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Sample records for partially hydrated hafnium

  1. Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

    NARCIS (Netherlands)

    Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

    2010-01-01

    Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the

  2. The unfolding effects on the protein hydration shell and partial molar volume: a computational study.

    Science.gov (United States)

    Del Galdo, Sara; Amadei, Andrea

    2016-10-12

    In this paper we apply the computational analysis recently proposed by our group to characterize the solvation properties of a native protein in aqueous solution, and to four model aqueous solutions of globular proteins in their unfolded states thus characterizing the protein unfolded state hydration shell and quantitatively evaluating the protein unfolded state partial molar volumes. Moreover, by using both the native and unfolded protein partial molar volumes, we obtain the corresponding variations (unfolding partial molar volumes) to be compared with the available experimental estimates. We also reconstruct the temperature and pressure dependence of the unfolding partial molar volume of Myoglobin dissecting the structural and hydration effects involved in the process.

  3. Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

    International Nuclear Information System (INIS)

    Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R.; Miller, Benjamin T.; Brooks, Bernard R.; Ichiye, Toshiko

    2015-01-01

    The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V E as a function of ethanol mole fraction X E is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water

  4. Metallurgy of zirconium and hafnium

    International Nuclear Information System (INIS)

    Baryshnikov, N.V.; Geger, V.Eh.; Denisova, N.D.; Kazajn, A.A.; Kozhemyakin, V.A.; Nekhamkin, L.G.; Rodyakin, V.V.; Tsylov, Yu.A.

    1979-01-01

    Considered are those properties of zirconium and of hafnium, which are of practical interest for the manufacture of these elements. Systematized are the theoretical and the practical data on the procedures for thermal decomposition of zirconia and for obtaining zirconium dioxide and hafnium dioxide by a thermal decomposition of compounds and on the hydrometallurgical methods for extracting zirconium and hafnium. Zirconium and hafnium fluorides and chlorides production procedures are described. Considered are the iodide and the electrolytic methods of refining zirconium and hafnium

  5. Investigation of colourless complexes of thorium, hafnium and zirconium

    International Nuclear Information System (INIS)

    Kiciak, S.; Stefanowicz, T.; Gontarz, H.; Swit, Z.

    1980-01-01

    The investigations conducted in the Institute of General Chemistry of Poznan Technical University in partial cooperation with Kharkhof Technical University related with thorium, hafnium and zirconium complexes are reviewed. (author)

  6. Properties of filmogen solutions and films of hafnium compounds

    International Nuclear Information System (INIS)

    Sviridova, A.I.

    1986-01-01

    Study on hafnium hydrolizing compound solutions, used for hafnium oxide homogeneous layer formation, is conducted. In particular, electric conductivity, acidity and refractive index were investigated depending on the sal on ether concentration and the storage time. Oxyhafnium nitrate, hafnium chloride in ethanol, dichlorodiethoxyhafnium, hafnium oxychloride were used as initial compounds. Hydrolysis of hafnium compounds in solution occurs partially; further process occurs in the thin layer on the optical element surface; final decomposition is performed under heat treatment. It is ascertained, that alcoholic-aqueous solutions of inorganic salts can be filmogen only at definite acidity, density and viscosity (1.33-2.5 cp.). It is also ascertained that refractive index values and transmission spectral boundary of coatings, produced from alkoxy compound solutions and from chloride salt solutions, are practically the same. Transmittance boundary in ultraviolet region of spectrum of oxide films produced from nitrate and chloride solutions, varies with the heating temperature increase differently

  7. SEPARATING HAFNIUM FROM ZIRCONIUM

    Science.gov (United States)

    Lister, B.A.J.; Duncan, J.F.

    1956-08-21

    A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

  8. Commercial production of metal hafnium and hafnium-based products

    International Nuclear Information System (INIS)

    Negodin, D.A.; Shtutsa, M.G.; Akhtonov, S.G.; Il'enko, E.V.; Kobyzev, A.M.

    2012-01-01

    Hafnium possesses a unique complex of physical and chemical properties which allow the application of products on its basis in various industries. Joint Stock Company 'Chepetsky Mechanical Plant' is the single enterprise which produces hafnium on the territory of Russia. The manufacture of metal hafnium with the total content of zirconium and hafnium, at least, 99,8 % of weights is developed at the present time at Joint Stock Company CHMZ. The weight of melted hafnium ingots is up to 1 ton. Manufacture of wide range of products from hafnium is implemented. The plates from a hafnium with thickness of 0.60 mm which are used for emergency control cartridges of VVER-440 reactors are the most critical product. It is shown that ingots and products obtained from metal hafnium correspond to the Russian and international standards for reactor materials in chemical composition, mechanical and corrosion properties.

  9. Electrochemical impedance spectroscopy of fully hydrated Nafion membranes at high and low hydrogen partial pressures

    International Nuclear Information System (INIS)

    Tsampas, M.N.; Brosda, S.; Vayenas, C.G.

    2011-01-01

    The proton transport mechanism in fully hydrated Nafion 117 membranes was examined via electrochemical impedance spectroscopy (EIS) and steady-state current–potential measurements both in a symmetric H 2 , Pt|Nafion|Pt, H 2 cell and in a H 2 , Pt|Nafion|Pt, air PEM fuel cell with hydrogen partial pressure values, P H 2 , varied between 0.5 kPa and 100 kPa. In agreement with recent studies it is found that for low P H 2 values the steady-state current–potential curves exhibit bistability and regions of positive slope. In these regions the Nyquist plots are found to exhibit negative real part impedance with a large imaginary component, while the Bode plots show a pronounced negative phase shift. These observations are consistent with the mechanism involving two parallel routes of proton conduction in fully hydrated Nafion membranes, one due to proton migration in the aqueous phase, the other due to proton transfer, probably involving tunneling, between adjacent sulfonate groups in narrow pores. The former mechanism dominates at high P H 2 values and the latter dominates in the low P H 2 region where the real part of the impedance is negative.

  10. Partial thermodynamic functions of hydrogen in complex hydrated vanadium(5) and tungsten(6) oxides

    International Nuclear Information System (INIS)

    Volkov, V.L.; Zakharova, G.S.

    2003-01-01

    The partial thermodynamic characteristics of hydrogen in the complex hydrated vanadium(5) and tungsten(6) oxides, obtained through the sol-gel method, of the general formula H 2 V 12-y W y O 31+δ ·nH 2 O (0 ≤ x ≤ 0.33) are determined through the emf method. The changes in these values (ΔG-bar(H 2 ), ΔH-bar(H 2 ) and ΔS-bar(H 2 )) in dependence on the compound composition are discussed. It is established that ΔG-bar(H 2 ) phases, amorphous to X-rays are determined by the ΔS-bar(H 2 ) value and crystalline ones by ΔH-bar(H 2 ). The scheme of the phase relationships of the H 2 O-H-WO 3 -V 2 O 5 system, whereto the given phases are related are presented [ru

  11. Zirconium and hafnium

    Science.gov (United States)

    Jones, James V.; Piatak, Nadine M.; Bedinger, George M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Zirconium and hafnium are corrosion-resistant metals that are widely used in the chemical and nuclear industries. Most zirconium is consumed in the form of the main ore mineral zircon (ZrSiO4, or as zirconium oxide or other zirconium chemicals. Zirconium and hafnium are both refractory lithophile elements that have nearly identical charge, ionic radii, and ionic potentials. As a result, their geochemical behavior is generally similar. Both elements are classified as incompatible because they have physical and crystallochemical properties that exclude them from the crystal lattices of most rock-forming minerals. Zircon and another, less common, ore mineral, baddeleyite (ZrO2), form primarily as accessory minerals in igneous rocks. The presence and abundance of these ore minerals in igneous rocks are largely controlled by the element concentrations in the magma source and by the processes of melt generation and evolution. The world’s largest primary deposits of zirconium and hafnium are associated with alkaline igneous rocks, and, in one locality on the Kola Peninsula of Murmanskaya Oblast, Russia, baddeleyite is recovered as a byproduct of apatite and magnetite mining. Otherwise, there are few primary igneous deposits of zirconium- and hafnium-bearing minerals with economic value at present. The main ore deposits worldwide are heavy-mineral sands produced by the weathering and erosion of preexisting rocks and the concentration of zircon and other economically important heavy minerals, such as ilmenite and rutile (for titanium), chromite (for chromium), and monazite (for rare-earth elements) in sedimentary systems, particularly in coastal environments. In coastal deposits, heavy-mineral enrichment occurs where sediment is repeatedly reworked by wind, waves, currents, and tidal processes. The resulting heavy-mineral-sand deposits, called placers or paleoplacers, preferentially form at relatively low latitudes on passive continental margins and supply 100 percent of

  12. High temperature evaporation of titanium, zirconium and hafnium carbides

    International Nuclear Information System (INIS)

    Gusev, A.I.; Rempel', A.A.

    1991-01-01

    Evaporation of cubic nonstoichiometric carbides of titanium, zirconium and hafnium in a comparatively low-temperature interval (1800-2700) with detailed crystallochemical sample certification is studied. Titanium carbide is characterized by the maximum evaporation rate: at T>2300 K it loses 3% of sample mass during an hour and at T>2400 K titanium carbide evaporation becomes extremely rapid. Zirconium and hafnium carbide evaporation rates are several times lower than titanium carbide evaporation rates at similar temperatures. Partial pressures of metals and carbon over the carbides studied are calculated on the base of evaporation rates

  13. SEPARATION OF HAFNIUM FROM ZIRCONIUM

    Science.gov (United States)

    Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

    1960-05-31

    The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

  14. Towards a universal method for calculating hydration free energies: a 3D reference interaction site model with partial molar volume correction.

    Science.gov (United States)

    Palmer, David S; Frolov, Andrey I; Ratkova, Ekaterina L; Fedorov, Maxim V

    2010-12-15

    We report a simple universal method to systematically improve the accuracy of hydration free energies calculated using an integral equation theory of molecular liquids, the 3D reference interaction site model. A strong linear correlation is observed between the difference of the experimental and (uncorrected) calculated hydration free energies and the calculated partial molar volume for a data set of 185 neutral organic molecules from different chemical classes. By using the partial molar volume as a linear empirical correction to the calculated hydration free energy, we obtain predictions of hydration free energies in excellent agreement with experiment (R = 0.94, σ = 0.99 kcal mol (- 1) for a test set of 120 organic molecules).

  15. Towards a universal method for calculating hydration free energies: a 3D reference interaction site model with partial molar volume correction

    International Nuclear Information System (INIS)

    Palmer, David S; Frolov, Andrey I; Ratkova, Ekaterina L; Fedorov, Maxim V

    2010-01-01

    We report a simple universal method to systematically improve the accuracy of hydration free energies calculated using an integral equation theory of molecular liquids, the 3D reference interaction site model. A strong linear correlation is observed between the difference of the experimental and (uncorrected) calculated hydration free energies and the calculated partial molar volume for a data set of 185 neutral organic molecules from different chemical classes. By using the partial molar volume as a linear empirical correction to the calculated hydration free energy, we obtain predictions of hydration free energies in excellent agreement with experiment (R = 0.94, σ = 0.99 kcal mol -1 for a test set of 120 organic molecules). (fast track communication)

  16. Calorimetric measurements on hafnium titanate

    International Nuclear Information System (INIS)

    Kandan, R.; Prabhakara Reddy, B.; Panneerselvam, G.; Nagarajan, K.

    2012-01-01

    Owing to its desirable nuclear and mechanical properties such as good absorption cross-section for thermal neutrons (105 barns), hafnium titanate (HfTiO 4 ) finds application as control rods for nuclear reactors. An accurate knowledge of the thermo physical properties of this material is necessary for design of control rod and for modeling its performance. Heat capacity is an important thermodynamic property that determines the temperature dependent variation of all other thermodynamic properties. Hence enthalpy increments of hafnium titanate (HfTiO 4 ) were measured in the temperature range 803-1663 K by employing the method of inverse drop calorimetry using high temperature differential calorimeter

  17. Effects of oxygen partial pressure and annealing temperature on the residual stress of hafnium oxide thin-films on silicon using synchrotron-based grazing incidence X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, Debaleen [Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700 064 (India); Sinha, Anil Kumar [ISU, Raja Ramanna Centre for Advanced Technology, Indore 452 013 (India); Homi Bhabha National Institute, BARC, Mumbai 400 094 (India); Chakraborty, Supratic, E-mail: supratic.chakraborty@saha.ac.in [Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700 064 (India)

    2016-10-30

    Highlights: • Residual stress estimation thin hafnium oxide film with thickness of <10 nm. • A mathematical expression is proposed for stress estimation of thin-film using GIXRD. • Residual stress varies with argon content in Ar/O{sub 2} plasma and annealing temperature. • Variation of stress is explained by IL swelling and enhanced structural relaxation. - Abstract: Synchrotron radiation-based grazing incidence X-ray diffraction (GI-XRD) technique is employed here to estimate the residual stress of < 10 nm thin hafnium oxide film deposited on Si (100) substrate at different argon/oxygen ratios using reactive rf sputtering. A decrease in residual stress, tensile in nature, is observed at higher annealing temperature for the samples deposited with increasing argon ratio in the Ar/O{sub 2} plasma. The residual stress of the films deposited at higher p{sub Ar} (Ar:O{sub 2} = 4:1) is also found to be decreased with increasing annealing temperature. But the stress is more or less constant with annealing temperature for the films deposited at lower Ar/O{sub 2} (1:4) ratio. All the above phenomena can be explained on the basis of swelling of the interfacial layer and enhanced structural relaxation in the presence of excess Hf in hafnium oxide film during deposition.

  18. Strong Static Magnetic Fields Increase the Gel Signal in Partially Hydrated DPPC/DMPC Membranes.

    Science.gov (United States)

    Tang, Jennifer; Alsop, Richard J; Schmalzl, Karin; Epand, Richard M; Rheinstädter, Maikel C

    2015-09-29

    NIt was recently reported that static magnetic fields increase lipid order in the hydrophobic membrane core of dehydrated native plant plasma membranes [Poinapen, Soft Matter 9:6804-6813, 2013]. As plasma membranes are multicomponent, highly complex structures, in order to elucidate the origin of this effect, we prepared model membranes consisting of a lipid species with low and high melting temperature. By controlling the temperature, bilayers coexisting of small gel and fluid domains were prepared as a basic model for the plasma membrane core. We studied molecular order in mixed lipid membranes made of dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) using neutron diffraction in the presence of strong static magnetic fields up to 3.5 T. The contribution of the hydrophobic membrane core was highlighted through deuterium labeling the lipid acyl chains. There was no observable effect on lipid organization in fluid or gel domains at high hydration of the membranes. However, lipid order was found to be enhanced at a reduced relative humidity of 43%: a magnetic field of 3.5 T led to an increase of the gel signal in the diffraction patterns of 5%. While all biological materials have weak diamagnetic properties, the corresponding energy is too small to compete against thermal disorder or viscous effects in the case of lipid molecules. We tentatively propose that the interaction between the fatty acid chains' electric moment and the external magnetic field is driving the lipid tails in the hydrophobic membrane core into a better ordered state.

  19. Strong Static Magnetic Fields Increase the Gel Signal in Partially Hydrated DPPC/DMPC Membranes

    Directory of Open Access Journals (Sweden)

    Jennifer Tang

    2015-09-01

    Full Text Available NIt was recently reported that static magnetic fields increase lipid order in the hydrophobic membrane core of dehydrated native plant plasma membranes [Poinapen, Soft Matter 9:6804-6813, 2013]. As plasma membranes are multicomponent, highly complex structures, in order to elucidate the origin of this effect, we prepared model membranes consisting of a lipid species with low and high melting temperature. By controlling the temperature, bilayers coexisting of small gel and fluid domains were prepared as a basic model for the plasma membrane core. We studied molecular order in mixed lipid membranes made of dimyristoyl-sn-glycero-3-phosphocholine (DMPC and dipalmitoyl-sn-glycero-3-phosphocholine (DPPC using neutron diffraction in the presence of strong static magnetic fields up to 3.5 T. The contribution of the hydrophobic membrane core was highlighted through deuterium labeling the lipid acyl chains. There was no observable effect on lipid organization in fluid or gel domains at high hydration of the membranes. However, lipid order was found to be enhanced at a reduced relative humidity of 43%: a magnetic field of 3.5 T led to an increase of the gel signal in the diffraction patterns of 5%. While all biological materials have weak diamagnetic properties, the corresponding energy is too small to compete against thermal disorder or viscous effects in the case of lipid molecules. We tentatively propose that the interaction between the fatty acid chains’ electric moment and the external magnetic field is driving the lipid tails in the hydrophobic membrane core into a better ordered state.

  20. Caffeic acid, morin hydrate and quercetin partially attenuate sulfur mustard-induced cell death by inhibiting the lipoxygenase pathway.

    Science.gov (United States)

    Kim, Shin; Jeong, Kwang-Joon; Cho, Sung Kweon; Park, Joo-Won; Park, Woo-Jae

    2016-11-01

    Sulfur mustard (SM) is an alkylating agent, which has been used as in chemical warfare in a number of conflicts. As the generation of reactive oxygen species (ROS), and adducts in DNA and proteins have been suggested as the mechanism underlying SM‑induced cytotoxicity, the present study screened several antioxidant candidates, including tannic acid, deferoxamine mesylate, trolox, vitamin C, ellagic acid and caffeic acid (CA) to assess their potential as therapeutic agents for SM‑induced cell death. Among several antioxidants, CA partially alleviated SM‑induced cell death in a dose‑dependent manner. Although CA treatment decreased the phosphorylation of p38 mitogen‑activated protein (MAP) kinase and p53, p38 MAP kinase inhibition by SB203580 did not affect SM‑induced cell death. As CA has also been reported as a 15‑lipoxygenase (15‑LOX) inhibitor, the role of 15‑LOX in SM‑induced cytotoxicity was also examined. Similar to the results observed with CA, treatment with PD146176, a specific 15‑LOX inhibitor, decreased SM‑induced cytotoxicity, accompanied by decreases in the production of tumor necrosis factor‑α and 15‑hydroxyeicosatetraenoic acid. Furthermore, the present study investigated the protective effects of two natural 15‑LOX inhibitors, morin hydrate and quercetin, in SM‑induced cytotoxicity. As expected, these inhibitors had similar protective effects against SM‑induced cytotoxicity. These antioxidants also reduced the generation of ROS and nitrate/nitrite. Therefore, the results of the present study indicated that the natural products, CA, quercetin and morin hydrate, offer potential as adjuvant therapeutic agents for SM‑induced toxicity, not only by reducing inflammation mediated by the p38 and LOX signaling pathways, but also by decreasing the generation of ROS and nitrate/nitrite.

  1. Hafnium carbide formation in oxygen deficient hafnium oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Rodenbücher, C. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); Hildebrandt, E.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Alff, L. [Technische Universität Darmstadt, Institute of Materials Science, 64287 Darmstadt (Germany); Szot, K. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); University of Silesia, A. Chełkowski Institute of Physics, 40-007 Katowice (Poland); Breuer, U. [Forschungszentrum Jülich GmbH, Central Institute for Engineering, Electronics and Analytics (ZEA-3), 52425 Jülich (Germany); Waser, R. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); RWTH Aachen, Institute of Electronic Materials (IWE 2), 52056 Aachen (Germany)

    2016-06-20

    On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO{sub 2−x}) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC{sub x}) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC{sub x} surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO{sub 2} thin films prepared and measured under identical conditions, the formation of HfC{sub x} was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

  2. Hafnium isotope stratigraphy of ferromanganese crusts

    Science.gov (United States)

    Lee; Halliday; Hein; Burton; Christensen; Gunther

    1999-08-13

    A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

  3. Ferroelectricity in undoped hafnium oxide

    International Nuclear Information System (INIS)

    Polakowski, Patrick; Müller, Johannes

    2015-01-01

    We report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4–20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization P r of up to 10 μC cm −2 as well as a read/write endurance of 1.6 × 10 5 cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems

  4. Hydration of alcohol clusters in 1-propanol-water mixture studied by quasielastic neutron scattering and an interpretation of anomalous excess partial molar volume.

    Science.gov (United States)

    Misawa, M; Inamura, Y; Hosaka, D; Yamamuro, O

    2006-08-21

    Quasielastic neutron scattering measurements have been made for 1-propanol-water mixtures in a range of alcohol concentration from 0.0 to 0.167 in mole fraction at 25 degrees C. Fraction alpha of water molecules hydrated to fractal surface of alcohol clusters in 1-propanol-water mixture was obtained as a function of alcohol concentration. Average hydration number N(ws) of 1-propanol molecule is derived from the value of alpha as a function of alcohol concentration. By extrapolating N(ws) to infinite dilution, we obtain values of 12-13 as hydration number of isolated 1-propanol molecule. A simple interpretation of structural origin of anomalous excess partial molar volume of water is proposed and as a result a simple equation for the excess partial molar volume is deduced in terms of alpha. Calculated values of the excess partial molar volumes of water and 1-propanol and the excess molar volume of the mixture are in good agreement with experimental values.

  5. Study of fine structure of deformed hafnium

    International Nuclear Information System (INIS)

    Voskresenskaya, L.A.; Petukhova, A.S.; Kovalev, K.S.

    1978-01-01

    Variations in the hafnium fine structure following the cold plastic deformation have been studied. The fine structure condition has been studied through the harmonic analysis of the profile of the X-ray diffraction line, obtained at the DRON-I installation. Received has been the dependence of the crystal lattice microdistortions value on the deformation extent for hafnium. This dependence is compared with the corresponding one for zirconium. It is found out that at all the deformations the microdistortion distribution is uniform. The microdistortion value grows with the increase in the compression. During the mechanical impact higher microdistortions of the crystal lattice occur in the hafnium rather than in zirconium

  6. Hafnium - material for chemical apparatus engineering

    International Nuclear Information System (INIS)

    Jennert, D.

    1981-01-01

    This work describes - on the background of available literature - the properties of hafnium in technical quality (DIN-material No. 2.6400) as material for chemical apparatus engineering. The occurence, refining, physical and chemical properties will be described as well as the material behavior. In conclusion, it has been found that there is, at present, sufficient information for the engineering of hafnium which has to be completed by additional investigations for special applications. (orig.) [de

  7. Hydrophobic hydration and anomalous excess partial molar volume of tert-butyl alcohol-water mixture studied by quasielastic neutron scattering

    International Nuclear Information System (INIS)

    Nakada, Masaru; Maruyama, Kenji; Misawa, Masakatsu; Yamamuro, Osamu

    2007-01-01

    Quasielastic neutron scattering has been used to investigate the hydration of alcohol clusters in tert-butyl alcohol-water mixture. The measurements were made in a range of alcohol concentration, x TBA , from 0.0 to 0.17 in mole fraction at 25degC. Fraction, α, of water molecules hydrated to fractal-surface of alcohol clusters in tert-butyl alcohol-water mixture was obtained as a function of alcohol concentration. Average hydration number N WS of tert-butyl alcohol molecule was derived from the value of α as a function of alcohol concentration. The value of N WS for an isolated alcohol molecule in water was 19-21. The anomalous excess partial molar volume of tert-butyl alcohol-water mixture was interpreted successfully by applying the same model with the same values of volume parameter as used for 1-propanol-water mixture, δ 1 (=-0.36 cm 3 ·mol -1 ) and δ 2 (=0.60 cm 3 ·mol -1 ). (author)

  8. Determination of hafnium by atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Yoshida, Isao; Kobayashi, Hiroshi; Ueno, Keihei.

    1977-01-01

    Optimum conditions for atomic absorption spectrophotometric determination of hafnium were investigated by use of a Jarrel-Ash AA-1 instrument which was equipped with a premixed gas burner slotted 50 mm in length and 0.4 mm in width. Absorption of hafnium, which was atomized in an nitrous oxide-acetylene flame, was measured on a resonance line at 307.29 nm. The absorption due to hafnium was enhanced in the presence of ammonium fluoride and iron(III) ion, as shown in Figs. 2 and 3, depending on their concentration. The highest absorption was attained by the addition of (0.15 -- 0.3)M ammonium fluoride, 0.07 M of iron(III) ion and 0.05 M of hydrochloric acid. An excess of the additives decreased the absorption. The presence of zirconium, which caused a significant interference in the ordinary analytical methods, did not affect the absorption due to hafnium, if the zirconium concentration is less than 0.2 M. A standard procedure was proposed; A sample containing a few mg of hafnium was dissolved in a 25-ml volumetric flask, and ammonium fluoride, ferric nitrate and hydrochloric acid were added so that the final concentrations were 0.3, 0.07 and 0.05 M, respectively. Atomic absorption was measured on the aqueous solution in a nitrous oxide-acetylene flame and the hafnium content was calculated from the absorbance. Sensitivity was as high as 12.5 μg of Hf/ml/l% absorption. The present method is especially recommendable to the direct determination of hafnium in samples containing zirconium. (auth.)

  9. Observation on the availability and tolerance of 0.1% bromfenac sodium hydrate ophthalmic solution in the partial substitution of glucocorticoid after LASEK

    Directory of Open Access Journals (Sweden)

    Zhi-Hui Deng

    2015-12-01

    Full Text Available AIM:To observe the availability and tolerance of 0.1% bromfenac sodium hydrate ophthalmic solution in the partial substitution of glucocorticoid after laser subepithelial keratomileusis(LASEK. METHODS:Totally 180 patients(180 eyesreceived LASEK were selected and divided into study group and control group according to different medications. The study group adopted 0.1% bromfenac sodium hydrate ophthalmic solution combined with glucocorticoid; the control group adopted glucocorticoid. The changes of visual acuity and intraocular pressure(IOPof two groups were recorded before and after surgery and the occurrence of diffuse larnellar kerafitis(DLKafter surgery were observed. RESULTS:After 1mo of surgery, visual acuity of study group was 1.25±0.22 while that of control group was 0.97±0.23(PP>0.05. After 1 and 3mo of surgery, IOP of study group was 12.29±2.71 and 12.67±2.33mmHg while that of control group was 14.26±2.65 and 14.56±2.61mmHg, the difference was statistically significant(PP>0.05. In terms of tolerance, the control group had 4 cases(4 eyestaking the IOP-lowering medication. The study group had no uncomfortable cases. The DLK level of the study group at 0, 1, 2 was 93.33%, 6.67%, 0%, respectively and those in control group was 75.56%, 17.78% and 6.67%, respectively, and the differences were significant(PCONCLUSION:0.1% bromfenac sodium hydrate ophthalmic solution can efficiently stabilize the patient's IOP after LASEK. The patient has a better visual acuity, visual function and fewer complications. The tolerance is also favorable. It is worthy of promotion.

  10. Titanium(IV), zirconium, hafnium and thorium

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    Titanium can exist in solution in a number of oxidation states. The titanium(IV) exists in acidic solutions as the oxo-cation, TiO 2+ , rather than Ti 4+ . Zirconium is used in the ceramics industry and in nuclear industry as a cladding material in reactors where its reactivity towards hydrolysis reactions and precipitation of oxides may result in degradation of the cladding. In nature, hafnium is found together with zirconium and as a consequence of the contraction in ionic radii that occurs due to the 4f -electron shell, the ionic radius of hafnium is almost identical to that of zirconium. All isotopes of thorium are radioactive and, as a consequence of it being fertile, thorium is important in the nuclear fuel cycle. The polymeric hydrolysis species that have been reported for thorium are somewhat different to those identified for zirconium and hafnium, although thorium does form the Th 4 (OH) 8 8+ species.

  11. Gravimetric determination of hafnium through its arsenate in carbide and boride of hafnium

    International Nuclear Information System (INIS)

    Rasulbekova, R.A.; Mamedov, I.A.

    1976-01-01

    A gravimetric method of determining hafnium through hydroarsenate has been recommended. The method differs from the known ones by its simplicity and by the recalculation coefficient which is more than by 50% smaller than that used in preparing a weight form of HfO 2 . Upon development of gravimetric determination of hafnium through hydro-and pyroarsenate, an investigation has been conducted with the aim to find some physico-chemical constants of hafnium hydroarsenate. The weighed amount of hafnium hydroarsenate is dissolved in sulphuric acid (2:5). The precipitate of hafnium hydroarsenate has been studied for recording infrared absorption spectra. Thermographic analysis of the precipitate has been performed. Thermogram reveals endothermal effect at 105 deg C and exothermal at 840 deg C. Water solubility of hafnium has been determined equal to 1.75x10 6 g mol/l. The corresponding solubility product of the precipitate has been calculated which is 2.1x10 -17 . It is shown that the method possesses certain selectivity, sufficient accuracy, and is rather fast. It has been established that determination can be performed in the presence of excess amounts of ions

  12. Method of separating hafnium from zirconium

    International Nuclear Information System (INIS)

    Megy, J.A.

    1980-01-01

    English. A new anhydrous method was developed for separating zirconium and hafnium, which gives higher separation factors and is more economical than previous methods. A molten phase, comprising a solution of unseparated zirconium and hafnium and a solvent metal, is first prepared. The molten metal phase is contacted with a fused salt phase which includes a zirconium salt. Zirconium and hafnium separation is effected by mutual displacement with hafnium being transported from the molten metal phase to the fused salt phase, while zirconium is transported from the fused salt phase to the molten metal phase. The solvent metal is less electropositive than zirconium. Zinc was chosen as the solvent metal, from a group which also included cadmium, lead, bismuth, copper, and tin. The fused salt phase cations are more electropositive than zirconium and were selected from a group comprising the alkali elements, the alkaline earth elements, the rare earth elements, and aluminum. A portion of the zirconium in the molten metal phase was oxidized by injecting an oxidizing agent, chlorine, to form zirconium tetrachlorid

  13. Kinetic studies on the hafnium nad deuterium

    International Nuclear Information System (INIS)

    Bing Wenzeng; Long Xinggui; Zhu Zuliang

    2009-04-01

    Through the method of reaction rate analysis in a constant volume reactor, the time dependence of the pressure drop of the hafnium deuteride formation are studied over a temperature range 573-873 K on a metal hydride thermodynamic and kinetic parameters measuring apparatus. The rate constants of the hafnium deuteride formation, which are 0.0530 s -1 , 0.0452 s -1 , 0.0319 s -1 , 0.0261 s -1 , are calculated at a serial temperatures of 573 K, 673 K, 773 K, 873 K and the initial pressure of 13 kPa. The activation energy of the reaction is (-10.1±1.5) kJ·mol -1 . Comparing the above results with those of titanium deuteride formation on the same measuring apparatus, the kinetic mechanism of the deuteride formation of hafnium and titanium is considered different. It is concluded that the reaction rate of hafnium absorbing deuterium may be controlled by phase transformation and surface oxidation. (authors)

  14. Recovery of hafnium values from loaded extraction solvent

    International Nuclear Information System (INIS)

    Abodishish, H.A.

    1989-01-01

    This patent describes an improvement in a process for recovering high purity hafnium hydroxide from a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains hafnium thiocyanate and thiocyanic acid. The improvement comprising reacting the organic solvent with ammonia to produce a reaction product in the form of a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains ammonium thiocyanite solution and hafnium hydroxide; separating the constituents of the reaction product in accordance with their respective specific gravities to produce a hafnium hydroxide sludge as one of the separation products; and removing the liquid component of the sludge to yield a high purity hafnium hydroxide ready for calcination to hafnium oxide

  15. Flotation separation of hafnium(IV) from aqueous solutions

    International Nuclear Information System (INIS)

    Downey, D.M.; Narick, C.N.; Cohen, T.A.

    1985-01-01

    A simple, rapid method for the separation of hafnium from aqueous solutions was investigated using sup(175+181)Hf tracer. Cationic hafnium complex ions were floated from dilute acid solutions with sodium lauryl sulfate (SLS) and anionic hafnium complexes were floated from basic and oxalic acid solutions with hexadecyltrimethyl ammonium bromide (HTMAB). The conditions necessary for quantitative recovery of the metal and mechanisms of flotation are described. (author)

  16. Flotation separation of hafnium(IV) from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Downey, D.M.; Narick, C.N.; Cohen, T.A.

    1985-09-01

    A simple, rapid method for the separation of hafnium from aqueous solutions was investigated using sup(175 + 181)Hf tracer. Cationic hafnium complex ions were floated from dilute acid solutions with sodium lauryl sulfate (SLS) and anionic hafnium complexes were floated from basic and oxalic acid solutions with hexadecyltrimethyl ammonium bromide (HTMAB). The conditions necessary for quantitative recovery of the metal and mechanisms of flotation are described. (author). 21 refs.; 5 figs.

  17. Titanium zirconium and hafnium coordination compounds with vanillin thiosemicarbazone

    International Nuclear Information System (INIS)

    Konunova, Ts.B.; Kudritskaya, S.A.

    1987-01-01

    Coordination compounds of titanium zirconium and hafnium tetrachlorides with vanillin thiosemicarbazone of MCl 4 x nLig composition, where n=1.5, 4 for titanium and 1, 2, 4 for zirconium and hafnium, are synthesized. Molar conductivity of ethanol solutions is measured; IR spectroscopic and thermochemical investigation are carried out. The supposition about ligand coordination via sulfur and azomethine nitrogen atoms is made. In all cases hafnium forms stable compounds than zirconium

  18. Niobium and hafnium grown on porous membranes

    International Nuclear Information System (INIS)

    Morant, C.; Marquez, F.; Campo, T.; Sanz, J.M.; Elizalde, E.

    2010-01-01

    In this work we report on a method for fabricating highly ordered nanostructures of niobium and hafnium metals by physical vapour deposition using two different templates: anodized aluminum oxide membranes (AAO) and zirconium onto AAO membranes (Zr/AAO). The growth mechanism of these metal nanostructures is clearly different depending on the material used as a template. A different morphology was obtained by using AAO or Zr/AAO templates: when the metal is deposited onto AAO membranes, nanospheres with ordered hexagonal regularity are obtained; however, when the metal is deposited onto a Zr/AAO template, highly ordered nanocones are formed. The experimental approach described in this work is simple and suitable for synthesizing nanospheres or nanoholes of niobium and hafnium metals in a highly ordered structure.

  19. Joint titrimetric determination of zirconium and hafnium

    International Nuclear Information System (INIS)

    Vazquez, Cristina; Botbol, Moises; Bianco de Salas, G.N.; Cornell de Casas, M.I.

    1980-01-01

    A method for the joint titrimetric determination of zirconium and hafnium, which are elements of similar chemical behaviour, is described. The disodic salt of the ethylendiaminetetracetic acid (EDTA) is used for titration, while xilenol orange serves as final point indicator. Prior to titration it is important to evaporate with sulfuric acid, the solution resulting from the zirconium depolymerization process, to adjust the acidity and to eliminate any interferences. The method, that allows the quick and precise determination of zirconium and hafnium in quantities comprised between 0.01 and mg, was applied to the analysis of raw materials and of intermediate and final products in the fabrication of zirconium sponge and zircaloy. (M.E.L.) [es

  20. Molten salt scrubbing of zirconium or hafnium tetrachloride

    International Nuclear Information System (INIS)

    Lee, E.D.; McLaughlin, D.F.

    1990-01-01

    This patent describes a continuous process for removing impurities of iron or aluminum chloride or both from vaporous zirconium or hafnium chloride or both. It comprises: introducing impure zirconium or hafnium chloride vapor or both into a middle portion of an absorbing column containing a molten salt phase, the molten salt phase absorbing the impurities of iron or aluminum chloride or both to produce chloride vapor stripped of zirconium or hafnium chloride; introducing sodium or potassium chloride or both into a top portion of the column; controlling the top portion of the column to between 300--375 degrees C.; heating a bottom portion of the column to 450--550 degrees C. To vaporize zirconium chloride or hafnium chloride or hafnium and zirconium chloride from the molten salt; withdrawing molten salt substantially free of zirconium and hafnium chloride from the bottom portion of the column; and withdrawing zirconium chloride or hafnium chloride or hafnium and zirconium chloride vapor substantially free of impurities of iron and aluminum chloride from the top of the column

  1. Investigation of ferromagnetism in oxygen deficient hafnium oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Hildebrandt, Erwin; Kurian, Jose; Krockenberger, Yoshiharu; Alff, Lambert [Institut fuer Materialwissenschaft, TU Darmstadt (Germany); Suter, Andreas [PSI, Villingen (Switzerland); Wilhelm, Fabrice; Rogalev, Andrei [ESRF, Grenoble (France)

    2008-07-01

    Oxygen deficient thin films of hafnium oxide were grown on single crystal r-cut and c-cut sapphire by reactive molecular beam epitaxy. RF-activated oxygen was used for the in situ oxidation of hafnium oxide thin films. Oxidation conditions were varied substantially in order to create oxygen deficiency in hafnium oxide films intentionally. The films were characterized by X-ray and magnetic measurements. X-ray diffraction studies show an increase in lattice parameter with increasing oxygen deficiency. Oxygen deficient hafnium oxide thin films also showed a decreasing bandgap with increase in oxygen deficiency. The magnetisation studies carried out with SQUID did not show any sign of ferromagnetism in the whole oxygen deficiency range. X-ray magnetic circular dichroism measurements also confirmed the absence of ferromagnetism in oxygen deficient hafnium oxide thin films.

  2. Preparation of hafnium carbide by chemical vapor deposition

    International Nuclear Information System (INIS)

    Hertz, Dominique.

    1974-01-01

    Hard, adhesive coatings of single-phase hafnium carbide were obtained by chemical vapor reaction in an atmosphere containing hafnium tetrachloride, methane and a large excess of hydrogen. By varying the gas phase composition and temperature the zones of formation of the different solid phases were studied and the growth of elementary hafnium and carbon deposits evaluated separately. The results show that the mechanism of hafnium carbide deposition does not hardly involve phenomene of homogeneous-phase methane decomposition or tetrachloride reduction by hydrogen unless the atmosphere is very rich or very poor in methane with respect to tetrachloride. However, hydrogen acting inversely on these two reactions, affects the stoichiometry of the substance deposited. The methane decomposition reaction is fairly slow, the reaction leading to hafnium carbide deposition is faster and that of tetrachloride reduction by hydrogen is quite fast [fr

  3. Assessing hafnium on hafnia as an oxygen getter

    International Nuclear Information System (INIS)

    O'Hara, Andrew; Demkov, Alexander A.; Bersuker, Gennadi

    2014-01-01

    Hafnium dioxide or hafnia is a wide band gap dielectric used in a range of electronic applications from field effect transistors to resistive memory. In many of these applications, it is important to maintain control over oxygen stoichiometry, which can be realized in practice by using a metal layer, specifically hafnium, to getter oxygen from the adjacent dielectric. In this paper, we employ density functional theory to study the thermodynamic stability of an interface between (100)-oriented monoclinic hafnia and hafnium metal. The nudged elastic band method is used to calculate the energy barrier for migration of oxygen from the oxide to the metal. Our investigation shows that the presence of hafnium lowers the formation energy of oxygen vacancies in hafnia, but more importantly the oxidation of hafnium through the migration of oxygen from hafnia is favored energetically

  4. On the phase formation of sputtered hafnium oxide and oxynitride films

    International Nuclear Information System (INIS)

    Sarakinos, K.; Music, D.; Mraz, S.; Baben, M. to; Jiang, K.; Nahif, F.; Braun, A.; Zilkens, C.; Schneider, J. M.; Konstantinidis, S.; Renaux, F.; Cossement, D.; Munnik, F.

    2010-01-01

    Hafnium oxynitride films are deposited from a Hf target employing direct current magnetron sputtering in an Ar-O 2 -N 2 atmosphere. It is shown that the presence of N 2 allows for the stabilization of the transition zone between the metallic and the compound sputtering mode enabling deposition of films at well defined conditions of target coverage by varying the O 2 partial pressure. Plasma analysis reveals that this experimental strategy facilitates control over the flux of the O - ions which are generated on the oxidized target surface and accelerated by the negative target potential toward the growing film. An arrangement that enables film growth without O - ion bombardment is also implemented. Moreover, stabilization of the transition sputtering zone and control of the O - ion flux without N 2 addition is achieved employing high power pulsed magnetron sputtering. Structural characterization of the deposited films unambiguously proves that the phase formation of hafnium oxide and hafnium oxynitride films with the crystal structure of HfO 2 is independent from the O - bombardment conditions. Experimental and theoretical data indicate that the presence of vacancies and/or the substitution of O by N atoms in the nonmetal sublattice favor the formation of the cubic and/or the tetragonal HfO 2 crystal structure at the expense of the monoclinic HfO 2 one.

  5. Analysis of hafnium in zirconium alloys

    International Nuclear Information System (INIS)

    Kondo, Isao; Sakai, Fumiaki; Ohuchi, Yoshifusa; Nakamura, Hisashi

    1977-01-01

    It is required to analyse alloying components and impurity elements in the acceptance analysis of zirconium alloys as the material for fuel cladding tubes and pressure tubes for advanced thermal reactors. Because of extreme similarity in chemical properties between zirconium and hafnium, about 100 ppm of hafnium is usually contained in zirconium alloys. Zircaloy-2 alloy and 2.5% Nb-zirconium with the addition of hafnium had been prepared as in-house standard samples for rapid analysis. Study was made on fluorescent X-ray analysis and emission spectral analysis to establish the analytical method. By using these in-house standard samples, acceptance analysis was successfully carried out for the fuel cladding tubes for advanced thermal reactors. Sulfuric acid solution was prepared from JAERI-Z 1, 2 and 3, the standard sample for zircaloy-2 prepared by the Analytical Committee on Nuclear Fuel and Reactor Materials, JAERI, and zirconium oxide (Hf 1 ppm/Zr). Standard Hf solution was added to the sulfuric acid solution step by step, to make up a series of the standard oxide samples by the precipitation process. By the use of these standard samples, the development of the analytical method and joint analysis were made by the three-member analytical technique research group including PNC. The analytical precision for the fluorescent X-ray analysis was improved by attaching a metallic yttrium filter to the window of an X-ray tube so as to suppress the effect due to zirconium matrix. The variation factor of the joint analysis was about 10% to show good agreement, and the indication value was determined. (Kobatake, H.)

  6. Molecular structure, vibrational, HOMO-LUMO, MEP and NBO analysis of hafnium selenite

    Science.gov (United States)

    Yankova, Rumyana; Genieva, Svetlana; Dimitrova, Ginka

    2017-08-01

    In hydrothermal condition hafnium selenite with estimated chemical composition Hf(SeO3)2·n(H2O) was obtained and characterized by powder X-Ray diffraction, IR spectroscopy and thermogravimetrical analysis. The composition of the obtained crystalline phase was established as dihydrate of tetraaqua complex of the hafnium selenite [Hf(SeO3)2(H2O)4]·2H2O. The results of the thermogravimetrical analysis are shown that the two hydrated water molecules are released in the temperature interval 80-110°C, while the four coordinated water molecules - at 210-300°C. By DFT method, with Becke's three parameter exchange-functional combined with gradient-corrected correlation functional of Lee, Yang and Parr and 6-31G(d), 6-311 + G(d,p) basis sets and LANL2DZ for Hf atom were calculated the molecular structure, vibrational frequencies and thermodynamic properties of the structure. The UV-Vis spectra and electronic properties are presented. The energy and oscillator strength calculated by time-dependent density functional theory corresponds well with the experimental ones. Molecular electrostatic potential (MEP) was performed. Mulliken population analysis on atomic charges was also calculated. The stability and intramolecular interactions are interpreted by NBO analysis.

  7. Efecto del almacenamiento al ambiente en semillas de Leucaena leucocephala cv. Cunningham sometidas a hidratación parcial Effect of storage under ambient conditions on seeds from Leucaena leucocephala cv. Cunningham subject to partial hydration

    Directory of Open Access Journals (Sweden)

    Yolanda González

    2012-12-01

    Full Text Available El objetivo del trabajo fue estudiar el efecto del almacenamiento al ambiente en la germinación de las semillas de Leucaena leucocephala cv. Cunningham sometidas a hidratación parcial. Los tratamientos fueron: control, sin escarificación (T0; escarificación térmica (ET con H2O a 80°C, durante dos minutos (T1; ET más hidratación parcial, en bandeja con agua corriente por 28 horas (T2; ET más hidratación parcial, en saco de yute humedecido con agua corriente por 28 horas (T3; ET más hidratación parcial, en bandeja con agua corriente y TMTD al 0,1% (plaguicida por 28 horas (T4; ET más hidratación parcial, en saco de yute humedecido con agua corriente y TMTD al 0,1% (plaguicida por 28 horas (T5. Las semillas hidratadas se deshidrataron durante 72 horas al aire y a la sombra, antes de almacenarlas. Se midió la germinación y la viabilidad a 0, 1, 2, 3, 4, 6, 18, 30 y 42 meses. Se utilizó un diseño totalmente aleatorizado y cuatro réplicas por tratamiento. Hubo diferencias significativas (PThe objective of the work was to study the effect of storage under ambient conditions on the germination of seeds from Leucaena leucocephala cv. Cunningham subject to partial hydration. The treatments were: control, no scarification (T0; thermal scarification (TS with H2O at 80ºC, for two minutes (T1; TS plus partial hydration, on tray with tap water for 28 hours (T2; TS plus partial hydration, in jute sac moist with tap water for 28 hours (T3; TS plus partial hydration in tray with tap water and TMTD at 0,1% (pesticide for 28 hours (T4; TS plus partial hydration, in jute sac moist with tap water and TMTD at 0,1% (pesticide for 28 hours (T5. The hydrated seeds were dehydrated during 72 hours exposed to air and under shade, before being stored. Germination and viability were measured after 0, 1, 2, 3, 4, 6, 18, 30 and 42 months. A completely randomized design and four replications per treatment were used. There were significant differences (P<0

  8. High temperature thermodynamics of solutions of oxygen in zirconium and hafnium

    International Nuclear Information System (INIS)

    Boureau, G.; Gerdanian, P.

    1984-01-01

    The Tian-Calvet microcalorimetric method has been applied to the determination at 1323 Kelvin of ΔH(O 2 ), the partial molar enthalpy of mixing of oxygen in zirconium and in hafnium. No measurable departure from Henry's law has been found for dilute solutions (ratio oxygen over metal smaller than 0.1). For concentrated solutions repulsive interactions are found in agreement with the existence of ordered structures at lower temperatures. The domain of homogeneity of zirconium has been found larger than previously assumed. (author)

  9. Primary hafnium metal sponge and other forms, approved standard 1973

    International Nuclear Information System (INIS)

    Anon.

    1975-01-01

    A specification is presented covering virgin hafnium metal commonly designated as sponge because of its porous, sponge-like texture; it may also be in other forms such as chunklets. The specification does not cover crystal bar

  10. Molten salt extractive distillation process for zirconium-hafnium separation

    International Nuclear Information System (INIS)

    McLaughlin, D.F.; Stoltz, R.A.

    1989-01-01

    This patent describes an improvement in a process for zirconium-hafnium separation. It utilizes an extractive distillation column with a mixture of zirconium and hafnium tetrachlorides introduced into a distillation column having a top and bottom with hafnium enriched overheads taken from the top of the column and a molten salt solvent circulated through the column to provide a liquid phase, and with molten salt solvent containing zirconium chloride being taken from the bottom of the distillation column. The improvements comprising: utilizing a molten salt solvent consisting principally of lithium chloride and at least one of sodium, potassium, magnesium and calcium chlorides; stripping of the zirconium chloride taken from the bottom of the distillation column by electrochemically reducing zirconium from the molten salt solvent; and utilizing a pressurized reflux condenser on the top of the column to add the hafnium chloride enriched overheads to the molten salt solvent previously stripped of zirconium chloride

  11. Internal Dosimetry for Inhalation of Hafnium Tritide Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Inkret, W.C.T.; Schillaci, M.E.; Boyce, M.K.; Cheng, Y.S.; Efurd, D.W.; Little, T.T.; Miller, G.; Musgrave, J.A.; Wermer, J.R

    2001-07-01

    Metal tritides with low dissolution rates may have residence times in the lungs which are considerably longer than the biological half-time normally associated with tritium in body water, resulting in long-term irradiation of the lungs by low energy {beta} particles and bremsstrahlung X rays. Samples of hafnium tritide were placed in a lung simulant fluid to determine approximate lung dissolution rates. Hafnium hydride samples were analysed for particle size distribution with a scanning electron microscope. Lung simulant data indicated a biological dissolution half-time for hafnium tritide on the order of 10{sup 5}d. Hafnium hydride particle sizes ranged between 2 and 10 {mu}m, corresponding to activity median aerodynamic diameters of 5 to 25 {mu}m. Review of in vitro dissolution data, development of a biokinetic model, and determination of secondary limits for 1 {mu}m AMAD particles are presented and discussed. (author)

  12. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    , not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

  13. New solvent extraction process for zirconium and hafnium

    International Nuclear Information System (INIS)

    Takahashi, M.; Katoh, Y.; Miyazaki, H.

    1984-01-01

    The authors' company developed a new solvent extraction process for zirconium and hafnium separation, and started production of zirconium sponge by this new process in September 1979. The process utilizes selective extraction of zirconium oxysulfate using high-molecular alkyl amine, and has the following advantages: 1. This extraction system has a separation factor as high as 10 to 20 for zirconium and hafnium in the range of suitable acid concentration. 2. In the scrubbing section, removal of all the hafnium that coexists with zirconium in the organic solvent can be effectively accomplished by using scrubbing solution containing hafnium-free zirconium sulfate. Consequently, hafnium in the zirconium sponge obtained is reduced to less than 50 ppm. 3. The extractant undergoes no chemical changes but is very stable for a long period. In particular, its solubility in water is small, about 20 ppm maximum, posing no environmental pollution problems such as are often caused by other process raffinates. At the present time, the zirconium and hafnium separation operation is very stable, and zirconium sponge made by this process can be applied satisfactorily to nuclear reactors

  14. Separation process of zirconium and hafnium

    International Nuclear Information System (INIS)

    Hure, J.; Saint-James, R.

    1955-01-01

    About the separation different processes of zirconium-hafnium, the extraction by solvent in cross-current is the most easily the process usable on an industrial scale. It uses tributyl phosphate as solvent, diluted with white spirit to facilitate the decanting. Some exploratory tests showed that nitric environment seemed the most favorable for extraction; but a lot of other factors intervene in the separation process. We studied the influence of the acidity successively, the NO 3 - ions concentration, the role of the cation coming with NO 3 - , as well as the influence of the concentration of zirconium in the solution on the separation coefficient β = α Zr / α Hf . (M.B.) [fr

  15. The interaction of fast neutrons with hafnium

    International Nuclear Information System (INIS)

    Smith, A.B.

    2002-01-01

    Elemental hafnium neutron total cross sections are measured from ∼0.75 to 4.5 MeV in steps of ∼40 keV. Differential neutron elastic-scattering cross sections are measured from ∼4.5 to 10.0 MeV in ∼0.5 MeV steps and at 40 scattering angles distributed between ∼17 and 160 deg. These data are combined with those found in the literature to construct a comprehensive experimental data base which is interpreted in terms of coupled-channels models. Physical characteristics of the resulting potentials are discussed. Comparisons are made with ENDF/B-6 (MAT 7200). A detailed report of this work is given by Smith (Smith, A., 2001. Argonne National Laboratory Report ANL/NDM-153)

  16. Dependences of molar volumes in solids, partial molal and hydrated ionic volumes of alkali halides on covalent and ionic radii and the golden ratio

    Czech Academy of Sciences Publication Activity Database

    Heyrovská, Raji

    2007-01-01

    Roč. 436, č. 1-3 (2007), s. 287-293 ISSN 0009-2614 R&D Projects: GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040702 Keywords : alkali halides * ionic hydration * golden ratio Subject RIV: BO - Biophysics Impact factor: 2.207, year: 2007

  17. High temperature diffusion of hafnium in tungsten and a tungsten-hafnium carbide alloy

    International Nuclear Information System (INIS)

    Ozaki, Y.; Zee, R.H.

    1994-01-01

    Refractory metals and ceramics are used extensively in energy systems due to their high temperature properties. This is particularly important in direct conversion systems where thermal to electric conversion efficiency is a direct function of temperature. Tungsten, which has the highest melting temperature among elemental metals, does not possess sufficient creep resistance at temperature above 1,600 K. Different dispersion strengthened tungsten alloys have been developed to extend the usefulness of tungsten to higher temperatures. One of these alloys, tungsten with 0.4 mole percent of finely dispersed HfC particles (W-HfC), has the optimum properties for high temperature applications. Hafnium carbide is used as the strengthening agent due to its high chemical stability and its compatibility with tungsten. The presence of HfC particles retards the rate of grain growth as well as restricting dislocation motion. Both of which are beneficial for creep resistance. The long term behavior of this alloy depends largely on the evolution of its microstructure which is governed by the diffusion of its constituents. Data on the diffusion of carbon in tungsten and tungsten self-diffusion are available, but no direct measurements have been made on the diffusion of hafnium in tungsten. The only diffusion data available are estimated from a coarsening study and these data are highly unreliable. In this study, the diffusion behavior of hafnium in pure tungsten and in a W-HfC alloy was directly measured by means of Secondary Ion Mass Spectroscopy (SIMS). The selection of the W-HfC alloy is due to its importance in high temperature engineering applications, and its higher recrystallization temperature. The presence of HfC particles in tungsten restricts grain growth resulting in better high temperature creep resistance. The higher recrystallization temperature allows measurements to be made over a wider range of temperatures at a relatively constant grain size

  18. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Science.gov (United States)

    2010-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of the...

  19. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Science.gov (United States)

    2010-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges resulting...

  20. Chloral Hydrate

    Science.gov (United States)

    ... if you are allergic to chloral hydrate, aspirin, tartrazine (a yellow dye in some processed foods and ... in, tightly closed, and out of reach of children. Store it at room temperature, away from excess ...

  1. Efectos combinados de escarificación y de hidratación parcial en la germinación de semillas frescas de leguminosas Combined effects of scarification and partial hydration on the germination of fresh legume seeds

    Directory of Open Access Journals (Sweden)

    Yolanda González

    2008-12-01

    SO4 at 96% during 10' (in seeds from Indigofera sp., Desmanthus virgatus and Centrosema pubescens, which were combined with a treatment of partial hydration in water at alternate temperature of 25/30ºC (optimum germination thermoperiod. The partial hydration was carried out until two hours before the beginning of visible germination; in the scarified seeds of Indigofera sp., D. virgatus, Crotalaria sp. and C. pubescens, this moment was reached at 15, 16, 16 and 19 hours, respectively. Air-dehydration took place for 48 hours, until reaching approximately the initial moisture content of the seeds (7-12% on fresh matter base. In all the species, except in D. virgatus, the partial hydration treatments increased the germination percentage, although they caused a higher germination rate. The partial hydration treatments in water are concluded to be adequate for increasing germination of the studied species, except in D. virgatus, under controlled conditions of caloric stress.

  2. Ground-state structures of Hafnium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Wei Chun; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technoloty, Multimedia University, Melaca Campus, 75450 Melaka (Malaysia)

    2015-04-24

    Hafnium (Hf) is a very large tetra-valence d-block element which is able to form relatively long covalent bond. Researchers are interested to search for substitution to silicon in the semi-conductor industry. We attempt to obtain the ground-state structures of small Hf clusters at both empirical and density-functional theory (DFT) levels. For calculations at the empirical level, charge-optimized many-body functional potential (COMB) is used. The lowest-energy structures are obtained via a novel global-minimum search algorithm known as parallel tempering Monte-Carlo Basin-Hopping and Genetic Algorithm (PTMBHGA). The virtue of using COMB potential for Hf cluster calculation lies in the fact that by including the charge optimization at the valence shells, we can encourage the formation of proper bond hybridization, and thus getting the correct bond order. The obtained structures are further optimized using DFT to ensure a close proximity to the ground-state.

  3. Hafnium carbide nanocrystal chains for field emitters

    International Nuclear Information System (INIS)

    Tian, Song; Li, Hejun; Zhang, Yulei; Ren, Jincui; Qiang, Xinfa; Zhang, Shouyang

    2014-01-01

    A hafnium carbide (HfC) nanostructure, i.e., HfC nanocrystal chain, was synthesized by a chemical vapor deposition (CVD) method. X-ray diffractometer, field-emission scanning electron microscope, transmission electron microscope, and energy-dispersive X-ray spectrometer were employed to characterize the product. The synthesized one-dimensional (1D) nanostructures with many faceted octahedral nanocrystals possess diameters of tens of nanometers to 500 nm and lengths of a few microns. The chain-like structures possess a single crystalline structure and preferential growth direction along the [1 0 0] crystal orientation. The growth of the chains occurred through the vapor–liquid–solid process along with a negative-feedback mechanism. The field emission (FE) properties of the HfC nanocrystal chains as the cold cathode emitters were examined. The HfC nanocrystal chains display good FE properties with a low turn-on field of about 3.9 V μm −1 and a high field enhancement factor of 2157, implying potential applications in vacuum microelectronics.

  4. Use of hafnium in control bars of nuclear reactors

    International Nuclear Information System (INIS)

    Ramirez S, J.R.; Alonso V, G.

    2003-01-01

    Recently the use of hafnium as neutron absorber material in nuclear reactors has been reason of investigation by virtue of that this material has nuclear properties as to the neutrons absorption and structural that can prolong the useful life of the control mechanisms of the nuclear reactors. In this work some of those more significant hafnium properties are presented like nuclear material. Also there are presented calculations carried out with the HELIOS code for fuel cells of uranium oxide and of uranium and plutonium mixed oxides under controlled conditions with conventional bars of boron carbide and also with similar bars to which are substituted the absorbent material by metallic hafnium, the results are presented in this work. (Author)

  5. Analytical study of zirconium and hafnium α-hydroxy carboxylates

    International Nuclear Information System (INIS)

    Terra, V.R.

    1991-01-01

    The analytical study of zirconium and hafnium α-hydroxy carboxylates was described. For this purpose dl-mandelic, dl-p-bromo mandelic, dl-2-naphthyl glycolic, and benzilic acids were prepared. These were used in conjunction with glycolic, dl-lactic, dl-2-hydroxy isovaleric, dl-2-hydroxy hexanoic, and dl-2-hydroxy dodecanoic acids in order to synthesize the zirconium(IV) and hafnium(IV) tetrakis(α-hydroxy carboxylates). The compounds were characterized by melting point determination, infrared spectroscopy, thermogravimetric analysis, calcination to oxides and X-ray diffractometry by the powder method. (C.G.C)

  6. Preparation of complexes of zirconium and hafnium tetrachlorides with phosphorus oxychloride

    International Nuclear Information System (INIS)

    McLaughlin, D.F.

    1989-01-01

    This patent describes an improvement in a method for separating hafnium tetrachloride from zirconium tetrachloride where a complex of zirconium-hafnium tetrachlorides and phosphorus oxychloride is prepared from zirconium-hafnium tetrachlorides and the complex of zirconium-hafnium tetrachlorides and phosphorus oxychloride is introduced into a distillation column, which distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and where a hafnium tetrachloride enriched stream is taken from the top of the column and a zirconium enriched tetrachloride stream is taken from the bottom of the column. The improvement comprising: prepurifying the zirconium-hafnium tetrachlorides, prior to preparation of the complex and introduction of the complex into a distillation column, to substantially eliminate iron chloride from the zirconium hafnium tetrachlorides, whereby buildup or iron chloride in the distillation column and in the reboiler is substantially eliminated and the column can be operated in a continuous, stable and efficient manner

  7. Separation process of zirconium and hafnium; Procede de separation du zirconium et du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Hure, J; Saint-James, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-07-01

    About the separation different processes of zirconium-hafnium, the extraction by solvent in cross-current is the most easily the process usable on an industrial scale. It uses tributyl phosphate as solvent, diluted with white spirit to facilitate the decanting. Some exploratory tests showed that nitric environment seemed the most favorable for extraction; but a lot of other factors intervene in the separation process. We studied the influence of the acidity successively, the NO{sub 3}{sup -} ions concentration, the role of the cation coming with NO{sub 3}{sup -}, as well as the influence of the concentration of zirconium in the solution on the separation coefficient {beta} = {alpha}{sub Zr} / {alpha}{sub Hf}. (M.B.) [French] Des differents procedes de separation zirconium-hafnium, l'extraction par solvant en contre-courant est le procede le plus facilement utilisable a l'echelle industrielle. On utilise comme solvant le phosphate de tributyle, dilue avec du white spirit pour faciliter les decantations. Des essais preliminaires ont montre que le milieu nitrique semblait le plus favorable a l'extraction; mais beaucoup d'autres facteurs interviennent dans le processus de separation. Nous avons etudie successivement l'influence de l'acidite, celle de la concentration en ions NO{sub 3}{sup -}, le role du cation accompagnant NO{sub 3}{sup -}, ainsi que l'influence de la concentration en zirconium de la solution sur le coefficient de separation {beta} = {alpha}{sub Zr} / {alpha}{sub Hf}. (MB)

  8. Separation of zirconium and hafnium using paper distribution chromatography

    International Nuclear Information System (INIS)

    Lebedeva, G.G.; Viktorova, M.E.

    1981-01-01

    A method is suggested of chromatographic separation of zirconium and hafnium in a CCl 4 -tributyl phosphate system (1:9) containing KCl as a salting-out agent in 5 M HNO 3 at 28-30 deg C. Zr and Hf are deterfmined in articiial mixtures under optimal chromatography conditions using visual colorimetry [ru

  9. X-Ray Photoemission Study of the Oxidation of Hafnium

    International Nuclear Information System (INIS)

    Chourasia, R.; Hickman, J.L.; Miller, R.L.; Nixon, G.A.; Seabolt, M.A.

    2011-01-01

    About 20 angstrom of hafnium were deposited on silicon substrates using the electron beam evaporation technique. Two types of samples were investigated. In one type, the substrate was kept at the ambient temperature. After the deposition, the substrate temperature was increased to 100, 200, and 300 degree C. In the other type, the substrate temperature was held fixed at some value during the deposition. For this type, the substrate temperatures used were 100, 200, 300, 400, 500, 550, and 600 degree C. The samples were characterized in situ by the technique of X-ray photoelectron spectroscopy. No trace of elemental hafnium is observed in the deposited overlayer. Also, there is no evidence of any chemical reactivity between the overlayer and the silicon substrate over the temperature range used. The hafnium overlayer shows a mixture of the dioxide and the suboxide. The ratio of the suboxide to dioxide is observed to be more in the first type of samples. The spectral data indicate that hafnium has a strong affinity for oxygen. The overlayer gets completely oxidized to form HfO 2 at substrate temperature around 300 degree C for the first type of samples and at substrate temperature greater than 550 degree C for the second type

  10. X-Ray Photoemission Study of the Oxidation of Hafnium

    Directory of Open Access Journals (Sweden)

    A. R. Chourasia

    2009-01-01

    Full Text Available About 20 Å of hafnium were deposited on silicon substrates using the electron beam evaporation technique. Two types of samples were investigated. In one type, the substrate was kept at the ambient temperature. After the deposition, the substrate temperature was increased to 100, 200, and 300∘C. In the other type, the substrate temperature was held fixed at some value during the deposition. For this type, the substrate temperatures used were 100, 200, 300, 400, 500, 550, and 600∘C. The samples were characterized in situ by the technique of X-ray photoelectron spectroscopy. No trace of elemental hafnium is observed in the deposited overlayer. Also, there is no evidence of any chemical reactivity between the overlayer and the silicon substrate over the temperature range used. The hafnium overlayer shows a mixture of the dioxide and the suboxide. The ratio of the suboxide to dioxide is observed to be more in the first type of samples. The spectral data indicate that hafnium has a strong affinity for oxygen. The overlayer gets completely oxidized to form HfO2 at substrate temperature around 300∘C for the first type of samples and at substrate temperature greater than 550∘C for the second type.

  11. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K

    1996-12-31

    Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

  12. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K.

    1995-12-31

    Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

  13. Modelling of Zirconium and Hafnium separation using continuous annular chromatography

    International Nuclear Information System (INIS)

    Moch-Setyadji; Endang Susiantini

    2014-01-01

    Nuclear degrees of zirconium in the form of a metal alloy is the main material for fuel cladding of NPP. Zirconium is also used as sheathing UO 2 kernel in the form of ZrC as a substitute of SiC in the fuel elements of High Temperature Reactor (HTR). Difficulty separating hafnium from zirconium because it has a lot of similarities in the chemical properties of Zr and Hf. Annular chromatography is a device that can be used for separating of zirconium and hafnium to obtain zirconium nuclear grade. Therefore, it is necessary to construct the mathematical modelling that can describe the separation of zirconium and hafnium in the annular chromatography containing anion resin dowex-1X8. The aim of research is to perform separation simulation by using the equilibrium model and mass transfer coefficient resulted from research. Zr and Hf feed used in this research were 26 and 1 g/l, respectively. Height of resin (L), angular velocity (ω) and the superficial flow rate (uz) was varied to determine the effect of each parameter on the separation of Zr and Hf. By using Kd and Dv values resulted previous research. Simulation results showed that zirconium and hafnium can be separated using a continuous annular chromatography with high resin (long bed) 50 cm, superficial flow rate of 0.001 cm/s, the rotation speed of 0.006 rad/min and 20 cm diameter annular. In these conditions the results obtained zirconium concentration of 10,303.226 g/m 3 and hafnium concentration of 12.324 g/m 3 (ppm). (author)

  14. Hafnium Resonance Parameter Analysis Using Neutron Capture and Transmission Experiments

    International Nuclear Information System (INIS)

    MJ Trbovich; DP Barry; RE Slovacck; Y Danon; RC Block; JA Burke; NJ Drindak; G Leinweber; RV Ballad

    2004-01-01

    The focus of this work is to determine resonance parameters for stable hafnium isotopes in the 0.005-200 eV region, with special emphasis on the overlapping 176 Hf and 178 Hf resonances near 8 eV. The large neutron cross section of hafnium, combined with its corrosion resistance and excellent mechanical properties, make it a useful material for controlling nuclear reactions. Experiments measuring neutron capture and transmission were performed at the Rensselaer Polytechnic Institute (RPI) electron linear accelerator (LINAC) using the time of flight method. 6 Li glass scintillation detectors were used for transmission experiments at flight path lengths of 15 and 25 m. Capture experiments were done using a sixteen section NaI(Tl) multiplicity detector at a flight path length of 25 m. These experiments utilized various thicknesses of metallic and isotopically-enriched liquid samples. The liquid samples were designed to provide information on the 176 Hf and 178 Hf contributions to the 8 eV doublet without saturation. Data analysis was done using the R-matrix Bayesian code SAMMY version M6 beta. SAMMY is able to account for experimental resolution effects for each of the experimental setups at the RPI LINAC, and also can correct for multiple scattering effects in neutron capture yield data. The combined capture and transmission data analysis yielded resonance parameters for all hafnium isotopes from 0.005-200 eV. Resonance integrals were calculated along with errors for each hafnium isotope using the NJOY [1] and INTER [2] codes. The isotopic resonance integrals calculated were significantly different than previously published values; however the calculated elemental hafnium resonance integral changed very little

  15. Electronic properties of hafnium oxide: A contribution from defects and traps

    Energy Technology Data Exchange (ETDEWEB)

    Gritsenko, Vladimir A., E-mail: grits@isp.nsc.ru; Perevalov, Timofey V.; Islamov, Damir R., E-mail: damir@isp.nsc.ru

    2016-02-15

    In the present article, we give a review of modern data and latest achievements pertaining to the study of electronic properties of oxygen vacancies in hafnium oxide. Hafnium oxide is a key dielectric for use in many advanced silicon devices. Oxygen vacancies in hafnium oxide largely determine the electronic properties of the material. We show that the electronic transitions between the states due to oxygen vacancies largely determine the optical absorption and luminescent properties of hafnium oxide. We discuss the role of oxygen vacancies as traps that facilitate charge transport in hafnium oxide films. Also, we demonstrate the fact that the electrical conductivity in hafnium oxide is controlled by the phonon-assisted tunnelling of charge carriers between traps that were identified as oxygen vacancies.

  16. Method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream

    International Nuclear Information System (INIS)

    Snyder, T.S.; Stolz, R.A.

    1992-01-01

    This patent describes a method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream from a sand chlorinator in which the silicon and metals present in sand fed to the chlorinator are converted to chlorides at temperatures over about 800 degrees C. It comprises cooling a vapor stream from a sand chlorinator, the vapor stream containing principally silicon tetrachloride, zirconium tetrachloride, and hafnium tetrachloride contaminated with ferric chloride, to a temperature of from about 335 degrees C to about 600 degrees C; flowing the vapor stream through a gaseous diffusion separative barrier to produce a silicon tetrachloride-containing vapor stream concentrated in zirconium tetrachloride and hafnium tetrachloride and a silicon tetrachloride-containing vapor stream depleted in zirconium tetrachloride and hafnium tetrachloride; adsorbing the ferric chloride in the separative barrier; and recovering the silicon tetrachloride stream concentrated in zirconium tetrachloride and hafnium tetrachloride separately from the silicon tetrachloride stream depleted in zirconium tetrachloride and hafnium tetrachloride

  17. Synthesis of Hafnium-Based Ceramic Materials for Ultra-High Temperature Aerospace Applications

    Science.gov (United States)

    Johnson, Sylvia; Feldman, Jay

    2004-01-01

    This project involved the synthesis of hafnium (Hf)-based ceramic powders and Hf-based precursor solutions that were suitable for preparation of Hf-based ceramics. The Hf-based ceramic materials of interest in this project were hafnium carbide (with nominal composition HE) and hafnium dioxide (HfO2). The materials were prepared at Georgia Institute of Technology and then supplied to research collaborators Dr. Sylvia Johnson and Dr. Jay Feldman) at NASA Ames Research Center.

  18. Elaboration and characterisation of yttrium oxide and hafnium oxide powders by the sol-gel process

    International Nuclear Information System (INIS)

    Hours, T.

    1988-01-01

    The two classical sol-gel processes, colloidal and polymeric are studied for the preparation of yttrium oxide and hafnium oxide high performance powders. In the colloidal process, controlled and reproducible conditions for the preparation of yttrium oxide and hafnium oxide sols from salts or alkoxides are developed and the hydrothermal synthesis monodisperse hafnium oxide colloids is studied. The polymeric process is studied with hafnium ethyl-hexylate, hydrolysis kinetics for controlled preparation of sols and gels is investigated. Each step of preparation is detailed and powders obtained are characterized [fr

  19. [Skin hydration and hydrating products].

    Science.gov (United States)

    Duplan, H; Nocera, T

    2018-05-01

    One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

  20. Design and fabrication of hafnium tube to control the power of the irradiation test fuel in HANARO

    Energy Technology Data Exchange (ETDEWEB)

    Kim, D. H.; Lee, C. B.; Kim, Y. M.; Yang, Y. S.; Jung, Y. H

    2003-05-01

    For the irradiation test at HANARO, non-instrumentation capsule was manufactured and hafnium tube was used to control LHGR of HANARO. Hafnium tube can control the irradiation condition of HANARO similar to that of commercial reactor. Hafnium tube thickness was determined by the LHGR calculated at OR-4 irradiation hole to be installed the non-instrumented capsule. To fabricate the hafnium tube with hafnium plate, the fabrication method was determined by using the hafnium mechanical properties. And the tensile strength of hafnium was confirmed by tensile test. This report is confirmed the LHGR control at the OR-4 and the Hafnium fabrication for in used which the AFPCAP non-instrumented irradiation capsule.

  1. Pentamethylcyclopentadienyl Zirconium and Hafnium Polyhydride Complexes : Synthesis, Structure, and Reactivity

    NARCIS (Netherlands)

    Visser, Cindy; Hende, Johannes R. van den; Meetsma, Auke; Hessen, Bart; Teuben, Jan H.

    2001-01-01

    The half-sandwich zirconium and hafnium N,N-dimethylaminopropyl complexes Cp*M[(CH2)3NMe2]Cl2 (Cp* = η5-C5Me5, M = Zr, 1; Hf, 2) and Cp*M[(CH2)3NMe2]2Cl (M = Zr, 3; Hf, 4) were synthesized by mono- or dialkylation of Cp*MCl3 with the corresponding alkyllithium and Grignard reagents. Hydrogenolysis

  2. Separation of zirconium from hafnium by ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Felipe, Elaine C.B.; Palhares, Hugo G.; Ladeira, Ana Claudia Q., E-mail: elainecfelipe@yahoo.com.br, E-mail: hugopalhares@gmail.com, E-mail: ana.ladeira@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2013-07-01

    Zirconium and hafnium are two of the most important metals for the nuclear industry. Hafnium occurs in all zirconium ores usually in the range 2 - 3%. However, for the most nuclear industry applications, it is necessary to use a zirconium of extremely pure level. The current work consists in the separation of zirconium and hafnium by the ion exchange method in order to obtain a zirconium concentrate of high purity. The zirconium and hafnium liquors were produced from the leaching of the Zr(OH){sub 4} and Hf(OH){sub 4} with nitric acid for 24 hours. From these two liquors it was prepared one solution containing 7.5 x 10{sup -2} mol L{sup -1} of Zr and 5.8 x 10{sup -3} mol L{sup -1} of Hf with acidity of 1 M. Ion exchange experiments were carried out in batch with the resins Dowex 50WX4, Dowex 50WX8 100, Dowex 50WX8 50, Amberlite IR-120 and Marathon C at constant temperature 28 deg C. Other variables such as, acidity and agitation were kept constant. The data were adjusted to Langmuir equation in order to calculate the maximum loading capacity (q{sub max}) of the resins, the distribution coefficient (K{sub d}) for Zr and Hf and the separation factor (α{sub Hf}{sup Zr} ). The results of maximum loading capacity (q{sub max}) for Zr and Hf, in mmol g{sup -}1, showed that the most suitable resins for columns experiments are: Dowex 50WX4 50 (q{sub max} Z{sub r} = 2.21, Hf = 0.18), Dowex 50WX8 50 (q{sub max} Zr = 1.89, Hf = 0.13) and Amberlite (q{sub max} Zr = 1.64, Hf = 0.12). However, separations factors, α{sub Hf}{sup Zr}, showed that the resins are not selective. (author)

  3. Evolution of the hafnium isotopic composition in the RBMK reactor

    International Nuclear Information System (INIS)

    Jurkevicius, A.; Remeikis, V.

    2002-01-01

    The isotopic composition of hafnium in the radial neutron flux sensor of the RBMK-1500 reactor, the rates of the neutron absorption on Hf isotopes and the neutron spectrum in the sensor were numerically modeled. The sequence SAS2 (Shielding Analysis Sequence) program from the package SCALE 4.4A and the HELIOS code system were used for calculations. It has been obtained that the overall neutron absorption rates in hafnium for the sensors located in the 2.4 % and 2.6 % enrichment uranium-erbium nuclear fuel assemblies are by 16 % and 19 % lower than in the 2.0 % enrichment uranium nuclear fuel assemblies. The overall neutron absorption rate in hafnium decreases 2.70-2.75 times due to the sensor burnup to 5800 MW d. The sensitivity of the Hf sensors to the thermal neutron flux increases twice due to the nuclear fuel assembly burnup to 3000 MW d. The corrective factors ξ d (I) at the different integral current I of the sensors and ξ td (E) at the different burnup E of the nuclear fuel assemblies were calculated. The obtained dependence ξ d (I) calculated numerically was compared to the experimental one determined by comparing signals of the fresh sensor and the sensor with the integral current I and by processing repeated calibration results of Hf sensors in RBMK-1500 reactors. The relative relationship coefficients K T (T FA ) were found for all RBMK-1500 nuclear fuel types. (author)

  4. Recovery of hafnium radioisotopes from a proton irradiated tantalum target

    International Nuclear Information System (INIS)

    Taylor, W.A.; Garcia, J.G.; Hamilton, V.T.; Heaton, R.C.; Jamriska, D.J.; Ott, M.A.; Philips, D.R.; Radzinski, S.D.

    1998-01-01

    The 178m2 Hf nucleus, with its long half-life (31 y) and high-spin isomeric state (16 + ) is desired for new and exotic nuclear physics studies. The Los Alamos Radioisotope Program irradiated a kilogram of natural tantalum at the Los Alamos Meson Physics Facility in early 1981. After fifteen years of decay, this target was ideal for the recovery of 178m2 Hf. There was more than a millicurie of 178m2 Hf produced during this irradiation and there has been a sufficient period of time for most of the other hafnium radioisotopes to decayed away. Traditionally, separation techniques for recovering hafnium isotopes from tantalum targets employ solvent extractions with reagents that are considered hazardous. These techniques are no longer condoned because they generate a mixed-waste (radioactive and hazardous components) that can not be treated for disposal. In this paper we describe a new and unique procedure for the recovery of hafnium radioisotopes from a highly radioactive, proton irradiated, tantalum target using reagents that do not contribute a hazardous waste component. (author)

  5. Zirconium and hafnium in the southeastern Atlantic States

    Science.gov (United States)

    Mertie, J.B.

    1958-01-01

    The principal source of zirconium and hafnium is zircon, though a minor source is baddeleyite, mined only in Brazil. Zircon is an accessory mineral in igneous, metamorphic, and sedimentary rocks, but rarely occurs in hardrock in minable quantities. The principal sources of zircon are therefore alluvial deposits, which are mined in many countries of five continents. The principal commercial deposits in the United States are in Florida, though others exist elsewhere in the southeastern Coastal Plain. The evidence indicates that conditions for the accumulation of workable deposits of heavy minerals were more favorable during the interglacial stages of the Pleistocene epoch than during Recent time. Therefore detrital ores of large volume and high tenor are more likely to be found in the terrace deposits than along the present beaches. Other concentrations of heavy minerals, however, are possible at favored sites close to the Fall Line where the Tuscaloosa formation rests upon the crystalline rocks of the Piedmont province. A score of heavy and semiheavy minerals occur in the detrital deposits of Florida, but the principal salable minerals are ilmenite, leucoxene, rutile, and zircon, though monazite and staurolite are saved at some mining plants. Commercial deposits of heavy minerals are generally required to have a tenor of 4 percent, though ores with a lower tenor can be mined at a profit if the content of monazite is notably high. The percentages of zircon in the concentrates ranges from 10 to 16 percent, and in eastern Florida from 13 to 15 percent. Thus the tenor in zircon of the ore-bearing sands ranges from 0.4 to 0.6 percent. The content of hafnium in zircon is immaterial for many uses, but for some purposes very high or very low tenors in hafnium are required. Alluvial zircon cannot be separated into such varieties, which, if needed, must be obtained from sources in bedrock. It thus becomes necessary to determine the Hf : Zr ratios in zircon from many kinds of

  6. On the stabilization of niobium(V) solutions by zirconium(IV) and hafnium(IV)

    DEFF Research Database (Denmark)

    Sørensen, E.; Bjerre, A.B.

    1992-01-01

    Niobium cannot be separated from zirconium or hafnium when these elements occur together in solution with common anions such as chloride and sulphate. This is ascribed to the co-polymerization of niobium(V) and the hydrolysed ionic species of zirconium(IV) and hafnium(IV) to form colloidal...

  7. Use of X-ray fluorescence analysis for the determination of hafnium in zircalloys

    International Nuclear Information System (INIS)

    Sato, I.M.; Salvador, V.L.R.; Lordello, A.R.

    1985-01-01

    The determination of hafnium at trace levels (ppm) in the presence of zirconium by X-ray fluorescence technique is presented. The samples were prepared in the form of double-layer pellets, with boric acid as the binding material. The most sensitive first order line of hafnium HfLα (0.157 nm), which is used analyticaly, has approximately 67% overlapping with second order line of zirconium ZrKα 1 , (0.079 nm). As the excitation potencial of zirconium is larger than hafnium, the best condition was selected, so that the interference of zirconium intensity would not be significant in hafnium analytical line. The method allowed the determination of hafnium above 5.0 ppm (LLd = 1.5 ppm) with an accuracy of less than 10%. (Author) [pt

  8. Preparation of complexes of zirconium and hafnium tetrachlorides with phosphorus oxychloride

    International Nuclear Information System (INIS)

    Snyder, T.S.; Stoltz, R.A.

    1989-01-01

    This patent describes an improvement in a method for separating hafnium chloride from zirconium chloride using a distillation column, with a hafnium chloride enriched vapor stream taken from the top of the column and a zirconium enriched chloride stream taken from the bottom of the column. The improvement comprising: purifying the zirconium-hafnium chloride in a molten salt purification vessel prior to or after introduction into the distillation column to substantially eliminate iron chloride from the zirconium-hafnium chloride by at least periodically removing iron chloride from the molten salt purification vessel by electrochemically plating iron onto an electrode in the molten salt purification vessel. The molten salt in the molten salt purification vessel consisting essentially of a mixture of chlorides selected from the group consisting of alkali metals, alkaline earth metals, zirconium, hafnium, aluminum, manganese, and zinc

  9. Properties of neutron-rich hafnium high-spin isomers

    CERN Multimedia

    Tungate, G; Walker, P M; Neyens, G; Billowes, J; Flanagan, K; Koester, U H; Litvinov, Y

    It is proposed to study highly-excited multi-quasiparticle isomers in neutron-rich hafnium (Z=72) isotopes. Long half-lives have already been measured for such isomers in the storage ring at GSI, ensuring their accessibility with ISOL production. The present proposal focuses on:\\\\ (i) an on-line experiment to measure isomer properties in $^{183}$Hf and $^{184}$Hf, and\\\\ (ii) an off-line molecular breakup test using REXTRAP, to provide Hf$^{+}$ beams for future laser spectroscopy and greater sensitivity for the future study of more neutron-rich isotopes.

  10. Studies on Optical and Electrical Properties of Hafnium Oxide Nanoparticles

    Science.gov (United States)

    Jayaraman, Venkatachalam; Sagadevan, Suresh; Sudhakar, Rajesh

    2017-07-01

    In this paper, the synthesis and physico-chemical properties of hafnium oxide nanoparticles (HfO2 NPs) are analyzed and reported. The synthesis was carried out by the precipitation route by using hafnium tetrachloride (HfCl4) as precursor material with potassium hydroxide (KOH) dissolved in Millipore water. In the precipitation technique, the chemical reaction is comparatively simple, low-cost and non-toxic compared to other synthetic methods. The synthesized HfO2 NPs were characterized by using powder x-ray diffraction (PXRD), ultraviolet-visible (UV-Vis) spectroscopy, Raman analysis, and high-resolution transmission electron microscopy (HRTEM). The monoclinic structure of the HfO2 NPs was resolved utilizing x-ray diffraction (XRD). The optical properties were studied from the UV-Vis absorption spectrum. The optical band gap of the HfO2NPs was observed to be 5.1 eV. The Raman spectrum shows the presence of HfO2 NPs. The HRTEM image showed that the HfO2 NPs were of spherical shape with an average particle size of around 28 nm. The energy-dispersive x-ray spectroscopy (EDS) spectrum obviously demonstrated the presence of HfO2 NPs. Analysis and studies on the dielectric properties of the HfO2 NPs such as the dielectric constant, the dielectric loss, and alternating current (AC) conductivity were carried out at varying frequencies and temperatures.

  11. Corrosion potentials of hafnium in molten alkaline-earth metal chlorides

    International Nuclear Information System (INIS)

    Kovalik, O.Yu.; Tkhaj, V.D.

    2000-01-01

    Corrosion potentials of hafnium in molten calcium, strontium and barium chlorides are measured and their temperature dependences are determined. It is stated that the corrosion potential of hafnium becomes more electropositive with an increase of the environment temperature. If the temperature is the same the potential shifts to the interval of more electronegative values in the row of CaCl 2 , SrCl 2 , BaCl 2 which corresponds to a lesser corrosion rate in environments positioned from left to right. the comparison of hafnium corrosion potentials with previously measured values for titanium and zirconium shows that a metal activity decrease results in a more electronegative corrosion potential [ru

  12. Hafnium-Based Contrast Agents for X-ray Computed Tomography.

    Science.gov (United States)

    Berger, Markus; Bauser, Marcus; Frenzel, Thomas; Hilger, Christoph Stephan; Jost, Gregor; Lauria, Silvia; Morgenstern, Bernd; Neis, Christian; Pietsch, Hubertus; Sülzle, Detlev; Hegetschweiler, Kaspar

    2017-05-15

    Heavy-metal-based contrast agents (CAs) offer enhanced X-ray absorption for X-ray computed tomography (CT) compared to the currently used iodinated CAs. We report the discovery of new lanthanide and hafnium azainositol complexes and their optimization with respect to high water solubility and stability. Our efforts culminated in the synthesis of BAY-576, an uncharged hafnium complex with 3:2 stoichiometry and broken complex symmetry. The superior properties of this asymmetrically substituted hafnium CA were demonstrated by a CT angiography study in rabbits that revealed excellent signal contrast enhancement.

  13. Comparative Assessment of Advanced Gay Hydrate Production Methods

    Energy Technology Data Exchange (ETDEWEB)

    M. D. White; B. P. McGrail; S. K. Wurstner

    2009-06-30

    Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

  14. Artificial Hydration and Nutrition

    Science.gov (United States)

    ... Crisis Situations Pets and Animals myhealthfinder Food and Nutrition Healthy Food Choices Weight Loss and Diet Plans ... Your Health Resources Healthcare Management Artificial Hydration and Nutrition Artificial Hydration and Nutrition Share Print Patients who ...

  15. Solvent extraction of zirconium and hafnium using MIBK-HSCN-HCL process

    International Nuclear Information System (INIS)

    Borges, J.A.L.; Cunha, O.G.C. da

    1985-01-01

    The separation process of zirconium and hafnium, using MIBK as extractant in a set of mixer-settler is described. The chemical analysis was done by X-ray fluorescence and emission spectrography. (Author) [pt

  16. Hafnium as a prospective absorber for VVER-1000 reactors of Ukraine

    International Nuclear Information System (INIS)

    Afanas'ev, A.A.; Konotop, Yu.F.; Odejchuk, N.L.

    2000-01-01

    Nuclear-physical parameters of hafnium having in mind its use as an absorber, are considered. Technical aspects of Hf production are exposed. Use of B 4 C/Hf absorber is twice cheaper than a standard one

  17. Spectrofluorimetric determination of hafnium and zirconium with 3,7-dihydroxyflavone

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Takushi; Suzuki, Osamu; Seuzuki, Tetsuo; Murata, Akira

    1986-04-01

    The absorptive and fluorescent characteristics of the hafnium and zirconium complexes of 3-hydroxyflavone and its 12 hydroxy and methoxy derivatives have been studied. The fluorescence of the 1:1 hafnium - 3,7-dihydroxyflavone complex (lambdasub(ex.)397 nm,lambdasub(em.) 465 nm) in 3 M hydrochloric acid has been used to determine 2-40 ng ml/sup -1/ of hafnium. The fluorescence of the 1:1 zirconium - 3,7-dihydroxyflavone complex (lambdasub(ex.) 395 nm, lambda sub(em.) 465 nm) at pH 2.0 in 0.02 M sulphate solution has been used to determine 2-40 ng ml/sup -1/ of zirconium. These methods are very sensitive and can be used for the simultaneous determination of hafnium and zirconium with an error of about 5%.

  18. Electronic structure of pentacene on hafnium studied by ultraviolet photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Kang, Seong Jun; Yi, Yeon Jin; Kim, Chung Yi; Whang, Chung Nam

    2005-01-01

    The electronic structure of pentacene on hafnium, which is a low work function metal, was analyzed by using ultraviolet photoelectron spectroscopy. The energy level alignment was studied by using the onset of the highest occupied molecular orbital level and the shift of the vacuum level of the pentacene layer, which was deposited on a clean hafnium surface in a stepwise manner. The measured onset of the highest occupied molecular orbital energy level was 1.52 eV from the Fermi level of hafnium. The vacuum level was shifted 0.28 eV toward higher binding energy with additional pentacene layers, which means an interfacial dipole exists at the interface between pentacene and hafnium. We confirm that a small electron injection barrier can be achieved by inserting a low work function metal in a pentacene thin-film transistor.

  19. Compositional characterization of hafnium alloy used as control rod material in nuclear reactor

    International Nuclear Information System (INIS)

    Sharma, P.K.; Bassan, M.K.T.; Avhad, D.K.; Singhal, R.K.

    2014-01-01

    Hafnium (Hf) is a heavy, steel-gray metal in the reactive metals group that is very closely related to zirconium (Zr) and forms a continuous solid-solution at all concentrations of zirconium and hafnium. Hafnium occurs naturally with zirconium at a ratio of approximately 1:50 and is produced exclusively as a co-product of nuclear-grade zirconium. It is used in a variety of applications where few substitutes are available. Thus with its relatively high thermal neutron absorption cross-section, hafnium's biggest application is as control rod material in nuclear reactors. During this work, major (Zirconium (Zr), Cobalt (Co) and Molybdenum (Mo)) and trace ((Iron (Fe), Nickel (Ni) and Titanium (Ti)) elements were measured in the bulk matrices of Hf. These materials are also associated with other impurities such as O, N, H etc.

  20. Evaluation of thermodynamic data on zirconium and hafnium halides and oxyhalides by means of transport experiments

    International Nuclear Information System (INIS)

    Dittmer, G.; Niemann, U.

    1987-01-01

    A consistent set of thermodynamic data for zirconium and hafnium halides, oxides and oxyhalides was achieved. It was found that formation enthalpies of gaseous compounds could be derived from solubility measurements together with theoretical estimations and a revision of literature data. Free energy functions were calculated employing statistical mechanics. Data for liquid and solid compounds were obtained via sublimation and vaporization data. Chemical equilibria of zirconium and hafnium with halogens are discussed. 51 refs.; 16 figs.; 14 tabs

  1. Investigation of chlorination of zirconium and hafnium and their compounds in discharge from hollow cathode

    International Nuclear Information System (INIS)

    Ioffe, R.B.; Korovin, Yu.I.

    1978-01-01

    The possibility is investigated of chlorinating various zirconium and hafnium compounds (metal, oxide, carbide) in a hot discharge from a hollow cathode with various chlorinating reagents: copper monochloride, nickel chloride, magnesium chloride, for the purpose of accelerating their entrance into the excitation zone. It has been shown thermodynamically and experimentally that chlorination of metal zirconium and hafnium and their carbides with copper monochloride in hot hollow cathode conditions provides a sharp increase in the intensity of the lines of these elements

  2. Knight shift in scandium and its alloys with hafnium and titanium

    International Nuclear Information System (INIS)

    Chachkhiani, Z.B.; Chechernikov, V.I.; Martynova, L.F.; Nidel'ko, V.I.; Chachkhiani, L.G.; Georgadze, G.S.

    1981-01-01

    Results of the investigation of NMR on 45 Sc nuclei and magnetic susceptibility of scandium and its solid solutions with titanium and hafnium are presented. It is shown that the existing hybridization of S and d zones in pure scandium and its alloys with titanium and hafnium affects the Knight shift reducing the value of the contact contribution. The temperature behaviour of the Knight shift from the temperature dependence and spin susceptibility of collectivized d electrons [ru

  3. Application of hafnium hydride control rod to large sodium cooled fast breeder reactor

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, Kazumi, E-mail: kazumi_ikeda@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Moriwaki, Hiroyuki, E-mail: hiroyuki_moriwaki@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Ohkubo, Yoshiyuki, E-mail: yoshiyuki_okubo@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Iwasaki, Tomohiko, E-mail: tomohiko.iwasaki@qse.tohoku.ac.jp [Department of Quantum Science and Energy Engineering, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai-shi, Miyagi-ken 980-8579 (Japan); Konashi, Kenji, E-mail: konashi@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Narita-cho, Oarai-machi, Higashi-Ibaraki-gun, Ibaraki-ken 311-1313 (Japan)

    2014-10-15

    Highlights: • Application of hafnium hydride control rod to large sodium cooled fast breeder reactor. • This paper treats application of an innovative hafnium hydride control rod to a large sodium cooled fast breeder reactor. • Hydrogen absorption triples the reactivity worth by neutron spectrum shift at H/Hf ratio of 1.3. • Lifetime of the control rod quadruples because produced daughters of hafnium isotopes are absorbers. • Nuclear and thermal hydraulic characteristics of the reactor are as good as or better than B-10 enriched boron carbide. - Abstract: This study treats the feasibility of long-lived hafnium hydride control rod in a large sodium-cooled fast breeder reactor by nuclear and thermal analyses. According to the nuclear calculations, it is found that hydrogen absorption of hafnium triples the reactivity by the neutron spectrum shift at the H/Hf ratio of 1.3, and a hafnium transmutation mechanism that produced daughters are absorbers quadruples the lifetime due to a low incineration rate of absorbing nuclides under irradiation. That is to say, the control rod can function well for a long time because an irradiation of 2400 EFPD reduces the reactivity by only 4%. The calculation also reveals that the hafnium hydride control rod can apply to the reactor in that nuclear and thermal characteristics become as good as or better than 80% B-10 enriched boron carbide. For example, the maximum linear heat rate becomes 3% lower. Owing to the better power distribution, the required flow rate decreases approximately by 1%. Consequently, it is concluded on desk analyses that the long lived hafnium hydride control rod is feasible in the large sodium-cooled fast breeder reactor.

  4. Dielectric response and ac conductivity analysis of hafnium oxide nanopowder

    International Nuclear Information System (INIS)

    Karahaliou, P K; Xanthopoulos, N; Krontiras, C A; Georga, S N

    2012-01-01

    The dielectric response of hafnium oxide nanopowder was studied in the frequency range of 10 -2 -10 6 MHz and in the temperature range of 20-180 °C. Broadband dielectric spectroscopy was applied and the experimental results were analyzed and discussed using the electric modulus (M*) and alternating current (ac) conductivity formalisms. The analyses of the dc conductivity and electric modulus data revealed the presence of mechanisms which are thermally activated, both with almost the same activation energy of 1.01 eV. A fitting procedure involving the superposition of the thermally activated dc conductivity, the universal dielectric responce and the near constant loss terms has been used to describe the frequency evolution of the real part of the specific electrical conductivity. The conductivity master curve was obtained, suggesting that the time-temperature superposition principle applies for the studied system, thus implying that the conductivity mechanisms are temperature independent.

  5. Amorphous Hafnium-Indium-Zinc Oxide Semiconductor Thin Film Transistors

    Directory of Open Access Journals (Sweden)

    Sheng-Po Chang

    2012-01-01

    Full Text Available We reported on the performance and electrical properties of co-sputtering-processed amorphous hafnium-indium-zinc oxide (α-HfIZO thin film transistors (TFTs. Co-sputtering-processed α-HfIZO thin films have shown an amorphous phase in nature. We could modulate the In, Hf, and Zn components by changing the co-sputtering power. Additionally, the chemical composition of α-HfIZO had a significant effect on reliability, hysteresis, field-effect mobility (μFE, carrier concentration, and subthreshold swing (S of the device. Our results indicated that we could successfully and easily fabricate α-HfIZO TFTs with excellent performance by the co-sputtering process. Co-sputtering-processed α-HfIZO TFTs were fabricated with an on/off current ratio of ~106, higher mobility, and a subthreshold slope as steep as 0.55 V/dec.

  6. Determination of hafnium with the inductively coupled plasma (ICP)

    International Nuclear Information System (INIS)

    Wuensch, G.; Pose, K.

    1985-01-01

    The relative intensities of 198 hafnium lines in the Ar-ICP are listed. Spectral interference tables are given for the 9 analytically best lines, covering the range of +-60 pm around the Hf-lines. They include measured (not calculated) data of the interferent equivalent concentrations (IEC) and the critical concentration ratios (CCR) for 115 lines of all 34 possibly interfering elements. In many cases, these IEC- or CCR-data differ by 1 or 2 orders of magnitude from those calculated from intensities observed in the NBS-copper arc. Since no intense Hf-line is free from spectral interferences, examples are given for the calculation of the most suitable line for a known matrix. (orig.) [de

  7. Separation of zirconium--hafnium by nitride precipitation

    International Nuclear Information System (INIS)

    Anderson, R.N.; Parlee, N.A.

    1977-01-01

    A method is described for the separation of a light reactive metal (e.g., zirconium) from a heavy reactive metal (e.g., hafnium) by forming insoluble nitrides of the metals in a molten metal solvent (e.g., copper) inert to nitrogen and having a suitable density for the light metal nitride to form a separate phase in the upper portion of the solvent and for the heavy metal nitride to form a separate phase in the lower portion of the solvent. Nitriding is performed by maintaining a nitrogen-containing atmosphere over the bath. The light and heavy metals may be an oxide mixture and carbothermically reduced to metal form in the same bath used for nitriding. The nitrides are then separately removed and decomposed to form the desired separate metals. 16 claims, 1 figure

  8. Systematic investigation of electromagnetic properties of all stable hafnium isotopes

    International Nuclear Information System (INIS)

    Napiorkowski, T.J.; Choinski, J.; Czosnyka, T.; Iwanicki, J.; Kownacki, J.; Zemlo, L.; Srebrny, J.; Starosta, K.; Boer, J. de.; Gollwitzer, A.; Loewe, M.; Wuerkner, M.; Guenther, C.; Weber, T.; Hagemann, G.; Sletten, G.

    1996-01-01

    In a systematic investigation of the electromagnetic structure of hafnium stable isotopes enriched targets of 176, 177, 178, 179, 180 Hf were Coulomb exciting using: 67 MeV 19 F beam from NBITAL FN Tandem, 125 MeV 32 S beam from MP Tandem in Accelerator Laboratory LMU and TU Munich, 225 MeV 58 Ni beam from NBITAL FN Tandem plus 2 Liniac Boosters complex. Scattered particle-gamma as well as p-γ-γ coincidence were registered. A further simultaneous analysis of Coulomb excitation cross section as a function of scattering angle of 19 F, 32 S, 58 Ni projectiles should be sufficient to deduce reduced probabilities of E2 transitions in ground state band

  9. Synthesis and characterization of hafnium oxide for luminescent applications

    International Nuclear Information System (INIS)

    Guzman Mendoza, J.; Aguilar Frutis, M.A.; Flores, G. Alarcon; Garcia Hipolito, M.; Azorin Nieto, J.; Rivera Montalvo, T.; Falcony, C.

    2008-01-01

    Full text: Hafnium oxide (HfO 2 ) is a material with a wide range of possible technological applications because it's chemical and physical properties such as high melting point, high chemical stability, high refraction index, high dielectric constant and hardness near to diamond in the tetragonal phase. The large energy gap and low phonon frequencies of the HfO 2 makes it appropriate as a host matrix for been doped with rare earth activators. Efficient luminescent materials find wide application in electroluminescent flat panel displays; color plasma displays panels, scintillators, cathode ray tubes, fluorescent lamps, lasers, etc. In recent years the study of luminescent materials based on HfO 2 has been intensified. Some groups have studied the optical properties of doped and undoped HfO 2 . In this contribution, Hafnium Oxide (HfO 2 ) films were prepared using the spray pyrolysis deposition technique. The material was synthesized using chlorides as raw materials in deionised water as solvent and deposited on Corning glass substrates at temperatures from 300 deg C to 600 deg C. For substrate temperatures lower than 400 deg C, the deposited films are amorphous, while for substrate temperatures higher than 450 deg C, the monoclinic phase of HfO 2 appears. Scanning electron microscopy with microprobe analysis was use to observe the microstructure and obtain the chemical composition of the films; rough surfaces with spherical particles were appreciated. UV and low energy X Ray radiations were used in order to achieve the thermoluminescent characterization of the films as a function of the deposition temperature

  10. In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

    Science.gov (United States)

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

    2004-12-01

    During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in

  11. Gas hydrate in nature

    Science.gov (United States)

    Ruppel, Carolyn D.

    2018-01-17

    Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

  12. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  13. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  14. Pyroelectricity of silicon-doped hafnium oxide thin films

    Science.gov (United States)

    Jachalke, Sven; Schenk, Tony; Park, Min Hyuk; Schroeder, Uwe; Mikolajick, Thomas; Stöcker, Hartmut; Mehner, Erik; Meyer, Dirk C.

    2018-04-01

    Ferroelectricity in hafnium oxide thin films is known to be induced by various doping elements and in solid-solution with zirconia. While a wealth of studies is focused on their basic ferroelectric properties and memory applications, thorough studies of the related pyroelectric properties and their application potential are only rarely found. This work investigates the impact of Si doping on the phase composition and ferro- as well as pyroelectric properties of thin film capacitors. Dynamic hysteresis measurements and the field-free Sharp-Garn method were used to correlate the reported orthorhombic phase fractions with the remanent polarization and pyroelectric coefficient. Maximum values of 8.21 µC cm-2 and -46.2 µC K-1 m-2 for remanent polarization and pyroelectric coefficient were found for a Si content of 2.0 at%, respectively. Moreover, temperature-dependent measurements reveal nearly constant values for the pyroelectric coefficient and remanent polarization over the temperature range of 0 ° C to 170 ° C , which make the material a promising candidate for IR sensor and energy conversion applications beyond the commonly discussed use in memory applications.

  15. Hafnium oxide nanoparticles: toward an in vitro predictive biological effect?

    International Nuclear Information System (INIS)

    Marill, Julie; Anesary, Naeemunnisa Mohamed; Zhang, Ping; Vivet, Sonia; Borghi, Elsa; Levy, Laurent; Pottier, Agnes

    2014-01-01

    Hafnium oxide, NBTXR3 nanoparticles were designed for high dose energy deposition within cancer cells when exposed to ionizing radiation. The purpose of this study was to assess the possibility of predicting in vitro the biological effect of NBTXR3 nanoparticles when exposed to ionizing radiation. Cellular uptake of NBTXR3 nanoparticles was assessed in a panel of human cancer cell lines (radioresistant and radiosensitive) by transmission electron microscopy. The radioenhancement of NBTXR3 nanoparticles was measured by the clonogenic survival assay. NBTXR3 nanoparticles were taken up by cells in a concentration dependent manner, forming clusters in the cytoplasm. Differential nanoparticle uptake was observed between epithelial and mesenchymal or glioblastoma cell lines. The dose enhancement factor increased with increase NBTXR3 nanoparticle concentration and radiation dose. Beyond a minimum number of clusters per cell, the radioenhancement of NBTXR3 nanoparticles could be estimated from the radiation dose delivered and the radiosensitivity of the cancer cell lines. Our preliminary results suggest a predictable in vitro biological effect of NBTXR3 nanoparticles exposed to ionizing radiation

  16. Studies of high-K isomers in hafnium nuclei

    International Nuclear Information System (INIS)

    Sletten, G.; Gjoerup, N.L.

    1991-01-01

    K-isomeric states built on high-Ω Nilsson orbitals from deformation-aligned high-j levels near the Fermi surface are found to cluster in the neutron rich Hf, W and Os nuclei. It has been shown that some of the high seniority states of this type have decay properties that indicate strong mixing of configurations and that in Osmium nuclei γ-softness cause strong deviations from the well established K-selection rule. Also in the Hafnium nuclei is the expected forbiddenness in isomeric decays an order of magnitude smaller than expected from the K-selection rule. A new 9 quasiparticle isomer has been discovered in 175 Hf at I=57/2. This isomer has the anomalous decay as the dominant mode. Other lower seniority states are also identified. At spin 35/2 and 45/2 the deformation aligned states become yrast, but the structure of the yrast line to even higher spins is not yet understood. (author)

  17. Luminescent determination of zirconium and hafnium with myricetin

    International Nuclear Information System (INIS)

    Talipov, Sh.T.; Zel'tser, L.E.; Morozova, L.A.; Tashkhodzhaev, A.T.

    1978-01-01

    Reaction of formation of 3, 5, 7, 3', 4', 5' - hexaoxiflavone - myricetin complexes with zirconium and hafnium ions has been the basis for development of luminescent method of determining these elements. Optimum conditions for complexing have been determined. For Hf they are : 8-9 HCl concentration, maximum fluorescence wave length (lambda fl.)of 520 nm, wave length of exciting light (lambda el) of 436 nm, for Zr lambda fl = 536nm, lambda el = 436 nm. Stable fluorescence establishes after 25 min. for Zr and after 15 min for Hf in the presence of 40% ethanol. Usage of various camouflage agents has permitted to attain high selectivity of the method. Possibility for determination of Zr with myricetin in the presence of a 10-time excess of Hf, Cr, Cu, 50-time excess of Mo and Ti is shown. Sensitivity of Zr determination is 2.0x10 μg -2 /ml, for Hf it is 9.0x10 μg -3 and mineral waters

  18. Impact of welan gum on tricalcium aluminate–gypsum hydration

    International Nuclear Information System (INIS)

    Ma Lei; Zhao Qinglin; Yao Chukang; Zhou Mingkai

    2012-01-01

    The retarding effect of welan gum on tricalcium aluminate–gypsum hydration, as a partial system of ordinary Portland cement (OPC) hydration, was investigated with several methods. The tricalcium aluminate–gypsum hydration behavior in the presence or absence of welan gum was researched by field emission gun scanning electron microscopy, X-ray diffraction and zeta potential analysis. Meanwhile, we studied the surface electrochemical properties and adsorption characteristics of welan gum by utilizing a zeta potential analyzer and UV–VIS absorption spectrophotometer. By adding welan gum, the morphology change of ettringite and retardation of hydration stages in tricalcium aluminate–gypsum system was observed. Moreover, we detected the adsorption behavior and zeta potential inversion of tricalcium aluminate and ettringite, as well as a rapid decrease in the zeta potential of tricalcium aluminate–gypsum system. The reduction on nucleation rate of ettringite and hydration activity of C 3 A was also demonstrated. Thus, through the adsorption effect, welan gum induces a retarding behavior in tricalcium aluminate–gypsum hydration. Highlights: ► Adsorption characteristics of welan gum on C 3 A and ettringite have been studied. ► C 3 A–gypsum hydration behavior and the hydration products are examined in L/S = 3. ► Welan gum retards the process of C 3 A–gypsum hydration. ► The addition of welan gum changes the nucleation growth of ettringite.

  19. Composition and microstructure of zirconium and hafnium germanates obtained by different chemical routes

    International Nuclear Information System (INIS)

    Utkin, A.V.; Prokip, V.E.; Baklanova, N.I.

    2014-01-01

    The phase composition and morphology of zirconium and hafnium germanates synthesized by ceramic and co-precipitation routes were studied. The products were characterized using high-temperature X-ray diffraction analysis (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and thermal (TG/DTA) analysis. To investigate the phase composition and stoichiometry of compounds the unit cell parameters were refined by full-profile Rietveld XRD analysis. The morphology of products and its evolution during high-temperature treatment was examined by SEM analysis. It was stated that there is the strong dependence of the phase composition and morphology of products on the preparation route. The ceramic route requires a multi-stage high-temperature treatment to obtain zirconium and hafnium germanates of 95% purity or more. Also, there are strong diffusion limitations to obtain hafnium germanate Hf 3 GeO 8 by ceramic route. On the contrary, the co-precipitation route leads to the formation of nanocrystalline single phase germanates of stoichiometric composition at a relatively low temperatures (less than 1000 °C). The results of quantitative XRD analysis showed the hafnium germanates are stoichiometric compounds in contrast to zirconium germanates that form a set of solid solutions. This distinction may be related to the difference in the ion radii of Zr and Hf. - Graphical abstract: The phase composition and morphology of zirconium and hafnium germanates synthesized by ceramic and co-precipitation routes were studied. It was stated that there is the strong dependence of the phase composition and morphology of products on the preparation route. Display Omitted - Highlights: • Zr and Hf germanates were synthesized by ceramic and co-precipitation routes. • The morphology of products depends on the synthesis parameters. • Zirconium germanates forms a set of solid solutions. • Hafnium germanates are stoichiometric compounds

  20. Hydration rate of obsidian.

    Science.gov (United States)

    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.

  1. Impact of Compound Hydrate Dynamics on Phase Boundary Changes

    Science.gov (United States)

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

    2006-12-01

    Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed

  2. Methane Hydrates: Chapter 8

    Science.gov (United States)

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

    2008-01-01

    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

  3. Bond formation in hafnium atom implantation into SiC induced by high-energy electron irradiation

    International Nuclear Information System (INIS)

    Yasuda, H.; Mori, H.; Sakata, T.; Naka, M.; Fujita, H.

    1992-01-01

    Bilayer films of Hf (target atoms)/α-SiC (substrate) were irradiated with 2 MeV electrons in an ultra-high voltage electron microscope (UHVEM), with the electron beam incident on the hafnium layer. As a result of the irradiation, hafnium atoms were implanted into the SiC substrate. Changes in the microstructure and valence electronic states associated with the implantation were studied by a combination of UHVEM and Auger valence electron spectroscopy. The implantation process is summarized as follows. (1) Irradiation with 2 MeV electrons first induces a crystalline-to-amorphous transition in α-SiC. (2) Hafnium atoms which have been knocked-off from the hafnium layer by collision with the 2 MeV electrons are implanted into the resultant amorphous SiC. (3) The implanted hafnium atoms make preferential bonding to carbon atoms. (4) With continued irradiation, the hafnium atoms repeat the displacement along the beam direction and the subsequent bonding with the dangling hybrids of carbon and silicon. The repetition of the displacement and subsequent bonding lead to the deep implantation of hafnium atoms into the SiC substrate. It is concluded that implantation successfully occurs when the bond strength between a constituent atom of a substrate and an injected atom is stronger than that between constituent atoms of a substrate. (Author)

  4. Determination of hafnium, molybdenum, and vanadium in niobium and niobium-based alloys by atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Ide, Kunikazu; Kobayashi, Takeshi; Sudo, Emiko.

    1985-01-01

    The analytical procedure is as follows: Weigh 1 g of a sample and put it into a 100 cm 3 PTFE beaker. Add 5 ml of distilled water and 5 ml of hydrofluoric acid, and then heat the solution on a hot plate, adding 3 ml of nitric acid dropwise. Dilute the solution to 100 cm 3 with distilled water. When hafnium is determined, add 2 g of diammonium titanium hexafluoride ((NH 4 ) 2 TiF 6 )) before dilution. Working standard solutions are prepared by adding the stock standard solutions of hafnium, molybdenum, and vanadium into niobium solutions. When hafnium is determined, add 2 g of (NH 4 ) 2 TiF 6 and the alloying elements in amounts corresponding to those in sample solutions into the working standard solutions. The tolerable amounts of hydrofluoric acid were 2.9 M, 2.1 M, and 3.1 M and those of nitric acid were 1.0 M, 1.6 M, and 1.6 M for hafnium, molybdenum, and vanadium, respectively. It was found that (NH 4 ) 2 TiF 6 greatly increased the sensitivity for hafnium determination. Niobium showed minus effect for hafnium and plus effect for molybdenum and vanadium. The atomic absorption of molybdenum and vanadium were not influenced by the presence of 20 % of each alloying element, while the atomic absorption of hafnium was given plus effect by 20 % of zirconium, iron, cobalt, nickel, manganese, chromium or vanadium and minus effect by 20 % tungsten. The analytical values of hafnium, molybdenum, and vanadium in niobium-based alloys by this method showed a good agreement with those by X-ray fluorescence analysis. The lower limits of determination (S/N=2) were 0.05, 0.001, and 0.002 % and the relative standard deviation were 3, 1, and 1.5 % for hafnium, molybdenum, and vanadium, respectively. (author)

  5. Separation of zirconium and hafnium from acompanying elements by paper chromatography in the systems of alcohol-acid

    International Nuclear Information System (INIS)

    Lebedeva, G.G.; Viktorova, M.E.

    1980-01-01

    Solvents have been chosen and investigated which provide expressed separation of zirconium and hafnium at the analysis of mineral raw materials by paper chromatography. The systems with HNO 3 and HCl containing methyl, ethyl, propyl and butyl alcohols have been studied as mobile phases for separation of zirconium and hafnium. It has been shown that alcohol contents and solvent acidity affect the Rsub(f) value of these elements. The C 2 H 5 OH-5MHCl and C 2 H 5 OH-5MHNO 3 systems are most optimal for pre-concentration of zirconium and hafnium

  6. ENTIRELY AQUEOUS SOLUTION-GEL ROUTE FOR THE PREPARATION OF ZIRCONIUM CARBIDE, HAFNIUM CARBIDE AND THEIR TERNARY CARBIDE POWDERS

    Directory of Open Access Journals (Sweden)

    Zhang Changrui

    2016-07-01

    Full Text Available An entirely aqueous solution-gel route has been developed for the synthesis of zirconium carbide, hafnium carbide and their ternary carbide powders. Zirconium oxychloride (ZrOCl₂.8H₂O, malic acid (MA and ethylene glycol (EG were dissolved in water to form the aqueous zirconium carbide precursor. Afterwards, this aqueous precursor was gelled and transformed into zirconium carbide at a relatively low temperature (1200 °C for achieving an intimate mixing of the intermediate products. Hafnium and the ternary carbide powders were also synthesized via the same aqueous route. All the zirconium, hafnium and ternary carbide powders exhibited a particle size of ∼100 nm.

  7. Plasma spraying of zirconium carbide – hafnium carbide – tungsten cermets

    Czech Academy of Sciences Publication Activity Database

    Brožek, Vlastimil; Ctibor, Pavel; Cheong, D.-I.; Yang, S.-H.

    2009-01-01

    Roč. 9, č. 1 (2009), s. 49-64 ISSN 1335-8987 Institutional research plan: CEZ:AV0Z20430508 Keywords : Plasma spraying * cermet coatings * microhardness * zirconium carbide * hafnium carbide * tungsten * water stabilized plasma Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass

  8. Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to ''living'' polymers

    International Nuclear Information System (INIS)

    Farnham, W.B.; Hertler, W.R.

    1988-01-01

    This patent describes a process for preparing ''living'' polymer. The process comprises contacting one or more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetra-coordinate organotitanium, organozirconium or organo-hafnium polymerization initiator, and ''living'' polymers produced thereby

  9. Vapor pressure, heat capacities, and phase transitions of tetrakis(tert-butoxy)hafnium

    Czech Academy of Sciences Publication Activity Database

    Fulem, Michal; Růžička, K.

    2011-01-01

    Roč. 311, Dec. (2011), s. 25-29 ISSN 0378-3812 Institutional research plan: CEZ:AV0Z10100521 Keywords : tetrakis(tert-butoxy)hafnium * MO precursor * vapor pressure * heat capacity * vaporization enthalpy * enthalpy of fusion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.139, year: 2011

  10. Separation of hafnium from zirconium in sulfuric acid solutions using pressurized ion exchange

    International Nuclear Information System (INIS)

    Hurst, F.J.

    1981-01-01

    High-resolution pressurized ion exchange has been used successfully to study and separate hafnium and zirconium sulfate complexes by chromatographic elution from Dowex 50W-X8 (15 to 25 μm) resin with sulfuric acid solutions. Techniques were developed to continuously monitor the column effluents for zirconium and hafnium by reaction with fluorometric and colorimetric reagents. Since neither reagent was specific for either metal ion, peak patterns were initially identified by using the stable isotopes 90 Zr and 180 Hf as fingerprints of their elution position. Distribution ratios for both zirconium and hafnium decrease as the inverse fourth power of the sulfuric acid concentration below 2N and as the inverse second power at higher acid concentration. The hafnium-to-zirconium separation factor is approximately constant (approx. 8) over the 0.5 to 3N range. Under certain conditions, an unseparated fraction was observed that was not retained by the resin. The amount of this fraction which is thought to be a polymeric hydrolysis product appears to be a function of metal and sulfuric acid concentrations. Conditions are being sought to give the highest zirconium concentration and the lowest acid concentration that can be used as a feed material for commercial scale-up in the continuous annular chromatographic (CAC) unit without formation of the polymer

  11. The corrosion behavior of hafnium in high-temperature-water environments

    Energy Technology Data Exchange (ETDEWEB)

    Rishel, D.M.; Smee, J.D.; Kammenzind, B.F.

    1999-10-01

    The high-temperature-water corrosion performance of hafnium is evaluated. Corrosion kinetic data are used to develop correlations that are a function of time and temperature. The evaluation is based on corrosion tests conducted in out-of-pile autoclaves and in out-of-flux locations of the Advanced Test Reactor (ATR) at temperatures ranging from 288 to 360 C. Similar to the corrosion behavior of unalloyed zirconium, the high-temperature-water corrosion response of hafnium exhibits three corrosion regimes: pretransition, posttransition, and spalling. In the pretransition regime, cubic corrosion kinetics are exhibited, whereas in the posttransition regime, linear corrosion kinetics are exhibited. Because of the scatter in the spalling regime data, it is not reasonable to use a best fit of the data to describe spalling regime corrosion. Data also show that neutron irradiation does not alter the corrosion performance of hafnium. Finally, the data illustrate that the corrosion rate of hafnium is significantly less than that of Zircaloy-2 and Zircaloy-4.

  12. HYDRATE CORE DRILLING TESTS

    Energy Technology Data Exchange (ETDEWEB)

    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

  13. Structural and hydration properties of amorphous tricalcium silicate

    International Nuclear Information System (INIS)

    Mori, K.; Fukunaga, T.; Shiraishi, Y.; Iwase, K.; Xu, Q.; Oishi, K.; Yatsuyanagi, K.; Yonemura, M.; Itoh, K.; Sugiyama, M.; Ishigaki, T.; Kamiyama, T.; Kawai, M.

    2006-01-01

    Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca 3 SiO 5 ) sample, where Ca 3 SiO 5 is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca 3 SiO 5 . The hydration of the milled Ca 3 SiO 5 with D 2 O proceeds as follows: the formation of hydration products such as Ca(OD) 2 rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca 3 SiO 5 is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca 3 SiO 5 for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage

  14. Electrochemical stability of ionic clathrate hydrates and their structural consideration

    International Nuclear Information System (INIS)

    Lee, Wonhee; Lim, Dongwook; Lee, Huen

    2013-01-01

    Although electrochemical stability is an essential factor in relation to the potential applications of ionic clathrate hydrates to solid electrolytes, most studies regarding the proton conductors have focused on their ionic conductivity and thermal stability. Solid electrolytes in various electrochemical devices have to endure the applied potentials; thus, we examined the linear sweep voltammograms of various tetraalkylammonium hydroxide hydrates in order to shed light on the trend of electrochemical stability depending on the hydrate structure. We revealed that the electrochemical stability of Me 4 NOH hydrates is mainly affected by both their ionic concentration and cage occupancy. In particular, the true clathrate structures of β-Me 4 NOH hydrates are more electrochemically stable than their α-forms that possess partially broken hydrogen bonds. We also observed that the binary THF–Pr 4 NOH and pure Bu 4 NOH clathrate hydrates exhibit greater electrochemical stability than those of pure Me 4 NOH hydrates having lower or similar ionic concentrations. These results are considered to arise from the fact that each of the Pr 4 N + and Bu 4 N + ions occupies an extended space comprising four cages, which leads to stabilization of the larger unit, whereas a Me 4 N + ion is completely included only in one cage

  15. Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

    Science.gov (United States)

    Lorenson, T.D.

    1999-01-01

    Molecular and isotopic composition of gases from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well demonstrate that the in situ gases can be divided into three zones composed of mixtures of microbial and thermogenic gases. Sediments penetrated by the well are thermally immature; thus the sediments are probably not a source of thermogenic gas. Thermogenic gas likely migrated from depths below 5000 m. Higher concentrations of gas within and beneath the gas hydrate zone suggest that gas hydrate is a partial barrier to gas migration. Gas hydrate accumulations occur wholly within zone 3, below the base of permafrost. The gas in gas hydrate resembles, in part, the thermogenic gas in surrounding sediments and gas desorbed from lignite. Gas hydrate composition implies that the primary gas hydrate form is Structure I. However, Structure II stabilizing gases are more concentrated and isotopically partitioned in gas hydrate relative to the sediment hosting the gas hydrate, implying that Structure II gas hydrate may be present in small quantities.

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

    Science.gov (United States)

    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. Reinforcement against crack propagation of PWR absorbers by development of boron-carbon-hafnium composites

    International Nuclear Information System (INIS)

    Provot, B.; Herter, P.

    2000-01-01

    In order to improve the mechanical behaviour of materials used as neutron absorbers in nuclear reactors, we have developed CERCER or CERMET composites with boron and hafnium. Thus a new composite B 4 C/HfB 2 has been especially studied. We have identified three kinds of degradation under irradiation (thermal gradient, swelling due to fission products and accidental corrosion) that induce imposed deformations cracking phenomena. Mechanical behaviour and crack propagation resistance have been studied by ball-on-three-balls and double torsion tests. A special device was developed to enable crack propagation and associated stress intensity factor measurements. Effects of structure and of a second phase are underline. First results show that these materials present crack initiation and propagation resistance much higher than pure boron carbide or hafnium diboride. We observe R-Curves effects, crack bridging or branching, crack arrests, and toughness increases that we can relate respectively to the composite structures. (author)

  18. Synthesis and characterization of hafnium oxide films for thermo and photoluminescence applications

    International Nuclear Information System (INIS)

    Guzman Mendoza, J.; Aguilar Frutis, M.A.; Flores, G. Alarcon; Garcia Hipolito, M.; Maciel Cerda, A.; Azorin Nieto, J.; Rivera Montalvo, T.; Falcony, C.

    2010-01-01

    Hafnium oxide (HfO 2 ) films were deposited by the ultrasonic spray pyrolysis process. The films were synthesized from hafnium chloride as raw material in deionized water as solvent and were deposited on corning glass substrates at temperatures from 300 to 600 deg. C. For substrate temperatures lower than 400 deg. C the deposited films were amorphous, while for substrate temperatures higher than 450 deg. C, the monoclinic phase of HfO 2 appeared. Scanning electron microscopy showed that the film's surface resulted rough with semi-spherical promontories. The films showed a chemical composition close to HfO 2 , with an Hf/O ratio of about 0.5. UV radiation was used in order to achieve the thermoluminescent characterization of the films; the 240 nm wavelength induced the best response. In addition, preliminary photoluminescence spectra, as a function of the deposition temperatures, are shown.

  19. Synthesis and characterization of Ho3+ doped hafnium oxide TLD for radiation dosimeter

    International Nuclear Information System (INIS)

    Sekar, Nandakumar; Ganesan, Bharanidharan; Sahib, Hajee Reyaz Ali; Aruna, Prakasarao; Ganesan, Singaravelu; Thamilkumar, P.; Rai, R.R.

    2017-01-01

    Cancer is a dreaded disease which is treated by Radiotherapy, Chemotherapy and Surgery. Radiotherapy plays a vital role in treatment of cancer and recently measurements of invivo radiation dosimetric in patient is of great interest due to high dose gradients in advanced technology like IMRT, IGRT etc. Hence, for the last few decades, a great degree of interest has been shown for the hafnium oxide for radiation dosimetric applications, due to its high dielectric constant, wide band gap and better interface properties such as chemical stability, conduction band offset and thermodynamic stability. In the present study, Synthesis and characterization of Ho 3+ doped Hafnium oxide were carried out and its applications towards radiation dosimeter were investigated

  20. Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

    Science.gov (United States)

    Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

    2018-04-12

    Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

  1. Zirconium and hafnium tetrachloride separation by extractive distillation with molten zinc chloride lead chloride solvent

    International Nuclear Information System (INIS)

    McLaughlin, D.F.; Stoltz, R.A.

    1988-01-01

    In an extractive distillation method for separating hafniuim tetrachloride from zirconium tetrachloride of the type wherein a mixture of zirconium and hafnium tetrachlorides is introduced into an extractive distillation column, which extractive distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and wherein a molten salt solvent is circulated into the reflux condenser and through the column to provide a liquid phase, and wherein molten salt solvent containing zirconium tetrachloride is taken from the reboiler and run through a stripper to remove zirconium tetrachloride product from the molten salt solvent and the stripped molten salt solvent is returned to the reflux condenser and hafnium tetrachloride enriched vapor is taken as product from the reflux condenser, the improvement is described comprising: the molten salt having a composition of at least 30 mole percent zinc chloride and at least 10 mole percent of lead chloride

  2. Preparation of hafnium metal by calciothermic reduction of HfO2

    International Nuclear Information System (INIS)

    Sharma, I.G.; Vijay, P.L.; Sehra, J.C.; Sundaram, C.V.

    1975-01-01

    Hafnium metal powder has been produced by the calciothermic reduction of hafnium oxide. The influence of various experimental parameters - such as amount of calcium in excess of stoichiometric requirement, temperature, and time of reduction - on the yield and purity of the metal has been studied. The metal powder obtained by reduction at 960 0 C (two hours) with a calcium excess of 70% analysed 600 ppm of oxygen and 147 ppm of nitrogen. A reduction efficiency of 96% has been achieved under these conditions. The refining of the powder by electron beam melting, fused salt electrolysis, and iodide process has been studied. The oxygen content in the metal could be brought down from 6900 to 148 ppm by electron beam melt-refining. (author)

  3. On-line separation of refractory hafnium and tantalum isotopes at the ISOCELE separator

    CERN Document Server

    Liang, C F; Obert, J; Paris, P; Putaux, J C

    1981-01-01

    By chemical evaporation technique, neutron deficient hafnium nuclei have been on-line separated at the ISOCELE facility, from the isobar rare-earth elements, in the metal-fluoride HfF/sub 3//sup +/ ion form. Half-lives of /sup 162-165/Hf have been measured. Similarly, tantalum has been selectively separated on the TaF/sub 4//sup +/ form. (4 refs) .

  4. Complexonometric determination of hafnium (4) in the presence of europium(3) or tantalum(5)

    International Nuclear Information System (INIS)

    Oziashvili, E.D.; Ehsakiya, K.E.; Sirakanyan, N.M.

    1986-01-01

    Complexonometric determination of hafnium in the presence of Ta or Eu in samples which can be decomposed by acids, i.e. in double borides has been investigated. Initial solutions are prepared by fusing with K 2 S 2 O 8 excess, the fusion was leached by hot water, H 2 SO L 4 was added and Hf was titrated by complexone 3 in the presence of xylenol orange

  5. Simplified method for gravimetric determination of zirconium or hafnium with α-hydroxy carboxylic acids

    International Nuclear Information System (INIS)

    Barbieri, R.S.; Rocha, J.C.; Terra, V.R.; Marques Netto, A.

    1989-01-01

    The conditions for gravimetric determination of zirconium or hafnium by glicoloc acids derivatives were studied by thermogravimetric analysis. The method utilized shownd that after precipitation, washing and drying of precipitates at 150 o C, the resulting solid was weighed in the form of [M (RCH(OH)COO) 4 ] (M = Zr, Hf; R + C 6 H 5 , β-C 10 H 7 , p-BrC 6 H 4 ). (author)

  6. Modified method for zirconium or hafnium gravimetric determination with glycolic acid derivatives

    International Nuclear Information System (INIS)

    Barbieri, R.S.; Rocha, J.C.; Terra, V.R.; Marques Neto, A.

    1989-01-01

    The conditions for gravimetric determination of zirconium or hafnium by glicolic acid derivatives were studied by thermogravimetric analysis. The method utilized shown that after precipitation, washing and drying of precipitates at 150 0 C, the resulting solid was weighed in the form of [M{RCH(OH)COO} 4 ] (M = Zr,Hf;R = C 6 H 5 , β-C 10 H 7 ,p-BrC 6 H 4 ). (author) [pt

  7. Electrodeposition in molten salts of metals used in nuclear industry: hafnium and uranium

    International Nuclear Information System (INIS)

    Serrano, K.

    1998-01-01

    The aim of this work is to study the electrodeposition in molten salts of metals used in nuclear industry: hafnium and uranium. The experiment is carried out in a molten alkaline halogenide medium in a temperature range between 670 and 750 degrees Celsius. The first part of this work concerns more particularly the electrochemical behaviour of the hafnium and uranium ions in the electrolytic solution. The reduction mechanisms of these ions have been studied by the use of three methods: cyclic voltametry, chrono-potentiometry and square wave voltametry. Results have shown that the process of metal deposition is difficult to explain because secondary reactions (as for instance: adsorption phenomena or cathodic deposit dissolution) occur. The uranium germination has then been studied by modelling of chrono-amperograms. The experiments have shown that the deposition is the result of the initial uranium crystal growth and depends on the electrolyte diffusion. The second part of this work deals with the implementation of hafnium and uranium deposition taking into account the preceding mechanistic studies. Depositions have all been observed by physical methods as for instance scanning electron microscopy. Particular experimental solutions (soluble anode, addition of fluoride ions to the electrolyte) have been used. The obtained deposition of hafnium is smooth and adheres very well to the substrate. The uranium depositions have been implemented with the use of a soluble anode. Uranium is deposited in a dendritic shape to the cathode. It has also been shown that the electro-kinetic parameters (temperature, uranium ions concentration, current density) have not an important influence on the dendritic morphology of the deposition. This morphology could be the consequence of particular convection movements to the surface of the cathode. (O.M.)

  8. Rhodium and Hafnium Influence on the Microstructure, Phase Composition, and Oxidation Resistance of Aluminide Coatings

    OpenAIRE

    Maryana Zagula-Yavorska; Małgorzata Wierzbińska; Jan Sieniawski

    2017-01-01

    A 0.5 μm thick layer of rhodium was deposited on the CMSX 4 superalloy by the electroplating method. The rhodium-coated superalloy was hafnized and aluminized or only aluminized using the Chemical vapour deposition method. A comparison was made of the microstructure, phase composition, and oxidation resistance of three aluminide coatings: nonmodified (a), rhodium-modified (b), and rhodium- and hafnium-modified (c). All three coatings consisted of two layers: the additive layer and the interdi...

  9. Radiation effects on the electrical properties of hafnium oxide based MOS capacitors.

    Energy Technology Data Exchange (ETDEWEB)

    Petrosky, J. C. (Air Force Institute of Technology, Wright-Patterson Air Force Base, OH); McClory, J. W. (Air Force Institute of Technology, Wright-Patterson Air Force Base, OH); Bielejec, Edward Salvador; Foster, J. C. (Air Force Institute of Technology, Wright-Patterson Air Force Base, OH)

    2010-10-01

    Hafnium oxide-based MOS capacitors were investigated to determine electrical property response to radiation environments. In situ capacitance versus voltage measurements were analyzed to identify voltage shifting as a result of changes to trapped charge with increasing dose of gamma, neutron, and ion radiation. In situ measurements required investigation and optimization of capacitor fabrication to include dicing, cleaning, metalization, packaging, and wire bonding. A top metal contact of 200 angstroms of titanium followed by 2800 angstroms of gold allowed for repeatable wire bonding and proper electrical response. Gamma and ion irradiations of atomic layer deposited hafnium oxide on silicon devices both resulted in a midgap voltage shift of no more than 0.2 V toward less positive voltages. This shift indicates recombination of radiation induced positive charge with negative trapped charge in the bulk oxide. Silicon ion irradiation caused interface effects in addition to oxide trap effects that resulted in a flatband voltage shift of approximately 0.6 V also toward less positive voltages. Additionally, no bias dependent voltage shifts with gamma irradiation and strong oxide capacitance room temperature annealing after ion irradiation was observed. These characteristics, in addition to the small voltage shifts observed, demonstrate the radiation hardness of hafnium oxide and its applicability for use in space systems.

  10. Correlations between nuclear data and integral slab experiments: the case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J.M

    1999-07-01

    The aim of this work was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular 'mock-up' reactor.In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods together with Monte Carlo- type simulations enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent's efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author)

  11. Correlations between nuclear data and integral slab experiments: the case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J M

    1999-07-01

    The aim of this work was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular 'mock-up' reactor.In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods together with Monte Carlo- type simulations enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent's efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author)

  12. Correlations between nuclear data and results of integral slab experiments. Case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J M

    1997-10-22

    The aim of this thesis was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular `mock-up` reactor. In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods (APOLLO2 code) together with Monte Carlo- type simulations (TRIPOLI4 code) enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent`s efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author) 128 refs.

  13. Historical methane hydrate project review

    Science.gov (United States)

    Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

    2013-01-01

    In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas 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 gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas 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 gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

  14. Development and characterization of ultrathin hafnium titanates as high permittivity gate insulators

    Science.gov (United States)

    Li, Min

    High permittivity or high-kappa materials are being developed for use as gate insulators for future ultrascaled metal oxide semiconductor field effect transistors (MOSFETs). Hafnium containing compounds are the leading candidates. Due to its moderate permittivity, however, it is difficult to achieve HfO2 gate structures with an EOT well below 1.0 nm. One approach to increase HfO2 permittivity is combining it with a very high-kappa material, such as TiO2. In this thesis, we systematically studied the electrical and physical characteristics of high-kappa hafnium titanates films as gate insulators. A series of HfxTi1-xO2 films with well-controlled composition were deposited using an MOCVD system. The physical properties of the films were analyzed using a variety of characterization techniques. X-ray micro diffraction indicates that the Ti-rich thin film is more immune to crystallization. TEM analysis showed that the thick stoichiometric HfTiO 4 film has an orthorhombic structure and large anisotropic grains. The C-V curves from the devices with the hafnium titanates films displayed relatively low hysteresis. In a certain composition range, the interfacial layer (IL) EOT and permittivity of HfxTi1-x O2 increases linearly with increasing Ti. The charge is negative for HfxTi1-xO2/IL and positive for Si/IL interface, and the magnitude increases as Hf increases. For ultra-thin films (less than 2 nm EOT), the leakage current increases with increasing HE Moreover, the Hf-rich sample has weaker temperature dependence of the current. In the MOSFET devices with the hafnium titanates films, normal transistor characteristics were observed, also electron mobility degradation. Next, we investigated the effects that different pre-deposition surface treatments, including HF dipping, NH3 surface nitridation, and HfO2 deposition, have on the electrical properties of hafnium titanates. Surface nitridation shows stronger effect than the thin HfO2 layer. The nitrided samples displayed a

  15. Overview: Nucleation of clathrate hydrates.

    Science.gov (United States)

    Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

    2016-12-07

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  16. Formation of submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Soloviev, V.; Ginsburg, G.D. (Reserch Institute of Geology and Mineral Resources of the Ocean ' ' VNII Okeangeologia' ' , St. Petersburg (Russian Federation))

    1994-03-01

    Submarine gas hydrates have been discoverd in the course of deep-sea drilling (DSDP and ODP) and bottom sampling in many offshore regions. This paper reports on expeditions carried out in the Black, Caspian and Okhotsk Seas. Gas hydrate accumulations were discovered and investigated in all these areas. The data and an analysis of the results of the deep-sea drilling programme suggest that the infiltration of gas-bearing fluids is a necessary condition for gas hydrate accumulation. This is confirmed by geological observations at three scale levels. Firstly, hydrates in cores are usually associated with comparatively coarse-grained, permeable sediments as well as voids and fractures. Secondly, hydrate accumulations are controlled by permeable geological structures, i.e. faults, diapirs, mud volcanos as well as layered sequences. Thirdly, in the worldwide scale, hydrate accumulations are characteristic of continental slopes and rises and intra-continental seas where submarine seepages also are widespread. Both biogenic and catagenic gas may occur, and the gas sources may be located at various distances from the accumulation. Gas hydrates presumably originate from water-dissolved gas. The possibility of a transition from dissolved gas into hydrate is confirmed by experimental data. Shallow gas hydrate accumulations associated with gas-bearing fluid plumes are the most convenient features for the study of submarine hydrate formation in general. These accumulations are known from the Black, Caspian and Okhotsk Seas, the Gulf of Mexico and off northern California. (au) (24 refs.)

  17. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  18. Dehydration behaviour of hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Dette, S.S.; Stelzer, T.; Jones, M.J.; Ulrich, J. [Martin-Luther-Universitaet Halle-Wittenberg, Zentrum fuer Ingenieurwissenschaften, Verfahrenstechnik/TVT, 06099 Halle (Germany)

    2010-07-15

    Immersing a crystalline solvate in a suitable anti-solvent can induce phase transformation to solvent-free solid phase. In certain cases the solvent-mediated phase transition results in the generation of hollow, tubular structures. Both the tube dimensions of sodium-2-keto-L-gulonate anhydrate (skga) and the dehydration kinetics of sodium-2-keto-L-gulonate monohydrate (skgm) can be modified by the antisolvent employed. An explanation for the variable dehydration behaviour of skgm in the antisolvents is presented here. Furthermore, other crystalline hydrates were dehydrated in dry methanol. Providing an operational window can be found, any hydrate material could possibly find use in the production of tubes (micro- or nanotubes for different applications). The experimental conditions selected (dry methanol as antisolvent, dehydration temperature at 25 C) for the dehydration did not lead to the anhydrate tube growth for all hydrates investigated. Based upon the results presented here a first hypothesis is presented to explain this effect. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Low-voltage bendable pentacene thin-film transistor with stainless steel substrate and polystyrene-coated hafnium silicate dielectric.

    Science.gov (United States)

    Yun, Dong-Jin; Lee, Seunghyup; Yong, Kijung; Rhee, Shi-Woo

    2012-04-01

    The hafnium silicate and aluminum oxide high-k dielectrics were deposited on stainless steel substrate using atomic layer deposition process and octadecyltrichlorosilane (OTS) and polystyrene (PS) were treated improve crystallinity of pentacene grown on them. Besides, the effects of the pentacene deposition condition on the morphologies, crystallinities and electrical properties of pentacene were characterized. Therefore, the surface treatment condition on dielectric and pentacene deposition conditions were optimized. The pentacene grown on polystyrene coated high-k dielectric at low deposition rate and temperature (0.2-0.3 Å/s and R.T.) showed the largest grain size (0.8-1.0 μm) and highest crystallinity among pentacenes deposited various deposition conditions, and the pentacene TFT with polystyrene coated high-k dielectric showed excellent device-performance. To decrease threshold voltage of pentacene TFT, the polystyrene-thickness on high-k dielectric was controlled using different concentration of polystyrene solution. As the polystyrene-thickness on hafnium silicate decreases, the dielectric constant of polystyrene/hafnium silicate increases, while the crystallinity of pentacene grown on polystyrene/hafnium silicate did not change. Using low-thickness polystyrene coated hafnium silicate dielectric, the high-performance and low voltage operating (pentacene thin film transistor (μ: ~2 cm(2)/(V s), on/off ratio, >1 × 10(4)) and complementary inverter (DC gains, ~20) could be fabricated.

  20. Extraction of zirconium and hafnium thiocyanates by CH3COCH2CH.(CH3)2-HSCN solvent from chloride medium

    International Nuclear Information System (INIS)

    Okada, A.T.

    1982-01-01

    A zirconium-hafnium separation process for application in nuclear industry is presented. The extraction of zirconium and hafnium thiocyanates in chloride medium by hexone-HSCN solvent was studied. The extraction process was developed, varying the parameters, such as, concentrations of the metals, the thiocyanate ion, the sulphate ion and free acidity in aqueous phase. (Author) [pt

  1. Gas hydrate cool storage system

    Science.gov (United States)

    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)

  2. THERMODYNAMIC MODEL OF GAS HYDRATES

    OpenAIRE

    Недоступ, В. И.; Недоступ, О. В.

    2015-01-01

    The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

  3. Solvent extraction of titanium(IV), zirconium(IV) and hafnium(IV) salicylates using liquid ion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthi, N M; Shinde, V M

    1989-02-01

    A solvent extraction method is proposed for the extraction of quadrivalent titanium, zirconium an hafnium from salicylate media using liquid ion exchangers such as Aliquat 336 and trioctylamine dissolved in xylene. The optimum conditions were evaluated from a critical study of the following: pH, salicylate concentration, amine concentration, diluent and period of equilibration. The method allows the separation of titanium, zirconium and hafnium from binary mixtures containing commonly associated metal ions and is applicable to the analysis of real samples such as BCS-CRM 387 nimonic 901, BCS-CRM 243/4 ferro-titanium, BCS-CRM 307 magnesium alloy and BCS-CRM 388 zircon. Titanium is determined either with hydrogen peroxide or by atomic absorption spectrometry whereas zirconium and hafnium are determined spectrophotometrically with Alizarin Red S and Zylenol Orange, respectively. The results of both separation and analysis are reported. The method is precise, accurate and fast.

  4. Use of hafnium in control bars of nuclear reactors; Uso de hafnio en barras de control de reactores nucleares

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez S, J.R.; Alonso V, G. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)]. e-mail: jrrs@nuclear.inin-mx

    2003-07-01

    Recently the use of hafnium as neutron absorber material in nuclear reactors has been reason of investigation by virtue of that this material has nuclear properties as to the neutrons absorption and structural that can prolong the useful life of the control mechanisms of the nuclear reactors. In this work some of those more significant hafnium properties are presented like nuclear material. Also there are presented calculations carried out with the HELIOS code for fuel cells of uranium oxide and of uranium and plutonium mixed oxides under controlled conditions with conventional bars of boron carbide and also with similar bars to which are substituted the absorbent material by metallic hafnium, the results are presented in this work. (Author)

  5. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina; Yamauchi, Kazuo; Li, Zongjin; Zhang, Xixiang; Ma, Hongyan; Ge, Shenguang

    2017-01-01

    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10

  6. Strong influence of polymer architecture on the microstructural evolution of hafnium-alkoxide-modified silazanes upon ceramization.

    Science.gov (United States)

    Papendorf, Benjamin; Nonnenmacher, Katharina; Ionescu, Emanuel; Kleebe, Hans-Joachim; Riedel, Ralf

    2011-04-04

    The present study focuses on the synthesis and ceramization of novel hafnium-alkoxide-modified silazanes as well as on their microstructure evolution at high temperatures. The synthesis of hafnia-modified polymer-derived SiCN ceramic nanocomposites is performed via chemical modification of a polysilazane and of a cyclotrisilazane, followed by cross-linking and pyrolysis in argon atmosphere. Spectroscopic investigation (i.e., NMR, FTIR, and Raman) shows that the hafnium alkoxide reacts with the N-H groups of the cyclotrisilazane; in the case of polysilazane, reactions of N-H as well as Si-H groups with the alkoxide are observed. Consequently, scanning and transmission electron microscopy studies reveal that the ceramic nanocomposites obtained from cyclotrisilazane and polysilazane exhibited markedly different microstructures, which is a result of the different reaction pathways of the hafnium alkoxide with cyclotrisilazane and with polysilazane. Furthermore, the two prepared ceramic nanocomposites are unexpectedly found to exhibit extremely different high-temperature behavior with respect to decomposition and crystallization; this essential difference is found to be related to the different distribution of hafnium throughout the ceramic network in the two samples. Thus, the homogeneous distribution of hafnium observed in the polysilazane-derived ceramic leads to an enhanced thermal stability with respect to decomposition, whereas the local enrichment of hafnium within the matrix of the cyclotrisilazane-based sample induces a pronounced decomposition upon annealing at high temperatures. The results indicate that the chemistry and architecture of the precursor has a crucial effect on the microstructure of the resulting ceramic material and consequently on its high-temperature behavior. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Hafnium at subduction zones: isotopic budget of input and output fluxes; L'hafnium dans les zones de subduction: bilan isotopique des flux entrant et sortant

    Energy Technology Data Exchange (ETDEWEB)

    Marini, J.Ch

    2004-05-15

    Subduction zones are the primary regions of mass exchanges between continental crust and mantle of Earth through sediment subduction toward the earth's mantle and by supply of mantellic magmas to volcanic arcs. We analyze these mass exchanges using Hafnium and Neodymium isotopes. At the Izu-Mariana subduction zone, subducting sediments have Hf and Nd isotopes equivalent to Pacific seawater. Altered oceanic crust has Hf and Nd isotopic compositions equivalent to the isotopic budget of unaltered Pacific oceanic crust. At Luzon and Java subduction zones, arc lavas present Hf isotopic ratios highly radiogenic in comparison to their Nd isotopic ratios. Such compositions of the Luzon and Java arc lavas are controlled by a contamination of their sources by the subducted oceanic sediments. (author)

  8. Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

    Science.gov (United States)

    De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

    2017-12-01

    A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

  9. Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

    International Nuclear Information System (INIS)

    Kukli, Kaupo; Ritala, Mikko; Sajavaara, Timo; Haenninen, Timo; Leskelae, Markku

    2006-01-01

    Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205-300 o C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75-1.80. Calcium oxide films grown without Al 2 O 3 capping layer occurred hygroscopic and converted to Ca(OH) 2 after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al 2 O 3 capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 o C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO 2 growth cycles at 230 and 300 o C. HfCl 4 was used as a hafnium precursor. When grown at 230 o C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 o C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca 2 Hf 7 O 16 or Ca 6 Hf 19 O 44 . At 300 o C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca 2 Hf 7 O 16 . The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8-14.2

  10. A study of a production process for hafnium-free zirconium from zircon

    International Nuclear Information System (INIS)

    Ratanalert, N.

    1985-01-01

    The purpose of this experiment was to extract and purify the zirconium from zircon. The effects of time of extraction and stripping of zirconium, concentration of feed solution, concentration of hydrochloric acid in stripping process, equilibrium curve of extraction of zirconium and hafnium and equilibrium curve of stripping zirconium or scrubbing hafnium were studied from standard zirconium and hafnium. The results, subsequently were applied to the extraction procedures for zirconium from zircon. Minus 100 mesh zircon was fused with sodium hydroxide in the ratio of 1 : 6 at 700 degree C for l hour. After fusion the zirconate was leached with water and dissolved in hot concentrated hydrochloric acid. Zirconyl chloride octahydrate crystallized out when the solution was cooled. An agueons solution of zirconyl chloride was used as the feed to the hexone - thiocyanate solvent extraction process. This was prepared by dissolving zirconyl chloride octahydrate crystal in waster. This zirconium feed solution in 1 M HCl and 1 M N H 4 CNS was extracted with 2.7 m N H 4 CNS in hexone and then stripped with 3.6 M HCl the aqueous phase was got rid of thiocyanate ion by extracting with pure hexone, then the zirconium in aqueous phase was precipitated with sulfuric acid and ammonium hydroxide at pH 1.8 - 2.0 and zirconium oxide was obtained by ignition at 700 degree C. The process could be modified to improve the purity of zirconium by using cation exchange resin to get rid of thiocyanate ion after solvent extraction process

  11. Different Mechanism Effect between Gas-Solid and Liquid-Solid Interface on the Three-Phase Coexistence Hydrate System Dissociation in Seawater: A Molecular Dynamics Simulation Study

    Directory of Open Access Journals (Sweden)

    Zhixue Sun

    2017-12-01

    Full Text Available Almost 98% of methane hydrate is stored in the seawater environment, the study of microscopic mechanism for methane hydrate dissociation on the sea floor is of great significance to the development of hydrate production, involving a three-phase coexistence system of seawater (3.5% NaCl + hydrate + methane gas. The molecular dynamics method is used to simulate the hydrate dissociation process. The dissociation of hydrate system depends on diffusion of methane molecules from partially open cages and a layer by layer breakdown of the closed cages. The presence of liquid or gas phases adjacent to the hydrate has an effect on the rate of hydrate dissociation. At the beginning of dissociation process, hydrate layers that are in contact with liquid phase dissociated faster than layers adjacent to the gas phase. As the dissociation continues, the thickness of water film near the hydrate-liquid interface became larger than the hydrate-gas interface giving more resistance to the hydrate dissociation. Dissociation rate of hydrate layers adjacent to gas phase gradually exceeds the dissociation rate of layers adjacent to the liquid phase. The difficulty of methane diffusion in the hydrate-liquid side also brings about change in dissociation rate.

  12. Ductile flow of methane hydrate

    Science.gov (United States)

    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.

  13. Laser coating of hafnium on Ti6Al4 for biomedical applications

    CSIR Research Space (South Africa)

    Phume, L

    2012-12-01

    Full Text Available Al4V FOR BIOMEDICAL APPLICATIONS Lerato Phume 1, 2, S.L. Pityana 1, 2, C. Meacock 1, A.P.I Popoola 2 1. National Laser Centre, Council for Scientific and Industrial Research, P.O. Box 395, Pretoria, 0001, South Africa 2. Department of Chemical... and Metallurgical Engineering, Tshwane University of Technology, Private Bag X 680, Pretoria, 0001, South Africa (b) (c) (e) To investigate laser surface coating of Ti6Al4V with preplaced Hafnium powder, to determine the influence of the energy density...

  14. Improvement of aging kinetics and precipitate size refinement in Mg–Sn alloys by hafnium additions

    Energy Technology Data Exchange (ETDEWEB)

    Behdad, S. [Department of Mechanical and Materials Engineering, Florida International University, Miami, FL 33174 (United States); Zhou, L. [Department of Materials Science and Engineering and Advanced Materials Processing and Analysis Center, University of Central Florida, Orlando, FL 32816 (United States); Henderson, H.B.; Manuel, M.V. [Department of Materials Science and Engineering, University of Florida, Gainesville, FL 32611 (United States); Sohn, Y. [Department of Materials Science and Engineering and Advanced Materials Processing and Analysis Center, University of Central Florida, Orlando, FL 32816 (United States); Agarwal, A. [Department of Mechanical and Materials Engineering, Florida International University, Miami, FL 33174 (United States); Boesl, B., E-mail: bboesl@fiu.edu [Department of Mechanical and Materials Engineering, Florida International University, Miami, FL 33174 (United States)

    2016-01-10

    Two Mg–Sn alloys were microalloyed by addition of Hafnium and their age-hardening response was studied at 200 °C. Time to reach peak hardness was significantly reduced and improved by Hf addition. TEM study showed Hf clusters in the close vicinity and at the surface of Mg{sub 2}Sn precipitates, which confirms that Hf clusters act as additional nucleation centers for Mg{sub 2}Sn precipitate formation. Our results support the validity of thermokinetic criterion proposed by Mendis for selection of microalloying elements in order to refine precipitate size, accelerate aging kinetics and enhance peak hardness.

  15. Critical evaluation of the determination of zirconium and hafnium by instrumental and radiochemical neutron activation analysis

    International Nuclear Information System (INIS)

    Burger, Mario; Kraehenbuehl, Urs

    1991-01-01

    Neutron activation analysis (instrument or radiochemical) is suitable for the determination of zirconium and hafnium in samples of geochemical origin only when sufficient attention is paid to inter-fering nuclides. The size of the necessary correction for INAA depends on the composition of the sample; this problem is discussed. The radio-chemical technique which is recommended involves separation of the samples, precipitations and anion-exchange separation. Results are given for various standard reference materials and for meteorites. (author). 12 refs.; 1 fig.; 9 tabs

  16. Complexing of zirconium and hafnium with ortho-aminobenzoic acid and paraaminobenzoic acid

    International Nuclear Information System (INIS)

    Alekseeva, I.I.; Nemzer, I.I.; Yuranova, L.I.; Borisova, V.V.; Prozorovskaya, Z.N.

    1977-01-01

    Formation of complexes between zirconium and hafnium and ortho- and para-aminobenzoic acids has been studied by the kinetic method. It has been found that at pH=1.3-2.0 and concentrations of metals 10 -5 -10 -6 mole complex compounds are formed with composition Me:L=1:2 and 1:1 (Me=Zr, Hf; L=ortho- or para-aminobenzoic acids). Stepwise constants and overall effective constants of complex formation have been calculated

  17. Investigation of interaction of zirconium and hafnium tetrafluorides with strontium fluoride

    International Nuclear Information System (INIS)

    Ratnikova, I.D.; Korenev, Yu.M.; Novoselova, A.V.

    1980-01-01

    Diagrams of the condensated state of systems SrF 2 -EF 4 have been plotted, where E represents Zr, Hf. In these systems, three intermediate compounds of Sr 3 EF 10 , Sr 2 EF 8 and Sr EF 6 compositions are formed. All those compounds melt incongruently at temperatures of 982, 865 and 750 deg C, respectively - zirconium salt; at temperatures of 1000, 900 and 820 deg C - hafnium salts. Fluoro-metallates of composition 2:1, and 1:1, exist in two polymorphic forms. Tetrafluorides were found to dissolve in strontium fluoride: they form solid solutions having fluorite structure

  18. Near net shape processing of zirconium or hafnium metals and alloys

    International Nuclear Information System (INIS)

    Evans, S.C.

    1992-01-01

    This patent describes a process for producing a metal shape. It comprises: plasma arc melting a metal selected from zirconium, hafnium and alloys thereof comprising at least about 90 w/o of these metals to form a liquid pool; pouring the metal form the pool into a mold to form a near net shape; and reducing the metal from its near net shape to a final size while maintaining the metal temperature below the alpha-beta transition temperature throughout the size reducing step

  19. Flow assurance intervention, hydrates remediation

    Energy Technology Data Exchange (ETDEWEB)

    Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)

    2012-07-01

    This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

  20. Calcium Aluminate Cement Hydration Model

    Directory of Open Access Journals (Sweden)

    Matusinović, T.

    2011-01-01

    Full Text Available Calcium aluminate cement (AC is a very versatile special cement used for specific applications. As the hydration of AC is highly temperature dependent, yielding structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. The kinetics of AC hydration is a complex process and the use of single mechanisms models cannot describe the rate of hydration during the whole stage.This paper examines the influence of temperature (ϑ=5–20 °C and water-to-cement mass ratio (mH /mAC = 0.4; 0.5 and 1.0 on hydration of commercial iron-rich AC ISTRA 40 (producer: Istra Cement, Pula, Croatia, which is a part of CALUCEM group, Figs 1–3. The flow rate of heat generation of cement pastes as a result of the hydration reactions was measured with differential microcalorimeter. Chemically bonded water in the hydrated cement samples was determined by thermo-gravimetry.Far less heat is liberated when cement and water come in contact for the first time, Fig. 1, than in the case for portland cement (PC. Higher water-to-cement ratio increases the heat evolved at later ages (Fig. 3 due to higher quantity of water available for hydration. A significant effect of the water-to-cement ratio on the hydration rate and hydration degree showed the importance of water as being the limiting reactant that slows down the reaction early. A simplified stoichiometric model of early age AC hydration (eq. (8 based on reaction schemes of principal minerals, nominally CA, C12A7 and C4AF (Table 1, was employed. Hydration kinetics after the induction period (ϑ < 20 °C had been successfully described (Fig. 4 and Table 2 by a proposed model (eq. (23 which simultaneously comprised three main mechanisms: nucleation and growth, interaction at phase boundary, and mass transfer. In the proposed kinetic model the nucleation and growth is proportional to the amount of reacted minerals (eq

  1. Shifting Focus: From Hydration for Performance to Hydration for Health.

    Science.gov (United States)

    Perrier, Erica T

    2017-01-01

    Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

  2. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  3. Thermal behaviour of hafnium diethylenetriaminepentaacetate studied using the perturbed angular correlation technique

    Energy Technology Data Exchange (ETDEWEB)

    Chain, Cecilia Y. [Universidad Nacional de La Plata (Argentina). Dept. de Fisica; Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), La Plata (Argentina). IFLP-CCT; Consejo Nacional de Investigaciones Cientificas y Tecnicas, Buenos Aires (Argentina); Rivas, Patricia [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), La Plata (Argentina). IFLP-CCT; Consejo Nacional de Investigaciones Cientificas y Tecnicas, Buenos Aires (Argentina); Universidad Nacional de La Plata (Argentina). Facultad de Ciencias Agrarias y Forestales; Pasquevich, Alberto F. [Universidad Nacional de La Plata (Argentina). Dept. de Fisica; Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), La Plata (Argentina). IFLP-CCT; Comision de Investigaciones Cientificas de la Provincia de Buenos Aires (CIC-PBA) (Argentina)

    2014-07-01

    Polyaminecarboxilic ligands like diethylenetriaminepentaacetic acid form stable complexes with many heavy metal ions, excelling as cation chelants especially in the field of radiopharmacy. The aim of this work is to characterize, by using the Time Differential Perturbed Angular Correlations (TDPAC) technique, the hyperfine interactions at hafnium sites in hafnium diethylenetriaminepentaacetate and to investigate their evolution as temperature increases. TDPAC results for KHfDTPA.3H{sub 2}O obtained by chemical synthesis yield a well defined and highly asymmetric interaction of quadrupole frequency ω{sub Q} = 141 Mrad/s, which is consistent with the existence of a unique site for the metal in the crystal lattice. The thermal behaviour of the chelate is investigated by means of differential scanning calorimetry and thermogravimetrical analyses revealing that an endothermic dehydration of KHfDTPA.3H{sub 2}O takes place in one step between 80 C and 180 C. The anhydrous KHfDTPA thus arising is characterized by a fully asymmetric and well defined interaction of quadrupole frequency ω{sub Q} = 168 Mrad/s. (orig.)

  4. Rare-earth hafnium oxide materials for magnetohydrodynamic (MHD) generator application

    Energy Technology Data Exchange (ETDEWEB)

    Marchant, D. D; Bates, J. L.

    1979-01-01

    Several ceramic materials based on rare-earth hafnium oxides have been identified as potential high-temperature electrodes and low-temperature current leadouts for open cycle coal-fired MHD generator channels. The electrode-current leadouts combination must operate at temperatures between 400 and 2000K with an electrical conductivity greater than 10/sup -2/ ohm/sup -1/ cm/sup -1/. The electrodes will be exposed to flowing (linear flow rates up to 100 m/s) potassium seeded coal combustion gases (plasma core temperatures between 2400 to 3200/sup 0/K) and coal slag. During operation the electrodes must conduct direct electric current at densities near 1.5 amp/cm/sup 2/. Consequently, the electrodes must be resistant to electrochemical decompositions and interactions with both the coal slag and potassium salts (e.g., K/sub 2/SO/sub 4/, K/sub 2/CO/sub 3/). The current leadout materials are placed between the hot electrodes and the water-cooled copper structural members and must have electrical conductivities greater than 10/sup -2/ ohm/sup -1/ cm/sup -1/ between 1400 and 400/sup 0/K. The current leadouts must be thermally and electrochemically compatible with the electrode, copper, and potassium salts. Ideally, the electrodes and current leadouts should exhibit minimal ionic conductivity. The fabrication, electrical conductivity, and electrochemical corrosion of rare-earth hafnium oxide materials are discussed. (WHK)

  5. Thermal behaviour of hafnium diethylenetriaminepentaacetate studied using the perturbed angular correlation technique

    International Nuclear Information System (INIS)

    Chain, Cecilia Y.; Rivas, Patricia

    2014-01-01

    Polyaminecarboxilic ligands like diethylenetriaminepentaacetic acid form stable complexes with many heavy metal ions, excelling as cation chelants especially in the field of radiopharmacy. The aim of this work is to characterize, by using the Time Differential Perturbed Angular Correlations (TDPAC) technique, the hyperfine interactions at hafnium sites in hafnium diethylenetriaminepentaacetate and to investigate their evolution as temperature increases. TDPAC results for KHfDTPA.3H 2 O obtained by chemical synthesis yield a well defined and highly asymmetric interaction of quadrupole frequency ω Q = 141 Mrad/s, which is consistent with the existence of a unique site for the metal in the crystal lattice. The thermal behaviour of the chelate is investigated by means of differential scanning calorimetry and thermogravimetrical analyses revealing that an endothermic dehydration of KHfDTPA.3H 2 O takes place in one step between 80 C and 180 C. The anhydrous KHfDTPA thus arising is characterized by a fully asymmetric and well defined interaction of quadrupole frequency ω Q = 168 Mrad/s. (orig.)

  6. Preparation, structure and properties of hafnium compounds in the system Hf-C-N-O

    International Nuclear Information System (INIS)

    Brundiers, G.D.

    1975-08-01

    Highly dense, homogenous and single phase hafnium carbonitride samples (with low oxygen content) were prepared in the whole concentration range of the ternary cubic carbonitrides. Stoichiometric hafnium oxicarbides were also prepared within the range of solubility. The procedure involved the hot pressing of powders of HfC, HfN, Hf, Hf-Oxide and carbon at temperatures of 3,000 0 C and pressures up to 550 kpf/cm 2 using a novel technique. Small single crystals of slightly substoichiometric HfN were also repared. The densification of the powders was studied as a function of the non-metal concentration. Carbonitrides with N/Hf ratio of 0.37 were prepared in a high temperature autoclave operating at medium pressures by the reaction of HfC with nitrogen. All the samples were characterized by density measurements, chemical, X-ray and metallographic analysis and in some cases with the aid of quantitative metallography and microprobe analysis. Typical properties investigated were lattice parameter, thermal expansion, microhardness and electrical resistivity as function of the non-metal content. For specific concentrations extreme values in the properties are attained. With the aid of the valence electron concentration (VEC) parameter, the properties can be correlated with the density of states of electrons at the Fermi level. (orig./HK) [de

  7. Titrimetric determination of thiocyanate in solutions of the hafnium-zirconium separation process

    International Nuclear Information System (INIS)

    Vazquez, Cristina; Botbol, Moises; Hernandez, M.H.

    1980-01-01

    The control of the thiocyanate concentration is necessary during the process of separating hafnium from zirconium by the hexone-thiocyanate method. Said control is carried out by titrimetric determination of thiocyanate in aqueous and organic solutions containing hydrochloric acid and ammonium thiocyanate in presence or absence of zirconium and/or hafnium. The method consists in a redox volumetric analysis using a cerium (IV) salt as titrating agent, and ferroine as the final point indicator. Owing to the instability of thiocyanate in an acid medium it is necessary to know previously if the decomposition of solutions with different concentration of ammonium thiocyanate and hydrochloric acid may have an influence upon the analytic results or may even invalidate them. In order to obtain reliable results, it must be taken into account that the stability of the solutions depends on the thiocyanate concentration, the acidity and the time elapsed from the moment the sample is taken until the test is performed. The decomposition process can be slowed down by cooling the solutions. This method allows to control the plant and does not require any special equipment. (M.E.L) [es

  8. Correlations between nuclear data and results of integral slab experiments. Case of hafnium

    International Nuclear Information System (INIS)

    Palau, J.M.

    1997-01-01

    The aim of this thesis was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular 'mock-up' reactor. In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods (APOLLO2 code) together with Monte Carlo- type simulations (TRIPOLI4 code) enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope 177 Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent's efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author)

  9. Correlations between nuclear data and integral slab experiments: the case of hafnium

    International Nuclear Information System (INIS)

    Palau, J.M.

    1999-01-01

    The aim of this work was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular 'mock-up' reactor.In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods together with Monte Carlo- type simulations enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope 177 Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent's efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author)

  10. Highly substituted zirconium and hafnium cyclopentadienyl bifunctional β-diketiminate complexes – Synthesis, structure, and catalytic activity towards ethylene polymerization

    Czech Academy of Sciences Publication Activity Database

    Havlík, A.; Lamač, Martin; Pinkas, Jiří; Varga, Vojtěch; Růžička, A.; Olejník, R.; Horáček, Michal

    2015-01-01

    Roč. 786, JUN 2015 (2015), s. 71-80 ISSN 0022-328X R&D Projects: GA ČR GAP106/10/0924 Institutional support: RVO:61388955 Keywords : Zirconium * Hafnium * Cyclopentadienyl Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.336, year: 2015

  11. Differential perturbed angular correlation: use of physico-chemical study of some hafnium complexes derivates of hydroxy acids and EDTA

    International Nuclear Information System (INIS)

    Silveira, J.G. da.

    1981-01-01

    Measures of quadrupolar interaction to nucleus level of the metal, in some hafnium complexes are presented, including the analysis by combustion, microanalysis, infrared spectroscopy and thermogravimetry. The hyperfine interaction parameters, the temperature effects and the thermal neutrons capture effects over the irradiated Hf Y (Y = EDTA) are also studied. (author)

  12. Alcohol cosurfactants in hydrate antiagglomeration.

    Science.gov (United States)

    York, J Dalton; Firoozabadi, Abbas

    2008-08-28

    Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at

  13. STEREOCHEMICAL ASPECTS OF HYDRATION OF CARBOHYDRATES IN AQUEOUS-SOLUTIONS .3. DENSITY AND ULTRASOUND MEASUREMENTS

    NARCIS (Netherlands)

    GALEMA, SA; HOILAND, H

    1991-01-01

    Density and ultrasound measurements have been performed in aqueous solutions of pentoses, hexoses, methylpyranosides, and disaccharides as a function of molality of carbohydrate (0-0.3 mol kg-1). Partial molar volumes, partial molar isentropic compressibilities, and hydration numbers have been

  14. Obsidian hydration dates glacial loading?

    Science.gov (United States)

    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.

  15. Hydration water and microstructure in calcium silicate and aluminate hydrates

    International Nuclear Information System (INIS)

    Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

    2006-01-01

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

  16. Hydration dependent dynamics in RNA

    International Nuclear Information System (INIS)

    Olsen, Greg L.; Bardaro, Michael F.; Echodu, Dorothy C.; Drobny, Gary P.; Varani, Gabriele

    2009-01-01

    The essential role played by local and collective motions in RNA function has led to a growing interest in the characterization of RNA dynamics. Recent investigations have revealed that even relatively simple RNAs experience complex motions over multiple time scales covering the entire ms-ps motional range. In this work, we use deuterium solid-state NMR to systematically investigate motions in HIV-1 TAR RNA as a function of hydration. We probe dynamics at three uridine residues in different structural environments ranging from helical to completely unrestrained. We observe distinct and substantial changes in 2 H solid-state relaxation times and lineshapes at each site as hydration levels increase. By comparing solid-state and solution state 13 C relaxation measurements, we establish that ns-μs motions that may be indicative of collective dynamics suddenly arise in the RNA as hydration reaches a critical point coincident with the onset of bulk hydration. Beyond that point, we observe smaller changes in relaxation rates and lineshapes in these highly hydrated solid samples, compared to the dramatic activation of motion occurring at moderate hydration

  17. Permafrost-associated gas hydrate: is it really approximately 1% of the global system?

    Science.gov (United States)

    Ruppel, Carolyn

    2015-01-01

    Permafrost-associated gas hydrates are often assumed to contain ∼1 % of the global gas-in-place in gas hydrates based on a study26 published over three decades ago. As knowledge of permafrost-associated gas hydrates has grown, it has become clear that many permafrost-associated gas hydrates are inextricably linked to an associated conventional petroleum system, and that their formation history (trapping of migrated gas in situ during Pleistocene cooling) is consistent with having been sourced at least partially in nearby thermogenic gas deposits. Using modern data sets that constrain the distribution of continuous permafrost onshore5 and subsea permafrost on circum-Arctic Ocean continental shelves offshore and that estimate undiscovered conventional gas within arctic assessment units,16 the done here reveals where permafrost-associated gas hydrates are most likely to occur, concluding that Arctic Alaska and the West Siberian Basin are the best prospects. A conservative estimate is that 20 Gt C (2.7·1013 kg CH4) may be sequestered in permafrost-associated gas hydrates if methane were the only hydrate-former. This value is slightly more than 1 % of modern estimates (corresponding to 1600 Gt C to 1800 Gt C2,22) for global gas-in-place in methane hydrates and about double the absolute estimate (11.2 Gt C) made in 1981.26

  18. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.

    1991-06-01

    Full Text Available There is an hypothesis that the mechanism o f gypsum hydration and dehydration is performed through two simultaneous phenomena. In this study we try to clear up this phenomenon using chlorides as accelerators or a mixture of ethanol-methanol as retarders to carry out the gypsum setting. Natural Mexican gypsum samples and a hemihydrate prepared in the laboratory are used. The following analytical techniques are used: MO, DRX, DTA, TG and DTG. In agreement with the obtained results, it can be concluded: that colloid formation depends on the action of accelerators or retarders and the crystals are a consequence of the quantity of hemihydrate formed.

    En el mecanismo de hidratación y deshidratación del yeso existe la hipótesis de que éste se efectúa por dos fenómenos simultáneos. Este estudio intenta esclarecer estos fenómenos, empleando: cloruros como aceleradores o mezcla etanol-metanol como retardadores para efectuar el fraguado del yeso. Se emplean muestras de yeso de origen natural mexicano y hemihydrate preparado en laboratorio; se utilizan técnicas analíticas: MO, DRX, DTA, TG y DTG. De acuerdo a los resultados obtenidos se puede deducir: que la formación del coloide depende de la acción de los agentes aceleradores o retardadores y que los cristales son consecuencia de la cantidad de hemihidrato formado.

  19. Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

    Science.gov (United States)

    Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

    2017-12-01

    Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

  20. A high yield process for hydrate formation

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F. [Univ. of Roma La Sapienza, Roma (Italy). Dept. of Chemical Engineering

    2008-07-01

    Due to the large quantities of natural gas stored in deep ocean hydrates, hydrate reservoirs are a substantial energy resource. Hydrates concentrate methane by as much as a factor of 164. As such, several natural gas transportation and storage systems using gas hydrates have been studied, and many of them are nearing practical use. In these systems, the hydrate is produced as a slurry by a spray process at approximately 7 megapascal (MPa), and then shaped into pellets. The use of a spray process, instead of a conventional stirred vessel is necessary in order to reach high hydrate concentrations in the hydrate-ice system. This paper presented a new procedure to produce a bulk of concentrated methane hydrate in a static traditional reactor at moderate pressure, controlling pressure and temperature in the interval between ice melting and the hydrate equilibrium curve. This paper discussed the experimental procedure which included formation of methane hydrate at approximately 5 MPa and 2 degrees Celsius in a reaction calorimeter at a volume of two liters. Results were also discussed. It was concluded that the procedure seemed suitable for the development of a gas hydrate storage and transport technology. It was found that the spray procedure took more time, but could be sped up and made continuous by using two vessels, one for hydrate formation and the other for hydrate concentration. The advantage was the production of a concentrated hydrate, using a simpler equipment and working at lower pressures respect to the spray process. 9 refs., 5 figs.

  1. A thermally robust and thickness independent ferroelectric phase in laminated hafnium zirconium oxide

    Directory of Open Access Journals (Sweden)

    S. Riedel

    2016-09-01

    Full Text Available Ferroelectric properties in hafnium oxide based thin films have recovered the scaling potential for ferroelectric memories due to their ultra-thin-film- and CMOS-compatibility. However, the variety of physical phenomena connected to ferroelectricity allows a wider range of applications for these materials than ferroelectric memory. Especially mixed HfxZr1-xO2 thin films exhibit a broad compositional range of ferroelectric phase stability and provide the possibility to tailor material properties for multiple applications. Here it is shown that the limited thermal stability and thick-film capability of HfxZr1-xO2 can be overcome by a laminated approach using alumina interlayers.

  2. Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

    Directory of Open Access Journals (Sweden)

    Fu-Chien Chiu

    2013-01-01

    Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

  3. Thermal expansion studies on Hafnium titanate (HfTiO4)

    International Nuclear Information System (INIS)

    Panneerselvam, G.; Subramanian, G.G.S.; Antony, M.P.

    2006-01-01

    The lattice thermal expansion characteristics of hafnium titanate (HfTiO 4 ) have been studied by measuring the lattice parameter as a function of temperature by high temperature X-ray diffraction technique (HT-XRD) in the temperature range 298-1973K. Percentage linear thermal expansion and mean linear thermal expansion coefficients were computed from the lattice parameter data. The thermal expansion of HfTiO 4 is highly anisotropic. The expansivity along 'a' axis is large; as compared to the expansivity along 'b' axis which is negative below 1073 K. The percentage linear thermal expansion in the temperature range 298-1973 K along a, b and c axis are 2.74, 0.901 and 1.49 respectively. Thermal expansion values obtained in the present study are in reasonable agreement with the existing thermal expansion data. (author)

  4. Density and surface tension of melts of zirconium and hafnium fluorides with lithium fluoride

    International Nuclear Information System (INIS)

    Katyshev, S.F.; Artemov, V.V.; Desyatnik, V.N.

    1988-01-01

    A study was conducted to determine the temperature dependence of the density and surface tension of melts of LiF-ZrF 4 and LiF-HfF 4 . Density and surface tension were determined by the method of maximum pressure in an argon bubble. On the basis of experimental data over the entire concentration range the molar volumes and their relative deviations from the additive molar volumes were calculated for 1100 0 K. The positive deviations of the molar volumes from additivity in the LiF-HfF 4 system (22.45%) were greater than in the LiF-ZrF 4 system (15.75%). This indicated that the reaction with lithium fluoride is intensified with the switch to the hafnium fluoride. Results also demonstrated that the fluorides are surface-active components in the molten mixtures

  5. Extraction of hafnium with chelating agents from aqueous-alcoholic solutions

    International Nuclear Information System (INIS)

    Hala, J.; Prihoda, J.

    1975-01-01

    The extraction was studied of hafnium into solutions of N-benzoyl-N-phenylhydroxylamine, 2-thenoyltrifluoroacetone and di-n-butylphosphoric acid in benzene, toluene, chloroform and tetrachloromethane from aqueous alcoholic solutions with a formal acidity of 2M-HClO 4 . Methyl-, ethyl-, n- and isopropyl- and tert-butyl alcohol were used as organic components in the mixed aqueous-organic phase. In the extraction into N-benzoyl-N-phenylhydroxylamine the presence of the alcohols resulted in synergic effects analogous to the previously described extraction by substituted benzoylpyrazolone. With the other two extractants, the effect of the alcohols was antagonistic, due to the interaction of alcohol or water with the reagent in the organic phase, and to the decrease in the reagent distribution constant. (author)

  6. Interface and oxide traps in high-κ hafnium oxide films

    International Nuclear Information System (INIS)

    Wong, H.; Zhan, N.; Ng, K.L.; Poon, M.C.; Kok, C.W.

    2004-01-01

    The origins of the interface trap generation and the effects of thermal annealing on the interface and bulk trap distributions are studied in detail. We found that oxidation of the HfO 2 /Si interface, removal of deep trap centers, and crystallization of the as-deposited film will take place during the post-deposition annealing (PDA). These processes will result in the removal of interface traps and deep oxide traps and introduce a large amount of shallow oxide traps at the grain boundaries of the polycrystalline film. Thus, trade-off has to be made in considering the interface trap density and oxide trap density when conducting PDA. In addition, the high interface trap and oxide trap densities of the HfO 2 films suggest that we may have to use the SiO 2 /HfO 2 stack or hafnium silicate structure for better device performance

  7. Wake-up effects in Si-doped hafnium oxide ferroelectric thin films

    International Nuclear Information System (INIS)

    Zhou, Dayu; Xu, Jin; Li, Qing; Guan, Yan; Cao, Fei; Dong, Xianlin; Müller, Johannes; Schenk, Tony; Schröder, Uwe

    2013-01-01

    Hafnium oxide based ferroelectric thin films have shown potential as a promising alternative material for non-volatile memory applications. This work reports the switching stability of a Si-doped HfO 2 film under bipolar pulsed-field operation. High field cycling causes a “wake-up” in virgin “pinched” polarization hysteresis loops, demonstrated by an enhancement in remanent polarization and a shift of negative coercive voltage. The rate of wake-up is accelerated by either reducing the frequency or increasing the amplitude of the cycling field. We suggest de-pinning of domains due to reduction of the defect concentration at bottom electrode interface as origin of the wake-up

  8. Atom-vacancy ordering and magnetic susceptibility of nonstoichiometric hafnium carbide

    International Nuclear Information System (INIS)

    Gusev, A.I.; Zyryanova, A.N.

    1999-01-01

    Experimental results on magnetic susceptibility of nonstoichiometric hafnium carbide HfC y (0.6 0.71 , HfC 0.78 and HfC 0.83 in the range of 870-930 K the anomalies are revealed which are associated with superstructure short-range ordering in a non-metallics sublattice. It is shown that a short-range order in HfC 0.71 and HfC 0.78 carbides corresponds to Hf 3 C 2 ordered phase, and in HfC 0.83 carbide - to Hf 6 C 5 ordered phase. HfC 0.78 carbide is found to possesses zero magnetic susceptibility in temperature range 910-980 K [ru

  9. Sub-10 nm low current resistive switching behavior in hafnium oxide stack

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Y., E-mail: houyi@pku.edu.cn, E-mail: lfliu@pku.edu.cn [Institute of Microelectronics, Peking University, 100871 Beijing (China); IMEC, Kapeldreef 75, B-3001 Heverlee (Belgium); Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200D, B-3001 Heverlee (Belgium); Celano, U.; Xu, Z.; Vandervorst, W. [IMEC, Kapeldreef 75, B-3001 Heverlee (Belgium); Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200D, B-3001 Heverlee (Belgium); Goux, L.; Fantini, A.; Degraeve, R.; Youssef, A.; Jurczak, M. [IMEC, Kapeldreef 75, B-3001 Heverlee (Belgium); Liu, L., E-mail: houyi@pku.edu.cn, E-mail: lfliu@pku.edu.cn; Cheng, Y.; Kang, J. [Institute of Microelectronics, Peking University, 100871 Beijing (China)

    2016-03-21

    In this letter, a tip-induced cell relying on the conductive atomic force microscope is proposed. It is verified as a referable replica of an integrated resistive random access memory (RRAM) device. On the basis of this cell, the functionality of sub-10 nm resistive switching is confirmed in hafnium oxide stack. Moreover, the low current switching behavior in the sub-10 nm dimension is found to be more pronounced than that of a 50 × 50 nm{sup 2} device. It shows better ON/OFF ratio and low leakage current. The enhanced memory performance is ascribed to a change in the shape of the conductive filament as the device dimensions are reduced to sub-10 nm. Therefore, device downscaling provides a promising approach for the resistance optimization that benefits the RRAM array design.

  10. Solvent extraction of hafnium(IV) by dinonylnaphthalene sulfonic acid from mixed aqueous-organic media

    International Nuclear Information System (INIS)

    Hala, J.; Piperkovova, H.

    1979-01-01

    The extraction of hafnium(IV) by heptane and toluene solutions of dinonylnaphthalene sulfonic acid (HD) from mixed aqueous-organic solutions has been studied. Alcohols, ketones, carboxylic acids, cyclic ethers, dimethylsulfoxide and dimethylformamide were used as the organic component of the mixed phase. Methanol, ethanol, formic acid and dioxane increased the extractability of Hf(IV) whereas other solvents showed only an antagonistic effect. The results were discussed from the point of view of the changes in micellar structure of HD, and compared with the uptake of Hf(IV) by resinous cation exchangers. The solubilization by HD of alcohols, carboxylic acids and dimethylsulfoxide was demonstrated by using the corresponding 14 C and 35 S labelled compounds. (author)

  11. Study of bulk Hafnium oxide (HfO2) under compression

    Science.gov (United States)

    Pathak, Santanu; Mandal, Guruprasad; Das, Parnika

    2018-04-01

    Hafnium oxide (HfO2) is a technologically important material. This material has K-value of 25 and band gap 5.8 eV. A k value of 25-30 is preferred for a gate dielectric [1]. As it shows good insulating and capacitive properties, HfO2 is being considered as a replacement to SiO2 in microelectronic devices as gate dielectrics. On the other hand because of toughening mechanism due to phase transformation induced by stress field observed in these oxides, HFO2 has been a material of investigations in various configurations for a very long time. However the controversies about phase transition of HfO2 under pressure still exists. High quality synchrotron radiation has been used to study the structural phase transition of HfO2 under pressure.

  12. Separation of hafnium from zirconium in their tetrachloride solution in molten alkali metal chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Salyulev, A B; Kudyakov, V Ya; Smirnov, M V; Moskalenko, N I [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

    1984-08-01

    The coefficient of HfCl/sub 4/ and ZrCl/sub 4/ separation in the process of vapour sublimation from their solutions in molten NaCl, KCl, CsCl, NaCl-KCl and NaCl-CsCl equimolar mixtures is found to vary in the series from approximately 1.10 to approximately 1.22 and practically not to depend on the temperature (in the 600-910 deg) range and concentration (2-25 mol.% ZrCl/sub 4/+HfCl/sub 4/). HfCl/sub 4/ and ZrCl/sub 4/ are shown to form almost perfect solutions with each other, which in their turn form imperfect solutions with molten alkali metal chlorides, with the strength of hafnium complex chloride anions increasing higher than that of zirconium in the series from NaCl to CsCl.

  13. Separation of hafnium from zirconium in their tetrachloride solution in molten alkali metal chlorides

    International Nuclear Information System (INIS)

    Salyulev, A.B.; Kudyakov, V.Ya.; Smirnov, M.V.; Moskalenko, N.I.

    1984-01-01

    The coefficient of HfCl 4 and ZrCl 4 separation in the process of vapour sublimation from their solutions in molten NaCl, KCl, CsCl, NaCl-KCl and NaCl-CsCl equimolar mixtures is found to vary in the series from approximately 1.10 to approximately 1.22 and practically not to depend on the temperature (in the 600-910 deg) range and concentration (2-25 mol.% ZrCl 4 +HfCl 4 ). HfCl 4 and ZrCl 4 are shown to form almost perfect solutions with each other, which in their turn form imperfect solutions with molten alkali metal chlorides, with the strength of hafnium complex chloride anions increasing higher than that of zirconium in the series from NaCl to CsCl

  14. Influence of plastic deformation on nitriding of a molybdenum-hafnium alloy

    International Nuclear Information System (INIS)

    Lakhtin, Yu.M.; Kogan, Ya.D.; Shashkov, D.P.; Likhacheva, T.E.

    1982-01-01

    The influence of a preliminary plastic strain on the structure and properties of molybdenum alloy with 0.2 wt.% Hf upon nitriding in the ammonia medium at 900-1200 deg C during 1-6 h is investigated. The study of microhardness distribution across the nitrided layer thickness has shown that with increase of the degree of preliminary plastic strain up to 50 % the nitrided layer hardness decreases and with further reduction growth up to 90 % - increases. Nitriding sharply (hundred times) increases wear resistance of molybdenum alloy with hafnium addition. At the reduction degree 25 % the wear resistance is less than at other values of percentage reduction in area owing to the minimum thickness of the nitride zone. The alloy strained before nitriding by 25 % has shown the best results during heat resistance testing

  15. Hafnium at subduction zones: isotopic budget of input and output fluxes

    International Nuclear Information System (INIS)

    Marini, J.Ch.

    2004-05-01

    Subduction zones are the primary regions of mass exchanges between continental crust and mantle of Earth through sediment subduction toward the earth's mantle and by supply of mantellic magmas to volcanic arcs. We analyze these mass exchanges using Hafnium and Neodymium isotopes. At the Izu-Mariana subduction zone, subducting sediments have Hf and Nd isotopes equivalent to Pacific seawater. Altered oceanic crust has Hf and Nd isotopic compositions equivalent to the isotopic budget of unaltered Pacific oceanic crust. At Luzon and Java subduction zones, arc lavas present Hf isotopic ratios highly radiogenic in comparison to their Nd isotopic ratios. Such compositions of the Luzon and Java arc lavas are controlled by a contamination of their sources by the subducted oceanic sediments. (author)

  16. Rapid screening of nuclear grade zirconium silicate without separation of hafnium from the bulk matrix

    International Nuclear Information System (INIS)

    Venkatesh, Manisha; Sharma, P.K.; Avhad, D.K.; Basu, H.; Singhal, R.K.; Reddy, A.V.R.

    2014-01-01

    Zirconium silicate, also zirconium orthosilicate, (ZrSiO 4 ) is a chemical compound, and occurs in nature as zircon, a silicate mineral. The concentration of Hafnium in nuclear grade Zirconium must be less than 0.2% w/w of Zr. In view of this it must be accurately chemically characterized before issuing a certification for export under non nuclear category. As the chemistry of Zr and Hf is similar, it is difficult to separate Hf by direct wet chemical method. During this work, concentration of Hf in zirconium silicate was measured by Field Portable X-ray Fluorescence (FPXRF) and results obtained were validated by using detailed chemical method. FPXRF spectrometry has become a common analytical technique for on-site screening and fast turnaround analysis of contaminant elements in environmental samples

  17. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.

    1999-01-01

    and experimental data are presented showing that C(3)A can hydrate at lower humidities than either C3S or C2S. It is suggested that the initiation of hydration during exposure to water vapour is nucleation controlled. When C(3)A hydrates at low humidity, the characteristic hydration product is C(3)AH(6......Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations...

  18. Storage capacity of hydrogen in gas hydrates

    International Nuclear Information System (INIS)

    Tsuda, Takaaki; Ogata, Kyohei; Hashimoto, Shunsuke; Sugahara, Takeshi; Sato, Hiroshi; Ohgaki, Kazunari

    2010-01-01

    The storage capacity of H 2 in the THF, THT, and furan hydrates was studied by p-V-T measurements. We confirmed that the storage and release processes of H 2 in all hydrates could be performed reversibly by pressure swing without destroying of hydrate cages. H 2 absorption in both THT and furan hydrates is much faster than THF hydrate in spite of same unit-cell structure. On the other hand, the storage amounts of H 2 are coincident in the all additive hydrates and would reach at about 1.0 mass% asymptotically.

  19. Gas hydrates forming and decomposition conditions analysis

    Directory of Open Access Journals (Sweden)

    А. М. Павленко

    2017-07-01

    Full Text Available The concept of gas hydrates has been defined; their brief description has been given; factors that affect the formation and decomposition of the hydrates have been reported; their distribution, structure and thermodynamic conditions determining the gas hydrates formation disposition in gas pipelines have been considered. Advantages and disadvantages of the known methods for removing gas hydrate plugs in the pipeline have been analyzed, the necessity of their further studies has been proved. In addition to the negative impact on the process of gas extraction, the hydrates properties make it possible to outline the following possible fields of their industrial use: obtaining ultrahigh pressures in confined spaces at the hydrate decomposition; separating hydrocarbon mixtures by successive transfer of individual components through the hydrate given the mode; obtaining cold due to heat absorption at the hydrate decomposition; elimination of the open gas fountain by means of hydrate plugs in the bore hole of the gushing gasser; seawater desalination, based on the hydrate ability to only bind water molecules into the solid state; wastewater purification; gas storage in the hydrate state; dispersion of high temperature fog and clouds by means of hydrates; water-hydrates emulsion injection into the productive strata to raise the oil recovery factor; obtaining cold in the gas processing to cool the gas, etc.

  20. Extraction of hafnium by 1-phenyl-3-methyl-4-benzoyl-5-pyralozone from aqueous-alcoholic solutions

    International Nuclear Information System (INIS)

    Hala, J.; Prihoda, J.

    1975-01-01

    Extraction of hafnium by 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HL) in benzene, toluene, chloroform and tetrachloromethane from aqueous-alcoholic solutions of the formal acidity of 2M-HClO 4 was studied. Methyl, ethyl, n- and isopropyl, tert-butyl and allyl alcohol as well as ethylene glycol monomethyl ether and propylene glycol were used as organic components of the mixed aqueous-organic phase. Their presence in some cases resulted in a synergic increase in the distribution ratio of hafnium. The increase is interpreted using the results of a slope analysis and measurements of the alcohol distribution and the relative permittivity of the organic phase. It is suggested that HfL 4 molecules were solvated by alcohol molecules in the organic phase. At high alcohol concentration synergism changed into antagonism. This was caused by changes in the distribution of HL and its interaction with the alcohol in the organic phase. (author)

  1. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

    Science.gov (United States)

    Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J

    2012-05-30

    Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate

  2. Results for heterogeneous poisoning of the critical HTR-test facility KAHTER using absorber elements containing hafnium and boron

    International Nuclear Information System (INIS)

    Drueke, V.; Filges, D.; Nabi, R.; Neef, R.D.; Paul, N.; Schaal, H.

    1979-10-01

    Experiments and checking computations for investigating the initial-core poisoning of the pebble bed high temperature reactor are described. Following the example of the THTR-300, THTR absorber elements poisoned with hafnium/boron were added to the THTR fuel- and graphite elements of the KAHTER core. Three different hafnium-boron poisoned core loadings, corresponding to 2.7, 5.3 and 8% reactivity compensation, were used in the experiments. For purposes of comparison, two cores exclusively boron poisoned were also studied. The poisoning of these cores correspond to 2.7 and 8% reactivity compensation. The experiments and checking computations should serve to test the accuracy of the theoretical models and data sets in modeling the reactivity effects of absorber poisoned elements in the THTR. In particular, the applicability of the nuclear data of hafnium and the treatment of resonance calculations should be verified. In addition, to determining critical masses and ksub(eff), special emphasis was placed in the experiments on the exact determination of all reactivity effects. In some cases, repeated loading of a configuration also provided a measure of the reproducibility of ksub(eff). The experiments were checked computationally using the GAMTEREX code package and the program system RSYST. These two computation packages contain different data bases, - although the hafnium data are identical -, and the computing models differ in certain phases of the calculations. Both code systems compute ksub(eff) values to within the present accuracy requirements, whereas the program system RSYST gives better agreement with experimental measurements. (orig.) 891 RW/orig. 892 RDG [de

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

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    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. Methods to determine hydration states of minerals and cement hydrates

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 2 SO 4 –H 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

  5. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina

    2017-05-13

    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10 was conducted for tricalcium silicate (C3S) to interpret long-term hydration process and investigate the formation, structure and properties of C-S-H. Based on results from XRD, IR, SEM, NMR and so forth, loose and dense clusters of C-S-H with analogous C/S ratio were obtained along with the corresponding chemical formulae proposed as Ca5Si4O13∙6.2H2O. Crystalline structure inside C-S-H was observed by TEM, which was allocated at the foil-like proportion as well as the edge of wrinkles of the product. The long-term hydration process of C3S in dilute suspension could be sketchily described as migration of calcium hydroxide and in-situ growth of C-S-H with equilibrium silicon in aqueous solution relatively constant and calcium varied.

  6. Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

    Science.gov (United States)

    Dai, S.; Seol, Y.

    2015-12-01

    In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

  7. Ion-bombardment-induced reduction in vacancies and its enhanced effect on conductivity and reflectivity in hafnium nitride films

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Zhiqing; Wang, Jiafu; Hu, Chaoquan; Zhang, Xiaobo; Dang, Jianchen; Gao, Jing; Zheng, Weitao [Jilin University, School of Materials Science and Engineering, Key Laboratory of Mobile Materials, MOE, and State Key Laboratory of Superhard Materials, Changchun (China); Zhang, Sam [Nanyang Technological University, School of Mechanical and Aerospace Engineering, Singapore (Singapore); Wang, Xiaoyi [Chinese Academy of Sciences, Key Laboratory of Optical System Advanced Manufacturing Technology, Changchun Institute of Optics, Fine Mechanics and Physics, Changchun (China); Chen, Hong [Jilin University, Department of Control Science and Engineering, Changchun (China)

    2016-08-15

    Although the role of ion bombardment on electrical conductivity and optical reflectivity of transition metal nitrides films was reported previously, the results were controversial and the mechanism was not yet well explored. Here, we show that proper ion bombardment, induced by applying the negative bias voltage (V{sub b}), significantly improves the electrical conductivity and optical reflectivity in rocksalt hafnium nitride films regardless of level of stoichiometry (i.e., in both near-stoichiometric HfN{sub 1.04} and over-stoichiometric HfN{sub 1.17} films). The observed improvement arises from the increase in the concentration of free electrons and the relaxation time as a result of reduction in nitrogen and hafnium vacancies in the films. Furthermore, HfN{sub 1.17} films have always much lower electrical conductivity and infrared reflectance than HfN{sub 1.04} films for a given V{sub b}, owing to more hafnium vacancies because of larger composition deviation from HfN exact stoichiometry (N:Hf = 1:1). These new insights are supported by good agreement between experimental results and theoretical calculations. (orig.)

  8. Optimization of linear and branched alkane interactions with water to simulate hydrophobic hydration

    Science.gov (United States)

    Ashbaugh, Henry S.; Liu, Lixin; Surampudi, Lalitanand N.

    2011-08-01

    Previous studies of simple gas hydration have demonstrated that the accuracy of molecular simulations at capturing the thermodynamic signatures of hydrophobic hydration is linked both to the fidelity of the water model at replicating the experimental liquid density at ambient pressure and an accounting of polarization interactions between the solute and water. We extend those studies to examine alkane hydration using the transferable potentials for phase equilibria united-atom model for linear and branched alkanes, developed to reproduce alkane phase behavior, and the TIP4P/2005 model for water, which provides one of the best descriptions of liquid water for the available fixed-point charge models. Alkane site/water oxygen Lennard-Jones cross interactions were optimized to reproduce the experimental alkane hydration free energies over a range of temperatures. The optimized model reproduces the hydration free energies of the fitted alkanes with a root mean square difference between simulation and experiment of 0.06 kcal/mol over a wide temperature range, compared to 0.44 kcal/mol for the parent model. The optimized model accurately reproduces the temperature dependence of hydrophobic hydration, as characterized by the hydration enthalpies, entropies, and heat capacities, as well as the pressure response, as characterized by partial molar volumes.

  9. Effects of substituting D2O for H2O on SANS measurements of hydrating cement

    International Nuclear Information System (INIS)

    Sabine, T.M.; Prior, M.J.

    2002-01-01

    Full text: Small angle neutron scattering (SANS) measurements of cement have been found useful in the investigation of the shape and growth of particles formed during hydration. Calorimetric measurements of hydrating cement samples have shown that the substitution of D 2 O for H 2 O has the effect of slowing the hydration process. In order to throw some light on this phenomenon, we have measured SANS profiles from cement samples hydrating in H 2 O and D 2 O. This involved obtaining SANS profiles at half-hourly intervals during the initial stage of hydration. The only instruments capable of this at present are located at the Hahn-Meitner Institute in Berlin and at the Nuclear Physics Institute at Rez near Prague. Initial experiments carried out on the V12a UltraSANS diffractometer at The Hahn-Meitner Institute were only partially successful owing to excessive multiple scattering in the D 2 O samples. Subsequent measurements were therefore carried out on the similar instrument at Rez near Prague which operates at a shorter neutron wavelength. Results from these measurements show profound differences in the evolution of cements hydrating in D 2 O and those hydrating in H 2 O

  10. Partial Cancellation

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. Partial Cancellation. Full Cancellation is desirable. But complexity requirements are enormous. 4000 tones, 100 Users billions of flops !!! Main Idea: Challenge: To determine which cross-talker to cancel on what “tone” for a given victim. Constraint: Total complexity is ...

  11. Is Br2 hydration hydrophobic?

    Science.gov (United States)

    Alcaraz-Torres, A; Gamboa-Suárez, A; Bernal-Uruchurtu, M I

    2017-02-28

    The spectroscopic properties of bromine in aqueous systems suggest it can behave as either hydrophilic or hydrophobic solute. In small water clusters, the halogen bond and the hydrogen-halogen interaction are responsible for its specific way of binding. In water hydrates, it is efficiently hosted by two different cages forming the crystal structure and it has been frequently assumed that there is little or no interaction between the guest and the host. Bromine in liquid solution poses a challenging question due to its non-negligible solubility and the large blue shift measured in its absorption spectra. Using a refined semi-empirical force field, PM3-PIF, we performed a Born-Oppenheimer molecular dynamics study of bromine in liquid water. Here we present a detailed study in which we retrieved the most representative hydration structures in terms of the most frequent positions around bromine and the most common water orientations. Albeit being an approximate description of the total hydration phenomenon, it captures the contribution of the leading molecular interactions in form of the recurrent structures. Our findings confirm that the spectroscopic signature is mainly caused by the closest neighbors. The dynamics of the whole first hydration shell strongly suggests that the external molecules in that structure effectively isolate the bulk from the presence of bromine. The solvation structure fluctuates from a hydrophilic to a hydrophobic-like environment along the studied trajectory.

  12. Hydration modeling of calcium sulphates

    NARCIS (Netherlands)

    de Korte, A.C.J.; Brouwers, H.J.H.; Al-Mattarneh, Hashem; Mustapha, Kamal N.; Nuruddin, Muhd Fadhil

    2008-01-01

    The CEMHYD3D model has been extended at the University of Twente in the last ten years [1,2]. At present the cement hydration model is extended for the use of gypsum. Although gypsum was present in the model already, the model was not suitable for high contents of gypsum and did not include the

  13. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Directory of Open Access Journals (Sweden)

    Sposito Garrison

    2002-09-01

    Full Text Available Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

  14. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Science.gov (United States)

    Sutton, Rebecca; Sposito, Garrison

    2002-01-01

    Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

  15. Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties; Hydratation des argiles gonflantes: sequence d'hydratation multi-echelle determination des energies macroscopiques a partir des proprietes microscopiques

    Energy Technology Data Exchange (ETDEWEB)

    Salles, F

    2006-10-15

    smectites: it is responsible for the structure of porosity in a dry state and of the evolution of the pore sizes as a function of the RH and it modifies the hydration sequence by its mobility inside the interlayer space. The distinction between various types of water in the smectite structure is also achieved by thermo-poro-metry at different RH: water bound to the cations and surfaces, water structured by porosity and free water. This distinction is important to understand the behaviour of smectite and in particular the diffusion properties in clayey materials. The importance of the cation nature is also highlighted by the energetic model. Electrostatic calculations using the PACHA formalism (Electronegativities Equalization method) show that, for the small cations, the hydration energy of the layers is predominant. To obtain these results, we determine the surface enthalpies for the dry state, which show a coherent evolution as a function of the cation partial charge with the increase of pore sizes and thus with particle sizes. Then, using a theoretical model, we calculated swelling energies, surface hydration energies and cation hydration energies. The behaviour of mixed purified clay displays a behaviour closer to that of a calcic clay for the experiments carried out, in contradiction with the fact that the Na cation is the most abundant. This observation implies results on the clay properties, different from that expected for hydration properties, swelling and interlayer cation mobility within the framework of the radioactive waste. (author)

  16. Nano-scale Radiotherapy-NBTXR3 Hafnium Oxide Nanoparticles as Promising Cancer Therapy

    International Nuclear Information System (INIS)

    Maggiorella, L.; Barouch, G.; Devaux, C.; Pottier, A.; Levy, L.; Deutsch, E.; Bourhis, J.; Borghi, E.

    2011-01-01

    Complete text of publication follows: Background: There is considerable interest in approaches that could improve the therapeutic window of radiotherapy, which represents a crucial modality of treatment in oncology. We present the rationale for designing NBTXR3 nanoparticles activated by radiotherapy and validate the concept. We performed the Monte Carlo calculations for the first time based on the 'local model' simulation that showed a dose enhancement of radiation to tumour cells of approximately nine-fold. NBTXR3 was shown to deposit high energy when the ionizing radiation source is 'on' and to have chemically inert behavior in cellular and subcellular systems demonstrated by very good systemic tolerance, thus decreasing potential health hazards. Material and Methods: We used conventional methods, implemented in different ways, to explore interactions of high Z matter and ionizing radiation with biological systems. In addition, microtomography was performed to explore the nanoparticle volume occupancy inside the tumour and its persistence overtime in mouse tumour models. The antitumour activity of NBTXR3 and tolerance were evaluated in Ewing tumour (A673) and fibrosarcoma (HT1080) using high energy source. Results and Conclusion: We created and developed NBTXR3 nanoparticles with a crystalline hafnium oxide core which provide high electron density structure and inert behavior in biological media. NBTXR3 nanoparticles' characteristics, size, charge and shape, allow for efficient interaction with biological entities, cell membrane binding and cellular uptake. The nanoparticles were shown to form clusters at the subcellular level in tumour models. Of most importance, we show NBTXR3 intra-tumour bioavailability with dispersion of nanoparticles in the three dimensions and persistence within the tumour structure, supporting the use of NBTXR3 as effective antitumour therapeutic agent. Antitumour activity of NBTXR3 showed marked advantage in terms of survival, tumour

  17. Hafnium-doped hydroxyapatite nanoparticles with ionizing radiation for lung cancer treatment.

    Science.gov (United States)

    Chen, Min-Hua; Hanagata, Nobutaka; Ikoma, Toshiyuki; Huang, Jian-Yuan; Li, Keng-Yuan; Lin, Chun-Pin; Lin, Feng-Huei

    2016-06-01

    Recently, photodynamic therapy (PDT) is one of the new clinical options by generating cytotoxic reactive oxygen species (ROS) to kill cancer cells. However, the optical approach of PDT is limited by tissue penetration depth of visible light. In this study, we propose that a ROS-enhanced nanoparticle, hafnium-doped hydroxyapatite (Hf:HAp), which is a material to yield large quantities of ROS inside the cells when the nanoparticles are bombarded with high penetrating power of ionizing radiation. Hf:HAp nanoparticles are generated by wet chemical precipitation with total doping concentration of 15mol% Hf(4+) relative to Ca(2+) in HAp host material. The results show that the HAp particles could be successfully doped with Hf ions, resulted in the formation of nano-sized rod-like shape and with pH-dependent solubility. The impact of ionizing radiation on Hf:HAp nanoparticles is assessed by using in-vitro and in-vivo model using A549 cell line. The 2',7'-dichlorofluorescein diacetate (DCFH-DA) results reveal that after being exposed to gamma rays, Hf:HAp could significantly lead to the formation of ROS in cells. Both cell viability (WST-1) and cytotoxicity (LDH) assay show the consistent results that A549 lung cancer cell lines are damaged with changes in the cells' ROS level. The in-vivo studies further demonstrate that the tumor growth is inhibited owing to the cells apoptosis when Hf:HAp nanoparticles are bombarded with ionizing radiation. This finding offer a new therapeutic method of interacting with ionizing radiation and demonstrate the potential of Hf:HAp nanoparticles in tumor treatment, such as being used in a palliative treatment after lung surgical procedure. Photodynamic therapy (PDT) is one of the new clinical options by generating cytotoxic reactive oxygen species (ROS) to kill cancer cells. Unfortunately, the approach of PDT is usually limited to the treatment of systemic disease and deeper tumor, due to the limited tissue penetration depth of visible

  18. Characterization of hafnium oxide resistive memory layers deposited on copper by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Briggs, B.D.; Bishop, S.M. [SUNY College of Nanoscale Science and Engineering, 255 Fuller Road, Albany, NY 12203 (United States); Leedy, K.D. [Air Force Research Laboratory, 2241 Avionics Circle, Wright Patterson Air Force Base, Dayton, OH 45433 (United States); Cady, N.C., E-mail: ncady@albany.edu [SUNY College of Nanoscale Science and Engineering, 255 Fuller Road, Albany, NY 12203 (United States)

    2014-07-01

    Hafnium oxide-based resistive memory devices have been fabricated on copper bottom electrodes. The HfO{sub x} active layers in these devices were deposited by atomic layer deposition (ALD) at 250 °C with tetrakis(dimethylamido)hafnium(IV) as the metal precursor and an O{sub 2} plasma as the reactant. Depth profiles of the HfO{sub x} by X-ray photoelectron spectroscopy and secondary ion mass spectroscopy revealed a copper concentration on the order of five atomic percent throughout the HfO{sub x} film. In addition to the Cu doped HfO{sub x}, a thin layer (20 nm) of Cu{sub x}O is present at the surface. This surface layer is believed to have formed during the ALD process, and greatly complicates the analysis of the switching mechanism. The resistive memory structures fabricated from the ALD HfO{sub x} exhibited non-polar resistive switching, independent of the top metal electrode (Ni, Pt, Al, Au). Resistive switching current voltage (I–V) curves were analyzed using Schottky emission and ionic hopping models to gain insight into the physical mechanisms underpinning the device behavior. During the forming process it was determined that, at voltages in excess of 2.5 V, an ionic hopping model is in good agreement with the I–V data. The extracted ion hopping distance ∼ 4 Å was within the range of interatomic spacing of HfO{sub 2} during the forming process consistent with ionic motion of Cu{sup 2+} ions. Lastly the on state I–V data was dominated at larger voltages by Schottky emission with an estimated barrier height of ∼ 0.5 eV and a refractive index of 2.59. The consequence of the Schottky emission analysis indicates the on state resistance to be a product of a Pt/Cu{sub 2}O/Cu filament(s)/Cu{sub 2}O/Cu structure. - Highlights: • HfO{sub 2} was grown via atomic layer deposition at 250 and 100 °C on Cu substrates. • A Cu{sub 2}O surface layer and Cu doping were observed in post-deposition of HfO{sub 2}. • Resistive memory devices were fabricated and

  19. Partial processing

    International Nuclear Information System (INIS)

    1978-11-01

    This discussion paper considers the possibility of applying to the recycle of plutonium in thermal reactors a particular method of partial processing based on the PUREX process but named CIVEX to emphasise the differences. The CIVEX process is based primarily on the retention of short-lived fission products. The paper suggests: (1) the recycle of fission products with uranium and plutonium in thermal reactor fuel would be technically feasible; (2) it would, however, take ten years or more to develop the CIVEX process to the point where it could be launched on a commercial scale; (3) since the majority of spent fuel to be reprocessed this century will have been in storage for ten years or more, the recycling of short-lived fission products with the U-Pu would not provide an effective means of making refabrication fuel ''inaccessible'' because the radioactivity associated with the fission products would have decayed. There would therefore be no advantage in partial processing

  20. Partial gigantism

    Directory of Open Access Journals (Sweden)

    М.М. Karimova

    2017-05-01

    Full Text Available A girl with partial gigantism (the increased I and II fingers of the left foot is being examined. This condition is a rare and unresolved problem, as the definite reason of its development is not determined. Wait-and-see strategy is recommended, as well as correcting operations after closing of growth zones, and forming of data pool for generalization and development of schemes of drug and radial therapeutic methods.

  1. Observed gas hydrate morphologies in marine sediment

    Energy Technology Data Exchange (ETDEWEB)

    Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M. [Geotek Ltd., Daventry, Northamptonshire (United Kingdom)

    2008-07-01

    The morphology of gas hydrate in marine sediments determines the basic physical properties of the sediment-hydrate matrix and provides information regarding the formation of gas hydrate deposits, and the nature of the disruption that will occur on dissociation. Small-scale morphology is useful in estimating the concentrations of gas hydrate from geophysical data. It is also important for predicting their response to climate change or commercial production. Many remote techniques for gas hydrate detection and quantification depend on hydrate morphology. In this study, morphology of gas hydrate was examined in HYACINTH pressure cores from recent seagoing expeditions. Visual and infrared observations from non-pressurized cores were also used. The expeditions and pressure core analysis were described in detail. This paper described the difference between two types of gas hydrate morphologies, notably pore-filling and grain-displacing. Last, the paper addressed the impact of hydrate morphology. It was concluded that a detailed morphology of gas hydrate is an essential component for a full understanding of the past, present, and future of any gas hydrate environment. 14 refs., 4 figs.

  2. Influence of fluorosurfactants on hydrate formation rates

    Energy Technology Data Exchange (ETDEWEB)

    Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

    2008-07-01

    Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

  3. Influence of smectite hydration and swelling on atrazine sorption behavior.

    Science.gov (United States)

    Chappell, Mark A; Laird, David A; Thompson, Michael L; Li, Hui; Teppen, Brian J; Aggarwal, Vaneet; Johnston, Cliff T; Boyd, Stephen A

    2005-05-01

    Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer

  4. Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties

    International Nuclear Information System (INIS)

    Salles, F.

    2006-10-01

    smectites: it is responsible for the structure of porosity in a dry state and of the evolution of the pore sizes as a function of the RH and it modifies the hydration sequence by its mobility inside the interlayer space. The distinction between various types of water in the smectite structure is also achieved by thermo-poro-metry at different RH: water bound to the cations and surfaces, water structured by porosity and free water. This distinction is important to understand the behaviour of smectite and in particular the diffusion properties in clayey materials. The importance of the cation nature is also highlighted by the energetic model. Electrostatic calculations using the PACHA formalism (Electronegativities Equalization method) show that, for the small cations, the hydration energy of the layers is predominant. To obtain these results, we determine the surface enthalpies for the dry state, which show a coherent evolution as a function of the cation partial charge with the increase of pore sizes and thus with particle sizes. Then, using a theoretical model, we calculated swelling energies, surface hydration energies and cation hydration energies. The behaviour of mixed purified clay displays a behaviour closer to that of a calcic clay for the experiments carried out, in contradiction with the fact that the Na cation is the most abundant. This observation implies results on the clay properties, different from that expected for hydration properties, swelling and interlayer cation mobility within the framework of the radioactive waste. (author)

  5. Application of the electrical characterization to the study of the hydrated phases of the cement with coal bottom ash; Aplicacion de la caracterizacion electrica al estudio de las fases hidratadas de cemento con adicion de escorias de centrales termicas

    Energy Technology Data Exchange (ETDEWEB)

    Menendez, E.; Frutos, J. de; Alvaro, A. M.

    2014-02-01

    The present paper investigates the influence of using Bottom and Fly Ash as partial replacement of cement in the hydration process. Through measurements of electrical impedance spectroscopy (EIS) and X -ray diffraction (XRD), we analyze from the early stages to the hydration process to the end. Values of EIS, XRD and its relation, are used to determine transformation of hydrated phases, and for each of the substitutions, is indicated as modified the hydrated phase as a function of time and compared it with the reference material. It also proves the relevance of using EIS measures in real time, and as non destructive testing to characterize the hydration process of these materials. (Author)

  6. Characterization of methane-hydrate formation inferred from insitu Vp-density relationship for hydrate-bearing sediment cores obtained off the eastern coast of India

    Science.gov (United States)

    Kinoshita, M.; Hamada, Y.; Hirose, T.; Yamada, Y.

    2017-12-01

    correlation may be explained by a (partial) replacement of pore water with hydrate because the density of hydrate is lower than the water.

  7. Recoil Induced Room Temperature Stable Frenkel Pairs in a-Hafnium Upon Thermal Neutron Capture

    Science.gov (United States)

    Butz, Tilman; Das, Satyendra K.; Dey, Chandi C.; Ghoshal, Shamik

    2013-11-01

    Ultrapure hafnium metal (110 ppm zirconium) was neutron activated with a thermal neutron flux of 6:6 · 1012 cm-2s-1 in order to obtain 181Hf for subsequent time differential perturbed angular correlation (TDPAC) experiments using the nuclear probe 181Hf(β-) 181Ta. Apart from the expected nuclear quadrupole interaction (NQI) signal for a hexagonal close-packed (hcp) metal, three further discrete NQIs were observed with a few percent fraction each. The TDPAC spectra were recorded for up to 11 half lives with extreme statistical accuracy. The fitted parameters vary slightly within the temperature range between 248 K and 373 K. The signals corresponding to the three additional sites completely disappear after `annealing' at 453 K for one minute. Based on the symmetry of the additional NQIs and their temperature dependencies, they are tentatively attributed to Frenkel pairs produced by recoil due to the emission of a prompt 5:694 MeV -ray following thermal neutron capture and reported by the nuclear probe in three different positions. These Frenkel pairs are stable up to at least 373 K.

  8. The energy landscape of glassy dynamics on the amorphous hafnium diboride surface

    Science.gov (United States)

    Nguyen, Duc; Mallek, Justin; Cloud, Andrew N.; Abelson, John R.; Girolami, Gregory S.; Lyding, Joseph; Gruebele, Martin

    2014-11-01

    Direct visualization of the dynamics of structural glasses and amorphous solids on the sub-nanometer scale provides rich information unavailable from bulk or conventional single molecule techniques. We study the surface of hafnium diboride, a conductive ultrahigh temperature ceramic material that can be grown in amorphous films. Our scanning tunneling movies have a second-to-hour dynamic range and single-point current measurements extend that to the millisecond-to-minute time scale. On the a-HfB2 glass surface, two-state hopping of 1-2 nm diameter cooperatively rearranging regions or "clusters" occurs from sub-milliseconds to hours. We characterize individual clusters in detail through high-resolution (single cluster vertical displacements, we can reconstruct the local free energy landscape of individual clusters, complete with activation barrier height, a reaction coordinate in nanometers, and the shape of the free energy landscape basins between which hopping occurs. The experimental images are consistent with the compact shape of α-relaxors predicted by random first order transition theory, whereas the rapid hopping rate, even taking less confined motion at the surface into account, is consistent with β-relaxations. We make a proposal of how "mixed" features can show up in surface dynamics of glasses.

  9. Characteristics of laser produced plasmas of hafnium and tantalum in the 1-7 nm region

    Science.gov (United States)

    Li, Bowen; Otsuka, Takamitsu; Sokell, Emma; Dunne, Padraig; O'Sullivan, Gerry; Hara, Hiroyuki; Arai, Goki; Tamura, Toshiki; Ono, Yuichi; Dinh, Thanh-Hung; Higashiguchi, Takeshi

    2017-11-01

    Soft X-ray (SXR) spectra from hafnium and tantalum laser produced plasmas were recorded in the 1-7 nm region using two Nd:YAG lasers with pulse lengths of 170 ps and 10 ns, respectively, operating at a range of power densities. The maximum focused peak power density was 2. 3 × 1014 W cm-2 for 170 ps pulses and 1. 8 × 1012 W cm-2 for 10 ns pulses, respectively. Two intense quasicontinuous intensity bands resulting from n = 4 - n = 4 and n = 4 - n = 5 unresolved transition arrays (UTAs) dominate both sets of experimental spectra. Comparison with calculations performed with the Cowan suite of atomic structure codes as well as consideration of previous experimental and theoretical results aided identification of the most prominent features in the spectra. For the 10 ns spectrum, the highest ion stage that could be identified from the n = 4 - n = 5 arrays were lower than silver-like Hf25+ and Ta26+ (which has a 4 d 104 f ground configuration) indicating that the plasma temperature attained was too low to produce ions with an outermost 4 d subshell, while for the 170 ps plasmas the presence of significantly higher stages was deduced and lines due to 4 d-5 p transitions were clearly evident. Furthermore, we show an enhancement of emission from tantalum using dual laser irradiation, and the effect of pre-pulse durations and delay times between two pulses are demonstrated.

  10. Ferroelectric transistors with monolayer molybdenum disulfide and ultra-thin aluminum-doped hafnium oxide

    Science.gov (United States)

    Yap, Wui Chung; Jiang, Hao; Liu, Jialun; Xia, Qiangfei; Zhu, Wenjuan

    2017-07-01

    In this letter, we demonstrate ferroelectric memory devices with monolayer molybdenum disulfide (MoS2) as the channel material and aluminum (Al)-doped hafnium oxide (HfO2) as the ferroelectric gate dielectric. Metal-ferroelectric-metal capacitors with 16 nm thick Al-doped HfO2 are fabricated, and a remnant polarization of 3 μC/cm2 under a program/erase voltage of 5 V is observed. The capability of potential 10 years data retention was estimated using extrapolation of the experimental data. Ferroelectric transistors based on embedded ferroelectric HfO2 and MoS2 grown by chemical vapor deposition are fabricated. Clockwise hysteresis is observed at low program/erase voltages due to slow bulk traps located near the 2D/dielectric interface, while counterclockwise hysteresis is observed at high program/erase voltages due to ferroelectric polarization. In addition, the endurances of the devices are tested, and the effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, are observed. Reliable writing/reading in MoS2/Al-doped HfO2 ferroelectric transistors over 2 × 104 cycles is achieved. This research can potentially lead to advances of two-dimensional (2D) materials in low-power logic and memory applications.

  11. Silicon-doped hafnium oxide anti-ferroelectric thin films for energy storage

    Science.gov (United States)

    Ali, Faizan; Liu, Xiaohua; Zhou, Dayu; Yang, Xirui; Xu, Jin; Schenk, Tony; Müller, Johannes; Schroeder, Uwe; Cao, Fei; Dong, Xianlin

    2017-10-01

    Motivated by the development of ultracompact electronic devices as miniaturized energy autonomous systems, great research efforts have been expended in recent years to develop various types of nano-structural energy storage components. The electrostatic capacitors characterized by high power density are competitive; however, their implementation in practical devices is limited by the low intrinsic energy storage density (ESD) of linear dielectrics like Al2O3. In this work, a detailed experimental investigation of energy storage properties is presented for 10 nm thick silicon-doped hafnium oxide anti-ferroelectric thin films. Owing to high field induced polarization and slim double hysteresis, an extremely large ESD value of 61.2 J/cm3 is achieved at 4.5 MV/cm with a high efficiency of ˜65%. In addition, the ESD and the efficiency exhibit robust thermal stability in 210-400 K temperature range and an excellent endurance up to 109 times of charge/discharge cycling at a very high electric field of 4.0 MV/cm. The superior energy storage performance together with mature technology of integration into 3-D arrays suggests great promise for this recently discovered anti-ferroelectric material to replace the currently adopted Al2O3 in fabrication of nano-structural supercapacitors.

  12. Hafnium Films and Magnetic Shielding for TIME, A mm-Wavelength Spectrometer Array

    Science.gov (United States)

    Hunacek, J.; Bock, J.; Bradford, C. M.; Butler, V.; Chang, T.-C.; Cheng, Y.-T.; Cooray, A.; Crites, A.; Frez, C.; Hailey-Dunsheath, S.; Hoscheit, B.; Kim, D. W.; Li, C.-T.; Marrone, D.; Moncelsi, L.; Shirokoff, E.; Steinbach, B.; Sun, G.; Trumper, I.; Turner, A.; Uzgil, B.; Weber, A.; Zemcov, M.

    2018-04-01

    TIME is a mm-wavelength grating spectrometer array that will map fluctuations of the 157.7-μm emission line of singly ionized carbon ([CII]) during the epoch of reionization (redshift z ˜ 5-9). Sixty transition-edge sensor (TES) bolometers populate the output arc of each of the 32 spectrometers, for a total of 1920 detectors. Each bolometer consists of gold absorber on a ˜ 3 × 3 mm silicon nitride micro-mesh suspended near the corners by 1 × 1 × 500 μm silicon nitride legs targeting a photon-noise-dominated NEP ˜ 1 × 10^{-17} W/√{Hz} . Hafnium films are explored as a lower-T_c alternative to Ti (500 mK) for TIME TESs, allowing thicker support legs for improved yield. Hf T_c is shown to vary between 250 and 450 mK when varying the resident Ar pressure during deposition. Magnetic shielding designs and simulations are presented for the TIME first-stage SQUIDs. Total axial field suppression is predicted to be 5 × 10^7.

  13. Tuning the magnetic properties of pure hafnium by high pressure torsion

    International Nuclear Information System (INIS)

    Cepeda-Jiménez, C.M.; Beltrán, J.I.; Hernando, A.; García, M.A.; Ynduráin, F.; Zhilyaev, A.; Pérez-Prado, M.T.

    2017-01-01

    This work demonstrates that room temperature (RT) ferromagnetism might be triggered in pure hafnium (Hf), a classic paramagnet, by severe plastic deformation (SPD) via high pressure torsion (HPT). The origin of this phenomenon is elucidated by a combined approach including density functional theory (DFT) calculations and transmission electron microscopy (TEM). In particular, it is shown that the elastic lattice distorsions induced in pure Hf as a consequence of grain refinement down to the nanocrystalline regime by HPT lead to the development of a new monoclinic crystalline structure that exhibits a spontaneous magnetization at RT. DFT calculations are utilized to prove that local stretching of the original pure Hf hexagonal close packed (hcp) lattice along specific pyramidal directions, due to the presence of internal stresses in the deformed nanostructure, may give rise to the emergence of the monoclinic phase, which is endowed with a net magnetic moment. An excellent agreement is found between DFT calculations and experimental TEM observations, which provide a first evidence of the presence of the pure Hf monoclinic crystal lattice. This work shows that SPD may constitute a viable, yet widely unexplored, strategy to tune the magnetic properties and, in particular, to induce RT ferromagnetism in bulk non-magnetic metals.

  14. Fire extinction utilizing carbon dioxide hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Hatakeyama, T.; Aida, E.; Yokomori, T.; Ohmura, R.; Ueda, T. [Keio Univ., Hiyoshi, Kohoku-ku, Yokohama (Japan)

    2008-07-01

    Clathrate hydrates formed with nonflammable gases may be suitable for use as fire extinguishing agents because dissociation of the hydrates results in the temperature decrease in the combustion field and the nonflammable gases released from the dissociated hydrates prevent the supply of the oxygen to the combustion field. This paper discussed experiments in which ordinary ice and dry ice were used to evaluate the performance of CO{sub 2} hydrate as a fire extinguishing agent. The paper described the apparatus and procedure for the preparation of CO{sub 2} hydrate crystals. A schematic of the reactor to form CO{sub 2} hydrate and a photograph of CO{sub 2} hydrate crystal formed in the study were also presented. Other illustrations, photographs, and tables that were presented included a schematic diagram of the experimental apparatus used for the flame extinction experiments; a photograph of CO{sub 2} hydrate powder; sequential video graphs of the flame extinction by the supply of CO{sub 2} hydrate crystals to the methanol pool flame and the relevant illustration; and heat of CO{sub 2} hydrate dissociation, water vaporization and sublimation of dry ice. It was concluded that the critical mass of the CO{sub 2} hydrate required to extinguish a flame was much less than that of ordinary ice, indicating the superiority of CO{sub 2} hydrate to the ice. In addition, the experiments also revealed that the size of the CO{sub 2} hydrate particles had a significant effect on the performance of flame extinction. 5 refs., 2 tabs., 7 figs.

  15. In-Pile Experiment of a New Hafnium Aluminide Composite Material to Enable Fast Neutron Testing in the Advanced Test Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Donna Post Guillen; Douglas L. Porter; James R. Parry; Heng Ban

    2010-06-01

    A new hafnium aluminide composite material is being developed as a key component in a Boosted Fast Flux Loop (BFFL) system designed to provide fast neutron flux test capability in the Advanced Test Reactor. An absorber block comprised of hafnium aluminide (Al3Hf) particles (~23% by volume) dispersed in an aluminum matrix can absorb thermal neutrons and transfer heat from the experiment to pressurized water cooling channels. However, the thermophysical properties, such as thermal conductivity, of this material and the effect of irradiation are not known. This paper describes the design of an in-pile experiment to obtain such data to enable design and optimization of the BFFL neutron filter.

  16. An Examination of the Prediction of Hydrate Formation Conditions in the Presence of Thermodynamic Inhibitors

    Directory of Open Access Journals (Sweden)

    Carollina de M. Molinari O. Antunes

    Full Text Available Abstract Gas hydrates are crystalline compounds, solid structures where water traps small guest molecules, typically light gases, in cages formed by hydrogen bonds. They are notorious for causing problems in oil and gas production, transportation and processing. Gas hydrates may form at pressures and temperatures commonly found in natural gas and oil production pipelines, thus causing partial or complete pipe blockages. In order to inhibit hydrate formation, chemicals such as alcohols (e.g., ethanol, methanol, mono-ethylene glycol and salts (sodium, magnesium or potassium chloride are injected into the produced stream. The purpose of this work is to briefly review the literature on hydrate formation in mixtures containing light gases (hydrocarbons and carbon dioxide and water in the presence of thermodynamic inhibitors. Four calculation methods to predict hydrate formation in those systems were examined and compared. Three commercial packages (Multiflash®, PVTSim® and CSMGem and a hydrate prediction routine in Fortran90 using the van der Waals and Platteeuw theory and the Peng-Robinson equation of state were tested. Predictions given by the four methods were compared to independent experimental data from the literature. In general, the four methods were found to be reasonably accurate. CSMGem and Multiflash® showed the best results.

  17. Computational phase diagrams of noble gas hydrates under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk [Centre for Science at Extreme Conditions and SUPA, School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3FD (United Kingdom)

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  18. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    1998-01-01

    This report deals with gas phase hydration of pure cement clinker minerals at reduced relative humidities. This is an important subject in relation to modern high performance concrete which may self-desiccate during hydration. In addition the subject has relevance to storage stability where...... prehydration may occur. In the report both theoretical considerations and experimental data are presented. It is suggested that the initiation of hydration during water vapour exposure is nucleation controlled....

  19. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

    Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn D.

    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.

  20. Rapid formation of nanocrystalline HfO2 powders from amorphous hafnium hydroxide under ultrasonically assisted hydrothermal treatment

    International Nuclear Information System (INIS)

    Meskin, Pavel E.; Sharikov, Felix Yu.; Ivanov, Vladimir K.; Churagulov, Bulat R.; Tretyakov, Yury D.

    2007-01-01

    Peculiarities of hafnium hydroxide hydrothermal decomposition were studied by in situ heat flux calorimetry for the first time. It was shown that this process occurs in one exothermal stage (ΔH = -17.95 kJ mol -1 ) at 180-250 deg. C resulting in complete crystallization of amorphous phase with formation of pure monoclinic HfO 2 . It was found that the rate of m-HfO 2 formation can be significantly increased by combining hydrothermal treatment with simultaneous ultrasonic activation

  1. Physical Properties of Gas Hydrates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Gabitto, Jorge [Prairie View A& M University; Tsouris, Costas [ORNL

    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.

  2. Accelerated hydration of high silica cements

    International Nuclear Information System (INIS)

    Walker, Colin; Yui, Mikazu

    2012-01-01

    Current Japanese designs for high level radioactive waste (HLW) repositories anticipate the use of both bentonite (buffer and backfill material) and cement based materials. Using hydrated Ordinary Portland Cement (OPC) as a grouting material is undesirable because the associated high pH buffer will have an undisputed detrimental effect on the performance of the bentonite buffer and backfill and of the host rock by changing its porosity. Instead, hydrated low pH cement (LopHC) grouting materials are being developed to provide a pH inferior or equal to 11 to reduce these detrimental effects. LopHC grouting materials use mixtures of superfine OPC (SOPC) clinker and silica fume (SF), and are referred as high silica cements (HSC). The focus of the present study was to identify the development of the unhydrated and hydrated mineral assemblage and the solution chemistry during the hydration of HSC. Since hydration experiments of cementitious materials are notably slow, a ball mill was used to accelerate hydration. This was done for two reasons. Firstly, to develop a method to rapidly hydrate cement based materials without the need for higher temperatures (which can alter the mineral assemblage), and secondly, to ensure that the end point of hydration was reached in a reasonable time frame and so to realize the final mineralogy and solution chemistry of hydrated HSC

  3. Microstructure of natural hydrate host sediments

    International Nuclear Information System (INIS)

    Jones, K.W.; Kerkar, P.B.; Mahajan, D.; Lindquist, W.B.; Feng, H.

    2007-01-01

    There is worldwide interest in the study of natural gas hydrate because of its potential impact on world energy resources, control on seafloor stability, significance as a drilling hazard and probable impact on climate as a reservoir of a major greenhouse gas. Gas hydrates can (a) be free floating in the sediment matrix (b) contact, but do not cement, existing sediment grains, or (c) actually cement and stiffen the bulk sediment. Seismic surveys, often used to prospect for hydrates over a large area, can provide knowledge of the location of large hydrate concentrations because the hydrates within the sediment pores modify seismic properties. The ability to image a sample at the grain scale and to determine the porosity, permeability and seismic profile is of great interest since these parameters can help in determining the location of hydrates with certainty. We report here on an investigation of the structure of methane hydrate sediments at the grain-size scale using the synchrotron radiation-based computed microtomography (CMT) technique. Work has started on the measurements of the changes occurring as tetrahydrofuran hydrate, a surrogate for methane hydrate, is formed in the sediment

  4. Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

    International Nuclear Information System (INIS)

    Matsuoka, Daisuke; Nakasako, Masayoshi

    2013-01-01

    Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

  5. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    Science.gov (United States)

    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…

  6. The energy landscape of glassy dynamics on the amorphous hafnium diboride surface

    International Nuclear Information System (INIS)

    Nguyen, Duc; Girolami, Gregory S.; Mallek, Justin; Cloud, Andrew N.; Abelson, John R.; Lyding, Joseph; Gruebele, Martin

    2014-01-01

    Direct visualization of the dynamics of structural glasses and amorphous solids on the sub-nanometer scale provides rich information unavailable from bulk or conventional single molecule techniques. We study the surface of hafnium diboride, a conductive ultrahigh temperature ceramic material that can be grown in amorphous films. Our scanning tunneling movies have a second-to-hour dynamic range and single-point current measurements extend that to the millisecond-to-minute time scale. On the a-HfB 2 glass surface, two-state hopping of 1–2 nm diameter cooperatively rearranging regions or “clusters” occurs from sub-milliseconds to hours. We characterize individual clusters in detail through high-resolution (<0.5 nm) imaging, scanning tunneling spectroscopy and voltage modulation, ruling out individual atoms, diffusing adsorbates, or pinned charges as the origin of the observed two-state hopping. Smaller clusters are more likely to hop, larger ones are more likely to be immobile. HfB 2 has a very high bulk glass transition temperature T g , and we observe no three-state hopping or sequential two-state hopping previously seen on lower T g glass surfaces. The electronic density of states of clusters does not change when they hop up or down, allowing us to calibrate an accurate relative z-axis scale. By directly measuring and histogramming single cluster vertical displacements, we can reconstruct the local free energy landscape of individual clusters, complete with activation barrier height, a reaction coordinate in nanometers, and the shape of the free energy landscape basins between which hopping occurs. The experimental images are consistent with the compact shape of α-relaxors predicted by random first order transition theory, whereas the rapid hopping rate, even taking less confined motion at the surface into account, is consistent with β-relaxations. We make a proposal of how “mixed” features can show up in surface dynamics of glasses

  7. Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

    Science.gov (United States)

    Quevedo Lopez, Manuel Angel

    Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

  8. Protective coatings of hafnium dioxide by atomic layer deposition for microelectromechanical systems applications

    Energy Technology Data Exchange (ETDEWEB)

    Berdova, Maria, E-mail: maria.berdova@aalto.fi [Aalto University, Department of Materials Science and Engineering, 02150, Espoo (Finland); Wiemer, Claudia; Lamperti, Alessio; Tallarida, Grazia; Cianci, Elena [Laboratorio MDM, IMM CNR, Via C. Olivetti 2, 20864, Agrate Brianza, MB (Italy); Lamagna, Luca; Losa, Stefano; Rossini, Silvia; Somaschini, Roberto; Gioveni, Salvatore [STMicroelectronics, Via C. Olivetti 2, 20864, Agrate Brianza, MB (Italy); Fanciulli, Marco [Laboratorio MDM, IMM CNR, Via C. Olivetti 2, 20864, Agrate Brianza, MB (Italy); Università degli studi di Milano Bicocca, Dipartimento di Scienza dei Materiali, 20126, Milano (Italy); Franssila, Sami, E-mail: sami.franssila@aalto.fi [Aalto University, Department of Materials Science and Engineering, 02150, Espoo (Finland)

    2016-04-15

    Graphical abstract: - Highlights: • Atomic layer deposition of HfO{sub 2} from (CpMe){sub 2}Hf(OMe)Me or Hf(NMeEt){sub 4} and ozone for potential applications in microelectromechanical systems. • ALD HfO{sub 2} protects aluminum substrates from degradation in moist environment and at the same time retains good reflectance properties of the underlying material. • The resistance of hafnium dioxide to moist environment is independent of chosen precursors. - Abstract: This work presents the investigation of HfO{sub 2} deposited by atomic layer deposition (ALD) from either HfD-CO4 or TEMAHf and ozone for microelectromechanical systems (MEMS) applications, in particular, for environmental protection of aluminum micromirrors. This work shows that HfO{sub 2} films successfully protect aluminum in moist environment and at the same time retain good reflectance properties of underlying material. In our experimental work, the chemical composition, crystal structure, electronic density and roughness of HfO{sub 2} films remained the same after one week of humidity treatment (relative humidity of 85%, 85 °C). The reflectance properties underwent only minor changes. The observed shift in reflectance was only from 80–90% to 76–85% in 400–800 nm spectral range when coated with ALD HfO{sub 2} films grown with Hf(NMeEt){sub 4} and no shift (remained in the range of 68–83%) for films grown from (CpMe){sub 2}Hf(OMe)Me.

  9. Hydration in soccer: a review

    Directory of Open Access Journals (Sweden)

    Monteiro Cristiano Ralo

    2003-01-01

    Full Text Available Hydration should be considered before, during and after the exercise. This review intends to approach the main points of hydration process in soccer. The replacement of fluids during exercise is proportional to some factors, such as: exercise intensity; climatic conditions; the athlete's acclimatization; the athlete's physical conditioning; physiologic individual characteristics and the player's biomechanics. Performance is improved when players ingest not only water but also carbohydrate. The rates that carbohydrate and water are absorbed by the organism are limited by the rates of gastric emptying and intestinal absorption. The composition of drinks offered to the players should be influenced by the relative importance of the need of supplying carbohydrates or water; it should be remembered that the depletion of carbohydrate can result in fatigue and decrease of performance, but it is not usually a life-threatening condition. The addition of carbohydrate in these drinks increases the concentrations of blood glucose, increases the use of external fuel through the increase of the glucose oxidation in the muscles and it spares muscle glycogen. So, the ingestion of carbohydrate before and during the exercise can delay the emergence of fatigue and increase the players' performance. Several tactics can be used to avoid dehydration, like hyperhydration before exercise and player's acclimatization. The ideal situation to restore the player's fluid losses is between the sessions of exercises. Since soccer is a sport with quite peculiar characteristics related to hydration, the players should be concerned and educated about the importance of fluid ingestion before, during and after the exercise.

  10. Weakly hydrated surfaces and the binding interactions of small biological solutes.

    Science.gov (United States)

    Brady, John W; Tavagnacco, Letizia; Ehrlich, Laurent; Chen, Mo; Schnupf, Udo; Himmel, Michael E; Saboungi, Marie-Louise; Cesàro, Attilio

    2012-04-01

    Extended planar hydrophobic surfaces, such as are found in the side chains of the amino acids histidine, phenylalanine, tyrosine, and tryptophan, exhibit an affinity for the weakly hydrated faces of glucopyranose. In addition, molecular species such as these, including indole, caffeine, and imidazole, exhibit a weak tendency to pair together by hydrophobic stacking in aqueous solution. These interactions can be partially understood in terms of recent models for the hydration of extended hydrophobic faces and should provide insight into the architecture of sugar-binding sites in proteins.

  11. Gas Hydrates | Alaska Division of Geological & Geophysical Surveys

    Science.gov (United States)

    Preliminary Report - Cascadia Margin Gas Hydrates, Volume 204 Initial Report Mallik 2002 GSC Bulletin 585 : Scientific results from the Mallik 2002 gas hydrate production well program Offshore gas hydrate sample

  12. Simulation and Characterization of Methane Hydrate Formation

    Science.gov (United States)

    Dhakal, S.; Gupta, I.

    2017-12-01

    The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate

  13. Formation rate of natural gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Mork, Marit

    2002-07-01

    The rate of methane hydrate and natural gas hydrate formation was measured in a 9.5 litre stirred tank reactor of standard design. The experiments were performed to better understand the performance and scale-up of a reactor for continuous production of natural gas hydrates. The hydrate formation rate was measured at steady-state conditions at pressures between 70 and 90 bar and temperatures between 7 and 15 deg C. Between 44 and 56 % of the gas continuously supplied to the reactor was converted to hydrate. The experimental results show that the rate of hydrate formation is strongly influenced by gas injection rate and pressure. The effect of stirring rate is less significant and subcooling has no observable effect on the formation rate. Hydrate crystal concentration and gas composition do not influence the hydrate formation rate. Observations of produced hydrate crystals indicate that the crystals are elongated, about 5 micron in diameter and 10 micron long. Analysis of the results shows that the rate of hydrate formation is dominated by gas-liquid mass transfer. A mass transfer model, the bubble-to-crystal model, was developed for the hydrate formation rate in a continuous stirred tank reactor, given in terms of concentration driving force and an overall mass transfer coefficient. The driving force is the difference between the gas concentration at the gas-liquid interface and at the hydrate crystal surface. These concentrations correspond to the solubility of gas in water at experimental temperature and pressure and the solubility of gas at hydrate equilibrium temperature and experimental pressure, respectively. The overall mass transfer coefficient is expressed in terms of superficial gas velocity and impeller power consumption, parameters commonly used in study of stirred tank reactors. Experiments and modeling show that the stirred tank reactor has a considerable potential for increased production capacity. However, at higher hydrate production rates the

  14. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    KAUST Repository

    Ramos-Gonzá lez, R.; Garcí a-Cerda, L. A.; Alshareef, Husam N.; Gnade, Bruce E.; Quevedo-Ló pez, Manuel Angel Quevedo

    2010-01-01

    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  15. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    KAUST Repository

    Ramos-González, R.

    2010-03-01

    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  16. Free energy of hydration of niobium oxide

    International Nuclear Information System (INIS)

    Plodinec, M.J.

    1996-01-01

    Some of the glasses being formulated by SRTC researchers contain niobium oxide. In this report, the free energy of hydration of the oxide is calculated from the free energies of formation of the oxide, the hydroxide, and water. This value can be used in calculations of the free energy of hydration of glasses containing niobium

  17. Investigations into surfactant/gas hydrate relationship

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)

    2007-03-15

    Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

  18. 75 FR 9886 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2010-03-04

    ... DEPARTMENT OF ENERGY Methane 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... the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice on potential...

  19. Raman Spectroscopic Studies of Methane Gas Hydrates

    DEFF Research Database (Denmark)

    Hansen, Susanne Brunsgaard; Berg, Rolf W.

    2009-01-01

    A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.......A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory....

  20. Multicomponent modelling of Portland cement hydration reactions

    NARCIS (Netherlands)

    Ukrainczyk, N.; Koenders, E.A.B.; Van Breugel, K.

    2012-01-01

    The prospect of cement and concrete technologies depends on more in depth understanding of cement hydration reactions. Hydration reaction models simulate the development of the microstructures that can finally be used to estimate the cement based material properties that influence performance and

  1. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    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

  2. Experimental Setup to Characterize Bentonite Hydration Processes

    International Nuclear Information System (INIS)

    Bru, A.; Casero, D.; Pastor, J. M.

    2001-01-01

    We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

  3. Volume of hydration in terminal cancer patients.

    Science.gov (United States)

    Bruera, E; Belzile, M; Watanabe, S; Fainsinger, R L

    1996-03-01

    In this retrospective study we reviewed the volume and modality of hydration of consecutive series of terminal cancer patients in two different settings. In a palliative care unit 203/290 admitted patients received subcutaneous hydration for 12 +/- 8 days at a daily volume of 1015 +/- 135 ml/day. At the cancer center, 30 consecutive similar patients received intravenous hydration for 11.5 +/- 5 days (P > 0.2) but at a daily volume of 2080 +/- 720 ml/day (P palliative care unit patients required discontinuation of hydration because of complications. Hypodermoclysis was administered mainly as a continuous infusion, an overnight infusion, or in one to three 1-h boluses in 62 (31%), 98 (48%) and 43 (21%) patients, respectively. Our findings suggest that, in some settings, patients may be receiving excessive volumes of hydration by less comfortable routes such as the intravenous route. Increased education and research in this area are badly needed.

  4. Hydration shells exchange charge with their protein

    DEFF Research Database (Denmark)

    Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert

    2010-01-01

    . In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity......Investigation of the interaction between a protein and its hydration shells is an experimental and theoretical challenge. Here, we used ultrasonic pressure waves in aqueous solutions of a protein to explore the conformational states of the protein and its interaction with its hydration shells...... the presence of an ultrasonic pressure, a protein and its hydration shells are in thermodynamic and charge equilibrium, i.e. a protein and its hydration shells exchange charges. The ultrasonic wave disrupts these equilibria which are regained within 30–45 min after the ultrasonic pressure is shut off....

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    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

  6. HYDRATION PROCESS AND MECHANICAL PROPERTIES OF CEMENT PASTE WITH RECYCLED CONCRETE POWDER AND SILICA SAND POWDER

    Directory of Open Access Journals (Sweden)

    Jaroslav Topič

    2017-11-01

    Full Text Available Recycled concrete powder (RCP mostly consisting of cement paste could be reused as partial cement replacement. The aim of this paper is to compare hydration and mechanical properties of RCP and two types of silica sand powder (SSP. Comparison of those materials combined with cement can highlight the binder properties of recycled concrete powder. Using of two types of SSP also show an influence of their fines on hydration process and mechanical properties. Particle size analysis and calorimetric measurement were carried out and mechanical properties such as bulk density, dynamic Young’s modulus and compression strength were examine. Calorimetric measurement proves the presence of exposed non-hydrated particles in RCP that can react again. However lower density of old cement paste in RCP overweight the mentioned potential of RCP and mechanical properties are decreasing compared with reference cement paste and cement paste SSP.

  7. Corrosion resistant surface for vanadium nitride and hafnium nitride layers as function of grain size

    Science.gov (United States)

    Escobar, C. A.; Caicedo, J. C.; Aperador, W.

    2014-01-01

    In this research it was studied vanadium nitride (VN) and hafnium nitride (HfN) film, which were deposited onto silicon (Si (100)) and AISI 4140 steel substrates via r.f. magnetron sputtering technique in Ar/N2 atmosphere with purity at 99.99% for both V and Hf metallic targets. Both films were approximately 1.2±0.1 μm thick. The crystallography structures that were evaluated via X-ray diffraction analysis (XRD) showed preferential orientations in the Bragg planes VN (200) and HfN (111). The chemical compositions for both films were characterized by EDX. Atomic Force Microscopy (AFM) was used to study the morphology; the results reveal grain sizes of 78±2 nm for VN and 58±2 nm for HfN and roughness values of 4.2±0.1 nm for VN and 1.5±0.1 nm for HfN films. The electrochemical performance in VN and HfN films deposited onto steel 4140 were studied by Tafel polarization curves and impedance spectroscopy methods (EIS) under contact with sodium chloride at 3.5 wt% solution, therefore, it was found that the corrosion rate decreased about 95% in VN and 99% for HfN films in relation to uncoated 4140 steel, thus demonstrating, the protecting effect of VN and HfN films under a corrosive environment as function of morphological characteristics (grain size). VN(grain size)=78±2.0 nm, VN(roughness)=4.2±0.1 nm, VN(corrosion rate)=40.87 μmy. HfN(grain size)=58±2.0 nm, HfN(roughness)=1.5±0.1 nm, HfN(corrosion rate)=0.205 μmy. It was possible to analyze that films with larger grain size, can be observed smaller grain boundary thus generating a higher corrosion rate, therefore, in this work it was found that the HfN layer has better corrosion resistance (low corrosion rate) in relation to VN film which presents a larger grain size, indicating that the low grain boundary in (VN films) does not restrict movement of the Cl- ion and in this way the corrosion rate increases dramatically.

  8. Synthesis and characterization of hafnium carbide microcrystal chains with a carbon-rich shell via CVD

    International Nuclear Information System (INIS)

    Tian, Song; Li, Hejun; Zhang, Yulei; Liu, Sen; Fu, Yangxi; Li, Yixian; Qiang, Xinfa

    2013-01-01

    Graphical abstract: Novel HfC microcrystal chains have been synthesized via a catalyst-assisted chemical vapor deposition process. SEM results show the chains have a periodically changing diameter and a nanoscale sharpening tip. Analysis of TEM/SAED/EELS/EDX data shows the single-crystal chains grow along a [0 0 1] direction and consist of a HfC core and a thin carbon-rich shell with embedded HfC nanocrystallites surrounding the core. This work achieves the controllable preparation of nanoscale HfC sharpening tips for application as a point electron emission source and facilitates the application of HfC ultrafast laser-triggered tips in attosecond science. Highlights: •HfC microcrystal chains were synthesized by a catalyst-assisted CVD. •The chains grow along a [0 0 1] direction and have a periodically changing diameter. •Single-crystal HfC core is sheathed by a thin carbon-rich shell. •A growth mechanism model is proposed to explain the growth of microcrystal chians. •This work achieves the controllable preparation of nanoscale HfC sharpening tips. -- Abstract: Novel hafnium carbide (HfC) microcrystal chains, with a periodically changing diameter and a nanoscale sharpening tip at the chain end, have been synthesized via a catalyst-assisted chemical vapor deposition (CVD) process. The as-synthesized chains with many octahedral microcrystals have diameters of between several hundreds of nm and 6 μm and lengths of ∼500 μm. TEM diffraction studies show that the chains are single-crystalline HfC and preferentially grow along a [0 0 1] crystal orientation. TEM/EELS/EDX analysis proves the chains are composed of a HfC core and a thin (several tens of nm to 100 nm) carbon-rich shell with the embedded HfC nanocrystallites (typically below 10 nm) surrounding the core. The growth mechanism model for the chains based on the vapor–liquid–solid process, the vapor–solid process, and the HfC crystal growth characteristics is discussed

  9. Hafnium in peralkaline and peraluminous boro-aluminosilicate glass, and glass subcomponents: a solubility study

    International Nuclear Information System (INIS)

    Davis, Linda L.; Darab, John G.; Qian, Maoxu; Zhao, Donggao; Palenik, Christopher S.; Li, Hong; Strachan, Denis M.; Li, Liyu

    2003-01-01

    A relationship between the solubility of hafnia (HfO2) and the host glass composition was explored by determining the solubility limits of HfO2 in peralkaline and peraluminous borosilicate glasses in the system SiO2-Al2O3-B2O3-Na2O, and in glasses in the system SiO2-Na2O-Al2O3 in air at 1450 C. The only Hf-bearing phase to crystallize in the peralkaline borosilicate melts is hafnia, while in the boron-free melts sodium-hafnium silicates crystallize. All peraluminous borosilicate melts crystallize hafnia, but the slightly peraluminous glasses also have sector-zoned hafnia crystals that contain Al and Si. The more peraluminous borosilicate glasses also crystallize a B-containing mullite. The general morphology of the hafnia crystals changes as peralkalinity (Na2O/(Na2O+Al2O3)) decreases, as expected in melts with increasing viscosity. In all of the glasses with Na2O > Al2O3, the solubility of hafnia is linearly and positively correlated with Na2O/(Na2O + Al2O3) or Na2O - Al2O3 (excess sodium), despite the presence of 5 to 16 mol% B2O3. The solubility of hafnia is higher in the sodium-aluminum borosilicate glasses than in the sodium-aluminosilicate glasses, suggesting that the boron is enhancing the effect that excess sodium has on the incorporation of Hf into the glass structure. The results of this solubility study are compared to other studies of high-valence cation solubility in B-free silicate melts. From this, for peralkaline B-bearing glasses, it is shown that, although the solubility limits are higher, the solution behavior of hafnia is the same as in B-free silicate melts previously studied. By comparison, also, it is shown that in peraluminous melts, there must be a different solution mechanism for hafnia: different than for peralkaline sodium-aluminum borosilicate glasses and different than for B-free silicate melts studied by others

  10. Nano-crystals of cerium–hafnium binary oxide: Their size-dependent structure

    Energy Technology Data Exchange (ETDEWEB)

    Raitano, Joan M. [Department of Applied Physics and Applied Mathematics, Materials Science and Engineering Program, Columbia University, New York, NY 10027 (United States); Khalid, Syed [National Synchrotron Light Source, Brookhaven National Laboratory, Upton, NY 11973 (United States); Marinkovic, Nebojsa [Chemical Engineering Department, Columbia University, 500 W 120th St, Mudd 801, New York, NY 10027 (United States); Chan, Siu-Wai, E-mail: sc174@columbia.edu [Department of Applied Physics and Applied Mathematics, Materials Science and Engineering Program, Columbia University, New York, NY 10027 (United States)

    2015-09-25

    Highlights: • (1 − x)CeO{sub 2}–xHfO{sub 2} was precipitated (0 < x < 1) and calcined in air. • For x ⩽ 0.14, crystallites ⩽140 nm in size exhibit only the fluorite structure. • This low hafnia solubility is attributable to no auto-reduction (Ce{sup 3+} = 0). • The low solubility is also due to the high temperature required for homogenization. • Coarsening is lessened as Hf{sup 4+} ions slow cation diffusion in these crystallites. - Abstract: Cerium oxide (CeO{sub 2}, “ceria”) and hafnium oxide (HfO{sub 2}, “hafnia”) were aqueously co-precipitated and subsequently calcined to allow for homogenization. The size of the (1−x)CeO{sub 2}–xHfO{sub 2} crystallites, determined by the Scherrer equation, varied from 140 nm for x = 0 to 15 nm for x = 0.73. For x ⩽ 0.14, only cubic structures are visible in X-ray diffractograms, and the lattice parameters are consistent with the values expected for structurally cubic solid solutions of hafnia in ceria. At x = 0.26, tetragonal and monoclinic phases nucleated with the former not being observed in the bulk phase diagram for ceria–hafnia. Therefore, the solubility limit of the cubic structure is between x = 0.14 and x = 0.26 for 40–61 nm crystallites, the sizes of these respective compositions. More specifically, for the 40 nm crystallites of x = 0.26 (1 − x)CeO{sub 2}–xHfO{sub 2}, 15% of the hafnia remains in a structurally cubic solid solution with ceria based on the observed cubic lattice parameter. The compositional domain for the cubic fluorite structure in this study is narrower than other nanostructured (1 − x)CeO{sub 2}–xHfO{sub 2} studies, especially studies with crystallite sizes less than 10 nm, but wider than observed in the bulk and helps to expand the size regime over which the relationship between crystallite size and phase stability is known. The extent of this cubic-structure domain is mainly attributable to the intermediate crystallite size and the roughly zero Ce{sup 3

  11. Gas Hydrate Storage of Natural Gas

    Energy Technology Data Exchange (ETDEWEB)

    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

  12. Can hydrate dissolution experiments predict the fate of a natural hydrate system?

    Energy Technology Data Exchange (ETDEWEB)

    Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

    2008-07-01

    Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

  13. Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

    Directory of Open Access Journals (Sweden)

    Shuhua LIU

    2017-02-01

    Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

  14. Calcium and magnesium silicate hydrates

    International Nuclear Information System (INIS)

    Lothenbach, B.; L'Hopital, E.; Nied, D.; Achiedo, G.; Dauzeres, A.

    2015-01-01

    Deep geological disposals are planed to discard long-lived intermediate-level and high-level radioactive wastes. Clay-based geological barriers are expected to limit the ingress of groundwater and to reduce the mobility of radioelements. In the interaction zone between the cement and the clay based material alteration can occur. Magnesium silicate hydrates (M-S-H) have been observed due to the reaction of magnesium sulfate containing groundwater with cements or in the interaction zone between low-pH type cement and clays. M-S-H samples synthesized in the laboratory showed that M-S-H has a variable composition within 0.7 ≤ Mg/Si ≤ 1.5. TEM/EDS analyses show an homogeneous gel with no defined structure. IR and 29 Si NMR data reveal a higher polymerization degree of the silica network in M-S-H compared to calcium silicate hydrates (C-S-H). The presence of mainly Q 3 silicate tetrahedrons in M-S-H indicates a sheet like or a triple-chain silica structure while C-S-H is characterised by single chain-structure. The clear difference in the silica structure and the larger ionic radius of Ca 2+ (1.1 Angstrom) compared to Mg 2+ (0.8 Angstrom) make the formation of an extended solid solution between M-S-H and C-S-H gel improbable. In fact, the analyses of synthetic samples containing both magnesium and calcium in various ratios indicate the formation of separate M-S-H and C-S-H gels with no or very little uptake of magnesium in CS-H or calcium in M-S-H

  15. Constant rate natural gas production from a well in a hydrate reservoir

    International Nuclear Information System (INIS)

    Ji Chuang; Ahmadi, Goodarz; Smith, Duane H.

    2003-01-01

    Using a computational model, production of natural gas at a constant rate from a well that is drilled into a confined methane hydrate reservoir is studied. It is assumed that the pores in the reservoir are partially saturated with hydrate. A linearized model for an axisymmetric condition with a fixed well output is used in the analysis. For different reservoir temperatures and various well outputs, time evolutions of temperature and pressure profiles, as well as the gas flow rate in the hydrate zone and the gas region, are evaluated. The distance of the decomposition front from the well as a function of time is also computed. It is shown that to maintain a constant natural gas production rate, the well pressure must be decreased with time. A constant low production rate can be sustained for a long duration of time, but a high production rate demands unrealistically low pressure at the well after a relatively short production time. The simulation results show that the process of natural gas production in a hydrate reservoir is a sensitive function of reservoir temperature and hydrate zone permeability

  16. Detection and Production of Methane Hydrate

    Energy Technology Data Exchange (ETDEWEB)

    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

  17. Basics of development of gas hydrate deposits

    Energy Technology Data Exchange (ETDEWEB)

    Makogon, Yuri F.; Holditch, Stephen A.; Makogon, Taras Y.

    2005-07-01

    Natural gas hydrate deposits could possibly be an important energy resource during this century. However, many problems associated with producing these deposits must first be solved. The industry must develop new technologies to produce the gas, to forecast possible tectonic cataclysms in regions of gas hydrate accumulations, and to prevent damage to the environment. These global issues must be addressed by every company or country who wants to produce gas hydrate deposits. Cooperative research between industry and universities can lead to technology breakthroughs in coming years. This paper reviews the Messoyakha field and the Blake Ridge and Nankai areas to explain a methodology for estimating how much gas might be producible from gas hydrate deposits (GHDs) under various conditions. The Messoyakha field is located on land, while the Blake Ridge and Nankai areas are offshore. Messoyakha is the first and the only GHD where gas production from hydrates has reached commercial flow rates. The Blake Ridge GHD has been studied for 20 years and 11 wells have been drilled to collect gas-hydrate samples. The potential resources of gas (gas in place) from Blake Ridge is estimated at 37.7Oe10{sup 12} m{sup 3} (1.330 Tcf) in hydrate form and 19.3Oe10{sup 12}m{sup 3} (681 Bcf) [5] in free gas. To estimate how much of the potential resource can be produced we need a thorough understanding of both the geologic and the thermodynamic characteristics of the formations. (Author)

  18. Gas hydrate exploration activities in Korea

    Energy Technology Data Exchange (ETDEWEB)

    Keun-Pil Park, K.P. [Korea Inst. of Geoscience and Mineral Resources, Gas Hydrate R and D Organization, Ministry of Knowledge Economy, Yuseong-gu, Daejeon (Korea, Republic of)

    2008-07-01

    Korea's first gas hydrate research project was launched in 1996 to study the gas hydrate potential in the Ulleung Basin of the East Sea. It involved a series of laboratory experiments followed by a preliminary offshore seismic survey and regional reconnaissance geophysical and marine geological surveys. The bottom simulating reflector (BSR) was interpreted to show wide area distribution in the southern part of the Ulleung Basin, and its average burial depth was 187 m below the sea floor in the East Sea. A three-phase 10-year National Gas Hydrate Development Program was launched in 2004 to estimate the potential reserves in the East Sea. It will involve drilling to identify natural gas hydrates and to determine the most optimized production methods. Drilling sites were proposed based on five indicators that imply gas hydrate occurrence, notably BSR, gas vent, enhanced seismic reflection, acoustic blanking and gas seeping structure. The UBGH-X-01 gas hydrate expedition in the East Sea Ulleung Basin involved 5 logging while drilling (LWD) surveys at three high priority sites. One wire line logging was implemented at the site of the UBGH09. A total 334 m of non-pressurized conventional cores and 16 pressure cores were obtained in late 2007. The UBGH-X-01 was successfully completed, recovering many natural samples of gas hydrate from 3 coring sites in the East Sea. 7 refs., 12 figs.

  19. Gas Hydrates Research Programs: An International Review

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Science.gov (United States)

    Braun, Doris E.; Griesser, Ulrich J.

    2018-01-01

    The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

  1. Methane hydrate stability and anthropogenic climate change

    Directory of Open Access Journals (Sweden)

    D. Archer

    2007-07-01

    Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO2.

    Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

    The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

  2. Tapping methane hydrates for unconventional natural gas

    Science.gov (United States)

    Ruppel, Carolyn

    2007-01-01

    Methane hydrate is an icelike form of concentrated methane and water found in the sediments of permafrost regions and marine continental margins at depths far shallower than conventional oil and gas. Despite their relative accessibility and widespread occurrence, methane hydrates have never been tapped to meet increasing global energy demands. With rising natural gas prices, production from these unconventional gas deposits is becoming economically viable, particularly in permafrost areas already being exploited for conventional oil and gas. This article provides an overview of gas hydrate occurrence, resource assessment, exploration, production technologies, renewability, and future challenges.

  3. On the electrolytic generation of hydrated electron

    International Nuclear Information System (INIS)

    Ghosh Mazumdar, A.S.; Guha, S.N.

    1975-01-01

    Investigations on the electrolytic generation of hydrated electron in oxygenated as well as oxygen-free solutions at different pH were undertaken. Since sup(-e)aq is known to react rapidly with O 2 yielding the transient O 2 - ion, the latter was looked for through its interaction with phosphite ions resulting in their oxidation near the cathode. It appears from the results that in electrolytic processes, the primary electron (esup(-)sub(cathode)) probably reacts directly with reactive solutes like oxygen, bypassing the hydration step. Data obtained in oxygen-free solutions, however, support the possible formation of hydrated electron at least in alkaline solutions. (author)

  4. Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

    Directory of Open Access Journals (Sweden)

    Jianzhong Zhao

    2015-01-01

    Full Text Available The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower temperature and higher pressure can promote hydrate formation, but they can increase production cost. So these factors should be considered synthetically. The investigation will promote the advance of gas storage technology in hydrates.

  5. Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

    Science.gov (United States)

    Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

    2007-12-01

    A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

  6. A Hydrate Database: Vital to the Technical Community

    Directory of Open Access Journals (Sweden)

    D Sloan

    2007-06-01

    Full Text Available Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML to connect various hydrate databases. The accompanying four articles on laboratory hydrate data by Smith et al., on field hydrate data by L?wner et al., on hydrate modeling by Wang et al., and on construction of a Chinese gas hydrate system by Xiao et al. provide details of GHML in their respective areas.

  7. A search for long-lived radionuclides produced by fast-neutron irradiations of copper, silver, europium, terbium, and hafnium

    International Nuclear Information System (INIS)

    Meadows, J.W.; Smith, D.L.; Ikeda, Y.; Konno, C.

    1990-01-01

    Identical sample packets, each containing samples of elemental copper, silver, europium, terbium, and hafnium, as well as titanium, iron and nickel as dosimeters, have been irradiated in three distinct accelerator neutron fields (at Argonne National Laboratory and Los Alamos National Laboratory in the U.S.A., and Japan Atomic Energy Research Institute, Tokai, Japan) as part of an interlaboratory research collaboration to search for the production of long-lived radionuclides for fusion waste disposal applications. This paper is a progress report on this project. To date, we have detected the following activities, and have obtained preliminary experimental cross section values for several of these: Ag-106m,108m,110m; Eu-150m,152g,154; Tb-158,160; and Hf-175,178m2,179m2,181. (author). 11 refs, 1 fig., 4 tabs

  8. Improved DC performance of AlGaN/GaN high electron mobility transistors using hafnium oxide for surface passivation

    International Nuclear Information System (INIS)

    Liu, Chang; Chor, Eng Fong; Tan, Leng Seow

    2007-01-01

    Improved DC performance of AlGaN/GaN high electron mobility transistors (HEMTs) have been demonstrated using reactive-sputtered hafnium oxide (HfO 2 ) thin film as the surface passivation layer. Hall data indicate a significant increase in the product of sheet carrier concentration (n s ) and electron mobility (μ n ) in the HfO 2 -passivated HEMTs, compared to the unpassivated HEMTs. This improvement in electron carrier characteristics gives rise to a 22% higher I Dmax and an 18% higher g mmax in HEMTs with HfO 2 passivation relative to the unpassivated devices. On the other hand, I gleak of the HEMTs decreases by nearly one order of magnitude when HfO 2 passivation is applied. In addition, drain current is measured in the subthreshold regime. Compared to the unpassivated HEMTs, HfO 2 -passivated HEMTs exhibit a much smaller off-state I D , indicating better turn-off characteristics

  9. About the structure and stability of complex carbonates of thorium (IV), cerium (IV), zirconium (IV), hafnium (IV)

    International Nuclear Information System (INIS)

    Dervin, Jacqueline

    1972-01-01

    This research thesis addressed the study of complex carbonates of cations of metals belonging to the IV A column, i.e. thorium (IV), zirconium (IV), hafnium (IV), and also cerium (IV) and uranium (VI), and more particularly focused on ionic compounds formed in solution, and also on the influence of concentration and nature of cations on stability and nature of the formed solid. The author first presents methods used in this study, discusses their precision and scope of validity. She reports the study of the formation of different complex ions which have been highlighted in solution, and the determination of their formation constants. She reports the preparation and study of the stability domain of solid complexes. The next part reports the use of thermogravimetric analysis, IR spectrometry, and crystallography for the structural study of these compounds

  10. Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

    Science.gov (United States)

    Mora, M.; Vera, E.; Aperador, W.

    2016-02-01

    In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers.

  11. Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

    International Nuclear Information System (INIS)

    Mora, M; Vera, E; Aperador, W

    2016-01-01

    In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers. (paper)

  12. Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

    Science.gov (United States)

    Avdellidou, C.; Delbo', M.; Fienga, A.

    2018-04-01

    Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

  13. Oceanic hydrates: more questions than answers

    International Nuclear Information System (INIS)

    Laherrere, Jean

    2000-01-01

    Methane hydrates create problems by blocking pipelines and casing; they are also accused of contributing to environmental problems (e.g. global warming). Methane hydrates are also found in permafrost areas and in oceanic sediments where the necessary temperature and pressure for stability occur. Claims for the widespread occurrence in thick oceanic deposits are unfounded: apparently indirect evidence from seismic reflectors, seismic hydrocarbon indicators, logs and free samples is unreliable. At one time, hydrate was seen as a static, biogenic, continuous, huge resource but that view is changing to one of a dynamic, overpressurised, discontinuous and unreliable resource. Only Japan and India are currently showing any serious interest in hydrates. Academic research has raised more questions than answers. It is suggested that more hard exploratory evidence rather than theoretical study is required

  14. Vibrational dynamics of hydration water in amylose

    CERN Document Server

    Cavatorta, F; Albanese, G; Angelini, N

    2002-01-01

    We present a study of the dynamical properties of hydration water associated with amylose helices, based on low-temperature vibrational spectra collected using the TOSCA inelastic spectrometer at ISIS. The structural constraints of the polysaccharidic chains favour the formation of a high-density structure for water, which has been suggested by Imberty and Perez on the basis of conformational analysis. According to this model, hydration water can only enter the pores formed by six adjacent helices and completely fills the pores at a hydration level of about 0.27-g water/g dry amylose. Our measurements show that the dynamical behaviour of hydration water is similar to that observed in high-density amorphous ice. (orig.)

  15. Separation of water through gas hydrate formation

    DEFF Research Database (Denmark)

    Boch Andersen, Torben; Thomsen, Kaj

    2009-01-01

    Gas hydrate is normally recognized as a troublemaker in the oil and gas industry. However, gas hydrate has some interesting possibilities when used in connection with separation of water. Nordic Sugar has investigated the possibility of using gas hydrates for concentration of sugar juice. The goal...... of the project was to formulate an alternative separation concept, which can replace the traditional water evaporation process in the sugar production. Work with the separation concept showed that gas hydrates can be used for water separation. The process is not suitable for sugar production because of large...... volumes and the needs for high pressure. The process could be interesting for concentration of heat sensitive, high value products...

  16. Hydration states of AFm cement phases

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  17. ConocoPhillips Gas Hydrate Production Test

    Energy Technology Data Exchange (ETDEWEB)

    Schoderbek, David [ConocoPhillips Co., Houston, TX (United States); Farrell, Helen [ConocoPhillips Co., Houston, TX (United States); Howard, James [ConocoPhillips Co., Houston, TX (United States); Raterman, Kevin [ConocoPhillips Co., Houston, TX (United States); Silpngarmlert, Suntichai [ConocoPhillips Co., Houston, TX (United States); Martin, Kenneth [ConocoPhillips Co., Houston, TX (United States); Smith, Bruce [ConocoPhillips Co., Houston, TX (United States); Klein, Perry [ConocoPhillips Co., Houston, TX (United States)

    2013-06-30

    Work began on the ConocoPhillips Gas Hydrates Production Test (DOE award number DE-NT0006553) on October 1, 2008. This final report summarizes the entire project from January 1, 2011 to June 30, 2013.

  18. Hydrate Control for Gas Storage Operations

    Energy Technology Data Exchange (ETDEWEB)

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  19. Further studies on hydration of alkynes by the PtCl4-CO catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Israelsohn, Osnat; Vollhardt, K. Peter C.; Blum, Jochanan

    2002-01-18

    Under CO atmosphere, between 80 and 120 C, a glyme solution of PtCl{sub 4} forms a carbonyl compound that promotes hydration of internal as well as terminal alkynes to give aldehyde-free ketones. The catalytic process depends strongly on the electronic and steric nature of the substrates. Part of the carbonyl functions of the catalyst can be replaced by phosphine ligands. Chiral DIOP reacts with the PtCl{sub 4}-CO compound to give a catalyst that promotes partial kinetic resolution of a racemic alkyne. Replacement of part of the CO by polystyrene-bound diphenylphosphine enables to attach the catalyst to the polymeric support. Upon entrapment of the platinum compound in a silica sol-gel matrix, it reacts as a partially recyclable catalyst. A reformulated mechanism for the PdCl{sub 4}-CO catalyzed hydration is suggested on the basis of the present study.

  20. The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yinbin, E-mail: miao2@illinois.edu [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Mo, Kun [Nuclear Engineering Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Cui, Bai [Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, Lincoln, NE 68588 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Chen, Wei-Ying [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Miller, Michael K.; Powers, Kathy A. [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37830 (United States); McCreary, Virginia; Gross, David [Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Almer, Jonathan [X-ray Science Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Robertson, Ian M. [Department of Material Science and Engineering, University of Wisconsin-Madison, Madison, WA 53706 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Stubbins, James F. [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)

    2015-03-15

    This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.

  1. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

    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 was 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 included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining 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. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  2. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Directory of Open Access Journals (Sweden)

    Doris E. Braun

    2018-02-01

    Full Text Available The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis, gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations. Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (dehydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules and (form III differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

  3. Preservation of methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

    A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

  4. Geological controls on the occurrence of gas hydrate from core, downhole log, and seismic data in the Shenhu area, South China Sea

    Science.gov (United States)

    Xiujuan Wang,; ,; Collett, Timothy S.; Lee, Myung W.; Yang, Shengxiong; Guo, Yiqun; Wu, Shiguo

    2014-01-01

    Multi-channel seismic reflection data, well logs, and recovered sediment cores have been used in this study to characterize the geologic controls on the occurrence of gas hydrate in the Shenhu area of the South China Sea. The concept of the "gas hydrate petroleum system" has allowed for the systematic analysis of the impact of gas source, geologic controls on gas migration, and the role of the host sediment in the formation and stability of gas hydrates as encountered during the 2007 Guangzhou Marine Geological Survey Gas Hydrate Expedition (GMGS-1) in the Shenhu area. Analysis of seismic and bathymetric data identified seventeen sub-linear, near-parallel submarine canyons in this area. These canyons, formed in the Miocene, migrated in a northeasterly direction, and resulted in the burial and abandonment of canyons partially filled by coarse-grained sediments. Downhole wireline log (DWL) data were acquired from eight drill sites and sediment coring was conducted at five of these sites, which revealed the presence of suitable reservoirs for the occurrence of concentrated gas hydrate accumulations. Gas hydrate-bearing sediment layers were identified from well log and core data at three sites mainly within silt and silt clay sediments. Gas hydrate was also discovered in a sand reservoir at one site as inferred from the analysis of the DWL data. Seismic anomalies attributed to the presence of gas below the base of gas hydrate stability zone, provided direct evidence for the migration of gas into the overlying gas hydrate-bearing sedimentary sections. Geochemical analyses of gas samples collected from cores confirmed that the occurrence of gas hydrate in the Shenhu area is controlled by the presence thermogenic methane gas that has migrated into the gas hydrate stability zone from a more deeply buried source.

  5. Adsorption of water and carbon dioxide on hematite and consequences for possible hydrate formation.

    Science.gov (United States)

    Kvamme, Bjørn; Kuznetsova, Tatiana; Kivelae, Pilvi-Helina

    2012-04-07

    The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decline in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide into the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures, conditions which may lead to formation of hydrates from residual water dissolved in carbon dioxide and carbon dioxide. The critical question is whether the water at certain temperatures and pressures will drop out as liquid droplets first, and then form hydrates, or alternatively, adsorb on the pipeline surfaces, and subsequently form hydrates heterogeneously. In this work, we used several different basis sets of density functional theory in ab initio calculations to estimate the charge distribution of hematite (the dominating component of rust) crystals. These rust particles were embedded in water and chemical potential for adsorbed water molecules was estimated through thermodynamic integration and compared to similar estimates for water clusters of the same size. While the generated charges were not unique, the use of high order approximations and different basis sets provides a range of likely charge distributions. Values obtained for the chemical potential of water in different surroundings indicated that it would be thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based on this formation mechanism. Depending on the basis set and approximations, the estimated gain for water to adsorb on the hematite surface rather than condense as droplets varied between -1.7 kJ mole(-1) and -3.4 kJ mole(-1). The partial charge distribution on the hematite surface is incompatible with the hydrate structure, and thus hydrates will be unable to attach to the surface. The behavior of water outside the immediate vicinity of hematite (beyond 3

  6. Hydration studies of calcium sulfoaluminate cements blended with fly ash

    Energy Technology Data Exchange (ETDEWEB)

    García-Maté, M.; De la Torre, A.G. [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Universidad de Málaga, 29071 Málaga (Spain); León-Reina, L. [Servicios Centrales de Apoyo a la Investigación, Universidad de Málaga, 29071 Málaga (Spain); Aranda, M.A.G. [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Universidad de Málaga, 29071 Málaga (Spain); CELLS-Alba synchrotron, Carretera BP 1413, Km. 3.3, E-08290 Cerdanyola, Barcelona (Spain); Santacruz, I., E-mail: isantacruz@uma.es [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Universidad de Málaga, 29071 Málaga (Spain)

    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.

  7. The influence of Na2O on the hydration of C3A II. Suspension hydration

    NARCIS (Netherlands)

    Spierings, G.A.C.M.; Stein, H.N.

    1976-01-01

    The influence of Na2O on the hydration of C3A was studied in suspensions from the start of the reaction onwards. The heat evolution rate in very early stages of the hydration, measured at varying NaOH concentrations, and SEM, indicate that at NaOH concentrations larger then 0.1 M the reaction

  8. Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

    International Nuclear Information System (INIS)

    Li, Gang; Li, Xiao-Sen; Li, Bo; Wang, Yi

    2014-01-01

    The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

  9. Geomechanical response of permafrost-associated hydrate deposits to depressurization-induced gas production

    Science.gov (United States)

    Rutqvist, J.; Moridis, G.J.; Grover, T.; Collett, T.

    2009-01-01

    In this simulation study, we analyzed the geomechanical response during depressurization production from two known hydrate-bearing permafrost deposits: the Mallik (Northwest Territories, Canada) deposit and Mount Elbert (Alaska, USA) deposit. Gas was produced from these deposits at constant pressure using horizontal wells placed at the top of a hydrate layer (HL), located at a depth of about 900??m at the Mallik site and 600??m at the Mount Elbert site. The simulation results show that general thermodynamic and geomechanical responses are similar for the two sites, but with substantially higher production and more intensive geomechanical responses at the deeper Mallik deposit. The depressurization-induced dissociation begins at the well bore and then spreads laterally, mainly along the top of the HL. The depressurization results in an increased shear stress within the body of the receding hydrate and causes a vertical compaction of the reservoir. However, its effects are partially mitigated by the relatively stiff permafrost overburden, and compaction of the HL is limited to less than 0.4%. The increased shear stress may lead to shear failure in the hydrate-free zone bounded by the HL overburden and the downward-receding upper dissociation interface. This zone undergoes complete hydrate dissociation, and the cohesive strength of the sediment is low. We determined that the likelihood of shear failure depends on the initial stress state as well as on the geomechanical properties of the reservoir. The Poisson's ratio of the hydrate-bearing formation is a particularly important parameter that determines whether the evolution of the reservoir stresses will increase or decrease the likelihood of shear failure.

  10. The expression of proinflammatory genes in epidermal keratinocytes is regulated by hydration status.

    Science.gov (United States)

    Xu, Wei; Jia, Shengxian; Xie, Ping; Zhong, Aimei; Galiano, Robert D; Mustoe, Thomas A; Hong, Seok J

    2014-04-01

    Mucosal wounds heal more rapidly, exhibit less inflammation, and are associated with minimal scarring when compared with equivalent cutaneous wounds. We previously demonstrated that cutaneous epithelium exhibits an exaggerated response to injury compared with mucosal epithelium. We hypothesized that treatment of injured skin with a semiocclusive dressing preserves the hydration of the skin and results in a wound healing phenotype that more closely resembles that of mucosa. Here we explored whether changes in hydration status alter epidermal gene expression patterns in rabbit partial-thickness incisional wounds. Using microarray studies on injured epidermis, we showed that global gene expression patterns in highly occluded versus non-occluded wounds are distinct. Many genes including IL-1β, IL-8, TNF-α (tumor necrosis factor-α), and COX-2 (cyclooxygenase 2) are upregulated in non-occluded wounds compared with highly occluded wounds. In addition, decreased levels of hydration resulted in an increased expression of proinflammatory genes in human ex vivo skin culture (HESC) and stratified keratinocytes. Hierarchical analysis of genes using RNA interference showed that both TNF-α and IL-1β regulate the expression of IL-8 through independent pathways in response to reduced hydration. Furthermore, both gene knockdown and pharmacological inhibition studies showed that COX-2 mediates the TNF-α/IL-8 pathway by increasing the production of prostaglandin E2 (PGE2). IL-8 in turn controls the production of matrix metalloproteinase-9 in keratinocytes. Our data show that hydration status directly affects the expression of inflammatory signaling in the epidermis. The identification of genes involved in the epithelial hydration pathway provides an opportunity to develop strategies to reduce scarring and optimize wound healing.

  11. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  12. Hydration of urea and alkylated urea derivatives

    Science.gov (United States)

    Kaatze, Udo

    2018-01-01

    Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

  13. Implantation of titanium, chromium, yttrium, molybdenum, silver, hafnium, tantalum, tungsten and platinum ions generated by a metal vapor vacuum ion source into 440C stainless steel

    International Nuclear Information System (INIS)

    Sasaki, Jun; Hayashi, Kazunori; Sugiyama, Kenji; Ichiko, Osami; Hashiguchi, Yoshihiro

    1992-01-01

    Titanium, yttrium, molybdenum, silver, chromium, hafnium, tantalum, tungsten and platinum ions generated by a metal vapor vacuum arc (MEVVA) ion source were implanted into 440C stainless steel in the dose region 10 17 ions cm -2 with extraction voltages of up to 70 kV. Glow discharge spectroscopy (GDS), friction coefficient, and Vickers microhardness of the specimens were studied. Grooves made by friction tests were investigated by electron probe microanalysis (EPMA). GDS showed incorporation of carbon in the yttrium, hafnium, tantalum, tungsten and platinum implanted specimens, as well as titanium implanted samples. A large amount of oxygen was observed in the yttrium implanted specimen. The friction coefficient was measured by reciprocating sliding of an unimplanted 440C ball without lubricant at a load of 0.245 N. The friction decreased and achieved a stable state after implantation of titanium, hafnium and tantalum. The friction coefficient of the platinum implanted specimen showed a gradual decrease after several cycles of sliding at high friction coefficient. The yttrium implanted sample exhibited a decreased but slightly unstable friction coefficient. Results from EPMA showed that the implanted elements, which gave decreased friction, remained even after sliding of 200 cycles. Implantation of chromium, molybdenum, silver and tungsten did not provide a decrease in friction and the implants were gone from the wear grooves after the sliding tests. (orig.)

  14. Hydrates on tap: scientists say natural gas hydrates may be tough nut to crack

    Energy Technology Data Exchange (ETDEWEB)

    Mahoney, J.

    2001-12-01

    Gas hydrates are methane molecules trapped in cages of water molecules, yielding a substance with a slushy, sherbet-like consistency. Drilling for hydrates is similar to conventional oil and gas drilling, however, the secret to economic production still remains hidden. Hydrates exist in abundance in such places as deep ocean floor and below ground in some polar regions. The real challenge lies in producing gas from this resource, inasmuch as there is no existing technology for production of gas specifically from methane hydrates. This paper describes an international research program, involving a five-country partnership to spud the first of three wells into the permafrost of the Mackenzie River Delta in the Northwest Territories. The project, worth about $15 million, has brought together public funding and expertise from Japan, Germany, India as well as the Canadian and US Geological Surveys and the US Dept. of Energy in an effort to gain information on the production response of gas hydrates. The operator of the project is Japan Petroleum Exploration Company of Canada, a subsidiary of Japan National Oil Corporation. Since Japan is poor in domestic hydrocarbon resources, but is surrounded by deep water that contains potential for gas hydrates, Japan has a great deal riding on the success of this project. Germany and the United States are also very much interested. Current thinking is that gas is in contact with the hydrates and that it should be possible to develop a free gas reservoir as if it were a conventional deposit. As the free gas is drawn off, the pressure is reduced on the hydrates in contact with it , the hydrates dissociate from the gas and replenish the conventional reservoir. So far this is still only a theory, but it appears to be a sensible approach to hydrate production. 1 photo.

  15. Experimental Determination of Refractive Index of Gas Hydrates

    DEFF Research Database (Denmark)

    Bylov, Martin; Rasmussen, Peter

    1997-01-01

    . For methane hydrate (structure I) the refractive index was found to be 1.346 and for natural gas hydrate (structure II) it was found to be 1.350. The measurements further suggest that the gas hydrate growth rate increases if the water has formed hydrates before. The induction time, on the other hand, seems......The refractive indexes of methane hydrate and natural gas hydrate have been experimentally determined. The refractive indexes were determined in an indirect manner making use of the fact that two non-absorbing materials will have the same refractive index if they cannot be distinguished visually...

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

    Science.gov (United States)

    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

  17. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    Energy Technology Data Exchange (ETDEWEB)

    Richard Sigal; Kent Newsham; Thomas Williams; Barry Freifeld; Timothy Kneafsey; Carl Sondergeld; Shandra Rai; Jonathan Kwan; Stephen Kirby; Robert Kleinberg; Doug Griffin

    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. 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. The Hot Ice No. 1 well was drilled from the surface to a measured depth of 2300 ft. There was almost 100% core recovery from the bottom of surface casing at 107 ft to total depth. Based on the best estimate of the bottom of the methane hydrate stability zone (which used new data obtained from Hot Ice No. 1 and new analysis of data from adjacent wells), core was recovered over its complete range. Approximately 580 ft of porous, mostly frozen, sandstone and 155 of conglomerate were recovered in the Ugnu Formation and approximately 215 ft of porous sandstone were recovered in the West Sak Formation. There were gas shows in the bottom

  18. Experimental investigation of methane release from hydrate formation in sandstone through both hydrate dissociation and CO{sub 2} sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Husebo, J.; Graue, A.; Kvamme, B. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology; Stevens, J.; Howard, J.J. [ConocoPhillips, Ponca City, OK (United States); Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States)

    2008-07-01

    Large amounts of natural gas trapped in hydrate reservoirs are found in Arctic regions and in deep offshore locations around the world. Natural gas production from hydrate deposits offer significant potential for future energy needs. However, research is needed in order to propose potential production schemes for natural gas hydrates. Natural gas molecules can be freed from hydrate structured cages by depressurization, by heating and by exposing the hydrate to a substance that will form a thermodynamically more stable hydrate structure. This paper provided a comparison of two approaches for releasing methane from methane hydrate in porous sandstone. The study scope covered the dissociation rate of methane hydrate in porous media through depressurization, and also referred to previous work done on producing methane from hydrates in sandstone while sequestering carbon dioxide (CO{sub 2}). The study was conducted in a laboratory setting. The paper discussed the experimental design which included the placing of a pressure- and temperature-controlled sample holder inside the bore of a magnetic resonance imager. The experimental procedures were then outlined, with reference to hydrate formation; carbon dioxide sequestration; hydrate dissociation experiments with constant volume; and hydrate dissociation experiments at constant pressure. The constant volume experiments demonstrated that in order to dissociate a large amount of hydrate, the initial depressurization had to be significantly lower than the hydrate stability pressure. 9 refs., 9 figs.

  19. Strength Estimation for Hydrate-Bearing Sediments From Direct Shear Tests of Hydrate-Bearing Sand and Silt

    Science.gov (United States)

    Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu

    2018-01-01

    Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation Sh ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available.

  20. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

    Science.gov (United States)

    Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

    2014-12-01

    The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

  1. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.

    2014-07-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  2. Effect of overpressure on gas hydrate distribution

    Energy Technology Data Exchange (ETDEWEB)

    Bhatnagar, G.; Chapman, W.G.; Hirasaki, G.J. [Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering; Dickens, G.R.; Dugan, B. [Rice Univ., Houston, TX (United States). Dept. of Earth Sciences

    2008-07-01

    Natural gas hydrate systems can be characterized by high sedimentation rates and/or low permeability sediments, which can lead to pore pressure higher than hydrostatic. This paper discussed a study that examined this effect of overpressure on gas hydrate and free gas distribution in marine sediments. A one-dimensional numerical model that coupled sedimentation, fluid flow, and gas hydrate formation was utilized. In order to quantify the relative importance of sedimentation rates and low permeability sediments, a dimensionless sedimentation-compaction group (scN) was defined, that compared the absolute permeability of the sediments to the sedimentation rate. Higher values of scN mean higher permeability or low sedimentation rate which generally yield hydrostatic pore pressure while lower values of scN normally create pore pressure greater than hydrostatic. The paper discussed non-hydrostatic consolidation in gas hydrate systems, including mass balances; constitutive relationships; normalized variables; and dimensionless groups. A numerical solution to the problem was presented. It was concluded that simulation results demonstrated that decreasing scN not only increased pore pressure above hydrostatic values, but also lowered the lithostatic stress gradient and gas hydrate saturation. This occurred because overpressure resulted in lower effective stress, causing higher porosity and lower bulk density of the sediment. 16 refs., 5 figs., 1 appendix.

  3. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

    2014-01-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  4. Methane hydrates in quaternary climate change

    International Nuclear Information System (INIS)

    Kennett, J. P.; Hill, T. M.; Behl, R. J.

    2005-01-01

    The hydrate reservoir in marine sediments is known to contain a large volume of exchangeable carbon stored as solid methane hydrate and associated free gas. This reservoir has been shown to be potentially unstable in response to changing intermediate water temperature and sea level (pressure). Evidence continues to grow for past episodes of major methane release at times of climatic warming. Yet few studies of late Quaternary climate change include methane hydrates as an integral part of the global climate system, in spite of the largest known oscillations at this time in sea level and upper ocean temperature changes for the Cenozoic or earlier, conditions that favor instability of the methane hydrate reservoir. Abrupt increases in atmospheric methane recorded in polar ice cores are widely believed to have resulted, not from ocean-floor methane degassing, but instead from continental wetland activation, a hypothesis thus far unsupported by geological data. Furthermore, as part of this Wetland Methane Hypothesis, the abrupt methane increases have been seen as a response to climatic warming rather than contributing significantly to the change. An alternative view (formulated as the Clathrate Gun Hypothesis) is that the speed, magnitude and timing of abrupt climate change in the recent geologic past are consistent with the process of major degassing of methane hydrates. We summarize aspects of this hypothesis here and needs to test this hypothesis. (Author)

  5. Blue LED irradiation to hydration of skin

    Science.gov (United States)

    Menezes, Priscila F. C.; Requena, Michelle B.; Lizarelli, Rosane F., Z.; Bagnato, Vanderlei S.

    2015-06-01

    Blue LED system irradiation shows many important properties on skin as: bacterial decontamination, degradation of endogenous skin chromophores and biostimulation. In this clinical study we prove that the blue light improves the skin hydration. In the literature none authors reports this biological property on skin. Then this study aims to discuss the role of blue light in the skin hydration. Twenty patients were selected to this study with age between 25-35 years old and phototype I, II and III. A defined area from forearm was pre determined (A = 4.0 cm2). The study was randomized in two treatment groups using one blue light device (power of 5.3mW and irradiance of 10.8mW/cm2). The first treatment group was irradiated with 3J/cm2 (277seconds) and the second with 6J/cm2 (555 seconds). The skin hydration evaluations were done using a corneometer. The measurements were collected in 7, 14, 21 and 30 days, during the treatment. Statistical test of ANOVA, Tukey and T-Student were applied considering 5% of significance. In conclusion, both doses were able to improve the skin hydration; however, 6J/cm2 has kept this hydration for 30 days.

  6. Effects of Nanosilica on Early Age Stages of Cement Hydration

    Directory of Open Access Journals (Sweden)

    Forood Torabian Isfahani

    2017-01-01

    Full Text Available Effects of nanosilica on cement hydration have been broadly investigated in the literature and early age cement hydration, as a whole, has been mainly considered, disregarding the substages of the hydration. The hydration of cement is characterized by different substages and nanosilica effect on the hydration could be a result of diverse, even contradictory, behavior of nanosilica in individual stages of the hydration. In this study, effects of nanosilica on different substages of cement hydration are investigated. Isothermal calorimetry results show that at early ages (initial 72 hours the effects of nanosilica depend on the phenomenon by which the hydration is governed: when the hydration is chemically controlled, that is, during initial reaction, dormant period, and acceleratory period, the hydration rate is accelerated by adding nanosilica; when the hydration is governed by diffusion process, that is, during postacceleratory period, the hydration rate is decelerated by adding nanosilica. The Thermal Gravimetric Analysis on the samples at the hardened state (after 28 days of curing reveals that, after adding nanosilica, the hydration degree slightly increased compared to the plain paste.

  7. Morphology studies on gas hydrates interacting with silica gel

    Energy Technology Data Exchange (ETDEWEB)

    Beltran, J.; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering

    2008-07-01

    Clathrate hydrates or gas hydrates are non-stoichiometric, crystalline compounds that form when small molecules come in contact with water at certain temperatures and pressures. Natural gas hydrates are found in the ocean bottom and in permafrost regions. It is thought that the amount of energy stored in natural hydrates is at least twice that of all other fossil fuels combined. In addition, trapping carbon dioxide as a hydrate in the bottom of the ocean has been suggested as an alternative means of reducing atmospheric carbon dioxide levels. Naturally occurring clathrates are found in close interaction with fine grained particles of very small mean pore diameters. Even though an increasing amount of hydrate equilibrium data for small diameter porous media has become available, the morphological behavior of hydrates subject to such conditions is yet to be explored. This paper presented a study that visually examined hydrate formation and decomposition of gas hydrates while interacting with fine grains of silica gel. The study showed still frames from high-resolution video recordings for hydrate formation and decomposition. The paper discussed the experiment including the apparatus as well as the results of hydrate formation and hydrate dissociation. This study enabled for the first time to observe clathrate morphology while hydrates interacted closely with fine grain particles with small mean pore diameters. 9 refs., 8 figs.

  8. Methane hydrates in nature - Current knowledge and challenges

    Science.gov (United States)

    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

  9. Numerical simulation of gas hydrate exploitation from subsea reservoirs in the Black Sea

    Science.gov (United States)

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

    2017-04-01

    Natural gas (methane) is the most environmental friendly source of fossil energy. When coal is replace by natural gas in power production the emission of carbon dioxide is reduced by 50 %. The vast amount of methane assumed in gas hydrate deposits can help to overcome a shortage of fossil energy resources in the future. To increase their potential for energy applications new technological approaches are being discussed and developed worldwide. 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 carbon dioxide injection) is numerically studied in the frame of the German research project »SUGAR - Submarine Gas Hydrate Reservoirs«. In order to simulate the exploitation of hydrate-bearing sediments in the subsea, an in-house simulation model HyReS which is implemented in the general-purpose software COMSOL Multiphysics is used. This tool turned out to be especially suited for the flexible implementation of non-standard correlations concerning heat transfer, fluid flow, hydrate kinetics, and other relevant model data. Partially based on the simulation results, the development of a technical concept and its evaluation are the subject of ongoing investigations, whereby geological and ecological criteria are to be considered. The results illustrate the processes and effects occurring during the gas production from a subsea gas hydrate deposit by depressurization. The simulation results from a case study for a deposit located in the Black Sea reveal that the production of natural gas by simple depressurization is possible but with quite low rates. It can be shown that the hydrate decomposition and thus the gas production strongly depend on the geophysical properties of the reservoir, the mass and heat transport within the reservoir, and

  10. Fuel cell membrane hydration and fluid metering

    Science.gov (United States)

    Jones, Daniel O.; Walsh, Michael M.

    1999-01-01

    A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel in order to mix its respective portion of liquid water with the corresponding portion of the stream. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

  11. Hydration dynamics of hyaluronan and dextran.

    Science.gov (United States)

    Hunger, Johannes; Bernecker, Anja; Bakker, Huib J; Bonn, Mischa; Richter, Ralf P

    2012-07-03

    Hyaluronan is a polysaccharide, which is ubiquitous in vertebrates and has been reported to be strongly hydrated in a biological environment. We study the hydration of hyaluronan in solution using the rotational dynamics of water as a probe. We measure these dynamics with polarization-resolved femtosecond-infrared and terahertz time-domain spectroscopies. Both experiments reveal that a subensemble of water molecules is slowed down in aqueous solutions of hyaluronan amounting to ∼15 water molecules per disaccharide unit. This quantity is consistent with what would be expected for the first hydration shell. Comparison of these results to the water dynamics in aqueous dextran solution, a structurally similar polysaccharide, yields remarkably similar results. This suggests that the observed interaction with water is a common feature for hydrophilic polysaccharides and is not specific to hyaluronan. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  12. Multicavity SCRF calculation of ion hydration energies

    International Nuclear Information System (INIS)

    Diercksen, B.H.F.; Karelson, M.; Tamm, T.

    1994-01-01

    The hydration energies of the proton, hydroxyl ion, and several inorganic ions were calculated using the multicavity self-consistent reaction field (MCa SCRF) method developed for the quantum-mechanical modeling of rotationally or flexible systems in dielectric media. The ionic complexes H 3 O + (H2O) 4 , OH - (H2O) 4 , NH + 4 (H2O) 4 , and Hal - (H2O) 4 , where Hal = F, Cl, or Br, have been studied. Each complex was divided between five spheres, corresponding to the central ion and four water molecules in their first coordination sphere, respectively. Each cavity was surrounded by a polarizable medium with the dielectric permittivity of water at room temperature (80). The ionic hydration energies of ions were divided into specific and nonspecific parts. After accounting for the cavity-formation energy using scaled particle theory, good agreement between the total calculated and experimental hydration energies was obtained for all ions studied

  13. Thermal expansion properties of calcium aluminate hydrates

    International Nuclear Information System (INIS)

    Song, Tae Woong

    1986-01-01

    In order to eliminate the effect of impurities and aggregates on the thermomechanical properties of the various calcium aluminate hydrates, and to prepare clinkers in which all calcium aluminates are mixed homogeneously, chemically pure CaO and Al 2 O 3 were weighed, blended and heated in various conditions. After quantitative X-ray diffractometry(QXRD), the synthesized clinker was hydrated and cured under the conditions of 30 deg C, W/C=0.5, relative humidity> 90% respectively during 24 hours. And then differential thermal analysis(DTA), thermogravimetry(TG), micro calorimetry, thermomechanical analysis(TMA) and scanning electron microanalysis(SEM) were applied to examine the thermal properties of samples containing, calcium aluminate hydrates in various quantity. (Author)

  14. THz characterization of hydrated and anhydrous materials

    Science.gov (United States)

    Sokolnikov, Andre

    2011-06-01

    The characterization of anhydrous and hydrated forms of materials is of great importance to science and industry. Water content poses difficulties for successful identification of the material structure by THz radiation. However, biological tissues and hydrated forms of nonorganic substances still may be investigated by THz radiation. This paper outlines the range of possibilities of the above characterization, as well as provides analysis of the physical mechanism that allows or prevents penetration of THz waves through the substance. THz-TDS is used to measure the parameters of the characterization of anhydrous and hydrated forms of organic and nonorganic samples. Mathematical methods (such as prediction models of time-series analysis) are used to help identifying the absorption coefficient and other parameters of interest. The discovered dependencies allow designing techniques for material identification/characterization (e.g. of drugs, explosives, etc. that may have water content). The results are provided.

  15. Relaxation mechanism of the hydrated electron.

    Science.gov (United States)

    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.

  16. Chemical alteration of cement hydrates by dissolution

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

    2000-01-01

    Cementitious material is a potential waste packaging and backfilling material for the radioactive waste disposal, and is expected to provide both physical and chemical containment. In particular, the sorption of radionuclides onto cementitious material and the ability to provide a high pH condition are very important parameters when considering the release of radionuclides from radioactive wastes. For the long term, in the geological disposal environment, cement hydrates will be altered by, for example, dissolution, chemical reaction with ions in the groundwater, and hydrothermal reaction. Once the composition or crystallinity of the constituent minerals of a cement hydrate is changed by these processes, the pH of the repository buffered by cementitious material and its sorption ability might be affected. However, the mechanism of cement alteration is not yet fully understood. In this study, leaching experiments of some candidate cements for radioactive waste disposal were carried out. Hydrated Ordinary Portland Cement (OPC), Blast Furnace Slag blended cement (OPC/BFS) and Highly containing Flyash and Silicafume Cement (HFSC) samples were contacted with distilled water at liquid:solid ratios of 10:1, 100:1 and 1000:1 at room temperature for 200 days. In the case of OPC, Ca(OH) 2 dissolved at high liquid:solid ratios. The specific surface area of all cement samples increased by leaching process. This might be caused by further hydration and change of composition of constituent minerals. A model is presented which predicts the leaching of cement hydrates and the mineral composition in the hydrated cement solid phase, including the incongruent dissolution of CSH gel phases and congruent dissolution of Ca(OH) 2 , Ettringite and Hydrotalcite. Experimental results of dissolution of Ca-O-H and Ca-Si-O-H phases were well predicted by this model. (author)

  17. Ground movements associated with gas hydrate production

    International Nuclear Information System (INIS)

    Siriwardane, H.J.; Kutuk, B.

    1992-03-01

    This report deals with a study directed towards a modeling effort on production related ground movements and subsidence resulting from hydrate dissociation. The goal of this research study was to evaluate whether there could be subsidence related problems that could be an impediment to hydrate production. During the production of gas from a hydrate reservoir, it is expected that porous reservoir matrix becomes more compressible which may cause reservoir compression (compaction) under the influence of overburden weight. The overburden deformations can propagate its influence upwards causing subsidence near the surface where production equipment will be located. In the present study, the reservoir compaction is modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The present study is expected to provide a ''lower bound'' solution to the subsidence caused by hydrate reservoir depletion. The reservoir compaction anticipated during hydrate production was modeled by using the finite element method, which is a powerful computer modeling technique. The ground movements at the reservoir roof (i.e. reservoir compression) cause additional stresses and disturbance in the overburden strata. In this study, the reservoir compaction was modeled by using the conventional ''stress equilibrium'' approach. In this approach, the overburden strata move under the influence of body force (i.e. self weight) in response to the ''cavity'' generated by reservoir depletion. The resulting stresses and ground movements were computed by using the finite element method. Based on the parameters used in this investigation, the maximum ground subsidence could vary anywhere from 0.50 to 6.50 inches depending on the overburden depth and the size of the depleted hydrate reservoir

  18. Irrigation port hydration in phacoemulsification surgery

    Directory of Open Access Journals (Sweden)

    Suzuki H

    2018-01-01

    Full Text Available Hisaharu Suzuki,1 Yoichiro Masuda,2 Yuki Hamajima,1 Hiroshi Takahashi3 1Department of Ophthalmology, Nippon Medical School Musashikosugi Hospital, Kawasaki City, Kanagawa, 2Department of Ophthalmology, The Jikei University, Katsushika Medical Center, Tokyo, 3Department of Ophthalmology, Nippon Medical School, Tokyo, Japan Background: In most cases, hydration is performed by water injection into the stromal tissue with a needle. The technique is simple, however it is sometimes troublesome.Purpose: We describe a simple technique for hydrating the corneal stroma in cataract surgery using an irrigation port.Patients and methods: The technique began by pushing the irrigation port against the corneal stroma for a few seconds during phacoemulsification, which generated edema in the corneal incision that subsequently prevented leakage. This procedure is called the hydration using irrigation port (HYUIP technique. A total of 60 eyes were randomized and placed in two groups, 30 eyes underwent surgeries using the HYUIP technique (HYUIP group and 30 eyes underwent surgeries without the HYUIP technique (control. The three points evaluated during each surgery included 1 the occurrence of anterior chamber collapse during the pulling out of the I/A tip after inserting the intraocular lens, 2 the need for conventional hydration, and 3 watertight completion at the end stage of surgery.Results: The anterior chamber collapse and the need for conventional hydration were significantly smaller in the HYUIP group compared to the control group. Regarding the self-sealing completion, no significant difference was observed between the two groups.Conclusion: The HYUIP technique is an effective method for creating self-sealing wound. In addition, this technique helps to prevent anterior chamber collapse. Keywords: cataract surgery, hydration, irrigation and aspiration, phacoemulsification, wound, self-sealing 

  19. Hydration and nutrition knowledge in adolescent swimmers. Does water intake affect urine hydration markers after swimming?

    Directory of Open Access Journals (Sweden)

    Cesare Altavilla

    2017-12-01

    Full Text Available Little data exists regarding nutritional knowledge and hydration in adolescent swimmers. The aim of this study was to assess the level of nutrition and hydration knowledge and to describe the fluid balance in adolescent swimmers during training. A study was carried out with a cross-sectional descriptive part and a longitudinal part with repeated measurements over five swimming sessions. Eighty-six adolescent swimmers completed a questionnaire to assess their sport nutrition and hydration knowledge. Fluid balance and urine hydration markers were studied during training. Swimmers showed a limited nutrition knowledge (33.26 % ± SD 12.59 and meagre hydration knowledge (28.61 % ± SD 28.59. Females showed lower scores than male swimmers in nutrition and hydration knowledge. Based on urine specific gravity, swimmers started the training close to the euhydrated threshold (1.019 g/mL ± SD 0.008. Although urine specific gravity and urine colour were reduced after the training, there were minimal changes in body mass (-0.12 Kg ± SD 0.31. Sweat loss (2.67 g/min ± SD 3.23 and the net changes in the fluid balance (-0.22 % ± SD 0.59 were low. The poor knowledge in nutrition and hydration encountered in the swimmers can justify the development of a strategy to incorporate nutritional education programmes for this group. Body water deficit from swimming activity seems to be easily replaced with the water intake to maintain hydration. After the training, the urine of swimmers was diluted regardless of their water intake. Dilution of urine did not reflect real hydration state in swimming.

  20. Thermal decomposition of uranyl sulphate hydrate

    International Nuclear Information System (INIS)

    Sato, T.; Ozawa, F.; Ikoma, S.

    1980-01-01

    The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

  1. Nanostructure of Calcium Silicate Hydrates in Cements

    KAUST Repository

    Skinner, L. B.; Chae, S. R.; Benmore, C. J.; Wenk, H. R.; Monteiro, P. J. M.

    2010-01-01

    Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure. © 2010 The American Physical Society.

  2. Nanostructure of Calcium Silicate Hydrates in Cements

    KAUST Repository

    Skinner, L. B.

    2010-05-11

    Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure. © 2010 The American Physical Society.

  3. Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

    Energy Technology Data Exchange (ETDEWEB)

    McConnell, Dan

    2018-02-25

    Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydrates and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.

  4. Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

    Directory of Open Access Journals (Sweden)

    Saravana Prakash Thirumuruganandham

    2010-01-01

    Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

  5. The rates measurement of methane hydrate formation and dissociation using micro-drilling system application for gas hydrate exploration

    Energy Technology Data Exchange (ETDEWEB)

    Bin Dou [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)]|[Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Reinicke, K.M. [Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Guosheng Jiang; Xiang Wu; Fulong Ning [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)

    2006-07-01

    When drilling through gas hydrate bearing formations, the energy supplied by virtue of the drilling process may lead to a destabilization of the hydrates surrounding the wellbore. Therefore, as the number of oil and gas fields being development in deepwater and onshore arctic environments increases, greater emphasis should be placed on quantifying the risks, gas hydrates pose to drilling operations. The qualification of these risks requires a comprehensive understanding of gas hydrate-formation and dissociation as a result of drilling induced processes. To develop the required understanding of gas hydrat formation and dissociation, the authors conducted laboratory experiments by using a micro-drilling system, to study the dissociation rates of methane hydrates contained in a tank reactor. The test facility used is a development of China University of Geosciences. The rates of methane hydrate formation and dissociation in the tank reactor were measured at steady-state conditions at pressures ranging from 0.1 to 25 MPa and temperatures ranging from -5 to 20 C. The experimental results show that the rate of hydrate formation is strongly influenced by the fluid system used to form the hydrates, pressure and temperature, with the influence of the temperature on methane hydrate dissociation being stronger than that of the pressure. Drilling speed, drilling fluids and hydrate dissociation inhibitors were also shown to influence hydrate dissociation rate. The derived results have been used to predict hydrate drilling stability for several drilling fluid systems.

  6. Marine Gas Hydrates - An Untapped Non-conventional Energy ...

    Indian Academy of Sciences (India)

    Table of contents. Marine Gas Hydrates - An Untapped Non-conventional Energy Resource · Slide 2 · Slide 3 · Slide 4 · Gas Hydrate Stability Zone · Slide 6 · Slide 7 · Exploration of gas hydrates (seismic) · Characteristics of BSR · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Distribution of Gas Hydrates in KG ...

  7. Hydrate bearing clayey sediments: Formation and gas production concepts

    KAUST Repository

    Jang, Jaewon; Santamarina, Carlos

    2016-01-01

    Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

  8. Standardization and software infrastructure for gas hydrate data communications

    Energy Technology Data Exchange (ETDEWEB)

    Kroenlein, K.; Chirico, R.D.; Kazakov, A.; Frenkel, M. [National Inst. of Standards and Technology, Boulder, CO (United States). Physical and Chemical Properties Div.; Lowner, R. [GeoForschungsZentrum Potsdam (Germany); Wang, W. [Chinese Academy of Science, Beijing (China). Computer Network Information Center; Smith, T. [MIT Systems, Flushing, NY (United States); Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Centre for Hydrate Research

    2008-07-01

    The perceived value of gas hydrates as an energy resource for the future has led to extensive hydrate research studies and experiments. The hydrate deposits are widely dispersed throughout the world, and many countries are now investigating methods of extracting gas hydrate resources. This paper described a gas hydrates markup language (GHML) developed as an international standard for data transfer and storage within the gas hydrates community. The language is related to a hydrates database developed to facilitate a greater understanding of naturally occurring hydrate interactions with geophysical processes, and aid in the development of hydrate technologies for resource recovery and storage. Recent updates to the GHML included the addition of ThermoML, a communication standard for thermodynamic data into the GHML schema. The standard will be used to represent all gas hydrates thermodynamic data. A new element for the description of crystal structures has also been developed, as well as a guided data capture tool. The tool is available free of charge and is publicly licensed for use by gas hydrate data producers. A web service has also been provided to ensure that access to GHML files for gas hydrates and data files are available for users. It was concluded that the tool will help to ensure data quality assurance for the conversion of data and meta-data within the database. 28 refs., 9 figs.

  9. Small angle X-ray scattering from hydrating tricalcium silicate

    International Nuclear Information System (INIS)

    Vollet, D.

    1983-01-01

    The small-angle X-ray scattering technique was used to study the structural evolution of hydrated tricalcium silicate at room temperature. The changes in specific area of the associated porosity and the evolution of density fluctuations in the solid hydrated phase were deduced from the scattering data. A correlation of these variations with the hydration mechanism is tried. (Author) [pt

  10. Hydrate bearing clayey sediments: Formation and gas production concepts

    KAUST Repository

    Jang, Jaewon

    2016-06-20

    Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

  11. Partial tooth gear bearings

    Science.gov (United States)

    Vranish, John M. (Inventor)

    2010-01-01

    A partial gear bearing including an upper half, comprising peak partial teeth, and a lower, or bottom, half, comprising valley partial teeth. The upper half also has an integrated roller section between each of the peak partial teeth with a radius equal to the gear pitch radius of the radially outwardly extending peak partial teeth. Conversely, the lower half has an integrated roller section between each of the valley half teeth with a radius also equal to the gear pitch radius of the peak partial teeth. The valley partial teeth extend radially inwardly from its roller section. The peak and valley partial teeth are exactly out of phase with each other, as are the roller sections of the upper and lower halves. Essentially, the end roller bearing of the typical gear bearing has been integrated into the normal gear tooth pattern.

  12. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

    Science.gov (United States)

    Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

    2017-08-30

    Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

  13. An Auger electron spectroscopy study on the anodization process of high-quality thin-film capacitors made of hafnium

    International Nuclear Information System (INIS)

    Noya, Atsushi; Sasaki, Katsutaka; Umezawa, Toshiji

    1989-01-01

    Formation process of the anodic oxide film of hafnium for use as a thin-film capacitor has been examined by the current-voltage characteristics of the anodization and the in-depth analysis of formed oxide using Auger electron spectroscopy. It is found that the oxide growth obeys three different rate laws such as the linear rate law at first and next the parabolic rate law during the constant current anodization, and then the reciprocal logarithmic rate law during the constant voltage anodization following after the constant current process. From the Auger electron spectroscopy analysis, it is found that the shape of the compositional depth profile of the grown oxide film varies associating with the rate law of oxidation obeyed. The variation of depth profile correlating with the rate law is discussed with respect to each elementary process such as the transport and/or the reaction of chemical species interpreted from the over-all behavior of anodization process. It is revealed that the stoichiometric film having an interface with sharp transition, which is favorable for obtaining excellent electrical properties of the capacitor, can be obtained under the condition that the phase-boundary reaction is the rate-determining step of the anodization. The constant voltage anodization process also satisfies such circumstances and therefore can be favorable method for preparing highquality thin-film capacitors. (author)

  14. Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

    International Nuclear Information System (INIS)

    Chisaka, Mitsuharu; Itagaki, Noriaki

    2016-01-01

    Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

  15. IER-297 CED-2: Final Design for Thermal/Epithermal eXperiments with Jemima Plates with Polyethylene and Hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Percher, C. M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Zywiec, W. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Heinrichs, D. P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2018-01-11

    This report presents the final design (CED-2) for IER-297, and focuses on 15 critical configurations using highly enriched uranium (HEU) Jemima plates moderated by polyethylene with and without hafnium diluent. The goal of the U.S. Nuclear Criticality Safety Program’s Thermal/Epithermal eXperiments (TEX) is to design and conduct new critical experiments to address high priority nuclear data needs from the nuclear criticality safety and nuclear data communities, with special emphasis on intermediate energy (0.625 eV – 100 keV) assemblies that can be easily modified to include various high priority diluent materials. The TEX (IER 184) CED-1 Report [1], completed in 2012, demonstrated the feasibility of meeting the TEX goals with two existing NCSP fissile assets, plutonium Zero Power Physics Reactor (ZPPR) plates and highly enriched uranium (HEU) Jemima plates. The first set of TEX experiments will focus on using the plutonium ZPPR plates with polyethylene moderator and tantalum diluents.

  16. Essays on partial retirement

    NARCIS (Netherlands)

    Kantarci, T.

    2012-01-01

    The five essays in this dissertation address a range of topics in the micro-economic literature on partial retirement. The focus is on the labor market behavior of older age groups. The essays examine the economic and non-economic determinants of partial retirement behavior, the effect of partial

  17. Obsidian Hydration Dating in the Undergraduate Curriculum.

    Science.gov (United States)

    Manche, Emanuel P.; Lakatos, Stephen

    1986-01-01

    Provides an overview of obsidian hydration dating for the instructor by presenting: (1) principles of the method; (2) procedures; (3) applications; and (4) limitations. The theory of the method and one or more laboratory exercises can be easily introduced into the undergraduate geology curriculum. (JN)

  18. Gas hydrate resource quantification in Uruguay

    International Nuclear Information System (INIS)

    Tomasini, J.; De Santa Ana, H.; Veroslavsky, G.

    2012-01-01

    The gas hydrates are crystalline solids formed by natural gas (mostly methane) and water, which are stable in thermobaric conditions given under high pressures and low temperatures. These conditions are given in permafrost zones and continental margin basins offshore in the nature

  19. Pentagonal dodecahedron methane hydrate cage and methanol ...

    Indian Academy of Sciences (India)

    methane hydrate in sea bed near continental margin and underneath of permafrost ... clathrate structure,6,7 IR spectroscopy analysis of vibra- tional form of guest .... Hydrogen (H71) of the hydroxyl group of methanol is found to have formed ...

  20. A new approach to model mixed hydrates

    Czech Academy of Sciences Publication Activity Database

    Hielscher, S.; Vinš, Václav; Jäger, A.; Hrubý, Jan; Breitkopf, C.; Span, R.

    2018-01-01

    Roč. 459, March (2018), s. 170-185 ISSN 0378-3812 R&D Projects: GA ČR(CZ) GA17-08218S Institutional support: RVO:61388998 Keywords : gas hydrate * mixture * modeling Subject RIV: BJ - Thermodynamics Impact factor: 2.473, year: 2016 https://www.sciencedirect.com/science/article/pii/S0378381217304983

  1. [Terminal phase hydration, pain and delirium

    DEFF Research Database (Denmark)

    Heick, A.

    2009-01-01

    Hydration of the terminal patient may relieve confusion and complaints of "dry mouth". But it may worsen oedema of the brain, lungs, and extremities, worsen terminal rattling and cause a need for frequent changing of diapers. The decision of whether and how to treat a dying patient with fluids...

  2. Hydration dynamics near a model protein surface

    International Nuclear Information System (INIS)

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

    2003-01-01

    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

  3. A positron annihilation study of hydrated DNA

    DEFF Research Database (Denmark)

    Warman, J. M.; Eldrup, Morten Mostgaard

    1986-01-01

    Positron annihilation measurements are reported for hydrated DNA as a function of water content and as a function of temperature (20 to -180.degree. C) for samples containing 10 and 50% wt of water. The ortho-positronium mean lifetime and its intensity show distinct variations with the degree...

  4. Gold(III)-Catalyzed Hydration of Phenylacetylene

    Science.gov (United States)

    Leslie, J. Michelle; Tzeel, Benjamin A.

    2016-01-01

    A guided inquiry-based experiment exploring the regioselectivity of the hydration of phenylacetylene is described. The experiment uses an acidic gold(III) catalyst in a benign methanol/water solvent system to introduce students to alkyne chemistry and key principles of green chemistry. The experiment can be easily completed in approximately 2 h,…

  5. [Terminal phase hydration, pain and delirium

    DEFF Research Database (Denmark)

    Heick, A.

    2009-01-01

    Hydration of the terminal patient may relieve confusion and complaints of "dry mouth". But it may worsen oedema of the brain, lungs, and extremities, worsen terminal rattling and cause a need for frequent changing of diapers. The decision of whether and how to treat a dying patient with fluids sh...

  6. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, Jos

    2010-01-01

    The alkali-binding capacity of C–S–H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C–S–H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data

  7. Partial molar volume of proteins studied by the three-dimensional reference interaction site model theory.

    Science.gov (United States)

    Imai, Takashi; Kovalenko, Andriy; Hirata, Fumio

    2005-04-14

    The three-dimensional reference interaction site model (3D-RISM) theory is applied to the analysis of hydration effects on the partial molar volume of proteins. For the native structure of some proteins, the partial molar volume is decomposed into geometric and hydration contributions using the 3D-RISM theory combined with the geometric volume calculation. The hydration contributions are correlated with the surface properties of the protein. The thermal volume, which is the volume of voids around the protein induced by the thermal fluctuation of water molecules, is directly proportional to the accessible surface area of the protein. The interaction volume, which is the contribution of electrostatic interactions between the protein and water molecules, is apparently governed by the charged atomic groups on the protein surface. The polar atomic groups do not make any contribution to the interaction volume. The volume differences between low- and high-pressure structures of lysozyme are also analyzed by the present method.

  8. Trap state passivation improved hot-carrier instability by zirconium-doping in hafnium oxide in a nanoscale n-metal-oxide semiconductor-field effect transistors with high-k/metal gate

    International Nuclear Information System (INIS)

    Liu, Hsi-Wen; Tsai, Jyun-Yu; Liu, Kuan-Ju; Lu, Ying-Hsin; Chang, Ting-Chang; Chen, Ching-En; Tseng, Tseung-Yuen; Lin, Chien-Yu; Cheng, Osbert; Huang, Cheng-Tung; Ye, Yi-Han

    2016-01-01

    This work investigates the effect on hot carrier degradation (HCD) of doping zirconium into the hafnium oxide high-k layer in the nanoscale high-k/metal gate n-channel metal-oxide-semiconductor field-effect-transistors. Previous n-metal-oxide semiconductor-field effect transistor studies demonstrated that zirconium-doped hafnium oxide reduces charge trapping and improves positive bias temperature instability. In this work, a clear reduction in HCD is observed with zirconium-doped hafnium oxide because channel hot electron (CHE) trapping in pre-existing high-k bulk defects is the main degradation mechanism. However, this reduced HCD became ineffective at ultra-low temperature, since CHE traps in the deeper bulk defects at ultra-low temperature, while zirconium-doping only passivates shallow bulk defects.

  9. Clathrate Hydrates for Thermal Energy Storage in Buildings: Overview of Proper Hydrate-Forming Compounds

    Directory of Open Access Journals (Sweden)

    Beatrice Castellani

    2014-09-01

    Full Text Available Increasing energy costs are at the origin of the great progress in the field of phase change materials (PCMs. The present work aims at studying the application of clathrate hydrates as PCMs in buildings. Clathrate hydrates are crystalline structures in which guest molecules are enclosed in the crystal lattice of water molecules. Clathrate hydrates can form also at ambient pressure and present a high latent heat, and for this reason, they are good candidates for being used as PCMs. The parameter that makes a PCM suitable to be used in buildings is, first of all, a melting temperature at about 25 °C. The paper provides an overview of groups of clathrate hydrates, whose physical and chemical characteristics could meet the requirements needed for their application in buildings. Simulations with a dynamic building simulation tool are carried out to evaluate the performance of clathrate hydrates in enhancing thermal comfort through the moderation of summer temperature swings and, therefore, in reducing energy consumption. Simulations suggest that clathrate hydrates have a potential in terms of improvement of indoor thermal comfort and a reduction of energy consumption for cooling. Cooling effects of 0.5 °C and reduced overheating hours of up to 1.1% are predicted.

  10. Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

    International Nuclear Information System (INIS)

    Anderson, Graydon K.

    2004-01-01

    The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

  11. Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

    Science.gov (United States)

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

    2005-01-01

    The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

  12. MORPHOLOGY OF METHANE HYDRATE HOST SEDIMENTS

    International Nuclear Information System (INIS)

    JONES, K.W.; FENG, H.; TOMOV, S.; WINTER, W.J.; EATON, M.; MAHAJAN, D.

    2004-01-01

    Results from simulated experiments in several laboratories show that host sediments influence hydrate formation in accord with known heterogeneity of host sediments at sites of gas hydrate occurrence (1). For example, in Mackenzie Delta, NWT Canada (Mallik 2L-38 well), coarser-grained units (pore-filling model) are found whereas in the Gulf of Mexico, the found hydrate samples do not appear to be lithologically controlled. We have initiated a systematic study of sediments, initially focusing on samples from various depths at a specific site, to establish a correlation with hydrate occurrence (or variations thereof) to establish differences in their microstructure, porosity, and other associated properties. The synchrotron computed microtomography (CMT) set-up at the X-27A tomography beam line at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory was used as a tool to study sediments from Blake Ridge at three sub bottom depths of 0.2, 50, and 667 meters. Results from the tomographic analysis of the deepest sample (667 m) are presented here to illustrate how tomography can be used to obtain new insights into the structures of methane hydrate host sediments. The investigation shows the internal grain/pore space resolution in the microstructure and a 3-D visualization of the connecting pathways obtained following data segmentation into pore space and grains within the sediment sample. The analysis gives the sample porosity, specific surface area, mean particle size, and tortuosity, as well. An earlier report on the experimental program has been given by Mahajan et al. (2)

  13. Multicomponent seismic methods for characterizing gas hydrate occurrences and systems in deep-water Gulf of Mexico

    Science.gov (United States)

    Haines, Seth S.; Lee, Myung W.; Collett, Timothy S.; Hardage, Bob A.

    2011-01-01

    In-situ characterization and quantification of natural gas hydrate occurrences remain critical research directions, whether for energy resource, drilling hazard, or climate-related studies. Marine multicomponent seismic data provide the full seismic wavefield including partial redundancy, and provide a promising set of approaches for gas hydrate characterization. Numerous authors have demonstrated the possibilities of multicomponent data at study sites around the world. We expand on this work by investigating the utility of very densely spaced (10’s of meters) multicomponent receivers (ocean-bottom cables, OBC, or ocean-bottom seismometers, OBS) for gas hydrate studies in the Gulf of Mexico and elsewhere. Advanced processing techniques provide high-resolution compressional-wave (PP) and converted shearwave (PS) reflection images of shallow stratigraphy, as well as P-wave and S-wave velocity estimates at each receiver position. Reflection impedance estimates can help constrain velocity and density, and thus gas hydrate saturation. Further constraint on velocity can be determined through identification of the critical angle and associated phase reversal in both PP and PS wideangle data. We demonstrate these concepts with examples from OBC data from the northeast Green Canyon area and numerically simulated OBS data that are based on properties of known gas hydrate occurrences in the southeast (deeper water) Green Canyon area. These multicomponent data capabilities can provide a wealth of characterization and quantification information that is difficult to obtain with other geophysical methods.

  14. Accuracy of free energies of hydration using CM1 and CM3 atomic charges.

    Science.gov (United States)

    Udier-Blagović, Marina; Morales De Tirado, Patricia; Pearlman, Shoshannah A; Jorgensen, William L

    2004-08-01

    Absolute free energies of hydration (DeltaGhyd) have been computed for 25 diverse organic molecules using partial atomic charges derived from AM1 and PM3 wave functions via the CM1 and CM3 procedures of Cramer, Truhlar, and coworkers. Comparisons are made with results using charges fit to the electrostatic potential surface (EPS) from ab initio 6-31G* wave functions and from the OPLS-AA force field. OPLS Lennard-Jones parameters for the organic molecules were used together with the TIP4P water model in Monte Carlo simulations with free energy perturbation theory. Absolute free energies of hydration were computed for OPLS united-atom and all-atom methane by annihilating the solutes in water and in the gas phase, and absolute DeltaGhyd values for all other molecules were computed via transformation to one of these references. Optimal charge scaling factors were determined by minimizing the unsigned average error between experimental and calculated hydration free energies. The PM3-based charge models do not lead to lower average errors than obtained with the EPS charges for the subset of 13 molecules in the original study. However, improvement is obtained by scaling the CM1A partial charges by 1.14 and the CM3A charges by 1.15, which leads to average errors of 1.0 and 1.1 kcal/mol for the full set of 25 molecules. The scaled CM1A charges also yield the best results for the hydration of amides including the E/Z free-energy difference for N-methylacetamide in water. Copyright 2004 Wiley Periodicals, Inc.

  15. Recurrent Partial Words

    Directory of Open Access Journals (Sweden)

    Francine Blanchet-Sadri

    2011-08-01

    Full Text Available Partial words are sequences over a finite alphabet that may contain wildcard symbols, called holes, which match or are compatible with all letters; partial words without holes are said to be full words (or simply words. Given an infinite partial word w, the number of distinct full words over the alphabet that are compatible with factors of w of length n, called subwords of w, refers to a measure of complexity of infinite partial words so-called subword complexity. This measure is of particular interest because we can construct partial words with subword complexities not achievable by full words. In this paper, we consider the notion of recurrence over infinite partial words, that is, we study whether all of the finite subwords of a given infinite partial word appear infinitely often, and we establish connections between subword complexity and recurrence in this more general framework.

  16. Partial dehydration and cryopreservation of Citrus seeds.

    Science.gov (United States)

    Graiver, Natalia; Califano, Alicia; Zaritzky, Noemí

    2011-11-01

    Three categories of seed storage behavior are generally recognized among plant species: orthodox, intermediate and recalcitrant. Intermediate seeds cannot be stored in liquid nitrogen (LN) without a previous partial dehydration process. The water content (WC) of the seeds at the moment of immersion in LN must be regarded as the most critical factor in cryopreservation. The purpose of this study was to investigate the basis of the optimal hydration status for cryopreservation of Citrus seeds: C. sinensis (sweet orange), C. paradisi (grapefruit), C. reticulata (mandarin) in LN. To study the tolerance to dehydration and LN exposure, seeds were desiccated by equilibration at relative humidities between 11 and 95%. Sorption isotherms were determined and modeled; lipid content of the seeds was measured. Seed desiccation sensitivity was quantified by the quantal response model. Differential scanning calorimetry (DSC) thermograms were determined on cotyledon tissue at different moisture contents to measure ice melting enthalpies and unfrozen WC. Samples of total seed lipid extract were also analyzed by DSC to identify lipid transitions in the thermograms. The limit of hydration for LN Citrus seeds treatment corresponded to the unfrozen WC in the tissue, confirming that seed survival strictly depended on avoidance of intracellular ice formation. Copyright © 2011 Society of Chemical Industry.

  17. The structure of hydrate bearing fine grained marine sediments

    Energy Technology Data Exchange (ETDEWEB)

    Priest, J.; Kingston, E.; Clayton, C. [Southampton Univ., Highfield (United Kingdom). School of Civil Engineering and the Environment; Schultheiss, P.; Druce, M. [Geotek Ltd., Daventry (United Kingdom)

    2008-07-01

    This paper discussed the structure of naturally occurring methane gas hydrates in fine-grained sediments from core samples recovered using in situ pressures from the eastern margin of the Indian Ocean. High resolution X-ray computed tomography (CT) images were taken of gas hydrate cores. The hydrate structure was examined and comparisons were made between low resolution X-ray images obtained on the cores prior to sub-sectioning and depressurization procedures. The X-ray images showed the presence of high-angle, sub-parallel veins within the recovered sediments. The scans indicated that the hydrates occurred as fracture filing veins throughout the core. Fracture orientation was predominantly sub-vertical. Thick millimetric hydrate veins were composed of sub-millimetric veins with variations in fracture angle. The analysis indicated that hydrate formation was episodic in nature and subject to changes in the stress regime. Results of the study showed that depressurization and subsequent freezing alter the structure of the sediment even when the gas hydrate has not been altered. A large proportion of the hydrate survived when outside of its stability region. The self-preserving behaviour of the hydrate was attributed to the endothermic nature of gas hydrate dissociation. It was concluded that the accurate physical characterization of gas hydrates can only be conducted when the core section remains under in situ stress conditions. 13 refs., 9 figs.

  18. Carbon dioxide hydrate formation in a fixed-bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Fan, S.; Lang, X. [South China Univ. of Technology, Guangzhou (China). Key Laboratory of Enhanced Heat Transfer and Energy Conservation; Wang, Y.; Liang, D. [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion and Guangzhou Center of Natural Gas Hydrate; Sun, X.; Jurcik, B. [Air Liquide Laboratories, Tsukuba (Japan)

    2008-07-01

    Gas hydrates are thermodynamically stable at high pressures and near the freezing temperature of pure water. Methane hydrates occur naturally in sediments in the deep oceans and permafrost regions and constitute an extensive hydrocarbon reservoir. Carbon dioxide (CO{sub 2}) hydrates are of interest as a medium for marine sequestration of anthropogenic carbon dioxide. Sequestering CO{sub 2} as hydrate has potential advantages over most methods proposed for marine CO{sub 2} sequestration. Because this technique requires a shallower depth of injection when compared with other ocean sequestration methods, the costs of CO{sub 2} hydrate sequestration may be lower. Many studies have successfully used different continuous reactor designs to produce CO{sub 2} hydrates in both laboratory and field settings. This paper discussed a study that involved the design and construction of a fixed-bed reactor for simulation of hydrate formation system. Water, river sands and carbon dioxide were used to simulate the seep kind of hydrate formation. Carbon dioxide gas was distributed as small bubbles to enter from the bottom of the fixed-bed reactor. The paper discussed the experimental data and presented a diagram of the gas hydrate reactor system. The morphology as well as the reaction characters of CO{sub 2} hydrate was presented in detail. The results were discussed in terms of experimental phenomena and hydrate formation rate. A mathematical model was proposed for describing the process. 17 refs., 7 figs.

  19. Indian National Gas Hydrate Program Expedition 01 report

    Science.gov (United States)

    Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.V.; ,

    2015-01-01

    Gas hydrate is a naturally occurring “ice-like” combination of natural gas and water that has the potential to serve as an immense resource of natural gas from the world’s oceans and polar regions. However, gas-hydrate recovery is both a scientific and a technical challenge and much remains to be learned about the geologic, engineering, and economic factors controlling the ultimate energy resource potential of gas hydrate. The amount of natural gas contained in the world’s gas-hydrate accumulations is enormous, but these estimates are speculative and range over three orders of magnitude from about 2,800 to 8,000,000 trillion cubic meters of gas. By comparison, conventional natural gas accumulations (reserves and undiscovered, technically recoverable resources) for the world are estimated at approximately 440 trillion cubic meters. Gas recovery from gas hydrate is hindered because the gas is in a solid form and because gas hydrate commonly occurs in remote Arctic and deep marine environments. Proposed methods of gas recovery from gas hydrate generally deal with disassociating or “melting” in situ gas hydrate by heating the reservoir beyond the temperature of gas-hydrate formation, or decreasing the reservoir pressure below hydrate equilibrium. The pace of energy-related gas hydrate assessment projects has accelerated over the past several years.

  20. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

    Energy Technology Data Exchange (ETDEWEB)

    Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1N 6N5 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

    2016-01-28

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  1. Natural gas hydrates. Experimental techniques and their applications

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Yuguang; Liu, Changling (eds.) [Qingdao Institute of Marine Geology (China). Gas Hydrate Laboratory

    2013-07-01

    Focuses on gas hydrate experiment in laboratory. Intends to provide practical significant parameters for gas hydrate exploration and exploitation in the oceanic and permafrost environments. Consists of different themes that present up-to-date information on hydrate experiments. ''Natural Gas Hydrates: Experimental Techniques and Their Applications'' attempts to broadly integrate the most recent knowledge in the fields of hydrate experimental techniques in the laboratory. The book examines various experimental techniques in order to provide useful parameters for gas hydrate exploration and exploitation. It provides experimental techniques for gas hydrates, including the detection techniques, the thermo-physical properties, permeability and mechanical properties, geochemical abnormalities, stability and dissociation kinetics, exploitation conditions, as well as modern measurement technologies etc.

  2. Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

    DEFF Research Database (Denmark)

    Takeya, Kei; Zhang, Caihong; Kawayama, Iwao

    2009-01-01

    For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has...... a characteristic broad absorption peak at 0.5 THz corresponding to the dipole moment of THF molecules. The refractive indices of THF and propane hydrates are 1.725 and 1.775 at 1 THz, respectively, and show a slight but clear difference from the refractive index of ice (1.79). THz-TDS is a potentially useful...... technique for the ondestructive inspection of gas hydrates. # 2009 The Japan Society of Applied Physics...

  3. Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

    Science.gov (United States)

    Camilleri, J; Sorrentino, F; Damidot, D

    2015-04-01

    BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited

  4. In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    Science.gov (United States)

    Lee, M.W.; Collett, T.S.

    2011-01-01

    In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

  5. LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

    KAUST Repository

    Lei, L.; Santamarina, Carlos

    2018-01-01

    Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

  6. Modeling dissociation behaviour of methane hydrate in porous soil media

    Energy Technology Data Exchange (ETDEWEB)

    Jayasinghe, A.G.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

    2008-07-01

    Gas hydrates, or clathrates, exist in the form of crystalline solid structures of hydrogen bonded water molecules where the lattice cages are occupied by guest gas molecules. Methane gas hydrates are the most common. As such, hydrate bearing sediments are considered to be a potential future energy resource. Gas hydrates also function as a source or sink for atmospheric methane, which may influence global warming. The authors emphasized that an understanding of the behaviour of soils containing gas hydrates is necessary in order to develop ways of recovering the vast gas resources that exist in the form of hydrates, particularly since hydrates are also suspected to be a potential factor in the initiation and propagation of submarine slope failures. Gas hydrate dissociation occurs when water and gas are released, resulting in an increase in pore fluid pressure, thereby causing significant reductions in effective stress leading to sediment failure. Dissociation may occur as a result of pressure reductions or increases in temperature. This study focused on the strength and deformation behaviour of hydrate bearing soils associated with temperature induced dissociation. Modeling the dissociation behavior of hydrates in porous soil media involves an understanding of the geomechanics of hydrate dissociation. This paper addressed the issue of coupling the hydrate dissociation problem with the soil deformation problem. A mathematical framework was constructed in which the thermally stimulated hydrate dissociation process in porous soil media under undrained conditions was considered with conduction heat transfer. It was concluded that a knowledge of geomechanical response of hydrate bearing sediments will enable better estimates of benefits and risks associated with the recovery process, thereby ensuring safe and economical exploration. 20 refs., 1 fig., 1 appendix.

  7. LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

    KAUST Repository

    Lei, L.

    2018-04-02

    Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

  8. George de Hevesy (1885-1966). Discoverer of hafnium, founder of radioanalytical chemistry and X-ray fluorescence analysis and father of nuclear medicine

    International Nuclear Information System (INIS)

    Niese, Siegfried

    2017-01-01

    George de Hevesy known as discoverer of hafnium, founder of radioanalytical chemistry and X-ray fluorescence analysis and father of nuclear medicine has done important research work in inorganic, physical and radioanalytical and physiological chemistry as well as in geochemistry, radiation biology and medicine. When he must flee for political reasons from a country he must change his colleagues, his equipments, and the topic of his work. It is extremely surprising that he could receive important results under such circumstances even at an advanced age. (author)

  9. A spanish mineral of zirconium and hafnium. Separation of the two elements by liquid-liquid extraction, using tributyl phosphate as chelating agent

    International Nuclear Information System (INIS)

    Ruiz Sanchez, F.; Cruz Castillo, F. de la; Fernandez Cellini, R.

    1962-01-01

    The zirconium and Hafnium oxides are obtained from a Spanish mineral of zircon with an average contest of 55% in ZrO 2 -HfO 2 . An alkaline fusion to open the mineral, followed by a purification by crystallization as (Zr O-Hf O)Cl 2 H 2 O or as (Zr-Hf) (SO 4 ) 2 . 4H 2 O, is used. A discussion of the best experimental conditions for opening the mineral and of the purification method is made. (Author) 45 refs

  10. FY1995 molecular control technology for mining of methane-gas-hydrate; 1995 nendo methane hydrate no bunshi seigyo mining

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    The objectives of the investigation are as follows: 1) developing a method to control formation/dissociation of methane-gas-hydrate, 2) developing a technology to displace methane gas by CO{sub 2} in methane-gas-hydrate deposit, 3) developing a technology to produce methane gas from the deposit efficiently. The final purpose of the project is to create new mining industry that solves both the problems of energy and global environment. 1) Clustering of water molecules is found to play the key role in the methane gas hydrate formation. 2) Equilibrium properties and kinetics of gas hydrates formation and dissociation in bulk-scale gas-hydrate are clarified in the practical environmental conditions. 3) Particle size of hydrate deposit influences the formation and dissociation of bulk-scale gas-hydrate crystal. 4) Mass transfer between gas and liquid phase in turbulent bubbly flow is a function of bubble diameter. The mass transfer depends on interfacial dynamics. (NEDO)

  11. Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

    Science.gov (United States)

    Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

    2014-01-01

    The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins.

  12. The effects of silica fume and hydrated lime on the strength development and durability characteristics of concrete under hot water curing condition

    Directory of Open Access Journals (Sweden)

    Hamza Ali

    2017-01-01

    Full Text Available Sustainability is considered to be highly important for preserving continued industrial growth and human development. Concrete, being the world’s largest manufacturing material comprises cement as an essential binding component for strength development. However, excessive production of cement due to high degree of construction practices around the world frames cement as a leading pollutant of releasing significant amounts of CO2 in the atmosphere. To overcome this environmental degradation, silica fume and hydrated lime are used as partial replacements to cement. This paper begins with the examination of the partial replacement levels of hydrated lime and silica fume in concrete and their influence on the mechanical properties and durability characteristics of concrete. The effect of hot water curing on concrete incorporated with both silica fume and hydrated lime is also investigated in this paper. The results reported in this paper show that the use of silica fume as a partial replacement material improved both the mechanical properties and durability characteristics of concrete due to the formation of calcium silica hydrate crystals through the pozzolanic reaction. Although the hydrated lime did not significantly contribute in the development of strength, its presence enhanced the durability of concrete especially at long-term. The results also showed that hot water curing enhanced the strength development of concrete incorporated with silica fume due to the accelerated rate of both the hydration and pozzolanic reaction that takes place between silica fume and calcium hydroxide of the cement matrix particularly at early times. The results reported in this paper have significant contribution in the development of sustainable concrete. The paper does not only address the use of alternative binders as a partial replacement material in concrete but also suggest proper curing conditions for the proposed replacement materials. These practices

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

    Science.gov (United States)

    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

  14. Obsidian hydration dating of volcanic events

    Science.gov (United States)

    Friedman, I.; Obradovich, J.

    1981-01-01

    Obsidian hydration dating of volcanic events had been compared with ages of the same events determined by the 14C and KAr methods at several localities. The localities, ranging in age from 1200 to over 1 million yr, include Newberry Craters, Oregon; Coso Hot Springs, California; Salton Sea, California; Yellowstone National Park, Wyoming; and Mineral Range, Utah. In most cases the agreement is quite good. A number of factors including volcanic glass composition and exposuretemperature history must be known in order to relate hydration thickness to age. The effect of composition can be determined from chemical analysis or the refractive index of the glass. Exposure-temperature history requires a number of considerations enumerated in this paper. ?? 1981.

  15. Experimental techniques for cement hydration studies

    Directory of Open Access Journals (Sweden)

    Andreas Luttge

    2011-10-01

    Full Text Available Cement hydration kinetics is a complex problem of dissolution, nucleation and growth that is still not well understood, particularly in a quantitative way. While cement systems are unique in certain aspects they are also comparable to natural mineral systems. Therefore, geochemistry and particularly the study of mineral dissolution and growth may be able to provide insight and methods that can be utilized in cement hydration research. Here, we review mainly what is not known or what is currently used and applied in a problematic way. Examples are the typical Avrami approach, the application of Transition State Theory (TST to overall reaction kinetics and the problem of reactive surface area. Finally, we suggest an integrated approach that combines vertical scanning interferometry (VSI with other sophisticated analytical techniques such as atomic force microscopy (AFM and theoretical model calculations based on a stochastic treatment.

  16. Limitation of biocompatibility of hydrated nanocrystalline hydroxyapatite

    Science.gov (United States)

    Minaychev, V. V.; Teleshev, A. T.; Gorshenev, V. N.; Yakovleva, M. A.; Fomichev, V. A.; Pankratov, A. S.; Menshikh, K. A.; Fadeev, R. S.; Fadeeva, I. S.; Senotov, A. S.; Kobyakova, M. I.; Yurasova, Yu B.; Akatov, V. S.

    2018-04-01

    Nanostructured hydroxyapatite (HA) in the form of hydrated paste is considered to be a promising material for a minor-invasive surgical curing of bone tissue injure. However questions about adhesion of cells on this material and its biocompatibility still remain. In this study biocompatibility of paste-formed nanosized HA (nano-HA) by in vitro methods is investigated. Nano-HA (particles sized about 20 nm) was synthesized under conditions of mechano-acoustic activation of an aqueous reaction mixture of ammonium hydrophosphate and calcium nitrate. It was ascertained that nanocrystalline paste was not cytotoxic although limitation of adhesion, spreading and growth of the cells on its surface was revealed. The results obtained point on the need of modification of hydrated nano-HA in the aims of increasing its biocompatibility and osteoplastic potential.

  17. Predicting hydration energies for multivalent ions

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Stipp, Susan Louise Svane

    2014-01-01

    We have predicted the free energy of hydration for 40 monovalent and multivalent cations and anions using density functional theory and the implicit solvent model COnductor like Screening MOdel for Real Solvents (COSMO-RS) at the Becke-Perdew (BP)/Triple zeta valence with polarization functions...... (TZVP) level. Agreement with experimental data for monovalent and divalent ions is good and shows no significant systematic errors. Predictions are noticeably better than with standard COSMO. The agreement with experimental data for trivalent and tetravalent ions is slightly worse and shows systematic...... errors. Our results indicate that quantum chemical calculations combined with COSMO-RS solvent treatment is a reliable method for treating multivalent ions in solution, provided one hydration shell of explicit water molecules is included for metal cations. The accuracy is not high enough to allow...

  18. Advances in understanding hydration of Portland cement

    International Nuclear Information System (INIS)

    Scrivener, Karen L.; Juilland, Patrick; Monteiro, Paulo J.M.

    2015-01-01

    Progress in understanding hydration is summarized. Evidence supports the geochemistry dissolution theory as an explanation for the induction period, in preference to the inhibiting layer theory. The growth of C–S–H is the principal factor controlling the main heat evolution peak. Electron microscopy indicates that C–S–H “needles” grow from the surface of grains. At the peak, the surface is covered, but deceleration cannot be attributed to diffusion control. The shoulder peak comes from renewed reaction of C 3 A after depletion of sulfate in solution, but release of sulfate absorbed on C–S–H means that ettringite continues to form. After several days space becomes the major factor controlling hydration. The use of new analytical technique is improving our knowledge of the action of superplasticizers and leading to the design of molecules for different applications. Atomistic modeling is becoming a topic of increasing interest. Recent publications in this area are reviewed

  19. Phosphate vibrations as reporters of DNA hydration

    Science.gov (United States)

    Corcelli, Steven

    The asymmetric phosphate stretch vibrational frequency is extraordinarily sensitive to its local solvent environment. Using density functional theory calculations on the model compound dimethyl phosphate, the asymmetric phosphate stretch vibrational frequency was found to shift linearly with the magnitude of an electric field along the symmetry axis of the PO2 moiety (i.e. the asymmetric phosphate stretch is an excellent linear vibrational Stark effect probe). With this linear relationship established, asymmetric phosphate stretch vibrational frequencies were computed during the course of a molecular dynamics simulation of fully hydrated DNA. Moreover, contributions to shifts in the frequencies from subpopulations of water molecules (e.g. backbone, minor groove, major groove, etc.) were calculated to reveal how phosphate vibrations report the onset of DNA hydration in experiments that vary the relative humidity of non-condensing (dry) DNA samples.

  20. Advances in understanding hydration of Portland cement

    Energy Technology Data Exchange (ETDEWEB)

    Scrivener, Karen L., E-mail: Karen.scrivener@epfl.ch [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, 1015 (Switzerland); Juilland, Patrick [Sika Technology AG, Zürich (Switzerland); Monteiro, Paulo J.M. [Department of Civil and Environmental Engineering, University of California at Berkeley (United States)

    2015-12-15

    Progress in understanding hydration is summarized. Evidence supports the geochemistry dissolution theory as an explanation for the induction period, in preference to the inhibiting layer theory. The growth of C–S–H is the principal factor controlling the main heat evolution peak. Electron microscopy indicates that C–S–H “needles” grow from the surface of grains. At the peak, the surface is covered, but deceleration cannot be attributed to diffusion control. The shoulder peak comes from renewed reaction of C{sub 3}A after depletion of sulfate in solution, but release of sulfate absorbed on C–S–H means that ettringite continues to form. After several days space becomes the major factor controlling hydration. The use of new analytical technique is improving our knowledge of the action of superplasticizers and leading to the design of molecules for different applications. Atomistic modeling is becoming a topic of increasing interest. Recent publications in this area are reviewed.

  1. Modelling porewater chemistry in hydrated Portland cement

    International Nuclear Information System (INIS)

    Berner, U.R.

    1987-01-01

    Extensive employment of concrete is foreseen in radioactive waste repositories. A prerequisite for modelling the interactions between concrete and formation waters is characterization of the concrete system. Available experimental data from high pressure squeezing of cement pore-water indicate that, besides the high pH due to alkali hydroxide dissolution, cement composition itself influences the solubility determining solid phases. A model which simulates the hydration of Portland cement assuming complete hydration of the main clinker minerals is presented. The model also includes parameters describing the reactions between the cement and blending agents. Comparison with measured pore-water data generally gives a consistent picture and, as expected, the model gives correct predictions for pure Portland cements. For blended cements, the required additional parameters can, to some extent, be derived from pore-water analysis. 14 references, 1 figure, 4 tables

  2. Propane hydrate nucleation: Experimental investigation and correlation

    DEFF Research Database (Denmark)

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas

    2008-01-01

    supersaturation region. The experiments showed that the gas dissolution rate rather than the induction time of propane hydrate is influenced by a change in agitation. This was especially valid at high stirring rates when the water surface was severely disturbed.Addition of polyvinylpyrrolidone (PVP......) to the aqueous phase was found to reduce the gas dissolution rate slightly. However the induction times were prolonged quite substantially upon addition of PVP.The induction time data were correlated using a newly developed induction time model based on crystallization theory also capable of taking into account...... the presence of additives. In most cases reasonable agreement between the data and the model could be obtained. The results revealed that especially the effective surface energy between propane hydrate and water is likely to change when the stirring rate varies from very high to low. The prolongation...

  3. Non-invasive measurement of corneal hydration.

    Science.gov (United States)

    March, W F; Bauer, N J

    2001-01-01

    To investigate the feasibility of a confocal Raman spectroscopic technique for the noncontact assessment of corneal hydration in vivo in two legally blind subjects. A laser beam (632.8 nm; 15 mJ) was maintained on the cornea using a microscope objective lens (25x magnification, NA=0.5, f=10 mm) both for focusing the incident light as well as collecting the Raman backscattered light, in a 180 degrees backscatter configuration. An optical fiber, acting as the confocal pinhole for elimination of light from out-of-focus places, was coupled to a spectrometer that dispersed the collected light onto a sensitive array-detector for rapid spectral data acquisition over a range from 2,890 to 3,590 cm(-1). Raman spectra were recorded from the anterior 100 to 150 microm of the cornea over a period of time before and after topical application of a mild dehydrating solution. The ratio between the amplitudes of the signals at 3,400 cm(-1) (OH-vibrational mode of water) and 2,940 cm(-1) (CH-vibrational mode of proteins) was used as a measure of corneal hydration. High signal-to-noise ratio (SNR 25) Raman spectra were obtained from the human corneas using 15 mJ of laser light energy. Qualitative changes in the hydration of the anterior-most part of the corneas could be observed as a result of the dehydrating agent. Confocal Raman spectroscopy could potentially be applied clinically as a noncontact tool for the assessment of corneal hydration in vivo.

  4. Hydration benefits to courtship feeding in crickets

    OpenAIRE

    Ivy, T. M.; Johnson, J. C.; Sakaluk, S. K.

    1999-01-01

    The spermatophore transferred by male decorated crickets (Gryllodes sigillatus) at mating includes a large gelatinous spermatophylax that the female consumes after copulation. Although previous studies have shown that G. sigillatus females gain no nutritional benefits from consuming food gifts, there may be other benefits to their consumption. We examined potential hydration benefits to females by experimentally manipulating both the availability of water and the number of food gifts that fem...

  5. Unraveling halide hydration: A high dilution approach.

    Science.gov (United States)

    Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

    2014-07-28

    The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

  6. Reservoir Models for Gas Hydrate Numerical Simulation

    Science.gov (United States)

    Boswell, R.

    2016-12-01

    Scientific and industrial drilling programs have now providing detailed information on gas hydrate systems that will increasingly be the subject of field experiments. The need to carefully plan these programs requires reliable prediction of reservoir response to hydrate dissociation. Currently, a major emphasis in gas hydrate modeling is the integration of thermodynamic/hydrologic phenomena with geomechanical response for both reservoir and bounding strata. However, also critical to the ultimate success of these efforts is the appropriate development of input geologic models, including several emerging issues, including (1) reservoir heterogeneity, (2) understanding of the initial petrophysical characteristics of the system (reservoirs and seals), the dynamic evolution of those characteristics during active dissociation, and the interdependency of petrophysical parameters and (3) the nature of reservoir boundaries. Heterogeneity is ubiquitous aspect of every natural reservoir, and appropriate characterization is vital. However, heterogeneity is not random. Vertical variation can be evaluated with core and well log data; however, core data often are challenged by incomplete recovery. Well logs also provide interpretation challenges, particularly where reservoirs are thinly-bedded due to limitation in vertical resolution. This imprecision will extend to any petrophysical measurements that are derived from evaluation of log data. Extrapolation of log data laterally is also complex, and should be supported by geologic mapping. Key petrophysical parameters include porosity, permeability and it many aspects, and water saturation. Field data collected to date suggest that the degree of hydrate saturation is strongly controlled by/dependant upon reservoir quality and that the ratio of free to bound water in the remaining pore space is likely also controlled by reservoir quality. Further, those parameters will also evolve during dissociation, and not necessary in a simple

  7. The combined effect of thermodynamic promoters tetrahydrofuran and cyclopentane on the kinetics of flue gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas

    2015-01-01

    ) hydrate formation using a rocking cell apparatus. Hydrate formation and decomposition kinetics were investigated by constant cooling (hydrate nucleation temperature) and isothermal (hydrate nucleation time) methods. Improved (synergistic) hydrate formation kinetics (hydrate nucleation and growth) were...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

  8. Experimental solid state NMR of gas hydrates : problems and solutions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

    2008-07-01

    Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

  9. Effect of Gemini-type surfactant on methane hydrate formation

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, K.E.; Park, J.M.; Kim, C.U.; Chae, H.J.; Jeong, S.Y. [Korea Research Inst. of Chemical Technology, Jang-Dong, Yuseong-Gu, Daejeon (Korea, Republic of)

    2008-07-01

    Natural gas hydrates are formed from water and natural gas molecules at particular temperatures and pressures that become ice-like inclusion compounds. Gas hydrates offer several benefits such as energy resource potential and high storage capacity of natural gas in the form of hydrates. However, the application of natural gas hydrates has been deterred by its low formation rate and low conversion ratio of water into hydrate resulting in low actual storage capacity. This paper presented an experimental study to determine the effect of adding a novel Gemini-type surfactant on methane hydrate formation. The experimental study was described with reference to the properties of prepared diols and properties of prepared disulfonates. Gemini surfactant is the family of surfactant molecules possessing more than one hydrophobic tail and hydrophilic head group. They generally have better surface-active properties than conventional surfactants of equal chain length. The paper presented the results of the study in terms of the reactions of diols with propane sultone; storage capacity of hydrate formed with and without surfactant; and methane hydrate formation with and without disulfonate. It was concluded that the methane hydrate formation was accelerated by the addition of novel anionic Gemini-type surfactants and that hydrate formation was influenced by the surfactant concentration and alkyl chain length. For a given concentration, the surfactant with the highest chain length demonstrated the highest formation rate and storage capacity. 5 refs., 3 tabs., 4 figs.

  10. Carbon dioxide gas hydrates accumulation in freezing and frozen sediments

    Energy Technology Data Exchange (ETDEWEB)

    Chuvilin, E.; Guryeva, O. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology

    2008-07-01

    Carbon dioxide (CO{sub 2}) hydrates and methane hydrates can be formed, and exist under natural conditions. The permafrost area has been considered as an environment for the potential disposal of CO{sub 2}. The favorable factors for preserving CO{sub 2} in liquid and gas hydrate states in frozen sediments and under permafrost horizons are great thickness of frozen sediments; low permeability in comparison with thawed sediments; and favourable conditions for hydrates formation. Therefore, research on the formation and existence conditions of CO{sub 2} gas hydrates in permafrost and under permafrost sediments are of great importance for estimation of CO{sub 2} disposal conditions in permafrost, and for working out specific sequestration schemes. This paper presented the results of an experimental study on the process of carbon dioxide (CO{sub 2}) gas hydrates formation in the porous media of sediments under positive and negative temperatures. Sediment samples of various compositions including those selected in the permafrost area were used. The research was conducted in a special pressure chamber, which allowed to monitor pressure and temperature. The study used the monitoring results in order to make quantitative estimation of the kinetics of CO{sub 2} hydrates accumulation in the model sediments. Results were presented in terms of kinetics of CO{sub 2} hydrates accumulation in the porous media at positive and negative temperatures; kinetics of CO{sub 2} hydrates accumulation in various porous media; gas hydrate-former influence on kinetics of hydrates accumulation in frozen sediments; and influence of freezing on CO{sub 2} hydrates accumulation in porous media. It was concluded that hydrate accumulation took an active place in porous media not only under positive, but also under high negative temperatures, when the water was mainly in the form of ice in porous media. 27 refs., 3 tabs., 5 figs.

  11. Polymorphism in Br2 clathrate hydrates.

    Science.gov (United States)

    Goldschleger, I U; Kerenskaya, G; Janda, K C; Apkarian, V A

    2008-02-07

    The structure and composition of bromine clathrate hydrate has been controversial for more than 170 years due to the large variation of its observed stoichiometries. Several different crystal structures were proposed before 1997 when Udachin et al. (Udachin, K. A.; Enright, G. D.; Ratcliffe, C. I.; Ripmeester, J. A. J. Am. Chem. Soc. 1997, 119, 11481) concluded that Br2 forms only the tetragonal structure (TS-I). We show polymorphism in Br2 clathrate hydrates by identifying two distinct crystal structures through optical microscopy and resonant Raman spectroscopy on single crystals. After growing TS-I crystals from a liquid bromine-water solution, upon dropping the temperature slightly below -7 degrees C, new crystals of cubic morphology form. The new crystals, which have a limited thermal stability range, are assigned to the CS-II structure. The two structures are clearly distinguished by the resonant Raman spectra of the enclathrated Br2, which show long overtone progressions and allow the extraction of accurate vibrational parameters: omega(e) = 321.2 +/- 0.1 cm(-1) and omega(e)x(e) = 0.82 +/- 0.05 cm(-1) in TS-I and omega(e) = 317.5 +/- 0.1 cm(-1) and omega(e)x(e) = 0.70 +/- 0.1 cm(-1) in CS-II. On the basis of structural analysis, the discovery of the CS-II crystals implies stability of a large class of bromine hydrate structures and, therefore, polymorphism.

  12. The economics of exploiting gas hydrates

    International Nuclear Information System (INIS)

    Döpke, Lena-Katharina; Requate, Till

    2014-01-01

    We investigate the optimal exploitation of methane hydrates, a recent discovery of methane resources under the sea floor, mainly located along the continental margins. Combustion of methane (releasing CO2) and leakage through blow-outs (releasing CH4) contribute to the accumulation of greenhouse gases. A second externality arises since removing solid gas hydrates from the sea bottom destabilizes continental margins and thus increases the risk of marine earthquakes. We show that in such a model three regimes can occur: i) resource exploitation will be stopped in finite time, and some of the resource will stay in situ, ii) the resource will be used up completely in finite time, and iii) the resource will be exhausted in infinite time. We also show how to internalize the externalities by policy instruments. - Highlights: • We set up a model of optimal has hydrate exploitation • We incorporate to types of damages: contribution to global warming and geo-hazards • We characterize optimal exploitation paths and study decentralization with an exploitation tax. • Three regimes can occur: • i) exploitation in finite time and some of the stock remaining in situ, • ii) exploitation in finite time and the resource will be exhausted, • iii) exploitation and exhaustion in infinite time

  13. Raman spectroscopic studies of hydrogen clathrate hydrates.

    Science.gov (United States)

    Strobel, Timothy A; Sloan, E Dendy; Koh, Carolyn A

    2009-01-07

    Raman spectroscopic measurements of simple hydrogen and tetrahydrofuran+hydrogen sII clathrate hydrates have been performed. Both the roton and vibron bands illuminate interesting quantum dynamics of enclathrated H(2) molecules. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature, measuring the absolute H(2) content as a function of pressure, and with D(2) isotopic substitution. Quadruple occupancy of the large sII clathrate cavity shows the highest H(2) vibrational frequency, followed by triple and double occupancies. Singly occupied small cavities display the lowest vibrational frequency. The vibrational frequencies of H(2) within all cavity environments are redshifted from the free gas phase value. At 76 K, the progression from ortho- to para-H(2) occurs over a relatively slow time period (days). The rotational degeneracy of H(2) molecules within the clathrate cavities is lifted, observed directly in splitting of the para-H(2) roton band. Raman spectra from H(2) and D(2) hydrates suggest that the occupancy patterns between the two hydrates are analogous, increasing confidence that D(2) is a suitable substitute for H(2). The measurements suggest that Raman is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

  14. Electronic structure calculations of calcium silicate hydrates

    International Nuclear Information System (INIS)

    Sterne, P.A.; Meike, A.

    1995-11-01

    Many phases in the calcium-silicate-hydrate system can develop in cement exposed over long periods of time to temperatures above 25 C. As a consequence, chemical reactions involving these phases can affect the relative humidity and water chemistry of a radioactive waste repository that contains significant amounts of cement. In order to predict and simulate these chemical reactions, the authors are developing an internally consistent database of crystalline Ca-Si-hydrate structures. The results of first principles electronic structure calculations on two such phases, wollastonite (CaSiO 3 ) and xonotlite (Ca 6 Si 6 O 17 (OH) 2 ), are reported here. The calculated ground state properties are in very good agreement with experiment, providing equilibrium lattice parameters within about 1--1.4% of the experimentally reported values. The roles of the different types of oxygen atoms, which are fundamental to understanding the energetics of crystalline Ca-Si-hydrates are briefly discussed in terms of their electronic state densities. The good agreement with experiment for the lattice parameters and the consistency of the electronic density of states features for the two structures demonstrate the applicability of these electronic structure methods in calculating the fundamental properties of these phases

  15. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  16. Evaluation of Hydrate Inhibition Performance of Water-soluble Polymers using Torque Measurement and Differential Scanning Calorimeter

    International Nuclear Information System (INIS)

    Shin, Kyuchul; Park, Juwoon; Kim, Jakyung; Kim, Hyunho; Seo, Yutaek; Lee, Yohan; Seo, Yongwon

    2014-01-01

    In this work, hydrate inhibition performance of water-soluble polymers including pyrrolidone, caprolactam, acrylamide types were evaluated using torque measurement and high pressure differential scanning calorimeter (HP µ-DSC). The obtained experimental results suggest that the studied polymers represent the kinetic hydrate inhibition (KHI) performance. 0.5 wt% polyvinylcaprolactam (PVCap) solution shows the hydrate onset time of 34.4 min and subcooling temperature of 15.9 K, which is better KHI performance than that of pure water - hydrate onset time of 12.3 min and subcooling temperature of 6.0 K. 0.5 wt% polyvinylpyrrolidone (PVP) solution shows the hydrate onset time of 27.6 min and the subcooling temperature of 13.2 K while polyacrylamide-co-acrylic acid partial sodium salt (PAM-co-AA) solution shows less KHI performance than PVP solution at both 0.5 and 5.0 wt%. However, PAM-co-AA solution shows slow growth rate and low hydrate amount than PVCap. In addition to hydrate onset and growth condition, torque change with time was investigated as one of KHI evaluation methods. 0.5 wt% PVCap solution shows the lowest average torque of 6.4 N cm and 0.5 wt% PAM-co-AA solution shows the average torque of 7.2 N cm. For 0.5 wt% PVP solution, it increases 11.5 N cm and 5.0 wt% PAM-co-AA solution shows the maximum average torque of 13.4 N cm, which is similar to the average torque of pure water, 15.2 N cm. Judging from the experimental results obtained by both an autoclave and a HP µ-DSC, the PVCap solution shows the best performance among the KHIs in terms of delaying hydrate nucleation. From these results, it can be concluded that the torque change with time is useful to identify the flow ability of tested solution, and the further research on the inhibition of hydrate formation can be approached in various aspects using a HP µ-DSC

  17. Protein Hydration Thermodynamics: The Influence of Flexibility and Salt on Hydrophobin II Hydration.

    Science.gov (United States)

    Remsing, Richard C; Xi, Erte; Patel, Amish J

    2018-04-05

    The solubility of proteins and other macromolecular solutes plays an important role in numerous biological, chemical, and medicinal processes. An important determinant of protein solubility is the solvation free energy of the protein, which quantifies the overall strength of the interactions between the protein and the aqueous solution that surrounds it. Here we present an all-atom explicit-solvent computational framework for the rapid estimation of protein solvation free energies. Using this framework, we estimate the hydration free energy of hydrophobin II, an amphiphilic fungal protein, in a computationally efficient manner. We further explore how the protein hydration free energy is influenced by enhancing flexibility and by the addition of sodium chloride, and find that it increases in both cases, making protein hydration less favorable.

  18. Indian continental margin gas hydrate prospects : results of the Indian National Gas Hydrate Program (NGHP) expedition 01

    Energy Technology Data Exchange (ETDEWEB)

    Collett, T [United States Geological Survey, Denver, CO (United States); Riedel, M. [McGill Univ., Montreal, PQ (Canada). Dept. of Earth and Planetary Sciences; Cochran, J.R. [Columbia Univ., Palisades, NY (United States). Lamont Doherty Earth Observatory; Boswell, R. [United States Dept. of Energy, Morgantown, WV (United States). National Energy Technology Lab; Kumar, P. [Pushpendra Kumar Oil and Natural Gas Corp. Ltd., Mumbai (India). Inst. of Engineering and Ocean Technology; Sathe, A.V. [Oil and Natural Gas Corp. Ltd., Uttaranchal (India). KDM Inst. of Petroleum Exploration

    2008-07-01

    The geologic occurrence of gas hydrate deposits along the continental margins of India were investigated in the first expedition of the Indian National Gas Hydrate Program (NGHP). The objective was to determine the regional context and characteristics of the gas hydrate deposits through scientific ocean drilling, logging, and analytical activities. A research drill ship was the platform for the drilling operation. The geological and geophysical studies revealed 2 geologically distinct areas with inferred gas hydrate occurrences, notably the passive continental margins of the Indian Peninsula and along the Andaman convergent margin. The NGHP Expedition 01 focused on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these 2 diverse settings. The study established the presence of gas hydrates in Krishna-Godavari, Mahanadi and Andaman basins. Site 10 in the Krishna-Godavari Basin was discovered to be the one of the richest gas hydrate accumulations yet documented, while site 17 in the Andaman Sea had the thickest and deepest gas hydrate stability zone yet known. The existence of a fully-developed gas hydrate system in the Mahanadi Basin was also discovered. Most of the gas hydrate occurrences discovered during this expedition appeared to contain mostly methane which was generated by microbial processes. However, there was also evidence of a thermal origin for a portion of the gas within the hydrates of the Mahanadi Basin and the Andaman offshore area. Gas hydrate in the Krishna-Godavari Basin appeared to be closely associated with large scale structural features, in which the flux of gas through local fracture systems, generated by the regional stress regime, controlled the occurrence of gas hydrate. 3 refs., 1 tab., 2 figs.

  19. Microbial diversity in methane hydrate-bearing deep marine sediments core preserved in the original pressure.

    Science.gov (United States)

    Takahashi, Y.; Hata, T.; Nishida, H.

    2017-12-01

    In normal coring of deep marine sediments, the sampled cores are exposed to the pressure of the atmosphere, which results in dissociation of gas-hydrates and might change microbial diversity. In this study, we analyzed microbial composition in methane hydrate-bearing sediment core sampled and preserved by Hybrid-PCS (Pressure Coring System). We sliced core into three layers; (i) outside layer, which were most affected by drilling fluids, (ii) middle layer, and (iii) inner layer, which were expected to be most preserved as the original state. From each layer, we directly extracted DNA, and amplified V3-V4 region of 16S rRNA gene. We determined at least 5000 of nucleotide sequences of the partial 16S rDNA from each layer by Miseq (Illumina). In the all layers, facultative anaerobes, which can grow with or without oxygen because they can metabolize energy aerobically or anaerobically, were detected as majority. However, the genera which are often detected anaerobic environment is abundant in the inner layer compared to the outside layer, indicating that condition of drilling and preservation affect the microbial composition in the deep marine sediment core. This study was conducted as a part of the activity of the Research Consortium for Methane Hydrate Resources in Japan [MH21 consortium], and supported by JOGMEC (Japan Oil, Gas and Metals National Corporation). The sample was provided by AIST (National Institute of Advanced Industrial Science and Technology).

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

    Energy Technology Data Exchange (ETDEWEB)

    Deschner, Florian, E-mail: florian.deschner@gmail.com [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Lothenbach, Barbara; Winnefeld, Frank [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Neubauer, Jürgen [GeoZentrum Nordbayern, Mineralogy, University of Erlangen-Nuremberg, 91054 Erlangen (Germany)

    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.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    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

  2. Focus on the Development of Natural Gas Hydrate in China

    Directory of Open Access Journals (Sweden)

    Zhongfu Tan

    2016-05-01

    Full Text Available Natural gas hydrate, also known as combustible ice, and mainly composed of methane, is identified as a potential clean energy for the 21st century. Due to its large reserves, gas hydrate can ease problems caused by energy resource shortage and has gained attention around the world. In this paper, we focus on the exploration and development of gas hydrate as well as discussing its status and future development trend in China and abroad. We then analyze its opportunities and challenges in China from four aspects, resource, technology, economy and policy, with five forces model and Politics Economics Society Technology method. The results show China has abundance gas hydrate resource; however, backward technologies and inadequate investment have seriously hindered the future development of gas hydrate; thus, China should establish relevant cooperation framework and intuitional arrangement to attract more investment as well as breaking through technical difficulties to commercialization gas hydrate as soon as possible.

  3. Raman studies of methane-ethane hydrate metastability.

    Science.gov (United States)

    Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

    2009-03-05

    The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

  4. Enzyme hydration, activity and flexibility : A neutron scattering approach

    International Nuclear Information System (INIS)

    Kurkal-Siebert, V.; Finney, J.L.; Daniel, R.M.; Smith, Jeremy C.

    2006-01-01

    Recent measurements have demonstrated enzyme activity at hydrations as low as 3%. The question of whether the hydration-induced enzyme flexibility is important for activity is addressed by performing picosecond dynamic neutron scattering experiments on pig liver esterase powders at various temperatures as well as solutions. At all temperatures and hydrations investigated here, significant quasielastic scattering intensity is found in the protein, indicating the presence of anharmonic, diffusive motion. As the hydration increases a temperature-dependent dynamical transition appears and strengthens involving additional diffusive motion. At low temperature, increasing hydration resulted in lower flexibility of the enzyme. At higher temperatures, systems containing sufficient number of water molecules interacting with the protein exhibit increased flexibility. The implication of these results is that, although the additional hydration-induced diffusive motion and flexibility at high temperatures in the enzyme detected here may be related to increased activity, they are not required for the enzyme to function

  5. Thermal conductivity measurements in unsaturated hydrate-bearing sediments

    Science.gov (United States)

    Dai, Sheng; Cha, Jong-Ho; Rosenbaum, Eilis J.; Zhang, Wu; Seol, Yongkoo

    2015-08-01

    Current database on the thermal properties of hydrate-bearing sediments remains limited and has not been able to capture their consequential changes during gas production where vigorous phase changes occur in this unsaturated system. This study uses the transient plane source (TPS) technique to measure the thermal conductivity of methane hydrate-bearing sediments with various hydrate/water/gas saturations. We propose a simplified method to obtain thermal properties from single-sided TPS signatures. Results reveal that both volume fraction and distribution of the pore constituents govern the thermal conductivity of unsaturated specimens. Thermal conductivity hysteresis is observed due to water redistribution and fabric change caused by hydrate formation and dissociation. Measured thermal conductivity increases evidently when hydrate saturation Sh > 30-40%, shifting upward from the geometric mean model prediction to a Pythagorean mixing model. These observations envisage a significant drop in sediment thermal conductivity when residual hydrate/water saturation falls below ~40%, hindering further gas production.

  6. Dissolution mechanisms of CO2 hydrate droplets in deep seawaters

    International Nuclear Information System (INIS)

    Gabitto, Jorge; Tsouris, Costas

    2006-01-01

    Carbon dioxide dissolution at intermediate ocean depths was studied using physical and mass transfer models. Particle density and hydrate layer thickness were determined using existing field data. Pseudo-homogeneous and heterogeneous mass transfer models were proposed to study the dissolution process. Pseudo-homogeneous models do not seem to represent the dissolution process well. Although heterogeneous models interpret the physical behavior better, unresolved issues related to hydrate dissolution still remain. For example, solid hydrate forms on one side of the hydrate film while it dissolves on the other. Dissolution is a complex process that comprises at least two sequential steps. The global process is controlled by mass transfer inside the hydrate layer or by a dissolution reaction at the hydrate-water interface

  7. Natural gas storage in hydrates with the presence of promoters

    International Nuclear Information System (INIS)

    Sun Zhigao; Wang Ruzhu; Ma Rongsheng; Guo Kaihua; Fan Shuanshi

    2003-01-01

    Hydrate technology is being developed for the storage and transport of natural gas. Micellar surfectant solutions were found to increase the gas hydrate formation rate and storage capacity. An anionic surfactant, a nonionic surfactant, their mixtures and cyclopentane were used to improve the hydrate formation of a synthetic natural gas (methane=92.05 mol%, ethane=4.96 mol%, propane=2.99 mol%) in a quiescent system in this work. The effect of an anionic surfactant (sodium dodecyl sulfate) on natural gas storage in hydrates is more pronounced compared to the effect of a nonionic surfactant (dodecyl polysaccharide glycoside). Cyclopentane could reduce hydrate formation induction time but could not improve the hydrate formation rate and storage capacity

  8. A fast response hafnium selective polymeric membrane electrode based on N,N'-bis(α-methyl-salicylidene)-dipropylenetriamine as a neutral carrier

    International Nuclear Information System (INIS)

    Rezaei, B.; Meghdadi, S.; Zarandi, R. Fazel

    2008-01-01

    In this study a new hafnium selective sensor was fabricated from polyvinylchloride (PVC) matrix membrane containing neutral carrier N,N'-bis(α-methyl-salicylidene)-dipropylenetriamine (Mesaldpt) as a new ionophore, sodium tetraphenyl borate (NaTPB) as anionic discriminator and dioctyl phthalate (DOP) as plasticizing solvent mediator in tetrahydrofuran solvent. The electrode exhibits Nernstian response for Hf 4+ (Hafnium(IV)) over a wide concentration range (2.0 x 10 -7 to 1.0 x 10 -1 M) with the determination coefficient of 0.9966 and slope of 15.1 ± 0.1 mV decades -1 . The limit of detection is 1.9 x 10 -7 M. The electrode has a fast response time of 18 s and a working pH range of 4-8. The proposed membrane shows excellent discriminating ability towards Hf 4+ ion with regard to several alkali, alkaline earth transition and heavy metal ions. It can be used over a period of 1.5 months with good reproducibility. It is successfully applied for direct determination of Hf 4+ in solutions by standard addition method for real sample analysis

  9. A fast response hafnium selective polymeric membrane electrode based on N,N'-bis({alpha}-methyl-salicylidene)-dipropylenetriamine as a neutral carrier

    Energy Technology Data Exchange (ETDEWEB)

    Rezaei, B. [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)], E-mail: rezaei@cc.iut.ac.ir; Meghdadi, S.; Zarandi, R. Fazel [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2008-08-30

    In this study a new hafnium selective sensor was fabricated from polyvinylchloride (PVC) matrix membrane containing neutral carrier N,N'-bis({alpha}-methyl-salicylidene)-dipropylenetriamine (Mesaldpt) as a new ionophore, sodium tetraphenyl borate (NaTPB) as anionic discriminator and dioctyl phthalate (DOP) as plasticizing solvent mediator in tetrahydrofuran solvent. The electrode exhibits Nernstian response for Hf{sup 4+} (Hafnium(IV)) over a wide concentration range (2.0 x 10{sup -7} to 1.0 x 10{sup -1} M) with the determination coefficient of 0.9966 and slope of 15.1 {+-} 0.1 mV decades{sup -1}. The limit of detection is 1.9 x 10{sup -7} M. The electrode has a fast response time of 18 s and a working pH range of 4-8. The proposed membrane shows excellent discriminating ability towards Hf{sup 4+} ion with regard to several alkali, alkaline earth transition and heavy metal ions. It can be used over a period of 1.5 months with good reproducibility. It is successfully applied for direct determination of Hf{sup 4+} in solutions by standard addition method for real sample analysis.

  10. Influence of Hydrated Lime on the Properties and Permanent Deformation of the Asphalt Concrete Layers in Pavement

    Directory of Open Access Journals (Sweden)

    Al-Tameemi Ahmed F.

    2015-07-01

    Full Text Available Flexible or asphalt concrete pavement is the paving system most widely adopted all over the world. It has been recognized that there are many different types of the factors affecting the performance and durability of asphalt concrete pavement, including the service conditions, such as: the variation of temperature from mild to extremes and the repeated excessive axle loading as well as the inadequate quality of the raw materials. All of these when combined together are going to accelerate the occurrence of distresses in flexible pavement such as permanent deformation and fatigue cracking. As the result, there has an urgent need to enhance the ability of asphalt concrete mixture to resist distresses happened in pavement. Use of additives is one of the techniques adopted to improve pavement properties. It has been found that hydrated lime might be one of the effective additives because it is widely available and relatively cheap compared to other modifiers like polymers. This paper presents an experimental study of the hydrated-lime modified asphalt concrete mixtures. Five different percentages of the hydrated lime additive were investigated, namely (1, 1.5, 2, 2.5 and 3 percent. The hydrated lime additive was used as partial replacement of limestone filler by total weight of the aggregate. The designed Hot Mix Asphalt (HMA concretes are for the application of three pavement courses, i.e. Surface, Leveling and Base. These mixtures are designed and tested following Marshall procedure and uniaxial repeated loading to evaluate permanent deformation at different temperatures of 20°C, 40°C and 60°C. The experimental results show that the addition of hydrated lime as a partial replacement of ordinary limestone mineral filler results a significant improvement on mechanical properties and the resistant to permanent deformation of the designed asphalt concrete mixtures.

  11. Obsidian hydration profiles measured by sputter-induced optical emission.

    Science.gov (United States)

    Tsong, I S; Houser, C A; Yusef, N A; Messier, R F; White, W B; Michels, J W

    1978-07-28

    The variation of concentrations of hydrogen, sodium, potassium, lithium, calcium, magnesium, silicon, and aluminum as a function of depth in the hydration layer of obsidian artifacts has been determined by sputter-induced optical emission. The surface hydration is accompanied by dealkalization, and there is a buildup of alkaline earths, calcium and magnesium in the outermost layers. These results have clarified the phenomena underlying the obsidian hydration dating technique.

  12. [Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

    Science.gov (United States)

    Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

    2015-11-01

    Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

  13. Characteristics of Methane Hydrate Formation in Artificial and Natural Media

    OpenAIRE

    Peng Zhang; Qingbai Wu; Yuzhong Yang

    2013-01-01

    The formation of methane hydrate in two significantly different media was investigated, using silica gel as an artificial medium and loess as a natural medium. The methane hydrate formation was observed through the depletion of water in the matrix, measured via the matrix potential and the relationship between the matrix potential and the water content was determined using established equations. The velocity of methane hydrate nucleation slowed over the course of the reaction, as it relied on...

  14. Small angle neutron scattering from hydrated cement pastes

    International Nuclear Information System (INIS)

    Sabine, T.M.; Bertram, W.K.; Aldridge, L.P.

    1996-01-01

    Small angle neutron scattering (SANS) was used to study the microstructure of hydrating cement made with, and without silica fume. Some significant differences were found between the SANS spectra of pastes made from OPC (ordinary Portland cement) and DSP (made with silica fume and superplasticiser). The SANS spectra are interpreted in terms of scattering from simple particles. Particle growth was monitored during hydration and it was found that the growth correlated with the heat of hydration of the cement

  15. Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

    Science.gov (United States)

    Burchwell, A.; Cook, A.

    2015-12-01

    Characterizing gas hydrate in a reservoir typically involves a full suite of geophysical well logs. The most common method involves using resistivity measurements to quantify the decrease in electrically conductive water when replaced with gas hydrate. Compressional velocity measurements are also used because the gas hydrate significantly strengthens the moduli of the sediment. At many gas hydrate sites, nuclear well logs, which include the photoelectric effect, formation sigma, carbon/oxygen ratio and neutron porosity, are also collected but often not used. In fact, the nuclear response of a gas hydrate reservoir is not known. In this research we will focus on the nuclear log response in gas hydrate reservoirs at the Mallik Field at the Mackenzie Delta, Northwest Territories, Canada, and the Gas Hydrate Joint Industry Project Leg 2 sites in the northern Gulf of Mexico. Nuclear logs may add increased robustness to the investigation into the properties of gas hydrates and some types of logs may offer an opportunity to distinguish between gas hydrate and permafrost. For example, a true formation sigma log measures the thermal neutron capture cross section of a formation and pore constituents; it is especially sensitive to hydrogen and chlorine in the pore space. Chlorine has a high absorption potential, and is used to determine the amount of saline water within pore spaces. Gas hydrate offers a difference in elemental composition compared to water-saturated intervals. Thus, in permafrost areas, the carbon/oxygen ratio may vary between gas hydrate and permafrost, due to the increase of carbon in gas hydrate accumulations. At the Mallik site, we observe a hydrate-bearing sand (1085-1107 m) above a water-bearing sand (1107-1140 m), which was confirmed through core samples and mud gas analysis. We observe a decrease in the photoelectric absorption of ~0.5 barnes/e-, as well as an increase in the formation sigma readings of ~5 capture units in the water-bearing sand as

  16. Geomechanical Performance of Hydrate-Bearing Sediment in Offshore Environments

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Holditch; Tad Patzek; Jonny Rutqvist; George Moridis; Richard Plumb

    2008-03-31

    The objective of this multi-year, multi-institutional research project was to develop the knowledge base and quantitative predictive capability for the description of geomechanical performance of hydrate-bearing sediments (hereafter referred to as HBS) in oceanic environments. The focus was on the determination of the envelope of hydrate stability under conditions typical of those related to the construction and operation of offshore platforms. We have developed a robust numerical simulator of hydrate behavior in geologic media by coupling a reservoir model with a commercial geomechanical code. We also investigated the geomechanical behavior of oceanic HBS using pore-scale models (conceptual and mathematical) of fluid flow, stress analysis, and damage propagation. The objective of the UC Berkeley work was to develop a grain-scale model of hydrate-bearing sediments. Hydrate dissociation alters the strength of HBS. In particular, transformation of hydrate clusters into gas and liquid water weakens the skeleton and, simultaneously, reduces the effective stress by increasing the pore pressure. The large-scale objective of the study is evaluation of geomechanical stability of offshore oil and gas production infrastructure. At Lawrence Berkeley National Laboratory (LBNL), we have developed the numerical model TOUGH + Hydrate + FLAC3D to evaluate how the formation and disassociation of hydrates in seafloor sediments affects seafloor stability. Several technical papers were published using results from this model. LBNL also developed laboratory equipment and methods to produce realistic laboratory samples of sediments containing gas hydrates so that mechanical properties could be measured in the laboratory. These properties are required to run TOUGH + Hydrate + FLAC3D to evaluate seafloor stability issues. At Texas A&M University we performed a detailed literature review to determine what gas hydrate formation properties had been measured and reported in the literature. We

  17. Hydration of Portoguese cements, measurement and modelling of chemical shrinkage

    DEFF Research Database (Denmark)

    Maia, Lino; Geiker, Mette Rica; Figueiras, Joaquim A.

    2008-01-01

    form of the dispersion model. The development of hydration varied between the investigated cements; based on the measured data the degree of hydration after 24 h hydration at 20 C varied between 40 and 50%. This should be taken into account when comparing properties of concrete made from the different......Development of cement hydration was studied by measuring the chemical shrinkage of pastes. Five types of Portuguese Portland cement were used in cement pastes with . Chemical shrinkage was measured by gravimetry and dilatometry. In gravimeters results were recorded automatically during at least...

  18. Ethylene Separation via Hydrate Formation in W/O Emulsions

    Directory of Open Access Journals (Sweden)

    Yong Pan

    2015-05-01

    Full Text Available An hybrid absorption-hydration method was adopted to recover C2H4 from C2H4/CH4 binary gas mixtures and the hydrate formation conditions of C2H4/CH4 mixtures was studied experimentally in diesel in water (w/o emulsions. Span 20 at a concentration of 1.0 wt% in the aqueous phase was added to form water in diesel emulsions before hydrate formation and then hydrate in diesel slurry was separated after hydrate formation. The influences of initial gas-liquid volume ratio (53–142, pressure (3.4–5.4 MPa, temperature (274.15–278.15 K, water cuts (10–30 vol%, and the mole fraction of C2H4 in feed gas (13.19–80.44 mol% upon the C2H4 separation efficiency were systematically investigated. The experimental results show that ethylene can be enriched in hydrate slurry phase with high separation factor (S and recovery ratio (R. Most hydrate formation finished in 20 min, after that, the hydrate formation rate became very slow. The conclusion is useful for determining the suitable operation conditions when adopting an absorption-hydration method to separate C2H4/CH4.

  19. Methane Production and Carbon Capture by Hydrate Swapping

    DEFF Research Database (Denmark)

    Mu, Liang; von Solms, Nicolas

    2017-01-01

    There are essentially two different approaches to producing methane from natural gas hydrate reservoirs, either bring the hydrate out of its thermodynamic stability region or expose the hydrate to a substance that will form a more stable hydrate structure, forcing an in situ swapping of the trapped...... experimental runs were performed to examine the influence of operating conditions on methane production by CO2/(CO2 + N2) injection in the temperature range of 274.15–277.15 K and 7.039–10.107 MPa pressure. Our results show that the use of the (CO2 + N2) binary gas mixture is advantageous compared to the use...

  20. HYDRATION AND MICROSTRUCTURE OF BLENDED CEMENT WITH SODIUM POLYSTYRENE SULFONATE

    Directory of Open Access Journals (Sweden)

    Weifeng Li

    2017-03-01

    Full Text Available Polystyrene foamed plastic wastes are a kind of environmental pollutant. It could be recycled in cement industry as a chemical agent. In this paper, the effects of sodium polystyrene sulfonate (SPS on the hydration and microstructure of blended cement were investigated by calorimetry, X-ray diffraction (XRD, scanning electron microscopy (SEM and mercury intrusion porosimetry (MIP. SPS slightly delayed the hydration of alite and decreased its hydration degree. SPS did not change the phase compositions during hydration. SPS changed the morphology of ettringite (AFt and decreased the pore volumes and the sizes of pores.

  1. Effects of various vehicles on skin hydration in vivo.

    Science.gov (United States)

    Wiedersberg, S; Leopold, C S; Guy, R H

    2009-01-01

    The stratum corneum, the outermost layer of the skin, regulates the passive loss of water to the environment. Furthermore, it is well accepted that drug penetration is influenced by skin hydration, which may be manipulated by the application of moisturizing or oleaginous vehicles. Measurements of transepidermal water loss (TEWL), and of skin hydration using a corneometer, were used to assess the effect of different vehicles on stratum corneum barrier function in vivo in human volunteers. A microemulsion significantly increased skin hydration relative to a reference vehicle based on medium chain triglycerides; in contrast, Transcutol(R) lowered skin hydration. TEWL measurements confirmed these observations. Copyright 2009 S. Karger AG, Basel.

  2. Hyperbolic partial differential equations

    CERN Document Server

    Witten, Matthew

    1986-01-01

    Hyperbolic Partial Differential Equations III is a refereed journal issue that explores the applications, theory, and/or applied methods related to hyperbolic partial differential equations, or problems arising out of hyperbolic partial differential equations, in any area of research. This journal issue is interested in all types of articles in terms of review, mini-monograph, standard study, or short communication. Some studies presented in this journal include discretization of ideal fluid dynamics in the Eulerian representation; a Riemann problem in gas dynamics with bifurcation; periodic M

  3. Successful removable partial dentures.

    Science.gov (United States)

    Lynch, Christopher D

    2012-03-01

    Removable partial dentures (RPDs) remain a mainstay of prosthodontic care for partially dentate patients. Appropriately designed, they can restore masticatory efficiency, improve aesthetics and speech, and help secure overall oral health. However, challenges remain in providing such treatments, including maintaining adequate plaque control, achieving adequate retention, and facilitating patient tolerance. The aim of this paper is to review the successful provision of RPDs. Removable partial dentures are a successful form of treatment for replacing missing teeth, and can be successfully provided with appropriate design and fabrication concepts in mind.

  4. Beginning partial differential equations

    CERN Document Server

    O'Neil, Peter V

    2011-01-01

    A rigorous, yet accessible, introduction to partial differential equations-updated in a valuable new edition Beginning Partial Differential Equations, Second Edition provides a comprehensive introduction to partial differential equations (PDEs) with a special focus on the significance of characteristics, solutions by Fourier series, integrals and transforms, properties and physical interpretations of solutions, and a transition to the modern function space approach to PDEs. With its breadth of coverage, this new edition continues to present a broad introduction to the field, while also addres

  5. Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

    Science.gov (United States)

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

    2002-12-01

    appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

  6. Hydrated electron: a destroyer of perfluorinated carboxylates?

    International Nuclear Information System (INIS)

    Huang Li; Dong Wenbo; Hou Huiqi

    2006-01-01

    As a class, perfluorinated carboxylate (PFCA) was ranked among the most prominent organohalogen contaminants in environment with respect to thermal, chemical and biological inertness. Hydrated electron (e aq - ), a highly reactive and strongly reductive species, has been reported to readily decompose perfluoroaromatic compounds via intermolecular electron transfer process in aqueous solution. Question then arose: what would happen if perfluorinated carboxylates encountered with hydrated electron? Original laboratory trial on the interaction between F(CF 2 ) n COO - (n=1, 3, 7) and hydrated electron was attempted by using laser flash photolysis technique in this research work. Abundant hydrated electron (e aq - ) could be produced by photolysis of 1.25 x 10 -4 M K 4 Fe(CN) 6 in nitrogen saturated water. In the presence of F(CF 2 ) n COO - (n=1, 3, 7), the decay of e aq - was observed to enhance dramatically, indicating e aq - was able to attack PFCAs. On addition of perfluorinated carboxylates, the loss of e aq - was mainly due to the following channels. By mixing the solution of K 4 Fe(CN) 6 with excess K 3 Fe(CN) 6 and PFCAs, e aq - turned to decayed corresponding to mixed first- and second-order kinetics. Rate constants for the reactions of e aq - with PFCAs could be then easily determined by monitoring the decay of e aq - absorption at 690 nm. Since perfluorinated carboxylates were salts, the influence of ionic strength on k 3 was examined systematically by carrying out experiments of varying ionic strength ranging from 0.009 up to 0.102 M by adding NaClO 4 . In this manner, the second order rate constants for e-aq with CF 3 COO - , C 3 F 7 COO - , C 7 F 15 COO - were derived to be (1.9±0.2) x 10 6 M -1 S -1 (μ=0), (7.1±0.2) x 10 6 M -1 S -1 (μ=0) and (1.7±0.5) x10 7 M -1 S -1 (μ=0.009 M) respectively. Apparently, the length of F(CF 2 ) n group exerted substantial influence on the rate constant. Further study on byproducts analysis by ion chromatography

  7. Life Origination Hydrate Hypothesis (LOH-Hypothesis

    Directory of Open Access Journals (Sweden)

    Victor Ostrovskii

    2012-01-01

    Full Text Available The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis, according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides, DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor.

  8. Partial knee replacement - slideshow

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/presentations/100225.htm Partial knee replacement - series—Normal anatomy To use the sharing ... A.M. Editorial team. Related MedlinePlus Health Topics Knee Replacement A.D.A.M., Inc. is accredited ...

  9. A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl2 hydrates and MgCl2 hydrates for seasonal heat storage

    NARCIS (Netherlands)

    Pathak, A.D.; Gaastra-Nedea, S.V.; Zondag, H.A.; Rindt, C.C.M.; Smeulders, D.M.J.

    2016-01-01

    Salt hydrates store solar energy in chemical form via a reversible dehydration–hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The

  10. Suspension hydration of C3S [tricalcium silicate] at constant pH. II. Effect of previously formed hydrates and of additives

    NARCIS (Netherlands)

    McCurdy, K.G.; Stein, H.N.

    1973-01-01

    A retardation shown by the hydration of C3S at pH=11.5 can be prevented if before the addition of C3S there are present hydrate particles in the aqueous medium. These hydrate particles probably have the composition CSHn. This indicates a hydrate CSHn, precipitated from solution, as the retarding

  11. Withholding hydration and nutrition in newborns.

    Science.gov (United States)

    Porta, Nicolas; Frader, Joel

    2007-01-01

    In the twenty-first century, decisions to withhold or withdraw life-supporting measures commonly precede death in the neonatal intensive care unit without major ethical controversy. However, caregivers often feel much greater turmoil with regard to stopping medical hydration and nutrition than they do when considering discontinuation of mechanical ventilation or circulatory support. Nevertheless, forgoing medical fluids and food represents a morally acceptable option as part of a carefully developed palliative care plan considering the infant's prognosis and the burdens of continued treatment. Decisions to stop any form of life support should focus on the clinical circumstances, not the means used to sustain life.

  12. Beginning partial differential equations

    CERN Document Server

    O'Neil, Peter V

    2014-01-01

    A broad introduction to PDEs with an emphasis on specialized topics and applications occurring in a variety of fields Featuring a thoroughly revised presentation of topics, Beginning Partial Differential Equations, Third Edition provides a challenging, yet accessible,combination of techniques, applications, and introductory theory on the subjectof partial differential equations. The new edition offers nonstandard coverageon material including Burger's equation, the telegraph equation, damped wavemotion, and the use of characteristics to solve nonhomogeneous problems. The Third Edition is or

  13. Well log characterization of natural gas-hydrates

    Science.gov (United States)

    Collett, Timothy S.; Lee, Myung W.

    2012-01-01

    In the last 25 years there have been significant advancements in the use of well-logging tools to acquire detailed information on the occurrence of gas hydrates in nature: whereas wireline electrical resistivity and acoustic logs were formerly used to identify gas-hydrate occurrences in wells drilled in Arctic permafrost environments, more advanced wireline and logging-while-drilling (LWD) tools are now routinely used to examine the petrophysical nature of gas-hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Resistivity- and acoustic-logging tools are the most widely used for estimating the gas-hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. Recent integrated sediment coring and well-log studies have confirmed that electrical-resistivity and acoustic-velocity data can yield accurate gas-hydrate saturations in sediment grain-supported (isotropic) systems such as sand reservoirs, but more advanced log-analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. New well-logging tools designed to make directionally oriented acoustic and propagation-resistivity log measurements provide the data needed to analyze the acoustic and electrical anisotropic properties of both highly interbedded and fracture-dominated gas-hydrate reservoirs. Advancements in nuclear magnetic resonance (NMR) logging and wireline formation testing (WFT) also allow for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids(i.e., free water along with clay- and capillary-bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms

  14. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Carolyn Ann [Colorado School of Mines, Golden, CO (United States)

    2014-11-18

    Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathrate hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate

  15. Free energy landscape and molecular pathways of gas hydrate nucleation

    International Nuclear Information System (INIS)

    Bi, Yuanfei; Porras, Anna; Li, Tianshu

    2016-01-01

    Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

  16. Free energy landscape and molecular pathways of gas hydrate nucleation.

    Science.gov (United States)

    Bi, Yuanfei; Porras, Anna; Li, Tianshu

    2016-12-07

    Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

  17. Free energy landscape and molecular pathways of gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Bi, Yuanfei; Porras, Anna; Li, Tianshu, E-mail: tsli@gwu.edu [Department of Civil and Environmental Engineering, George Washington University, Washington DC 20052 (United States)

    2016-12-07

    Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p{sub B} histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p{sub B} histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

  18. Behaviour of gas production from type 3 hydrate reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Pooladi-Darvish, M. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering]|[Fekete Associates Inc., Calgary, AB (Canada); Zatsepina, O. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering; Hong, H. [Fekete Associates Inc., Calgary, AB (Canada)

    2008-07-01

    The possible role of gas hydrates as a potential energy resource was discussed with particular reference to methods for estimating the rate of gas production from hydrate reservoirs under different operating conditions. This paper presented several numerical simulations studies of gas production from type 3 hydrate reservoirs in 1-D and 2-D geometries. Type 3 reservoirs include gas production from hydrate-reservoirs that lie totally within the hydrate stability zone and are sandwiched by impermeable layers on top and bottom. The purpose of this study was to better understand hydrate decomposition by depressurization. The study questioned whether 1-D modeling of type 3 hydrate reservoirs is a reasonable approximation. It also determined whether gas rate increases or decreases with time. The important reservoir characteristics for determining the rate of gas production were identified. Last, the study determined how competition between fluid and heat flow affects hydrate decomposition. This paper also described the relation and interaction between the heat and fluid flow mechanisms in depressurization of type 3 hydrate reservoirs. All results of 1-D and 2-D numerical simulation and analyses were generated using the STARS simulator. It was shown that the rate of gas production depends on the initial pressure/temperature conditions and permeability of the hydrate bearing formation. A high peak rate may be achieved under favourable conditions, but this peak rate is obtained after an initial period where the rate of gas production increases with time. The heat transfer in the direction perpendicular to the direction of fluid flow is significant, requiring 2D modeling. The hydraulic diffusivity is low because of the low permeability of hydrate-bearing formations. This could result in competition between heat and fluid flow, thereby influencing the behaviour of decomposition. 6 refs., 3 tabs., 12 figs.

  19. Monopeptide versus Monopeptoid: Insights on Structure and Hydration of Aqueous Alanine and Sarcosine via X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; England, Alice; Prendergast, David; Saykally, Richard J.

    2009-11-19

    Despite the obvious significance, the aqueous interactions of peptides remain incompletely understood. Their synthetic analogues called peptoids (poly-N-substituted glycines), have recently emerged as a promising biomimetic material, particularly due to their robust secondary structure and resistance to denaturation. We describe comparative near-edge x-ray absorption fine structure (NEXAFS) spectroscopy studies of aqueous sarcosine, the simplest peptoid, and alanine, its peptide isomer, interpreted by density functional theory calculations. The sarcosine nitrogen K-edge spectrum is blue-shifted with respect to that of alanine, in agreement with our calculations; we conclude that this shift results primarily from the methyl group substitution on the nitrogen of sarcosine. Our calculations indicate that the nitrogen K-edge spectrum of alanine differs significantly between dehydrated and hydrated scenarios, while that of the sarcosine zwitterion is less affected by hydration. In contrast, the computed sarcosine spectrum is greatly impacted by conformational variations, while the alanine spectrum is not. This relates to a predicted solvent dependence for alanine, as compared to sarcosine. Additionally, we show the theoretical nitrogen K-edge spectra to be sensitive to the degree of hydration, indicating that experimental X-ray spectroscopy may be able to distinguish between bulk and partial hydration, such as found in confined environments near proteins and in reverse micelles.

  20. Transport Mechanisms for CO2-CH4 Exchange and Safe CO2 Storage in Hydrate-Bearing Sandstone

    Directory of Open Access Journals (Sweden)

    Knut Arne Birkedal

    2015-05-01

    Full Text Available CO2 injection in hydrate-bearing sediments induces methane (CH4 production while benefitting from CO2 storage, as demonstrated in both core and field scale studies. CH4 hydrates have been formed repeatedly in partially water saturated Bentheim sandstones. Magnetic Resonance Imaging (MRI and CH4 consumption from pump logs have been used to verify final CH4 hydrate saturation. Gas Chromatography (GC in combination with a Mass Flow Meter was used to quantify CH4 recovery during CO2 injection. The overall aim has been to study the impact of CO2 in fractured and non-fractured samples to determine the performance of CO2-induced CH4 hydrate production. Previous efforts focused on diffusion-driven exchange from a fracture volume. This approach was limited by gas dilution, where free and produced CH4 reduced the CO2 concentration and subsequent driving force for both diffusion and exchange. This limitation was targeted by performing experiments where CO2 was injected continuously into the spacer volume to maintain a high driving force. To evaluate the effect of diffusion length multi-fractured core samples were used, which demonstrated that length was not the dominating effect on core scale. An additional set of experiments is presented on non-fractured samples, where diffusion-limited transportation was assisted by continuous CO2 injection and CH4 displacement. Loss of permeability was addressed through binary gas (N2/CO2 injection, which regained injectivity and sustained CO2-CH4 exchange.

  1. Giordano Bruno crater on the Moon: Detection and Mapping of Hydration Features of Endogenic and/or Exogenic Nature

    Science.gov (United States)

    Saran Bhiravarasu, Sriram; Bhattacharya, Satadru; Chauhan, Prakash

    2017-10-01

    We analyze high resolution spectral and spatial data from the recent lunar missions and report the presence of strong hydration features within the inner flank, hummocky floor, ejecta and impact melt deposits of crater Giordano Bruno. Hydroxyl-bearing lithologies at Giordano Bruno are characterized primarily by a prominent absorption feature near 2800 nm, the band minima of which goes beyond 3000 nm. The hydration features are found to be associated with low-Ca pyroxene-bearing noritic lithologies along the inner crater flanks, whereas similar features are also seen within the hummocky crater floor in association with shocked plagioclase-bearing anorthositic lithology. Interestingly, the ejecta blanket is characterized by sharp, narrow features centered near 2800 nm similar to the features previously reported from Compton-Belkovich volcanic complex and central peak of crater Theophilus. The low-Ca pyroxene-bearing rock exposures within the crater inner flanks are characterized by both presence and absence of the hydration features. Enhanced hydration is also seen within the ejecta blanket covering the nearby Harkhebi K and J craters. We also analyze the impact melts and ejecta using radar images at regions interior and exterior to the Giordano Bruno crater rim.Anomalous behaviors of hydration feature associated with low-Ca pyroxene-rich exposures, its nature and occurrences within the impact melt sheets inside the crater along with the ejecta blankets could possibly indicate endogenic and/or exogenic nature of the observed hydration feature. Initial results indicate the presence of strongest hydration feature in the partially shadowed pole-facing slopes (with low-Ca pyroxene-bearing exposures) and its complete absence in the equator-facing sun-lit slopes. This hints at a possible exogenic origin, whereas the same feature occurring (with same mineral) under both sun-lit and shadowed conditions suggest it to be of magmatic origin. We propose that the heterogeneous

  2. Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

    Science.gov (United States)

    Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

    2015-03-04

    In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration.

  3. Nasogastric Hydration in Infants with Bronchiolitis Less Than 2 Months of Age.

    Science.gov (United States)

    Oakley, Ed; Bata, Sonny; Rengasamy, Sharmila; Krieser, David; Cheek, John; Jachno, Kim; Babl, Franz E

    2016-11-01

    To determine whether nasogastric hydration can be used in infants less than 2 months of age with bronchiolitis, and characterize the adverse events profile of these infants compared with infants given intravenous (IV) fluid hydration. A descriptive retrospective cohort study of children with bronchiolitis under 2 months of age admitted for hydration at 3 centers over 3 bronchiolitis seasons was done. We determined type of hydration (nasogastric vs IV fluid hydration) and adverse events, intensive care unit admission, and respiratory support. Of 491 infants under 2 months of age admitted with bronchiolitis, 211 (43%) received nonoral hydration: 146 (69%) via nasogastric hydration and 65 (31%) via IV fluid hydration. Adverse events occurred in 27.4% (nasogastric hydration) and 23.1% (IV fluid hydration), difference of 4.3%; 95%CI (-8.2 to 16.9), P = .51. The majority of adverse events were desaturations (21.9% nasogastric hydration vs 21.5% IV fluid hydration, difference 0.4%; [-11.7 to 12.4], P = .95). There were no pulmonary aspirations in either group. Apneas and bradycardias were similar in each group. IV fluid hydration use was positively associated with intensive care unit admission (38.5% IV fluid hydration vs 19.9% nasogastric hydration; difference 18.6%, [5.1-32.1], P = .004); and use of ventilation support (27.7% IV fluid hydration vs 15.1% nasogastric hydration; difference 12.6 [0.3-23], P = .03). Fewer infants changed from nasogastric hydration to IV fluid hydration than from IV fluid hydration to nasogastric hydration (12.3% vs 47.7%; difference -35.4% [-49 to -22], P hydration can be used in the majority of young infants admitted with bronchiolitis. Nasogastric hydration and IV fluid hydration had similar rates of complications. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. A unified approach for description of gas hydrate formation kinetics in the presence of kinetic promoters in gas hydrate converters

    International Nuclear Information System (INIS)

    ZareNezhad, Bahman; Varaminian, Farshad

    2013-01-01

    Highlights: • A unified kinetic model for description of promoted and non-promoted gas hydrate formation processes is presented. • Effects of impeller speed, promoter concentration and different kinetic promoters are investigated. • A unique region of gas hydrate formation is identified regarding gas hydrate formation processes. • The proposed model is useful for understanding the behavior of gas hydrate formation processes and design of GTH converters. - Abstract: The kinetic promoters have found wide applications in enhancing the rate of energy conversion and storage via gas hydrate formation processes. Effects of different kinetic promoters such as anionic surfactants sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBSA), and sodium dodecyl benzene sulfonate (SDBS); cationic surfactants, Cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide (DTAB) and non-ionic surfactants, alkylpolyglucoside (APG), dodecyl polysaccharide glycoside (DPG), TritonX-100 (TX100) on methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ) gas hydrate formation processes are investigated in this work. A macroscopic kinetic model based on the time variations of reaction chemical potential is also presented for global description of gas hydrate formation processes. Experimental gas hydrate formation data are employed to validate the proposed kinetic model. Effects of promoter’s concentrations and agitation intensities on the gas consumption profiles are also investigated. A universal correlation and a unified kinetic map have been proposed for macroscopic description of gas hydrate formation kinetics in the presence or absence of kinetic promoters. According to the presented unified kinetic map, a unique region of gas hydrate formation is identified for the first time. For negligible amounts of kinetic promoters, the presented region disappears and approaches to a unique path at high agitation intensities. The presented unified approach is

  5. Reuse of partially sulphated CFBC ash as an SO{sub 2} sorbent

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Y.; Jia, L.; Anthony, E.J. [Natural Resources Canada, Ottawa, ON (Canada). CANMET Energy; Nobili, M.; Telesca, A. [Basilicata Univ., Potenza (Italy). Dept. of Environmental Engineering and Physics; Montagnaro, F. [Naples Univ., Naples (Italy). Dept. of Chemistry

    2010-06-15

    Ash produced from circulating fluidized bed combustion (CFBC) boilers typically contains large amounts of unreacted calcium oxide (CaO) when limestone is added into the combustor for in situ removal of sulphur dioxide (SO{sub 2}). This paper reported on a study that evaluated the reactivation of partially sulphated ash obtained from an industrial circulating fluidized bed combustion (CFBC) boiler by hydration with liquid water and steam. A pilot-scale mini-CFBC was used to evaluate the results of reactivation on the bed ash by hydrating with liquid water and admixtures of sodium carbonate (Na{sub 2}CO{sub 3}) in solution or as powder. Re-sulphation tests on the hydrated samples were performed in a Cahn 1000 thermogravimetric analyzer (TGA) at 850 degrees C for 90 minutes in a simulated flue gas environment with sulphur dioxide (SO{sub 2}) concentration at 5000 ppm. Re-sulphation was carried out on unhydrated ash at the same conditions used in the baseline test. The TGA results showed that although liquid water and steam successfully hydrate and reactivate the unreacted CaO in the bed ash, the treated ashes sulphated to widely different extents. Attempts to reactivate fly ash with hydration failed, but the fly ash by itself was extremely reactive. When the treated ash was re-injected into the combustor with the fuel, the effect on SO{sub 2} removal efficiency was negligible if Na{sub 2}CO{sub 3} was added as powder. Doping with aqueous solution improved SO{sub 2} removal, but to a lesser extent than if only water hydration was used. Increasing the amount of water to reactivate the ash did not improve the sulphur capture capacity in the mini-CFBC. It was concluded that reactivation by water is the most practical way to reuse the partially sulphated bed ash as a sulphur sorbent. 21 refs., 7 tabs., 3 figs.

  6. Prospects of gas hydrate presence in the Chukchi sea

    Directory of Open Access Journals (Sweden)

    Т. В. Матвеева

    2017-08-01

    Full Text Available The purpose of this study is to forecast the scale and distribution character of gas hydrate stability zone in the Chukchi Sea under simulated natural conditions and basing on these results to estimate resource potential of gas hydrates within this area. Three types of stability zone have been identified. A forecast map of gas hydrate environment and potentially gas hydrate-bearing water areas in the Chukchi Sea has been plotted to a scale of 1:5 000 000. Mapping of gas hydrate stability zone allowed to give a justified forecast based on currently available data on geologic, fluid dynamic, cryogenic, geothermal and pressure-temperature conditions of gas hydrate formation in the Chukchi Sea. It is the first forecast of such kind that focuses on formation conditions for hydrates of various types and compositions in the Arctic seas offshore Russia. Potential amount of gas, stored beneath the Chukchi Sea in the form of hydrates, is estimated based on mapping of their stability zone and falls into the interval of 7·1011-11.8·1013 m3.

  7. Exploring the solid-form landscape of pharmaceutical hydrates

    DEFF Research Database (Denmark)

    Raijada, Dharaben Kaushikkumar; Bond, Andrew; Larsen, Flemming Hofmann

    2013-01-01

    To understand the transformation pathways amongst anhydrate/hydrate solid forms of sodium naproxen and to highlight the importance of a polymorphic dihydrate within this context.......To understand the transformation pathways amongst anhydrate/hydrate solid forms of sodium naproxen and to highlight the importance of a polymorphic dihydrate within this context....

  8. Hydration behaviour of synthetic saponite at variable relative humidity

    Indian Academy of Sciences (India)

    Hydration behaviour of synthetic saponite was examined by X-ray powder diffraction simulation at various relative humidities (RH). The basal spacing of the Ca-saponite increased stepwise with increase in RH. The (00) reflections observed reflect single or dual hydration states of smectite. Quasi-rational, intermediate, or ...

  9. The effect of stereochemistry on carbohydrate hydration in aqueous solutions

    NARCIS (Netherlands)

    Galema, Saskia Alexandra

    1992-01-01

    Although-carbohydrates are widely used, not much is known about the stereochemical aspects of hydration of carbohydrates. For D-aldohexoses, for example, there are eight different stereoisomers. Just how the hydroxy topology of a carbohydrate molecule influences the hydration behaviour in water is

  10. Spectroscopic determination of optimal hydration time of zircon surface

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Garcia R, G. [Instituto Tecnologico de Toluca, Division de Estudios del Posgrado, Av. Tecnologico s/n, Ex-Rancho La Virgen, 52140 Metepec, Estado de Mexico (Mexico); Garcia G, N., E-mail: eduardo.ordonez@inin.gob.m [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Av. Colon y Av. Tollocan, 50180 Toluca, Estado de Mexico (Mexico)

    2010-07-01

    When a mineral surface is immersed in an aqueous solution, it develops and electric charge produced by the amphoteric dissociation of hydroxyl groups created by the hydration of the solid surface. This is one influential surface property. The complete hydration process takes a time which is specific for each mineral species. The knowledge of the aqueous solution contact time for complete surface hydration is mandatory for further surface phenomena studies. This study deals with the optimal hydration time of the raw zircon (ZrSiO{sub 4}) surface comparing the classical potentiometric titrations with a fluorescence spectroscopy technique. The latter is easy and rea liable as it demands only one sample batch to determine the optimal time to ensure a total hydration of the zircon surface. The analytical results of neutron activation analysis showed the presence of trace quantities of Dy{sup 3+}, Eu{sup 3+} and Er{sup 3} in the bulk of zircon. The Dy{sup 3+} is structured in the zircon crystalline lattice and undergoes the same chemical reactions as zircon. Furthermore, the Dy{sup 3+} has a good fluorescent response whose intensity is enhanced by hydration molecules. The results show that, according to the potentiometric analysis, the hydration process for each batch (at least 8 sample batches) takes around 2 h, while the spectrometric method indicates only 5 minutes from only one batch. Both methods showed that the zircon surface have a 16 h optimal hydration time. (Author)

  11. Spectroscopic determination of optimal hydration time of zircon surface

    International Nuclear Information System (INIS)

    Ordonez R, E.; Garcia R, G.; Garcia G, N.

    2010-01-01

    When a mineral surface is immersed in an aqueous solution, it develops and electric charge produced by the amphoteric dissociation of hydroxyl groups created by the hydration of the solid surface. This is one influential surface property. The complete hydration process takes a time which is specific for each mineral species. The knowledge of the aqueous solution contact time for complete surface hydration is mandatory for further surface phenomena studies. This study deals with the optimal hydration time of the raw zircon (ZrSiO 4 ) surface comparing the classical potentiometric titrations with a fluorescence spectroscopy technique. The latter is easy and rea liable as it demands only one sample batch to determine the optimal time to ensure a total hydration of the zircon surface. The analytical results of neutron activation analysis showed the presence of trace quantities of Dy 3+ , Eu 3+ and Er 3 in the bulk of zircon. The Dy 3+ is structured in the zircon crystalline lattice and undergoes the same chemical reactions as zircon. Furthermore, the Dy 3+ has a good fluorescent response whose intensity is enhanced by hydration molecules. The results show that, according to the potentiometric analysis, the hydration process for each batch (at least 8 sample batches) takes around 2 h, while the spectrometric method indicates only 5 minutes from only one batch. Both methods showed that the zircon surface have a 16 h optimal hydration time. (Author)

  12. Evaluation of Nutritional Status and Hydration in Patients on Chronic ...

    African Journals Online (AJOL)

    Background: Nutrition and hydration of the dialysis patients have major influences on the outcomes of chronic hemodialysis. Purpose: To characterize the states of nutrition and hydration in patients on chronic hemodialysis at Jos University Teaching Hospital (JUTH) and to evaluate the usefulness of measurements by ...

  13. Phase equilibrium condition of marine carbon dioxide hydrate

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

    2013-01-01

    Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

  14. Unexpected Hydration of a Triple Bond During DNA Synthesis

    DEFF Research Database (Denmark)

    Fatthalla, Maha I.; Pedersen, Erik B.

    2016-01-01

    acidic conditions, polarizes the triple bond in the intercalator and this makes hydration of the triple bond possible during the DNA synthesis and an oligonucleotide with 1-(indol-3-yl)-2-(pyren-1-yl)ethanone as the intercalator is formed. Insertion of the unhydrated and hydrated linker systems gave...

  15. Solubility data for cement hydrate phases (25oC)

    International Nuclear Information System (INIS)

    Atkins, M.; Glasser, F.P.; Kindness, A.; Macphee, D.E.

    1991-05-01

    Solubility measurements were performed on most of the more thermodynamically-stable cement hydrate phases, at 25 o C. The results for each hydrate phase are summarised in the form of datasheets. Solubility properties are discussed, and where possible a K sp value is calculated. The data are compared with the data in the literature. (author)

  16. Potential natural gas hydrates resources in Indian Offshore areas

    Digital Repository Service at National Institute of Oceanography (India)

    Sethi, A.K.; Sathe, A.V.; Ramana, M.V.

    (geophysical proxies of gas hydrates). A qualitative map prepared based on the inferred BSRs brought out a deepwater area of about 80,000 sq.km unto 3000 m isobath as favourable for gas hydrate occurrence. Methodology for reprocessing of seismic data...

  17. Gas hydrate inhibition by perturbation of liquid water structure

    Science.gov (United States)

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

    2015-06-01

    Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

  18. Putting the Deep Biosphere and Gas Hydrates on the Map

    Science.gov (United States)

    Sikorski, Janelle J.; Briggs, Brandon R.

    2016-01-01

    Microbial processes in the deep biosphere affect marine sediments, such as the formation of gas hydrate deposits. Gas hydrate deposits offer a large source of natural gas with the potential to augment energy reserves and affect climate and seafloor stability. Despite the significant interdependence between life and geology in the ocean, coverage…

  19. Metallorganic chemical vapor deposition and atomic layer deposition approaches for the growth of hafnium-based thin films from dialkylamide precursors for advanced CMOS gate stack applications

    Science.gov (United States)

    Consiglio, Steven P.

    To continue the rapid progress of the semiconductor industry as described by Moore's Law, the feasibility of new material systems for front end of the line (FEOL) process technologies needs to be investigated, since the currently employed polysilicon/SiO2-based transistor system is reaching its fundamental scaling limits. Revolutionary breakthroughs in complementary-metal-oxide-semiconductor (CMOS) technology were recently announced by Intel Corporation and International Business Machines Corporation (IBM), with both organizations revealing significant progress in the implementation of hafnium-based high-k dielectrics along with metal gates. This announcement was heralded by Gordon Moore as "...the biggest change in transistor technology since the introduction of polysilicon gate MOS transistors in the late 1960s." Accordingly, the study described herein focuses on the growth of Hf-based dielectrics and Hf-based metal gates using chemical vapor-based deposition methods, specifically metallorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). A family of Hf source complexes that has received much attention recently due to their desirable properties for implementation in wafer scale manufacturing is the Hf dialkylamide precursors. These precursors are room temperature liquids and possess sufficient volatility and desirable decomposition characteristics for both MOCVD and ALD processing. Another benefit of using these sources is the existence of chemically compatible Si dialkylamide sources as co-precursors for use in Hf silicate growth. The first part of this study investigates properties of MOCVD-deposited HfO2 and HfSixOy using dimethylamido Hf and Si precursor sources using a customized MOCVD reactor. The second part of this study involves a study of wet and dry surface pre-treatments for ALD growth of HfO2 using tetrakis(ethylmethylamido)hafnium in a wafer scale manufacturing environment. The third part of this study is an investigation of

  20. NMR Studies of Protein Hydration and Protein-Ligand Interactions

    Science.gov (United States)

    Chong, Yuan

    Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be