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Sample records for hydrated hafnium tetrachloride

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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

  9. The vibrational spectra of some tetrachlorides in rare gas matrices with particular reference to the molecular shapes of ThCl4 and UCl4

    International Nuclear Information System (INIS)

    Arthers, S.A.; Beattie, I.R.

    1984-01-01

    Infrared spectra of tin, lead, hafnium, thorium, and uranium tetrachlorides isolated in inert gas matrices are reported. The results obtained for the tin, lead, and hafnium compounds follow the expected isotope patterns for a tetrahedral molecule except for the observation of additional weak features to high frequency of the all- 35 Cl isotopomers. By contrast for thorium tetrachloride the observed spectrum is not characteristic of a Tsub(d) molecule but can be fitted to a species with Csub(2v) symmetry. Similar results (although less detailed) were obtained for uranium tetrachloride. (author)

  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. Design of an Extractive Distillation Column for the Environmentally Benign Separation of Zirconium and Hafnium Tetrachloride for Nuclear Power Reactor Applications

    Directory of Open Access Journals (Sweden)

    Le Quang Minh

    2015-09-01

    Full Text Available Nuclear power with strengthened safety regulations continues to be used as an important resource in the world for managing atmospheric greenhouse gases and associated climate change. This study examined the environmentally benign separation of zirconium tetrachloride (ZrCl4 and hafnium tetrachloride (HfCl4 for nuclear power reactor applications through extractive distillation using a NaCl-KCl molten salt mixture. The vapor–liquid equilibrium behavior of ZrCl4 and HfCl4 over the molten salt system was correlated with Raoult’s law. The molten salt-based extractive distillation column was designed optimally using a rigorous commercial simulator for the feasible separation of ZrCl4 and HfCl4. The molten salt-based extractive distillation approach has many potential advantages for the commercial separation of ZrCl4 and HfCl4 compared to the conventional distillation because of its milder temperatures and pressure conditions, smaller number of required separation trays in the column, and lower energy requirement for separation, while still taking the advantage of environmentally benign feature by distillation. A heat-pump-assisted configuration was also explored to improve the energy efficiency of the extractive distillation process. The proposed enhanced configuration reduced the energy requirement drastically. Extractive distillation can be a promising option competing with the existing extraction-based separation process for zirconium purification for nuclear power reactor applications.

  12. Recovery of metal chlorides from their complexes by molten salt displacement

    International Nuclear Information System (INIS)

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

    1989-01-01

    This patent describes a process for recovering zirconium or hafnium chloride from a complex of zirconium or hafnium tetrachloride and phosphorus oxychloride. The process comprising: introducing liquid complex of zirconium or hafnium tetrachloride and phosphorus oxychloride into an upper portion of a feed column containing zirconium or hafnium tetrachloride vapor and phosphorus oxychloride vapor. The liquid complex absorbing zirconium or hafnium tetrachloride vapor and producing a bottoms liquid and also producing a phosphorus oxychloride vapor stripped of zirconium or hafnium tetrachloride; introducing the bottoms liquid into a molten salt containing displacement reactor, the reactor containing molten salt comprising at least 30 mole percent lithium chloride and at least 30 mole percent of at least one other alkali metal chloride, the reactor being heated to 30-450 0 C to displace phosphorus oxychloride from the complex and product zirconium or hafnium tetrachloride vapor and phosphorus oxychloride vapor and zirconium or hafnium tetrachloride-containing molten salt; introducing the zirconium or hafnium tetrachloride vapor and the phosphorus oxychloride vapor into the feed column below the point of introduction of the liquid stream; introducing the zirconium or hafnium tetrachloride containing-molten salt into a recovery vessel where zirconium or hafnium tetrachloride is removed from the molten salt to produce zirconium or hafnium tetrachloride product and zirconium or hafnium chloride-depleted molten salt; and recycling the zirconium or hafnium tetachloride-depleted molten salt to the displacement reactor

  13. 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.

  14. Process and operating device for an apparatus using a running liquid film and application to separation of Zr and Hf tetrachlorides

    International Nuclear Information System (INIS)

    Brun, R.

    1989-01-01

    A process is claimed allowing to maintain a thin film in a running film exchanger, by increasing the flow rate for a short time to establish a film all over the surface. Application is made to continuous condensation of zirconium and hafnium tetrachlorides, from the separation column, by absorption in a liquid solvent made of potassium chloroaluminate [fr

  15. 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

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. Production of titanium tetrachloride

    International Nuclear Information System (INIS)

    Perillo, P.M.; Botbol, O.

    1990-01-01

    This report presents a summary of results from theoperation of a laboratory scale for the production in batches of approximately 100 gs of titanium tetrachloride by chlorination with chloroform and carbon tetrachloride between 340 deg C and 540 deg C. Chlorination agent vapors were passed through a quartz column reacting with titanium oxide powder agglomerated in little spheres. Obtained titanium tetrachloride was condensed in a condenser, taken in a ballon and then purified by fractional distillation. Optimun temperature for chloroform was 400 deg C with 74 % yield and for carbon tetrachloride was 500 deg C with 69 % yield. (Author) [es

  6. 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.

  7. 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.)

  8. 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

  9. 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

  10. 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)

  11. 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.

  12. 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.

  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. 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.

  15. Compound list: carbon tetrachloride [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available carbon tetrachloride CCL4 00003 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LAT...EST/Human/in_vitro/carbon_tetrachloride.Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open-tgg...ates/LATEST/Rat/in_vitro/carbon_tetrachloride.Rat.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open...-tggates/LATEST/Rat/in_vivo/Liver/Single/carbon_tetrachloride.Rat.in_vivo.Liver.S...ingle.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/carbon_tetrachloride.Rat.in_vivo.Liver.Repeat.zip ...

  16. 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

  17. 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

  18. 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.

  19. 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

  20. 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)

  1. 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.

  2. 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

  3. 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.

  4. 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...

  5. 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

  6. 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%.

  7. 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...

  8. 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.

  9. 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

  10. 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)

  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. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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

  20. 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)

  1. 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

  2. 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.

  3. Transformation of carbon tetrachloride under sulfate reducing conditions

    NARCIS (Netherlands)

    Best, Jappe H. de; Salminen, E.; Doddema, Hans J.; Janssen, Dick B.; Harder, Wim

    1998-01-01

    The removal of carbon tetrachloride under sulfate reducing conditions was studied in an anaerobic packed-bed reactor. Carbon tetrachloride, up to a concentration of 30 µM, was completely converted. Chloroform and dichloromethane were the main transformation products, but part of the carbon

  4. Transformation of carbon tetrachloride under sulfate reducing conditions

    NARCIS (Netherlands)

    de Best, JH; Salminen, E; Doddema, HJ; Janssen, DB; Harder, W

    1997-01-01

    The removal of carbon tetrachloride under sulfate reducing conditions was studied in an anaerobic packed-bed reactor. Carbon tetrachloride, up to a concentration of 30 mu M, was completely converted. Chloroform and dichloromethane were the main transformation products, but part of the carbon

  5. 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)

  6. 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

  7. 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

  8. 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.

  9. 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)

  10. 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

  11. 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)

  12. Thermodynamic and kinetic studies in the systems alkali chloride-zinconium (or hafnium) tetrachloride: Part I. Vapour pressure measurements over hexachloro compounds and use of vapour pressure data in fractional decomposition

    International Nuclear Information System (INIS)

    Ray, H.S.; Bhat, B.G.; Reddy, G.S.; Biswas, A.K.

    1978-01-01

    A molten tin isoteniscope has been used to measure the vapour pressures over ZrCl 4 , HfCl 4 and the hexachlore zirconates (M 2 ZrCl 6 ) and the hexachloro hafnates (M 2 HfCl 6 ) of four alkali metals (M = Na,K,Rb,Cs). The method of preparation of these compounds and the effect of small amounts of residual alkali chlorides on the their vapour pressure are discussed. The pressure-temperature plots are examined in the light of some theoretical postulates. A scheme for separation of hafnium from zirconoium by multistage fractional decomposition of the hexachlore compounds of any alkali metal is described. The scheme, which is analogous to rectification in liquid-vapour systems, employs a countercurrent flow of Zr(Hf)Cl 4 in a gas stream and a moving bed of alkali chlorides. The separation is based on the difference in the dissociation equilibrium for zirconium and hafnium compounds. Stage calculations for such a scheme and the main conclusions of a computational work are presented. (author)

  13. 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)

  14. 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...

  15. 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.)

  16. Carbon tetrachloride treatment induces anorexia independently of hepatitis in rats.

    Science.gov (United States)

    Okamoto, T; Okabe, S

    2000-08-01

    Oxidative stress is involved in the development of anorexia. In the present study, we examined the possible involvement of anorexia in oxygen radical-induced hepatitis. A low dose of carbon tetrachloride (1 ml/kg of a 1:1 solution with olive oil) was orally administered to rats with and without food restriction. In rats with food restriction, carbon tetrachloride treatment induced hepatitis and reduced the body weight gain. In contrast, carbon tetrachloride treatment did not induce hepatitis in rats without food restriction, but the body weight was decreased. In these rats, the loss of body weight was accompanied by a decrease in food intake. The present results indicate that the administration of a low dose of carbon tetrachloride to rats without food restriction induced anorexia independently of hepatitis.

  17. Complexes of uranium tetrachlorides and thorium tetrachloride with N-methylpiperazine, 2-methylpiperazine, N-phenylpiperazine, N,N'-dimethylpiperazine and pyrazine

    Energy Technology Data Exchange (ETDEWEB)

    Manhas, B S; Trikha, A K [Punjabi Univ., Patiala (India). Dept. of Chemistry; Singh, M

    1979-01-01

    Stable complexes of uranium tetrachloride and thorium tetrachloride with the title ligands have been synthesised and characterised on the basis of elemental analyses, IR and electronic reflectance spectral studies and magnetic susceptibility measurements. The ligands probably coordinate in the chair conformation bridging the metal ions as indicated by IR spectral studies and insolubility of these complexes in common organic solvents. A coordination number of six for uranium (IV) is suggested by the electronic reflectance spectral and magnetic susceptibility data.

  18. Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

    Science.gov (United States)

    Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J. R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J. L.; Soubervielle-Montalvo, C.; Mani-Gonzalez, P. G.

    2016-06-01

    The final structure of HfO2 films grown by atomic layer deposition (ALD) after reaction with OH- ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl4 (hafnium tetrachloride), HfI4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO-H was studied employing the B3LYP (Becke 3-parameter, Lee-Yang-Parr) hybrid functional and the PBE (Perdew-Burke-Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  19. 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

  20. 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

  1. 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)

  2. 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)

  3. Thermodynamics of HfCl/sub 4/-KCl molten mixtures containing HfCl/sub 4/ up to 33. 3 mol. per cent

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-05-01

    Based on measurements of saturated vapour pressure in components of melted mixtures of HfCl/sub 4/-KCl, depending on temperature and concentration, calculated are the results of changes in activity coefficients of hafnium tetrachloride and potassium chloride on transition from diluted solutions, where the Henry law is met, to those concentrated where the law is disobeyed. Growth in the activity coefficient of HfCl/sub 4/ is due to dissociation of complex groups of HfCl/sub 6//sup 2 -/ into complexes with a lesser number of ligands and decreasing relative binding energy of Hf/sup 4 +/-Cl/sup -/ there. In this case, marked changes take place in partial enthalpy and entropy of hafnium tetrachloride mixing. Similar dependences are observed for potassium chloride, but they are expressed considerably weaker. Evaporation enthalpy and entropy are calculated for HfCl/sub 4/ and KCl monomers from their melted mixtures of various concentrations.

  4. Thermodynamics of HfCl4-KCl molten mixtures containing HfCl4 up to 33.3 mol. per cent

    International Nuclear Information System (INIS)

    Smirnov, M.V.; Salyulev, A.B.; Kudyakov, V.Ya.

    1980-01-01

    Based on measurements of saturated vapour pressure in components of melted mixtures of HfCl 4 -KCl, depending on temperature and concentration, calculated are the results of changes in activity coefficients of hafnium tetrachloride and potassium chloride on transition from diluted solutions, where the Henry law is met, to those concentrated where the law is disobeyed. Growth in the activity coefficient of HfCl 4 is due to dissociation of complex groups of HfCl 6 2- into complexes with a lesser number of ligands and decreasing relative binding energy of Hf 4+ -Cl - there. In this case, marked changes take place in partial enthalpy and entropy of hafnium tetrachloride mixing. Similar dependences are observed for potassium chloride, but they are expressed considerably weaker. Evaporation enthalpy and entropy are calculated for HfCl 4 and KCl monomers from their melted mixtures of various concentrations

  5. Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

    International Nuclear Information System (INIS)

    Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J.R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J.L.

    2016-01-01

    Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO 2 films grown by atomic layer deposition (ALD) after reaction with OH − ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl 4 (hafnium tetrachloride), HfI 4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  6. 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)

  7. Emissions of carbon tetrachloride from Europe

    Science.gov (United States)

    Graziosi, Francesco; Arduini, Jgor; Bonasoni, Paolo; Furlani, Francesco; Giostra, Umberto; Manning, Alistair J.; McCulloch, Archie; O'Doherty, Simon; Simmonds, Peter G.; Reimann, Stefan; Vollmer, Martin K.; Maione, Michela

    2016-10-01

    Carbon tetrachloride (CCl4) is a long-lived radiatively active compound with the ability to destroy stratospheric ozone. Due to its inclusion in the Montreal Protocol on Substances that Deplete the Ozone Layer (MP), the last two decades have seen a sharp decrease in its large-scale emissive use with a consequent decline in its atmospheric mole fractions. However, the MP restrictions do not apply to the use of carbon tetrachloride as feedstock for the production of other chemicals, implying the risk of fugitive emissions from the industry sector. The occurrence of such unintended emissions is suggested by a significant discrepancy between global emissions as derived from reported production and feedstock usage (bottom-up emissions), and those based on atmospheric observations (top-down emissions). In order to better constrain the atmospheric budget of carbon tetrachloride, several studies based on a combination of atmospheric observations and inverse modelling have been conducted in recent years in various regions of the world. This study is focused on the European scale and based on long-term high-frequency observations at three European sites, combined with a Bayesian inversion methodology. We estimated that average European emissions for 2006-2014 were 2.2 (± 0.8) Gg yr-1, with an average decreasing trend of 6.9 % per year. Our analysis identified France as the main source of emissions over the whole study period, with an average contribution to total European emissions of approximately 26 %. The inversion was also able to allow the localisation of emission "hot spots" in the domain, with major source areas in southern France, central England (UK) and Benelux (Belgium, the Netherlands, Luxembourg), where most industrial-scale production of basic organic chemicals is located. According to our results, European emissions correspond, on average, to 4.0 % of global emissions for 2006-2012. Together with other regional studies, our results allow a better constraint

  8. Test plan for the FY 1997 rebound study at the carbon tetrachloride soil vapor extraction site

    International Nuclear Information System (INIS)

    Rohay, V.J.; Tranbarger, R.K.

    1996-11-01

    This test plan describes the strategy and field measurements designed to evaluate the potential rebound of carbon tetrachloride vapor concentrations following cessation of soil vapor extraction (SVE) operations at the 200-ZP-2 Operable Unit in the 200 West Area of the Hanford Site. Soil vapor extraction was initiated in February 1992 as the preferred remedial alternative of the Carbon Tetrachloride Expedited Response Action for removal of carbon tetrachloride from the unsaturated zone beneath the primary carbon tetrachloride disposal sites. The magnitude, extent, and rate of rebound in carbon tetrachloride vapor concentrations will help determine the availability of additional carbon tetrachloride for removal using SVE. At the conclusion of the field measurements, a report will be completed to evaluate the results of the rebound study

  9. 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.

  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. 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

  12. Fabrication of bimetallic Ag/Fe immobilized on modified biochar for removal of carbon tetrachloride

    Institute of Scientific and Technical Information of China (English)

    Hongwei Wu; Qiyan Feng

    2017-01-01

    As an effective conventional absorbent,biochar exhibited limited adsorption ability toward small hydrophobic molecules.To enhance the adsorption capacity,a novel adsorbent was prepared by immobilizing nanoscale zero-valent iron onto modified biochar (MB) and then the elemental silver was attached to the surface of iron (Ag/Fe/MB).It's noted that spherical Ag/Fe nanoparticles with diameter of 51 nm were highly dispersed on the surface of MB.As the typical hydrophobic contaminant,carbon tetrachloride was selected for examining the removal efficiency of the adsorbent.The removal efficiencies of carbon tetrachloride by original biochar (OB),Ag/Fe,Ag/Fe/OB and Ag/Fe/MB were fully investigated.It's found that Ag/Fe/MB showed higher carbon tetrachloride removal efficiency,which is about 5.5 times higher than that of the OB sample due to utilizing the merits of high adsorption and reduction.Thermodynamic parameters revealed that the removal of carbon tetrachloride by Ag/Fe/MB was a spontaneous and exothermic process,which was affected by solution pH,initial carbon tetrachloride concentration and temperature.The novel Ag/Fe/MB composites provided a promising material for carbon tetrachloride removal from effluent.

  13. Study of the production of zirconium tetrachloride by chlorination of its oxide

    International Nuclear Information System (INIS)

    Seo, E.S.M.

    1983-01-01

    The studies carried out on the production of zirconium tetrachloride by chlorination of pure zirconium oxide with carbon tetrachloride and chlorine in the presence of carbon. In the process of chlorination with carbon tetrachloride, the chlorination efficiency increases with the rise in temperature at intervals between 450 and 750 0 C. The flow of the carbon tetrachloride vapour was 1.50l/min. Higher temperatures of 700 to 850 0 C were used for the zirconium oxide chlorination in the presence of carbon, and the flowrate of the chlorine gas used in the process was 0.50 l/min. Pure zirconium oxide chlorination as well as zirconium oxide - carbon misture chlorination have been studied in connection with the time of reaction at different temperatures and the apparent rate constant, the activation energies, the order of reaction in relation to the concentration of the gases (CCl 4 and Cl 2 ) and the content of carbon in the pellet have all been determined. (Author) [pt

  14. 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.

  15. 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

  16. Comparison of HfCl{sub 4}, HfI{sub 4}, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO{sub 2} films deposited by ALD: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Cortez-Valadez, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Fierro, C.; Farias-Mancilla, J.R. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); Vargas-Ortiz, A. [Universidad Autónoma de Sinaloa, Facultad de Ingeniería Mochis, Ciudad Universitaria, C.P. 81223 Los Mochis, Sinaloa (Mexico); Flores-Acosta, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Ramírez-Bon, R. [Centro de Investigación y Estudios Avanzados del IPN, Unidad Querétaro, Apdo. Postal 1-798, 76001 Querétaro, Qro. (Mexico); Enriquez-Carrejo, J.L. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); and others

    2016-06-15

    Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO{sub 2} films grown by atomic layer deposition (ALD) after reaction with OH{sup −} ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl{sub 4} (hafnium tetrachloride), HfI{sub 4} (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  17. Carbon tetrachloride ERA soil-gas baseline monitoring

    International Nuclear Information System (INIS)

    Fancher, J.D.

    1994-01-01

    From December 1991 through December 1993, Westinghouse Hanford Company performed routine baseline monitoring of selected wells ad soil-gas points twice weekly in the 200 West Area of the Hanford Site. This work supported the carbon Tetrachloride Expedited Response Action (ERA) and provided a solid baseline of volatile organic compound (VOC) concentrations in wells and in the subsurface at the ERA site. As site remediation continues, comparisons to this baseline can be one means of measuring the success of carbon tetrachloride vapor extraction. This report contains observations of the patterns and trends associated with data obtained during soil-gas monitoring at the 200 West Area: Monitoring performed since late 1991 includes monitoring soil-gas probes ad wellheads for volatile organic compounds (VOCs). This report reflects monitoring data collected from December 1991 through December 1993

  18. 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)

  19. 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)

  20. Analysis of titanium content in titanium tetrachloride solution

    Science.gov (United States)

    Bi, Xiaoguo; Dong, Yingnan; Li, Shanshan; Guan, Duojiao; Wang, Jianyu; Tang, Meiling

    2018-03-01

    Strontium titanate, barium titan and lead titanate are new type of functional ceramic materials with good prospect, and titanium tetrachloride is a commonly in the production such products. Which excellent electrochemical performance of ferroelectric tempreature coefficient effect.In this article, three methods are used to calibrate the samples of titanium tetrachloride solution by back titration method, replacement titration method and gravimetric analysis method. The results show that the back titration method has many good points, for example, relatively simple operation, easy to judgment the titration end point, better accuracy and precision of analytical results, the relative standard deviation not less than 0.2%. So, it is the ideal of conventional analysis methods in the mass production.

  1. 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.

  2. 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.

  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. 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

  5. Production kinetics of zirconium tetrachloride

    International Nuclear Information System (INIS)

    Sudjoko, D.; Masduki, B.; Sunardjo; Sulistyo, B.

    1996-01-01

    This research was intended to study the kinetics of zirconium tetrachloride production. The process was carried out in semi continuous reactor, equipped with heater, temperature controller, sublimator and scrubber. The variables investigated were time, temperature and the pellet forming pressure. Within the range of variables studied, the expression of the process in the chemical reaction controller region and diffusion controller region were both presented. (author)

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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

  11. Performance Evaluation Report for Soil Vapor Extraction Operations at the Carbon Tetrachloride Site, February 1992 - September 1998

    International Nuclear Information System (INIS)

    Rohay, V. J.

    1999-01-01

    Soil vapor extraction (SVE) is being used to remove carbon tetrachloride from the vadose zone at the 200-ZP-2 Operable Unit. The purpose of this report is to evaluate both the SVE system operating data and the effectiveness of SVE in remediating the carbon tetrachloride contamination. This report has been revised to cover the operating period from February 25, 1992 through September 30, 1998. The scope of the report includes the history of SVE operations at 200-ZP-2, the efficiency of those operations over time, the volume of vapor processed per extraction system, the change in carbon tetrachloride concentrations with time, the mass of carbon tetrachloride removed per site, and recommendations for future operations and evaluations. This revision includes an update to the carbon tetrachloride conceptual model

  12. Expedited response action proposal (EE/CA ampersand EA) for 200 West Area carbon tetrachloride plume

    International Nuclear Information System (INIS)

    1991-09-01

    The report contains the proposal for an expedited response action (ERA) for the remediation of carbon tetrachloride contamination in the unsaturated soils beneath the 200 West Area of the Hanford Site. It provides the US Environmental Protection Agency (EPA) and the Washington State Department of Ecology (Ecology) with information regarding the need for the ERA and an evaluation of alternatives to reduce the mobility, toxicity, and/or volume of the carbon tetrachloride in the unsaturated soils. This report is intended to aid the EPA and Ecology in selecting a preferred alternative for implementing the ERA. This proposal does not address remediation of carbon tetrachloride in the ground water underlying the 200 West Area; nor is the radioactive waste mixed with the carbon tetrachloride in the disposal site the subject of this ERA. This report has also been prepared to address the requirements for an environmental assessment (EA). The purpose of this ERA is to prevent, or at least minimize, further migration of carbon tetrachloride contamination from the unsaturated soils to uncontaminated areas. This action is needed to ensure that the environment and public health are adequately protected and to reduce the threat of further groundwater contamination. Information on the origin, nature, and extent of carbon tetrachloride (and co-contaminants), and other site characteristics used as a basis for evaluating remedial alternatives is presented

  13. Synthesis of zirconium by zirconium tetrachloride reduction by magnesio-thermia. Experimental study and modelling

    International Nuclear Information System (INIS)

    Basin, N.

    2001-01-01

    This work deals with the synthesis of zirconium. The ore is carbo-chlorinated to obtain the tetrachloride which is then purified by selective condensation and extractive distillation. Zirconium tetrachloride is then reduced by magnesium and the pseudo-alloy is obtained according to the global following reaction (Kroll process): ZrCl 4 + 2 Mg = 2 MgCl 2 . By thermodynamics, it has been shown that the volatilization of magnesium chloride and the formation of zirconium sub-chlorides are minimized when the combined effects of temperature and of dilution with argon are limited. With these conditions, the products, essentially zirconium and magnesium chloride, are obtained in equivalence ratio in the magnesio-thermia reaction. The global kinetics of the reduction process has been studied by a thermal gravimetric method. A thermo-balance device has been developed specially for this kinetics study. It runs under a controlled atmosphere and is coupled to a vapor tetrachloride feed unit. The transformation is modelled supposing that the zirconium and magnesium chloride formation result: 1)of the evaporation of magnesium from its liquid phase 2)of the transfer of magnesium and zirconium tetrachloride vapors towards the front of the reaction located in the gaseous phase 3)of the chemical reaction. In the studied conditions, the diffusion is supposed to be the limiting process. The influence of the following parameters: geometry of the reactive zone, temperature, scanning rate of the argon-zirconium tetrachloride mixture, composition of the argon-zirconium tetrachloride mixture has been experimentally studied and confronted with success to the model. (O.M.)

  14. 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

  15. 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.)

  16. 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

  17. 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)

  18. 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

  19. 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

  20. 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

  1. Transformation of carbon tetrachloride in an anaerobic packed-bed reactor without addition of another electron donor

    NARCIS (Netherlands)

    de Best, JH; Hunneman, P; Doddema, HJ; Janssen, DB; Harder, W; Doddema, Hans J.

    1999-01-01

    Carbon tetrachloride (52 mu M) was biodegraded for more than 72% in an anaerobic packed-bed reactor without addition of an external electron donor. The chloride mass balance demonstrated that all carbon tetrachloride transformed was completely dechlorinated. Chloroform and dichloromethane were

  2. Transformation of carbon tetrachloride in an anaerobic packed-bed reactor without addition of another electron donor

    NARCIS (Netherlands)

    Best, J.H. de; Hunneman, P.; Doddema, H.J.; Janssen, D.B.; Harder, W.

    1999-01-01

    Carbon tetrachloride (52 μM) was biodegraded for more than 72% in an anaerobic packed-bed reactor without addition of an external electron donor. The chloride mass balance demonstrated that all carbon tetrachloride transformed was completely dechlorinated. Chloroform and dichloromethane were

  3. 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.

  4. 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

  5. Liquid structure of vanadium tetrachloride from neutron diffraction study

    International Nuclear Information System (INIS)

    Gopala Rao, R.V.; Satpathy, B.M.

    1982-01-01

    Assuming the separation of the intermolecular scattering function into the radial and angular parts and using Egelstaff et al's orientational model for tetrachlorides, the structure of liquid vanadium tetrachloride has been studied. It has been observed that such a separation is approximate for this liquid and the introduction of a third correction term is required to account for the molecular structure function. The chlorine-chlorine partial structure and effective angle-averaged intermolecular chlorine-chlorine potential in the liquid has been evaluated. Without taking the third correction term, introduced to generate theoretically the molecular structure function, the centre structure function has been obtained in an approximate way from the experimentally observed molecular structure function and from it the centre radial distribution function, centre direct correlation function and the angle-averaged vanadium-vanadium effective potential has been evaluated. (author)

  6. 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

  7. 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

  8. In situ bioremediation for the Hanford carbon tetrachloride plume. Innovative technology summary report

    International Nuclear Information System (INIS)

    1999-04-01

    The 200 Area at Hanford (also called the Central Plateau) contains approximately 817 waste sites, 44 facilities to be demolished, and billions of gallons of contaminated groundwater resulting from chemical processing plants and associated waste facilities (e.g., waste tanks). From 1955 to 1973, carbon tetrachloride, nitrate, and other materials were discharged to subsurface liquid waste disposal facilities in the 200 Area. As much as 600,000 kilograms of carbon tetrachloride may have entered the soil column and a portion of this has contaminated the underlying aquifer. In Situ Bioremediation for the Hanford Carbon Tetrachloride Plume (ISB), which is the term used in this report for an in situ treatment process using indigenous micro-organisms with a computer based Accelerated Bioremediation Design Tool (ABDT), remediates groundwater contaminated with volatile organic compounds (VOCs) and nitrates under anaerobic conditions. ISB involves the injection of nutrients into the groundwater and subsequent extraction and re-injection of the groundwater to provide nutrient distribution in the aquifer

  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. 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.)

  11. 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

  12. 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.)

  13. 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.)

  14. 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.

  15. Hepatoprotective activity of Eugenia jambolana Lam. in carbon tetrachloride treated rats

    Science.gov (United States)

    Sisodia, S.S.; Bhatnagar, M.

    2009-01-01

    Objective: To estimate the hepatoprotective effects of the methanolic seed extract of Eugenia jambolana Lam. (Myrtaceae), in Wistar albino rats treated with carbon tetrachloride (CCl4). Materials and Methods: Liver damage in rats treated with CCl4 (1ml/kg/Bw, administered subcutaneously, on alternate days for one week) was studied by assessing parameters such as serum glutamate oxaloacetate transaminase (SGOT), serum glutamate pyruvate transaminase (SGPT), alkaline phosphatase (ALP), acid phosphatase (ACP) and bilirubin (total and direct). The effect of co-administration of Eugenia jambolana Lam. (doses 100, 200 and 400 mg/kg p. o.) on the above parameters was investigated. These biochemical observations were supplemented by weight and histological examination of liver sections. Liv.52® was used as positive control. Data were analyzed by one way ANOVA, followed by Scheff's/Dunnett's test. Results: Administration of Eugenia jambolana Lam. (doses 100, 200 and 400 mg/kg p. o.) significantly prevented carbon tetrachloride induced elevation of serum SGOT, SGPT, ALP, ACP and bilirubin (total and direct) level. Histological examination of the liver section revealed hepatic regeneration, after administration of various doses of Eugenia jambolana Lam. The results were comparable to that of Liv.52®. Conclusion: The study suggests preventive action of Eugenia jambolana Lam. in carbon tetrachloride induced liver toxicity. Hepatic cell regeneration process was dose dependent. PMID:20177577

  16. 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.

  17. 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)

  18. Dietary Antioxidants Effectiveness on Carbon Tetrachloride-Induced Hepatotoxicity in Adult Female Albino Rats

    International Nuclear Information System (INIS)

    EI-Sherbiny, E.M.; EI-Mahdy, A.A.

    2008-01-01

    Hepatic toxicity through carbon tetrachloride (CCI 4 ) induced lipid peroxidation was extensively used in experimental models to understand the cellular mechanisms behind oxidative damage and to evaluate the therapeutic potential of drugs and dietary antioxidants. The ameliorative effect of Aloe vera juice and carrot supplementation on hepato carcinogenesis induced by carbon tetrachloride in adult female albino rats was investigated. The carcinogenic process was determined by measuring gamma-glutamyl transpeptidase (GGT), ornithine carbamyl transferase (OCT), thiobarbituric acid reactive substances (TBARs), representing levels of lipid peroxides, and carcinoembryonic antigen (CEA) in the sera of female albino rats. Carbon tetrachloride significantly elevated the serum GGT, OCT activities and the level of TBARs. Administration of Aloe vera leaf juice filtrate after CCl 4 treatment resulted in a non-significant modification in GGT, OCT activities and significantly improved the level of TBARs in comparison with control. Supplementation of carrot to CCI 4 treated animals led to a great amelioration in OCT activity and TBARs level, whereas GGT activity was ameliorated but statistically changed compared to control. There was a non-significant alteration in the level of CEA in all treated groups compared to normal control one

  19. Summary of canister overheating incident at the Carbon Tetrachloride Expedited Response Action site

    Energy Technology Data Exchange (ETDEWEB)

    Driggers, S.A.

    1994-03-10

    The granular activated carbon (GAC)-filled canister that overheated was being used to adsorb carbon tetrachloride vapors drawn from a well near the 216-Z-9 Trench, a subsurface disposal site in the 200 West Area of the Hanford Site. The overheating incident resulted in a band of discolored paint on the exterior surface of the canister. Although there was no other known damage to equipment, no injuries to operating personnel, and no releases of hazardous materials, the incident is of concern because it was not anticipated. It also poses the possibility of release of carbon tetrachloride and other hazardous vapors if the incident were to recur. All soil vapor extraction system (VES) operations were halted until a better understanding of the cause of the incident could be determined and controls implemented to reduce the possibility of a recurrence. The focus of this report and the intent of all the activities associated with understanding the overheating incident has been to provide information that will allow safe restart of the VES operations, develop operational limits and controls to prevent recurrence of an overheating incident, and safely optimize recovery of carbon tetrachloride from the ground.

  20. 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

  1. 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)

  2. Preliminary evaluation of soil-heating technologies for the 200-ZP-2 carbon tetrachloride expedited response action

    International Nuclear Information System (INIS)

    Jackson, G.J.; Todd, M.E.; Tranbarger, R.K.

    1996-09-01

    The 200-ZP-2 Operable Unit is located in the 200 West Area of the Hanford Site. The US Department of Energy has been conducting an expedited response action to treat carbon tetrachloride contamination since 1992 at the operable unit at the direction of the US Environmental Protection Agency and the Washington State Department of Ecology. This document provides an analyses of the soil vapor extraction method used to extract carbon tetrachloride from the soil

  3. 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)

  4. Thermophysical Properties of Matter - The TPRC Data Series. Volume 4. Specific Heat - Metallic Elements and Alloys

    Science.gov (United States)

    1971-01-01

    Indium—Indium alloys—Iron—iron alloys— lanthanum — load—lead alloys—lithium—lithium alloya—«agnaslum—magnaalum alloys—manganas^ —naoganasa alloys—marcury...Germanium 21 Gold 22 Hafnium 23 Holmium 24 Indium 25 Iridium 26 Iron 27 Lanthanum 28 Lead 29 Lithium 30 Lutetium 31 Magnesium 32 Manganese 33...hexahydrate (ErC^-eHjO Erbium gallate (see Trierbium pentagallium 1 dodecaoxide) 4 5 65 822 Freon 10 (see Carbon tetrachloride) Freon 11

  5. 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

  6. 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

  7. 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

  8. A carbon tetrachloride-free synthesis of N-phenyltrifluoroacetimidoyl chloride.

    Science.gov (United States)

    Smith, Dylan G M; Williams, Spencer J

    2017-10-10

    N-Phenyltrifluoroacetimidoyl chloride (PTFAI-Cl) is a reagent widely used for the preparation of glycosyl N-phenyltrifluoroacetimidates. However, the most commonly applied method requires carbon tetrachloride, a hepatotoxic reagent that has been phased out under the Montreal Protocol. We report a new synthesis of N-phenyltrifluoroacetimidoyl chloride (PTFAI-Cl) using dichlorotriphenylphosphane and triethylamine. Copyright © 2017. Published by Elsevier Ltd.

  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. 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

  11. 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

  12. 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)

  13. 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)

  14. 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) .

  15. 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.

  16. Amelioration of carbon tetrachloride-induced hepatic injury by emulsified Antrodia extract

    Directory of Open Access Journals (Sweden)

    Wei-Chih Chang

    2018-03-01

    Full Text Available Objective(s: Antrodia cinnamomea (AC is found with anti-inflammatory and immunomodulatory biological activities. In this study, we investigated the anti-hepatitis effect of the emulsified AC extract from RO water or supercritical fluid CO2 with ethanol co-solvent extract methods of AC preparations. Materials and Methods: Five groups of eight to ten weeks male rats with a count of ten for each group were studied to evaluate the protection of two kinds of AC extract from hepatic injury. Acute liver injury of rats was induced by injecting 40% carbon tetrachloride (CCl4 1 mg/kg intraperitoneally. Positive and negative control groups rats were perfused with CCl4 or isotonic saline, respectively. Experimental groups received oral administration once/day of AC preparations before CCl4 treatment: water AC extract (WAE group, or emulsified AC extract from supercritical fluid extraction (EAE group for 5 days, and sacrificed on the 6th day and the blood and liver samples were collected under chloral hydrate anesthesia. The anti-inflammatory, antioxidant markers, and relevant signaling pathways were measured (AST, ALT, ROS, IL-1, IL-6, NO, and COX-2, MAPKs, and caspase-3. Results: EAE at 50 mg/kg significantly decreased the serum AST, ALT, IL-1, IL-6, NO, and ROS levels. Both extracts reduced the activation of p-ERK in the liver samples, but EAE inhibited COX-2 and caspase-3 protein expression better than WAE. The EAE ameliorated CCl4-induced hepatic injury significantly; as compared with WAE and the positive control. Conclusion: The hepatoprotection of EAE could be attributed to the antioxidant and anti-inflammatory effects of Antrodia.

  17. 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.

  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. 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

  20. Betaine reduces hepatic lipidosis induced by carbon tetrachloride in Sprague-Dawley rats.

    Science.gov (United States)

    Junnila, M; Barak, A J; Beckenhauer, H C; Rahko, T

    1998-10-01

    Carbon tetrachloride-injected rats were given liquid diets with and without betaine for 7 d. Hepatic lipidosis was induced by 4 daily injections of carbon tetrachloride (CCl4). Animals were killed and their livers and blood taken for analysis of betaine, S-adenosylmethionine (SAM), betaine homocysteine methyltransferase (BHMT), triglyceride, alanine aminotransferase and aspartate aminotransferase. Liver samples were also processed and stained for histological examination. Supplemental betaine reduced triglyceride in the liver and centrilobular hepatic lipidosis induced by the CCl4 injections. In both the control and experimental groups receiving betaine, liver betaine, BHMT and SAM were significantly higher than in their respective groups not receiving betaine. This study provides evidence that betaine protects the liver against CCl4-induced lipidosis and may be a useful therapeutic and prophylactic agent in ameliorating the harmful effects of CCl4.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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...

  6. 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.

  7. 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

  8. 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.

  9. 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)

  10. 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)

  11. 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.

  12. 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

  13. Studying preventive effects of Berberisintegerrimaon root on carbon tetrachloride induced hepatotoxicity in broilers

    Directory of Open Access Journals (Sweden)

    mohammadreza mohammadimalayeri

    2013-11-01

    Full Text Available Liver diseases and their economic losses have gained more importancealongside the development of integrated poultry industry. Studies have proved hepatotoxicity induced by carbon tetrachloride as one of the best experimental models of hepatotocicity. Barberries have been used widely in traditional medicine.The purpose of the present study was to evaluaterthe preventive effects of Berberisintegerrima root on carbon tetrachloride induced liver lesions in broilers.For this purpose, 80 day old Ross strain broilers were divided randomly to 8 study groupsconsisting of negative control, positive control which received IP 4ml/kg b.w. carbon tetrachloride twice in 25th and 28thdays , treatment controls consisting of 10,20 and 30 grams of  Berberisintegerrima root per kilogram of diet and treatment groups consisting of 10,20 and 30 gr. Of Berberis root / Kg diet + IPcarbontetrachloride 4ml/Kg b.w. twice in 25th and 28th days.At 29th day, blood samples were collected from animals, then they were sacrificed and their liver samples were fixed in 10% formalin solution. The blood samples were sent to laboratory to measure ALT,AST and ALP activities.Biochemical results didn't show any significant changes of ALT,AST and ALP activities between all study groups (P>0.05. Microscopic results showed significant decrease in pathologic lesions of 20 gr Berberis root /Kg diet treatment group in comparison with the positive control group(P

  14. Maresin 1, a Proresolving Lipid Mediator, Mitigates Carbon Tetrachloride-Induced Liver Injury in Mice

    Directory of Open Access Journals (Sweden)

    Ruidong Li

    2016-01-01

    Full Text Available Maresin 1 (MaR 1 was recently reported to have protective properties in several different animal models of acute inflammation by inhibiting inflammatory response. However, its function in acute liver injury is still unknown. To address this question, we induced liver injury in BALB/c mice with intraperitoneal injection of carbon tetrachloride with or without treatment of MaR 1. Our data showed that MaR 1 attenuated hepatic injury, oxidative stress, and lipid peroxidation induced by carbon tetrachloride, as evidenced by increased thiobarbituric acid reactive substances and reactive oxygen species levels were inhibited by treatment of MaR 1. Furthermore, MaR 1 increased activities of antioxidative mediators in carbon tetrachloride-treated mice liver. MaR 1 decreased indices of inflammatory mediators such as tumor necrosis factor-α, interleukin-6, interleukin-1β, monocyte chemotactic protein 1, myeloperoxidase, cyclooxygenase-2, and inducible nitric oxide synthase. Administration of MaR 1 inhibited activation of nuclear factor kappa B (NF-κb and mitogen-activated protein kinases (MAPKs in the liver of CCl4 treated mice. In conclusion, these results suggested the antioxidative, anti-inflammatory properties of MaR 1 in CCl4 induced liver injury. The possible mechanism is partly implicated in its abilities to inhibit ROS generation and activation of NF-κb and MAPK pathway.

  15. 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

  16. USE OF NARROW-DIAMETER DIRECT-PUSH WELLS TO CHARACTERIZE AND REMEDIATE CARBON TETRACHLORIDE IN THE 200 WEST AREA HANFORD SITE, WASHINGTON

    International Nuclear Information System (INIS)

    Rohay, V.J.

    2009-01-01

    This single page graphic shows several figures. The Hydraulic Hammer Rig (HHR) direct-push technology has been successfully used to characterize carbon tetrachloride in the vadose zone. Based on their favorable performance and radius of influence, HHR SVE wells have potential for future use in both monitoring and targeted SVE to achieve VOC cleanup goals at the carbon tetrachloride waste sites

  17. 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.

  18. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: Eric.Kennedy@newcastle.edu.au [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)

    2014-09-15

    Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  19. 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)

  20. 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

  1. 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

  2. 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.

  3. Correlation of NMR and refractometry to evaluate the stability constant on carbon tetrachloride

    International Nuclear Information System (INIS)

    Modarress, H.; Pouryazadanpanah, N.

    2004-01-01

    An equation has been suggested which correlate the NMR and refractometry results to evaluate the stability constant of electron donor complexes. Using this equation the stability constant of complexation between carbon tetrachloride and toluene in cyclohexane has been studied by refractometry and NMR spectroscopy

  4. 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)

  5. 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.

  6. 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...

  7. 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

  8. [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.

  9. 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

  10. 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

  11. Inhibitory effects of prior low-dose X-ray irradiation on carbon tetrachloride-induced hepatopathy in acatalasemic mice

    International Nuclear Information System (INIS)

    Yamaoka, Kiyonori; Kataoka, Takahiro; Taguchi, Takehito; Wang, Da-Hong; Mori, Shuji; Hanamoto, Katsumi; Kira, Shohei; Nomura, Takaharu

    2004-01-01

    The catalase activities in blood and organs of the acatalasemic (C3H/AnLCs b Cs b ) mouse of C3H strain are lower than those of the normal (C3H/AnLCs a Cs a ) mouse. We examined the effects of prior low-dose (0.5 Gy) X-ray irradiation, which reduced the oxidative damage under carbon tetrachloride-induced hepatopathy in the acatalasemic or normal mice. The acatalasemic mice showed a significantly lower catalase activity and a significantly higher glutathione peroxidase activity compared with those in the normal mice. Moreover, low-dose irradiation increased the catalase activity in the acatalasemic mouse liver to a level similar to that of the normal mouse liver. Pathological examinations and analyses of blood glutamic oxaloacetic and glutamic pyruvic transaminase activity and lipid peroxide levels showed that carbon tetrachloride induced hepatopathy was inhibited by low-dose irradiation. These findings may indicate that the free radical reaction induced by the lack of catalase and the administration of carbon tetrachloride is more properly neutralized by high glutathione peroxidase activity and low-dose irradiation in the acatalasemic mouse liver. (author)

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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

  17. Saturated steams pressure of HfCl/sub 4/-KCl molten mixtures

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-02-01

    A bellows null pressure gauge and the dynamic method were used to measure the total and partial pressures of saturated vapors of individual components of molten HfCl/sub 4/-KCl mixtures, as a function of temperature (260 to 1000 deg C) and composition (1.9 to 64.3 mol.% HfCl/sub 4/). Empirical equations expressing the relationship between pressure and temperature are presented. It is shown that in molten mixtures of hafnium tetrachloride with chlorides of alkaline metals its partial pressure dramatically increases when potassium chloride substitutes for cesium chloride.

  18. Saturated steams pressure of HfCl4-KCl molten mixtures

    International Nuclear Information System (INIS)

    Salyulev, A.B.; Smirnov, M.V.; Kudyakov, V.Ya.

    1980-01-01

    A bellows null pressure gauge and the dynamic method were used to measure the total and partial pressures of saturated vapors of individual components of molten HfCl 4 -KCl mixtures, as a function of temperature (260 to 1000 deg C) and composition (1.9 to 64.3 mol.% HfCl 4 ). Empirical equations expressing the relationship between pressure and temperature are presented. It is shown that in molten mixtures of hafnium tetrachloride with chlorides of alkaline metals its partial pressure dramatically increases when potassium chloride substitutes for cesium chloride

  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. 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.

  1. 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

  2. Protective Effect of the Persian Gulf brittle star Ophiocoma Erinaceus extract on carbon tetrachloride (CCl4 induced liver damage in adult male Wistar rats

    Directory of Open Access Journals (Sweden)

    Aida Soheili

    2015-12-01

    Full Text Available Background and Aim:  Brittle star possess  bioactive compounds which confer the wound healing capacity and regenerative potency of damaged  arms and organisms to this creature. The aim of the current study was to assess the   protective  effect  of  the  star extract on liver damages induced by carbon tetrachloride in adult male Wistar rats. Materials and Methods: In this experimental study, 32 adult male rats were randomly divided into 4 equal groups: control, Sham exposed, experimental 1 (treated with %25 extract and experimental 2 (treated with %50 extract of star Ophiocoma Erinaceus. The control group received no treatment. The sham exposed groups received carbon tetrachloride .(50% in olive oil .0.5 ml/kg for 7 days. The experimental groups firstly received carbon tetrachloride, then received %25, %50 brittle star extract as intragastric for 7 days. Finally, the animals were sacrificed, and their bodies and livers were weighed. Then, the livers sections were prepared and were examined by means of light microscope. Finally, the obtained  quantitative data was analyzed using SPSS (V; 20, Mini Tab software, ANOVA, and Tukey. at the significant level of P<0.001. Results: Carbon tetrachloride significantly decreased the rats’ body weight, but it increased their livers weight (P<0.001. Histopathological evaluations showed .extensive liver damage. On the other hand, treatment with brittle star extract .ncreased liver weight, reduced. body weight and significantly altered other induced changes by carbon tetrachloride on liver structure such as hepatocytes number, Kupffer cells, and arteritis, which indicated  the improvement of damaged liver tissue (P<0.001. Conclusion: It was found that brittle star extract can exert protective effects on  liver damages induced by carbon tetrachloride on male Wistar rat.

  3. 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

  4. Evaluation of Hepatoprotective Effects of Hydroalcoholic Extract of Green Pepper and Parsley on the Toxicity Induced by Carbon Tetrachloride in Rats

    Directory of Open Access Journals (Sweden)

    E Adibfard

    2014-02-01

    Background & aim: Green pepper and parsley have high antioxidant properties due to flavonoids and polyphenolic compounds. The aim of this study was to investigate the hepatoprotective effects of hydroalcoholic extract of green pepper and parsley on the toxicity induced by carbon tetrachloride in rats. Methods: In the present experimental study, 48 male Wistar rats were divided into six groups of eight. The first group (negative control received olive oil, the second group receiving tetrachloride carbon and olive oil in equal proportions. The third and fourth groups (treatment groups were treated with the tetrachloride carbon and olive oil equally and then exposed to extract of parsley and green pepper to the amount of 200 mg/kg separately. The fifth and six groups were treated with tetrachloride carbon and olive oil equally, and then separately exposed to 400 mg/kg of parsley and green pepper extract. The amount of total phenol and flavonoid samples and antioxidant activities were assessed by different methods. The collected data were analyzed by One-way ANOVA tests followed by Tukey test. Results: Intraperitoneal injection of 202, 191 and 183 In.U/L of carbon tetrachloride to positive control increased the activity of alkaline phosphatase, aspartate aminotransferase and alanine aminotransferase, respectively. The injection of carbon tetrachloride increased total bilirubin at the rate of4.8 mg/dl and also decreased protein and albumin at rate of 5.1 and 2.6 g/dl.Mqdartvtal respectively 1/5 and 6/2 g, was dL ( p <0.001. In the groups treated with the extract the activity of alkaline phosphatase, aspartate aminotransferase and alanine aminotransferase in the third to sixth groups were 121, 115 and 109, 130, 121 and 121, 112 109 and 98, 118, 114, and 119 respectively. The values of bilirubin, total protein and albumin, in the III group were: 3/8, 5/5 and 2/8, Group IV: 3/9, 5/3and 2/7, the V: 3/6, 5/8 and 3/1, the VI: 3/8, 5/6 and 3, respectively. Finaly, the amount

  5. 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)

  6. 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

  7. 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)

  8. 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.

  9. 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.

  10. 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)

  11. 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

  12. 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.

  13. Bioavailability of andrographolide and protection against carbon tetrachloride-induced oxidative damage in rats

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Haw-Wen [Department of Nutrition, China Medical University, Taichung, Taiwan (China); Huang, Chin-Shiu [Department of Health and Nutrition Biotechnology, Asia University, Taichung, Taiwan (China); Li, Chien-Chun [School of Nutrition, Chung Shan Medical University, Taichung, Taiwan (China); Department of Nutrition, Chung Shan Medical University Hospital, Taichung, Taiwan (China); Lin, Ai-Hsuan; Huang, Yu-Ju [Department of Nutrition, China Medical University, Taichung, Taiwan (China); Wang, Tsu-Shing [Department of Biomedical Science, Chung Shan Medical University, Taichung, Taiwan (China); Yao, Hsien-Tsung [Department of Nutrition, China Medical University, Taichung, Taiwan (China); Lii, Chong-Kuei [Department of Nutrition, China Medical University, Taichung, Taiwan (China); Department of Health and Nutrition Biotechnology, Asia University, Taichung, Taiwan (China)

    2014-10-01

    Andrographolide, a bioactive diterpenoid, is identified in Andrographis paniculata. In this study, we investigated the pharmacokinetics and bioavailability of andrographolide in rats and studied whether andrographolide enhances antioxidant defense in a variety of tissues and protects against carbon tetrachloride-induced oxidative damage. After a single 50-mg/kg administration, the maximum plasma concentration of andrographolide was 1 μM which peaked at 30 min. The bioavailability of andrographolide was 1.19%. In a hepatoprotection study, rats were intragastrically dosed with 30 or 50 mg/kg andrographolide for 5 consecutive days. The results showed that andrographolide up-regulated glutamate cysteine ligase (GCL) catalytic and modifier subunits, superoxide dismutase (SOD)-1, heme oxygenase (HO)-1, and glutathione (GSH) S-transferase (GST) Ya/Yb protein and mRNA expression in the liver, heart, and kidneys. The activity of SOD, GST, and GSH reductase was also increased in rats dosed with andrographolide (p < 0.05). Immunoblot analysis and EMSA revealed that andrographolide increased nuclear Nrf2 contents and Nrf2 binding to DNA, respectively. After the 5-day andrographolide treatment, one group of animals was intraperitoneally injected with carbon tetrachloride (CCl{sub 4}) at day 6. Andrographolide pretreatment suppressed CCl{sub 4}-induced plasma aminotransferase activity and hepatic lipid peroxidation (p < 0.05). These results suggest that andrographolide is quickly absorbed in the intestinal tract in rats with a bioavailability of 1.19%. Andrographolide protects against chemical-induced oxidative damage by up-regulating the gene transcription and activity of antioxidant enzymes in various tissues. - Highlights: • The bioavailability of andrographolide is 1.19% in rats. • Plasma concentration reaches 1 μM after giving 50 mg/kg andrographolide. • Andrographolide up-regulates Nrf2-dependent antioxidant genes. • Andrographolide increases antioxidant defense

  14. Bioavailability of andrographolide and protection against carbon tetrachloride-induced oxidative damage in rats

    International Nuclear Information System (INIS)

    Chen, Haw-Wen; Huang, Chin-Shiu; Li, Chien-Chun; Lin, Ai-Hsuan; Huang, Yu-Ju; Wang, Tsu-Shing; Yao, Hsien-Tsung; Lii, Chong-Kuei

    2014-01-01

    Andrographolide, a bioactive diterpenoid, is identified in Andrographis paniculata. In this study, we investigated the pharmacokinetics and bioavailability of andrographolide in rats and studied whether andrographolide enhances antioxidant defense in a variety of tissues and protects against carbon tetrachloride-induced oxidative damage. After a single 50-mg/kg administration, the maximum plasma concentration of andrographolide was 1 μM which peaked at 30 min. The bioavailability of andrographolide was 1.19%. In a hepatoprotection study, rats were intragastrically dosed with 30 or 50 mg/kg andrographolide for 5 consecutive days. The results showed that andrographolide up-regulated glutamate cysteine ligase (GCL) catalytic and modifier subunits, superoxide dismutase (SOD)-1, heme oxygenase (HO)-1, and glutathione (GSH) S-transferase (GST) Ya/Yb protein and mRNA expression in the liver, heart, and kidneys. The activity of SOD, GST, and GSH reductase was also increased in rats dosed with andrographolide (p < 0.05). Immunoblot analysis and EMSA revealed that andrographolide increased nuclear Nrf2 contents and Nrf2 binding to DNA, respectively. After the 5-day andrographolide treatment, one group of animals was intraperitoneally injected with carbon tetrachloride (CCl 4 ) at day 6. Andrographolide pretreatment suppressed CCl 4 -induced plasma aminotransferase activity and hepatic lipid peroxidation (p < 0.05). These results suggest that andrographolide is quickly absorbed in the intestinal tract in rats with a bioavailability of 1.19%. Andrographolide protects against chemical-induced oxidative damage by up-regulating the gene transcription and activity of antioxidant enzymes in various tissues. - Highlights: • The bioavailability of andrographolide is 1.19% in rats. • Plasma concentration reaches 1 μM after giving 50 mg/kg andrographolide. • Andrographolide up-regulates Nrf2-dependent antioxidant genes. • Andrographolide increases antioxidant defense in

  15. Graphene oxide-mediated rapid dechlorination of carbon tetrachloride by green rust

    DEFF Research Database (Denmark)

    Huang, Li-Zhi; Hansen, Hans Christian B.; Daasbjerg, Kim

    2017-01-01

    Graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of chlorinated aliphatic hydrocarbons. In this study as low amounts as ∼0.007 % of graphene oxide (GO) was found to catalyze the reduction of carbon tetrachloride by layered Fe(II)-Fe(III) hydroxide (Green R....... This study indicates that traces of graphene oxide can affect reaction pathways as well as kinetics for dechlorination processes in anoxic sediments by facilitating a partial dechlorination....

  16. 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.

  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. Carbon Tetrachloride Flow Behavior in Unsaturated Hanford Caliche Material: An Investigation of Residual Nonaqueous Phase Liquids

    International Nuclear Information System (INIS)

    Oostrom, Mart; Lenhard, Robert J.

    2003-01-01

    To obtain data that can be used to study the development of a residual NAPL saturation and to test corresponding models, a detailed transient experiment was conducted in a 170-cm long by 90-cm high by 5.5-cm wide flow cell. Fluid saturation measurements were obtained with a dual-energy gamma radiation system. The experimental conditions reflected those at the Hanford Site in Washington State, where an estimated 363-580 m3 of carbon tetrachloride was disposed to the subsurface. A key subsurface feature at the Hanford Site is a sloped Plio-Pleistocene caliche layer, which was reproduced in the experiment as a sloped lens in a medium-grained, uniform, sand matrix. The caliche contains considerable amounts of calcium carbonate and may have fluid wettability properties other than strongly water wet. A total of 800 ml of carbon tetrachloride was injected in the experimental domain at a rate of 0.5 ml min-1 from a small source area located at the surface. After apparent steady-state conditions were obtained with respect to carbon tetrachloride redistribution (i.e., the formation of residual DNAPL), saturation measurements indicate that all of the DNAPL that initially moved into the caliche, remained in this layer. This experimental result could not be reproduced with numerical multifluid flow simulations based on conventional constitutive relations between relative permeability, saturation, and fluid pressures. Water was subsequently applied to the surface at a constant rate over the full length of the caliche layer to study carbon tetrachloride displacement as a result of changing water saturations. Results show that as a result of this action, 29% of the DNAPL was removed from the caliche. However, the majority of the fluid remained in the caliche entrapped by water. Simulations with the multifluid flow simulator show that the current constitutive theory for relative permeability, saturation and capillary pressure does not describe displacement physics properly

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.)

  4. 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

  5. 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)

  6. Carbon tetrachloride desorption from activated carbon

    International Nuclear Information System (INIS)

    Jonas, L.A.; Sansone, E.B.

    1981-01-01

    Carbon tetrachloride was desorbed from a granular activated carbon subsequent to its adsorption under various vapor exposure periods. The varied conditions of exposure resulted in a range of partially saturated carbon beds which, when followed by a constant flow rate for desorption, generated different forms of the desorbing concentration versus time curve. A method of analyzing the desorption curves is presented which permits extraction of the various desorbing rates from the different desorption and to relate this to the time required for such regeneration. The Wheeler desorption kinetic equation was used to calculate the pseudo first order desorption rate constant for the carbon. The desorption rate constant was found to increase monotonically with increasing saturation of the bed, permitting the calculation of the maximum desorption rate constant for the carbon at 100% saturation. The Retentivity Index of the carbon, defined as the dimensionless ratio of the adsorption to the desorption rate constant, was found to be 681

  7. 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...

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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)

  13. 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.

  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. 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…

  16. 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

  17. REDUCTIVE DEHALOGENATION OF HEXACHLOROETHANE, CARBON TETRACHLORIDE, AND BROMOFORM BY ANTHRAHYDROQUINONE DISULFONATE AND HUMIC ACID

    Science.gov (United States)

    The reductive dehalogenation of hexachloroethane (CzCLj), carbon tetrachloride (CC14), and bromoform (CHBr3) was examined at 50 “C in aqueous solutions containing ei- ther (1) 500 pM of 2,6-anthrahydroquinone disulfonate (AHQDS), (2) 250 pM Fe2+, or (3) 250 pM HS-. The pH ranged ...

  18. 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

  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. Nuclear magnetic relaxation in picolines solutions in carbon tetrachloride

    International Nuclear Information System (INIS)

    Jurga, J.; Pajak, Z.; Jurga, K.; Jurga, S.

    1973-01-01

    Spin-lattice relaxation times of the ring and CH 3 group have been measured in order to establish the temperature dependence of the longitudinal relaxation times for picolins in carbon tetrachloride solutions. The information concerning the intramolecular contribution to the relaxation times have been obtained. The high resolution NPR spectrometer operating at 25 MHz has been used. The measurements have been performed in the temperature range from -60degC to 80degC. The experimental results are compared to the predictions given by the Nora Hill and Debye models and it has been found that the Nora Hill model fits the experimental data better than the Debye model. (S.B.)

  1. 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.

  2. 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)

  3. 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.

  4. Coagulation performance and floc characteristics of polytitanium tetrachloride (PTC) compared with titanium tetrachloride (TiCl4) and ferric chloride (FeCl3) in algal turbid water

    KAUST Repository

    Chekli, L.; Eripret, C.; Park, S.H.; Tabatabai, S. Assiyeh Alizadeh; Vronska, O.; Tamburic, B.; Kim, J.H.; Shon, H.K.

    2016-01-01

    Seasonal green algae blooms in freshwaters have raised attention on the need to develop novel effective treatment processes for the removal of algae in water. In the present study, the performance of newly developed polytitanium tetrachloride (PTC) coagulant for the removal of freshwater microalga Chlorella vulgaris has been investigated and compared with titanium tetrachloride (TiCl4) coagulant and the conventional ferric chloride (FeCl3) coagulant. The main benefit of using titanium-based coagulants is that the sludge produced after flocculation may be recycled into a valuable product: titanium dioxide photocatalyst. Both titanium-based coagulants achieved good flocculation over a broader pH range and coagulant dose compared to conventional FeCl3 coagulant. All three coagulants achieved comparable performance in terms of turbidity removal (i.e. turbidity removal efficiency >97%); although TiCl4 performed slightly better at the lower tested dose (i.e. <9 mg/L). Zeta potential measurements indicated that charge neutralisation may not be the sole mechanism involved in the coagulation of algae for all three coagulants. Analysis of the dynamic floc size variation during floc breakage showed no regrowth after floc breakage for the three coagulants. The flocs formed by both Ti-based coagulants were larger than those formed by FeCl3 and also grew at a faster rate. This study indicates that Ti-based coagulants are effective and promising coagulants for algae removal in water.

  5. Coagulation performance and floc characteristics of polytitanium tetrachloride (PTC) compared with titanium tetrachloride (TiCl4) and ferric chloride (FeCl3) in algal turbid water

    KAUST Repository

    Chekli, L.

    2016-11-11

    Seasonal green algae blooms in freshwaters have raised attention on the need to develop novel effective treatment processes for the removal of algae in water. In the present study, the performance of newly developed polytitanium tetrachloride (PTC) coagulant for the removal of freshwater microalga Chlorella vulgaris has been investigated and compared with titanium tetrachloride (TiCl4) coagulant and the conventional ferric chloride (FeCl3) coagulant. The main benefit of using titanium-based coagulants is that the sludge produced after flocculation may be recycled into a valuable product: titanium dioxide photocatalyst. Both titanium-based coagulants achieved good flocculation over a broader pH range and coagulant dose compared to conventional FeCl3 coagulant. All three coagulants achieved comparable performance in terms of turbidity removal (i.e. turbidity removal efficiency >97%); although TiCl4 performed slightly better at the lower tested dose (i.e. <9 mg/L). Zeta potential measurements indicated that charge neutralisation may not be the sole mechanism involved in the coagulation of algae for all three coagulants. Analysis of the dynamic floc size variation during floc breakage showed no regrowth after floc breakage for the three coagulants. The flocs formed by both Ti-based coagulants were larger than those formed by FeCl3 and also grew at a faster rate. This study indicates that Ti-based coagulants are effective and promising coagulants for algae removal in water.

  6. Synthesis of zirconium by zirconium tetrachloride reduction by magnesio-thermia. Experimental study and modelling; Elaboration de zirconium par reduction de tetrachlorure de zirconium par magnesothermie. Etude experimentale et modelisation

    Energy Technology Data Exchange (ETDEWEB)

    Basin, N

    2001-01-01

    This work deals with the synthesis of zirconium. The ore is carbo-chlorinated to obtain the tetrachloride which is then purified by selective condensation and extractive distillation. Zirconium tetrachloride is then reduced by magnesium and the pseudo-alloy is obtained according to the global following reaction (Kroll process): ZrCl{sub 4} + 2 Mg = 2 MgCl{sub 2}. By thermodynamics, it has been shown that the volatilization of magnesium chloride and the formation of zirconium sub-chlorides are minimized when the combined effects of temperature and of dilution with argon are limited. With these conditions, the products, essentially zirconium and magnesium chloride, are obtained in equivalence ratio in the magnesio-thermia reaction. The global kinetics of the reduction process has been studied by a thermal gravimetric method. A thermo-balance device has been developed specially for this kinetics study. It runs under a controlled atmosphere and is coupled to a vapor tetrachloride feed unit. The transformation is modelled supposing that the zirconium and magnesium chloride formation result: 1)of the evaporation of magnesium from its liquid phase 2)of the transfer of magnesium and zirconium tetrachloride vapors towards the front of the reaction located in the gaseous phase 3)of the chemical reaction. In the studied conditions, the diffusion is supposed to be the limiting process. The influence of the following parameters: geometry of the reactive zone, temperature, scanning rate of the argon-zirconium tetrachloride mixture, composition of the argon-zirconium tetrachloride mixture has been experimentally studied and confronted with success to the model. (O.M.)

  7. 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.

  8. 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.

  9. 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

  10. 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)

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. Solvent--solvent extraction of rhodium-103m from ruthenium-103 employing a sulfate-carbon tetrachloride medium

    International Nuclear Information System (INIS)

    Epperson, C.E.; Landolt, R.R.; Kessler, W.V.

    1976-01-01

    /sup 103m/Rh in equilibrium with parent 103 Ru was separated in yields of 94 percent of those theoretically possible. 103 Ru chloride was first converted to the tetroxide which was then extracted from an aqueous solution of the equilibrium mixture with carbon tetrachloride

  17. 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

  18. 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.

  19. 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.

  20. 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 ...

  1. 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

  2. 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

  3. 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

  4. 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)

  5. Vanadium purification by transformation to the tetrachloride and reduction by hydrogen. Study of the reduction mechanism

    International Nuclear Information System (INIS)

    Val, Christian

    1968-01-01

    The problem studied here is the production of very high purity metallic vanadium. By analogy with the method used for silicon or germanium production in electronics, the one employed here involves preparing the tetrachloride from the impure metal, purifying it by distillation, an easy process, and finally reducing this tetrachloride with hydrogen to obtain the pure metal. By this technique it has been possible to reduce the impurity content from about 5000 ppm to under 500 ppm and, in particular, to eliminate almost completely the nitrogen which is not removed by the normal purification methods. The author has studied the changes in the morphology of the deposit obtained as a function of the operational conditions. He has determined in particular the conditions leading to the formation of a compact deposit. He has shown that the deposition kinetics are very probably governed by an adsorbed phase reaction at the metal surface, (author) [fr

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. Properties of samples containing natural gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, determined using Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI)

    Science.gov (United States)

    Winters, W.J.

    1999-01-01

    As part of an ongoing laboratory study, preliminary acoustic, strength, and hydraulic conductivity results are presented from a suite of tests conducted on four natural-gas-hydrate-containing samples from the Mackenzie Delta JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The gas hydrate samples were preserved in pressure vessels during transport from the Northwest Territories to Woods Hole, Massachusetts, where multistep tests were performed using GHASTLI (Gas Hydrate And Sediment Test Laboratory Instrument), which recreates pressure and temperature conditions that are stable for gas hydrate. Properties and changes in sediment behaviour were measured before, during, and after controlled gas hydrate dissociation. Significant amounts of gas hydrate occupied the sample pores and substantially increased acoustic velocity and shear strength.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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...

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.)

  4. Degradation Kinetics of Carbon Tetrachloride by Sulfate Green Rust as Influenced by pH and Copper Ions

    Science.gov (United States)

    Chlorinated solvents such as trichloroethene (TCE, C2HCl3) and carbon tetrachloride (CT, CCl4) are priority groundwater contaminants at many EPA field sites. Green rust (GR) minerals are important corrosion products of zerovalent iron (Fe0) that has been used in permeable reactiv...

  5. 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

  6. 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

  7. 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

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Study of protective effect of Avicennia marina hydroethanolic leaf extract on testes tissue and spermatogenesis in male rat induced with carbon tetrachloride

    Directory of Open Access Journals (Sweden)

    Z soleimani

    2015-11-01

    Full Text Available Aim: The toxic chemical compounds are widelyused in the world. Carbon tetrachloride which is used in hygiene industries caused tissue disorders. Medicinal plants have protective effects in body tissues. In this study the protective effect of Avicennia marina leaf extract (MLE on spermatogenesis in male rat were induced with ccl4 investigating. Method and materials: The 42 male rats with 220-250 gr body weight were divided randomly in 6 groups(n=7: control (taking normal saline,0.5ml/day, i,p , sham(taking olive oil, 0.5ml/day, i,p single dose,group induced by ccl4(carbon tetrachloride 1:1 with olive oil,0.5ml single dose, i,p, treated groups: (1,2 and3 by carbon tetrachloride 1:1 with olive oil,0.5ml single dose and 200mg/Kg, 400mg/Kg and 800mg/kg MLE /day for 96 hrs, i,p. After the examination the blood samples were collected from heart directly and testosterone , FSH, LH , sperm count, sperm motility and GSI were analyzed and the microscopic studies of testes tissue were done. All data were expressed as mean±SEM. and statistical significance differences were accepted at P<0.05. Results: Our results showed that the carbon tetrachloride has necrotic effect in testes. The number of sperm and motility were increased and microscopic study of testes tissue showed the necrosis and inflammation with decrease in spermatogonia and spermatocytes comparedwith ccl4 induced only group significantly (P<0.001 and treated groups were no changed. Conclusion: the Avicennia marina hydroethanolic extract has antioxidant and flavonoids compounds which can protect the testes tissues from toxic chemical agents.

  14. The extraction of vanadium pentoxide from waste of titanium tetrachloride by various methods

    Directory of Open Access Journals (Sweden)

    Инна Михайловна Гунько

    2015-04-01

    Full Text Available In article the recovery possibility of vanadium pentoxide from wastes, formed as a result of purification from impurities of technical titanium tetrachloride is researched. The purification from impurities is realized by different methods – pulp of lower titanium chlorides, hydrocarbonic reducer and cascade-rectifying purification. Usage of these purification methods leads to formation of anthropogenic wastes. The researches is shown that processing of these wastes is reasonable for the purpose of vanadium pentoxide extraction

  15. 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

  16. 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

  17. 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

  18. 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.

  19. Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

    Science.gov (United States)

    Bindeman, Ilya N.; Lowenstern, Jacob B.

    2016-01-01

    Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature

  20. 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...

  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. 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.

  3. Anti-Agglomerator of Tetra-n-Butyl Ammonium Bromide Hydrate and Its Effect on Hydrate-Based CO2 Capture

    Directory of Open Access Journals (Sweden)

    Rong Li

    2018-02-01

    Full Text Available Tetra-n-butyl ammonium bromide (TBAB was widely used in the research fields of cold storage and CO2 hydrate separation due to its high phase change latent heat and thermodynamic promotion for hydrate formation. Agglomeration always occurred in the process of TBAB hydrate generation, which led to the blockage in the pipeline and the separation apparatus. In this work, we screened out a kind of anti-agglomerant that can effectively solve the problem of TBAB hydrate agglomeration. The anti-agglomerant (AA is composed of 90% cocamidopropyl dimethylamine and 10% glycerol, which can keep TBAB hydrate of 19.3–29.0 wt. % in a stable state of slurry over 72 h. The microscopic observation of the morphology of the TBAB hydrate particles showed that the addition of AA can greatly reduce the size of the TBAB hydrate particles. CO2 gas separation experiments found that the addition of AA led to great improvement on gas storage capacity, CO2 split fraction and separation factor, due to the increasing of contact area between gas phase and hydrate particles. The CO2 split fraction and separation factor with AA addition reached up to 70.3% and 42.8%, respectively.

  4. 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

  5. Halogeno Aldol Reaction of Ethyl Vinyl Ketone and Aldehydes Mediated by Titanium Tetrachloride

    Directory of Open Access Journals (Sweden)

    Guigen Li

    2000-12-01

    Full Text Available A three-component halogeno aldol reaction has been developed by using titanium tetrachloride as the halogen source as well as the Lewis acid mediator. The dehydration and elimination of hydrogen chloride were inhibited by conducting the reaction at 0 °C in dichloromethane or at room temperature with a shortened reaction time. Seven examples were examined, giving good to high yields (61 - 92% and modest stereoselectivity (syn/anti: 2.2/1.0 - 8.4/1.0.

  6. 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)

  7. Changes in structure and preferential cage occupancy of ethane hydrate and ethane-methane mixed gas hydrate under high pressure

    International Nuclear Information System (INIS)

    Hirai, H; Takahara, N; Kawamura, T; Yamamoto, Y; Yagi, T

    2010-01-01

    Structural changes and preferential cage occupancies were examined for ethane hydrate and ethane-methane mixed gas hydrates with five compositions in a pressure range of 0.2 to 2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed the following structural changes. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions, where sII and sH appeared. Above 2.1 GPa ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it was thought that ethane molecules were contained only in the large cage.

  8. Degradation Kinetics of Carbon Tetrachloride by Sulfate Green Rust as Influenced by pH and Copper Ions (Stillwater)

    Science.gov (United States)

    Chlorinated solvents such as trichloroethene (TCE, C2HCl3) and carbon tetrachloride (CT, CCl4) are priority groundwater contaminants at many EPA field sites. Green rust (GR) minerals are important corrosion products of zerovalent iron (Fe0) that has been used in permeable react...

  9. 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

  10. 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.

  11. Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

    Energy Technology Data Exchange (ETDEWEB)

    Marques de Toledo Camargo, R.

    2001-03-01

    The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

  12. 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...

  13. 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

  14. 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.

  15. Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

    Energy Technology Data Exchange (ETDEWEB)

    Myers, Greg [Consortium for Ocean Leadership, Washington, DC (United States)

    2014-02-01

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

  16. Pulse radiolysis of porphyrin and ferriporphyrin solutions in 2-propanol-carbon tetrachloride systems. Protonation and ligand exchange kinetics

    International Nuclear Information System (INIS)

    Brault, D.; Neta, P.

    1983-01-01

    Pulse radiolysis of aqueous and nonaqueous 2-propanol-acetone-carbon tetrachloride mixtures has been investigated by means of conductivity measurements and spectrophotometry. In these solvent mixtures, a pulse of hydrochloric acid originating from either primary events of solvent radiolysis or from further reactions of carbon tetrachloride with radicals derived from 2-propanol and acetone, is produced within ca 100 nanoseconds. Further production of hydrochloric acid occurs as a result of chain reactions involving hydrogen abstraction by CCl 3 or CCl 3 O 2 radicals. These latter radicals appear to be much more reactive and are likely to be involved in the reaction unless the solutions have been thoroughly deoxygenated. Protonation Reactions of porphyrins and ferriporphyrins, which do not react rapidly with the above radicals, were followed by means of spectrophotometric measurements. In turn, these reactions may be used to monitor hydrochloric acid formation. Spectrophotometric measurements on porphyrins corroborate conductivity results, although a quantitative comparison is not feasible because of differences in solvent properties. 6 figures

  17. An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

    Science.gov (United States)

    Chand, S.; Minshull, T.A.; Priest, J.A.; Best, A.I.; Clayton, C.R.I.; Waite, W.F.

    2006-01-01

    The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L–38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

  18. 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.

  19. 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)

  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. 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.

  2. 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.

  3. 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

  4. 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.

  5. Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

    Science.gov (United States)

    Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

    2009-01-01

    We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

  6. 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.

  7. Seismic-Scale Rock Physics of Methane Hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Amos Nur

    2009-01-08

    We quantify natural methane hydrate reservoirs by generating synthetic seismic traces and comparing them to real seismic data: if the synthetic matches the observed data, then the reservoir properties and conditions used in synthetic modeling might be the same as the actual, in-situ reservoir conditions. This approach is model-based: it uses rock physics equations that link the porosity and mineralogy of the host sediment, pressure, and hydrate saturation, and the resulting elastic-wave velocity and density. One result of such seismic forward modeling is a catalogue of seismic reflections of methane hydrate which can serve as a field guide to hydrate identification from real seismic data. We verify this approach using field data from known hydrate deposits.

  8. Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

    Energy Technology Data Exchange (ETDEWEB)

    Collett, Tim [U.S. Geological Survey, Boulder, CO (United States); Bahk, Jang-Jun [Korea Inst. of Geoscience and Mineral Resources, Daejeon (Korea); Frye, Matt [U.S. Bureau of Ocean Energy Management, Sterling, VA (United States); Goldberg, Dave [Lamont-Doherty Earth Observatory, Palisades, NY (United States); Husebo, Jarle [Statoil ASA, Stavenger (Norway); Koh, Carolyn [Colorado School of Mines, Golden, CO (United States); Malone, Mitch [Texas A & M Univ., College Station, TX (United States); Shipp, Craig [Shell International Exploration and Production Inc., Anchorage, AK (United States); Torres, Marta [Oregon State Univ., Corvallis, OR (United States); Myers, Greg [Consortium For Ocean Leadership Inc., Washington, DC (United States); Divins, David [Consortium For Ocean Leadership Inc., Washington, DC (United States); Morell, Margo [Consortium For Ocean Leadership Inc., Washington, DC (United States)

    2013-12-31

    This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, but these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.

  9. Transformation of carbon tetrachloride by Pseudomonas sp. strain KC under denitrification conditions

    International Nuclear Information System (INIS)

    Criddle, C.S.; DeWitt, J.T.; Grbic-Galic, D.; McCarty, P.L.

    1990-01-01

    A denitrifying Pseudomonas sp. (strain KC) capable of transforming carbon tetrachloride (CT) was isolated from groundwater aquifer solids. Major products of the transformation of 14 C-labeled CT by Pseudomonas strain KC under denitrification conditions were 14 CO 2 and an unidentified water-soluble fraction. Little or no chloroform was produced. Addition of dissolved trace metals, notably, ferrous iron and cobalt, to the growth medium appeared to enhance growth of Pseudomonas strain KC while inhibiting transformation of CT. It is hypothesized that transformation of CT by this organism is associated with the mechanism of trace-metal scavenging

  10. Energy from gas hydrates - assessing the opportunities and challenges for Canada: report of the expert panel on gas hydrates

    International Nuclear Information System (INIS)

    2008-09-01

    Gas hydrates form when water and natural gas combine at low temperatures and high pressures in regions of permafrost and in marine subseafloor sediments. Estimates suggest that the total amount of natural gas bound in hydrate form may exceed all conventional gas resources, or even the amount of all combined hydrocarbon energy. Gas from gas hydrate could provide a potentially vast new source of energy to offset declining supplies of conventional natural gas in North America and to provide greater energy security for countries such as Japan and India that have limited domestic sources. However, complex issues would need to be addressed if gas hydrate were to become a large part of the energy future of Canada. Natural Resources Canada asked the Council of Canadian Academies to assemble a panel of experts to examine the challenges for an acceptable operational extraction of gas hydrates in Canada. This report presented an overview of relevant contextual background, including some basic science; the medium-term outlook for supply and demand in markets for natural gas; broad environmental issues related to gas hydrate in its natural state and as a fuel; and an overview of Canada's contribution to knowledge about gas hydrate in the context of ongoing international research activity. The report also presented current information on the subject and what would be required to delineate and quantify the resource. Techniques for extracting gas from gas hydrate were also outlined. The report also addressed safety issues related to gas hydrate dissociation during drilling operations or release into the atmosphere; the environmental issues associated with potential leakage of methane into the atmosphere and with the large volumes of water produced during gas hydrate dissociation; and jurisdictional and local community issues that would need to be resolved in order to proceed with the commercial exploitation of gas hydrate. It was concluded that there does not appear to be

  11. 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.

  12. 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.

  13. Bioavailability of andrographolide and protection against carbon tetrachloride-induced oxidative damage in rats.

    Science.gov (United States)

    Chen, Haw-Wen; Huang, Chin-Shiu; Li, Chien-Chun; Lin, Ai-Hsuan; Huang, Yu-Ju; Wang, Tsu-Shing; Yao, Hsien-Tsung; Lii, Chong-Kuei

    2014-10-01

    Andrographolide, a bioactive diterpenoid, is identified in Andrographis paniculata. In this study, we investigated the pharmacokinetics and bioavailability of andrographolide in rats and studied whether andrographolide enhances antioxidant defense in a variety of tissues and protects against carbon tetrachloride-induced oxidative damage. After a single 50-mg/kg administration, the maximum plasma concentration of andrographolide was 1μM which peaked at 30min. The bioavailability of andrographolide was 1.19%. In a hepatoprotection study, rats were intragastrically dosed with 30 or 50mg/kg andrographolide for 5 consecutive days. The results showed that andrographolide up-regulated glutamate cysteine ligase (GCL) catalytic and modifier subunits, superoxide dismutase (SOD)-1, heme oxygenase (HO)-1, and glutathione (GSH) S-transferase (GST) Ya/Yb protein and mRNA expression in the liver, heart, and kidneys. The activity of SOD, GST, and GSH reductase was also increased in rats dosed with andrographolide (pandrographolide increased nuclear Nrf2 contents and Nrf2 binding to DNA, respectively. After the 5-day andrographolide treatment, one group of animals was intraperitoneally injected with carbon tetrachloride (CCl4) at day 6. Andrographolide pretreatment suppressed CCl4-induced plasma aminotransferase activity and hepatic lipid peroxidation (pandrographolide is quickly absorbed in the intestinal tract in rats with a bioavailability of 1.19%. Andrographolide protects against chemical-induced oxidative damage by up-regulating the gene transcription and activity of antioxidant enzymes in various tissues. Copyright © 2014 Elsevier Inc. All rights reserved.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. Towards CO2 sequestration and applications of CO2 hydrates: the effects of tetrahydrofuran on the phase equilibria of CO2 hydrates

    International Nuclear Information System (INIS)

    Khalik, M.S.; Peters, C.J.

    2006-01-01

    The increasing quantity of carbon dioxide (CO 2 ) in the atmosphere has caused widespread global concerns. Capturing CO 2 from its sources and stored it in the form of gas hydrates and application of CO 2 hydrates are among the proposed methods to overcome this problem. In order to make hydrate-based process more attractive, the use of cyclic ethers as promoters is suggested to reduce the required hydrate formation pressure and enhancing the corresponding kinetic rate. In the present work, tetrahydrofuran (THF) is chosen as a hydrate promoter, participating in forming hydrates and produces mixed hydrate together with CO 2 . The pressure and temperature ranges of hydrate stability region are carefully determined through phase equilibrium measurement of the ternary CO 2 , tetrahydrofuran (THF) and water systems. From the experimental results, it is confirmed that the presence of THF in CO 2 + water systems will extend the hydrate formation region to higher temperature at a constant pressure. The extension of the hydrate stability region is depended on the overall concentration of the ternary system. Moreover, four-phase equilibrium of H-Lw-Lv-V is observed in the system, which may be due to a liquid phase split. In the region where the four-phase equilibrium exists, the ternary system loses its concentration dependency of the hydrate equilibrium conditions. (Author)

  1. A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy

    International Nuclear Information System (INIS)

    Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Jorgen

    2006-01-01

    Recent 27 Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ iso = 5.0 ppm and the quadrupole product parameter P Q = 1.2 MHz, has been characterized in detail by 27 Al MAS and 27 Al{ 1 H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH) 6 3- or O x Al(OH) 6-x (3+x)- units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 o C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al 3+ for Ca 2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed

  2. 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.

  3. 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.

  4. 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

  5. Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

    Science.gov (United States)

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

    2009-10-22

    Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

  6. The U.S. Geological Survey’s Gas Hydrates Project

    Science.gov (United States)

    Ruppel, Carolyn D.

    2018-01-17

    The Gas Hydrates Project at the U.S. Geological Survey (USGS) focuses on the study of methane hydrates in natural environments. The project is a collaboration between the USGS Energy Resources and the USGS Coastal and Marine Geology Programs and works closely with other U.S. Federal agencies, some State governments, outside research organizations, and international partners. The USGS studies the formation and distribution of gas hydrates in nature, the potential of hydrates as an energy resource, and the interaction between methane hydrates and the environment. The USGS Gas Hydrates Project carries out field programs and participates in drilling expeditions to study marine and terrestrial gas hydrates. USGS scientists also acquire new geophysical data and sample sediments, the water column, and the atmosphere in areas where gas hydrates occur. In addition, project personnel analyze datasets provided by partners and manage unique laboratories that supply state-of-the-art analytical capabilities to advance national and international priorities related to gas hydrates.

  7. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    International Nuclear Information System (INIS)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

  8. Hydration behaviors of calcium silicate-based biomaterials.

    Science.gov (United States)

    Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

    2017-06-01

    Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

  9. Cryogenic-SEM investigation of CO{sub 2} hydrate morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Camps, A.P.; Milodowski, A.; Rochelle, C.; Williams, J.F.; Jackson, P. D. [British Geological Survey, Keyworth, Nottinghamshire (United Kingdom); Camps, A.P; Lovell, M.; Williams, J.F. [Leicester Univ., Leicester (United Kingdom). Dept. of Geology

    2008-07-01

    Gas hydrates occur naturally around the world in the shallow-marine geosphere, and are seen as a drilling hazard in the petroleum industry due to their role in the carbon cycle, and their possible contribution in past and present climate change. Hydrates are ice-like structures composed of cages of water molecules containing one or more guest molecules, such as methane and carbon dioxide (CO{sub 2}). CO{sub 2} hydrates also occur naturally on earth and are being investigated for their potential to store large volumes of CO{sub 2} to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. However, the mineralogy and formation processes of hydrates are relatively poorly understood. Different imaging techniques have been utilized to study gas hydrates, such as nuclear magnetic resonance, magnetic resonance imaging, and x-ray computed tomography. Scanning Electron Microscopy (SEM) at cryogenic temperatures is another technique to study hydrates, and has been used successfully for investigation of methane and CO{sub 2} hydrates. This paper presented a study that investigated CO{sub 2} hydrates formed in laboratories, using a cryogenic-SEM. The paper presented the study methods and observations, including euhedral crystalline carbon dioxide hydrate; acicular carbon dioxide hydrate; granoblastic carbon dioxide hydrate; and gas rich carbon dioxide hydrate. It was concluded that the investigation produced various different hydrate morphologies resulting from different formation conditions. Morphologies ranged from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. 22 refs., 6 figs., 1 appendix.

  10. 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

  11. 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.

  12. 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...

  13. 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.

  14. 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

  15. 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

  16. Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

    Energy Technology Data Exchange (ETDEWEB)

    McConnell, Daniel

    2017-12-30

    Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production.

    A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Leg II in 2009 and recently confirmed with coring in 2017.

    A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.

  17. 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

  18. 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 ...

  19. 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.

  20. An alternate metabolic hypothesis for a binary mixture of trichloroethylene and carbon tetrachloride: application of physiologically based pharmacokinetic (PBPK) modeling in rats.

    Science.gov (United States)

    Carbon tetrachloride (CC4) and trichloroethylene (TCE) are hepatotoxic volatile organic compounds (VOCs) and environmental contaminants. Previous physiologically based pharmacokinetic (PBPK) models describe the kinetics ofindividual chemical disposition and metabolic clearance fo...

  1. 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.

  2. 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

  3. 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.

  4. TOUGH+Hydrate v1.0 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George; Moridis, George J.; Kowalsky, Michael B.; Pruess, Karsten

    2008-03-01

    TOUGH+HYDRATE v1.0 is a new code for the simulation of the behavior of hydrate-bearing geologic systems. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH{sub 4}-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.0 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH{sub 4}, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is the first member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

  5. 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.

  6. 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....

  7. 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

  8. 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 ...

  9. Phase behavior of methane hydrate in silica sand

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang; Liu, Yu-Feng

    2014-01-01

    Highlights: • Hydrate p-T trace in coarse-grained sediment is consistent with that in bulk water. • Fine-grained sediment affects hydrate equilibrium for the depressed water activity. • Hydrate equilibrium in sediment is related to the pore size distribution. • The application of hydrate equilibrium in sediment depends on the actual condition. -- Abstract: Two kinds of silica sand powder with different particle size were used to investigate the phase behavior of methane hydrate bearing sediment. In coarse-grained silica sand, the measured temperature and pressure range was (281.1 to 284.2) K and (5.9 to 7.8) MPa, respectively. In fine-grained silica sand, the measured temperature and pressure range was (281.5 to 289.5) K and (7.3 to 16.0) MPa, respectively. The results show that the effect of coarse-grained silica sand on methane hydrate phase equilibrium can be ignored; however, the effect of fine-grained silica sand on methane hydrate phase equilibrium is significant, which is attributed to the depression of water activity caused by the hydrophilicity and negatively charged characteristic of silica particle as well as the pore capillary pressure. Besides, the analysis of experimental results using the Gibbs–Thomson equation shows that methane hydrate phase equilibrium is related to the pore size distribution of silica sand. Consequently, for the correct application of phase equilibrium data of hydrate bearing sediment, the geological condition and engineering requirement should be taken into consideration in gas production, resource evaluation, etc

  10. 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.

  11. 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

  12. Ab initio modelling of methane hydrate thermophysical properties.

    Science.gov (United States)

    Jendi, Z M; Servio, P; Rey, A D

    2016-04-21

    The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

  13. CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

    Science.gov (United States)

    Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

    2013-04-01

    In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with

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

    Science.gov (United States)

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

    2016-04-01

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

  16. 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

  17. Manufacture of Methane Hydrate using Carbon Nano Tubes

    International Nuclear Information System (INIS)

    Park, Sung Seek

    2010-02-01

    Methane hydrate is formed by physical binding between water molecule and gas such as methane, ethane, propane, or carbon dioxide, etc., which is captured in the cavities of water molecule under the specific temperature and pressure. More than 99% of naturally produced methane hydrate consists of methane, and is widely dispersed in the continental slope and continental Shelf of the Pacific and the Atlantic, the Antarctica etc. The reserve of fossil fuel is 500 billion carbon ton and the reserve of methane is 360 million carbon ton. The reserve of gas hydrate is more than 1 trillion carbon ton, which is twice the fossil fuel. Therefore, natural gas hydrate as a kind of gas hydrate is expected to replace fossil fuel as new energy source of 21st century. Also 1 m 3 hydrate of pure methane can be decomposed to the maximum of 216 m 3 methane at standard condition. If these characteristics of hydrate are reversely utilized, natural gas is fixed into water in the form of hydrate solid. Therefore, the hydrate is considered to be a great way to transport and store natural gas in large quantity. Especially the transportation cost is known to be 18∼25% less than the liquefied transportation. However, when natural gas hydrate is artificially formed, its reaction time may be too long and the gas consumption in water becomes relatively low, because the reaction rate between water and gas is low. Therefore, for the practical purpose in the application, the present investigation focuses on the rapid production of hydrates and increases gas consumption by adding MWCNT and NaCl into pure water. The results show that the equilibrium pressure in seawater is more higher than that in pure water, and methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 9K or above in seawater and 8K or above in pure water, respectively. Also, amount of consumed gas volume in pure water is more higher that in seawater at the same experimental conditions

  18. Resonance Raman spectroscopy of volatile organics -- Carbon tetrachloride

    International Nuclear Information System (INIS)

    Barletta, R.E.; Veligdan, J.T.

    1994-09-01

    Volatile organic chemicals are a class of pollutants which are regulated at very low levels by the EPA. Consequently a need exists as a part of site remediation efforts within DOE to develop technologies which will allow for the in situ monitoring of these chemicals. Resonance Raman spectroscopy is a potential technique to accomplish this if the resonance enhancement is sufficiently high. Carbon tetrachloride was selected as a test case. Measurements under resonance conditions at 248 nm showed an enhancement factor of 2 x 10 4 . Using this value an estimate of the sensitivity for both in situ and remote monitoring of CCl 4 was made. It was concluded that resonance Raman could be used to detect these chemicals at levels of regulatory interest. Future effort directed towards the development of a suitable probe as well as a field-portable system would be desirable. Such effort could be directed towards the solution of a particular monitoring problem within a DOE waste remediation project. Once developed, however, it should be easily generalized to the analysis of other VOC's in other environments

  19. 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.

  20. 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.

  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. Water Dynamics in the Hydration Shells of Biomolecules

    Science.gov (United States)

    2017-01-01

    The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

  3. 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.

  4. 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 have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

  5. 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.

  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. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  8. Constraining gas hydrate occurrence in the northern Gulf of Mexico continental slope : fine scale analysis of grain-size in hydrate-bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Hangsterfer, A.; Driscoll, N.; Kastner, M. [Scripps Inst. of Oceanography, La Jolla, CA (United States). Geosciences Research Division

    2008-07-01

    Methane hydrates can form within the gas hydrate stability zone (GHSZ) in sea beds. The Gulf of Mexico (GOM) contains an underlying petroleum system and deeply buried, yet dynamic salt deposits. Salt tectonics and fluid expulsion upward through the sediment column result in the formation of fractures, through which high salinity brines migrate into the GHSZ, destabilizing gas hydrates. Thermogenic and biogenic hydrocarbons also migrate to the seafloor along the GOMs northern slope, originating from the thermal and biogenic degradation of organic matter. Gas hydrate occurrence can be controlled by either primary permeability, forming in coarse-grained sediment layers, or by secondary permeability, forming in areas where hydrofracture and faulting generate conduits through which hydrocarbon-saturated fluids flow. This paper presented a study that attempted to determine the relationship between grain-size, permeability, and gas hydrate distribution. Grain-size analyses were performed on cores taken from Keathley Canyon and Atwater Valley in the GOM, on sections of cores that both contained and lacked gas hydrate. Using thermal anomalies as proxies for the occurrence of methane hydrate within the cores, samples of sediment were taken and the grain-size distributions were measured to see if there was a correlation between gas hydrate distribution and grain-size. The paper described the methods, including determination of hydrate occurrence and core analysis. It was concluded that gas hydrate occurrence in Keathley Canyon and Atwater Valley was constrained by secondary permeability and was structurally controlled by hydrofractures and faulting that acted as conduits through which methane-rich fluids flowed. 11 refs., 2 tabs., 5 figs.

  9. TOUGH+HYDRATE v1.2 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kowalsky, Michael B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pruess, Karsten [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-08-01

    TOUGH+HYDRATE v1.2 is a code for the simulation of the behavior of hydratebearing geologic systems, and represents the second update of the code since its first release [Moridis et al., 2008]. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH4-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy’s law is valid. TOUGH+HYDRATE v1.2 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is a member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95/2003, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

  10. Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

    Science.gov (United States)

    You, K.; Flemings, P. B.

    2017-12-01

    We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with

  11. 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)

  12. CLATHRATE HYDRATES FORMATION IN SHORT-PERIOD COMETS

    International Nuclear Information System (INIS)

    Marboeuf, Ulysse; Mousis, Olivier; Petit, Jean-Marc; Schmitt, Bernard

    2010-01-01

    The initial composition of current models of cometary nuclei is only based on two forms of ice: crystalline ice for long-period comets and amorphous ice for short-period comets. A third form of ice, i.e., clathrate hydrate, could exist within the short-period cometary nuclei, but the area of formation of this crystalline structure in these objects has never been studied. Here, we show that the thermodynamic conditions in the interior of short-period comets allow the existence of clathrate hydrates in Halley-type comets. We show that their existence is viable in the Jupiter family comets only when the equilibrium pressure of CO clathrate hydrate is at least 1 order of magnitude lower than the usually assumed theoretical value. We calculate that the amount of volatiles that could be trapped in the clathrate hydrate layer may be orders of magnitude greater than the daily amount of gas released at the surface of the nucleus at perihelion. The formation and the destruction of the clathrate hydrate cages could then explain the diversity of composition of volatiles observed in comets, as well as some pre-perihelion outbursts. We finally show that the potential clathrate hydrate layer in comet 67P/Churyumov-Gerasimenko would, unfortunately, be deep inside the nucleus, out of reach of the Rosetta lander. However, such a clathrate hydrate layer would show up by the gas composition of the coma.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRH-Theory): three-dimensional PC validation

    Science.gov (United States)

    Kadyshevich, E. A.; Dzyabchenko, A. V.; Ostrovskii, V. E.

    2014-04-01

    Size compatibility of the CH4-hydrate structure II and multi-component DNA fragments is confirmed by three-dimensional simulation; it is validation of the Life Origination Hydrate Theory (LOH-Theory).

  1. 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

  2. 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

  3. 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.)

  4. 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...

  5. 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.

  6. Study on molecular controlled mining system of methane hydrate; Methane hydrate no bunshi seigyo mining ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Kuriyagawa, M; Saito, T; Kobayashi, H; Karasawa, H; Kiyono, F; Nagaoki, R; Yamamoto, Y; Komai, T; Haneda, H; Takahashi, Y [National Institute for Resources and Environment, Tsukuba (Japan); Nada, H [Science and Technology Agency, Tokyo (Japan)

    1997-02-01

    Basic studies are conducted for the collection of methane from the methane hydrate that exists at levels deeper than 500m in the sea. The relationship between the hydrate generation mechanism and water cluster structure is examined by use of mass spectronomy. It is found that, among the stable liquid phase clusters, the (H2O)21H{sup +} cluster is the most stable. Stable hydrate clusters are in presence in quantities, and participate in the formation of hydrate crystal nuclei. For the elucidation of the nucleus formation mechanism, a kinetic simulation is conducted of molecules in the cohesion system consisting of water and methane molecules. Water molecules that array near methane molecules at the normal pressure is disarrayed under a higher pressure for rearray into a hydrate structure. Hydrate formation and breakdown in the three-phase equilibrium state of H2O, CH4, and CO2 at a low temperature and high pressure are tested, which discloses that supercooling is required for formation, that it is possible to extract CH4 first for replacement by guest molecule CO2 since CO2 is stabler than CH4 at a lower pressure or higher temperature, and that formation is easier to take place when the grain diameter is larger at the formation point since larger grain diameters result in a higher formation temperature. 3 figs.

  7. Dynamic morphology of gas hydrate on a methane bubble in water: Observations and new insights for hydrate film models

    Science.gov (United States)

    Warzinski, Robert P.; Lynn, Ronald; Haljasmaa, Igor; Leifer, Ira; Shaffer, Frank; Anderson, Brian J.; Levine, Jonathan S.

    2014-10-01

    Predicting the fate of subsea hydrocarbon gases escaping into seawater is complicated by potential formation of hydrate on rising bubbles that can enhance their survival in the water column, allowing gas to reach shallower depths and the atmosphere. The precise nature and influence of hydrate coatings on bubble hydrodynamics and dissolution is largely unknown. Here we present high-definition, experimental observations of complex surficial mechanisms governing methane bubble hydrate formation and dissociation during transit of a simulated oceanic water column that reveal a temporal progression of deep-sea controlling mechanisms. Synergistic feedbacks between bubble hydrodynamics, hydrate morphology, and coverage characteristics were discovered. Morphological changes on the bubble surface appear analogous to macroscale, sea ice processes, presenting new mechanistic insights. An inverse linear relationship between hydrate coverage and bubble dissolution rate is indicated. Understanding and incorporating these phenomena into bubble and bubble plume models will be necessary to accurately predict global greenhouse gas budgets for warming ocean scenarios and hydrocarbon transport from anthropogenic or natural deep-sea eruptions.

  8. Influence of Lithium Carbonate on C3A Hydration

    Directory of Open Access Journals (Sweden)

    Weiwei Han

    2018-01-01

    Full Text Available Lithium salts, known to ameliorate the effects of alkali-silica reaction, can make significant effects on cement setting. However, the mechanism of effects on cement hydration, especially the hydration of C3A which is critical for initial setting time of cement, is rarely reported. In this study, the development of pH value of pore solution, conductivity, thermodynamics, and mineralogical composition during hydration of C3A with or without Li2CO3 are investigated. The results demonstrate that Li2CO3 promotes C3A hydration through high alkalinity, due to higher activity of lithium ion than that of calcium ion in the solution and carbonation of C3A hydration products resulted from Li2CO3. Li2CO3 favors the C3A hydration in C3A-CaSO4·2H2O-Ca(OH2-H2O hydration system and affects the mineralogical variation of the ettringite phase(s.

  9. Hysteresis of methane hydrate formation/decomposition at subsea geological conditions

    International Nuclear Information System (INIS)

    Klapproth, Alice; Piltz, Ross; Peterson, Vanessa K.; Kennedy, Shane J.; Kozielski, Karen A.; Hartley, Patrick G.

    2009-01-01

    Full text: Gas hydrates are a major risk when transporting oil and gas in offshore subsea pipelines. Under typical conditions in these pipelines (at high pressure and low temperature) the formation of gas hydrates is favourable. The hydrates form large solid plugs that can block pipelines and can even cause them to burst. This represents a major problem for the gas mining industry, which currently goes to extreme measures to reduce the risk of hydrate formation because there is no reliable experimental data on hydrate processes. The mechanisms of gas hydrate formation, growth and inhibition are poorly understood. A clear understanding of the fundamental processes will allow development of cost effective technologies to avoid production losses in gas pipelines. We are studying the nucleation of the methane hydrates by measuring the hysteresis of hydrate formation/decomposition by neutron diffraction. When a gas hydrate is decomposed (melted) the resulting water has a 'supposed memory effect' raising the probability of rapid hydrate reformation. This rapid reformation does not occur for pure water where nucleation can be delayed by several hours (induction time) due to metastability [1]. The memory effect can only be destroyed by extreme heating of the effected area. Possible causes of this effect include residual water structure, persistent hydrate crystal lites remaining in solution and remaining dissolved gas. We will compare the kinetics of formation and the stability region of hydrate formation of 'memory' water for comparison with pure water. This information has important implications for the oil and gas industry because it should provide a better understanding of the role of multiple dissociation and reformation of gas hydrates in plug formation.

  10. 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.

  11. Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

    2008-07-01

    Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

  12. 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....

  13. 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.

  14. Reflective terahertz (THz) imaging: system calibration using hydration phantoms

    Science.gov (United States)

    Bajwa, Neha; Garritano, James; Lee, Yoon Kyung; Tewari, Priyamvada; Sung, Shijun; Maccabi, Ashkan; Nowroozi, Bryan; Babakhanian, Meghedi; Sanghvi, Sajan; Singh, Rahul; Grundfest, Warren; Taylor, Zachary

    2013-02-01

    Terahertz (THz) hydration sensing continues to gain traction in the medical imaging community due to its unparalleled sensitivity to tissue water content. Rapid and accurate detection of fluid shifts following induction of thermal skin burns as well as remote corneal hydration sensing have been previously demonstrated in vivo using reflective, pulsed THz imaging. The hydration contrast sensing capabilities of this technology were recently confirmed in a parallel 7 Tesla Magnetic Resonance (MR) imaging study, in which burn areas are associated with increases in local mobile water content. Successful clinical translation of THz sensing, however, still requires quantitative assessments of system performance measurements, specifically hydration concentration sensitivity, with tissue substitutes. This research aims to calibrate the sensitivity of a novel, reflective THz system to tissue water content through the use of hydration phantoms for quantitative comparisons of THz hydration imagery.Gelatin phantoms were identified as an appropriate tissue-mimicking model for reflective THz applications, and gel composition, comprising mixtures of water and protein, was varied between 83% to 95% hydration, a physiologically relevant range. A comparison of four series of gelatin phantom studies demonstrated a positive linear relationship between THz reflectivity and water concentration, with statistically significant hydration sensitivities (p hydration). The THz-phantom interaction is simulated with a three-layer model using the Transfer Matrix Method with agreement in hydration trends. Having demonstrated the ability to accurately and noninvasively measure water content in tissue equivalent targets with high sensitivity, reflective THz imaging is explored as a potential tool for early detection and intervention of corneal pathologies.

  15. 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.

  16. Hydrate Evolution in Response to Ongoing Environmental Shifts

    Energy Technology Data Exchange (ETDEWEB)

    Rempel, Alan [Univ. of Oregon, Eugene, OR (United States)

    2015-12-31

    Natural gas hydrates have the potential to become a vital domestic clean-burning energy source. However, past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. This project was designed to fill critical gaps in our understanding of domestic hydrate resources and improve forecasts for their response to environmental shifts. Project work can be separated into three interrelated components, each involving the development of predictive mathematical models. The first project component concerns the role of sediment properties on the development and dissociation of concentrated hydrate anomalies. To this end, we developed numerical models to predict equilibrium solubility of methane in twophase equilibrium with hydrate as a function of measureable porous medium characteristics. The second project component concerned the evolution of hydrate distribution in heterogeneous reservoirs. To this end, we developed numerical models to predict the growth and decay of anomalies in representative physical environments. The third project component concerned the stability of hydrate-bearing slopes under changing environmental conditions. To this end, we developed numerical treatments of pore pressure evolution and consolidation, then used "infinite-slope" analysis to approximate the landslide potential in representative physical environments, and developed a "rate-and-state" frictional formulation to assess the stability of finite slip patches that are hypothesized to develop in response to the dissociation of hydrate anomalies. The increased predictive capabilities that result from this work provide a framework for interpreting field observations of hydrate anomalies in terms of the history of environmental forcing that led to their development. Moreover

  17. An international effort to compare gas hydrate reservoir simulators

    Energy Technology Data Exchange (ETDEWEB)

    Wilder, J.W. [Akron Univ., Akron, OH (United States). Dept. of Theoretical and Applied Math; Moridis, G.J. [California Univ., Berkely, CA (United States). Earth Sciences Div., Lawrence Berkely National Lab.; Wilson, S.J. [Ryder Scott Co., Denver, CO (United States); Kurihara, M. [Japan Oil Engineering Co. Ltd., Tokyo (Japan); White, M.D. [Pacific Northwest National Laboratory Hydrology Group, Richland, WA (United States); Masuda, Y. [Tokyo Univ., Tokyo (Japan). Dept. of Geosystem Engineering; Anderson, B.J. [National Energy Technology Lab., Morgantown, WV (United States)]|[West Virginia Univ., Morgantown, WV (United States). Dept. of Chemical Engineering; Collett, T.S. [United States Geological Survey, Denver, CO (United States); Hunter, R.B. [ASRC Energy Services, Anchorage, AK (United States); Narita, H. [National Inst. of Advanced Industrial Science and Technology, MEthane hydrate Research Lab., Sapporo (Japan); Pooladi-Darvish, M. [Fekete Associates Inc., Calgary, AB (Canada); Rose, K.; Boswell, R. [National Energy Technology Lab., Morgantown, WV (United States)

    2008-07-01

    In this study, 5 different gas hydrate production scenarios were modeled by the CMG STARS, HydateResSim, MH-21 HYDRES, STOMP-HYD and the TOUGH+HYDRATE reservoir simulators for comparative purposes. The 5 problems ranged in complexity from 1 to 3 dimensional with radial symmetry, and in horizontal dimensions of 20 meters to 1 kilometer. The scenarios included (1) a base case with non-isothermal multi-fluid transition to equilibrium, (2) a base case with gas hydrate (closed-domain hydrate dissociation), (3) dissociation in a 1-D open domain, (4) gas hydrate dissociation in a one-dimensional radial domain, similarity solutions, (5) gas hydrate dissociation in a two-dimensional radial domain. The purpose of the study was to compare the world's leading gas hydrate reservoir simulators in an effort to improve the simulation capability of experimental and naturally occurring gas hydrate accumulations. The problem description and simulation results were presented for each scenario. The results of the first scenario indicated very close agreement among the simulators, suggesting that all address the basics of mass and heat transfer, as well as overall process of gas hydrate dissociation. The third scenario produced the initial divergence among the simulators. Other differences were noted in both scenario 4 and 5, resulting in significant corrections to algorithms within several of the simulators. The authors noted that it is unlikely that these improvements would have been identified without this comparative study due to a lack of real world data for validation purposes. It was concluded that the solution for gas hydrate production involves a combination of highly coupled fluid, heat and mass transport equations combined with the potential for formation or disappearance of multiple solid phases in the system. The physical and chemical properties of the rocks containing the gas hydrate depend on the amount of gas hydrate present in the system. Each modeling and

  18. 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

  19. [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.

  20. Hydrate phase equilibrium and structure for (methane + ethane + tetrahydrofuran + water) system

    International Nuclear Information System (INIS)

    Sun Changyu; Chen Guangjin; Zhang Lingwei

    2010-01-01

    The separation of methane and ethane through forming hydrate is a possible choice in natural gas, oil processing, or ethylene producing. The hydrate formation conditions of five groups of (methane + ethane) binary gas mixtures in the presence of 0.06 mole fraction tetrahydrofuran (THF) in water were obtained at temperatures ranging from (277.7 to 288.2) K. In most cases, the presence of THF in water can lower the hydrate formation pressure of (methane + ethane) remarkably. However, when the composition of ethane is as high as 0.832, it is more difficult to form hydrate than without THF system. Phase equilibrium model for hydrates containing THF was developed based on a two-step hydrate formation mechanism. The structure of hydrates formed from (methane + ethane + THF + water) system was also determined by Raman spectroscopy. When THF concentration in initial aqueous solution was only 0.06 mole fraction, the coexistence of structure I hydrate dominated by ethane and structure II hydrate dominated by THF in the hydrate sample was clearly demonstrated by Raman spectroscopic data. On the contrary, only structure II hydrate existed in the hydrate sample formed from (methane + ethane + THF + water) system when THF concentration in initial aqueous solution was increased to 0.10 mole fraction. It indicated that higher THF concentration inhibited the formation of structure I hydrate dominated by ethane and therefore lowered the trapping of ethane in hydrate. It implies a very promising method to increase the separation efficiency of methane and ethane.

  1. 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.

  2. 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.

  3. High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    Science.gov (United States)

    Sun, Y.; Goldberg, D.; Collett, T.; Hunter, R.

    2011-01-01

    A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis. ?? 2010 Elsevier Ltd.

  4. Amount of gas hydrate estimated from compressional- and shear-wave velocities at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

    Science.gov (United States)

    Lee, M.W.

    1999-01-01

    The amount of in situ gas hydrate concentrated in the sediment pore space at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well was estimated by using compressional-wave (P-wave) and shear-wave (S-wave) downhole log measurements. A weighted equation developed for relating the amount of gas hydrate concentrated in the pore space of unconsolidated sediments to the increase of seismic velocities was applied to the acoustic logs with porosities derived from the formation density log. A weight of 1.56 (W=1.56) and the exponent of 1 (n=1) provided consistent estimates of gas hydrate concentration from the S-wave and the P-wave logs. Gas hydrate concentration is as much as 80% in the pore spaces, and the average gas hydrate concentration within the gas-hydrate-bearing section from 897 m to 1110 m (excluding zones where there is no gas hydrate) was calculated at 39.0% when using P-wave data and 37.8% when using S-wave data.

  5. 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

  6. Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

    International Nuclear Information System (INIS)

    Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

    2017-01-01

    Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.

  7. Skin Hydration Assessment through Modern Non-Invasive Bioengineering Technologies.

    Science.gov (United States)

    Constantin, Maria-Magdalena; Poenaru, Elena; Poenaru, Calin; Constantin, Traian

    2014-03-01

    Non-invasive bioengineering technologies continuously discovered and developed in recent decades provide a significant input to research development and remarkably contribute to the improvement of medical education and care to our patients. Assessing skin hydration by using the capacitance method for a group of patients with allergic contact dermatitis versus healthy subjects, before and after applying a moisturiser (assessing the immediate and long-term effectiveness of hydration). For both groups, but especially for the patients with dry skin, there was a clear improvement of hydration, statistically significant after applying the moisturiser. In the case of the patients with allergic contact dermatitis, hydration was at a maximum immediately after the first application, and then maintained an increased level after 7 and 28 days, respectively. In the healthy subjects, the increase in hydration was lower, but progressive. The moisturiser determined an increase in hydration for all age groups, but those who showed the most obvious effect were the young adults (18-29 years old) with an increase of 19.9%.The maintenance effect of hydration lasted for 28 days, while the improvement was important for allergic skin (17.1%) and significant for healthy skin (10.9%). The assessment of epidermal hydration performed by using the corneometer showed very good hydration of the stratum corneum for both groups studied, with immediate and long-term effect. This study also showed that the degree of skin hydration was inversely proportional with age. The corneometer is easy to use, efficient and widely utilised in international studies for measurements in healthy or pathological conditions, for quantitative assessment of the effectiveness of various preparations intended for application to the skin surface, under well-controlled and standardised conditions.

  8. Precise structural analysis of methane hydrate by neutron diffraction

    International Nuclear Information System (INIS)

    Igawa, Naoki; Hoshikawa, Akinori; Ishii, Yoshinobu

    2006-01-01

    Methane hydrate has attracted great interest as an energy resource to replace natural gas since this material is deposited in the seafloor and the deposits are estimated to exceed those of natural gas. Understanding the physical proprieties, such as the temperature dependence of the crystal structure, helps to specify the optimum environmental temperature and pressure during drilling, transport, and storage of methane hydrate. Clathrate hydrates consisted of encaging atomic and/or molecular species as a guest and host water formed by a hydrogen bonding. Although many studies on the clathrate hydrate including methane hydrate were reported, no detailed crystallographic property has yet been cleared. We focused on the motion of methane in the clathrate hydrate by the neutron diffraction. The crystal structure of the methane hydrate was analyzed by the applying the combination of the Rietveld refinement and the maximum entropy method (MEM) to neutron powder diffraction. Temperature dependence of the scattering-length density distribution maps revealed that the motion of methane molecules differs between the shapes of dodecahedron and tetrakaidecahedron. (author)

  9. Efficient dechlorination of carbon tetrachloride by hydrophobic green rust intercalated with dodecanoate anions

    DEFF Research Database (Denmark)

    Ayala Luis, Karina Barbara; Ginette Anneliese Cooper, Nicola; Bender Koch, Christian

    2012-01-01

    similar to those found in heavily contaminated groundwater close to polluted industrial sites (14 988 mu M) was reduced mainly to the fully dechlorinated products carbon monoxide (CO, yields >54 and formic acid (HCOOH, yields >6. Minor formation of chloroform (CF), the only chlorinated degradation product......The reductive dechlorination of carbon tetrachloride (CT) by Fe-II-Fe-III hydroxide (green rust) intercalated with dodecanoate, (Fe4Fe2III)-Fe-II (OH)(12)(C12H23O2)(2)center dot gamma H2O (designated GR(C12)), at pH similar to 8 and at room temperature was investigated. CT at concentration levels...

  10. Outbreak of carbon tetrachloride poisoning in a color printing factory related to the use of isopropyl alcohol and an air conditioning system in Taiwan.

    Science.gov (United States)

    Deng, J F; Wang, J D; Shih, T S; Lan, F L

    1987-01-01

    Three workers from a color printing factory were admitted to community hospitals in 1985 with manifestations of acute hepatitis. One of the three had superimposed acute renal failure and pulmonary edema. An investigation was subsequently conducted at the plant to determine the etiology of the outbreak and the prevalence of liver disease among the remaining workers. Comprehensive medical evaluations were conducted, which included physical examinations, liver function tests, and serological screening for hepatitis. Seventeen of 25 workers from the plant had abnormal liver function tests 10 days after the outbreak, and a significant association was found between the presence of abnormal liver function tests and a history of recently having worked inside any of three rooms in which an interconnecting air conditioning system had been installed to cool the printing machines. After further investigation, it was determined that the incident occurred following inadvertent use of carbon tetrachloride to clean a pump in the printing machine. A simulation of the pump cleaning operation revealed ambient air levels of carbon tetrachloride of 300-500 ppm. Ultimately, it was concluded that the outbreak was in all likelihood due to the combined use of carbon tetrachloride and isopropyl alcohol in the cleaning operation. This outbreak underscores the importance of adopting appropriate industrial hygiene measures in a rapidly industrializing nation such as Taiwan.

  11. National Gas Hydrate Program Expedition 01 offshore India; gas hydrate systems as revealed by hydrocarbon gas geochemistry

    Science.gov (United States)

    Lorenson, Thomas; Collett, Timothy S.

    2018-01-01

    The National Gas Hydrate Program Expedition 01 (NGHP-01) targeted gas hydrate accumulations offshore of the Indian Peninsula and along the Andaman convergent margin. The primary objectives of coring were to understand the geologic and geochemical controls on the accumulation of methane hydrate and their linkages to underlying petroleum systems. Four areas were investigated: 1) the Kerala-Konkan Basin in the eastern Arabian Sea, 2) the Mahanadi and 3) Krishna-Godavari Basins in the western Bay of Bengal, and 4) the Andaman forearc Basin in the Andaman Sea.Upward flux of methane at three of the four of the sites cored during NGHP-01 is apparent from the presence of seafloor mounds, seismic evidence for upward gas migration, shallow sub-seafloor geochemical evidence of methane oxidation, and near-seafloor gas composition that resembles gas from depth.The Kerala-Konkan Basin well contained only CO2 with no detectable hydrocarbons suggesting there is no gas hydrate system here. Gas and gas hydrate from the Krishna-Godavari Basin is mainly microbial methane with δ13C values ranging from −58.9 to −78.9‰, with small contributions from microbial ethane (−52.1‰) and CO2. Gas from the Mahanadi Basin was mainly methane with lower concentrations of C2-C5 hydrocarbons (C1/C2 ratios typically >1000) and CO2. Carbon isotopic compositions that ranged from −70.7 to −86.6‰ for methane and −62.9 to −63.7‰ for ethane are consistent with a microbial gas source; however deeper cores contained higher molecular weight hydrocarbon gases suggesting a small contribution from a thermogenic gas source. Gas composition in the Andaman Basin was mainly methane with lower concentrations of ethane to isopentane and CO2, C1/C2 ratios were mainly >1000 although deeper samples were compositions range from −65.2 to −80.7‰ for methane, −53.1 to −55.2‰ for ethane is consistent with mainly microbial gas sources, although one value recorded of −35.4‰ for propane

  12. 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

  13. 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.

  14. Amino acid assisted dehalogenation of carbon tetrachloride by green rust

    DEFF Research Database (Denmark)

    Yin, Weizhao; Strobel, Bjarne W.; Hansen, Hans Chr. Bruun

    2017-01-01

    that reduce the formation of toxic by-products such as chloroform (CF). In this study, carbon tetrachloride (CT) dehalogenation by the chloride form of GR (GRCl) was tested in presence of glycine (GLY) and other selected amino acids. GLY, alanine (ALA) or serine (SER) all resulted in remarkable suppression...... of CF formation with only ~ 10% of CF recovery while sarcosine (SAR) showed insignificant effects. For two non-amino acid buffers, TRIS had little effect while HEPES resulted in a 40 times lower rate constant compared to experiments where no buffer was added. The FeII complexing properties of the amino...... acids and buffers caused variable extents of GRCl dissolution which was linearly correlated with CF suppression and dehalogenation rate. We hypothesize that the CF suppression seen for amino acids is caused by stabilization of carbene intermediates via the carbonyl group. Different effects on CF...

  15. Estimating pore-space gas hydrate saturations from well log acoustic data

    Science.gov (United States)

    Lee, Myung W.; Waite, William F.

    2008-07-01

    Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate-bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

  16. 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.)

  17. 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)

  18. Effect of Apitherapy Formulations against Carbon Tetrachloride-Induced Toxicity in Wistar Rats after Three Weeks of Treatment

    Directory of Open Access Journals (Sweden)

    Calin Vasile Andritoiu

    2014-08-01

    Full Text Available The human body is exposed nowadays to increasing attacks by toxic compounds in polluted air, industrially processed foods, alcohol and drug consumption that increase liver toxicity, leading to more and more severe cases of hepatic disorders. The present paper aims to evaluate the influence of the apitherapy diet in Wistar rats with carbon tetrachloride-induced hepatotoxicity, by analyzing the biochemical determinations (enzymatic, lipid and protein profiles, coagulation parameters, minerals, blood count parameters, bilirubin levels and histopathological changes at the level of liver, spleen and pancreas. The experiment was carried out on six groups of male Wistar rats. Hepatic lesions were induced by intraperitoneal injection of carbon tetrachloride (dissolved in paraffin oil, 10% solution. Two mL per 100 g were administered, every 2 days, for 2 weeks. Hepatoprotection was achieved with two apitherapy diet formulations containing honey, pollen, propolis, Apilarnil, with/without royal jelly. Biochemical results reveal that the two apitherapy diet formulations have a positive effect on improving the enzymatic, lipid, and protein profiles, coagulation, mineral and blood count parameters and bilirubin levels. The histopathological results demonstrate the benefits of the two apitherapy diet formulations on reducing toxicity at the level of liver, spleen and pancreas in laboratory animals.

  19. 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 have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

  20. 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

  1. India National Gas Hydrate Program Expedition 02 Technical Contributions

    Science.gov (United States)

    Collett, T. S.; Kumar, P.; Shukla, K. M.; Nagalingam, J.; Lall, M. V.; Yamada, Y.; Schultheiss, P. J.; Holland, M.; Waite, W. F.

    2017-12-01

    The National Gas Hydrate Program Expedition 02 (NGHP-02) was conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India. The primary objective of this expedition was the exploration and discovery of highly saturated gas hydrate occurrences in sand reservoirs that would be targets of future production testing. The first 2 months of the expedition were dedicated to logging while drilling (LWD) operations with a total of 25 holes being drilled and logged. The next 3 months were dedicated to coring operations at 10 of the most promising sites. NGHP-02 downhole logging, coring and formation pressure testing have confirmed the presence of large, highly saturated, gas hydrate accumulations in coarse-grained sand-rich depositional systems throughout the Krishna-Godavari Basin within the regions defined during NGHP-02 as Area-B, Area-C, and Area-E. The nature of the discovered gas hydrate occurrences closely matched pre-drill predictions, confirming the project developed depositional models for the sand-rich depositional facies in the Krishna-Godavari and Mahanadi Basins. The existence of a fully developed gas hydrate petroleum system was established in Area-C of the Krishna-Godavari Basin with the discovery of a large slope-basin interconnected depositional system, including a sand-rich, gas-hydrate-bearing channel-levee prospect at Sites NGHP-02-08 and -09. The acquisition of closely spaced LWD and core holes in the Area-B L1 Block gas hydrate accumulation have provided one of the most complete three-dimensional petrophysical-based views of any known gas hydrate reservoir system in the world. It was concluded that Area-B and Area-C in the area of the greater Krishna-Godavari Basin contain important world-class gas hydrate accumulations and represent ideal sites for consideration of future gas hydrate production testing.

  2. Experimental Investigation into the Combustion Characteristics of Propane Hydrates in Porous Media

    Directory of Open Access Journals (Sweden)

    Xiang-Ru Chen

    2015-02-01

    Full Text Available The combustion characteristics of both pure propane hydrates and the mixtures of hydrates and quartz sands were investigated by combustion experiments. The flame propagation, flame appearance, burning time and temperature in different hydrate layers were studied. For pure propane hydrate combustion, the initial flame falls in the “premixed” category. The flame propagates very rapidly, mainly as a result of burnt gas expansion. The flame finally self-extinguishes with some proportion of hydrates remaining unburned. For the hydrate-sand mixture combustion, the flame takes the form of many tiny discontinuous flames appearing and disappearing at different locations. The burn lasts for a much shorter amount of time than pure hydrate combustion. High porosity and high hydrate saturation is beneficial to the combustion. The hydrate combustion is the combustion of propane gas resulting from the dissociation of the hydrates. In both combustion test scenarios, the hydrate-dissociated water plays a key role in the fire extinction, because it is the main resistance that restrains the heat transfer from the flame to the hydrates and that prevents the hydrate-dissociated gas from releasing into the combustion zone.

  3. Kinetic Hydration Heat Modeling for High-Performance Concrete Containing Limestone Powder

    Directory of Open Access Journals (Sweden)

    Xiao-Yong Wang

    2017-01-01

    Full Text Available Limestone powder is increasingly used in producing high-performance concrete in the modern concrete industry. Limestone powder blended concrete has many advantages, such as increasing the early-age strength, reducing the setting time, improving the workability, and reducing the heat of hydration. This study presents a kinetic model for modeling the hydration heat of limestone blended concrete. First, an improved hydration model is proposed which considers the dilution effect and nucleation effect due to limestone powder addition. A degree of hydration is calculated using this improved hydration model. Second, hydration heat is calculated using the degree of hydration. The effects of water to binder ratio and limestone replacement ratio on hydration heat are clarified. Third, the temperature history and temperature distribution of hardening limestone blended concrete are calculated by combining hydration model with finite element method. The analysis results generally agree with experimental results of high-performance concrete with various mixing proportions.

  4. 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

  5. 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...

  6. 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 

  7. Hydrate-Bearing Clayey Sediments: Morphology, Physical Properties, Production and Engineering/Geological Implications

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Sheng [Georgia Tech Research Corporation, Atlanta, GA (United States); Santamarina, J. Carlos [King Abdulaziz Univ., Jeddah (Saudi Arabia)

    2017-12-30

    Fine-grained sediments host more than 90 percent of global gas hydrate accumulation. However, hydrate formation in clay-dominated sediments is less understood and characterized than other types of hydrate occurrence. There is an inadequate understanding of hydrate formation mechanisms, segregation structures, hydrate lens topology, system connectivity, and physical macro-scale properties of clay-dominated hydrate-bearing sediments. This situation hinders further analyses of the global carbon budget as well as engineering challenges/solutions related to hydrate instability and production. This project studies hydrate-bearing clay-dominated sediments with emphasis on the enhanced fundamental understanding of hydrate formation and resulting morphology, the development laboratory techniques to emulate natural hydrate formations, the assessment of analytical tools to predict physical properties, the evaluation of engineering and geological implications, and the advanced understanding of gas production potential from finegrained sediments.

  8. Hydration for the prevention of contrast medium-induced nephropathy. An update

    International Nuclear Information System (INIS)

    Heinrich, M.; Uder, M.

    2006-01-01

    Contrast medium-induced nephropathy (CIN) continues to be one of the most common causes of hospital-acquired acute renal failure. Since most of the clinical studies on the prophylactic use of different drugs to prevent CIN produced disappointing results, hydration remains the mainstay of prophylaxis. A number of recent prospective randomized trials provided further evidence of the effectiveness of hydration and relevant information regarding the optimization of hydration protocols. It was shown that a bolus hydration solely during examination is not sufficient to prevent CIN. In addition, isotonic 0.9% saline was superior to the commonly used halfisotonic 0.45% saline in another trial. An outpatient hydration protocol including oral hydration before the examination followed by forced intravenous hydration over 6 hrs. beginning 30 to 60 min. prior to examination seems to be comparable to the usual hydration over 24 hrs. Another hydration protocol, which could also be very attractive especially for outpatients, included the infusion of sodium bicarbonate. In a recent trial, hydration with sodium bicarbonate, given as a bolus for 1 hr. prior to examination followed by an infusion for 6 hrs. after examination, was more effective than hydration with sodium chloride for the prophylaxis of CIN. However, there is still a lack of large-scale, multi-center trials comparing different hydration protocols and investigating their influence on clinically relevant endpoints such as mortality or the need for dialysis. (orig.)

  9. The effect of hydrate promoters on gas uptake.

    Science.gov (United States)

    Xu, Chun-Gang; Yu, Yi-Song; Ding, Ya-Long; Cai, Jing; Li, Xiao-Sen

    2017-08-16

    Gas hydrate technology is considered as a promising technology in the fields of gas storage and transportation, gas separation and purification, seawater desalination, and phase-change thermal energy storage. However, to date, the technology is still not commercially used mainly due to the low gas hydrate formation rate and the low gas uptake. In this study, the effect of hydrate promoters on gas uptake was systematically studied and analyzed based on hydrate-based CH 4 storage and CO 2 capture from CO 2 /H 2 gas mixture experiments. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC) were employed to analyze the microstructures and gas compositions. The results indicate that the effect of the hydrate promoter on the gas uptake depends on the physical and chemical properties of the promoter and gas. A strong polar ionic promoter is not helpful towards obtaining the ideal gas uptake because a dense hydrate layer is easily formed at the gas-liquid interface, which hinders gas diffusion from the gas phase to the bulk solution. For a weak polar or non-polar promoter, the gas uptake depends on the dissolution characteristics among the different substances in the system. The lower the mutual solubility among the substances co-existing in the system, the higher the independence among the substances in the system; this is so that each phase has an equal chance to occupy the hydrate cages without or with small interactions, finally leading to a relatively high gas uptake.

  10. 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

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

    Science.gov (United States)

    White, M. D.

    2011-12-01

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

  12. 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.

  13. 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)

  14. 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

  15. 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.

  16. 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

  17. Methane hydrate induced permeability modification for multiphase flow in unsaturated porous media

    Science.gov (United States)

    Seol, Yongkoo; Kneafsey, Timothy J.

    2011-08-01

    An experimental study was performed using X-ray computed tomography (CT) scanning to capture three-dimensional (3-D) methane hydrate distributions and potential discrete flow pathways in a sand pack sample. A numerical study was also performed to develop and analyze empirical relations that describe the impacts of hydrate accumulation habits within pore space (e.g., pore filling or grain cementing) on multiphase fluid migration. In the experimental study, water was injected into a hydrate-bearing sand sample that was monitored using an X-ray CT scanner. The CT images were converted into numerical grid elements, providing intrinsic sample data including porosity and phase saturations. The impacts of hydrate accumulation were examined by adapting empirical relations into the flow simulations as additional relations governing the evolution of absolute permeability of hydrate bearing sediment with hydrate deposition. The impacts of pore space hydrate accumulation habits on fluid migration were examined by comparing numerical predictions with experimentally measured water saturation distributions and breakthrough curves. A model case with 3-D heterogeneous initial conditions (hydrate saturation, porosity, and water saturation) and pore body-preferred hydrate accumulations best captured water migration behavior through the hydrate-bearing sample observed in the experiment. In the best matching model, absolute permeability in the hydrate bearing sample does not decrease significantly with increasing hydrate saturation until hydrate saturation reaches about 40%, after which it drops rapidly, and complete blockage of flow through the sample can occur as hydrate accumulations approach 70%. The result highlights the importance of permeability modification due to hydrate accumulation habits when predicting multiphase flow through high-saturation, reservoir quality hydrate-bearing sediments.

  18. Hydrates plugs dissociation in pipelines; Dissociation des bouchons d'hydrates de gaz dans les conduites petrolieres sous-marines

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Hong, D.

    2005-03-15

    Natural gas hydrates plugs cause problems during drilling, well operations, production, transportation and processing of oil and gas. Especially, it is a very serious problem in off-shore oil transportation where low temperature and high pressure become more and more favourable to gas hydrate formation as the new production wells are more and more deeper. Up to now, although many studies have been developed concerning the possibility of preventing pipe plugging, there is limited information in open literature on hydrate plugs dissociation and all models in literature are numerically complicated. In this study, hydrate plugs are formed from water in n-dodecane mixture with addition of a dispersant E102B in two different experimental apparatus in order to obtain hydrates plugs with different sizes (diameter of 7, 10.75 and 12 cm). Then, the plugs are dissociated by the method of two-sided depressurization. In this paper, we propose a numerical model which describes the dissociation of gas hydrate plugs in pipelines. The numerical model, which is constructed for cylindrical coordinates and for two-sided pressurization, is based on enthalpy method. We present also an approximate analytical model which has an average error 2.7 % in comparison with the numerical model. The excellent agreement between our experimental results, literature data and the two models shows that the models give a good prediction independently of the pipeline diameter, plug porosity and gas. The simplicity of the analytical model will make it easier in industrial applications. (author)

  19. Ultrasonic sound speed of hydrating calcium sulphate hemihydrate; part 2, the correlation of sound velocity to hydration degree

    NARCIS (Netherlands)

    de Korte, A.C.J.; Brouwers, Jos; Fischer, H.B; Matthes, C.; Beuthan, C.

    2011-01-01

    In this article the sound velocity through a mix is correlated to the hydration degree of the mix. Models are presented predicting the sound velocity through fresh slurries and hardened products. These two states correspond to the starting and finishing point of the hydration process. The present

  20. Ultrasonic sound speed of hydrating calcium sulphate hemihydrate; Part 2, The correlation of sound velocity to hydration degree

    NARCIS (Netherlands)

    Korte, de A.C.J.; Brouwers, H.J.H.; Fischer, H.B.; Mattes, Chr.; Beutha, C.

    2011-01-01

    In this article the sound velocity through a mix is correlated to the hydration degree of the mix. Models are presented predicting the sound velocity through fresh slurries and hardened products. These two states correspond to the starting and finishing point of the hydration process. The present

  1. n-Electrons of heteroatoms in hydrogen bond and luminescence

    International Nuclear Information System (INIS)

    Karyakin, A.V.

    1985-01-01

    Hydrogen bond energy in the process of interaction between water molecules, water molecules and heteroatoms of organic solvents, water molecules and inorganic compounds, is determined, its mechanism being studied. On the basis of X-ray structure and IR-spectroscopic data water state in easily hydrolized compounds of zirconium and hafnium, including sulfates, nitrates, oxychlorides etc. is analyzed. Water state in uranyl nitrate hydrates, the structure of the compounds and their behaviour when they are extracted by TBP, are considered. The reasons for stability of uranyl nitrate hydrates are discussed. The effect of n-electrons of heteroatoms of simple aromatic compound on structural spectra of luminescence in aliphatic and inorganic matrices is investigated

  2. Towards understanding the role of amines in the SO2 hydration and the contribution of the hydrated product to new particle formation in the Earth's atmosphere.

    Science.gov (United States)

    Lv, Guochun; Nadykto, Alexey B; Sun, Xiaomin; Zhang, Chenxi; Xu, Yisheng

    2018-08-01

    By theoretical calculations, the gas-phase SO 2 hydration reaction assisted by methylamine (MA) and dimethylamine (DMA) was investigated, and the potential contribution of the hydrated product to new particle formation (NPF) also was evaluated. The results show that the energy barrier for aliphatic amines (MA and DMA) assisted SO 2 hydration reaction is lower than the corresponding that of water and ammonia assisted SO 2 hydration. In these hydration reactions, nearly barrierless reaction (only a barrier of 0.1 kcal mol -1 ) can be found in the case of SO 2  + 2H 2 O + DMA. These lead us to conclude that the SO 2 hydration reaction assisted by MA and DMA is energetically facile. The temporal evolution for hydrated products (CH 3 NH 3 + -HSO 3 - -H 2 O or (CH 3 ) 2 NH 2 + -HSO 3 - -H 2 O) in molecular dynamics simulations indicates that these complexes can self-aggregate into bigger clusters and can absorb water and amine molecules, which means that these hydrated products formed by the hydration reaction may serve as a condensation nucleus to initiate the NPF. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Stages of Gas-Hydrate Evolution on the Northern Cascadia Margin

    Directory of Open Access Journals (Sweden)

    the IODP Expedition 311 Scientists

    2006-09-01

    Full Text Available Natural gas hydrate occurs beneath many continental slopes and in arctic permafrost areas. Recent studies have indicated that the largest deposits of gas hydrate might lie in nearly horizontal layers several hundred meters beneath the seafloor of continental slopes, especially in the large, accretionary sedimentary prisms of subduction zones. Expedition 311 of the Integrated Ocean Drilling Program (IODP investigated the formation of gas hydrate in the accretionary prism of the Cascadia subduction zone (Fig. 1. The primary objectives of Expedition 311 were to test and constraingeological models of gas hydrate formation by upward fluidand methane transport in accretionary prisms. We specifi -cally sought to (a determine the mechanisms that controlthe nature, magnitude, and distribution of the gas hydrate,(b find the pathways of the fluid migration required to formlarge concentrations of gas hydrate, (c examine the effectsof gas hydrate on the physical properties of the host sediment,and (d investigate the microbiology and geochemistryassociated with the occurrence of gas hydrate. Furthermore,we concentrated on the contrast between methane transportby focused fl ow in fault zones and by dispersed pervasiveupward flow at various scales of permeability.

  4. 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)

  5. 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)

  6. Biological effects of pesticides on rats treated with carbon tetrachloride

    International Nuclear Information System (INIS)

    Abdel Kader, S.M.

    1990-01-01

    The present study investigates the effect of repeated oral doses of the organophosphorus pesticide, cytrolane on normal and pretreated rate with different oral doses of carbon tetrachloride. For that purpose the effect of cytrolane, CCl 4 and their potential interaction had been studied on brain and erythrocyte acetylcholinesterase (Ache), plasma cholinesterase (Ch E), liver succinic dehydrogenase (SDH), serum alkaline phosphatase (SAP), liver succinic dehydrogenas (SDH), serum alkaline phosphatase (SAP), glutamic oxaloacetic (GOT) and glutamic pyruvic (GPT) transaminases. It also investigates the effect of an acute oral dose of cytrolane at short time intervals (1/2-24 hours) on brain and blood ache of normal and pretreated rate with a single oral dose of CCl 4 . The distribution and excretion of 1 4cc1 4 at different time intervals (2,6 and 24 hours) in normal rats and in rats pretreated with o.89 mg cytrolane/kg/day for a week had been determined in different organs, expired air, urine and faeces

  7. Current sources of carbon tetrachloride (CCl4) in our atmosphere

    Science.gov (United States)

    Sherry, David; McCulloch, Archie; Liang, Qing; Reimann, Stefan; Newman, Paul A.

    2018-02-01

    Carbon tetrachloride (CCl4 or CTC) is an ozone-depleting substance whose emissive uses are controlled and practically banned by the Montreal Protocol (MP). Nevertheless, previous work estimated ongoing emissions of 35 Gg year-1 of CCl4 into the atmosphere from observation-based methods, in stark contrast to emissions estimates of 3 (0-8) Gg year-1 from reported numbers to UNEP under the MP. Here we combine information on sources from industrial production processes and legacy emissions from contaminated sites to provide an updated bottom-up estimate on current CTC global emissions of 15-25 Gg year-1. We now propose 13 Gg year-1 of global emissions from unreported non-feedstock emissions from chloromethane and perchloroethylene plants as the most significant CCl4 source. Additionally, 2 Gg year-1 are estimated as fugitive emissions from the usage of CTC as feedstock and possibly up to 10 Gg year-1 from legacy emissions and chlor-alkali plants.

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. Experimental determination of methane hydrate formation in the presence of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Dong, T.B.; Wang, L.Y.; Liu, A.X.; Guo, X.Q.; Chen, G.J.; Ma, Q.L.; Li, G.W. [China Univ. of Petroleum, Beijng (China). State Key Laboratory of Heavy Oil Processing

    2008-07-01

    Gas hydrates are non-stoichiometric inclusion compounds that are created by a lattice of water molecules. The host molecule has a strong hydrogen bond and encages low molecular weight gases or volatile liquids. The guest molecules favor hydrate formation. Historically, gas hydrates have been thought to be problematic during natural gas transportation because the formed solid hydrate can block pipelines and cause tubing and casing collapse. However, the discovery of huge deposits of gas hydrates in deep-sea sediments and in permafrost has renewed interest in gas hydrates as a new energy resource. This paper discussed a study that is a part of an ongoing experimental and computational program dealing with the thermodynamics of gas hydrate formation in ammonia-water systems. The purpose of the study was to develop a new method to separate and recycle the vent gas of ammonia synthesis by forming or dissociating hydrate. The hydrate-forming conditions of methane in ammonia and water system were studied and reported in this paper with reference to the experimental apparatus and procedure. The materials and preparation of samples were also explained. The experimental results showed that the ammonia had an inhibitive effect on the hydrate formation. 26 refs., 2 tabs., 3 figs.

  16. The structural response of the cornea to changes in stromal hydration.

    Science.gov (United States)

    Hayes, Sally; White, Tomas; Boote, Craig; Kamma-Lorger, Christina S; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M

    2017-06-01

    The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS 2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas ( p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration ( H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations ( p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. © 2017 The Authors.

  17. Influence of limestone on the hydration of Portland cements

    International Nuclear Information System (INIS)

    Lothenbach, Barbara; Le Saout, Gwenn; Gallucci, Emmanuel; Scrivener, Karen

    2008-01-01

    The influence of the presence of limestone on the hydration of Portland cement was investigated. Blending of Portland cement with limestone was found to influence the hydrate assemblage of the hydrated cement. Thermodynamic calculations as well as experimental observations indicated that in the presence of limestone, monocarbonate instead of monosulfate was stable. Thermodynamic modelling showed that the stabilisation of monocarbonate in the presence of limestone indirectly stabilised ettringite leading to a corresponding increase of the total volume of the hydrate phase and a decrease of porosity. The measured difference in porosity between the 'limestone-free' cement, which contained less than 0.3% CO 2 , and a cement containing 4% limestone, however, was much smaller than calculated. Coupling of thermodynamic modelling with a set of kinetic equations which described the dissolution of the clinker, predicted quantitatively the amount of hydrates. The quantities of ettringite, portlandite and amorphous phase as determined by TGA and XRD agreed well with the calculated amounts of these phases after different periods of time. The findings in this paper show that changes in the bulk composition of hydrating cements can be followed by coupled thermodynamic models. Comparison between experimental and modelled data helps to understand in more detail the dominating processes during cement hydration

  18. 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.

  19. Gas hydrate drilling transect across northern Cascadia margin - IODP Expedition 311

    Science.gov (United States)

    Riedel, M.; Collett, T.; Malone, M.J.; Collett, T.S.; Mitchell, M.; Guerin, G.; Akiba, F.; Blanc-Valleron, M.; Ellis, M.; Hashimoto, Y.; Heuer, V.; Higashi, Y.; Holland, M.; Jackson, P.D.; Kaneko, M.; Kastner, M.; Kim, J.-H.; Kitajima, H.; Long, P.E.; Malinverno, A.; Myers, Gwen E.; Palekar, L.D.; Pohlman, J.; Schultheiss, P.; Teichert, B.; Torres, M.E.; Trehu, A.M.; Wang, Jingyuan; Worthmann, U.G.; Yoshioka, H.

    2009-01-01

    A transect of four sites (U1325, U1326, U1327 and U1329) across the northern Cascadia margin was established during Integrated Ocean Drilling Program Expedition 311 to study the occurrence and formation of gas hydrate in accretionary complexes. In addition to the transect sites, a fifth site (U1328) was established at a cold vent with active fluid flow. The four transect sites represent different typical geological environments of gas hydrate occurrence across the northern Cascadia margin from the earliest occurrence on the westernmost first accreted ridge (Site U1326) to the eastward limit of the gas hydrate occurrence in shallower water (Site U1329). Expedition 311 complements previous gas hydrate studies along the Cascadia accretionary complex, especially ODP Leg 146 and Leg 204 by extending the aperture of the transect sampled and introducing new tools to systematically quantify the gas hydrate content of the sediments. Among the most significant findings of the expedition was the occurrence of up to 20 m thick sand-rich turbidite intervals with gas hydrate concentrations locally exceeding 50% of the pore space at Sites U1326 and U1327. Moreover, these anomalous gas hydrate intervals occur at unexpectedly shallow depths of 50-120 metres below seafloor, which is the opposite of what was expected from previous models of gas hydrate formation in accretionary complexes, where gas hydrate was predicted to be more concentrated near the base of the gas hydrate stability zone just above the bottom-simulating reflector. Gas hydrate appears to be mainly concentrated in turbidite sand layers. During Expedition 311, the visual correlation of gas hydrate with sand layers was clearly and repeatedly documented, strongly supporting the importance of grain size in controlling gas hydrate occurrence. The results from the transect sites provide evidence for a structurally complex, lithology-controlled gas hydrate environment on the northern Cascadia margin. Local shallow

  20. Theoretical description of biomolecular hydration - Application to A-DNA

    International Nuclear Information System (INIS)

    Garcia, A.E.; Hummer, G.; Soumpasis, D.M.

    1994-01-01

    The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG) 5 ] 2 and [d(C 5 G 5 )] 2 . We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers

  1. 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

    In 2015, the Indian National Gas Hydrate Program (NGHP) Drilling Expedition 02 was carried out off the eastern margin of the Indian Peninsula in order to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. One of the target areas (area B) is located on the axial and flank of an anticline, where the BSR is identified 100 m beneath the summit of anticline. 3 sites were drilled in the crest. The lower potential hydrate zone II was suggested by downhole logging (LWD) at 270-290 m below seafloor across the top of anticline. Core samples from this interval is characterized by a higher natural gamma radiation, gamma-ray-based higher bulk density and lower porosity, and higher electrical resistivity. All these features are in good agreement with LWD results. During this expedition, numerous special core sampling operations (PCAT) were carried out, keeping its insitu pressure in a pressure-tight vessel. They enabled acquiring insitu P-wave velocity and gamma-ray attenuation density measurements. In-situ X-CT images exhibit very clear hydrate distribution as lower density patches. Hydrate-bearing sediments exhibit a Vp-density trend that is clearly different from the ordinary formation. Vp values are significantly higher than 2 km/s whereas the density remains constant at 2-2.2 g/cm3 in hydrate zones. At some hydrate-bearing sediments, we noticed that Vp is negatively correlated to the density in the deeper portion (235-285 mbsf). On the other hand, in the shallower portion they are positively correlated. From lithostratigraphy the shallower portion consists of sand, whereas deeper portion are silty-clay dominant. We infer that the sand-dominant, shallower hydrate is a pore-filling type, and Vp is correlated positively to density. On the other hand, the clay-dominant, deeper hydrate is filled in vertical veins, and Vp is negatively correlated to density. Negative

  2. 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...

  3. Geologic implications of gas hydrates in the offshore of India: Results of the National Gas Hydrate Program Expedition 01

    Digital Repository Service at National Institute of Oceanography (India)

    Collett, T.S.; Boswell, R.; Cochran, J.R.; Kumar, P.; Lall, M.; Mazumdar, A.; Ramana, M.V.; Ramprasad, T.; Riedel, M.; Sain, K.; Sathe, A.V.; Vishwanath, K.; NGHP Expedition 01 Scientific Party

    in Japan (Tsujii et al., 2009) and in the Gulf of Mexico (Boswell et al., 2012a) and the pace of gas-hydrate energy-assessment projects continues to accelerate. Beyond a future energy resource, gas hydrates may in some cases represent a significant...

  4. 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.

  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. Methane hydrates. A possible energy source in the twenty-first century

    International Nuclear Information System (INIS)

    Sorassi, S.

    1998-01-01

    The morphological characteristics of particular crystal structures, to be found in nature both in arctic and Antarctic regions and under seas and oceans, and consisting of water and gas molecules, the so-called 'gas hydrates', are dealt with. Technical problems related to gas recovery (methane in particular) from hydrates, above all under sea level, mainly due to their reduced stability, are examined. On the ground of these considerations, various gas recovery methods from hydrate fields are described. An overall evaluation of methane availability as hydrates all over the world, as well as a comparison between extraction costs from hydrate and well as a comparison between extraction costs from hydrate and conventional fields, are made. Finally, short-term programmes on research and development of methane hydrate fields in some areas of the Earth are described [it

  7. Detailed evaluation of gas hydrate reservoir properties using JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well downhole well-log displays

    Science.gov (United States)

    Collett, T.S.

    1999-01-01

    The JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well project was designed to investigate the occurrence of in situ natural gas hydrate in the Mallik area of the Mackenzie Delta of Canada. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas-hydrate-bearing sediments. Downhole logging tool strings deployed in the Mallik 2L-38 well included the Schlumberger Platform Express with a high resolution laterolog, Array Induction Imager Tool, Dipole Shear Sonic Imager, and a Fullbore Formation Microlmager. The downhole log data obtained from the log- and core-inferred gas-hydrate-bearing sedimentary interval (897.25-1109.5 m log depth) in the Mallik 2L-38 well is depicted in a series of well displays. Also shown are numerous reservoir parameters, including gas hydrate saturation and sediment porosity log traces, calculated from available downhole well-log and core data. The gas hydrate accumulation delineated by the Mallik 2L-38 well has been determined to contain as much as 4.15109 m3 of gas in the 1 km2 area surrounding the drill site.

  8. Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

    Science.gov (United States)

    Biswas, Biswajit; Singh, Prashant Chandra

    2015-11-11

    The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes.

  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. Characteristics of Methane Hydrate Formation in Artificial and Natural Media

    Directory of Open Access Journals (Sweden)

    Qingbai Wu

    2013-03-01

    Full Text Available 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 water transfer to the hydrate surfaces with lower Gibbs free energy after nucleation. Significant differences in the reactions in the two types of media arose from differences in the water retention capacity and lithology of media due to the internal surface area and pore size distributions. Compared with methane hydrate formation in silica gel, the reaction in loess was much slower and formed far less methane hydrate. The results of this study will advance the understanding of how the properties of the environment affect the formation of gas hydrates in nature.

  11. Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

    Science.gov (United States)

    Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

    2018-04-01

    We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

  12. 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....

  13. 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

  14. Observation of microstructure of hydrated Ca3SiO5

    International Nuclear Information System (INIS)

    Mori, Kazuhiro; Sato, Takashi; Fukunaga, Toshiharu; Oishi, Koji; Kimura, Katsuhiko; Iwase, Kenji; Sugiyama, Masaaki; Itoh, Keiji; Shikanai, Fumihito; Wuernisha, Tuerxun; Yonemura, Masao; Sulistyanintyas, Dyah; Tsukushi, Itaru; Takata, Shinich; Otomo, Toshiya; Kamiyma, Takashi; Kawai, Masayoshi

    2006-01-01

    Quasi-elastic neutron scattering experiments were carried out to evaluate the hydration rate of tricalcium silicate (Ca 3 SiO 5 ). Furthermore, in the early hydration period, a variation in surface roughness of Ca 3 SiO 5 was observed in nano-scale by the small-angle neutron scattering. From these results, it was found that the hydration rate of Ca 3 SiO 5 is suppressed when the surface of Ca 3 SiO 5 becomes rough through the creation of hydration products C-S-H gel and Ca(OH) 2 , and this roughness is associated with changes in the Ca 3 SiO 5 hydration rate

  15. The workings of a molecular thermometer: the vibrational excitation of carbon tetrachloride by a solvent.

    Science.gov (United States)

    Graham, Polly B; Matus, Kira J M; Stratt, Richard M

    2004-09-15

    An intriguing energy-transfer experiment was recently carried out in methanol/carbon tetrachloride solutions. It turned out to be possible to watch vibrational energy accumulating in three of carbon tetrachloride's modes following initial excitation of O-H and C-H stretches in methanol, in effect making those CCl(4) modes "molecular thermometers" reporting on methanol's relaxation. In this paper, we use the example of a CCl(4) molecule dissolved in liquid argon to examine, on a microscopic level, just how this kind of thermal activation occurs in liquid solutions. The fact that even the lowest CCl(4) mode has a relatively high frequency compared to the intermolecular vibrational band of the solvent means that the only solute-solvent dynamics relevant to the vibrational energy transfer will be extraordinarily local, so much so that it is only the force between the instantaneously most prominent Cl and solvent atoms that will significantly contribute to the vibrational friction. We use this observation, within the context of a classical instantaneous-pair Landau-Teller calculation, to show that energy flows into CCl(4) primarily via one component of the nominally degenerate, lowest frequency, E mode and does so fast enough to make CCl(4) an excellent choice for monitoring methanol relaxation. Remarkably, within this theory, the different symmetries and appearances of the different CCl(4) modes have little bearing on how well they take up energy from their surroundings--it is only how high their vibrational frequencies are relative to the solvent intermolecular vibrational band edge that substantially favors one mode over another.

  16. 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)

  17. Modelling the incongruent dissolution of hydrated cement minerals

    International Nuclear Information System (INIS)

    Berner, U.R.

    1988-01-01

    Hydrated calciumsilicates are the main constituents of hydrated portland cements. Their chemistry will strongly influence the longterm behaviour of a concrete system envisioned in use in radioactive waste repositories. Experimental data show that hydrated calciumsilicates dissolve incongruently, depending on the calcium/silicon ratio of the solid. A model that simulates the incongruent dissolution behaviour of these hydrated calciumsilicates is presented. In the model the hydrated calciumcilicates are represented as a mixture of two congruently soluble components. The dissolution of the particular components is described using the concept of variable activities in the solid state. Each component's activity in the solid state is obtained from a large body of solubility data by applying the Gibbs-Duhem equation for nonideal mixtures. Using this approach a simplified set of equations, which describe the solubility of the components as a function of the calcium/silicon ratio of the solid, is derived. As an application, the degradation of a standard portland cement in pure water and in a carbonate-rich groundwater is modelled. (orig.)

  18. Theoretical description of biomolecular hydration - Application to A-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, A.E.; Hummer, G. [Los Alamos National Laboratory, NM (United States); Soumpasis, D.M. [Max Planck Inst. for Biophysical Chemistry, Goettingen (Germany)

    1994-12-31

    The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG){sub 5}]{sub 2} and [d(C{sub 5}G{sub 5})]{sub 2}. We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers.

  19. Assessment of the Mutagenic Potential of Carbon Disulfide, Carbon Tetrachloride, Dichloromethane, Ethylene Dichloride, and Methyl Bromide: A Comparative Analysis in Relation to Ethylene Dibromide

    Science.gov (United States)

    The document provides an evaluation of the mutagenic potential of five alternative fumigants to ethylene dibromide(EDB). These include carbon disulfide(CS2), carbon tetrachloride(CCl4), dichloromethane(DCM), ethylene dichloride(EDC), and methyl bromide (MB). Of the five proposed ...

  20. Hepatoprotective effects of setarud against carbon tetrachloride-induced liver injury in rats.

    Science.gov (United States)

    Khorshid, Hamid Reza Khorram; Azonov, Jahan A; Novitsky, Yury A; Farzamfar, Bardia; Shahhosseiny, Mohammad Hassan

    2008-01-01

    To assess the hepatoprotective activity of a new herbal drug "setarud" in experimental liver fibrosis, 48 male Wistar rats were divided into four groups: controls, carbon tetrachloride (CCl4) group, and two treatment groups that received CCl4 and setarud at doses of 0.02 or 0.04 g/Kg/day for 30 days. Body weight gain, biochemical liver tests, bile flow rate and composition, and changes in liver morphology in the four groups were studied. CCl4 administration led to morphological and biochemical evidence of liver injury as compared to untreated controls. Setarud administration led to significant protection against CCl4-induced changes in body weight gain, liver morphology, bile flow and concentration. It was also associated with significantly lower serum liver enzyme levels (pliver disease are warranted.