first 36 h of hydration of tricalcium silicate was obtained using the high neutron flux at the sample position of the time-of-flight spectrometer (TOFTOF), FRM II in Garching, Germany, together with {sup 29}Si NMR and X-ray diffraction measurements. A rapid increase in the amount of constrained water was observed at the beginning of the induction period. This is attributed to the formation of an early C-S-H with a large specific surface area (around 800 m{sup 2}/g). During subsequent hydration, the amount of constrained water, as given by the total surface area of the hydration products, is controlled by (a) the formation of new metastable early C-S-H which increases total surface area and (b) polymerisation processes which reduce total surface area. The relative contribution of these processes varies during hydration.

  6. Sludge ash/hydrated lime on the geotechnical properties of soft soil.

    PubMed

    Lin, Deng-Fong; Lin, Kae-Long; Hung, Min-Jui; Luo, Huan-Lin

    2007-06-25

    In this study, an effort to improve the properties and strength of soil, sewage sludge ash (SSA) and hydrated lime are applied to stabilize soft cohesive subgrade soil. Five different ratios (in weight percentage), 0%, 2%, 4%, 8%, and 16%, of sludge ash/hydrated lime are proposed for mixture with cohesive soil. Then, the effects of the different proportions of SSA/hydrated lime on soft cohesive soil are studied. Test results indicate that the unconfined compressive strength of specimens with additives was raised from three to seven times better than that of the untreated soil, and swelling behaviors were also effectively reduced for those specimens. Results of triaxial compression test indicate that the shear strength parameter, c, rose with an increased amount of additives and improved from 30 to 50-70kPa. On the whole, SSA/hydrated lime could particularly improve the geotechnical properties of cohesive subgrade soil. PMID:17141407

  7. Silicon nitride/silicon carbide composite powders

    DOEpatents

    Dunmead, Stephen D.; Weimer, Alan W.; Carroll, Daniel F.; Eisman, Glenn A.; Cochran, Gene A.; Susnitzky, David W.; Beaman, Donald R.; Nilsen, Kevin J.

    1996-06-11

    Prepare silicon nitride-silicon carbide composite powders by carbothermal reduction of crystalline silica powder, carbon powder and, optionally, crystalline silicon nitride powder. The crystalline silicon carbide portion of the composite powders has a mean number diameter less than about 700 nanometers and contains nitrogen. The composite powders may be used to prepare sintered ceramic bodies and self-reinforced silicon nitride ceramic bodies.

  8. Clathrate hydrates in cometary nuclei and porosity

    NASA Technical Reports Server (NTRS)

    Smoluchowski, R.

    1988-01-01

    Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

  9. Carbon dioxide hydrate and floods on Mars

    NASA Technical Reports Server (NTRS)

    Milton, D. J.

    1974-01-01

    Ground ice on Mars probably consists largely of carbon dioxide hydrate. This hydrate dissociates upon release of pressure at temperatures between 0 and 10 C. The heat capacity of the ground would be sufficient to produce up to 4% (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near-surface temperature was in this range would have produced chaotic terrain and flood channels.

  10. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    SciTech Connect

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-05-21

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.

  11. X-ray Diffraction Analysis of ProRoot Mineral Trioxide Aggregate Hydrated at Different pH Values

    PubMed Central

    Akhavan, Hengameh; Mohebbi, Pooneh; Firouzi, Amir; Noroozi, Mehdi

    2016-01-01

    Introduction: The aim of this study was to compare the chemical compounds of white ProRoot mineral trioxide aggregate (WMTA) hydrated at different pH environments. Methods and Materials: Mixed samples of WMTA were kept in acidic (pH=5.4), neutral (pH=7.4) and alkaline (pH=9.4) environments for 48 h. Then, X-ray diffraction (XRD) analysis was performed for both hydrated and powder forms of WMTA. Portlandite crystalline structures of environments were compared from three aspects: intensity (height of the peak, corresponding to the concentration), crystallinity (peak area/total area) and crystal size (full-width at half-maximum of the peak). Results: After matching the peaks of each sample with those of the International Center for Diffraction Data (ICDD) database, the main constituent of all set cements and powder form was found to be bismuth oxide. Acidic environment exhibited lower intensity and crystallinity of portlandite in comparison with neutral environment. Conclusion: The highest concentration and crystallinity of portlandite were observed in WMTA samples hydrated at neutral pH and the highest crystal size was detected after hydration in alkaline pH. PMID:27141218

  12. Effects of suspension pH and mineral dissolution on carbon dioxide hydrate formation

    NASA Astrophysics Data System (ADS)

    Lee, W.; Lamorena, R. B.

    2008-12-01

    CO2 sequestration as a form of hydrate into geological formations could be significantly affected by soil mineral heterogeneity potentially contributing to the stochastic behavior of hydrate formation. In this study, we controlled the pH of soil mineral suspensions (Na-montmorillonite, kaolinite mixture, and pyrite) by the addition of 2M/10M NaOH and 2M/10M HCl before the dissolution of CO2. The soil mineral suspensions were prepared in deionized water (DIW) and NaCl (3.5 %) solutions. The formation of mass of CO2 hydrates was observed in most of the soil mineral suspensions at 30 bar and 0.3°C. In montmoril