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Sample records for hydrate dissociation mechanisms

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

    Directory of Open Access Journals (Sweden)

    Zhixue Sun

    2017-12-01

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

  2. Simulating the effect of hydrate dissociation on wellhead stability during oil and gas development in deepwater

    Science.gov (United States)

    Li, Qingchao; Cheng, Yuanfang; Zhang, Huaiwen; Yan, Chuanliang; Liu, Yuwen

    2018-02-01

    It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development (OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.

  3. A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

    KAUST Repository

    Sá nchez, Marcelo; Gai, Xuerui; Santamarina, Carlos

    2016-01-01

    , hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical

  4. 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

  5. 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.

  6. Dissociation behavior of methane gas hydrate in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Qiang, C.; Yu-gang, Y.; Chang-ling, L. [Ministry of Land and Resources, Quindao (China). Qingdao Inst. of Marine Geology; Qing-guo, M. [Qingdao Univ. College of Chemical Engineering and Environment, Shandong, Qingdao (China)

    2008-07-01

    Gas hydrates are ice-like compounds that form by natural gas and water and are considered to be a new energy resource. In order to make good use of this resource, it is important to know the hydrate dissociation process. This paper discussed an investigation of methane hydrate dissociation through a simulation experiment. The paper discussed the gas hydrates dissociation experiment including the apparatus and experiment equipment, including methane gas supply; reaction cell; temperature controller; pressure maintainer; and gas flow meter. The paper also presented the method and material including iso-volumetric dissociation and normal pressure dissociation. Last, results and discussion of the results were presented. A comparison of five different particle sizes did not reveal any obvious effects that were related to the porous media, mostly likely because the particle size was too large. 15 refs., 2 tabs., 4 figs.

  7. 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.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  9. 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.

  10. Predictions of hydrate plug dissociation with electrical heating

    Energy Technology Data Exchange (ETDEWEB)

    Davies, S.R.; Ivanic, J.; Sloan, E.D.

    2005-07-01

    The rate of dissociation for cylindrical hydrate plugs by the application of radial electrical heating was investigated for structure I and structure II hydrates for pressures of 7 MPa (1000 psia) and 14 MPa (2000 psia). Heating rates of 2.3 kWm{sup -3}, 4.5 kWm-3 and 6.8 kWm{sup -3} were investigated for a plug 91.4 cm (36 inches) in length and 2.54 cm (1 inch) in diameter. A heat transfer model was developed in cylindrical coordinates based on Fourier's Law with a boundary condition of constant heat flux at the pipe wall. The equation set was solved numerically using a finite difference grid and the standard explicit scheme. The model was found to replicate well the experimental observations with no fitted parameters. A computer program was formulated to allow the practicing engineer to simulate the dissociation of industrial hydrates with minimal complexity. This program was incorporated into the latest version of our CSMPlug program which has been used by a number of energy companies to predict hydrate plug dissociation rates in the field. (Author)

  11. 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.

  12. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.

    1991-06-01

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

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

  13. 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

  14. A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

    KAUST Repository

    Sánchez, Marcelo

    2016-11-30

    Gas hydrate bearing sediments (HBS) are natural soils formed in permafrost and sub-marine settings where the temperature and pressure conditions are such that gas hydrates are stable. If these conditions shift from the hydrate stability zone, hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical behavior of HBS is very complex and its modeling poses great challenges. This paper presents a new geomechanical model for hydrate bearing sediments. The model incorporates the concept of partition stress, plus a number of inelastic mechanisms proposed to capture the complex behavior of this type of soil. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation. The model was applied and validated against experimental data from triaxial and oedometric tests conducted on manufactured and natural specimens involving different hydrate saturation, hydrate morphology, and confinement conditions. Particular attention was paid to model the HBS behavior during hydrate dissociation under loading. The model performance was highly satisfactory in all the cases studied. It managed to properly capture the main features of HBS mechanical behavior and it also assisted to interpret the behavior of this type of sediment under different loading and hydrate conditions.

  15. Gas hydrate dissociation off Svalbard induced by isostatic rebound rather than global warming.

    Science.gov (United States)

    Wallmann, Klaus; Riedel, M; Hong, W L; Patton, H; Hubbard, A; Pape, T; Hsu, C W; Schmidt, C; Johnson, J E; Torres, M E; Andreassen, K; Berndt, C; Bohrmann, G

    2018-01-08

    Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

  16. Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

    Full Text Available The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity. The phase equilibrium of methane hydrate under different experimental conditions was investigated. The effects of the particle size of silica sand as well as a mixture of bentonite clay and silica sand on methane hydrate formation and its dissociation were studied. The kinetics of hydrate formation was studied under different subcooling conditions to observe its effects on the induction time of hydrate formation. The amount of methane gas encapsulated in hydrate was computed using a real gas equation. The Clausius-Clapeyron equation is used to estimate the enthalpy of hydrate dissociation with measured phase equilibrium data.

  17. Dissociation heat of mixed-gas hydrate composed of methane and ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hachikubo, A.; Nakagawa, R.; Kubota, D.; Sakagami, H.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan)

    2008-07-01

    Formation and dissociation processes of natural gas hydrates in permafrost, marine and lake sediments are highly controlled by their thermal properties. Dissociation heat of gas hydrates can be estimated from phase equilibrium data using the Clausius-Clapeyron equation. However, this method is applicable for pure gas hydrate and at a temperature of 0 degrees Celsius. Direct calorimetric measurements on gas hydrates using a calorimeter have been developed to obtain thermal properties of gas hydrates, including dissociation heat and heat capacity. Studies have shown that a structure 2 gas hydrate appears in appropriate gas composition of methane and ethane. This paper investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. Raman spectroscopy was used to confirm the appearance of a structure 2 gas hydrate. The paper identified the experimental procedure and discussed sample preparation, Raman spectroscopy, and calorimetric measurements. A schematic diagram of the calorimeter was also presented. It was concluded that in most cases, two stages of dissociation were found at the dissociation process. 15 refs., 6 figs.

  18. 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

  19. Heat Transfer Analysis of Methane Hydrate Sediment Dissociation in a Closed Reactor by a Thermal Method

    Directory of Open Access Journals (Sweden)

    Mingjun Yang

    2012-05-01

    Full Text Available The heat transfer analysis of hydrate-bearing sediment involved phase changes is one of the key requirements of gas hydrate exploitation techniques. In this paper, experiments were conducted to examine the heat transfer performance during hydrate formation and dissociation by a thermal method using a 5L volume reactor. This study simulated porous media by using glass beads of uniform size. Sixteen platinum resistance thermometers were placed in different position in the reactor to monitor the temperature differences of the hydrate in porous media. The influence of production temperature on the production time was also investigated. Experimental results show that there is a delay when hydrate decomposed in the radial direction and there are three stages in the dissociation period which is influenced by the rate of hydrate dissociation and the heat flow of the reactor. A significant temperature difference along the radial direction of the reactor was obtained when the hydrate dissociates and this phenomenon could be enhanced by raising the production temperature. In addition, hydrate dissociates homogeneously and the temperature difference is much smaller than the other conditions when the production temperature is around the 10 °C. With the increase of the production temperature, the maximum of ΔToi grows until the temperature reaches 40 °C. The period of ΔToi have a close relation with the total time of hydrate dissociation. Especially, the period of ΔToi with production temperature of 10 °C is twice as much as that at other temperatures. Under these experimental conditions, the heat is mainly transferred by conduction from the dissociated zone to the dissociating zone and the production temperature has little effect on the convection of the water in the porous media.

  20. 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)

  1. Dissociation behavior of pellet shaped mixed gas hydrate samples that contain propane as a guest

    International Nuclear Information System (INIS)

    Kawamura, Taro; Sakamoto, Yasuhide; Ohtake, Michika; Yamamoto, Yoshitaka; Komai, Takeshi; Haneda, Hironori; Yoon, Ji-Ho; Ohga, Kotaro

    2006-01-01

    The dissociation kinetics of mixed gas hydrates that contain propane as a guest molecule have been investigated. The mixed gas hydrates used in this work were artificially prepared using the binary gas mixture of methane-propane and the ternary gas mixture of methane-ethane-propane. The crystal structures and the guest compositions of the mixed hydrates were clearly identified by using Raman spectroscopy and gas chromatography. The dissociation rates of the gas hydrates observed under several isothermal and isobaric conditions were discussed with an analytical model. The isobaric conditions were achieved by pressurizing with mixed gases using buffer cylinders, which had similar compositions to those of the initial gases used for synthesizing each hydrate sample. Interestingly, the calculated result agreed well with the experimentally observed results only when the composition of the vapor phase was assumed to be identical with that of the hydrate phase instead of the bulk (equilibrium) gas composition

  2. Hydrate dissociation conditions for gas mixtures containing carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons using SAFT

    International Nuclear Information System (INIS)

    Li Xiaosen; Wu Huijie; Li Yigui; Feng Ziping; Tang Liangguang; Fan Shuanshi

    2007-01-01

    A new method, a molecular thermodynamic model based on statistical mechanics, is employed to predict the hydrate dissociation conditions for binary gas mixtures with carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons in the presence of aqueous solutions. The statistical associating fluid theory (SAFT) equation of state is employed to characterize the vapor and liquid phases and the statistical model of van der Waals and Platteeuw for the hydrate phase. The predictions of the proposed model were found to be in satisfactory to excellent agreement with the experimental data

  3. Gas hydrate dissociation prolongs acidification of the Anthropocene oceans

    OpenAIRE

    Boudreau, B.P.; Luo, Y.; Meysman, F.J.R.; Middelburg, J

    2015-01-01

    Anthropogenic warming of the oceans can release methane (CH4) currently stored in sediments as gas hydrates. This CH4 will be oxidized to CO2, thus increasing the acidification of the oceans. We employ a biogeochemical model of the multimillennial carbon cycle to determine the evolution of the oceanic dissolved carbonate system over the next 13?kyr in response to CO2 from gas hydrates, combined with a reasonable scenario for long-term anthropogenic CO2 emissions. Hydrate-derived CO2 will appr...

  4. Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

    Science.gov (United States)

    Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

    2010-09-09

    Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

  5. Direct observation of characteristic dissociation behaviors of hydrate-bearing cores by rapid-scanning X-ray CT imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ebinuma, T.; Oyama, H.; Utiumi, T.; Nagao, J.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohiraku, Sapporo (Japan)

    2008-07-01

    Methane hydrate has significant potential as a new source of energy. Major considerations in developing production methods of methane from hydrates are the fundamental properties of hydrate-bearing sediments, and the dissociation behavior of methane hydrate and the gas and water flow generated by its dissociation in sediments. Marine methane hydrates occur several hundred meters below the sea floor, in a variety of forms. The pore-space filling-type is considered to be the most suited to exploitation, as it is contained within the pore spaces of sandy sediments, and has relatively larger gas permeability compared to other forms. However, shallow sandy sediments are not usually consolidated, and methane hydrate is unstable at normal pressure and temperature. Therefore, common methods are not suitable, and new experimental methods have been developed to study the properties of hydrate-bearing sediment and its dissociation process. This paper presented the results of an experimental study involving the dissociation of artificial methane-hydrate-bearing sediments. The experiment was performed using X-ray computed tomography in order to directly observe dissociation behavior in the sediments and the gas and water flows generated by dissociation. The paper described the depressurization process and presented a schematic diagram of rapid scanning X-ray computed tomography scanner and core holder with tri-axial structure. The experimental apparatus for dissociation of methane hydrate was also illustrated. The thermal stimulation process and hot water injection process were explained. It was concluded that dissociation by depressurization demonstrated that the temperature reduction induced by depressurization depended on the phase equilibrium state of methane hydrate, and that dissociation preferentially occurred at the periphery of the core. This behavior was due to the heat flux from the outside of the core, where the heat flux controlled the dissociation rate. 10 refs

  6. Gas hydrate dissociation prolongs acidification of the Anthropocene oceans

    NARCIS (Netherlands)

    Boudreau, B.P.; Luo, Yiming; Meysman, Filip J R; Middelburg, J.J.; Dickens, G.R.

    2015-01-01

    Anthropogenic warming of the oceans can release methane (CH4) currently stored in sediments as gas hydrates. This CH4 will be oxidized to CO2, thus increasing the acidification of the oceans. We employ a biogeochemical model of the multimillennial carbon cycle to determine the evolution of the

  7. Geochemical evidences of methane hydrate dissociation in Alaskan Beaufort Margin during Holocene

    Science.gov (United States)

    Uchida, M.; Rella, S.; Kubota, Y.; Kumata, H.; Mantoku, K.; Nishino, S.; Itoh, M.

    2017-12-01

    Alaskan Beaufort margin bear large abundances of sub-sea and permafrost methane hydrate[Ruppel, 2016]. During the Last Glacial, previous reported direct and indirect evidences accumulated from geochemical data from marginal sea sediment suggests that methane episodically released from hydrate trapped in the seafloor sediments[Kennett et al., 2000; Uchida et al., 2006, 2008; Cook et al, 2011]. Here we analyzed stable isotopes of foraminifera and molecular marker derived from the activity of methanotrophic bacteria from piston cores collected by the 2010 R/V Mirai cruise in Alaskan Beaufort Margin. Our data showed highly depleted 13C compositions of benthic foraminifera, suggesting indirect records of enhanced incorporation of 13C-depleted CO2 formed by methanotrophic process that use 12C-enriched methane as their main source of carbon. This is the first evidence of methane hydrate dissociation in Alaskan margin. Here we discussed timing of signals of methane dissociation with variability of sea ice and intermediate Atlantic water temperature. The dissociation of methane hydrate in the Alaskan Margin may be modulated by Atlantic warm intermediate water warming. Our results suggest that Arctic marginal regions bearing large amount methane hydrate may be a profound effect on future warming climate changes.

  8. Insights into the dynamics of in situ gas hydrate formation and dissociation at the Bush Hill gas hydrate field, Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Solomon, Evan A.; Kastner, Miriam; Robertson, Gretchen; Jannasch, Hans; Weinstein, Yishai

    2005-07-01

    Four newly designed flux meters called the MOSQUITO (Multiple Orifice Sampler and Quantitative Injection Tracer Observer), capable of measuring fluid flow rates and sampling pore fluid chemistry simultaneously, and two temperature loggers were deployed for 430 days adjacent to the Bush Hill hydrate mound in the northern Gulf of Mexico (GC 185). The main objective of the deployment was to understand how chemistry, temperature, and subsurface hydrology dynamically influence the growth and dissociation of the gas hydrate mound. The flux meters were deployed in a mussel field, in bacterial mats, in a tubeworm field, and at a background site approximately 100 m southwest of the hydrate mound. Results from the longterm chemical monitoring suggest that this system is not in dynamic equilibrium. Gas hydrate actively formed within the mussel field adjacent to the most active gas vent, in the tubeworm field, and at the background site. The hydrology is variable with upward flow rates ranging from 1-90 cm/yr and downward flow rates from 3-130 cm/yr. Two distinct hydrologic pulsing events were sampled across the three mound sites, which advect a fluid from depth that further stabilizes the gas hydrate deposit. The hydrogeochemistry at Bush Hill seems to be influenced by multiple mechanisms such as active formation of gas hydrate, fluid influx and outflux due to active venting of CH4 at transient methane seeps at and near the mound, local salt tectonics, and density driven convection. The fluxes of fluid, solutes, and methane may have a significant impact on the seafloor biochemical environment and the water column chemistry at Bush Hill. (Author)

  9. Hydrate thermal dissociation behavior and dissociation enthalpies in methane-carbon dioxide swapping process

    DEFF Research Database (Denmark)

    Mu, Liang; von Solms, Nicolas

    2018-01-01

    The swapping of methane with carbon dioxide in hydrate has been proposed as a potential strategy for geologic sequestration of carbon dioxide and production of methane from natural hydrate deposits. However, this strategy requires a better understanding of the thermodynamic characteristics of CH4...... and CO2 hydrate as well as (CH4 + CO2) or (CH4 + CO2 + N2) mixed hydrates (since (CO2 + N2) gas mixture is often used as the swapping gas), along with the thermal physics property changes during gas exchange. In this study, a high pressure micro-differential scanning calorimetry (HP μ-DSC) was performed...

  10. 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

  11. Molecular dynamics study of CO2 hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

    Science.gov (United States)

    English, Niall J; Clarke, Elaine T

    2013-09-07

    Equilibrium and non-equilibrium molecular dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar CO2 hydrate interfaces in liquid water at 300-320 K. Different guest compositions, at 85%, 95%, and 100% of maximum theoretical occupation, led to statistically-significant differences in the observed initial dissociation rates. The melting temperatures of each interface were estimated, and dissociation rates were observed to be strongly dependent on temperature, with higher dissociation rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model developed previously was applied to fit the observed dissociation profiles, and this helps to identify clearly two distinct régimes of break-up; a second well-defined region is essentially independent of composition and temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. From equilibrium MD of the two-phase systems at their melting point, the relaxation times of the auto-correlation functions of fluctuations in number of enclathrated guest molecules were used as a basis for comparison of the variation in the underlying, non-equilibrium, thermal-driven dissociation rates via Onsager's hypothesis, and statistically significant differences were found, confirming the value of a fluctuation-dissipation approach in this case.

  12. Use of Computed X-ray Tomographic Data for Analyzing the Thermodynamics of a Dissociating Porous Sand/Hydrate Mixture

    Science.gov (United States)

    Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

    2002-02-28

    X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation.

  13. Use of computed X-ray tomographic data for analyzing the thermodynamics of a dissociating porous sand/hydrate mixture

    International Nuclear Information System (INIS)

    Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

    2002-01-01

    X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation

  14. Ab Initio Study of Hydration and Proton Dissociation in Ionomer Membranes

    International Nuclear Information System (INIS)

    Idupulapati, Nagesh B.; Devanathan, Ramaswami; Dupuis, Michel

    2010-01-01

    We present a comparative study of proton dissociation in various functional acidic units that are promising candidates as building blocks for polymeric electrolyte membranes. Minimum energy structures for four acidic moieties with clusters of 1-6 water molecules were determined using density functional theory at the B3LYP/6-311G** level starting from chemically rational initial configurations. The perfluoro sulfonyl imide acid group (CF3CF2SO2NHSO2CF3) was observed to be the strongest acid, due to the substantial electron withdrawing effect of both fluorocarbon groups. The hydrophilic functional group (CH3OC6H3OCH3C6H4SO3H) of sulfonated polyetherether ketone (SPEEK) membrane was found to be the strongest base with the acidic proton dissociation requiring the addition of six water molecules and the hydrated proton being more tightly bound to the conjugate base. Even though both perfluoro sulfonyl imides and sulfonic acids (hydrophilic functional groups for sulfonyl imide and Nafion ionomers respectively) required only three water molecules to exhibit spontaneous proton dissociation, the largest possible solvent-separated hydronium ion was attained only for the sulfonyl imide moiety. These results provide a scientific basis for understanding the improved conductivity of perfluorinated sulfonyl imide-based membranes relative to that of the widely-used Nafion membrane.

  15. DNA under Force: Mechanics, Electrostatics, and Hydration

    Directory of Open Access Journals (Sweden)

    Jingqiang Li

    2015-02-01

    Full Text Available Quantifying the basic intra- and inter-molecular forces of DNA has helped us to better understand and further predict the behavior of DNA. Single molecule technique elucidates the mechanics of DNA under applied external forces, sometimes under extreme forces. On the other hand, ensemble studies of DNA molecular force allow us to extend our understanding of DNA molecules under other forces such as electrostatic and hydration forces. Using a variety of techniques, we can have a comprehensive understanding of DNA molecular forces, which is crucial in unraveling the complex DNA functions in living cells as well as in designing a system that utilizes the unique properties of DNA in nanotechnology.

  16. Mechanism and kinetics of hydrated electron diffusion

    International Nuclear Information System (INIS)

    Tay, Kafui A.; Coudert, Francois-Xavier; Boutin, Anne

    2008-01-01

    Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps -1 at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ mol -1 . Through analysis of Arrhenius plots and the application of a simple random walk model it is demonstrated that the computed rate constant for exchange of an excess electron is indeed the phenomenological rate constant associated with the diffusive process

  17. 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.

  18. Experimental setting for assessing mechanical strength of gas hydrate pellet

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, S.J.; Choi, J.H.; Koh, B.H. [Dongguk Univ., Phil-dong, Chung-gu, Seoul (Korea, Republic of). Dept. of Mechanical Engineering

    2008-07-01

    Due to the constant increase in global demand for clean energy, natural gas production from stranded medium and small size gas wells has drawn significant interest. Because the ocean transport of natural gas in the form of solid hydrate pellets (NGHP) has been estimated to be economically feasible, several efforts have been made to develop a total NGHP ocean transport chain. The investigation of mechanical strength of solid-form hydrate pellet has been an important task in fully exploiting the benefit of gas hydrate in the perspective of mass transportation and storage. This paper provided the results of a preliminary study regarding the assessment of mechanical properties of the gas hydrate pellet. The preliminary study suggested some of the key issues regarding formation and strength of gas hydrate pellets. Instead of utilizing the gas hydrate pellet, the study focused on a preliminary test setup for developing the ice pellet which was readily applied to the gas hydrate pellet in the future. The paper described the pelletization of ice powder as well as the experimental setup. Several photographs were illustrated, including samples of ice pellets; compression test for ice pellet using air press and load cell; and the initiation of crack in the cross section of an ice pellet. It was found that mechanical strength, especially, compression strength was not significantly affected by different level of press-forming force up to a certain level. 4 refs., 1 tab., 4 figs.

  19. Molecular-dynamics study of propane-hydrate dissociation: Fluctuation-dissipation and non-equilibrium analysis.

    Science.gov (United States)

    Ghaani, Mohammad Reza; English, Niall J

    2018-03-21

    Equilibrium and non-equilibrium molecular-dynamics (MD) simulations have been performed to investigate thermal-driven break-up of planar propane-hydrate interfaces in contact with liquid water over the 260-320 K range. Two types of hydrate-surface water-lattice molecular termination were adopted, at the hydrate edge with water, for comparison: a 001-direct surface cleavage and one with completed cages. Statistically significant differences in melting temperatures and initial break-up rates were observed between both interface types. Dissociation rates were observed to be strongly dependent on temperature, with higher rates at larger over-temperatures vis-à-vis melting. A simple coupled mass and heat transfer model, developed previously, was applied to fit the observed dissociation profiles, and this helps us to identify clearly two distinct hydrate-decomposition régimes; following a highly temperature-dependent break-up phase, a second well-defined stage is essentially independent of temperature, in which the remaining nanoscale, de facto two-dimensional system's lattice framework is intrinsically unstable. Further equilibrium MD-analysis of the two-phase systems at their melting point, with consideration of the relaxation times gleaned from the auto-correlation functions of fluctuations in a number of enclathrated guest molecules, led to statistically significant differences between the two surface-termination cases; a consistent correlation emerged in both cases between the underlying, non-equilibrium, thermal-driven dissociation rates sampled directly from melting with that from an equilibrium-MD fluctuation-dissipation approach.

  20. Hydration Control of the Mechanical and Dynamical Properties of Cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Petridis, Loukas; O’Neill, Hugh M.; Johnsen, Mariah [Ripon College, Ripon, Wisconsin 54971, United States; Fan, Bingxin [Department; Schulz, Roland [Department; Mamontov, Eugene; Maranas, Janna [Department; Langan, Paul [Department; Smith, Jeremy C. [Department

    2014-10-13

    The mechanical and dynamical properties of cellulose, the most abundant biomolecule on earth, are essential for its function in plant cell walls and advanced biomaterials. Cellulose is almost always found in a hydrated state, and it is therefore important to understand how hydration influences its dynamics and mechanics. Here, the nanosecond-time scale dynamics of cellulose is characterized using dynamic neutron scattering experiments and molecular dynamics (MD) simulation. The experiments reveal that hydrated samples exhibit a higher average mean-square displacement above ~240 K. The MD simulation reveals that the fluctuations of the surface hydroxymethyl atoms determine the experimental temperature and hydration dependence. The increase in the conformational disorder of the surface hydroxymethyl groups with temperature follows the cellulose persistence length, suggesting a coupling between structural and mechanical properties of the biopolymer. In the MD simulation, 20% hydrated cellulose is more rigid than the dry form, due to more closely packed cellulose chains and water molecules bridging cellulose monomers with hydrogen bonds. This finding may have implications for understanding the origin of strength and rigidity of secondary plant cell walls. The detailed characterization obtained here describes how hydration-dependent increased fluctuations and hydroxymethyl disorder at the cellulose surface lead to enhancement of the rigidity of this important biomolecule.

  1. Mechanical Dissociation of Retinal Neurons with Vibration

    Science.gov (United States)

    Motomura, Tamami; Hayashida, Yuki; Murayama, Nobuki

    The neuromorphic device, which implements the functions of biological neural circuits by means of VLSI technology, has been collecting much attention in the engineering fields in the last decade. Concurrently, progress in neuroscience research has revealed the nonlinear computation in single neuron levels, suggesting that individual neurons are not merely the circuit elements but computational units. Thus, elucidating the properties of neuronal signal processing is thought to be an essential step for developing the next generation of neuromorphic devices. In the present study, we developed a method for dissociating single neurons from specific sublayers of mammalian retinas with using no proteolytic enzymes but rather combining tissue incubation in a low-Ca2+ medium and the vibro-dissociation technique developed for the slices of brains and spinal cords previously. Our method took shorter time of the procedure, and required less elaborated skill, than the conventional enzymatic method did; nevertheless it yielded enough number of the cells available for acute electrophysiological experiments. The isolated retinal neurons were useful for measuring the nonlinear membrane conductances as well as the spike firing properties under the perforated-patch whole-cell configuration. These neurons also enabled us to examine the effects of proteolytic enzymes on the membrane excitability in those cells.

  2. Comparing the symptoms and mechanisms of "dissociation" in dissociative identity disorder and borderline personality disorder.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F; Korzekwa, Marilyn

    2017-01-01

    A total of 75 patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised as having dissociative identity disorder (DID), and 100 patients were diagnosed with the Structured Interview for DSM-IV Personality as having borderline personality disorder (BPD). Both groups were administered the Multidimensional Inventory of Dissociation (MID). DID patients had significantly higher MID scores than BPD patients, different distributions of MID scores, and different MID subscale profiles in 3 ranges of MID scores (0-15, 15-30, 30-45). The core MID symptoms-exhibited at all ranges of MID scores-for DID patients (the presence of alters, identity confusion, and memory problems) and BPD patients (flashbacks, identity confusion, and memory problems) were ostensibly similar but were considered to be mostly produced by different underlying processes. Multiple regression analyses showed that the core MID symptoms of DID patients had different predictors than did the core MID symptoms of BPD patients. Alter identities seemed to generate most-but not all-dissociative phenomena in DID patients, whereas only the 24% highest scoring BPD patients (MID ≥45) seemed to manifest alter-driven dissociative experiences. Most BPD dissociative experiences appeared to be due to 5 other mechanisms: (a) BPD-specific, stress-driven, rapid shifts of self-state; (b and c) nondefensive disruptions of the framework of perceptual organization with or without an accompanying BPD-specific, dissociation-like disintegration of affective/neurocognitive functioning; (d) a defensive distancing or detachment from distress (i.e., simple depersonalization); and (e) Allen, Console, and Lewis's (1999) severe absorptive detachment.

  3. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 1 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first single-phase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled

  4. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first singlephase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled

  5. Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

    OpenAIRE

    Jin-Rong Zhong; Xin-Yang Zeng; Feng-He Zhou; Qi-Dong Ran; Chang-Yu Sun; Rui-Qin Zhong; Lan-Ying Yang; Guang-Jin Chen; Carolyn A. Koh

    2016-01-01

    The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15?K), as determined by the stable C-H region Raman peaks and A L/A S value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to sm...

  6. Calibration and validation of a numerical model against experimental data of methane hydrate formation and dissociation in a sandy porous medium

    Science.gov (United States)

    Yin, Z.; Moridis, G. J.; Chong, Z. R.; Linga, P.

    2017-12-01

    Methane hydrates (MH) are known to trap enormous amounts of CH4 in oceanic and permafrost-associated deposits, and are being considered as a potential future energy source. Several powerful numerical simulators were developed to describe the behavior of natural hydrate-bearing sediments (HBS). The complexity and strong nonlinearities in HBS do not allow analytical solutions for code validation. The only reliable method to develop confidence in these models is through comparisons to laboratory and/or field experiments. The objective of this study is to reproduce numerically the results from earlier experiments of MH formation and depressurization (and the corresponding fluid production) in 1.0L reactor involving unconsolidated sand, thus validating and calibrating the TOUGH+Hydrate v1.5 simulator. We faithfully describe the reactor geometry and the experimental process that involves both hydrate formation and dissociation. We demonstrate that the laboratory experiments can only be captured by a kinetic hydration model. There is an excellent agreement between observations and predictions (a) of the cumulative gas depletion (during formation) and production (during dissociation) and (b) of pressure over time. The temperature agreement is less satisfactory, and the deviations are attributed to the fixed locations of the limited number of sensors that cannot fully capture the hydrate heterogeneity. We also predict the spatial distributions over time of the various phase (gas, aqueous and hydrate) saturations. Thus, hydrates form preferentially along the outer boundary of the sand core, and the hydrate front moves inward leaving a significant portion of the sand at the center hydrate-free. During depressurization, dissociation advances again inward from the reactor boundary to the center of the reactor. As expected, methane gas accumulates initially at the locations of most intense dissociation, and then gradually migrates to the upper section of the reactor because of

  7. Clathrate hydrate dissociation conditions of refrigerants R404A, R406A, R408A and R427A: Experimental measurements and thermodynamic modeling

    International Nuclear Information System (INIS)

    Hashemi, Hamed; Babaee, Saeedeh; Mohammadi, Amir H.; Naidoo, Paramespri; Ramjugernath, Deresh

    2015-01-01

    Highlights: • The application of refrigerant hydrates in cold storage systems is investigated. • Hydrate dissociation conditions of various refrigerants have been measured. • A correlative thermodynamic model was applied to the data. • Enthalpy of dissociation for the refrigerants studied calculated. • Experimental measurements performed over a wide range of pressures. - Abstract: Clathrate hydrate dissociation conditions were measured for four “alternative” refrigerants, viz. R404A, R406A, R408A and R427A. The experimental measurements were performed within the pressure range of (0.079 to 9.995) MPa and temperatures ranging from (272.7 to 288.7) K. An isochoric pressure-search method was used to perform the measurements. A thermodynamic model based on the van der Waals–Platteeuw (vdW–P) model was applied for the prediction of the dissociation conditions which were compared to the experimental measurements. The fluid phase was modeled using the MHV2 G E -EoS mixing rule along with the UNIFAC (original) activity model. The van der Waals–Platteeuw (vdW–P) model was used for the modeling of the hydrate phase. There was reasonable agreement between the experimental and predicted values

  8. Effects of Geomechanical Mechanism on the Gas Production Behavior: A Simulation Study of Class-3 Type Four-Way-Closure Ridge Hydrate Deposit Offshore Southwestern Taiwan

    Science.gov (United States)

    Wu, Cheng-Yueh; Chiu, Yung-Cheng; Huang, Yi-Jyun; Hsieh, Bieng-Zih

    2017-04-01

    The future energy police of Taiwan will heavily rely on the clean energy, including renewable energy and low-carbon energy, to meet the target of mitigating CO2 emission. In addition to developing the renewable energies like solar and wind resources, Taiwan will increase the natural gas consumption to obtain enough electrical power with low-carbon emission. The vast resources of gas hydrates recognized in southwestern offshore Taiwan makes a great opportunity for Taiwan to have own energy resources in the future. Therefore, Taiwan put significant efforts on the evaluation of gas hydrate reserves recently. Production behavior of natural gas dissociated from gas hydrate deposits is an important issue to the hydrate reserves evaluation. The depressurization method is a useful engineering recovery method for gas production from a class-3 type hydrate deposit. The dissociation efficiency will be affected by the pressure drawdown disturbance. However, when the pore pressure of hydrate deposits is depressurized for gas production, the rock matrix will surfer more stresses and the formation deformation might be occurred. The purpose of this study was to investigate the effects of geomechanical mechanism on the gas production from a class-3 hydrate deposit using depressurization method. The case of a class-3 type hydrate deposit of Four-Way-Closure Ridge was studied. In this study a reservoir simulator, STARS, was used. STARS is a multiphase flow, heat transfer, geo-chemical and geo-mechanical mechanisms coupling simulator which is capable to simulate the dissociation/reformation of gas hydrate and the deformation of hydrate reservoirs and overburdens. The simulating ability of STARTS simulator was validated by duplicating the hydrate comparison projects of National Energy Technology Lab. The study target, Four-Way-Closure (FWC) Ridge hydrate deposit, was discovered by the bottom simulating reflectors (BSRs). The geological parameters were collected from the geological and

  9. Kinetics of the Formation and Dissociation of Gas Hydrates from CO2-CH4 Mixtures

    Directory of Open Access Journals (Sweden)

    Devinder Mahajan

    2012-07-01

    Full Text Available Sequestration of carbon dioxide (CO2 in the form of its hydrates in natural methane (CH4 hydrate reservoirs, via CO2/CH4 exchange, is an attractive pathway that also yields valuable CH4 gas as product. In this paper, we describe a macroscale experiment to form CO2 and CH4-CO2 hydrates, under seafloor-mimic conditions, in a vessel fitted with glass windows that provides visualization of hydrates throughout formation and dissociation processes. Time resolved pressure and temperature data as well as images of hydrates are presented. Quantitative gas conversions with pure CO2, calculated from gas chromatographic measurements yielded values that range from 23 – 59% that correspond to the extent of formed hydrates. In CH4-rich CH4-CO2 mixed gas systems, CH4 hydrates were found to form preferentially.

  10. Exposure to buffer solution alters tendon hydration and mechanics.

    Science.gov (United States)

    Safa, Babak N; Meadows, Kyle D; Szczesny, Spencer E; Elliott, Dawn M

    2017-08-16

    A buffer solution is often used to maintain tissue hydration during mechanical testing. The most commonly used buffer solution is a physiological concentration of phosphate buffered saline (PBS); however, PBS increases the tissue's water content and decreases its tensile stiffness. In addition, solutes from the buffer can diffuse into the tissue and interact with its structure and mechanics. These bathing solution effects can confound the outcome and interpretation of mechanical tests. Potential bathing solution artifacts, including solute diffusion, and their effect on mechanical properties, are not well understood. The objective of this study was to measure the effects of long-term exposure of rat tail tendon fascicles to several concentrations (0.9-25%) of NaCl, sucrose, polyethylene glycol (PEG), and SPEG (NaCl+PEG) solutions on water content, solute diffusion, and mechanical properties. We found that with an increase in solute concentration the apparent water content decreased for all solution types. Solutes diffused into the tissue for NaCl and sucrose, however, no solute diffusion was observed for PEG or SPEG. The mechanical properties changed for both NaCl solutions, in particular after long-term (8h) incubation the modulus and equilibrium stress decreased compared to short-term (15min) for 25% NaCl, and the cross sectional area increased for 0.9% NaCl. However, the mechanical properties were unchanged for both PEG and SPEG except for minor alterations in stress relaxation parameters. This study shows that NaCl and sucrose buffer solutions are not suitable for long-term mechanical tests. We therefore propose using PEG or SPEG as alternative buffer solutions that after long-term incubation can maintain tissue hydration without solute diffusion and produce a consistent mechanical response. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Effects of cyclopentane on CO2 hydrate formation and dissociation as a co-guest molecule for desalination

    International Nuclear Information System (INIS)

    Zheng, Jia-nan; Yang, Ming-jun; Liu, Yu; Wang, Da-yong; Song, Yong-chen

    2017-01-01

    Highlights: • CP decreases CO 2 hydrate phase equilibrium pressure by forming CO 2 -CP hydrates. • The increase of CP can’t decrease hydrates phase equilibrium pressure unlimitedly. • Higher CP concentration lowers CO 2 hydrate gas uptake. • The optimal CP molar ratio is 0.01 based on hydrate phase equilibrium and gas uptake. - Abstract: Cyclopentane (CP) is considered to be a potential co-guest molecule in carbon dioxide (CO 2 ) hydrate-based desalination. The experimental thermodynamic data of CO 2 -CP hydrates were measured for a salt solution, where CP was chosen as a hydrate promoter. Seven experimental cases (62 cycles) were studied with different molar ratios of CP/water (0, 0.0025, 0.005, 0.0075, 0.01, 0.02, and 0.03). Hydrate phase equilibrium data were generated using an isochoric method, and the hydrate saturations were calculated based on gas uptake. The results indicated that the increase in CP concentration significantly decreased the CO 2 hydrate equilibrium pressure to a certain limit; the hydrate saturation also decreased during this process. Also, it was determined that CP encouraged the formation of s-II double CO 2 -CP hydrates, which are different from s-I simple CO 2 hydrate. The CO 2 -CP guest provides a strengthened stability and moderate hydrate phase equilibrium conditions for hydrate-based desalination. The recommended optimal molar ratio of CP is 0.01 when the increase in equilibrium was more than 10 K, and the decrease in hydrate saturation was less than 2%.

  12. 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

  13. Experimental study and thermodynamic modelling of methane clathrate hydrate dissociation conditions in silica gel porous media in the presence of methanol aqueous solution

    International Nuclear Information System (INIS)

    Hashemi, Hamed; Javanmardi, Jafar; Zarifi, Mojdeh; Eslamimanesh, Ali; Mohammadi, Amir H.

    2012-01-01

    Highlights: ► Phase equilibria of hydrates of methane in confined silica gel pores are reported. ► Dissociation data in the presences of methanol aqueous solution are also measured. ► A thermodynamic model is developed for prediction of the obtained data. ► Acceptable agreement is found between the obtained data and the predicted results. - Abstract: In this work, the phase equilibria of clathrate hydrates of methane in the presence of pure water and 0.035 mass fraction of methanol aqueous solution in confined silica gel pores with (10 and 15) nm mean diameters are measured and reported. A thermodynamic model is also developed for prediction of the obtained experimental hydrate dissociation data. The Valderrama–Patel–Teja (VPT-EoS) equation of state (EoS) accompanied with the non-density dependent (NDD) mixing rules coupled with a previously developed activity model are applied to evaluate the fugacity of the species present and the activity coefficient of water in methanol aqueous solution. Acceptable agreement between the reported data and the predicted results using the proposed model and an existing method reported in the literature demonstrates the reliability of the presented model.

  14. 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.

  15. 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.

  16. Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

    Science.gov (United States)

    Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

    2015-09-23

    The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

  17. Investigation of the mechanical behaviour of gas-hydrate bearing clayey sediments from the Gulf of Guinea using in-situ geotechnical measurements

    Science.gov (United States)

    Taleb, F.; Garziglia, S.; Sultan, N.

    2017-12-01

    Expanding needs for energy resources and concerns about climate change have moved industrial and academic interests towards regions where specific thermobaric conditions allow the formation of gas hydrates (GH). While significant advances have been made to characterize the fabric and structure of these metastable geo-compounds, considerable uncertainty remains regarding the impact of their mechanical properties on the seafloor morphology and stability. This is particularly true for gas hydrates-bearing fine-grained sediments, which remain challenging to preserve or synthesise prior to laboratory testing. As a step towards understanding the mechanical consequences of the concentration and distribution of GH in this type of sediments, this work uses acoustic and geotechnical in situ measurements collected in a high gas flux system offshore Nigeria. Acoustic measurements of compressional wave velocity were shown to be convenient means of both detecting and quantifying gas hydrates in marine sediments. Geotechnical data derived from piezocone readings and their distribution in normalised soil classification charts allowed identifying distinct features of gas hydrates-bearing clayey sediments; such as a mechanical behaviour sharing similarities with that of cemented clays. Correlations between acoustic and piezocone data showed that the stiffness and strength tend to generally increase with increasing GH concentrations. However, several sediment intervals sharing the same hydrates concentration have revealed different features of mechanical behaviour. This was linked to the presence of various GH morphologies within the marine sediments such as groups of hydrate veins or massive hydrate nodules. This in-situ approach allowing both understanding the heterogeneous distribution of GH and characterising their host sediment seems key to assess the potential link between seafloor stability and GH dissociation/dissolution caused by human activities or by natural environmental

  18. Determining the mechanism and parameters of hydrate formation and loss in glucose.

    Science.gov (United States)

    Scholl, Sarah K; Schmidt, Shelly J

    2014-11-01

    Water-solid interactions are known to play a major role in the chemical and physical stability of food materials. Despite its extensive use throughout the food industry, the mechanism and parameters of hydrate formation and loss in glucose are not well characterized. Hydrate formation in alpha-anhydrous glucose (α-AG) and hydrate loss in glucose monohydrate (GM) were studied under equilibrium conditions at various relative humidity (RH) values using saturated salt slurries for 1 y. The mechanism of hydrate formation and hydrate loss were determined through mathematical modeling of Dynamic Vapor Sorption data and Raman spectroscopy was used to confirm the mechanisms. The critical temperature for hydrate loss in GM was determined using thermogravimetric analysis (TGA). The moisture sorption profiles of α-AG and GM were also studied under dynamic conditions using an AquaSorp Isotherm Generator. Hydrate formation was observed at and above 68% RH at 25 °C and the conversion of α-AG to GM can best be described as following a nucleation mechanism, however, diffusion and/or geometric contraction mechanisms were also observed by Raman spectroscopy subsequent to the coalescence of initial nucleation sites. Hydrate loss was observed to occur at and below 11% RH at 25 °C during RH storage and at 70 °C during TGA. The conversion of GM to α-AG follows nucleation and diffusion mechanisms. Hydrate formation was evident under dynamic conditions in α-AG and GM prior to deliquescence. This research is the first to report hydrate formation and loss parameters for crystalline α-AG and GM during extended storage at 25 ˚C. © 2014 Institute of Food Technologists®

  19. Using open hole and cased-hole resistivity logs to monitor gas hydrate dissociation during a thermal test in the mallik 5L-38 research well, Mackenzie Delta, Canada

    Science.gov (United States)

    Anderson, B.I.; Collett, T.S.; Lewis, R.E.; Dubourg, I.

    2008-01-01

    Gas hydrates, which are naturally occurring ice-like combinations of gas and water, have the potential to provide vast amounts of natural gas from the world's oceans and polar regions. However, producing gas economically from hydrates entails major technical challenges. Proposed recovery methods such as dissociating or melting gas hydrates by heating or depressurization are currently being tested. One such test was conducted in northern Canada by the partners in the Mallik 2002 Gas Hydrate Production Research Well Program. This paper describes how resistivity logs were used to determine the size of the annular region of gas hydrate dissociation that occurred around the wellbore during the thermal test in the Mallik 5L-38 well. An open-hole logging suite, run prior to the thermal test, included array induction, array laterolog, nuclear magnetic resonance and 1.1-GHz electromagnetic propagation logs. The reservoir saturation tool was run both before and after the thermal test to monitor formation changes. A cased-hole formation resistivity log was run after the test.Baseline resistivity values in each formation layer (Rt) were established from the deep laterolog data. The resistivity in the region of gas hydrate dissociation near the wellbore (Rxo) was determined from electromagnetic propagation and reservoir saturation tool measurements. The radius of hydrate dissociation as a function of depth was then determined by means of iterative forward modeling of cased-hole formation resistivity tool response. The solution was obtained by varying the modeled dissociation radius until the modeled log overlaid the field log. Pretest gas hydrate production computer simulations had predicted that dissociation would take place at a uniform radius over the 13-ft test interval. However, the post-test resistivity modeling showed that this was not the case. The resistivity-derived dissociation radius was greatest near the outlet of the pipe that circulated hot water in the wellbore

  20. Effects of C3H8 on hydrate formation and dissociation for integrated CO2 capture and desalination technology

    International Nuclear Information System (INIS)

    Yang, Mingjun; Zheng, Jianan; Liu, Weiguo; Liu, Yu; Song, Yongchen

    2015-01-01

    Hydrate-based technology has been developing for decades to meet the demands in industrial applications. With the global demands for reduced carbon dioxide (CO 2 ) emissions and more fresh water, CHBD (CO 2 hydrate-based desalination) was proposed and has developed rapidly. In this study, to provide basic data for the improvement of CHBD, the thermodynamic and kinetic characteristics of CO 2 and propane (C 3 H 8 ) mixed-gas hydrates in salt solution were experimentally investigated in which C 3 H 8 was chosen as the hydrate formation promoter. We studied nine experimental cases (54 cycles) with different C 3 H 8 proportions (ranging from 0 to 13%) and different initial solution saturations (30%, 40% and 50%). The hydrate phase equilibrium data were generated using the isochoric method, and the hydrate formation saturations were calculated using the relative gas uptake equation. The results indicated that the increase in the C 3 H 8 proportion significantly decreases the gas mixture hydrate equilibrium pressure. Additionally, the relative gas uptake was reduced as the C 3 H 8 proportion increased. A lower relative gas uptake was obtained at a lower gas pressure for the same gas mixture. The initial solution saturation exhibited an insignificant effect on the hydrate phase equilibrium conditions. When the initial solution saturations increased from 30% to 50%, the relative gas uptake decreased. - Highlights: • C 3 H 8 improves the thermodynamics and kinetics of CO 2 hydrates formation. • Hydrates equilibrium pressure decreases with the increase of C 3 H 8 proportion. • Higher C 3 H 8 proportion and/or solution saturation decrease relative gas uptake. • Initial pressure and solution saturation has interactive effect on gas uptake.

  1. QUANTUM MECHANICAL STUDY OF THE COMPETITIVE HYDRATION BETWEEN PROTONATED QUINAZOLINE AND LI+, NA+, AND CA2+ IONS

    Science.gov (United States)

    Hydration reactions are fundamental to many biological functions and environmental processes. The energetics of hydration of inorganic and organic chemical species influences their fate and transport behavior in the environment. In this study, gas-phase quantum mechanical calcula...

  2. Mechanisms for adsorption of organic bases on hydrated smectite surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laird, D.A.; Fleming, P.D.

    1999-08-01

    The environmental fate of anthropogenic organic bases introduced to soils and sediments, either deliberately as pesticides or inadvertently as contaminants, depends, to a large extent, on reactions between those compounds and the surfaces of soil mineral and organic constituents. Mechanisms by which organic bases are adsorbed on hydrated smectite surfaces were investigated. Three Ca-saturated reference smectites (Otay, SPV, and Panther Creek) were dispersed in distilled water containing 5 {micro}mol of pyridine or 3-butylpyridine. The pH was adjusted to between 7.5 and 3 using 0.01 M HCl. After a 2-h equilibration, the amounts of pyridine or 3-butylpyridine adsorbed on the clay and the amount of Ca desorbed from the clay were determined. Negligible amounts of pyridine were adsorbed by the Ca-smectites in the neutral systems (pH > 7); however, most of the added pyridine was adsorbed on the smectites in the acidified systems (pH < 5). Equivalent amounts of Ca{sup 2+} were desorbed from the clays, indicating that pyridine was adsorbed as a protonated species by cation exchange. By contrast, 40 to 90% of added 3-butylpyridine was adsorbed on the smectites at neutral pHs, whereas only small amounts of Ca{sup 2+} were desorbed. The results suggest that 3-butylpyridine is initially retained by hydrophobic bonding between the alkyl side chain of the molecule and hydrophobic nanosites located between the charge sites on smectite surfaces. Surface acidity catalyzed protonation 1 to 1.5 pH units above the pK{sub a} of the bases.

  3. Electrical Conductive Mechanism of Gas Hydrate-Bearing Reservoirs in the Permafrost Region of Qilian Mountain

    Science.gov (United States)

    Peng, C.; Zou, C.; Tang, Y.; Liu, A.; Hu, X.

    2017-12-01

    In the Qilian Mountain, gas hydrates not only occur in pore spaces of sandstones, but also fill in fractures of mudstones. This leads to the difficulty in identification and evaluation of gas hydrate reservoir from resistivity and velocity logs. Understanding electrical conductive mechanism is the basis for log interpretation. However, the research is insufficient in this area. We have collected well logs from 30 wells in this area. Well logs and rock samples from DK-9, DK-11 and DK-12 wells were used in this study. The experiments including SEM, thin section, NMR, XRD, synthesis of gas hydrate in consolidated rock cores under low temperature and measurement of their resistivity and others were performed for understanding the effects of pore structure, rock composition, temperature and gas hydrate on conductivity. The results show that the porosity of reservoir of pore filling type is less than 10% and its clay mineral content is high. As good conductive passages, fractures can reduce resistivity of water-saturated rock. If fractures in the mudstone are filled by calcite, resistivity increases significantly. The resistivity of water-saturated rock at 2°C is twice of that at 18°C. The gas hydrate formation process in the sandstone was studied by resistivity recorded in real time. In the early stage of gas hydrate formation, the increase of residual water salinity may lead to the decrease of resistivity. In the late stage of gas hydrate formation, the continuity decrease of water leads to continuity increase of resistivity. In summary, fractures, rock composition, temperature and gas hydrate are important factors influencing resistivity of formation. This study is helpful for more accurate evaluation of gas hydrate from resistivity log. Acknowledgment: We acknowledge the financial support of the National Special Program for Gas Hydrate Exploration and Test-production (GZH201400302).

  4. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Directory of Open Access Journals (Sweden)

    Thomas M. Vlasic

    2016-08-01

    Full Text Available This work uses density functional theory (DFT to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane, at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  5. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Energy Technology Data Exchange (ETDEWEB)

    Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D., E-mail: alejandro.rey@mcgill.ca [Department of Chemical Engineering, McGill University, Montreal H3A 0C5 (Canada)

    2016-08-15

    This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  6. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Science.gov (United States)

    Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D.

    2016-08-01

    This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  7. Clathrate hydrates - the energy of the future an overview and a postulated formation mechanism

    International Nuclear Information System (INIS)

    Pratt, R.M.

    2000-01-01

    Clathrate hydrates are non-stoichiometric compounds that form when water and certain low molecular weight hydrocarbons coexist at high pressures and low temperatures. The majority of the earth hydrocarbons are in the hydrate phase and are primarily located along the ocean bottoms and to a lesser degree in the permafrost regions. In addition, hydrate formation is induced in undersea gas transmission lines and causes costly pipeline plugs and requires expensive inhibition measures to be taken. Therefore, both a stick and a carrot motivate hydrate research. They are a costly and dangerous nuisance to the oil and gas industry and represent a tremendous, untapped energy resource of the future. The formation mechanism of clathrate hydrate formation has always been shrouded in mystery, and an ongoing debate has ensued as to whether their formation is a bulk or surface phenomenon. Molecular dynamics simulation and fractal modeling suggest that this may be an irrelevant issue and that two independent factors contribute to the symmetrical ordered structure of clathrate hydrates: hydrophobic hydration of hydrocarbon molecules in water and formation of linked cavities as these small clusters aggregate. (Author)

  8. Effect of temperature dependence of the Langmuir constant molecular pair potentials on gas hydrates formation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari, B.; Enayati, M. [Iranian Offshore Oil Co., Tehran (Iran, Islamic Republic of); Heidaryan, E. [Islamic Azad Univ., Tehran (Iran, Islamic Republic of). Masjidosolayman Branch

    2008-07-01

    Theoretical methods show that crystalline hydrates can form from single-phase systems consisting of both vapor water with gaseous hydrate former and liquid water with dissolved hydrate former. Two phase systems consist of both liquid water with gaseous hydrate former and with liquid hydrate former on the surface. This paper presented a Langmuir constant related model for the prediction of equilibrium pressures and cage occupancies of pure component hydrates. Intermolecular potentials were fit to quantum mechanical energies to obtain the Langmuir constants, which differed from the procedure utilized with the vdWP model. The paper described the experimental method and model calculations. This included the Fugacity model and Van der Waals and Platteeuw model. The paper also discussed pair potential of non-spherical molecules, including the multicentre (site-site) potential; Gaussian overlap potential; Lennard-Jones potential; and Kihara generalized pair potential. It was concluded that fraction of occupied cavities is a function of pair potentials between hard core and empty hydrate lattice. These pair potentials could be calculated from some model as Kihara cell potential, Gaussian potential, Lennard-Jones potential and multicentre pair potential. 49 refs., 3 figs.

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

    Directory of Open Access Journals (Sweden)

    Jaroslav Topič

    2017-11-01

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

  10. Mechanisms of Coupled Vibrational Relaxation and Dissociation in Carbon Dioxide.

    Science.gov (United States)

    Armenise, Iole; Kustova, Elena

    2018-05-21

    A complete vibrational state-specific kinetic scheme describing dissociating carbon dioxide mixtures is proposed. CO 2 symmetric, bending and asymmetric vibrations and dissociation-recombination are strongly coupled through inter-mode vibrational energy transfers. Comparative study of state-resolved rate coefficients is carried out; the effect of different transitions may vary considerably with temperature. A non-equilibrium 1-D boundary layer flow typical to hypersonic planetary entry is studied in the state-to-state approach. To assess the sensitivity of fluid-dynamic variables and heat transfer to various vibrational transitions and chemical reactions, corresponding processes are successively included to the kinetic scheme. It is shown that vibrational-translational (VT) transitions in the symmetric and asymmetric modes do not alter the flow and can be neglected whereas the VT 2 exchange in the bending mode is the main channel of vibrational relaxation. Inter-mode vibrational exchanges affect the flow implicitly, through energy redistribution enhancing VT relaxation; the dominating role belongs to near-resonant transitions between symmetric and bending modes as well as between CO molecules and CO 2 asymmetric mode. Strong coupling between VT 2 relaxation and chemical reactions is emphasized. While vibrational distributions and average vibrational energy show strong dependence on the kinetic scheme, the heat flux is more sensitive to chemical reactions.

  11. Evidence for faulting related to dissociation of gas hydrate and release of methane off the southeastern United States

    Science.gov (United States)

    Dillon, William P.; Danforth, W.W.; Hutchinson, D.R.; Drury, R.M.; Taylor, M.H.; Booth, J.S.

    1998-01-01

    This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). An irregular, faulted, collapse depression about 38 x 18 km in extent is located on the crest of the Blake Ridge offshore from the south- eastern United States. Faults disrupt the sea floor and terminate or sole out about 40-500 m below the sea floor at the base of the gas hydrate stable zone, which is identified from the location of the bottom simulating reflection (BSR). Normal faults are common but reverse faults and folds also are widespread. Folds commonly convert upward into faults. Sediment diapirs and deposits of sediments that were erupted onto the sea floor are also present. Sea-floor depressions at faults may represent locations of liquid/gas vents. The collapse was probably caused by overpressures and by the decoupling of the overlying sediments by gassy muds that existed just beneath the zone of gas hydrate stability.

  12. Computation of Hydration Free Energies Using the Multiple Environment Single System Quantum Mechanical/Molecular Mechanical Method.

    Science.gov (United States)

    König, Gerhard; Mei, Ye; Pickard, Frank C; Simmonett, Andrew C; Miller, Benjamin T; Herbert, John M; Woodcock, H Lee; Brooks, Bernard R; Shao, Yihan

    2016-01-12

    A recently developed MESS-E-QM/MM method (multiple-environment single-system quantum mechanical molecular/mechanical calculations with a Roothaan-step extrapolation) is applied to the computation of hydration free energies for the blind SAMPL4 test set and for 12 small molecules. First, free energy simulations are performed with a classical molecular mechanics force field using fixed-geometry solute molecules and explicit TIP3P solvent, and then the non-Boltzmann-Bennett method is employed to compute the QM/MM correction (QM/MM-NBB) to the molecular mechanical hydration free energies. For the SAMPL4 set, MESS-E-QM/MM-NBB corrections to the hydration free energy can be obtained 2 or 3 orders of magnitude faster than fully converged QM/MM-NBB corrections, and, on average, the hydration free energies predicted with MESS-E-QM/MM-NBB fall within 0.10-0.20 kcal/mol of full-converged QM/MM-NBB results. Out of five density functionals (BLYP, B3LYP, PBE0, M06-2X, and ωB97X-D), the BLYP functional is found to be most compatible with the TIP3P solvent model and yields the most accurate hydration free energies against experimental values for solute molecules included in this study.

  13. The mechanical properties and hydration characteristics of cement pastes containing added-calcium coal gangue

    Energy Technology Data Exchange (ETDEWEB)

    Dongxu Li; Xuyan Song [Nanjing University of Technology, Nanjing (China). College of Material Science and Engineering

    2008-04-15

    The mechanical properties of several kinds of coal gangue calcined with limestone were researched so as to find the optimum way of calcinations with limestone. The microstructure and property of hydration process of cement pastes containing added-calcium coal gangue were analyzed by means of scanning electron microscope (SEM) and the method of mercury in trusion poremeasurement. When the proper amounst of gypsum and fluorite were taken as mineralizers in the course of calcinations of added-calcium coal gangue, the activity of coal gangue can be effectively improved. The results of mechanical property and structural characteristics such as hydration, hydration products and microstructure etc. of cement pastes containing added-calcium coal gangue are consistent.

  14. Dissociation mechanisms and dynamics of doubly charged CD3CN observed by PEPIPICO spectroscopy

    International Nuclear Information System (INIS)

    Harada, C.; Tada, S.; Yamamoto, K.; Senba, Y.; Yoshida, H.; Hiraya, A.; Wada, S.; Tanaka, K.; Tabayashi, K.

    2006-01-01

    Dissociation of free acetonitrile-d 3 molecule, CD 3 CN induced by core level excitation was studied near the nitrogen K-edge by time-of-flight fragment mass spectroscopy. A variety of atomic and molecular fragment cations such as D + , CD n + , C 2 D n + , and CD n CN + were detected using the effusive CD 3 CN beam. Photoelectron-photoion-photoion coincidence technique was applied to analyse the dissociation mechanisms and dynamics of doubly charged CD 3 CN 2+ following the N(1s-π * ) excitation. The charge separation mechanisms of core-excited CD 3 CN were discussed in connection with Auger final state distributions

  15. 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.

  16. Mechanical behavior of a composite interface: Calcium-silicate-hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Palkovic, Steven D.; Moeini, Sina; Büyüköztürk, Oral, E-mail: obuyuk@mit.edu [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Yip, Sidney [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-07-21

    The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces.

  17. Correlation diagram approach to the dissociative ionization mechanisms of methanol

    International Nuclear Information System (INIS)

    Momigny, J.; Wankenne, H.; Krier, C.

    1980-01-01

    A systematic survey is made of the dissociation processes from the ground state and from the electronically excited states of CH 3 OH + . Most metastable processes occurring in the mass spectrum of CD 3 OH are studied also, including measurement of the kinetic energy release and appearance potentials. It is shown that if ionic species such as CH 2 OH + , CH 2 O + and HCO + are present in the mass spectrum of CH 3 OH, the isomers CH 3 O + , HCOH + and COH + are also present. The precursors of these ions having been identified by the metastable processes, correlation diagrams are used to show that, from the first ionization potential of CH 3 OH to 14 eV, the only exception being CH 3 O + which results from an electronically spin-forbidden predissociation, the fragment ions can be considered to result from adiabatic decay of the ground state of CH 3 OH + . The potential barriers involved in these adiabatic processes result either from conical intersection or from avoided-crossing between the ground state of CH 3 OH + and the electronically excited states occurring up to 14 eV. At higher energies, many non-adiabatic processes occur; for example, the appearance of CD 2 O + and the electronically excited states of HCO + and COH + ions. It is shown additionally that kinetic energy releases observed in the collision-induced processes CH 3 OH + → CH 2 OH + + H and CH 2 OH + → HCO + + H 2 are in good agreement with the mechanistic approach via the correlation diagram for the appearance of the non-collision-induced ion processes. (orig.)

  18. Analyzing angular distributions for two-step dissociation mechanisms in velocity map imaging.

    Science.gov (United States)

    Straus, Daniel B; Butler, Lynne M; Alligood, Bridget W; Butler, Laurie J

    2013-08-15

    Increasingly, velocity map imaging is becoming the method of choice to study photoinduced molecular dissociation processes. This paper introduces an algorithm to analyze the measured net speed, P(vnet), and angular, β(vnet), distributions of the products from a two-step dissociation mechanism, where the first step but not the second is induced by absorption of linearly polarized laser light. Typically, this might be the photodissociation of a C-X bond (X = halogen or other atom) to produce an atom and a momentum-matched radical that has enough internal energy to subsequently dissociate (without the absorption of an additional photon). It is this second step, the dissociation of the unstable radicals, that one wishes to study, but the measured net velocity of the final products is the vector sum of the velocity imparted to the radical in the primary photodissociation (which is determined by taking data on the momentum-matched atomic cophotofragment) and the additional velocity vector imparted in the subsequent dissociation of the unstable radical. The algorithm allows one to determine, from the forward-convolution fitting of the net velocity distribution, the distribution of velocity vectors imparted in the second step of the mechanism. One can thus deduce the secondary velocity distribution, characterized by a speed distribution P(v1,2°) and an angular distribution I(θ2°), where θ2° is the angle between the dissociating radical's velocity vector and the additional velocity vector imparted to the product detected from the subsequent dissociation of the radical.

  19. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    NARCIS (Netherlands)

    Bollmann, Tjeerd Rogier Johannes; Antipina, L.Y.; Temmen, M.; Reichling, M.; Sorokin, P.B.

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CaF2(111). Hydration layers confined between the graphene and the

  20. Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Na; Li, Hongxu [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China); Liu, Xiaoming, E-mail: liuxm@ustb.edu.cn [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China)

    2016-08-15

    Highlights: • Nanocrystalline regions in size of ∼5 nm were found in the amorphous C-A-S-H gel. • A hydration model was proposed to clarify the hydration mechanism. • The developed cementitious materials are environmentally acceptable. - Abstract: A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5 nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

  1. Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials

    International Nuclear Information System (INIS)

    Zhang, Na; Li, Hongxu; Liu, Xiaoming

    2016-01-01

    Highlights: • Nanocrystalline regions in size of ∼5 nm were found in the amorphous C-A-S-H gel. • A hydration model was proposed to clarify the hydration mechanism. • The developed cementitious materials are environmentally acceptable. - Abstract: A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5 nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

  2. Conditional dissociation as a punishment mechanism in the evolution of cooperation

    Science.gov (United States)

    Qu, Xinglong; Zhou, Changli; Cao, Zhigang; Yang, Xiaoguang

    2016-05-01

    Recent studies show that conditional dissociation, a.k.a. post-interaction partner-refusal, can promote the emergence and stability of cooperation. However, in most of these studies, players' strategies are restricted to pure ones, which is obviously inconsistent with many biological and economic situations. Another concern with line of these studies is that conditional dissociation is often combined with other mechanisms. These mechanisms may favor cooperation per se, leaving it unclear whether conditional dissociation is indeed a key factor. In this paper, we study a clean model, pruning all the factors other than conditional dissociation that may favor cooperation. We find that conditional dissociation, which could be viewed as a variant of peer punishment, does promote cooperation, no matter whether mixed strategies are allowed or not. This confirms the previous findings in the literature. In addition, compared with the pure strategy scenario, cooperators are less competitive when mixed strategies are allowed. Our main finding is supported by both the numerical simulations and the theoretical analysis of Neutrally Stable Strategy. We also find that cooperative behavior is favored when waiting time and/or the population's lifespan are longer.

  3. The crucial effect of early-stage gelation on the mechanical properties of cement hydrates

    Science.gov (United States)

    Ioannidou, Katerina; Kanduč, Matej; Li, Lunna; Frenkel, Daan; Dobnikar, Jure; Del Gado, Emanuela

    2016-07-01

    Gelation and densification of calcium-silicate-hydrate take place during cement hydration. Both processes are crucial for the development of cement strength, and for the long-term evolution of concrete structures. However, the physicochemical environment evolves during cement formation, making it difficult to disentangle what factors are crucial for the mechanical properties. Here we use Monte Carlo and Molecular Dynamics simulations to study a coarse-grained model of cement formation, and investigate the equilibrium and arrested states. We can correlate the various structures with the time evolution of the interactions between the nano-hydrates during the preparation of cement. The novel emerging picture is that the changes of the physicochemical environment, which dictate the evolution of the effective interactions, specifically favour the early gel formation and its continuous densification. Our observations help us understand how cement attains its unique strength and may help in the rational design of the properties of cement and related materials.

  4. Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

    Science.gov (United States)

    Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

    2018-06-01

    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

  5. A QUANTUM MECHANICAL STUDY OF THE PROTONATION AND COVALENT HYDRATION OF QUINAZOLINE IN THE PRESENCE OF METAL CATIONS

    Science.gov (United States)

    We have investigated the protonation and reversible covalent hydration of quinazoline in the presence of Li+, Na+, and Ca2+ ions using ab initio quantum mechanical calculations at the MP2/6-31G**//HF/6-31G*level of theory. Proton affinities, enthalpies of hydration at 298.15K (DH...

  6. The mechanism of vapor phase hydration of calcium oxide: implications for CO2 capture.

    Science.gov (United States)

    Kudłacz, Krzysztof; Rodriguez-Navarro, Carlos

    2014-10-21

    Lime-based sorbents are used for fuel- and flue-gas capture, thereby representing an economic and effective way to reduce CO2 emissions. Their use involves cyclic carbonation/calcination which results in a significant conversion reduction with increasing number of cycles. To reactivate spent CaO, vapor phase hydration is typically performed. However, little is known about the ultimate mechanism of such a hydration process. Here, we show that the vapor phase hydration of CaO formed after calcination of calcite (CaCO3) single crystals is a pseudomorphic, topotactic process, which progresses via an intermediate disordered phase prior to the final formation of oriented Ca(OH)2 nanocrystals. The strong structural control during this solid-state phase transition implies that the microstructural features of the CaO parent phase predetermine the final structural and physicochemical (reactivity and attrition) features of the product hydroxide. The higher molar volume of the product can create an impervious shell around unreacted CaO, thereby limiting the efficiency of the reactivation process. However, in the case of compact, sintered CaO structures, volume expansion cannot be accommodated in the reduced pore volume, and stress generation leads to pervasive cracking. This favors complete hydration but also detrimental attrition. Implications of these results in carbon capture and storage (CCS) are discussed.

  7. Mechanical Dissociation of Platelet Aggregates in Blood Stream

    Science.gov (United States)

    Hoore, Masoud; Fedosov, Dmitry A.; Gompper, Gerhard; Complex; Biological Fluids Group Team

    2017-11-01

    von Willebrand factor (VWF) and platelet aggregation is a key phenomenon in blood clotting. These aggregates form critically in high shear rates and dissolve reversibly in low shear rates. The emergence of a critical shear rate, beyond which aggregates form and below which they dissolve, has an interesting impact on aggregation in blood flow. As red blood cells (RBCs) migrate to the center of the vessel in blood flow, a RBC free layer (RBC-FL) is left close to the walls into which the platelets and VWFs are pushed back from the bulk flow. This margination process provides maximal VWF-platelet aggregation probability in the RBC-FL. Using mesoscale hydrodynamic simulations of aggregate dynamics in blood flow, it is shown that the aggregates form and grow in RBC-FL wherein shear rate is high for VWF stretching. By growing, the aggregates penetrate to the bulk flow and get under order of magnitude lower shear rates. Consequently, they dissolve and get back into the RBC-FL. This mechanical limitation for aggregates prohibits undesired thrombosis and vessel blockage by aggregates, while letting the VWFs and platelets to aggregate close to the walls where they are actually needed. The support by the DFG Research Unit FOR 1543 SHENC and CPU time Grant by the Julich Supercomputing Center are acknowledged.

  8. Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Mendoza, Oscar, E-mail: oamendoz@unal.edu.co [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia); Giraldo, Carolina [Cementos Argos S.A., Medellín (Colombia); Camargo, Sergio S. [Engenharia Metalúrgica e de Materiais, Universidade Federal do Rio de Janeiro/COPPE, Rio de Janeiro (Brazil); Tobón, Jorge I. [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia)

    2015-08-15

    This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure.

  9. Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

    International Nuclear Information System (INIS)

    Mendoza, Oscar; Giraldo, Carolina; Camargo, Sergio S.; Tobón, Jorge I.

    2015-01-01

    This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure

  10. Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

    Directory of Open Access Journals (Sweden)

    N. J. Biderman

    2016-05-01

    Full Text Available Two sets of diffusion-reaction numerical simulations using a finite difference method (FDM were conducted to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,GaSe2 (CIGS and Cu2ZnSn(S, Se4 (CZTSSe or CZTS via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases the equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. According to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.

  11. Observation of ice sheet formation on methane and ethane gas hydrates using a scanning confocal microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nagao, J.; Shimomura, N.; Ebinuma, T.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira, Sapporo (Japan). Methane Hydrate Research Lab.

    2008-07-01

    Interest in gas hydrates has increased in recent years due to the discovery of large deposits under the ocean floor and in permafrost regions. Natural gas hydrates, including methane, is expected to become a new energy source and a medium for energy storage and transportation. Gas hydrates consist of an open network of water molecules that are hydrogen-bonded in a similar manner to ice. Gas molecules are interstitially engaged under high pressures and low temperatures. Although the dissociation temperature of methane hydrate under atmospheric pressure is about 193 K, studies have shown that methane hydrate can be stored at atmospheric pressure and 267 K for 2 years. Because of this phenomenon, known as self-preservation, transportation and storage of methane hydrate can occur at temperature conditions milder than those for liquefied methane gas at atmospheric pressure. This study examined the surface changes of methane and ethane hydrates during dissociation using an optical microscope and confocal scanning microscope (CSM). This paper reported on the results when the atmospheric gas pressure was decreased. Ice sheets formed on the surfaces of methane and ethane gas hydrates due to depressurizing dissociation of methane and ethane hydrates when the methane and ethane gas pressures were decreased at designated temperatures. The dissociation of methane gas hydrate below below 237 K resulted in the generation of small ice particles on the hydrate surface. A transparent ice sheet formed on the hydrate surface above 242 K. The thickness of the ice sheet on the methane hydrate surface showed the maximum of ca. 30 {mu}m at 253 K. In the case of ethane hydrates, ice particles and ice sheets formed below 262 and 267 respectively. Since the ice particles and ice sheets were formed by water molecules generated during the gas hydrate dissociation, the mechanism of ice sheet formation depends on the dissociation rate of hydrate, ice particle sintering rate, and water molecule

  12. The I2 dissociation mechanisms in the chemical oxygen-iodine laser revisited.

    Science.gov (United States)

    Waichman, K; Barmashenko, B D; Rosenwaks, S

    2012-06-28

    The recently suggested mechanism of I(2) dissociation in the chemical oxygen-iodine laser (COIL) [K. Waichman, B. D. Barmashenko, and S. Rosenwaks, J. Appl. Phys. 106, 063108 (2009); and J. Chem. Phys. 133, 084301 (2010)] was largely based on the suggestion of V. N. Azyazov, S. Yu. Pichugin, and M. C. Heaven [J. Chem. Phys. 130, 104306 (2009)] that the vibrational population of O(2)(a) produced in the chemical generator is high enough to play an essential role in the dissociation. The results of model calculations based on this mechanism agreed very well with measurements of the small signal gain g, I(2) dissociation fraction F, and temperature T in the COIL. This mechanism is here revisited, following the recent experiments of M. V. Zagidullin [Quantum Electron. 40, 794 (2010)] where the observed low population of O(2)(b, v = 1) led to the conclusion that the vibrational population of O(2)(a) at the outlet of the generator is close to thermal equilibrium value. This value corresponds to a very small probability, ∼0.05, of O(2)(a) energy pooling to the states O(2)(X,a,b, v > 0). We show that the dissociation mechanism can reproduce the experimentally observed values of g, F, and T in the COIL only if most of the energy released in the processes of O(2)(a) energy pooling and O(2)(b) quenching by H(2)O ends up as vibrational energy of the products, O(2)(X,a,b), where the vibrational states v = 2 and 3 are significantly populated. We discuss possible reasons for the differences in the suggested vibrational population and explain how these differences can be reconciled.

  13. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    Institute of Scientific and Technical Information of China (English)

    Tjeerd R. J. Bollmann[1,2; Liubov Yu. Antipina[3,4; Matthias Temmen[2; Michael Reichling[2; Pavel B. Sorokin[5

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CAF2(111). Hydration layers confined between the graphene and the CaF2 substrate, resulting from the graphene's preparation under ambient conditions on the hydrophilic substrate surface, are found to electronically modify the graphene as the material's electron density transfers from graphene to the hydration layer. Density functional theory (DFT) calculations predict that the first 2 to 3 water layers adjacent to the graphene hole-dope the graphene by several percent of a unit charge per unit cell.

  14. Contrast between the mechanisms for dissociative electron attachment to CH3SCN and CH3NCS

    Science.gov (United States)

    Miller, Thomas M.; Viggiano, Albert A.; Shuman, Nicholas S.

    2018-05-01

    The kinetics of thermal electron attachment to methyl thiocyanate (CH3SCN), methyl isothiocyanate (CH3NCS), and ethyl thiocyanate (C2H5SCN) were measured using flowing afterglow-Langmuir probe apparatuses at temperatures between 300 and 1000 K. CH3SCN and C2H5SCN undergo inefficient dissociative attachment to yield primarily SCN- at 300 K (k = 2 × 10-10 cm3 s-1), with increasing efficiency as temperature increases. The increase is well described by activation energies of 0.17 eV (CH3SCN) and 0.14 eV (C2H5SCN). CN- product is formed at product but at a rate at 300 K that is below our detection threshold (k differentiating the two mechanisms. The kinetic modeling reproduces the CH3NCS data only if dissociation through the transient anion is considered.

  15. Structure and dynamics of hydrated Fe(II) and Fe(III) ions. Quantum mechanical and molecular mechanical simulations

    International Nuclear Information System (INIS)

    Remsungnen, T.

    2002-11-01

    Classical molecular dynamics (MD) and combined em ab initio quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations have been performed to investigate structural, dynamical and energetical properties of Fe(II), and Fe(III) transition metal ions in aqueous solution. In the QM/MM-MD simulations the ion and its first hydration sphere were treated at the Hartree-Fock ab initio quantum mechanical level, while ab initio generated pair plus three-body potentials were employed for the remaining system. For the classical MD simulation the pair plus three-body potential were employed for all ion-water interactions. The coordination number of the first hydration shell is 100 % of 6 in both cases. The number of waters in the second hydration shell obtained from classical simulations are 13.4 and 15.1 for Fe(II) and Fe(III), respectively, while QM/MM-MD gives the values of 12.4 and 13.4 for Fe(II) and Fe(III). The energies of hydration obtained from MD and QM/MM-MD for Fe(II) are 520 and 500 kcal/mol, and for Fe(III) 1160 and 1100 kcal/mol respectively. The mean residence times of water in the second shell obtained from QM/MM-MD are 24 and 48 ps for Fe(II) and Fe(III), respectively. In contrast to the data obtained from classical MD simulation, the QM/MM-MD values are all in good agreement with the experimental data available. These investigations and results clearly indicate that many-body effects are essential for the proper description of all properties of the aqueous solution of both Fe(II) and Fe(III) ions. (author)

  16. Structural determinants of hydration, mechanics and fluid flow in freeze-dried collagen scaffolds.

    Science.gov (United States)

    Offeddu, G S; Ashworth, J C; Cameron, R E; Oyen, M L

    2016-09-01

    Freeze-dried scaffolds provide regeneration templates for a wide range of tissues, due to their flexibility in physical and biological properties. Control of structure is crucial for tuning such properties, and therefore scaffold functionality. However, the common approach of modeling these scaffolds as open-cell foams does not fully account for their structural complexity. Here, the validity of the open-cell model is examined across a range of physical characteristics, rigorously linking morphology to hydration and mechanical properties. Collagen scaffolds with systematic changes in relative density were characterized using Scanning Electron Microscopy, X-ray Micro-Computed Tomography and spherical indentation analyzed in a time-dependent poroelastic framework. Morphologically, all scaffolds were mid-way between the open- and closed-cell models, approaching the closed-cell model as relative density increased. Although pore size remained constant, transport pathway diameter decreased. Larger collagen fractions also produced greater volume swelling on hydration, although the change in pore diameter was constant, and relatively small at ∼6%. Mechanically, the dry and hydrated scaffold moduli varied quadratically with relative density, as expected of open-cell materials. However, the increasing pore wall closure was found to determine the time-dependent nature of the hydrated scaffold response, with a decrease in permeability producing increasingly elastic rather than viscoelastic behavior. These results demonstrate that characterizing the deviation from the open-cell model is vital to gain a full understanding of scaffold biophysical properties, and provide a template for structural studies of other freeze-dried biomaterials. Freeze-dried collagen sponges are three-dimensional microporous scaffolds that have been used for a number of exploratory tissue engineering applications. The characterization of the structure-properties relationships of these scaffolds is

  17. In vivo confirmation of hydration based contrast mechanisms for terahertz medical imaging using MRI

    Science.gov (United States)

    Bajwa, Neha; Sung, Shijun; Garritano, James; Nowroozi, Bryan; Tewari, Priyamvada; Ennis, Daniel B.; Alger, Jeffery; Grundfest, Warren; Taylor, Zachary

    2014-09-01

    Terahertz (THz) detection has been proposed and applied to a variety of medical imaging applications in view of its unrivaled hydration profiling capabilities. Variations in tissue dielectric function have been demonstrated at THz frequencies to generate high contrast imagery of tissue, however, the source of image contrast remains to be verified using a modality with a comparable sensing scheme. To investigate the primary contrast mechanism, a pilot comparison study was performed in a burn wound rat model, widely known to create detectable gradients in tissue hydration through both injured and surrounding tissue. Parallel T2 weighted multi slice multi echo (T2w MSME) 7T Magnetic Resonance (MR) scans and THz surface reflectance maps were acquired of a full thickness skin burn in a rat model over a 5 hour time period. A comparison of uninjured and injured regions in the full thickness burn demonstrates a 3-fold increase in average T2 relaxation times and a 15% increase in average THz reflectivity, respectively. These results support the sensitivity and specificity of MRI for measuring in vivo burn tissue water content and the use of this modality to verify and understand the hydration sensing capabilities of THz imaging for acute assessments of the onset and evolution of diseases that affect the skin. A starting point for more sophisticated in vivo studies, this preliminary analysis may be used in the future to explore how and to what extent the release of unbound water affects imaging contrast in THz burn sensing.

  18. Hydro-mechanical properties of pressure core sediments recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02

    Science.gov (United States)

    Yoneda, J.; Oshima, M.; Kida, M.; Kato, A.; Konno, Y.; Jin, Y.; Waite, W. F.; Jang, J.; Kumar, P.; Tenma, N.

    2017-12-01

    Pressure coring and analysis technology allows for gas hydrate to be recovered from the deep seabed, transferred to the laboratory and characterized while continuously maintaining gas hydrate stability. For this study, dozens of hydrate-bearing pressure core sediment subsections recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02 were tested with Pressure Core Non-destructive Analysis Tools (PNATs) through a collaboration between Japan and India. PNATs, originally developed by AIST as a part of the Japanese National hydrate research program (MH21, funded by METI) conducted permeability, compression and consolidation tests under various effective stress conditions, including the in situ stress state estimated from downhole bulk density measurements. At the in situ effective stress, gas hydrate-bearing sediments had an effective permeability range of 0.01-10mD even at pore-space hydrate saturations above 60%. Permeability increased by 10 to 100 times after hydrate dissociation at the same effective stress, but these post-dissociation gains were erased when effective stress was increased from in situ values ( 1 MPa) to 10MPa in a simulation of the depressurization method for methane extraction from hydrate. Vertical-to-horizontal permeability anisotropy was also investigated. First-ever multi-stage loading tests and strain-rate alternation compression tests were successfully conducted for evaluating sediment strengthening dependence on the rate and magnitude of effective confining stress changes. In addition, oedometer tests were performed up to 40MPa of consolidation stress to simulate the depressurization method in ultra-deep sea environments. Consolidation curves measured with and without gas hydrate were investigated over a wide range of effective confining stresses. Compression curves for gas hydrate-bearing sediments were convex downward due to high hydrate saturations. Consolidation tests show that

  19. Effect of Fly Ash and Silica Fume on the Mechanical Properties of Cement Paste at Different Stages of Hydration

    Science.gov (United States)

    2015-08-10

    All materials were placed in a clean, labeled stainless steel mixing bowl and weighed to the nearest ten thousandth of a pound. The cement and fly...on the Mechanical Properties of Cement Paste at Different Stages of Hydration This thesis investigates the effect of fly ash and silica fume on... cement paste hydration. Percentages of each additive will replace the cement by volume to be studied at five ages. These percentages will be compared

  20. Evaluation of mechanical strength and hydrate products evolution of calcium aluminate cement, for endodontic applications

    International Nuclear Information System (INIS)

    Luz, A.P.; Borba, N.Z.; Pandolfelli, V.C.

    2011-01-01

    Mineral trioxide aggregate (MTA) is the most used retrograde filling cement in the endodontic area. Nevertheless, although its composition is similar to the conventional Portland cement, its high cost, long setting time and low mechanical strength have led to a continuous search for new alternative materials. Considering these aspects, the mechanical strength and crystalline phase evolution of a calcium aluminate cement (CAC), during its hydration process, have been evaluated in this work aiming to apply such material for endodontic treatments. Secar 71 cement samples were prepared and kept in contact with water or SBF (simulated body fluid) during 15 days at 37 deg C. Compressive strength, apparent porosity, X ray diffraction and thermogravimetric tests were carried out for the samples evaluation after 1, 3, 7 and 15 days. The main identified phases were CAH_1_0, C_2AH_8, C_3AH_6 and AH_3. Moreover, when in the presence of SBF, some changes in the amount of the hydrates in the CAC samples were observed, which affected the mechanical behavior of the cement. (author)

  1. Observation of Coherent and Incoherent Dissociation Mechanisms in the Angular Distribution of Atomic Photofragment Alignment

    International Nuclear Information System (INIS)

    Bracker, A.S.; Lee, Y.T.; Bracker, A.S.; Wouters, E.R.; Suits, A.G.; Lee, Y.T.; Lee, Y.T.; Vasyutinskii, O.S.

    1998-01-01

    We have analyzed the recoil angle dependence of chlorine atom angular momentum alignment for the dissociation of chlorine molecules at 355nm. This angular distribution was isolated from ion image measurements, which map a three-dimensional velocity vector distribution of state-selectively-ionized photofragments into a two-dimensional spatial distribution. Using a general quantum mechanical method to simulate the alignment angular distribution, we show that there are clear contributions to alignment from both incoherent and coherent components of a perpendicular optical transition in the molecule. copyright 1998 The American Physical Society

  2. Capillary pressure controlled methane hydrate and ice growth-melting patterns in porous media : synthetic silica versus natural sandstone

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, R.; Tohidi, B.; Webber, B. [Heriot-Watt Univ., Centre for Gas Research, Edinburgh (United Kingdom). Inst. of Petroleum Engineering

    2008-07-01

    Although naturally-occurring gas hydrates (or clathrate hydrates) in marine sediments can pose a hazard to deepwater hydrocarbon production operations, they represent a potential strategic energy reserve. Gas hydrates can also provide a means for deep ocean carbon dioxide disposal through sequestration/storage. They have long-term importance with respect to ocean margin stability, methane release, and global climate change. However, fundamental knowledge is still lacking regarding the mechanisms of hydrate growth, accumulation and distribution within the subsurface. Marine sediments which host gas hydrates are commonly fine-grained silts, muds, and clays with narrow mean pore diameters, leading to speculation that capillary phenomena could play a significant role in controlling hydrate distribution in the seafloor, and may be partly responsible for discrepancies between observed and predicted hydrate stability zone thicknesses. A close relationship between hydrate inhibition and pore size has been confirmed through previous laboratory studies. Clathrate stability has been significantly reduced in narrow pores. However, the focus of investigations has generally been hydrate dissociation conditions in porous media, with capillary controls on the equally important process of hydrate growth being largely overlooked. This paper presented the results of an experimental investigation into methane hydrate growth and dissociation equilibria in natural medium grained sandstone. The study also compared data with that previously measured for mesoporous silica glasses. The paper discussed solid-liquid phase behaviour in confined geometries including hysteresis in porous media. It also discussed the experimental equipment and method. It was concluded that, as for synthetic silicas, hydrate growth and dissociation in the sandstone were characterised by a measurable hysteresis between opposing transitions, notably hydrate (or ice) formation occurring at temperatures lower than

  3. Modes of occurrence and accumulation mechanism of methane hydrate -result of meti exploratory test wells ''Tokai-Oki To Kumano-Nada''

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Tetsuya; Namikawa, Takatoshi; Nakamizu, Masaru; Tsuji, Yoshihiro; Okui, Toshiharu; Kawasaki, Masayuki; Ochiai, Koji

    2005-07-01

    In the Nankai Trough, offshore central Japan, seismic data indicates widespread existence of BSR, which is interpreted as an indicator of bottom boundary of methane hydrate bearing zone. Methane hydrate is regarded as future possible natural gas resource. However, the volume, distribution and occurrence of hydrate have been poorly understood. In order to obtain data for the understanding of methane hydrate occurrence and volume estimation, METI exploratory test wells ''Tokai-oki to Kumano-nada'' were drilled from January to May in 2004. First, LWD (Logging While Drilling) was carried out at 16 sites that were selected based on 2D and 3D seismic interpretation. Secondly, coring was carried out at 4 sites where high concentration of methane hydrate was expected based on resistivity log curve. In addition, continuous formation temperature measurement was carried out in order to investigate in-situ temperature condition in hydrate bearing sediments. Coring was carried out using both ODP type core sampler and PTCS (Pressure Temperature Core Sampler). PTCS coring were mainly focused on the hydrate bearing zone. Hydrate was confirmed in the pore space of turbidite sandstone layer in two of these sites, while it was confirmed as massive or layered condition in mud in one of the sites. Coring results suggest that most of hydrate were concentrated in sand layers in the alternation of sand and mud. The evidence may indicates permeable sandstone is ideal for hydrate accumulation. Hydrate dissociation and gas measurement test on board was also carried out and natural hydrate saturation data, which may calibrate logging results, was obtained. (Author)

  4. Coupled numerical modeling of gas hydrates bearing sediments from laboratory to field-scale conditions

    Science.gov (United States)

    Sanchez, M. J.; Santamarina, C.; Gai, X., Sr.; Teymouri, M., Sr.

    2017-12-01

    Stability and behavior of Hydrate Bearing Sediments (HBS) are characterized by the metastable character of the gas hydrate structure which strongly depends on thermo-hydro-chemo-mechanical (THCM) actions. Hydrate formation, dissociation and methane production from hydrate bearing sediments are coupled THCM processes that involve, amongst other, exothermic formation and endothermic dissociation of hydrate and ice phases, mixed fluid flow and large changes in fluid pressure. The analysis of available data from past field and laboratory experiments, and the optimization of future field production studies require a formal and robust numerical framework able to capture the very complex behavior of this type of soil. A comprehensive fully coupled THCM formulation has been developed and implemented into a finite element code to tackle problems involving gas hydrates sediments. Special attention is paid to the geomechanical behavior of HBS, and particularly to their response upon hydrate dissociation under loading. The numerical framework has been validated against recent experiments conducted under controlled conditions in the laboratory that challenge the proposed approach and highlight the complex interaction among THCM processes in HBS. The performance of the models in these case studies is highly satisfactory. Finally, the numerical code is applied to analyze the behavior of gas hydrate soils under field-scale conditions exploring different features of material behavior under possible reservoir conditions.

  5. Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron

    Science.gov (United States)

    Borgis, Daniel; Rossky, Peter J.; Turi, László

    2007-11-01

    We present a kinetic analysis of the nonadiabatic decay mechanism of an excited state hydrated electron to the ground state. The theoretical treatment is based on a quantized, gap dependent golden rule rate constant formula which describes the nonadiabatic transition rate between two quantum states. The rate formula is expressed in terms of quantum time correlation functions of the energy gap and of the nonadiabatic coupling. These gap dependent quantities are evaluated from three different sets of mixed quantum-classical molecular dynamics simulations of a hydrated electron equilibrated (a) in its ground state, (b) in its first excited state, and (c) on a hypothetical mixed potential energy surface which is the average of the ground and the first excited electronic states. The quantized, gap dependent rate results are applied in a phenomenological kinetic equation which provides the survival probability function of the excited state electron. Although the lifetime of the equilibrated excited state electron is computed to be very short (well under 100fs), the survival probability function for the nonequilibrium process in pump-probe experiments yields an effective excited state lifetime of around 300fs, a value that is consistent with the findings of several experimental groups and previous theoretical estimates.

  6. Numerical simulation studies of gas production scenarios from hydrate accumulations at the Mallik Site, McKenzie Delta, Canada

    International Nuclear Information System (INIS)

    Moridis, George J.; Collett, Timothy S.; Dallimore, Scott R.; Satoh, Tohru; Hancock, Stephen; Weatherill, Brian

    2002-01-01

    The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. An 1150 m deep gas hydrate research well was drilled at the site in 1998. The objective of this study is the analysis of various gas production scenarios from several gas-hydrate-bearing zones at the Mallik site. The TOUGH2 general-purpose simulator with the EOSHYDR2 module were used for the analysis. EOSHYDR2 is designed to model the non-isothermal CH(sub 4) (methane) release, phase behavior and flow under conditions typical of methane-hydrate deposits by solving the coupled equations of mass and heat balance, and can describe any combination of gas hydrate dissociation mechanisms. Numerical simulations indicated that significant gas hydrate production at the Mallik site was possible by drawing down the pressure on a thin free-gas zone at the base of the hydrate stability field. Gas hydrate zones with underlying aquifers yielded significant gas production entirely from dissociated gas hydrate, but large amounts of produced water. Lithologically isolated gas-hydrate-bearing reservoirs with no underlying free gas or water zones, and gas-hydrate saturations of at least 50% were also studied. In these cases, it was assumed that thermal stimulation by circulating hot water in the well was the method used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increases with gas-hydrate saturation, the initial formation temperature, the temperature of the circulating water in the well, and the formation thermal conductivity. Methane production appears to be less sensitive to the rock and hydrate specific heat and permeability of the formation

  7. Experimental hydrate formation and gas production scenarios based on CO{sub 2} sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, J.C.; Howard, J.J. [ConocoPhillips, Bartlesville, OK (United States). Reservoir Laboratories; Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States); Ersland, G.; Husebo, J.; Graue, A. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology

    2008-07-01

    Gas hydrate production strategies have focused on depressurization or thermal stimulation of the reservoir, which in turn leads to hydrate dissociation. In order to evaluate potential production scenarios, the recovery efficiency of the natural gas from hydrate must be known along with the corresponding amounts of produced water. This study focused on the exchange of carbon dioxide (CO{sub 2}) with the natural gas hydrate and the subsequent release of free methane (CH{sub 4}). Laboratory experiments that investigated the rates and mechanisms of hydrate formation in coarse-grained porous media have shown the significance of initial water saturation and salinity on forming methane hydrates. Many of the experiments were performed in a sample holder fitted with an MRI instrument for monitoring hydrate formation. Hydrate-saturated samples were subjected to different procedures to release methane. The rates and efficiency of the exchange process were reproducible over a series of initial conditions. The exchange process was rapid and efficient in that no free water was observed in the core with MRI measurements. Injection of CO{sub 2} into the whole-core hydrate-saturated pore system resulted in methane production at the outlet end. Permeability measurements on these hydrate saturated cores during hydrate formation decreased to low values, but enough for gas transport. The lower permeability values remained constant during the methane-carbon dioxide exchange process in the hydrate structure. 12 refs., 9 figs.

  8. Study on small-strain behaviours of methane hydrate sandy sediments using discrete element method

    Energy Technology Data Exchange (ETDEWEB)

    Yu Yanxin; Cheng Yipik [Department of Civil, Environmental and Geomatic Engineering, University College London (UCL), Gower Street, London, WC1E 6BT (United Kingdom); Xu Xiaomin; Soga, Kenichi [Geotechnical and Environmental Research Group, Department of Engineering, University of Cambridge, Trumpington Street, Cambridge, CB2 1PZ (United Kingdom)

    2013-06-18

    Methane hydrate bearing soil has attracted increasing interest as a potential energy resource where methane gas can be extracted from dissociating hydrate-bearing sediments. Seismic testing techniques have been applied extensively and in various ways, to detect the presence of hydrates, due to the fact that hydrates increase the stiffness of hydrate-bearing sediments. With the recognition of the limitations of laboratory and field tests, wave propagation modelling using Discrete Element Method (DEM) was conducted in this study in order to provide some particle-scale insights on the hydrate-bearing sandy sediment models with pore-filling and cementation hydrate distributions. The relationship between shear wave velocity and hydrate saturation was established by both DEM simulations and analytical solutions. Obvious differences were observed in the dependence of wave velocity on hydrate saturation for these two cases. From the shear wave velocity measurement and particle-scale analysis, it was found that the small-strain mechanical properties of hydrate-bearing sandy sediments are governed by both the hydrate distribution patterns and hydrate saturation.

  9. 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.

  10. Changes Of Hydration Level In Type I Collagen And Glycosaminoglycans Synthesized In The Rat’s Skin Under The Mechanical Stress

    Directory of Open Access Journals (Sweden)

    Alexandr M. Ponomarenko

    2013-01-01

    Full Text Available Changes of Hydratation Level Of Type I Collagen And Glycosaminoglycans That Are Synthesized In The Rat’s Skin Under The Mechanical Stress. The effect of the mechanical stress on the levels of hydratation of type I collagen and glycosaminoglycans that are synthesized in it, has been studied in vitro using the rats’ skin. The measured hydration of isotherms has shown that mechanical stress in the skin increases and decreases the amount of absorbed water in glycosaminoglycans and in collagen, respectively. Сalculated the average amounts of water molecules in collagen tripeptide and glycosaminoglycans disaccharide unit in the inside and outside layers of their hydrate shells

  11. Experimental study on hydration damage mechanism of shale from the Longmaxi Formation in southern Sichuan Basin, China

    Directory of Open Access Journals (Sweden)

    Xiangjun Liu

    2016-03-01

    Full Text Available As a serious problem in drilling operation, wellbore instability restricts efficient development of shale gas. The interaction between the drilling fluid and shale with hydration swelling property would have impact on the generation and propagation mechanism of cracks in shale formation, leading to wellbore instability. In order to investigate the influence of the hydration swelling on the crack propagation, mineral components and physicochemical properties of shale from the Lower Silurian Longmaxi Formation (LF were investigated by using the XRD analysis, cation exchange capabilities (CEC analysis, and SEM observation, and we researched the hydration mechanism of LF shale. Results show that quartz and clay mineral are dominated in mineral composition, and illite content averaged 67% in clay mineral. Meanwhile, CEC of the LF shale are 94.4 mmol/kg. The process of water intruding inside shale along microcracks was able to be observed through high power microscope, meanwhile, the hydration swelling stress would concentrate at the crack tip. The microcracks would propagate, bifurcate and connect with each other, with increase of water immersing time, and it would ultimately develop into macro-fracture. Moreover, the macrocracks extend and coalesce along the bedding, resulting in the rock failure into blocks. Hydration swelling is one of the major causes that lead to wellbore instability of the LF shale, and therefore improving sealing capacity and inhibition of drilling fluid system is an effective measure to stabilize a borehole.

  12. Shallow methane hydrate system controls ongoing, downslope sediment transport in a low-velocity active submarine landslide complex, Hikurangi Margin, New Zealand

    Science.gov (United States)

    Mountjoy, Joshu J.; Pecher, Ingo; Henrys, Stuart; Crutchley, Gareth; Barnes, Philip M.; Plaza-Faverola, Andreia

    2014-11-01

    Morphological and seismic data from a submarine landslide complex east of New Zealand indicate flow-like deformation within gas hydrate-bearing sediment. This "creeping" deformation occurs immediately downslope of where the base of gas hydrate stability reaches the seafloor, suggesting involvement of gas hydrates. We present evidence that, contrary to conventional views, gas hydrates can directly destabilize the seafloor. Three mechanisms could explain how the shallow gas hydrate system could control these landslides. (1) Gas hydrate dissociation could result in excess pore pressure within the upper reaches of the landslide. (2) Overpressure below low-permeability gas hydrate-bearing sediments could cause hydrofracturing in the gas hydrate zone valving excess pore pressure into the landslide body. (3) Gas hydrate-bearing sediment could exhibit time-dependent plastic deformation enabling glacial-style deformation. We favor the final hypothesis that the landslides are actually creeping seafloor glaciers. The viability of rheologically controlled deformation of a hydrate sediment mix is supported by recent laboratory observations of time-dependent deformation behavior of gas hydrate-bearing sands. The controlling hydrate is likely to be strongly dependent on formation controls and intersediment hydrate morphology. Our results constitute a paradigm shift for evaluating the effect of gas hydrates on seafloor strength which, given the widespread occurrence of gas hydrates in the submarine environment, may require a reevaluation of slope stability following future climate-forced variation in bottom-water temperature.

  13. Synthesis, formation mechanism and sensing properties of WO3 hydrate nanowire netted-spheres

    International Nuclear Information System (INIS)

    Yan, Aihua; Xie, Changsheng; Zeng, Dawen; Cai, Shuizhou; Hu, Mulin

    2010-01-01

    Tungsten oxide hydrate nanowire netted-spheres were successfully synthesized in the glycol solution using a facile solvothermal approach. The nanowires with uniform diameter of 4-6 nm are actually a kind of tungsten oxide hydrate/surfactant hybrid materials. The influence of surfactant, solvent, time and temperature on tailoring morphology was investigated in detail. The possible formation process of WO 3 hydrate nanowire netted-sphere was proposed. Sensing properties of such WO 3 hydrate sensor show that the desirable sensing characteristics towards 100 ppm ammonia gas at 320 o C were obtained, such as rapid response (18.3 s), high sensitivity, good reproducibility and stability.

  14. Gas hydrate geohazards in shallow sediments and their impact on the design of subsea systems

    Energy Technology Data Exchange (ETDEWEB)

    Peters, D.; Hatton, G. [Shell Global Solutions Inc., Houston, TX (United States); Mehta, A. [Shell Malaysia Exploration and Production, Sarawak (Malaysia); Hadley, C. [Shell Exploration and Production Inc., Houston, TX (United States)

    2008-07-01

    This paper described the challenges that exist in producing gas hydrates in deepwater and Arctic environments as a potential source of methane gas. In order to safely produce hydrocarbon reservoirs far beneath near-mudline hydrates, it is important to understand and manage the geohazard risks associated with wells that pass through hydrate-bearing sediments. Since these wells may produce for decades, the temperature of near-mudline sediments may increase above the hydrate dissociation temperature for hundreds of meters from the well. This can result in the release of large quantities of gas causing a volume change that can impact the subsea system in many ways. As the fluids of an underlying reservoir flow to the mudline, heat carried by the fluids warms nearwell sediments and dissociates hydrates, which releases gas that can displace and fracture near well soil. This gas release may be calculated with numerical simulations that model heat and mass transfer in hydrate-bearing sediments. The model simulations require information on the nature and distribution of hydrates within the sediments, the melting behaviour of the hydrates, the thermal and mechanical properties of these shallow sediments, and the amount of hydrates contained in the sediments. However, this information is costly to acquire and characterize with certainty for an offshore development. Therefore, it is important to understand what information, processes, and calculations are needed in order to ensure safe, robust systems to produce the hydrocarbon reservoirs far below the hydrates. It was concluded that the relation between the quantity of gas released and dissociated gas quantities must be well understood. The hydrate concentration is a critical reservoir parameter for reservoirs with severe geohazard risk. 6 refs., 6 figs.

  15. Assessment of hydration process and mechanical properties of cemented paste backfill by electrical resistivity measurement

    Science.gov (United States)

    Xu, Wenbin; Tian, Xichun; Cao, Peiwang

    2018-04-01

    Cemented paste backfill (CPB) is an emerging mine backfill technique that allows environmentally hazardous tailings to return to the underground openings or stopes, thereby maximising the safety, efficiency and productivity of operation. Uniaxial compressive strength (UCS) is one of the most commonly used parameters for evaluating the mechanical performance of CPB; the prediction of the UCS of CPB structures from early to advanced ages is of great practical importance. This study aims to investigate the predictability of the UCS of CPB during the hydration process based on electrical resistivity (ER) measurement. For this purpose, the samples prepared at different cement-to-tailing ratios and solid contents were subjected to the ER test during the whole hydration process and UCS tests at 3, 7, 28 days of curing periods. The effect of cement-to-tailing ratio and solid content on the ER and UCS of CPB samples was obtained; the UCS values were correlated with the corresponding ER data. Microstructural analysis was also performed on CPB samples to understand the effect of microstructure on the ER data. The result shows that the ER of CPB decreases first and then increases with the speed which is faster in the previous part than the latter. The ER and UCS of CPB samples increased with increasing cement-to-tailing ratio and solid content and curing periods. A logarithmic relationship is established for each mixture in order to predict the UCS of CPB based on ER. Scanning electron microscope analyses have revealed that the microstructure of the CPB changes with the age from the initial floc to honeycomb, and eventually to the compact clumps. The ER properties of CPB samples were highly associated with their respective microstructural properties. The major output of this study is that ER test is effectively capable for a preliminary prediction of the UCS of CPB.

  16. 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.

  17. Production of Hydrated Metal Ions by Fast Ion or Atom Beam Sputtering. Collision-Induced Dissociation and Successive Hydration Energies of Gaseous Cu+ with 1-4 Water Molecules

    NARCIS (Netherlands)

    Magnera, Thomas F.; David, Donald E.; Stulik, Dusan; Orth, Robert G.; Jonkman, Harry T.; Michl, Josef

    1989-01-01

    Low-temperature sputtering of frozen aqueous solutions of metal salts, of hydrated crystalline transition-metal salts, of frosted metal surfaces, and of frosted metal salts with kiloelectronvolt energy rare gas atoms or ions produces copious amounts of cluster ions, among which M+(H2O)n and/or

  18. The effect of irradiation and hydration upon the mechanical properties of tendon

    International Nuclear Information System (INIS)

    Smith, C.W.; Kearney, J.N.

    1996-01-01

    Irradiation sterilization is in wide use among tissue banks, for both hard and soft tissue grafts. Irradiation of tendon can impair its mechanical properties. Following implantation of a tendon graft, re-vascularization and resorption processes reduce its mechanical performance. Tendon with severely impaired properties may not be suitable for use as a load-bearing graft, e.g. as anterior cruciate ligament replacement. An important factor determining the extent of the reduction of the mechanical performance is the condition of the tendon during irradiation, especially the presence of water. There has not yet been a study of the effects of both irradiation dose and hydration on tendon mechanical properties. This study measured the changes in tensile mechanical properties, including strength and stiffness, following γ irradiation doses of 15 kGy (1.5 MRad) and 25 kGy irradiated tendons was lower compared to fresh tendons, whereas the strength of the frozen irradiated tendons was very similar to that of the fresh. The tangent modulus of both of the freeze-dried irradiated groups were lower than the fresh tendons, as was the 15 kGy frozen group. The modulus of the 25 kGy frozen irradiated group was similar to the fresh. The general pattern of the results indicate that the two freeze-dried tendon groups were more affected than the frozen irradiated, and of the frozen irradiated groups the 25 kGy group was least affected. The results fit well with suggested mechanisms for the action of irradiation upon collagen; that intramolecular crosslinking and scission of the tropocollagen α chains occur when water is present, and α chain scission alone occurs when water is absent. Irradiation of tendons for use as grafts may produce minimal deleterious changes if the irradiation is performed while the tendon is frozen with water present. (Author)

  19. Hypothetical physicochemical mechanisms of some intracellular processes: The hydrate hypothesis of mitosis and DNA replication

    International Nuclear Information System (INIS)

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

    2007-01-01

    A DNA replication, mitosis, and binary fission hydrate hypothesis (MRH hypothesis) allowing non-trivial explanations for the physicochemical mechanisms of some intracellular processes is proposed. The hypothesis has a thermodynamic basis and is initiated by original experimental calorimetric and kinetic studies of the behavior of functional organic polymer and monomer substances in highly concentrated aqueous solutions. Experimental data demonstrating the occurrence of a short-range ordering in concentrated aqueous solutions of such substances are included. Hypothetical simple non-enzymatic unified mechanisms for the natural processes of DNA local unwinding preceding the start of duplication, DNA replication, formation and disappearance of the protein bonds between sister chromatids in the centromere region of eukaryotic DNA and in the centromere-like region of prokaryotic DNA, moving of daughter chromosomes apart to the opposite sides of cells in late anaphase, and formation of the nuclear envelopes in telophase and intracellular membranes between the newly formed nuclei in cytokinesis are formulated. The nature of a number of other intracellular phenomena is discussed

  20. Kinetics and mechanism of the dissociation of chlorophyll and its metalloanalogues in proton-donating media

    International Nuclear Information System (INIS)

    Berezin, B.D.; Drobysheva, A.N.; Karmanova, L.P.

    1976-01-01

    The kinetics of the dissociation of chlorophyll a and its metalloanalogues (Zn 2+ and Cd 2+ complexes of chlorophyllic acid) have been investigated in t-butyl alcohol-trichloracetic acid mixtures. The dissociation reaction is kinetically firts-order with respect to the complex. The rate constants and the activation energies and entropies for the dissociation reaction have been calculated. In order to determine the order of the reaction with respect to the protogenic species, a study was made of the ionisation of m-nitroaniline in t-butyl alcohol at 25 0 C in the trichloroacetic acid concentration range from 0.15 to 4.75 M. The dissociation reaction of chlorophyll and its zinc-containing metalloanalogue has been shown to be of second order with respect to the solvated proton. The cadmium complex dissociates by a second-order reaction with respect to trichloroacetic acid

  1. Mechanisms for the Production of Fast HI from Dissociation of H2 on Saturn

    Science.gov (United States)

    Liu, Xianming; Johnson, Paul; Malone, Charles; Young, Jason; Kanik, Isik; Shemansky, Donald

    2010-05-01

    Images of the Saturn system obtained by the Cassini UVIS at a pixel resolution of 0.1 × 0.1 Saturn radii (Rs) reveal atomic hydrogen in ballistic and escaping trajectories sourced at the top of the thermosphere, primarily in the southern sunlit hemisphere. The main feature in the image is a distinctive H Lyman-α plume structure with FWHM of 0.56 Rs at the exobase sub-solar limb at ~ -13.5° latitude constituting the core of the distributed outward flow of atomic hydrogen from the sunlit hemisphere, with a counterpart on the anti-solar side peaking near the equator above the exobase limb. The structure of the image indicates that part of the out-flowing population is sub-orbital and re-enters the thermosphere in ~ 5 hour time scale. A larger and more broadly distributed component fills the magnetosphere to beyond 45 Rs in the orbital plane and 20 Rs latitudinally above and below the plane in an asymmetric distribution in local time. Molecular hydrogen emission in extreme and far ultraviolet regions collected with the H Lyman-α into the image mosaic reveals a distinctive resonance property correlated with the atomic hydrogen plume and shows a strong deviation of H2 X 1Σg+ from local thermodynamic equilibrium in the main source region. The inferred approximate globally averaged energy deposition at the top of the thermosphere from the production of the hot atomic hydrogen accounts for the measured atmospheric temperature. Possible processes for the fast atomic hydrogen formation from dissociation of H2 include the excitation of singlet-ungerade states and doubly excited states by photons and electrons, and the excitation of the singlet-gerade and triplet states by electrons, and chemical reactions involving the formation and dissociative recombination of H3+. Based on the available laboratory measurements and quantum mechanics calculations, the assessment of various mechanisms for H2 - H production, especially those producing H atoms with sufficient energy to

  2. Le problème des hydrates dans le contexte de la production et du transport polyphasiques des pétroles bruts et des gaz naturels. Première partie : physico-chimie de la formation et de la dissociation des hydrates Hydrates Problem Within the Framework of Multiphase Production and Transport of Crude Oils and Natural Gases. Part One: Physical-Chemistry of Hydrates Formation and Dissociation

    Directory of Open Access Journals (Sweden)

    Behar E.

    2006-11-01

    Full Text Available L'exploitation en mer des gisements de combustibles fossiles fluides a amplifié le besoin d'accroître nos connaissances sur les hydrates qui sont susceptibles de boucher les installations de production, de traitement et de transport. Dans cette publication, la structure moléculaire des hydrates I, II et H est rappelée, ensuite l'analyse physico-chimique de leur formation est succinctement décrite tant sur les plans thermodynamique que cinétique. Enfin, les remèdes possibles aux problèmes rencontrés par les compagnies opératrices sont indiqués, essentiellement les inhibiteurs thermodynamiques classiques tels que les alcools ou les sels qui diminuent la température de formation des hydrates, et les additifs dispersants qui évitent la croissance et/ou l'agglomération des cristaux. Pour terminer, une boucle pilote de circulation originale est présentée, ses caractéristiques qui permettent la validation des additifs dispersants dans des conditions hydrodynamiques et physico-chimiques représentatives étant soulignées. Offshore exploitation of fossil fluid fuels has emphasized the need of improving our knowledge on hydrates which can plug production, treatment and transport facilities. In this paper, the molecular structure of I, II and H hydrates is recalled, then the physical-chemistry of their formation is briefly reviewed from both the thermodynamic and the kinetic points of view. Finally, the possible remedies to the problems met by operating companies are described, mainly classical thermodynamic inhibitors such as alcohols or salts which decrease the hydrates formation temperature, and dispersant additives which avoid crystals growth and/or agglomeration. At last an original circulation loop at pilot scale is presented, its characteristics which allow the testing of dispersant additives under representative hydrodynamic and physico-chemical conditions being outlined.

  3. Effect of the crystal chemistry on the hydration mechanism of swelling micas

    Science.gov (United States)

    Pavón, Esperanza; Alba, María D.; Castro, Miguel A.; Cota, A.; Osuna, Francisco J.; Pazos, M. Carolina

    2017-11-01

    Swelling and dehydration under minor changes in temperature and water vapor pressure is an important property that clays and clay minerals exhibit. In particular, their interlayer space, the solid-water interface and the layers' collapse and re-expansion have received much attention because it affects to the dynamical properties of interlayer cations and thus the transfer and fate of water and pollutants. In this contribution, the dehydration and rehydration mechanism of a swelling high-charge mica family is examined by in situ X-ray Diffraction. The effect of the aluminosilicate layer charge and the physicochemical properties of the interlayer cations on these processes are analyzed. The results showed that the dehydration temperature and the number of steps involved in this process are related to the layer charge of the silicate and the physicochemical properties of the interlayer cations. Moreover, the ability to adsorb water molecules in a confined space with high electric field by the interlayer cations does not only depend on their hydration enthalpy but also on the electrostatic parameters of these cations.

  4. A study of sorption mechanism onto cement hydrates by isotherm measurements

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari

    2003-01-01

    In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In particular, the sorption of radionuclides onto cement material, which controls the aqueous concentrations of elements in the porewater, is a very important parameter when considering the release of radionuclides from the near field of a repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium and thorium onto Ordinary Portland Cement (OPC) and Calcium Silicate Hydrate (C-S-H gel), to justify and support this assumption. In addition, the effect of competitive sorption between thorium and uranium and other groundwater ions is studied by examining sorption using a range of sodium chloride concentrations to simulate different groundwater ionic strengths. Based on the experimental results, we have showed that: Caesium and strontium sorb by substitution for Ca in C-S-H phases and the presence of some calcium sites with different ion-exchange log K values is suggested; Thorium would be fixed in a surface co-precipitation to form a solubility-limiting phase. The results of sorption experiments are reasonably well modelled by the ion-exchange model for caesium and strontium and the surface co-precipitation model for thorium, respectively. (author)

  5. Investigation of C3 S hydration mechanism by transmission electron microscope (TEM) with integrated Super-XTM EDS system.

    Science.gov (United States)

    Sakalli, Y; Trettin, R

    2017-07-01

    Tricalciumsilicate (C 3 S, Alite) is the major component of the Portland cement clinker. Hydration of Alite is decisive in influencing the properties of the resulting material. This is due to its high content in cement. The mechanism of the hydration of C 3 S is very complicated and not yet fully understood. There are different models describing the hydration of C 3 S in various ways. In this work for a better understanding of hydration mechanism, the hydrated C 3 S was investigated by using the transmission electron microscope (TEM) and for the first time, the samples for the investigations were prepared by using of focused ion beam from sintered pellets of C 3 S. Also, an FEI Talos F200x with an integrated Super-X EDS system was used for the investigations. FEI Talos F200X combines outstanding high-resolution S/TEM and TEM imaging with energy dispersive X-ray spectroscopy signal detection, and 3D chemical characterization with compositional mapping. TEM is a very powerful tool for material science. A high energy beam of electrons passes through a very thin sample, and the interactions between the electrons and the atoms can be used to observe the structure of the material and other features in the structure. TEM can be used to study the growth of layers and their composition. TEM produces high-resolution, two-dimensional images and will be used for a wide range of educational, science and industry applications. Chemical analysis can also be performed. The purpose of these investigations was to get the information about the composition of the C-S-H phases and some details of the nanostructure of the C-S-H phases. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

  6. Dissociating the role of prefrontal and premotor cortices in controlling inhibitory mechanisms during motor preparation.

    Science.gov (United States)

    Duque, Julie; Labruna, Ludovica; Verset, Sophie; Olivier, Etienne; Ivry, Richard B

    2012-01-18

    Top-down control processes are critical to select goal-directed actions in flexible environments. In humans, these processes include two inhibitory mechanisms that operate during response selection: one is involved in solving a competition between different response options, the other ensures that a selected response is initiated in a timely manner. Here, we evaluated the role of dorsal premotor cortex (PMd) and lateral prefrontal cortex (LPF) of healthy subjects in these two forms of inhibition by using an innovative transcranial magnetic stimulation (TMS) protocol combining repetitive TMS (rTMS) over PMd or LPF and a single pulse TMS (sTMS) over primary motor cortex (M1). sTMS over M1 allowed us to assess inhibitory changes in corticospinal excitability, while rTMS was used to produce transient disruption of PMd or LPF. We found that rTMS over LPF reduces inhibition associated with competition resolution, whereas rTMS over PMd decreases inhibition associated with response impulse control. These results emphasize the dissociable contributions of these two frontal regions to inhibitory control during motor preparation. The association of LPF with competition resolution is consistent with the role of this area in relatively abstract aspects of control related to goal maintenance, ensuring that the appropriate response is selected in a variable context. In contrast, the association of PMd with impulse control is consistent with the role of this area in more specific processes related to motor preparation and initiation.

  7. Dissociating the role of prefrontal and premotor cortices in controlling inhibitory mechanisms during motor preparation

    Science.gov (United States)

    Duque, Julie; Labruna, Ludovica; Verset, Sophie; Olivier, Etienne; Ivry, Richard B.

    2012-01-01

    Top-down control processes are critical to select goal-directed actions in flexible environments. In humans, these processes include two inhibitory mechanisms that operate during response selection: one is involved in solving a competition between different response options, the other ensures that a selected response is initiated timely. Here, we evaluated the role of dorsal premotor cortex (PMd) and lateral prefrontal cortex (LPF) of healthy subjects in these two forms of inhibition by using an innovative transcranial magnetic stimulation (TMS) protocol combining repetitive TMS (rTMS) over PMd or LPF and a single pulse TMS (sTMS) over primary motor cortex (M1). sTMS over M1 allowed us to assess inhibitory changes in corticospinal excitability, while rTMS was used to produce transient disruption of PMd or LPF. We found that rTMS over LPF reduces inhibition associated with competition resolution whereas rTMS over PMd decreases inhibition associated with response impulse control. These results emphasize the dissociable contributions of these two frontal regions to inhibitory control during motor preparation. The association of LPF with competition resolution is consistent with the role of this area in relatively abstract aspects of control related to goal maintenance, ensuring that the appropriate response is selected in a variable context. In contrast, the association of PMd with impulse control is consistent with the role of this area in more specific processes related to motor preparation and initiation. PMID:22262879

  8. Strong-field dissociation of CS2+ via a pump/dump-like mechanism

    Science.gov (United States)

    Severt, T.; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Jochim, Bethany; Carnes, K. D.; Zeng, S.; Esry, B. D.; Ben-Itzhak, I.; Uhlíková, T.

    2014-05-01

    Laser-induced dissociation of the quasi-bound electronic ground state of CS2+ is investigated in intense laser pulses (pump/dump-like mechanism to explain this observed feature. Contrary to the conventional pump/dump control scheme, this process occurs within a single laser pulse, where the time delay is caused by the molecular structure. The process begins when the vibrational wavepacket in the electronic ground state of CS2+ is pumped into the electronic first excited state's continuum by a single photon. After a period of stretching at an energy above the potential barrier, the emission of a second photon is stimulated by the same laser pulse, most likely at the Condon point. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, Grants DE-FG02-86ER13491 and DE-FG02-09ER16115. TU supported by GACR and MetaCentrum.

  9. 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

  10. Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism

    Science.gov (United States)

    Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

    2015-01-01

    Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in-situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h~0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding. PMID:25856773

  11. Mechanical Performance of Asphalt Mortar Containing Hydrated Lime and EAFSS at Low and High Temperatures.

    Science.gov (United States)

    Moon, Ki Hoon; Falchetto, Augusto Cannone; Wang, Di; Riccardi, Chiara; Wistuba, Michael P

    2017-07-03

    In this paper, the possibility of improving the global response of asphalt materials for pavement applications through the use of hydrated lime and Electric Arc-Furnace Steel Slag (EAFSS) was investigated. For this purpose, a set of asphalt mortars was prepared by mixing two different asphalt binders with fine granite aggregate together with hydrated lime or EAFSS at three different percentages. Bending Beam Rheometer (BBR) creep tests and Dynamic Shear Rheometer (DSR) complex modulus tests were performed to evaluate the material response both at low and high temperature. Then, the rheological Huet model was fitted to the BBR creep results for estimating the impact of filler content on the model parameters. It was found that an addition of hydrated lime and EAFSS up to 10% and 5%, respectively, results in satisfactory low-temperature performance with a substantial improvement of the high-temperature behavior.

  12. Mechanical Performance of Asphalt Mortar Containing Hydrated Lime and EAFSS at Low and High Temperatures

    Directory of Open Access Journals (Sweden)

    Ki Hoon Moon

    2017-07-01

    Full Text Available In this paper, the possibility of improving the global response of asphalt materials for pavement applications through the use of hydrated lime and Electric Arc-Furnace Steel Slag (EAFSS was investigated. For this purpose, a set of asphalt mortars was prepared by mixing two different asphalt binders with fine granite aggregate together with hydrated lime or EAFSS at three different percentages. Bending Beam Rheometer (BBR creep tests and Dynamic Shear Rheometer (DSR complex modulus tests were performed to evaluate the material response both at low and high temperature. Then, the rheological Huet model was fitted to the BBR creep results for estimating the impact of filler content on the model parameters. It was found that an addition of hydrated lime and EAFSS up to 10% and 5%, respectively, results in satisfactory low-temperature performance with a substantial improvement of the high-temperature behavior.

  13. A dissociation mechanism for the [a+c] dislocation in GaN

    International Nuclear Information System (INIS)

    Nellist, P D; Hirsch, P B; Lozano, J G; Rhode, S; Zhang, S; Kappers, M J; Humphreys, C J; Horton, M K; Moram, M A; Yasuhara, A; Okunishi, E; Sahonta, S-L

    2014-01-01

    Mixed-type [a+c] dislocations can be identified in atomic-resolution high-angle annular dark-field scanning transmission electron microscope images of GaN viewed along [0001] by use of a Burgers loop analysis and by observation of the depth-dependent displacements associated with the Eshelby twist. These dislocations are found to be able to dissociate resulting in a fault that lies perpendicular to the dislocation glide plane. Consideration of the bonding that occurs in such a fault allows the dissociation reaction to be proposed, and the proposed fault agrees with the experimental images when kinks are incorporated into the model

  14. Unraveling the reaction mechanism on nitrile hydration catalyzed by [Pd(OH2)4]2+: insights from theory.

    Science.gov (United States)

    Tílvez, Elkin; Menéndez, María I; López, Ramón

    2013-07-01

    Density functional theory methodologies combined with continuum and discrete-continuum descriptions of solvent effects were used to investigate the [Pd(OH2)4](2+)-catalyzed acrylonitrile hydration to yield acrylamide. According to our results, the intramolecular hydroxide attack mechanism and the external addition mechanism of a water molecule with rate-determining Gibbs energy barriers in water solution of 27.6 and 28.3 kcal/mol, respectively, are the most favored. The experimental kinetic constants of the hydration started by hydroxide, k(OH), and water, k(H2O), attacks for the cis-[Pd(en)(OH2)2](2+)-catalyzed dichloroacetonitrile hydration rendered Gibbs energy barriers whose energy difference, 0.7 kcal/mol, is the same as that obtained in the present study. Our investigation reveals the nonexistence of the internal attack of a water ligand for Pd-catalyzed nitrile hydration. At the low pHs used experimentally, the equilibrium between [Pd(OH2)3(nitrile)](2+) and [Pd(OH2)2(OH)(nitrile)](+) is completely displaced to [Pd(OH2)3(nitrile)](2+). Experimental studies in these conditions stated that water acts as a nucleophile, but they could not distinguish whether it was a water ligand, an external water molecule, or a combination of both possibilities. Our theoretical explorations clearly indicate that the external water mechanism becomes the only operative one at low pHs. On the basis of this mechanistic proposal it is also possible to ascribe an (1)H NMR signal experimentally detected to the presence of a unidentate iminol intermediate and to explain the influence of nitrile concentration reported experimentally for nitriles other than acrylonitrile in the presence of aqua-Pd(II) complexes. Therefore, our theoretical point of view on the mechanism of nitrile hydration catalyzed by aqua-Pd(II) complexes can shed light on these relevant processes at a molecular level as well as afford valuable information that can help in designing new catalysts in milder and more

  15. Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg2+ Effects by Quantum Chemical Calculations.

    Science.gov (United States)

    Wang, Se; Wang, Zhuang

    2017-11-11

    The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg 2+ effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR 2+ direct photolysis pathways were de-ethylation (N7-C8 bond cleavage) and decarboxylation (C2-C5 bond cleavage). Furthermore, the presence of Mg 2+ changed the order of the wavelength at maximum electronic absorbance (NOR⁺-Mg 2+ direct photolysis of NOR⁰, NOR⁺, and NOR 2+ . The calculated TS results indicated that the presence of Mg 2+ increased E a for most direct photolysis pathways of NOR, while it decreased E a for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR⁰ and the defluorination of NOR⁺.

  16. Physical and Mechanical Properties of Surface Sediments and methane hydrate-bearing sediments in the Shenhu area of South China Sea

    Science.gov (United States)

    Jiang, J.; Shen, Z.; Jia, Y.

    2017-12-01

    Methane hydrates are superior energy resources and potential predisposing factors of geohazard. With the success in China's persistent exploitation of methane hydrates in the Shenhu area of South China Sea for 60 days, there is an increasing demand for detailed knowledge of sediment properties and hazard assessment in this area. In this paper, the physical and mechanical properties of both the surface sediments and methane hydrate-bearing sediments (MHBS) in the exploitation area, the Shenhu area of South China Sea, were investigated using laboratory geotechnical experiments, and triaxial tests were carried out on remolded sediment samples using a modified triaxial apparatus. The results show that sediments in this area are mainly silt with high moisture content, high plasticity, low permeability and low shear strength. The moisture content and permeability decrease while the shear strength increases with the increasing depth. The elastic modulus and peak strength of MHBS increase with the increasing effective confining pressure and higher hydrate saturation. The cohesion increases with higher hydrate saturation while the internal friction angle is barely affected by hydrate saturation. The obtained results demonstrate clearly that methane hydrates have significant impacts on the physical and mechanical properties of sediments and there is still a wide gap in knowledge about MHBS.

  17. 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.

  18. A mechanism for vertebrate Hedgehog signaling: recruitment to cilia and dissociation of SuFu-Gli protein complexes.

    Science.gov (United States)

    Tukachinsky, Hanna; Lopez, Lyle V; Salic, Adrian

    2010-10-18

    In vertebrates, Hedgehog (Hh) signaling initiated in primary cilia activates the membrane protein Smoothened (Smo) and leads to activation of Gli proteins, the transcriptional effectors of the pathway. In the absence of signaling, Gli proteins are inhibited by the cytoplasmic protein Suppressor of Fused (SuFu). It is unclear how Hh activates Gli and whether it directly regulates SuFu. We find that Hh stimulation quickly recruits endogenous SuFu-Gli complexes to cilia, suggesting a model in which Smo activates Gli by relieving inhibition by SuFu. In support of this model, we find that Hh causes rapid dissociation of the SuFu-Gli complex, thus allowing Gli to enter the nucleus and activate transcription. Activation of protein kinase A (PKA), an inhibitor of Hh signaling, blocks ciliary localization of SuFu-Gli complexes, which in turn prevents their dissociation by signaling. Our results support a simple mechanism in which Hh signals at vertebrate cilia cause dissociation of inactive SuFu-Gli complexes, a process inhibited by PKA.

  19. A mechanism for vertebrate Hedgehog signaling: recruitment to cilia and dissociation of SuFu–Gli protein complexes

    Science.gov (United States)

    Tukachinsky, Hanna; Lopez, Lyle V.

    2010-01-01

    In vertebrates, Hedgehog (Hh) signaling initiated in primary cilia activates the membrane protein Smoothened (Smo) and leads to activation of Gli proteins, the transcriptional effectors of the pathway. In the absence of signaling, Gli proteins are inhibited by the cytoplasmic protein Suppressor of Fused (SuFu). It is unclear how Hh activates Gli and whether it directly regulates SuFu. We find that Hh stimulation quickly recruits endogenous SuFu–Gli complexes to cilia, suggesting a model in which Smo activates Gli by relieving inhibition by SuFu. In support of this model, we find that Hh causes rapid dissociation of the SuFu–Gli complex, thus allowing Gli to enter the nucleus and activate transcription. Activation of protein kinase A (PKA), an inhibitor of Hh signaling, blocks ciliary localization of SuFu–Gli complexes, which in turn prevents their dissociation by signaling. Our results support a simple mechanism in which Hh signals at vertebrate cilia cause dissociation of inactive SuFu–Gli complexes, a process inhibited by PKA. PMID:20956384

  20. Furfural: The Unimolecular Dissociative Photoionization Mechanism of the Simplest Furanic Aldehyde.

    Science.gov (United States)

    Winfough, Matthew; Voronova, Krisztina; Muller, Giel; Laguisma, Gabrielle; Sztáray, Bálint; Bodi, Andras; Meloni, Giovanni

    2017-05-11

    The unimolecular dissociation reactions of energy-selected furfural cations have been studied by imaging photoelectron photoion coincidence spectroscopy at the vacuum-ultraviolet (VUV) beamline of the Swiss Light Source. In the photon energy range of 10.9-14.5 eV, furfural ions decay by numerous fragmentation channels. Modeling the breakdown diagram yielded the 0 K appearance energies of 10.95 ± 0.10, 11.16, and 12.03 eV for the c-C 4 H 3 O-CO + (m/z = 95), c-C 4 H 4 O + (m/z = 68), and c-C 3 H 3 + (m/z = 39) fragment ions, respectively, formed by parallel dissociation channels. An internal conversion from the A″ to the A' electronic state via a conical intersection takes place along the reaction coordinate in the case of the H-loss channel (c-C 4 H 3 O-CO + formation). Quantum chemical calculations and experimental results confirmed a fast conversion to the A' state and that the rate-determining step is a tight transition state on the potential energy surface. Appearance energies were also derived for the sequential dissociation products from the furan cation, c-C 4 H 4 O + , for the formation of CH 2 CO + (m/z = 42), C 3 H 4 + (m/z = 40), and CHO + (m/z = 29) at 12.81, 12.80, and 13.34 eV, respectively. Statistical rate theory modeling of the breakdown diagram can also be used to predict the fractional ion abundances and thermal shifts in mass spectrometric pyrolysis studies to help assigning the m/z channels either to ionization of the neutrals or to dissociative ionization processes, with potential use for combustion diagnostics. The cationic geometry optimizations yielded functional-dependent spurious DFT minima and a deviating planar MP2 optimized geometry, which are briefly discussed.

  1. Dissociation mechanism of HNIW ions investigated by chemical ionization and electron impact mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rongjie; Xiao, Hemiao [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

    2006-04-15

    Chemical Ionization (CI) with Collision-Induced Dissociation (CID) spectroscopy and Electron Impacting (EI) with metastable Mass analyzed Ion Kinetic Energy (MIKE) spectroscopy have been applied to study ionic dissociations of Hexanitrohexaazaisowurtzitane (HNIW). Similarities and differences between EI/MIKE and CI/CID mass spectra of HNIW were analyzed. In EI mass spectra, the ions [HNIW-n NO{sub 2}]{sup +} (n=2-5), such as the ion at m/z 347, were less frequent (1-2% relative abundance), but in CI mass spectra, these ions were very abundant. For some ions of large molar mass from HNIW, their dissociations pathways from parent ions to daughter ions were built according to CID and MIKE spectra. Molecular ions of HNIW with a protonated nitro group at five-member ring seem more stable than at six-member ring. The HNIW ions losing five of six nitro groups are very stable based on CID spectra, which agrees with some research results for thermal decomposition of HNIW in literature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  2. A Study on the quantification of hydration and the strength development mechanism of cementitious materials including amorphous phases by using XRD/Rietveld method

    International Nuclear Information System (INIS)

    Yamada, Kazuo; Hoshino, Seiichi; Hirao, Hiroshi; Yamashita, Hiroki

    2008-01-01

    X-ray diffraction (XRD)/Rietveld method was applied to measure the phase composition of cement. The quantative analysis concerning the progress of hydration was accomplished in an error of about the maximum 2-3% in spite of including amorphous materials such as blast furnace slag, fly ash, silica fume and C-S-H. The influence of the compressive strength on the lime stone fine powder mixture material was studied from the hydration analysis by Rietveld method. The two stages were observed in the strength development mechanism of cement; the hydration promotion of C 3 S in the early stage and the filling of cavities by carbonate hydrate for the longer term. It is useful to use various mixture materials for the formation of the resource recycling society and the durability improvement of concrete. (author)

  3. A Molecular Dynamics-Quantum Mechanics Theoretical Study of DNA-Mediated Charge Transport in Hydrated Ionic Liquids.

    Science.gov (United States)

    Meng, Zhenyu; Kubar, Tomas; Mu, Yuguang; Shao, Fangwei

    2018-05-08

    Charge transport (CT) through biomolecules is of high significance in the research fields of biology, nanotechnology, and molecular devices. Inspired by our previous work that showed the binding of ionic liquid (IL) facilitated charge transport in duplex DNA, in silico simulation is a useful means to understand the microscopic mechanism of the facilitation phenomenon. Here molecular dynamics simulations (MD) of duplex DNA in water and hydrated ionic liquids were employed to explore the helical parameters. Principal component analysis was further applied to capture the subtle conformational changes of helical DNA upon different environmental impacts. Sequentially, CT rates were calculated by a QM/MM simulation of the flickering resonance model based upon MD trajectories. Herein, MD simulation illustrated that the binding of ionic liquids can restrain dynamic conformation and lower the on-site energy of the DNA base. Confined movement among the adjacent base pairs was highly related to the increase of electronic coupling among base pairs, which may lead DNA to a CT facilitated state. Sequentially combining MD and QM/MM analysis, the rational correlations among the binding modes, the conformational changes, and CT rates illustrated the facilitation effects from hydrated IL on DNA CT and supported a conformational-gating mechanism.

  4. Influence of supplementary cementitious materials on water transport kinetics and mechanical properties of hydrated lime and cement mortars

    Directory of Open Access Journals (Sweden)

    Ince, C.

    2015-06-01

    Full Text Available The purpose of this paper is an investigation of the possible role of supplementary cementitious materials (SCMs on water transport kinetics and mechanical properties of hydrated lime (CL90 and Portland cement (PC mortars. The properties of hydrated lime are significantly different from those of cement and therefore modifying fresh and hardened properties of these mortars are vital for mortar/substrate optimisation in masonry construction. The parameters investigated in this paper often are the main barriers to the use of hydrated lime in construction practice. The results show that transfer sorptivity and time to dewater freshly-mixed hydrated lime mortars can be modified when binder is partially replaced with SCMs. Compressive strength of CL90 mortars is increased systematically with the increased replacement levels of SCMs and the results are supported with the microstructural images. The ability to modify the water transport kinetics and mechanical properties allows compatibility between the mortar and the substrate unit in masonry construction.El objetivo de este artículo es investigar el papel de los materiales cementantes suplementarios (SCMs en la cinética de transporte del agua y en las propiedades mecánicas de los morteros de cal hidratada (CL90 y cemento Portland. Las propiedades de la cal hidratada son significativamente diferentes a las del cemento y por lo tanto el control de las propiedades de los morteros frescos y endurecidos es fundamental en la optimización mortero/substrato en albañilería. Los parámetros estudiados en este trabajo son a menudo las principales barreras para el uso de la cal hidratada en la práctica de la construcción. Los resultados indican que la absortividad y el tiempo necesario para deshidratar morteros de cal hidratada recién mezclados pueden ser controlados cuando el conglomerante es parcialmente remplazado por SCMs. La resistencia a compresión de los morteros CL90 aumenta sistem

  5. Dissociation in small molecules

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1982-01-01

    The study of molecular dissociation processes is one of the most interesting areas of modern spectroscopy owing to the challenges presented bt even the simplest of diatomic molecules. This paper reviews the commonly used descriptions of molecular dissociation processes for diatomic molecules, the selection rules for predissociation, and a few of the principles to be remembered when one is forced to speculate about dissociation mechanisms in a new molecule. Some of these points will be illustrated by the example of dissociative ionization in O 2

  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. New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

    International Nuclear Information System (INIS)

    Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

    2016-01-01

    The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

  8. 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.

  9. 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.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  11. Discrete element analysis of the mechanical properties of deep-sea methane hydrate-bearing soils considering interparticle bond thickness

    Science.gov (United States)

    Jiang, Mingjing; He, Jie; Wang, Jianfeng; Zhou, Yaping; Zhu, Fangyuan

    2017-12-01

    Due to increasing global energy demands, research is being conducted on the mechanical properties of methane hydrate-bearing soils (MHBSs), from which methane hydrate (MH) will be explored. This paper presents a numerical approach to study the mechanical properties of MHBSs. The relationship between the level of MH saturation and the interparticle bond thickness is first obtained by analyzing the scanning electron microscope images of MHBS samples, in which is the bridge connecting the micromechanical behavior captured by the DEM with the macroscopic properties of MHBSs. A simplified thermal-hydromechanical (THM) bond model that considers the different bond thicknesses is then proposed to describe the contact behavior between the soil particles and those incorporated into the discrete element method (DEM). Finally, a series of biaxial compression tests are carried out with different MH saturations under different effective confining pressures to analyze the mechanical properties of deep-sea MHBSs. The results of the DEM numerical simulation are also compared with the findings from triaxial compression tests. The results show that the macromechanical properties of deep-sea MHBSs can be qualitatively captured by the proposed DEM. The shear strength, cohesion, and volumetric contraction of deep-sea MHBSs increase with increasing MH saturation, although its influence on the internal friction angle is obscure. The shear strength and volumetric contraction increase with increasing effective confining pressure. The peak shear strength and the dilation of MHBSs increase as the critical bond thickness increases, while the residual deviator stress largely remains the same at a larger axial strain. With increasing the axial strain, the percentage of broken bonds increases, along with the expansion of the shear band.

  12. Monte-Carlo simulations of geminate electron-hole pair dissociation in a molecular heterojunction: a two-step dissociation mechanism

    International Nuclear Information System (INIS)

    Offermans, Ton; Meskers, Stefan C.J.; Janssen, Rene A.J.

    2005-01-01

    The Monte-Carlo simulations are used to investigate the dissociation of a Coulomb correlated charge pair at an idealized interface between an electron accepting and an electron donating molecular material. In the simulations the materials are represented by cubic lattices of sites, with site the energies spread according to Gaussian distributions. The influence of temperature, applied external fields, and the width of the Gaussian densities of states distribution for both the electron and the hole transporting material are investigated. The results show that the dissociation of geminate charge pairs is assisted by disorder and the results can be understood in terms of a two-step model. In the first step, the slow carrier in the most disordered material jumps away from the interface. In the following, second step, the reduced Coulombic attraction allows the faster carrier in the less disordered material to escape from the interface by thermally activated hopping. When the rate for geminate recombination at the interface is very low ( -1 ) the simulations predict a high yield for carrier collection, as observed experimentally. Comparison of the simulated and experimentally observed temperature dependence of the collection efficiency indicates that at low temperature dissociation of the geminate charge pairs may be one of the factors limiting the device performance

  13. Decomposition of methane hydrate for hydrogen production using microwave and radio frequency in-liquid plasma methods

    International Nuclear Information System (INIS)

    Rahim, Ismail; Nomura, Shinfuku; Mukasa, Shinobu; Toyota, Hiromichi

    2015-01-01

    This research involves two in-liquid plasma methods of methane hydrate decomposition, one using radio frequency wave (RF) irradiation and the other microwave radiation (MW). The ultimate goal of this research is to develop a practical process for decomposition of methane hydrate directly at the subsea site for fuel gas production. The mechanism for methane hydrate decomposition begins with the dissociation process of methane hydrate formed by CH_4 and water. The process continues with the simultaneously occurring steam methane reforming process and methane cracking reaction, during which the methane hydrate is decomposed releasing CH_4 into H_2, CO and other by-products. It was found that methane hydrate can be decomposed with a faster rate of CH_4 release using microwave irradiation over that using radio frequency irradiation. However, the radio frequency plasma method produces hydrogen with a purity of 63.1% and a CH conversion ratio of 99.1%, which is higher than using microwave plasma method which produces hydrogen with a purity of 42.1% and CH_4 conversion ratio of 85.5%. - Highlights: • The decomposition of methane hydrate is proposed using plasma in-liquid method. • Synthetic methane hydrate is used as the sample for decomposition in plasma. • Hydrogen can be produced from decomposition of methane hydrate. • Hydrogen purity is higher when using radio frequency stimulation.

  14. Electron microscopic evidence for the myosin head lever arm mechanism in hydrated myosin filaments using the gas environmental chamber

    International Nuclear Information System (INIS)

    Minoda, Hiroki; Okabe, Tatsuhiro; Inayoshi, Yuhri; Miyakawa, Takuya; Miyauchi, Yumiko; Tanokura, Masaru; Katayama, Eisaku; Wakabayashi, Takeyuki; Akimoto, Tsuyoshi; Sugi, Haruo

    2011-01-01

    Research highlights: → We succeeded in recording structural changes of hydrated myosin cross-bridges. → We succeeded in position-marking the cross-bridges with site-directed antibodies. → We recorded cross-bridge movement at different regions in individual cross-bridge. → The movement was smallest at the cross-bridge-subfragment two boundary. → The results provide evidence for the cross-bridge lever arm mechanism. -- Abstract: Muscle contraction results from an attachment-detachment cycle between the myosin heads extending from myosin filaments and the sites on actin filaments. The myosin head first attaches to actin together with the products of ATP hydrolysis, performs a power stroke associated with release of hydrolysis products, and detaches from actin upon binding with new ATP. The detached myosin head then hydrolyses ATP, and performs a recovery stroke to restore its initial position. The strokes have been suggested to result from rotation of the lever arm domain around the converter domain, while the catalytic domain remains rigid. To ascertain the validity of the lever arm hypothesis in muscle, we recorded ATP-induced movement at different regions within individual myosin heads in hydrated myosin filaments, using the gas environmental chamber attached to the electron microscope. The myosin head were position-marked with gold particles using three different site-directed antibodies. The amplitude of ATP-induced movement at the actin binding site in the catalytic domain was similar to that at the boundary between the catalytic and converter domains, but was definitely larger than that at the regulatory light chain in the lever arm domain. These results are consistent with the myosin head lever arm mechanism in muscle contraction if some assumptions are made.

  15. Free energies of binding from large-scale first-principles quantum mechanical calculations: application to ligand hydration energies.

    Science.gov (United States)

    Fox, Stephen J; Pittock, Chris; Tautermann, Christofer S; Fox, Thomas; Christ, Clara; Malcolm, N O J; Essex, Jonathan W; Skylaris, Chris-Kriton

    2013-08-15

    Schemes of increasing sophistication for obtaining free energies of binding have been developed over the years, where configurational sampling is used to include the all-important entropic contributions to the free energies. However, the quality of the results will also depend on the accuracy with which the intermolecular interactions are computed at each molecular configuration. In this context, the energy change associated with the rearrangement of electrons (electronic polarization and charge transfer) upon binding is a very important effect. Classical molecular mechanics force fields do not take this effect into account explicitly, and polarizable force fields and semiempirical quantum or hybrid quantum-classical (QM/MM) calculations are increasingly employed (at higher computational cost) to compute intermolecular interactions in free-energy schemes. In this work, we investigate the use of large-scale quantum mechanical calculations from first-principles as a way of fully taking into account electronic effects in free-energy calculations. We employ a one-step free-energy perturbation (FEP) scheme from a molecular mechanical (MM) potential to a quantum mechanical (QM) potential as a correction to thermodynamic integration calculations within the MM potential. We use this approach to calculate relative free energies of hydration of small aromatic molecules. Our quantum calculations are performed on multiple configurations from classical molecular dynamics simulations. The quantum energy of each configuration is obtained from density functional theory calculations with a near-complete psinc basis set on over 600 atoms using the ONETEP program.

  16. Hydrated Ordinary Portland Cement as a Carbonic Cement: The Mechanisms, Dynamics, and Implications of Self-Sealing and CO2 Resistance in Wellbore Cements

    Energy Technology Data Exchange (ETDEWEB)

    Guthrie, George Drake Jr. [Los Alamos National Laboratory; Pawar, Rajesh J. [Los Alamos National Laboratory; Carey, James William [Los Alamos National Laboratory; Karra, Satish [Los Alamos National Laboratory; Harp, Dylan Robert [Los Alamos National Laboratory; Viswanathan, Hari S. [Los Alamos National Laboratory

    2017-07-28

    This report analyzes the dynamics and mechanisms of the interactions of carbonated brine with hydrated Portland cement. The analysis is based on a recent set of comprehensive reactive-transport simulations, and it relies heavily on the synthesis of the body of work on wellbore integrity that we have conducted for the Carbon Storage Program over the past decade.

  17. 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

  18. Numerical analysis of wellbore instability in gas hydrate formation during deep-water drilling

    Science.gov (United States)

    Zhang, Huaiwen; Cheng, Yuanfang; Li, Qingchao; Yan, Chuanliang; Han, Xiuting

    2018-02-01

    Gas hydrate formation may be encountered during deep-water drilling because of the large amount and wide distribution of gas hydrates under the shallow seabed of the South China Sea. Hydrates are extremely sensitive to temperature and pressure changes, and drilling through gas hydrate formation may cause dissociation of hydrates, accompanied by changes in wellbore temperatures, pore pressures, and stress states, thereby leading to wellbore plastic yield and wellbore instability. Considering the coupling effect of seepage of drilling fluid into gas hydrate formation, heat conduction between drilling fluid and formation, hydrate dissociation, and transformation of the formation framework, this study established a multi-field coupling mathematical model of the wellbore in the hydrate formation. Furthermore, the influences of drilling fluid temperatures, densities, and soaking time on the instability of hydrate formation were calculated and analyzed. Results show that the greater the temperature difference between the drilling fluid and hydrate formation is, the faster the hydrate dissociates, the wider the plastic dissociation range is, and the greater the failure width becomes. When the temperature difference is greater than 7°C, the maximum rate of plastic deformation around the wellbore is more than 10%, which is along the direction of the minimum horizontal in-situ stress and associated with instability and damage on the surrounding rock. The hydrate dissociation is insensitive to the variation of drilling fluid density, thereby implying that the change of the density of drilling fluids has a minimal effect on the hydrate dissociation. Drilling fluids that are absorbed into the hydrate formation result in fast dissociation at the initial stage. As time elapses, the hydrate dissociation slows down, but the risk of wellbore instability is aggravated due to the prolonged submersion in drilling fluids. For the sake of the stability of the wellbore in deep

  19. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

    International Nuclear Information System (INIS)

    Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

    2011-01-01

    The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C 3 S, β-C 2 S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of β-C 2 S and the 30-70 (T1-C 3 S and β-C 2 S mixture) are higher than those from hydration of T1-C 3 S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C 2 S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 2 9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

  20. 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

  1. The mechanisms and process of acephate degradation by hydroxyl radical and hydrated electron

    Directory of Open Access Journals (Sweden)

    Yuanyuan Huang

    2018-02-01

    Full Text Available The degradation process of acephate in aqueous solution with ·OH and eaq− produced by 60Co-γ irradiation and electron pulse radiolysis was studied in the present paper. In the aqueous solution, acephate reacted with eaq− and transformed to transient species which can absorb weakly in the wavelength range of 300–400 nm and decay very fast. According to the decay of hydrated electron, the reaction rate constant of eaq− and acephate is (3.51 ± 0.076 × 109 dm3·mol−1·s−1. The transient species produced in the reaction of ·OH and acephate do not distinctly absorb the light in the wavelength range of 300–700 nm, so the decay and kinetics of the transient species cannot determinedirectly. The competing reaction of KSCN oracephate with ·OH were studied to obtain the reaction rate constant of ·OH and acephate, which is (9.1 ± 0.11 × 108 dm3·mol−1·s−1. Although acetylamide and inorganic ions were determined in the products of the reaction of acephate with ·OH or eaq−, the concentration of inorganic ions in the products of the reaction of acephate with ·OH is higher than that in the product of the reaction of acephate with eaq−. Moreover, there were sulfide in the products of the reaction of acephatewith eaq−. The degradation pathways of acephate by ·OH and eaq− were also proposed based on the products from GC-MS.

  2. Influence of Electron Molecule Resonant Vibrational Collisions over the Symmetric Mode and Direct Excitation-Dissociation Cross Sections of CO2 on the Electron Energy Distribution Function and Dissociation Mechanisms in Cold Pure CO2 Plasmas.

    Science.gov (United States)

    Pietanza, L D; Colonna, G; Laporta, V; Celiberto, R; D'Ammando, G; Laricchiuta, A; Capitelli, M

    2016-05-05

    A new set of electron-vibrational (e-V) processes linking the first 10 vibrational levels of the symmetric mode of CO2 is derived by using a decoupled vibrational model and inserted in the Boltzmann equation for the electron energy distribution function (eedf). The new eedf and dissociation rates are in satisfactory agreement with the corresponding ones obtained by using the e-V cross sections reported in the database of Hake and Phelps (H-P). Large differences are, on the contrary, found when the experimental dissociation cross sections of Cosby and Helm are inserted in the Boltzman equation. Comparison of the corresponding rates with those obtained by using the low-energy threshold energy, reported in the H-P database, shows differences up to orders of magnitude, which decrease with the increasing of the reduced electric field. In all cases, we show the importance of superelastic vibrational collisions in affecting eedf and dissociation rates either in the direct electron impact mechanism or in the pure vibrational mechanism.

  3. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    Science.gov (United States)

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-03-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.

  4. 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...

  5. 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

    the reservoir is minimized. Our results clearly indicate that the formation of mixed CH4-CO2-hydrates is an important aspect in the conversion process. The experimental studies have shown that the injection of heated CO2 into the hydrate reservoir induces a variety of spatial and temporal processes which result in substantial bulk heterogeneity. Current numerical simulators are not able to predict these process dynamics and it is important to improve available transport-reaction models (e.g. to include the effect of bulk sediment permeability on the conversion dynamics). Our results confirm that experimental studies are important to better understand the mechanisms of hydrate dissociation and conversion at CO2-injection conditions as a basis towards the development of a suitable hydrate conversion technology. The application of non-invasive analytical methods such as Magnetic Resonance Imaging (MRI) and Raman microscopy are important tools, which were applied to resolve process dynamics on the pore scale. Additionally, the NESSI system is being modified to allow high-pressure flow-through experiments under triaxial loading to better simulate hydrate-sediment mechanics. This aspect is important for overall process development and evaluation of process safety issues.

  6. 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)

  7. 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.

  8. Levels of word processing and incidental memory: dissociable mechanisms in the temporal lobe.

    Science.gov (United States)

    Castillo, E M; Simos, P G; Davis, R N; Breier, J; Fitzgerald, M E; Papanicolaou, A C

    2001-11-16

    Word recall is facilitated when deep (e.g. semantic) processing is applied during encoding. This fact raises the question of the existence of specific brain mechanisms supporting different levels of information processing that can modulate incidental memory performance. In this study we obtained spatiotemporal brain activation profiles, using magnetic source imaging, from 10 adult volunteers as they performed a shallow (phonological) processing task and a deep (semantic) processing task. When phonological analysis of the word stimuli into their constituent phonemes was required, activation was largely restricted to the posterior portion of the left superior temporal gyrus (area 22). Conversely, when access to lexical/semantic representations was required, activation was found predominantly in the left middle temporal gyrus and medial temporal cortex. The differential engagement of each mechanism during word encoding was associated with dramatic changes in subsequent incidental memory performance.

  9. 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

  10. The Sense of Agency in Autism Spectrum Disorders: a Dissociation between Prospective and Retrospective Mechanisms?

    Directory of Open Access Journals (Sweden)

    Tiziana eZalla

    2015-09-01

    Full Text Available While a large number of studies have reported impairments in social and interpersonal abilities in individuals with autism spectrum disorder (ASD, relatively few studies have focused on self-related knowledge in this population. One of the processes implicated in the physical dimension of the Self is the sense of agency (SoA, i.e., the experience of initiating and controlling one’s own actions and producing desired changes in the world via these actions. So far, the few studies investigating SoA in ASD have reported contrasting results, with some showing spared, others impaired SoA. Here, we review the existing literature and suggest that the distinction between prospective and retrospective mechanisms of the SoA might help reconcile the existing findings. In the light of a multi-componential model of SoA, we propose the view that a specific impairment at the level of prospective mechanisms acting on internal agency signals (i.e., the intention, action selection, or command produced to achieve the goal may be responsible for the reduced SoA in ASD, along with spared retrospective mechanisms. Future research should shed light on the impact of abnormal SoA on social and self-related dysfunctions in ASD.

  11. Dissociation in decision bias mechanism between probabilistic information and previous decision

    Directory of Open Access Journals (Sweden)

    Yoshiyuki eKaneko

    2015-05-01

    Full Text Available Target detection performance is known to be influenced by events in the previous trials. It has not been clear, however, whether this bias effect is due to the previous sensory stimulus, motor response, or decision. Also it remains open whether or not the previous trial effect emerges via the same mechanism as the effect of knowledge about the target probability. In the present study, we asked normal human subjects to make a decision about the presence or absence of a visual target. We presented a pre-cue indicating the target probability before the stimulus, and also a decision-response mapping cue after the stimulus so as to tease apart the effect of decision from that of motor response. We found that the target detection performance was significantly affected by the probability cue in the current trial and also by the decision in the previous trial. While the information about the target probability modulated the decision criteria, the previous decision modulated the sensitivity to target-relevant sensory signals (d-prime. Using functional magnetic resonance imaging, we also found that activation in the left intraparietal sulcus was decreased when the probability cue indicated a high probability of the target. By contrast, activation in the right inferior frontal gyrus was increased when the subjects made a target-present decision in the previous trial, but this change was observed specifically when the target was present in the current trial. Activation in these regions was associated with individual-difference in the decision computation parameters. We argue that the previous decision biases the target detection performance by modulating the processing of target-selective information, and this mechanism is distinct from modulation of decision criteria due to expectation of a target.

  12. Dissociation in decision bias mechanism between probabilistic information and previous decision

    Science.gov (United States)

    Kaneko, Yoshiyuki; Sakai, Katsuyuki

    2015-01-01

    Target detection performance is known to be influenced by events in the previous trials. It has not been clear, however, whether this bias effect is due to the previous sensory stimulus, motor response, or decision. Also it remains open whether or not the previous trial effect emerges via the same mechanism as the effect of knowledge about the target probability. In the present study, we asked normal human subjects to make a decision about the presence or absence of a visual target. We presented a pre-cue indicating the target probability before the stimulus, and also a decision-response mapping cue after the stimulus so as to tease apart the effect of decision from that of motor response. We found that the target detection performance was significantly affected by the probability cue in the current trial and also by the decision in the previous trial. While the information about the target probability modulated the decision criteria, the previous decision modulated the sensitivity to target-relevant sensory signals (d-prime). Using functional magnetic resonance imaging (fMRI), we also found that activation in the left intraparietal sulcus (IPS) was decreased when the probability cue indicated a high probability of the target. By contrast, activation in the right inferior frontal gyrus (IFG) was increased when the subjects made a target-present decision in the previous trial, but this change was observed specifically when the target was present in the current trial. Activation in these regions was associated with individual-difference in the decision computation parameters. We argue that the previous decision biases the target detection performance by modulating the processing of target-selective information, and this mechanism is distinct from modulation of decision criteria due to expectation of a target. PMID:25999844

  13. Hydration products and mechanical properties of hydroceramics solidified waste for simulated Non-alpha low and intermediate level radioactive wastes

    International Nuclear Information System (INIS)

    Wang Jin; Hong Ming; Wang Junxia; Li Yuxiang; Teng Yuancheng; Wu Xiuling

    2011-01-01

    In this paper, simulated non-alpha low and intermediate level radioactive wastes was handled as curing object and that of 'alkali-slag-coal fly ash-metakaolin' hydroceramics waste forms were prepared by hydrothermal synthesis method. The hydration products were analyzed by X ray diffraction. The composition of hydrates and the compressive strength of waste forms were determined and measured. The results indicate that the main crystalline phase of hydration products were analcite when the temperature was 150 to 180 degree C and the salt content ratio was 0.10 to 0.30. Analcite diffraction peaks in hydration products is increasing when the temperature was raised and the reaction time prolonged. Strength test results show that the solidified waste forms have superior compressive strength. The compressive strength gradually decreased with the increase in salt content ratio in waste forms. (authors)

  14. Dissociation reactions of the 11Be one-neutron halo: the interplay between structure and reaction mechanism

    International Nuclear Information System (INIS)

    Anne, R.; Lewitowicz, M.; Saint-Laurent, M.G.; Arnell, S.E.; Jonson, B.; Nilsson, T.; Nyman, G.; Wilhelmsen Rolander, K.; Esbensen, H.; Wolski, D.

    1992-01-01

    Reactions of a radioactive 11 Be beam at 41 MeV/u have been investigated. The absolute magnitude of the differential cross-sections of the forward neutrons in the exclusive ( 10 Be + n) channel can be accounted for quantitatively in a simple model. The narrow distribution from high-Z targets turns out to arise from Coulomb dissociation whereas the broad distribution from the beryllium target is due to diffraction dissociation

  15. 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 ...

  16. The dissociation mechanism and thermodynamic properties of HCl(aq) in hydrothermal fluids (to 700 °C, 60 kbar) by ab initio molecular dynamics simulations

    Science.gov (United States)

    Mei, Yuan; Liu, Weihua; Brugger, Joël; Sherman, David M.; Gale, Julian D.

    2018-04-01

    HCl is one of the most significant volatiles in the Earth's crust. It is well established that chloride activity and acidity (pH) play important roles in controlling the solubility of metals in aqueous hydrothermal fluids. Thus, quantifying the dissociation of HCl in aqueous solutions over a wide range of temperature and pressure is crucial for the understanding and numerical modeling of element mobility in hydrothermal fluids. Here we have conducted ab initio molecular dynamics (MD) simulations to investigate the mechanism of HCl(aq) dissociation and to calculate the thermodynamic properties for the dissociation reaction at 25-700 °C, 1 bar to 60 kbar, i.e. including high temperature and pressure conditions that are geologically important, but difficult to investigate via experiments. Our results predict that HCl(aq) tends to associate with increasing temperature, and dissociate with increasing pressure. In particular, HCl(aq) is highly dissociated at extremely high pressures, even at high temperatures (e.g., 60 kbar, 600-700 °C). At 25 °C, the calculated logKd values (6.79 ± 0.81) are close to the value (7.0) recommended by IUPAC (International Union of Pure and Applied Chemistry) and some previous experimental and theoretical studies (Simonson et al.., 1990; Sulpizi and Sprik, 2008, 2010). The MD simulations indicate full dissociation of HCl at low temperature; in contrast, some experiments were interpreted assuming significant association at high HCl concentrations (≥1 m HCltot) even at room T (logKd ∼0.7; e.g., Ruaya and Seward, 1987; Sretenskaya, 1992; review in Tagirov et al., 1997). This discrepancy is most likely the result of difficulties in the experimental determination of minor (if any) concentration of associated HCl(aq) under ambient conditions, and thus reflects differences in the activity models used for the interpretation of the experiments. With increasing temperature, the discrepancy between our MD results and previous experimental

  17. 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.

  18. Binding of Divalent Cations to Polygalacturonate: A Mechanism Driven by the Hydration Water.

    Science.gov (United States)

    Huynh, Uyen T D; Lerbret, Adrien; Neiers, Fabrice; Chambin, Odile; Assifaoui, Ali

    2016-02-11

    We have investigated the interactions between polygalacturonate (polyGal) and four divalent cations (M(2+) = Ba(2+), Ca(2+), Mg(2+), Zn(2+)) that differ in size and affinity for water. Our results evidence that M(2+)-polyGal interactions are intimately linked to the affinity of M(2+) for water. Mg(2+) interacts so strongly with water that it remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. In contrast, the other cations form transient ionic pairs with polyGal by releasing preferentially one water molecule (for Zn(2+)) or two (for Ca(2+) and Ba(2+)), which corresponds to monodentate and bidentate binding modes with carboxylates, respectively. The mechanism for the binding of these three divalent cations to polyGal can be described by two steps: (i) monocomplexation and formation of point-like cross-links between polyGal chains (at low M(2+)/Gal molar ratios, R) and (ii) dimerization (at higher R). The threshold molar ratio, R*, between these two steps depends on the nature of divalent cations and is lower for calcium ions (R* 0.3). This difference may be explained by the intermediate affinity of Ca(2+) for water with respect to those of Zn(2+) and Ba(2+), which may induce the formation of cross-links of intermediate flexibility. By comparison, the lower and higher flexibilities of the cross-links formed by Zn(2+) and Ba(2+), respectively, may shift the formation of dimers to higher molar ratios (R*).

  19. Gas hydrate formation in deep-sea sediments - on the role of sediment-mechanical process determination; Gashydratbildung in Tiefseesedimenten - zur Rolle der sedimentmechanischen Prozesssteuerung

    Energy Technology Data Exchange (ETDEWEB)

    Feeser, V. [Kiel Univ. (Germany). Geologisch-Palaeontologisches Inst.

    1997-12-31

    Slope failures in gas hydrate regions are encountered throughout the oceans. The stability of seafloor slopes can be assessed and predicted by means of calculation methods based on mechanical laws and parameters which describe the deformation behaviour and/or mechanical strength of the slope-forming sediments. Thermodynamic conditions conducive to the formation of gas hydrates in marine sediments differ from conditions prevailing in exclusively water-filled systems. The present contribution describes the relevant energetic conditions on the basis of a simple spherical model giving due consideration to petrographic parameters. Depending on pore size distribution, lithological stress conditions, pore water pressure, and sediment strength gas hydrates will either develop as a cementing phase or as segregated lenses. (MSK) [Deutsch] In den Weltmeeren ereignen sich immer wieder Hangrutschungen in Gashydratgebieten. Die zur Beurteilung und Prognonse von Hangstabilitaeten zu verwendenden Berechnungsverfahren erfordern Stoffgesetze und Parameter, welche das Deformations-und/oder Festigkeitsverhalten der hangbildenden Sedimente beschreiben. Die thermodynamischen Bildungsbedingungen von Gashydraten in marinen Sedimenten unterscheiden sich von den Bedingungen in ausschliesslich wassergefuellten Systemen. Unter Einbeziehung petrographischer Eigenschaften werden die energetischen Bedingungen beschrieben. Dazu dient ein einfaches Kugelmodell. Je nach vorhandenem Porenraumspektrum, lithostatischen Spannungsverhaeltnissen, Porenwasserdruck und Sedimentfestigkeit wachsen Gashydrate als Porenraumzement oder als segregierte Linsen.

  20. Promoting mechanism of N-doped single-walled carbon nanotubes for O2 dissociation and SO2 oxidation

    Science.gov (United States)

    Chen, Yanqiu; Yin, Shi; Chen, Yang; Cen, Wanglai; Li, Jianjun; Yin, Huaqiang

    2018-03-01

    Although heteroatom doping in carbon based catalysts have recently received intensive attentions, the role of the intrinsically porous structure of practical carbon materials and their potential synergy with doping atoms are still unclear. To investigate the complex effects, a range of N-doped single-walled carbon nanotubes (SWCNTs) were used to investigate their potential use for O2 dissociation and the subsequent SO2 oxidation using density functional theory. It is found that graphite N doping can synergize with the outer surface of SWCNTs to facilitate the dissociation of O2. The barrier for the dissociation on dual graphite N-doped SWCNT-(8, 8) is as low as 0.3 eV, and the subsequent SO2 oxidation is thermodynamically favorable and kinetically feasible. These results spotlight on developing promising carboncatalyst via utilization of porous gemometry and heteroatom-doping of carbon materials simultaneously.

  1. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly.

    Science.gov (United States)

    Ram, Dushad; Ashoka, H G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  2. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly

    OpenAIRE

    Ram, Dushad; Ashoka, H. G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  3. Hyperglycemia associated dissociative fugue (organic dissociative disorder in an elderly

    Directory of Open Access Journals (Sweden)

    Dushad Ram

    2015-01-01

    Full Text Available Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  4. 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.

  5. Transport Mechanisms for CO2-CH4 Exchange and Safe CO2 Storage in Hydrate-Bearing Sandstone

    Directory of Open Access Journals (Sweden)

    Knut Arne Birkedal

    2015-05-01

    Full Text Available CO2 injection in hydrate-bearing sediments induces methane (CH4 production while benefitting from CO2 storage, as demonstrated in both core and field scale studies. CH4 hydrates have been formed repeatedly in partially water saturated Bentheim sandstones. Magnetic Resonance Imaging (MRI and CH4 consumption from pump logs have been used to verify final CH4 hydrate saturation. Gas Chromatography (GC in combination with a Mass Flow Meter was used to quantify CH4 recovery during CO2 injection. The overall aim has been to study the impact of CO2 in fractured and non-fractured samples to determine the performance of CO2-induced CH4 hydrate production. Previous efforts focused on diffusion-driven exchange from a fracture volume. This approach was limited by gas dilution, where free and produced CH4 reduced the CO2 concentration and subsequent driving force for both diffusion and exchange. This limitation was targeted by performing experiments where CO2 was injected continuously into the spacer volume to maintain a high driving force. To evaluate the effect of diffusion length multi-fractured core samples were used, which demonstrated that length was not the dominating effect on core scale. An additional set of experiments is presented on non-fractured samples, where diffusion-limited transportation was assisted by continuous CO2 injection and CH4 displacement. Loss of permeability was addressed through binary gas (N2/CO2 injection, which regained injectivity and sustained CO2-CH4 exchange.

  6. A dissociative quantum mechanical/molecular mechanical molecular dynamics simulation and infrared experiments reveal characteristics of the strongly hydrolytic arsenic(III).

    Science.gov (United States)

    Canaval, Lorenz R; Lutz, Oliver M D; Weiss, Alexander K H; Huck, Christian W; Hofer, Thomas S

    2014-11-17

    This work presents a hybrid ab initio quantum mechanical/molecular mechanical simulation at the RI-MP2 level of theory investigating the hydrolysis process of arsenic(III), ultimately leading to arsenous acid (H3AsO3). A newly implemented dissociative water model has been applied to treat the interactions in the classical region, which is capable of describing non-neutral water species such as hydroxide and oxonium ions. Three stages of hydrolysis have been observed during the simulation and besides profound dynamical considerations, detailed insights into structural changes and atomic partial charge shifts are presented. In particular, the geometrical properties of H-bonds involved in each of the three proton transfer events and subsequent proton hopping reactions are discussed. A Laguerre tessellation analysis has been employed to estimate the molecular volume of H3AsO3. Estimations of pKa values of the arsenic(III)-aquo-complexes have been obtained at the G4 and CBS-Q//B3 levels of theory using a thermodynamic cycle, whereas rate constants for the final hydrolysis step have been determined via reaction path optimization and transition state theory. Newly recorded Fourier transform infrared (FT-IR) spectroscopy measurements have been compared to power spectra obtained from the simulation data, confirming its quality. The simulation findings, as well as results from computational spectroscopic calculations utilizing the PT2-VSCF methodology, proved valuable for the interpretation of the experimental FT-IR data, elucidating the particularities of the strongly observed IR Raman noncoincidence effect.

  7. Computational Material Modeling of Hydrated Cement Paste Calcium Silicate Hydrate (C-S-H) Chemistry Structure - Influence of Magnesium Exchange on Mechanical Stiffness: C-S-H Jennite

    Science.gov (United States)

    2015-04-27

    MODELING OF C-S-H Material chemistry level modeling following the principles and techniques commonly grouped under Computational Material Science is...Henmi, C. and Kusachi, I. Monoclinic tobermorite from fuka, bitchu-cho, Okoyama Perfecture. Japan J. Min. Petr. Econ . Geol. (1989)84:374-379. [22...31] Liu, Y. et al. First principles study of the stability and mechanical properties of MC (M=Ti, V, Zr, Nb, Hf and Ta) compounds. Journal of Alloys and Compounds. (2014) 582:500-504. 10

  8. 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.

  9. Multiphoton dissociation of polyatomic molecules

    International Nuclear Information System (INIS)

    Schulz, P.A.

    1979-10-01

    The dynamics of infrared multiphoton excitation and dissociation of SF 6 was investigated under collision free conditions by a crossed laser-molecular beam method. In order to understand the excitation mechanism and to elucidate the requirements of laser intensity and energy fluence, a series of experiments were carried out to measure the dissociation yield dependences on energy fluence, vibrational temperature of SF 6 , the pulse duration of the CO 2 laser and the frequency in both one and two laser experiments. Translational energy distributions of the SF 5 dissociation product measured by time of flight and angular distributions and the dissociation lifetime of excited SF 6 as inferred from the observation of secondary dissociation of SF 5 into SF 4 and F during the laser pulse suggest that the dynamics of dissociation of excited molecules is dominated by complete energy randomization and rapid intramolecular energy transfer on a nanosecond timescale, and can be adequately described by RRKM theory. An improved phenomenological model including the initial intensity dependent excitation, a rate equation describing the absorption and stimulated emission of single photons, and the unimolecular dissociation of excited molecules is constructed based on available experimental results. The model shows that the energy fluence of the laser determines the excitation of molecules in the quasi-continuum and the excess energy with which molecules dissociate after the laser pulse. The role played by the laser intensity in multiphoton dissociation is more significant than just that of overcoming the intensity dependent absorption in the lowest levels. 63 references

  10. 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.

  11. 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.

  12. The adsorption and dissociation of water molecule on goethite (010) surface: A DFT approach

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Long, E-mail: shuweixia@ouc.edu.cn [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Xiu, Fangyuan [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Qiu, Meng [Qingdao Institute of Bioenergy and Bioprocess Technology (China); Xia, Shuwei; Yu, Liangmin [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China)

    2017-01-15

    Graphical abstract: The optimized structure of hydrated goethite (010) surface with medium water coverage (water density about 6.7 H{sub 2}O/nm{sup 2}). - Highlights: • Stable adsorption and dissociation structure of H{sub 2}O on goethite (010) surface was investigated by DFT. • Reasonable path for water dissociation was proposed by transitional state analysis. • The mechanism of water adsorption on goethite and binding nature were revealed by PDOS. - Abstract: Using density functional theory (DFT) calculation, we investigate the configuration, stability and electronic properties of fresh cleaved (010) goethite surface (Pnma) and this surface exposed to water monolayer at low, medium and high coverage. Water is predicted to be chemisorbed to the surface, together with the surface reconstruction. The interaction energy of the most stable configuration of both low and medium coverage per water molecule is almost the same (−1.17 eV), while that of high coverage is much lower (less than 1.03 eV). It indicates that highly hydrated surface is less stable. PDOS analysis reveals the adsorption of H{sub 2}O is due to the formation of Fe−O bond, caused by overlapping of Fe's 3d and O's 2p orbitals. Dissociation processes at low and medium water coverage are non-spontaneous; while at high coverage, it can undertake spontaneously both thermodynamically and dynamically. The dissociation paths of all three water coverage are the similar. The proton from one adsorbed water is likely to dissociate to bind to the vicinal surface μ{sub 3}−O as an intermediate product; the proton belonged to μ{sub 3}−O transferred to the neighbor surface μ{sub 2}−O as the dissociative configuration.

  13. Natural Gas Hydrate as a Storage Mechanism for Safe, Sustainable and Economical Production from Offshore Petroleum Reserves

    Directory of Open Access Journals (Sweden)

    Michael T. Kezirian

    2017-06-01

    Full Text Available Century Fathom presents an innovative process to utilize clathrate hydrates for the production, storage and transportation of natural gas from off-shore energy reserves in deep ocean environments. The production scheme was developed by considering the preferred state of natural gas in the deep ocean and addressing the hazards associated with conventional techniques to transport natural gas. It also is designed to mitigate the significant shipping cost inherent with all methods. The resulting proposed scheme restrains transport in the hydrate form to the ocean and does not attempt to supply energy to the residential consumer. Instead; the target recipients are industrial operations. The resulting operational concept is intrinsically safer by design; environmentally sustainable and significantly cost-effective compared with currently proposed schemes for the use of natural gas hydrates and has the potential to be the optimal solution for new production of reserves; depending on the distance to shore and capacity of the petroleum reserve. A potential additional benefit is the byproduct of desalinated water.

  14. Collagen tissue treated with chitosan solution in H2O/CO2 mixtures: Influence of clathrates hydrates on the structure and mechanical properties.

    Science.gov (United States)

    Chaschin, Ivan S; Bakuleva, Natalia P; Grigoriev, Timofei E; Krasheninnikov, Sergey V; Nikitin, Lev N

    2017-03-01

    A mixture of water/carbon dioxide is a "green" perspective solvent from the viewpoint of biomedical applications. Clathrate hydrates are formed this solvent under certain conditions and a very interesting question is the impact of clathrates hydrates on the structure and properties of bovine pericardium, which is used in biomedicine, in particular as a main part of biological heart valve prostheses. The aim of the present work is to investigate the influence of clathrates on the structure and mechanical properties of the collagen tissue treated with chitosan in H 2 O/CO 2 mixtures under pressure 3.0-3.5MPa and temperatures 2-4°C. It was first found that the clathrate hydrates in this media due to the strong fluctuations "bomb" collagen tissue of bovine pericardium, which is manifested in the appearance of numerous small gaps (pores) with mean size of 225±25nm and large pores with size of 1-3μ on the surface and within collagen matrices. High porosity leads to averaging characteristics of the organization structure in tissues with different orientation of the collagen fibers. As a result, the mechanical properties of the collagen tissue with a different orientation of the collagen fibrils become similar, which is quite different from their original properties. The structural changes caused by the influence of the environment clathrate hydrates led to a significant decrease of the tensile strength (30-47% in total, p<0.05) and initial elastic moduli (74-83%, p<0.05). However, the final elastic moduli and the maximum tensile virtually unchanged compared to the control. Nevertheless, it was found that the direct deposition of chitosan from the H 2 O/CO 2 mixtures with clathrate improve the mechanical-strength properties of the porous matrices. We believe that these improved mechanical properties are achieved due to particularly deep and uniform impregnation of the collagen matrix with chitosan from its pressurized solutions in H 2 O/CO 2 mixtures. Copyright © 2016

  15. 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

  16. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

    Directory of Open Access Journals (Sweden)

    Dolado, J. S.

    2011-06-01

    Full Text Available The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C3S, β-C2S and their blends are studied by Nitrogen sorption and nanoindentation experiments. The surface area and nanoporosity of C-S-H gels formed from the hydration of β-C2S and the 30-70 (T1-C3S and β-C2S mixture are higher than those from hydration of T1-C3S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nanoindentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C2S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 29Si magic-angle-spinning (MAS NMR, of the C-S-H gels.La caracterización textural y mecánica de geles C-S-H formados a partir de la hidratación de muestras puras de T1-C3S, ß-C2S y sus mezclas ha sido estudiada por medio de adsorción de nitrógeno y nanoindentación. El área superficial y la nano-porosidad de los geles formados durante la hidratación del ß-C2S y la mezcla 30-70 (T1-C3S- ß-C2S son mayores que los correspondientes a los geles del T1-C3S, y la mezcla 70-30; esta diferencia disminuye con el tiempo de hidratación. Estos cambios coinciden con los resultados de nanoindentación que indican un aumento de volumen relativo de las fases C-S-H con una densidad menor en el caso del ß-C2S y la mezcla 30-70. Al aumentar el tiempo de hidratación, el volumen relativo de fases C-S-H de mayor densidad aumenta a expensas de aquellas de menor densidad. Importantes correlaciones cuantitativas se establecen entre las características texturales y la longitud de cadena media del gel C-S-H, determinada mediante RMN-MAS de 29Si.

  17. Hydrate Equilibrium Data for CO2+N-2 System in the Presence of Tetra-n-butylammonium Fluoride (TBAF) and Mixture of TBAF and Cyclopentane (CP)

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; Coquelet, Christophe

    2016-01-01

    Hydrates can be used for CO2 capture from flue gases (hydrate crystallization). In this work, hydrate equilibrium data were measured and compared with literature data. The isochoric method was used to determine the gas hydrate dissociation points. Different CO2+N2 gas mixtures were used...

  18. A Novel Robot System Integrating Biological and Mechanical Intelligence Based on Dissociated Neural Network-Controlled Closed-Loop Environment.

    Directory of Open Access Journals (Sweden)

    Yongcheng Li

    Full Text Available We propose the architecture of a novel robot system merging biological and artificial intelligence based on a neural controller connected to an external agent. We initially built a framework that connected the dissociated neural network to a mobile robot system to implement a realistic vehicle. The mobile robot system characterized by a camera and two-wheeled robot was designed to execute the target-searching task. We modified a software architecture and developed a home-made stimulation generator to build a bi-directional connection between the biological and the artificial components via simple binomial coding/decoding schemes. In this paper, we utilized a specific hierarchical dissociated neural network for the first time as the neural controller. Based on our work, neural cultures were successfully employed to control an artificial agent resulting in high performance. Surprisingly, under the tetanus stimulus training, the robot performed better and better with the increasement of training cycle because of the short-term plasticity of neural network (a kind of reinforced learning. Comparing to the work previously reported, we adopted an effective experimental proposal (i.e. increasing the training cycle to make sure of the occurrence of the short-term plasticity, and preliminarily demonstrated that the improvement of the robot's performance could be caused independently by the plasticity development of dissociated neural network. This new framework may provide some possible solutions for the learning abilities of intelligent robots by the engineering application of the plasticity processing of neural networks, also for the development of theoretical inspiration for the next generation neuro-prostheses on the basis of the bi-directional exchange of information within the hierarchical neural networks.

  19. A Novel Robot System Integrating Biological and Mechanical Intelligence Based on Dissociated Neural Network-Controlled Closed-Loop Environment.

    Science.gov (United States)

    Li, Yongcheng; Sun, Rong; Wang, Yuechao; Li, Hongyi; Zheng, Xiongfei

    2016-01-01

    We propose the architecture of a novel robot system merging biological and artificial intelligence based on a neural controller connected to an external agent. We initially built a framework that connected the dissociated neural network to a mobile robot system to implement a realistic vehicle. The mobile robot system characterized by a camera and two-wheeled robot was designed to execute the target-searching task. We modified a software architecture and developed a home-made stimulation generator to build a bi-directional connection between the biological and the artificial components via simple binomial coding/decoding schemes. In this paper, we utilized a specific hierarchical dissociated neural network for the first time as the neural controller. Based on our work, neural cultures were successfully employed to control an artificial agent resulting in high performance. Surprisingly, under the tetanus stimulus training, the robot performed better and better with the increasement of training cycle because of the short-term plasticity of neural network (a kind of reinforced learning). Comparing to the work previously reported, we adopted an effective experimental proposal (i.e. increasing the training cycle) to make sure of the occurrence of the short-term plasticity, and preliminarily demonstrated that the improvement of the robot's performance could be caused independently by the plasticity development of dissociated neural network. This new framework may provide some possible solutions for the learning abilities of intelligent robots by the engineering application of the plasticity processing of neural networks, also for the development of theoretical inspiration for the next generation neuro-prostheses on the basis of the bi-directional exchange of information within the hierarchical neural networks.

  20. Application of a Multi-Scale form of Terzaghi’s Effective Stress Principle for Unsaturated Expansive Clays to Simulate Hydro-Mechanical Behavior During Hydration

    Directory of Open Access Journals (Sweden)

    Mainka Julia

    2016-01-01

    Full Text Available Our recently developed multi-scale form of Terzaghi’s effective stress principle for unsaturated swelling clays that was rigorously derived by periodic homogenization starting from micro- and nano-mechanical analyses is applied to numerically simulate one-dimensional swelling pressure tests of compacted bentonites during hydration. The total macroscopic stress captures the coupling between disjoining forces at the nanoscopic scale of clay platelets and capillary effects at the microscopic scale of clay aggregates over the entire water content range. The numerical results allow to draw conclusions on the water transfer mechanism between inter- and intra-aggregate pores during hydration and consequently on the evolution of the external swelling pressure resulting from the competition between capillary and disjoining forces. In addition, such application highlights the abilities and the limits of the electrical double-layer theory to compute the disjoining pressure in the nano-pores. For large platelet distances, in the range of osmotic swelling, the nature of the disjoining pressure is electro-chemical and can be computed from Poisson-Boltzmann theory. Conversely, at small distances, in the crystalline swelling, a solvation component has to be added to account for the molecular nature of the solvent. As a first improvement of the nano-scale description the solvent is treated as a hard sphere fluid using Density Functional Theory.

  1. Study on gas hydrate as a new energy resource in the twenty first century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byung Jae; Kim, Won Sik; Oh, Jae Ho [Korea Institute of Geology Mining and Materials, Taejon (Korea)] [and others

    1998-12-01

    Methane hydrate, a special type of clathrate hydrates, is a metastable solid compound mainly consisted of methane and water and generally called as gas hydrate. It is stable in the specific low- temperature/high-pressure conditions. Very large amount of methane that is the main component of natural gas, is accumulated in the form of methane hydrate subaquatic areas. Methane hydrate are the major reservoir of methane on the earth. On the other hand, the development and transmission through pipeline of oil and natural gas in the permafrost and deep subaquatic regions are significantly complicated by formation and dissociation of methane hydrate. The dissociation of natural methane hydrates caused by increasing temperature and decreasing pressure could cause the atmospheric pollution and geohazard. The formation, stable existence and dissociation of natural methane hydrates depend on the temperature, pressure, and composition of gas and characteristics of the interstitial waters. For the study on geophysical and geological conditions for the methane hydrate accumulation and to find BSR in the East Sea, Korea, the geophysical surveys using air-gun system, multibeam echo sounder, SBP were implemented in last September. The water temperature data vs. depth were obtained to determine the methane hydrate stability zone in the study area. The experimental equilibrium condition of methane hydrate was also measured in 3 wt.% sodium chloride solution. The relationship between Methane hydrate formation time and overpressure was analyzed through the laboratory work. (author). 49 refs., 6 tabs., 26 figs.

  2. [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.

  3. Kinetics and mechanism of transitions involving the lamellar, cubic, inverted hexagonal, and fluid isotropic phases of hydrated monoacylglycerides monitored by time-resolved X-ray diffraction

    International Nuclear Information System (INIS)

    Caffrey, M.

    1987-01-01

    A study of the dynamics and mechanism of the various thermotropic phase transitions undergone by the hydrated monoacylglycerides monoolein and monoelaidin, in the temperature range of 20-120 0 C and from 0 to 5 M NaCl, has been undertaken. Measurements were made by using time-resolved X-ray diffraction at the Cornell High-Energy Synchrotron Source. The lamellar chain order/disorder, lamellar/cubic (body centered, space group No.8), cubic (body centered, No.8)/cubic (primitive No.4), cubic (body centered, No.12)/cubic (primitive, No.4), cubic (primitive, No.4)/fluid isotropic, cubic (body centered, No.12)/inverted hexagonal, cubic (primitive, No.4)/inverted hexagonal, and hexagonal/fluid isotropic transitions were examined under active heating and passive cooling by using a jump in temperature to effect phase transformation. All of the transitions with the exception of the cubic (body centered, No.8)/cubic (primitive, No.4) and the cubic (body centered, No.12)/cubic (primitive, No.4) cooling transitions were found (1) to be repeatable, (2) to be reversible, and (3) to have an upper bound on the transit time (time required to complete the transition) of ≤ 3s. In addition to the time-resolved measurements, data were obtained on the stability of the various phases in the temperature range of 20-120 0 C and from 0 to 5 M NaCl. In the case of fully hydrated monoolein, high salt strongly favors the hexagonal over the cubic (body centered, No.8) phase and slightly elevates the hexagonal/fluid isotropic transition temperature. With fully hydrated monoelaidin, the hexagonal phase which is not observed in the absence of salt becomes the dominant phase at high salt concentration

  4. Mechanistic insights into a hydrate contribution to the Paleocene-Eocene carbon cycle perturbation from coupled thermohydraulic simulations

    Science.gov (United States)

    Minshull, T. A.; Marín-Moreno, H.; Armstrong McKay, D. I.; Wilson, P. A.

    2016-08-01

    During the Paleocene-Eocene Thermal Maximum (PETM), the carbon isotopic signature (δ13C) of surface carbon-bearing phases decreased abruptly by at least 2.5 to 3.0‰. This carbon isotope excursion (CIE) has been attributed to widespread methane hydrate dissociation in response to rapid ocean warming. We ran a thermohydraulic modeling code to simulate hydrate dissociation due to ocean warming for various PETM scenarios. Our results show that hydrate dissociation in response to such warming can be rapid but suggest that methane release to the ocean is modest and delayed by hundreds to thousands of years after the onset of dissociation, limiting the potential for positive feedback from emission-induced warming. In all of our simulations at least half of the dissociated hydrate methane remains beneath the seabed, suggesting that the pre-PETM hydrate inventory needed to account for all of the CIE is at least double that required for isotopic mass balance.

  5. Underlying mechanisms and effects of hydrated lime and selenium application on cadmium uptake by rice (Oryza sativa L.) seedlings.

    Science.gov (United States)

    Huang, Gaoxiang; Ding, Changfeng; Guo, Fuyu; Li, Xiaogang; Zhang, Taolin; Wang, Xingxiang

    2017-08-01

    A pot experiment was conducted to investigate the effects of selenium (Se) and hydrated lime (Lime), applied alone or simultaneously (Se+Lime), on growth and cadmium (Cd) uptake and translocation in rice seedlings grown in an acid soil with three levels of Cd (slight, mild, and moderate contamination). In the soil with 0.41 mg kg -1 Cd (slight Cd contamination), Se addition alone significantly decreased Cd accumulation in the root and shoot by 35.3 and 40.1%, respectively, but this tendency weakened when Cd level in the soil increased. However, Se+Lime treatment effectively reduced Cd accumulation in rice seedlings in the soil with higher Cd levels. The results also showed that Se application alone strongly increased Cd concentration in the iron plaque under slight Cd contamination, which was suggested as the main reason underlying the inhibition of Cd accumulation in rice seedlings. Se+Lime treatment also increased the ability of the iron plaques to restrict Cd uptake by rice seedlings across all Cd levels and dramatically decreased the available Cd concentration in the soil. These results suggest that Se application alone would be useful in the soil with low levels of Cd, and the effect would be enhanced when Se application is combined with hydrated lime at higher Cd levels.

  6. 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.

  7. A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

    Science.gov (United States)

    White, M. D.

    2012-12-01

    The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. 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. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, 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. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially 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, nonaqueous liquid, 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 simulations that predict

  8. 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.

  9. Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity

    International Nuclear Information System (INIS)

    Bach, T.T.H.; Chabas, E.; Pochard, I.; Cau Dit Coumes, C.; Haas, J.; Frizon, F.; Nonat, A.

    2013-01-01

    Low-pH cements, also referred to as low-alkalinity cements, can be designed by replacing significant amounts of Portland cement by pozzolanic materials. Their pore solution is characterized by a pH near 11, and an alkali concentration much lower than that of Portland cement. This work investigates the retention of sodium and potassium by a hydrated low-pH cement comprising 60% Portland cement and 40% silica fume. It is shown that sorption of potassium is higher than that of sodium and mainly results from counterion charge balancing of the C-S-H negative surface charge. To explain the greater retention of potassium compared to sodium, it is postulated that potassium, unlike sodium, may enter the interlayer of C-S-H to compensate the negative charges in the interlayer, in addition to the external surfaces. This assumption is supported by structural characterization of C-S-H using X-ray diffraction

  10. Atrioventricular Dissociation after Electroconvulsive Therapy

    Directory of Open Access Journals (Sweden)

    Siegfried William Yu

    2011-01-01

    Full Text Available Electroconvulsive therapy (ECT is increasingly used as a treatment for psychiatric disorders. Cardiac effects are the principal cause of medical complications in these patients. We report a case of atrioventricular (AV dissociation that occurred after ECT that was treated with pacemaker implantation. The mechanisms contributing to the onset of AV dissociation in this patient, and the management and rationale for device therapy, in light of the most recent guidelines, are reviewed.

  11. 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.

  12. Theoretical study of the mechanism of formation of a chemical bond between two ions: A+ and B+. Application to CO++. Interpretation of N2O++ photo-dissociation mechanisms

    International Nuclear Information System (INIS)

    Levasseur, Nathalie

    1989-01-01

    This research thesis reports the theoretical study of the mechanism of formation of a chemical bond between two positively charged species, within the frame of the valence-bond theory and in the CO model case. The analysis in terms of orthogonal and non orthogonal orbitals leads to two very different interpretations, and allows potential curves of doubly charged diatomic ions to be simply explained, the generally evoked model to be put into question again, and a predictive model to be developed. The theoretical determination of N 2 O potential energy surfaces and of the first states of N 2 O ++ ( 3 Σ - , 1 Δ, 1 Σ + et 3 Π) allowed experimental results of N 2 O ++ photo-dissociation to be at least qualitatively understood and interpreted. Moreover, the study of electronic configurations involved in dissociation, showed that the model elaborated for a diatomic molecule is also valid for a triatomic system [fr

  13. A New Critical State Model for Geomechanical Behavior of Methane Hydrate-Bearing Sands

    Science.gov (United States)

    Lin, J. S.; Xing, P.; Rutqvist, J.; Seol, Y.; Choi, J. H.

    2014-12-01

    Methane hydrate bearing sands behave like sands once the hydrate has dissociated, but could exhibit a substantial increase in the shear strength, stiffness and dilatancy as the degree of hydrate saturation increases. A new critical state model was developed that incorporates the spatially mobilized plane (SMP) concept, which has been proven effective in modeling mechanical behavior of sands. While this new model was built on the basic constructs of the critical state model, important enhancements were introduced. The model adopted the t-stress concept, which defined the normal and shear stress on the SMP, in describing the plastic behavior of the soil. In this connection the versatile Matsuoka-Nakai yield criterion was also employed, which defined the general three dimensional yield behavior. The resulting constitutive law was associated in the t-stress space, but became non-associated in the conventional p-q stress space as it should be for sands. The model also introduced a generalized degree of hydrate saturation concept that was modified from the pioneering work of the Cambridge group. The model gives stress change when the sands are subjected to straining, and/or to hydrate saturation changes. The performance of the model has been found satisfactory using data from laboratory triaxial tests on reconstituted samples and core samples taken from Nankai Trough, Japan. The model has been implemented into FLAC3D. A coupling example with the multiphase flow code, TOUGH+, is presented which simulates the mechanical behavior of a sample when the surrounding temperature has been raised, and the hydrate undergoes state change and no longer resides in the stability zone.

  14. Simulation of microwave stimulation for the production of gas from methane hydrate sediment

    International Nuclear Information System (INIS)

    Zhao, Jiafei; Fan, Zhen; Wang, Bin; Dong, Hongsheng; Liu, Yu; Song, Yongchen

    2016-01-01

    Graphical abstract: Schematic diagram illustrating the process of gas production in hydrate-bearing sediment induced by microwave stimulation. Temperature gradients caused by the drop of microwave penetration depth appear in the sediment, leading to a rapid dissociation rate at the upper part of reservoir. - Highlights: • Hydrate dissociation behavior was analyzed in porous media by microwave stimulation. • Microwave stimulation provides sufficient energy conversion for hydrate dissociation. • Hydrate saturation and specific heat capacity of sediment mainly affect efficiency. • Heat conduction decreases temperature gradients promoting homogeneous dissociation. - Abstract: Natural gas hydrates dissociate via an endothermic process. One of the key requirements for any production technique is to supply the heat necessary for this dissociation. In this study, first, a microwave stimulation model for the production of gas from methane hydrate sediment is developed, which includes mass transport, energy conversion and conservation, and intrinsic kinetic reactions as the governing equations. In addition, the theoretical mixing rule of Lichtenecker and Rother is introduced for calculating the average dielectric data of the sediment containing methane hydrates, which affects the penetration of microwaves into the sediment. Next, simulations are performed for investigating gas production, as well as effects of initial water saturation, initial hydrate saturation, and sediment thermal properties induced by microwave stimulation. Moreover, the energy efficiency ratio is employed in the simulation. The simulation results show that microwave stimulation provides timely energy conversion sufficient for promoting the dissociation of hydrates, with rapid, continuous gas production. Temperature gradients caused by the decrease of the microwave penetration depth appear in the reservoir, leading to a rapid dissociation rate in the upper part of the sediment. The energy

  15. 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

  16. A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Gharagheizi, Farhad; Mohammadi, Amir H.

    2012-01-01

    We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the r......We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot...... in exponential form is used to represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results...

  17. Petrophysical Characterization and Reservoir Simulator for Methane Gas Production from Gulf of Mexico Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kishore Mohanty; Bill Cook; Mustafa Hakimuddin; Ramanan Pitchumani; Damiola Ogunlana; Jon Burger; John Shillinglaw

    2006-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Estimates of the amounts of methane sequestered in gas hydrates worldwide are speculative and range from about 100,000 to 270,000,000 trillion cubic feet (modified from Kvenvolden, 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In this project novel techniques were developed to form and dissociate methane hydrates in porous media, to measure acoustic properties and CT properties during hydrate dissociation in the presence of a porous medium. Hydrate depressurization experiments in cores were simulated with the use of TOUGHFx/HYDRATE simulator. Input/output software was developed to simulate variable pressure boundary condition and improve the ease of use of the simulator. A series of simulations needed to be run to mimic the variable pressure condition at the production well. The experiments can be matched qualitatively by the hydrate simulator. The temperature of the core falls during hydrate dissociation; the temperature drop is higher if the fluid withdrawal rate is higher. The pressure and temperature gradients are small within the core. The sodium iodide concentration affects the dissociation pressure and rate. This procedure and data will be useful in designing future hydrate studies.

  18. 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

  19. 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.

  20. 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

    angle x-ray scattering (WAXD) that characterize how additives affect both the hydrated microstructure development and the original grain size. In particular, SPs alter the morphology of the hydrated phases, which no longer grow with the classic fibrillar structure on the grain surface, but nucleate in solution as globular structures. All this information converges in a quantitative, and at molecular level, description of the mechanisms involved in the setting process of one of the materials most widely used by human beings

  1. In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

    Science.gov (United States)

    Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

    2017-05-01

    Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

  2. Predictive Mechanical Characterization of Macro-Molecular Material Chemistry Structures of Cement Paste at Nano Scale - Two-phase Macro-Molecular Structures of Calcium Silicate Hydrate, Tri-Calcium Silicate, Di-Calcium Silicate and Calcium Hydroxide

    Science.gov (United States)

    Padilla Espinosa, Ingrid Marcela

    Concrete is a hierarchical composite material with a random structure over a wide range of length scales. At submicron length scale the main component of concrete is cement paste, formed by the reaction of Portland cement clinkers and water. Cement paste acts as a binding matrix for the other components and is responsible for the strength of concrete. Cement paste microstructure contains voids, hydrated and unhydrated cement phases. The main crystalline phases of unhydrated cement are tri-calcium silicate (C3S) and di-calcium silicate (C2S), and of hydrated cement are calcium silicate hydrate (CSH) and calcium hydroxide (CH). Although efforts have been made to comprehend the chemical and physical nature of cement paste, studies at molecular level have primarily been focused on individual components. Present research focuses on the development of a method to model, at molecular level, and analysis of the two-phase combination of hydrated and unhydrated phases of cement paste as macromolecular systems. Computational molecular modeling could help in understanding the influence of the phase interactions on the material properties, and mechanical performance of cement paste. Present work also strives to create a framework for molecular level models suitable for potential better comparisons with low length scale experimental methods, in which the sizes of the samples involve the mixture of different hydrated and unhydrated crystalline phases of cement paste. Two approaches based on two-phase cement paste macromolecular structures, one involving admixed molecular phases, and the second involving cluster of two molecular phases are investigated. The mechanical properties of two-phase macromolecular systems of cement paste consisting of key hydrated phase CSH and unhydrated phases C3S or C2S, as well as CSH with the second hydrated phase CH were calculated. It was found that these cement paste two-phase macromolecular systems predicted an isotropic material behavior. Also

  3. A computational study on the energetics and mechanisms for the dissociative adsorption of SiHx(x = 1-4) on W(1 1 1) surface

    Science.gov (United States)

    Lin, Y. H.; Raghunath, P.; Lin, M. C.

    2016-01-01

    The adsorption and dissociation mechanisms of SiHx(x = 1-4) species on W(1 1 1) surface have been investigated by using the periodic density functional theory with the projector-augmented wave approach. The adsorption of all the species on four surface sites: top (T), bridge (B), shallow (S), and deep (D) sites have been analyzed. For SiH4 on a top site, T-SiH4(a), it is more stable with an adsorption energy of 2.6 kcal/mol. For SiH3, the 3-fold shallow site is most favorable with adsorption energy of 46.0 kcal/mol. For SiH2, its adsorption on a bridge site is most stable with 73.0 kcal/mol binding energy, whereas for SiH and Si the most stable adsorption configurations are on 3-fold deep sites with very high adsorption energies, 111.8 and 134.7 kcal/mol, respectively. The potential energy surfaces for the dissociative adsorption of all SiHx species on the W(1 1 1) surface have been constructed using the CINEB method. The barriers for H-atom migration from SiHx(a) to its neighboring W atoms, preferentially on B-sites, were predicted to be 0.4, 1.0, 4.5 and, 8.0 kcal/mol, respectively, for x = 4, 3, 2, and 1, respectively. The adsorption energy of the H atom on a bridge site on the clean W(1 1 1) surface was predicted to be 65.9 kcal/mol, which was found to be slightly affected by the co-adsorption of SiHx-1 within ± 1 kcal/mol.

  4. Double-dissociation between the mechanism leading to impulsivity and inattention in Attention Deficit Hyperactivity Disorder: A resting-state functional connectivity study.

    Science.gov (United States)

    Sanefuji, Masafumi; Craig, Michael; Parlatini, Valeria; Mehta, Mitul A; Murphy, Declan G; Catani, Marco; Cerliani, Leonardo; Thiebaut de Schotten, Michel

    2017-01-01

    Two core symptoms characterize Attention Deficit Hyperactivity Disorder (ADHD) subtypes: inattentiveness and hyperactivity-impulsivity. While previous brain imaging research investigated ADHD as if it was a homogenous condition, its two core symptoms may originate from different brain mechanisms. We, therefore, hypothesized that the functional connectivity of cortico-striatal and attentional networks would be different between ADHD subtypes. We studied 165 children (mean age 10.93 years; age range, 7-17 year old) diagnosed as having ADHD based on their revised Conner's rating scale score and 170 typical developing individuals (mean age 11.46 years; age range, 7-17 year old) using resting state functional fMRI. Groups were matched for age, IQ and head motion during the MRI acquisition. We fractionated the ADHD group into predominantly inattentive, hyperactive-impulsive and combined subtypes based on their revised Conner's rating scale score. We then analyzed differences in resting state functional connectivity of the cortico-striatal and attentional networks between these subtypes. We found a double dissociation of functional connectivity in the cortico-striatal and ventral attentional networks, reflecting the subtypes of the ADHD participants. Particularly, the hyperactive-impulsive subtype was associated with increased connectivity in cortico-striatal network, whereas the inattentive subtype was associated with increased connectivity in the right ventral attention network. Our study demonstrated for the first time a right lateralized, double dissociation between specific networks associated with hyperactivity-impulsivity and inattentiveness in ADHD children, providing a biological basis for exploring symptom dimensions and revealing potential targets for more personalized treatments. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. First-principles investigation of methanethiol adsorption and dissociation mechanisms on the high-Miller-index vicinal surface Cu(4 1 0)

    International Nuclear Information System (INIS)

    Raouafi, Faycal; Lassoued, Karima; Seydou, Mahamadou; Taleb, Abdelhafed; Diawara, Boubakar

    2016-01-01

    In this work, we present detailed investigations of methanethiol adsorption on a Cu(4 1 0) surface within the framework of the self-consistent first-principles calculations as implemented in the Vienna ab initio simulation package (VASP). In particular, the adsorption sites, the surface coverage rate and electronic properties have been determined and compared to experimental values. The results indicate that the favorable adsorption site in the case of low coverage rate is a bridge on the step followed by the hollow site on the terrace. The adsorption significantly affects the outermost layer of the surface mainly for a higher coverage rate in a (2  ×  2) supercell. The nature of the chemisorption process on the surface is analyzed by means of the density of states which, combined with charge density difference and atomic charge calculations, confirms the ionic character of the S–Cu bond. The specific effect of the presence of steps is highlighted by comparing the adsorption on the (1 0 0) terrace to the adsorption on the extended Cu(1 0 0) surface. Compared to the flat Cu(1 0 0), it is found here that while the stability is almost the same at p(2  ×  2) coverage, the CH 3 S/Cu(4 1 0) becomes more stable than CH 3 S/Cu(1 0 0) at c(2  ×  2) coverage with 0.30 eV per molecule. The mechanism of methanethiol dissociation is explored by the nudged elastic band method and demonstrates that the most favorable path is dissociation followed by migration of hydrogen from the step to its most stable position (hollow on the terrace) with energy barriers less than 0.5 eV. (paper)

  6. Submarine slope failures in the Beaufort Sea; Influence of gas hydrate decomposition

    Science.gov (United States)

    Grozic, J. L.; Dallimore, S.

    2012-12-01

    The continental shelf of the Beaufort Sea is composed of complex of marine and non-marine sequences of clay, silt, and sand. In many areas of the shelf these sediments contain occurrences of ice-bonded permafrost and associated pressure and temperature conditions that are conducive to the occurrence of methane gas hydrates. This complex environment is undergoing dramatic warming, where changes in sea level, ocean bottom temperatures, and geothermal regimes are inducing permafrost thawing and gas hydrate decomposition. Decomposition is inferred to be occurring at the base and top of the gas hydrate stability zone, which will cause sediment weakening and the generation of excess water and free gas. In such settings, the overlying permafrost cap may act as a permeability barrier, which could result in significant excess pore pressures and reduction in sediment stability. The shelf to slope transition is thought to be an area of extensive regional instability with acoustic records indicating there is upwards of 500 km of slumps and glides extending over the entire Beaufort margin. Some of these slide regions are coincident with up-dip limit of the permafrost gas hydrate stability zone. In this paper, a two dimensional model of the Beaufort shelf was constructed to examine the influence of gas hydrate decomposition on slope stability. The model relies on available data on the Beaufort sediments generated from offshore hydrocarbon exploration in the 1980s and 90s, as well as knowledge available from multidisciplinary marine research programs conducted in the outer shelf area. The slope stability model investigates the influence of marine transgression and ocean bottom warming by coupling soil deformation with hydrate dissociation during undrained conditions. By combining mechanical and thermal loading of the sediment, a more accurate indication of slope stability was obtained. The stability analysis results indicate a relatively low factor of safety for the Beaufort

  7. Investigation of mechanical properties of hydrate-bearing pressure core sediments recovered from the Eastern Nankai Trough using transparent acrylic cell triaxial testing system (TACTT-system)

    Science.gov (United States)

    Yoneda, J.; Masui, A.; Konno, Y.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Tenma, N.; Nagao, J.

    2014-12-01

    Natural gas hydrate-bearing pressure core sediments have been sheared in compression using a newly developed Transparent Acrylic Cell Triaxial Testing (TACTT) system to investigate the geophysical and geomechanical behavior of sediments recovered from the deep seabed in the Eastern Nankai Trough, the first Japanese offshore production test region. The sediments were recovered by hybrid pressure core system (hybrid PCS) and pressure cores were cut by pressure core analysis tools (PCATs) on board. These pressure cores were transferred to the AIST Hokkaido centre and trimmed by pressure core non-destructive analysis tools (PNATs) for TACTT system which maintained the pressure and temperature conditions within the hydrate stability boundary, through the entire process of core handling from drilling to the end of laboratory testing. An image processing technique was used to capture the motion of sediment in a transparent acrylic cell, and digital photographs were obtained at every 0.1% of vertical strain during the test. Analysis of the optical images showed that sediments with 63% hydrate saturation exhibited brittle failure, although nonhydrate-bearing sediments exhibited ductile failure. In addition, the increase in shear strength with hydrate saturation increase of natural gas hydrate is in agreement with previous data from synthetic gas hydrate. This research was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program by the Ministry of Economy, Trade and Industry (METI).

  8. 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.

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

    International Nuclear Information System (INIS)

    Vollet, D.

    1983-01-01

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

  10. Phase equilibrium modeling of gas hydrate systems for CO2 capture

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2012-01-01

    to form from vapor phases with initial mole fractions of CO2 at or above 0.15.The two models are validated against mixed hydrate equilibrium data found in literature. Both dissociation pressures and hydrate compositions are considered in the validation process.With the fitted parameters, Model I predicts...

  11. Flue gas injection into gas hydrate reservoirs for methane recovery and carbon dioxide sequestration

    International Nuclear Information System (INIS)

    Yang, Jinhai; Okwananke, Anthony; Tohidi, Bahman; Chuvilin, Evgeny; Maerle, Kirill; Istomin, Vladimir; Bukhanov, Boris; Cheremisin, Alexey

    2017-01-01

    Highlights: • Flue gas was injected for both methane recovery and carbon dioxide sequestration. • Kinetics of methane recovery and carbon dioxide sequestration was investigated. • Methane-rich gas mixtures can be produced inside methane hydrate stability zones. • Up to 70 mol% of carbon dioxide in the flue gas was sequestered as hydrates. - Abstract: Flue gas injection into methane hydrate-bearing sediments was experimentally investigated to explore the potential both for methane recovery from gas hydrate reservoirs and for direct capture and sequestration of carbon dioxide from flue gas as carbon dioxide hydrate. A simulated flue gas from coal-fired power plants composed of 14.6 mol% carbon dioxide and 85.4 mol% nitrogen was injected into a silica sand pack containing different saturations of methane hydrate. The experiments were conducted at typical gas hydrate reservoir conditions from 273.3 to 284.2 K and from 4.2 to 13.8 MPa. Results of the experiments show that injection of the flue gas leads to significant dissociation of the methane hydrate by shifting the methane hydrate stability zone, resulting in around 50 mol% methane in the vapour phase at the experimental conditions. Further depressurisation of the system to pressures well above the methane hydrate dissociation pressure generated methane-rich gas mixtures with up to 80 mol% methane. Meanwhile, carbon dioxide hydrate and carbon dioxide-mixed hydrates were formed while the methane hydrate was dissociating. Up to 70% of the carbon dioxide in the flue gas was converted into hydrates and retained in the silica sand pack.

  12. 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.

  13. 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.

  14. Physical, mechanical and hydration kinetics of particleboards manufactured with woody biomass (Cupressus lusitanica, Gmelina arborea, Tectona grandis), agricultural resources, and Tetra Pak packages.

    Science.gov (United States)

    Moya, Róger; Camacho, Diego; Oporto, Gloria S; Soto, Roy F; Mata, Julio S

    2014-02-01

    Lignocellulosic wastes resulting from agricultural activities as well as Tetra Pak residues from urban centres can cause significant levels of pollution. A possible action to minimize this problem is to use them in the production of particleboards. The purpose of this study was to evaluate the physical, mechanical, and hydration properties of particleboards manufactured with the mixture of woody biomass (Cupressus lusitanica, Gmelina arborea, and Tectona grandis) and either agricultural wastes [pineapple leaves (Ananas comosus) and palm residues (Elaeis guineensis)] or Tetra Pak residues (TP). The results show that the particleboards prepared with TP and woody biomass can reduce the swelling and water absorption in up to 40% and 50% compared with particleboards without TP. Also, these particleboards had increased flexure resistance and shear stress (up to 100%) compared with those without TP. On the contrary, particleboards prepared with pineapple leaves in combination with woody biomass showed the lowest mechanical properties, particularly for tensile strength, hardness, glue-line shear, and nail and screw evaluation.

  15. 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.

  16. Diffraction dissociation

    International Nuclear Information System (INIS)

    Abarbanel, H.

    1972-01-01

    An attempt is made to analyse the present theoretical situation in the field of diffraction scattering. Two not yet fully answered questions related with a typical diffraction process AB→CD, namely: what is the structure of the transition matrix elements, and what is the structure of the exchange mechanism responsible for the scattering, are formulated and various proposals for answers are reviewed. Interesting general statement that the products (-1)sup(J)P, where J and P are respectively spin and parity, is conserved at each vertex has been discussed. The exchange mechanism in diffractive scattering has been considered using the language of the complex J-plane as the most appropriate. The known facts about the exchange mechanism are recalled and several routs to way out are proposed. The idea to consider the moving pole and associated branch points as like a particle and the associated two and many particle unitarity cuts is described in more details. (S.B.)

  17. Hydrate equilibrium data for the CO2 + N2 system with the use of tetra-n-butylammonium bromide (TBAB), cyclopentane (CP) and their mixture

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; von Solms, Nicolas

    2016-01-01

    Carbon Dioxide capture and sequestration (CCS) is nowadays an important area of research for decreasing CO2 emissions worldwide. Hydrates can become of great importance in the future as they form the basis for a new technology that can be used for CO2 capture from flue gases (hydrate...... crystallization). In this work hydrate equilibrium data are measured and compared with literature data. In particular, experimental results for hydrate dissociation with several promoters are presented. The isochoric method is used to determine the gas hydrate dissociation points. Different CO2 + N2 gas mixtures...

  18. 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 ...

  19. Reservoir Models for Gas Hydrate Numerical Simulation

    Science.gov (United States)

    Boswell, R.

    2016-12-01

    Scientific and industrial drilling programs have now providing detailed information on gas hydrate systems that will increasingly be the subject of field experiments. The need to carefully plan these programs requires reliable prediction of reservoir response to hydrate dissociation. Currently, a major emphasis in gas hydrate modeling is the integration of thermodynamic/hydrologic phenomena with geomechanical response for both reservoir and bounding strata. However, also critical to the ultimate success of these efforts is the appropriate development of input geologic models, including several emerging issues, including (1) reservoir heterogeneity, (2) understanding of the initial petrophysical characteristics of the system (reservoirs and seals), the dynamic evolution of those characteristics during active dissociation, and the interdependency of petrophysical parameters and (3) the nature of reservoir boundaries. Heterogeneity is ubiquitous aspect of every natural reservoir, and appropriate characterization is vital. However, heterogeneity is not random. Vertical variation can be evaluated with core and well log data; however, core data often are challenged by incomplete recovery. Well logs also provide interpretation challenges, particularly where reservoirs are thinly-bedded due to limitation in vertical resolution. This imprecision will extend to any petrophysical measurements that are derived from evaluation of log data. Extrapolation of log data laterally is also complex, and should be supported by geologic mapping. Key petrophysical parameters include porosity, permeability and it many aspects, and water saturation. Field data collected to date suggest that the degree of hydrate saturation is strongly controlled by/dependant upon reservoir quality and that the ratio of free to bound water in the remaining pore space is likely also controlled by reservoir quality. Further, those parameters will also evolve during dissociation, and not necessary in a simple

  20. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P; Frey, H -M; Gerber, T; Mischler, B; Radi, P P; Tzannis, A -P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  1. Effect of changes in seafloor temperature and sea-level on gas hydrate stability

    Energy Technology Data Exchange (ETDEWEB)

    Garg, S.K.; Pritchett, W. [Science Applications International Corp., San Diego, CA (United States)

    2008-07-01

    Natural gas hydrates occur in oceanic sediments and in permafrost regions around the world. As a greenhouse gas, large amounts of methane released from the global hydrate reservoir would have a significant impact on Earth's climate. The role of methane released by hydrate dissociation in climate change is uncertain. However, changes in global climate such as glaciation and warming can destabilize the hydrates. During the last glacial maximum, the sea level dropped about 100 meters. It has been suggested that the sea-level fall was associated with gas hydrate instability and seafloor slumping. This paper investigated the effect of changes in seafloor temperature and sea level on gas hydrate stability and on gas venting at the seafloor. A one-dimensional numerical computer model (simulator) was developed to describe methane hydrate formation, decomposition, reformation, and distribution with depth below the seafloor in the marine environment. The simulator was utilized to model hydrate distributions at two sites, notably Blake Ridge, located offshore South Carolina and Hydrate Ridge, located off the coast of Oregon. The numerical models for the two sites were conditioned by matching the sulfate, chlorinity, and hydrate distribution measurements. The effect of changes in seafloor temperature and sea-level on gas hydrate stability were then investigated. It was concluded that for Blake Ridge, changes in hydrate concentration were small. Both the changes in seafloor temperature and sea-level led to a substantial increase in gas venting at the seafloor for Hydrate Ridge. 17 refs., 8 figs.

  2. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  3. 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)

  4. Study of the mechanism of a kinetic inhibitor on the crystallization of methane hydrate; Etude du mecanisme d'action d'un inhibiteur cinetique sur la cristallisation de l'hydrate de methane

    Energy Technology Data Exchange (ETDEWEB)

    Pic, J.St.

    2000-01-14

    In the offshore exploitation of liquid fuels, problems of line plugging often occur, especially due to gas hydrates crystallization. At the present time, operators resort to antifreeze additives, which efficiency is defeated either by harder operating conditions or by a more severe environmental legislation. So research recently shifted towards a new class of 'low dosage inhibitors'. In order to understand the influence of such additives, we designed a high pressure reactor, fitted with a liquid injection device and an in situ turbidimetric sensor. Access to both the particle size distribution of the suspension during the first stages of crystallization, and the total gas consumption, allows us to characterize the kinetics of methane hydration formation. First, we developed an original experimental procedure, which generates an initial 'breeding' of the solution, and thus improves the mastering of nucleation. The induction time then becomes one of the relevant parameters to investigate the performance of inhibitors. Afterwards, we performed a first series of experiments which allowed us to determine the influence of the operating conditions (pressure and stirring) on the evolution of the particle size distribution, in the absence of additives. Then, we pointed out the inhibiting effect of a model kinetic inhibitor, polyvinylpyrrolidone. When dissolved in the solution before crystallization occurs, it increases the induction delay, decreases the gas consumption rate and also slows down the birth of new particles for several hours. On the contrary, when injected in the medium during crystallization, this polymer no more affects the reaction kinetics. At last, we raise the bases for a modelling, taking into account the elementary crystallization processes of nucleation, growth and particles agglomeration. A parametric study has been confronted to the experimental data. It enables us to suggest hypotheses regarding the effect of gas hydrates kinetic

  5. Low- and high-frequency cortical brain oscillations reflect dissociable mechanisms of concurrent speech segregation in noise.

    Science.gov (United States)

    Yellamsetty, Anusha; Bidelman, Gavin M

    2018-04-01

    Parsing simultaneous speech requires listeners use pitch-guided segregation which can be affected by the signal-to-noise ratio (SNR) in the auditory scene. The interaction of these two cues may occur at multiple levels within the cortex. The aims of the current study were to assess the correspondence between oscillatory brain rhythms and determine how listeners exploit pitch and SNR cues to successfully segregate concurrent speech. We recorded electrical brain activity while participants heard double-vowel stimuli whose fundamental frequencies (F0s) differed by zero or four semitones (STs) presented in either clean or noise-degraded (+5 dB SNR) conditions. We found that behavioral identification was more accurate for vowel mixtures with larger pitch separations but F0 benefit interacted with noise. Time-frequency analysis decomposed the EEG into different spectrotemporal frequency bands. Low-frequency (θ, β) responses were elevated when speech did not contain pitch cues (0ST > 4ST) or was noisy, suggesting a correlate of increased listening effort and/or memory demands. Contrastively, γ power increments were observed for changes in both pitch (0ST > 4ST) and SNR (clean > noise), suggesting high-frequency bands carry information related to acoustic features and the quality of speech representations. Brain-behavior associations corroborated these effects; modulations in low-frequency rhythms predicted the speed of listeners' perceptual decisions with higher bands predicting identification accuracy. Results are consistent with the notion that neural oscillations reflect both automatic (pre-perceptual) and controlled (post-perceptual) mechanisms of speech processing that are largely divisible into high- and low-frequency bands of human brain rhythms. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Intrahippocampal Pathways Involved in Learning/Memory Mechanisms are Affected by Intracerebral Infusions of Amyloid-β25-35 Peptide and Hydrated Fullerene C60 in Rats.

    Science.gov (United States)

    Gordon, Rita; Podolski, Igor; Makarova, Ekaterina; Deev, Alexander; Mugantseva, Ekaterina; Khutsyan, Sergey; Sengpiel, Frank; Murashev, Arkady; Vorobyov, Vasily

    2017-01-01

    Primary memory impairments associated with increased level of amyloid-β (Aβ) in the brain have been shown to be linked, partially, with early pathological changes in the entorhinal cortex (EC) which spread on the whole limbic system. While the hippocampus is known to play a key role in learning and memory mechanisms, it is as yet unclear how its structures are involved in the EC pathology. In this study, changes in memory and neuronal morphology in male Wistar rats intrahippocampally injected with Aβ25-35 were correlated on days 14 and 45 after the injection to reveal specific cognitive-structural associations. The main focus was on the dentate gyrus (DG) and hippocampal areas of CA1 and CA3 because of their involvement in afferent flows from EC to the hippocampus through tri-synaptic (EC → DG → CA3 → CA1) and/or mono-synaptic (EC → CA1) pathways. Evident memory impairments were observed at both time points after Aβ25-35 injection. However, on day 14, populations of morphological intact neurons were decreased in CA3 and, drastically, in CA1, and the DG supramedial bundle was significantly damaged. On day 45, this bundle largely and CA1 neurons partially recovered, whereas CA3 neurons remained damaged. We suggest that Aβ25-35 primarily affects the tri-synaptic pathway, destroying the granular cells in the DG supramedial area and neurons in CA3 and, through the Schaffer collaterals, in CA1. Intrahippocampal pretreatment with hydrated fullerene C60 allows the neurons and their connections to survive the amyloidosis, thus supporting the memory mechanisms.

  7. 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)

  8. 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)

  9. 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.

  10. Mecanismos de hidratação do óxido de magnésio Mechanisms of magnesium oxide hydration

    Directory of Open Access Journals (Sweden)

    L. F. Amaral

    2007-12-01

    Full Text Available O óxido de magnésio, MgO, é uma importante matéria-prima para a indústria de refratários por ser um material de elevada refratariedade (ponto de fusão próximo a 2800 °C, resistente a escórias básicas, e de custo competitivo. No entanto, em presença de água, o MgO rapidamente se hidrata formando hidróxido de magnésio, Mg(OH2. Essa reação leva a uma expansão volumétrica de até três vezes, limitando sua aplicação em concretos refratários. Para desenvolver soluções que minimizem este problema, torna-se necessário um melhor entendimento do mecanismo pelo qual o MgO se hidrata e quais as principais variáveis envolvidas. Dois mecanismos distintos para esta reação foram propostos: a dissolução seguida de precipitação e b reação em uma única etapa ocorrendo diretamente na superfície das partículas. Este trabalho apresenta uma revisão crítica com relação aos mecanismos propostos e sua potencial aplicação em concretos refratários contendo MgO. Suspensões aquosas de MgO e diferentes técnicas de caracterização (ensaios reológicos oscilatórios, medidas de expansão volumétrica aparente e condutividade iônica permitiram correlacionar os mecanismos apresentados, principalmente com respeito à cinética da reação de hidratação.Magnesium oxide, MgO, is an important raw material for refractories industry due to its high refractoriness (melting point of approximately 2800 ºC, corrosion resistance in basic environment and competitive cost. Nevertheless, MgO presents a great tendency to react with water producing magnesium hydroxide, Mg(OH2. This reaction generates a threefold volumetric expansion and could lead to material breakdown inhibiting its application in refractory castables. In order to develop solutions to minimize this effect, a further understanding of the magnesia hydration mechanism and the main variables involved in this reaction is required. Two different mechanisms were proposed: a

  11. Two Mechanisms for Methane Release at the Paleocene/Eocene Boundary

    Science.gov (United States)

    Katz, M. E.; Cramer, B. S.; Mountain, G. S.; Mountain, G. S.; Katz, S.; Miller, K. G.; Miller, K. G.

    2001-12-01

    The rapid global warming of the Paleocene/Eocene thermal maximum (PETM) has been attributed to a massive methane release from marine gas hydrate reservoirs. Two mechanisms have been proposed for this methane release. The first relies on a deepwater circulation change and water temperature increase that was sufficiently large and rapid to trigger massive thermal dissociation of gas hydrate frozen beneath the seafloor (Dickens et al., 1995). The second relies on slope failure (via erosion or seismic activity) of the oversteepened continental margins of the western North Atlantic to allow methane to escape from gas reservoirs trapped between the hydrate-bearing sediments and the underlying reef front (Katz et al., in press). We evaluate thermal dissociation by modeling heat flow through the sediments to show the effect of the temperature change on the gas hydrate stability zone through time. We use Paleocene bottom water temperatures (constrained by isotope records) and assume an instantaneous water temperature increase (i.e., no time allotted for ocean circulation change and water mass mixing). This yields an end-member minimum estimate of >2350 years necessary to melt all gas hydrate at locations shallower than 1570m; gas hydrates at greater depths remain frozen. We also use this model to predict the amount of C12-enriched methane that could have contributed to the carbon isotope excursion (CIE). Using reasonable methane distributions within sediments, we conclude that thermal dissociation alone cannot account for the full magnitude of the CIE. We propose that thermal dissociation did not initiate the CIE; rather, a different mechanism injected a large amount of carbon into the atmosphere, causing global greenhouse warming that could have led to subsequent thermal dissociation. Methane remains a plausible source for this initial carbon injection; however, initial release would have resulted from mechanical disruption of sediments rather than thermal dissociation

  12. 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

  13. 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

  14. Cannabinoid transmission in the prelimbic cortex bidirectionally controls opiate reward and aversion signaling through dissociable kappa versus μ-opiate receptor dependent mechanisms.

    Science.gov (United States)

    Ahmad, Tasha; Lauzon, Nicole M; de Jaeger, Xavier; Laviolette, Steven R

    2013-09-25

    Cannabinoid, dopamine (DA), and opiate receptor pathways play integrative roles in emotional learning, associative memory, and sensory perception. Modulation of cannabinoid CB1 receptor transmission within the medial prefrontal cortex (mPFC) regulates the emotional valence of both rewarding and aversive experiences. Furthermore, CB1 receptor substrates functionally interact with opiate-related motivational processing circuits, particularly in the context of reward-related learning and memory. Considerable evidence demonstrates functional interactions between CB1 and DA signaling pathways during the processing of motivationally salient information. However, the role of mPFC CB1 receptor transmission in the modulation of behavioral opiate-reward processing is not currently known. Using an unbiased conditioned place preference paradigm with rats, we examined the role of intra-mPFC CB1 transmission during opiate reward learning. We report that activation or inhibition of CB1 transmission within the prelimbic cortical (PLC) division of the mPFC bidirectionally regulates the motivational valence of opiates; whereas CB1 activation switched morphine reward signaling into an aversive stimulus, blockade of CB1 transmission potentiated the rewarding properties of normally sub-reward threshold conditioning doses of morphine. Both of these effects were dependent upon DA transmission as systemic blockade of DAergic transmission prevented CB1-dependent modulation of morphine reward and aversion behaviors. We further report that CB1-mediated intra-PLC opiate motivational signaling is mediated through a μ-opiate receptor-dependent reward pathway, or a κ-opiate receptor-dependent aversion pathway, directly within the ventral tegmental area. Our results provide evidence for a novel CB1-mediated motivational valence switching mechanism within the PLC, controlling dissociable subcortical reward and aversion pathways.

  15. Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

    Science.gov (United States)

    Lunine, J. I.; Stevenson, D. J.

    1985-01-01

    The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

  16. Ground movements associated with gas hydrate production

    International Nuclear Information System (INIS)

    Siriwardane, H.J.; Kutuk, B.

    1992-03-01

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

  17. Methane Hydrate in Confined Spaces: An Alternative Storage System.

    Science.gov (United States)

    Borchardt, Lars; Casco, Mirian Elizabeth; Silvestre-Albero, Joaquin

    2018-03-14

    Methane hydrate inheres the great potential to be a nature-inspired alternative for chemical energy storage, as it allows to store large amounts of methane in a dense solid phase. The embedment of methane hydrate in the confined environment of porous materials can be capitalized for potential applications as its physicochemical properties, such as the formation kinetics or pressure and temperature stability, are significantly changed compared to the bulk system. We review this topic from a materials scientific perspective by considering porous carbons, silica, clays, zeolites, and polymers as host structures for methane hydrate formation. We discuss the contribution of advanced characterization techniques and theoretical simulations towards the elucidation of the methane hydrate formation and dissociation process within the confined space. We outline the scientific challenges this system is currently facing and look on possible future applications for this technology. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Maximum Recoverable Gas from Hydrate Bearing Sediments by Depressurization

    KAUST Repository

    Terzariol, Marco

    2017-11-13

    The estimation of gas production rates from hydrate bearing sediments requires complex numerical simulations. This manuscript presents a set of simple and robust analytical solutions to estimate the maximum depressurization-driven recoverable gas. These limiting-equilibrium solutions are established when the dissociation front reaches steady state conditions and ceases to expand further. Analytical solutions show the relevance of (1) relative permeabilities between the hydrate free sediment, the hydrate bearing sediment, and the aquitard layers, and (2) the extent of depressurization in terms of the fluid pressures at the well, at the phase boundary, and in the far field. Close form solutions for the size of the produced zone allow for expeditious financial analyses; results highlight the need for innovative production strategies in order to make hydrate accumulations an economically-viable energy resource. Horizontal directional drilling and multi-wellpoint seafloor dewatering installations may lead to advantageous production strategies in shallow seafloor reservoirs.

  19. Infrared spectroscopy for monitoring gas hydrates in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Dobbs, G.T.; Luzinova, Y.; Mizaikoff, B. [Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry; Raichlin, Y.; Katzir, A. [Tel-Aviv Univ., Tel-Aviv (Israel). Shool of Physics and Astronomy

    2008-07-01

    This paper introduced the first principles for monitoring gas hydrate formation and dissociation in aqueous solution by evaluating state-responsive infrared (IR) absorption features of water with fiberoptic evanescent field spectroscopy. A first order linear functional relationship was also derived according to Lambert Beer's law in order to quantify the percentage gas hydrate within the volume of water probed via the evanescent field. In addition, spectroscopic studies evaluating seafloor sediments collected from a gas hydrate site in the Gulf of Mexico revealed minimal spectral interferences from sediment matrix components. As such, evanescent field sensing strategies were established as a promising perspective for monitoring the dynamics of gas hydrates in oceanic environments. 21 refs., 5 figs.

  20. 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.

  1. 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.

  2. 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.

  3. Preservation of methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

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

  4. Hydro-bio-geomechanical properties of hydrate-bearing sediments from Nankai Trough

    Science.gov (United States)

    Santamarina, J.C.; Dai, Shifeng; Terzariol, M.; Jang, Jeonghwan; Waite, William F.; Winters, William J.; Nagao, J.; Yoneda, J.; Konno, Y.; Fujii, T.; Suzuki, K.

    2015-01-01

    Natural hydrate-bearing sediments from the Nankai Trough, offshore Japan, were studied using the Pressure Core Characterization Tools (PCCTs) to obtain geomechanical, hydrological, electrical, and biological properties under in situ pressure, temperature, and restored effective stress conditions. Measurement results, combined with index-property data and analytical physics-based models, provide unique insight into hydrate-bearing sediments in situ. Tested cores contain some silty-sands, but are predominantly sandy- and clayey-silts. Hydrate saturations Sh range from 0.15 to 0.74, with significant concentrations in the silty-sands. Wave velocity and flexible-wall permeameter measurements on never-depressurized pressure-core sediments suggest hydrates in the coarser-grained zones, the silty-sands where Sh exceeds 0.4, contribute to soil-skeletal stability and are load-bearing. In the sandy- and clayey-silts, where Sh < 0.4, the state of effective stress and stress history are significant factors determining sediment stiffness. Controlled depressurization tests show that hydrate dissociation occurs too quickly to maintain thermodynamic equilibrium, and pressure–temperature conditions track the hydrate stability boundary in pure-water, rather than that in seawater, in spite of both the in situ pore water and the water used to maintain specimen pore pressure prior to dissociation being saline. Hydrate dissociation accompanied with fines migration caused up to 2.4% vertical strain contraction. The first-ever direct shear measurements on never-depressurized pressure-core specimens show hydrate-bearing sediments have higher sediment strength and peak friction angle than post-dissociation sediments, but the residual friction angle remains the same in both cases. Permeability measurements made before and after hydrate dissociation demonstrate that water permeability increases after dissociation, but the gain is limited by the transition from hydrate saturation

  5. Fear Memory Recall Potentiates Opiate Reward Sensitivity through Dissociable Dopamine D1 vs. D4 Receptor-Dependent Memory Mechanisms in the Prefrontal Cortex.

    Science.gov (United States)

    Li, Jing Jing; Szkudlarek, Hanna; Renard, Justine; Hudson, Roger; Rushlow, Walter; Laviolette, Steven R

    2018-04-23

    Disturbances in prefrontal cortical (PFC) dopamine (DA) transmission are well-established features of psychiatric disorders involving pathological memory processing, such as post-traumatic stress disorder (PTSD) and opioid addiction. Transmission through PFC DA D4 receptors (D4R) has been shown to potentiate the emotional salience of normally non-salient emotional memories whereas transmission through PFC DA D1 receptors (D1R) has been demonstrated to selectively block recall of reward or aversion-related associative memories. In the present study, using a combination of fear conditioning and opiate reward conditioning in male rats, we examined the role of PFC D4/D1R signaling during the processing of fear-related memory acquisition and recall and subsequent sensitivity to opiate reward memory formation. We report that PFC D4R activation potentiates the salience of normally sub-threshold fear conditioning memory cues and simultaneously potentiates the rewarding effects of systemic or intra-ventral tegmental area (VTA) morphine conditioning cues. In contrast, blocking the recall of salient fear memories with intra-PFC D1R activation, blocks the ability of fear memory recall to potentiate systemic or intra-VTA morphine place preference. These effects were dependent upon dissociable PFC phosphorylation states involving calcium-calmodulin-kinase II (CaMKII-α) or extracellular-signal-related-kinase 1-2 (ERK 1/2), following intra-PFC D4 or D1R activation, respectively. Together, these findings reveal new insights into how aberrant PFC DAergic transmission and associated downstream molecular signaling pathways may modulate fear-related emotional memory processing and concomitantly increase opioid addiction vulnerability. Significance Statement: Post-traumatic stress disorder is highly comorbid with addiction. In this study, we use a translational model of fear memory conditioning to examine how transmission through dopamine D1 or D4 receptors, in the prefrontal cortex

  6. Comparing the sensitivity of permafrost and marine gas hydrate to climate warming

    International Nuclear Information System (INIS)

    Taylor, A.E.; Dallimore, S.R.; Hyndman, R.D.; Wright, F.

    2005-01-01

    The sensitivity of Arctic subpermafrost gas hydrate at the Mallik borehole was compared to temperate marine gas hydrate located offshore southwestern Canada. In particular, a finite element geothermal model was used to determine the sensitivity to the end of the ice age, and contemporary climate warming of a 30 m thick methane hydrate layer lying at the base of a gas hydrate stability zone prior to 13.5 kiloannum (ka) before present (BP). It was suggested that the 30 m gas-hydrate-bearing layer would have disappeared by now, according to the thermal signal alone. However, the same gas-hydrate-bearing layer underlying permafrost would persist until at least 4 ka after present, even with contemporary climate warming. The longer time for subpermafrost gas hydrate comes from the thawing pore ice at the base of permafrost, at the expense of dissociation of the deeper gas hydrate. The dissociation of underlying gas hydrate from climate surface warming is buffered by the overlying permafrost

  7. Impact of pore-water freshening on clays and the compressibility of hydrate-bearing reservoirs during production

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Junbong [U.S. Geological Survey, Woods Hole, MA; Cao, Shuang [Louisiana State University, Baton Rouge, LA; Waite, William [U.S. Geological Survey, Woods Hole, MA; Jung, Jongwon [Chungbuk National University, Cheongju-si, Chungbuk, South Korea

    2017-06-25

    Gas production efficiency from natural hydrate-bearing sediments depends in part on geotechnical properties of fine-grained materials, which are ubiquitous even in sandy hydrate-bearing sediments. The responses of fine-grained material to pore fluid chemistry changes due to freshening during hydrate dissociation could alter critical sediment characteristics during gas production activities. We investigate the electrical sensitivity of fine grains to pore fluid freshening and the implications of freshening on sediment compression and recompression parameters.

  8. 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

  9. 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.

  10. Wavepacket theory of collisional dissociation in molecules

    International Nuclear Information System (INIS)

    Kulander, K.

    1980-01-01

    An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H 2 system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process

  11. 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

  12. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  13. Preliminary Experimental Examination Of Controls On Methane Expulsion During Melting Of Natural Gas Hydrate Systems

    Science.gov (United States)

    Kneafsey, T. J.; Flemings, P. B.; Bryant, S. L.; You, K.; Polito, P. J.

    2013-12-01

    Global climate change will cause warming of the oceans and land. This will affect the occurrence, behavior, and location of subseafloor and subterranean methane hydrate deposits. We suggest that in many natural systems local salinity, elevated by hydrate formation or freshened by hydrate dissociation, may control gas transport through the hydrate stability zone. We are performing experiments and modeling the experiments to explore this behavior for different warming scenarios. Initially, we are exploring hydrate association/dissociation in saline systems with constant water mass. We compare experiments run with saline (3.5 wt. %) water vs. distilled water in a sand mixture at an initial water saturation of ~0.5. We increase the pore fluid (methane) pressure to 1050 psig. We then stepwise cool the sample into the hydrate stability field (~3 degrees C), allowing methane gas to enter as hydrate forms. We measure resistivity and the mass of methane consumed. We are currently running these experiments and we predict our results from equilibrium thermodynamics. In the fresh water case, the modeled final hydrate saturation is 63% and all water is consumed. In the saline case, the modeled final hydrate saturation is 47%, the salinity is 12.4 wt. %, and final water saturation is 13%. The fresh water system is water-limited: all the water is converted to hydrate. In the saline system, pore water salinity is elevated and salt is excluded from the hydrate structure during hydrate formation until the salinity drives the system to three phase equilibrium (liquid, gas, hydrate) and no further hydrate forms. In our laboratory we can impose temperature gradients within the column, and we will use this to investigate equilibrium conditions in large samples subjected to temperature gradients and changing temperature. In these tests, we will quantify the hydrate saturation and salinity over our meter-long sample using spatially distributed temperature sensors, spatially distributed

  14. Dissociation in mediation

    Directory of Open Access Journals (Sweden)

    Daniela Muraru

    2008-01-01

    Full Text Available This paper approaches several texts that are part of the so-called discourse of mediation, adopting a pragma-dialectical perspective of the theory of dissociation. It is an attempt to identify the uses of dissociative patterns, with special emphasis on the indicators of dissociation. The paper investigates the various uses of the concept of dissociation as a discursive technique in the argumentation on the different aspects that are involved in international conflict, such as the discussion of the notion of peace. The purpose is to identify the role of dissociation, as a device strategically used by the mediator to help the parties minimize the disagreement space, and come to a conflict resolution.

  15. The effect of Pd ensemble structure on the O2 dissociation and CO oxidation mechanisms on Au—Pd(100) surface alloys

    Science.gov (United States)

    Oǧuz, Ismail-Can; Mineva, Tzonka; Guesmi, Hazar

    2018-01-01

    The reactivity of various Pd ensembles on the Au—Pd(100) alloy catalyst toward CO oxidation was investigated by using density functional theory (DFT). This study was prompted by the search for efficient catalysts operating at low temperature for the CO oxidation reaction that is of primary environmental importance. To this aim, we considered Pd modified Au(100) surfaces including Pd monomers, Pd dimers, second neighboring Pd atoms, and Pd chains in a comparative study of the minimum energy reaction pathways. The effect of dispersion interactions was included in the calculations of the O2 dissociation reaction pathway by using the DFT-D3 scheme. The addition of the dispersion interaction strongly improves the adsorption ability of O2 on the Au—Pd surface but does not affect the activation energy barriers of the Transitions States (TSs). As for O2 to dissociate, it is imperative that the TS has lower activation energy than the O2 desorption energy. DFT-D3 is found to favor, in some cases, O2 dissociation on configurations being identified from uncorrected DFT calculations as inactive. This is the case of the second neighboring Pd configuration for which uncorrected DFT predicts positive Gibbs free energy (ΔG) of the O2 adsorption, therefore an endergonic reaction. With the addition of D3 correction, ΔG becomes negative that reveals a spontaneous O2 adsorption. Among the investigated Au—Pd (100) ensembles, the Pd chain dissociates most easily O2 and highly stabilizes the dissociated O atoms; however, it has an inferior reactivity toward CO oxidation and CO2 formation. Indeed, CO strongly adsorbs on the palladium bridge sites and therefore poisoning the surface Pd chain. By contrast, the second neighboring Pd configuration that shows somewhat lower ability to dissociate O2 turns out to be more reactive in the CO2 formation step. These results evidence the complex effect of Pd ensembles on the CO oxidation reaction. Associative CO oxidation proceeds with high

  16. Effect of gas hydrates melting on seafloor slope stability

    Science.gov (United States)

    Sultan, N.; Cochonat, P.; Foucher, J. P.; Mienert, J.; Haflidason, H.; Sejrup, H. P.

    2003-04-01

    Quantitative studies of kinetics of gas hydrate formation and dissociation is of a particular concern to the petroleum industry for an evaluation of environmental hazards in deep offshore areas. Gas hydrate dissociation can generate excess pore pressure that considerably decreases the strength of the soil. In this paper, we present a theoretical study of the thermodynamic chemical equilibrium of gas hydrate in soil, which is based on models previously reported by Handa (1989), Sloan (1998) and Henry (1999). Our study takes into account the influence of temperature, pressure, pore water chemistry, and the pore size distribution of the sediment. This model fully accounts for the latent heat effects, as done by Chaouch and Briaud (1997) and Delisle et al. (1998). It uses a new formulation based on the enthalpy form of the law of conservation of energy. The model allows for the evaluation of the excess pore pressure generated during gas hydrate dissociation using the Soave’s (1972) equation of state. Fluid flow in response to the excess pore pressure is simulated using the finite element method. In the second part of the paper, we present and discuss an application of the model through a back-analysis of the case of the giant Storegga slide on the Norwegian margin. Two of the most important changes during and since the last deglaciation (hydrostatic pressure due to the change of the sea level and the increase of the sea water temperature) were considered in the calculation. Simulation results are presented and discussed. Chaouch, A., &Briaud, J.-L., 1997. Post melting behavior of gas hydrates in soft ocean sediments, OTC-8298, in 29th offshore technology conference proceedings, v. 1, Geology, earth sciences and environmental factors: Society of Petroleum Engineers, p. 217-224. Delisle, G.; Beiersdorf, H.; Neben, S.; Steinmann, D., 1998. The geothermal field of the North Sulawesi accretionary wedge and a model on BSR migration in unstable depositional environments. in

  17. 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.

  18. Radiative capture versus Coulomb dissociation

    International Nuclear Information System (INIS)

    Esbensen, H.; Physics

    2006-01-01

    Measurements of the Coulomb dissociation of 8 B have been used to infer the rate of the inverse radiative proton capture on 7 Be. The analysis is usually based on the assumptions that the two processes are related by detailed balance and described by E1 transitions. However, there are corrections to this relation. The Coulomb form factors for the two processes, for example, are not identical. There are also E2 transitions and higher-order effects in the Coulomb dissociation, and the nuclear induced breakup cannot always be ignored. While adding first-order E2 transitions enhances the decay energy spectrum, the other mechanisms cause a suppression at low relative energies. The net result may accidentally be close to the conventional first-order E1 calculation, but there are differences which cannot be ignored if accuracies of 10% or better are needed

  19. Radiative Capture versus Coulomb Dissociation

    International Nuclear Information System (INIS)

    Esbensen, Henning

    2006-01-01

    Measurements of the Coulomb dissociation of 8B have been used to infer the rate of the inverse radiative proton capture on 7Be. The analysis is usually based on the assumptions that the two processes are related by detailed balance and described by E1 transitions. However, there are corrections to this relation. The Coulomb form factors for the two processes, for example, are not identical. There are also E2 transitions and higher-order effects in the Coulomb dissociation, and the nuclear induced breakup cannot always be ignored. While adding first-order E2 transitions enhances the decay energy spectrum, the other mechanisms cause a suppression at low relative energies. The net result may accidentally be close to the conventional first-order E1 calculation, but there are differences which cannot be ignored if accuracies of 10% or better are needed

  20. Permeability of sediment cores from methane hydrate deposit in the Eastern Nankai Trough, Japan

    Science.gov (United States)

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

    2013-12-01

    Effective and absolute permeability are key parameters for gas production from methane-hydrate-bearing sandy sediments. Effective and/or absolute permeability have been measured using methane-hydrate-bearing sandy cores and clayey and silty cores recovered from Daini Atsumi Knoll in the Eastern Nankai Trough during the 2012 JOGMEC/JAPEX Pressure coring operation. Liquid-nitrogen-immersed cores were prepared by rapid depressurization of pressure cores recovered by a pressure coring system referred to as the Hybrid PCS. Cores were shaped cylindrically on a lathe with spraying of liquid nitrogen to prevent hydrate dissociation. Permeability was measured by a flooding test or a pressure relaxation method under near in-situ pressure and temperature conditions. Measured effective permeability of hydrate-bearing sediments is less than tens of md, which are order of magnitude less than absolute permeability. Absolute permeability of clayey cores is approximately tens of μd, which would perform a sealing function as cap rocks. Permeability reduction due to a swelling effect was observed for a silty core during flooding test of pure water mimicking hydrate-dissociation-water. Swelling effect may cause production formation damage especially at a later stage of gas production from methane hydrate deposits. This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI).

  1. CH4 recovery and CO2 sequestration using flue gas in natural gas hydrates as revealed by a micro-differential scanning calorimeter

    International Nuclear Information System (INIS)

    Lee, Yohan; Kim, Yunju; Lee, Jaehyoung; Lee, Huen; Seo, Yongwon

    2015-01-01

    Highlights: • The extent of the replacement was improved due to the enclathration of N 2 in small cages. • The dissociation enthalpies of the replaced gas hydrates were measured. • There was no noticeable heat flow change during the CH 4 –flue gas replacement. • The replacement could occur without significant destruction of gas hydrates. - Abstract: The CH 4 –flue gas replacement in naturally occurring gas hydrates has attracted significant attention due to its potential as a method of exploitation of clean energy and sequestration of CO 2 . In the replacement process, the thermodynamic and structural properties of the mixed gas hydrates are critical factors to predict the heat flow in the hydrate-bearing sediments and the heat required for hydrate dissociation, and to evaluate the CO 2 storage capacity of hydrate reservoirs. In this study, the 13 C NMR and gas composition analyses confirmed that the preferential enclathration of N 2 molecules in small 5 12 cages of structure I hydrates improved the extent of the CH 4 recovery. A high pressure micro-differential scanning calorimeter (HP μ-DSC) provided reliable hydrate stability conditions and heat of dissociation values in the porous silica gels after the replacement, which confirmed that CH 4 in the hydrates was successfully replaced with flue gas. A heat flow change associated with the dissociation and formation of hydrates was not noticeable during the CH 4 –flue gas replacement. Therefore, this study reveals that CH 4 –flue gas swapping occurs without structural transitions and significant hydrate dissociations

  2. Energy distribution in dissociations of polyatomic molecules

    International Nuclear Information System (INIS)

    Koernig, S.A.

    1989-01-01

    In this thesis studies are reported of fragmentation processes in polyatomic molecules. In order to find out which dessocaciation reactions take place, how they are brought about by the internal energy of the reactant, and to investigate the structure of the dissociating 'transition state', the fragment mass and the corresponding kinetic energy release (KER) are determined by differential translational spectroscopy using a position and time sensitive two-particle coincidence detector. The results are interpreted using the statistical theory of unimolecular dissociation. It turns out that the standard assumptions of the theory, especially in calculating KER-distributions, are not realistic in all molecules considered. Dissociation is induced by the neutralization with alkali metal vapour. In ch. 2 the experimental method and the analysis of the data (dissociation pathways, branching ratios and ε-d-distributions) are introduced and exemplified by measurements of cyclohexane, which represents the upper limit in precursor and fragment mass accessible in the apparatus. In ch. 3 a study is reported of the molecules methylchloride (CH 3 Cl) and the acetylradical (CH 3 CO). In spite of their similar geometric structures, completely different dissociation mechanisms have been found. Methylchloride dissociates via a repulsive state; acetyl radicals show energy scrambling. The energy distribution from dissociating acetyl exemplifies dynamical effects in the dissociation. In ch. 4 an investigation of a number of prototype hydrocarbons is presented. The dissociation pathways of several small linear alkanes indicate that neutralization takes place to unknown repulsive potentials, of which the position and steepness are determined from the kinetic energy release. (author). 118 refs.; 40 figs.; 5 tabs

  3. 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.

  4. Gas hydrates: entrance to a methane age or climate threat?

    International Nuclear Information System (INIS)

    Krey, Volker; Nakicenovic, Nebojsa; Grubler, Arnulf; O'Neill, Brian; Riahi, Keywan; Canadell, Josep G; Abe, Yuichi; Andruleit, Harald; Archer, David; Hamilton, Neil T M; Johnson, Arthur; Kostov, Veselin; Lamarque, Jean-Francois; Langhorne, Nicholas; Nisbet, Euan G; Riedel, Michael; Wang Weihua; Yakushev, Vladimir

    2009-01-01

    Methane hydrates, ice-like compounds in which methane is held in crystalline cages formed by water molecules, are widespread in areas of permafrost such as the Arctic and in sediments on the continental margins. They are a potentially vast fossil fuel energy source but, at the same time, could be destabilized by changing pressure-temperature conditions due to climate change, potentially leading to strong positive carbon-climate feedbacks. To enhance our understanding of both the vulnerability of and the opportunity provided by methane hydrates, it is necessary (i) to conduct basic research that improves the highly uncertain estimates of hydrate occurrences and their response to changing environmental conditions, and (ii) to integrate the agendas of energy security and climate change which can provide an opportunity for methane hydrates-in particular if combined with carbon capture and storage-to be used as a 'bridge fuel' between carbon-intensive fossil energies and zero-emission energies. Taken one step further, exploitation of dissociating methane hydrates could even mitigate against escape of methane to the atmosphere. Despite these opportunities, so far, methane hydrates have been largely absent from energy and climate discussions, including global hydrocarbon assessments and the Fourth Assessment Report of the Intergovernmental Panel on Climate Change.

  5. Electron spin resonance study on γ-ray-induced radical species in ethylene hydrate

    International Nuclear Information System (INIS)

    Takeya, Kei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

    2007-01-01

    Electron spin resonance (ESR) study on γ-irradiated synthetic ethylene hydrate was performed to investigate induced radicals and their thermal stability. ESR spectra of induced 3-butenyl radical (.CH 2 C 2 H 3 =CH 2 ,g=2.0039±0.0005,A α =2.2±0.1mTandA β =3.0±0.1mT) and induced ethyl radical (.C 2 H 5 , g=2.0044±0.0005, A α =2.2±0.1mT and A β =2.7±0.1mT) were observed in irradiated ethylene hydrate. The decay of the 3-butenyl radicals was observed above 200 K with the activation energy of 51.9±4.4kJ/mol. The obvious decay of ethyl radicals starts above 240 K that is close to the dissociation temperature of ethylene hydrate at atmospheric pressure. The activation energy of the ethyl radical decay is estimated as 63.4±8.2kJ/mol and nearly equal to the enthalpy change of ethylene hydrate into liquid water and gaseous ethylene. It is suggested that the decay of ethyl radicals would be caused by the hydrate dissociation and that ethylene hydrate dissociates into water (supercooled) and ethylene at 240-265 K.

  6. Relation of submarine landslide to hydrate occurrences in Baiyun Depression, South China Sea

    Science.gov (United States)

    Sun, Yunbao; Zhang, Xiaohua; Wu, Shiguo; Wang, Lei; Yang, Shengxiong

    2018-02-01

    Submarine landslides have been observed in the Baiyun Depression of the South China Sea. The occurrence of hydrates below these landslides indicates that these slope instabilities may be closely related to the massive release of methane. In this study, we used a simple Monte-Carlo model to determine the first-order deformation pattern of a gravitationally destabilizing slope. The results show that a stress concentration occurs due to hydrate dissociation on the nearby glide surface and on top of a gas chimney structure. Upon the dissolution of the gas hydrate, slope failure occurs due to the excess pore pressure generated by the dissociation of the gas hydrates. When gas hydrates dissociate at shallow depths, the excess pore pressure generated can be greater than the total stress acting at those points, along with the forces that resist sliding. Initially, the failure occurs at the toe of the slope, then extends to the interior. Although our investigation focused only on the contribution of hydrate decomposition to submarine landslide, this process is also affected by both the slope material properties and topography.

  7. Hydrate phase equilibria of furan, acetone, 1,4-dioxane, TBAC and TBAF

    International Nuclear Information System (INIS)

    Kamran-Pirzaman, Arash; Pahlavanzadeh, Hassan; Mohammadi, Amir H.

    2013-01-01

    Highlights: • Experimental hydrate dissociation conditions are reported for CO 2 /methane + some water soluble/insoluble hydrate formers. • An isochoric pressure-search method was used to generate the experimental data. • The data are compared with the corresponding literature data in the presence of pure water. • The hydrate promotion effects of acetone, 1,4-dioxane, furan, TBAC and TBAF are discussed. -- Abstract: In this communication, we first report experimental hydrate dissociation pressures for the methane/carbon dioxide + furan/acetone/1,4-dioxane + water and the methane + tetra n-butyl ammonium chloride (TBAC) + water as well as the carbon dioxide + tetra n-butyl ammonium floride (TBAF) + water systems in the temperature ranges of (269.9 to 303.3) K. An isochoric pressure-search method was used to generate the experimental data. The hydrate dissociation data are compared with the corresponding literature data, if exists, and the literature data in the presence of pure water and acceptable agreement is observed. A discussion is made on hydrate promotion effects of acetone, 1,4-dioxane, furan, TBAC and TBAF

  8. 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.

  9. 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.

  10. 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.

  11. Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

    Science.gov (United States)

    Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

    2018-05-01

    Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

  12. [Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

    Science.gov (United States)

    Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

    2015-11-01

    Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

  13. Hydration of Portland cement with additions of calcium sulfoaluminates

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  14. Experimental preparation of Kr/Xe hydrate at pressures up to 160 bar

    International Nuclear Information System (INIS)

    Simonis, R.

    1985-06-01

    A compound called gas (mixture) hydrate is formed under pressurized atmosphere by reaction of krypton, xenon and a mixture of both with water. The study under review reports on preparing such hydrates experimentally under pressures up to 160 bar. The dissociation function of the hydrates is determined by low and medium-pressure experiments. Observing the formation process it was found that a hydrate layer is formed at the interface of gas and water, its separating effect almost inhibiting continuance of hydrate reactions. Strong stirring will avoid or destroy the separating layer. It is shown that at pressures above 50 bar the dissociation function psub(D) (T) gets non-linear with logarithmic pressure plotting above the absolute, reciprocal temperature. The medium-temperature experiments show that the density of the gas consisting of Xe or Kr and Xe, respectively, reaches higher values than that of the water. In this case, the system collapses and the gas is found at the bottom of the pressure flask, and the water in the top region. The gas samples taken during the mixed hydrate preparation show that Kr is accumulated in the gaseous phase, and Xe in the hydrate phase. (orig./RB) [de

  15. In-situ study of the thermal properties of hydrate slurry by high pressure DSC

    Energy Technology Data Exchange (ETDEWEB)

    Sari, O.; Hu, J.; Brun, F.; Erbeau, N. [Institute of Thermal Engineering, University of Applied Sciences of Western Switzerland, Yverdon-les-Bains (Switzerland); Homsy, P. [Nestec, Vevey (Switzerland); Logel, J.-C. [Axima Refrigeration, Bischheim (France)

    2008-07-01

    Knowing the enthalpy of hydrate slurry is very essential for energy balance and industrial applications. No direct measurement processes had been developed in this field in the past time. A new experimental method with special device has been developed to carry out on-line measurement of the thermal properties for hydrate slurry under dynamic conditions. With this special device, it is possible to deliver the hydrate slurry to the high pressure DSC (Differential Scanning Calorimetry) directly from the production tank or pipes. Thermal data acquisition will be performed afterwards by DSC. The investigated conditions were at pressure of 30 bar and temperature of {approx}+7 {sup o}C. The dissociation enthalpy of CO{sub 2} hydrate slurry was about 54 kJ/kg, corresponding 10.8% of solid fraction. The on-line measurement results for CO{sub 2} hydrate slurry give a good tendency to apply this phase change slurry to the industrial refrigeration process. (author)

  16. Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2013-01-01

    Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V...

  17. Photo-dissociation of hydrogen passivated dopants in gallium arsenide

    International Nuclear Information System (INIS)

    Tong, L.; Larsson, J.A.; Nolan, M.; Murtagh, M.; Greer, J.C.; Barbe, M.; Bailly, F.; Chevallier, J.; Silvestre, F.S.; Loridant-Bernard, D.; Constant, E.; Constant, F.M.

    2002-01-01

    A theoretical and experimental study of the photo-dissociation mechanisms of hydrogen passivated n- and p-type dopants in gallium arsenide is presented. The photo-induced dissociation of the Si Ga -H complex has been observed for relatively low photon energies (3.48 eV), whereas the photo-dissociation of C As -H is not observed for photon energies up to 5.58 eV. This fundamental difference in the photo-dissociation behavior between the two dopants is explained in terms of the localized excitation energies about the Si-H and C-H bonds

  18. 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

  19. Duality in diffraction dissociations

    International Nuclear Information System (INIS)

    Santoro, Alberto.

    1977-01-01

    Diffractive dissociations (aN→a*πN) are naturally explained and a model that accounts for the three-variable correlation (mass-transfer-Jackson angle correlation) is presented. This model takes into account the three possible exchanges: t (pion), u(a*) and s(a) channel exchanger. The physical consequences of the model are: a strong mass-slope correlation due to the zeros of the amplitude, a factorization of diffractive dissociations (factorization of the Pomeron), the possibility of extending this model to double diffractive dissociation and diffraction by nuclei. This model was applied to the NN→NπN reaction. Using the usual parameters of the Deck model, a comparison is made with experiments for all available distributions. the strong slope of the peak at 1400 MeV is naturally explained [fr

  20. Multicavity SCRF calculation of ion hydration energies

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  1. THz characterization of hydrated and anhydrous materials

    Science.gov (United States)

    Sokolnikov, Andre

    2011-06-01

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

  2. Study on gas hydrate as a new energy resource in the 21th century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

    1999-12-01

    Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

  3. Dissociative symptoms in kleptomania.

    Science.gov (United States)

    Grant, Jon E

    2004-02-01

    Many patients with kleptomania report an altered state of consciousness during acts of theft. The purpose of this investigation was to clarify a possible link between dissociation and kleptomania, a disabling disorder whose phenomenology remains understudied. 26 adult outpatients who met DSM-IV criteria for kleptoania were administered the Dissociative Experiences Scale and compared to 22 normal controls. The patients with kleptomania had scores that differed significantly from those reported by normal controls. There were no statistically significant differences by sex. Because kleptomania patients seeking treatment with medication may differ from others with kleptomania, further studies are needed.

  4. Controls on methane expulsion during melting of natural gas hydrate systems. Topic area 2

    Energy Technology Data Exchange (ETDEWEB)

    Flemings, Peter [Univ. of Texas, Austin, TX (United States)

    2016-01-14

    1.1. Project Goal The project goal is to predict, given characteristic climate-induced temperature change scenarios, the conditions under which gas will be expelled from existing accumulations of gas hydrate into the shallow ocean or directly to the atmosphere. When those conditions are met, the fraction of the gas accumulation that escapes and the rate of escape shall be quantified. The predictions shall be applicable in Arctic regions and in gas hydrate systems at the up dip limit of the stability zone on continental margins. The behavior shall be explored in response to two warming scenarios: longer term change due to sea level rise (e.g. 20 thousand years) and shorter term due to atmospheric warming by anthropogenic forcing (decadal time scale). 1.2. Project Objectives During the first budget period, the objectives are to review and categorize the stability state of existing well-studied hydrate reservoirs, develop conceptual and numerical models of the melting process, and to design and conduct laboratory experiments that dissociate methane hydrate in a model sediment column by systematically controlling the temperature profile along the column. The final objective of the first budget period shall be to validate the models against the experiments. In the second budget period, the objectives are to develop a model of gas flow into sediment in which hydrate is thermodynamically stable, and conduct laboratory experiments of this process to validate the model. The developed models shall be used to quantify the rate and volume of gas that escapes from dissociating hydrate accumulations. In addition, specific scaled simulations characteristic of Arctic regions and regions near the stability limit at continental margins shall be performed. 1.3. Project Background and Rationale The central hypothesis proposed is that hydrate melting (dissociation) due to climate change generates free gas that can, under certain conditions, propagate through the gas hydrate stability

  5. Hydrate phase equilibria of CO2+N2+aqueous solution of THF, TBAB or TBAF system

    DEFF Research Database (Denmark)

    Sfaxi, Imen Ben Attouche; Durand, Isabelle; Lugo, Rafael

    2014-01-01

    We report hydrate dissociation conditions of CO2 (15 and 30mol%)+N2 (85 and 70mol%) in the presence of aqueous solutions of THF, TBAB or TBAF. The concentrations of TBAB and TBAF in the aqueous solutions are 5wt% and 9wt% while THF concentration in aqueous solution is 3mol%. Two different experim...

  6. 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

  7. Dissociation and psychosis in dissociative identity disorder and schizophrenia.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F

    2012-01-01

    Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia.

  8. Quarkonium suppression: Gluonic dissociation vs. colour screening

    Indian Academy of Sciences (India)

    mechanism comes into play for the initial conditions taken from the self screened parton cascade model in these studies. Keywords. Quark gluon plasma; J ψ; suppression; dissociation; colour screening. PACS No. 12.38.M. 1. Introduction. The last two decades have seen hectic activity towards identifying unique signatures ...

  9. 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.

  10. 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.

  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. 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.

  13. Dissociative Identity Disorder

    Science.gov (United States)

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  14. Neurophysiological correlates of dissociative symptoms

    NARCIS (Netherlands)

    Kruijs, van der S.J.M.; Bodde, N.M.G; Carrette, E.C.B.; Lazeron, R.H.C; Vonck, K.E.J.; Boon, P.A.J.M.; Langereis, G.R.; Cluitmans, P.J.M.; Feijs, L.M.G.; Hofman, P.A.M.; Backes, W.H.; Jansen, J.F.A.; Aldenkamp, A.P.

    2014-01-01

    Objective: Dissociation is a mental process with psychological and somatoform manifestations, which is closely related to hypnotic suggestibility and essentially shows the ability to obtain distance from reality. An increased tendency to dissociate is a frequently reported characteristic of patients

  15. THERMODYNAMICS OF ETHANOLAMMONIUM CATIONES DISSOCIATION IN AQUEOUS SOLUTIONS

    Directory of Open Access Journals (Sweden)

    R. E. Khoma

    2017-03-01

    Full Text Available The literature data on the thermodynamics of ethanolamines onium cations dissociation have been systematized and generalized. The correlation between these cations dissociation thermodynamic functions (DH and DS and physicochemical properties (Tmp., Tbp, Pp, lgPow et al. has been revealed. There was a correlation between lipophilicity determined experimentally and calculated by QSAR. For monoethanolammonium, diethanolammonium, and their N-methyl and N-ethyl derivatives it was found dissociation thermodynamic functions to depend on bases lgPow. Acid-base dissociation of TRIS and triethanolamine onium cations does not correspond to said relationship because TRIS (primary amine, TEA (tertiary amine act differently on aqueous solutions of SO2. TEA, unlike MEA, DEA and MMEA, has a salting out effect towards sulfur dioxide because of competing hydration that promotes sulfite «onium» salts hydrolysis. TRIS promotes S(IV → S(VI sulphooxidation, in contrast to another ethanolamines. Enthalpy–enthropy compensation with isothermodynamic temperature 303 K has been recorded. The revealed correlations may be useful in developing of procedures for air sanitary cleaning from acidic gases; chemisorbents immobilized for gas and ion exchange chromatography; potentiometric methods for fluorocomplex acids determinations. The use of monoethanolamine is most promising to obtain chemisorbents because the thermodynamic functions of its onium cation acid-base dissociation are least dependent on temperature compared to other etanolammonium cations.

  16. 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

  17. 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

  18. Top-Down Charge Transfer Dissociation (CTD) of Gas-Phase Insulin: Evidence of a One-Step, Two-Electron Oxidation Mechanism

    Science.gov (United States)

    Li, Pengfei; Kreft, Iris; Jackson, Glen P.

    2018-02-01

    Top-down analyses of protonated insulin cations of charge states of 4+, 5+, or 6+ were performed by exposing the isolated precursor ions to a beam of helium cations with kinetic energy of more than 6 keV, in a technique termed charge transfer dissociation (CTD). The 100 ms charge transfer reaction resulted in approximately 20% conversion efficiency to other intact charge exchange products (CTnoD), and a range of low abundance fragment ions. To increase backbone and sulfide cleavages, and to provide better structural information than straightforward MS2 CTD, the CTnoD oxidized products were isolated and subjected to collisional activation at the MS3 level. The MS3 CTD/CID reaction effectively broke the disulfide linkages, separated the two chains, and yielded more structurally informative fragment ions within the inter-chain cyclic region. CTD also provided doubly oxidized intact product ions at the MS2 level, and resonance ejection of the singly oxidized product ion revealed that the doubly oxidized product originates directly from the isolated precursor ion and not from consecutive CTD reactions of a singly oxidized intermediate. MS4 experiments were employed to help identify potential radical cations and diradical cations, but the results were negative or inconclusive. Nonetheless, the two-electron oxidation process is a demonstration of the very large potential energy (>20 eV) available through CTD, and is a notable capability for a 3D ion trap platform.

  19. Numerical modeling of the simulated gas hydrate production test at Mallik 2L-38 in the pilot scale pressure reservoir LARS - Applying the "foamy oil" model

    Science.gov (United States)

    Abendroth, Sven; Thaler, Jan; Klump, Jens; Schicks, Judith; Uddin, Mafiz

    2014-05-01

    In the context of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) we conducted a series of experiments in the LArge Reservoir Simulator (LARS) at the German Research Centre of Geosciences Potsdam. These experiments allow us to investigate the formation and dissociation of hydrates at large scale laboratory conditions. We performed an experiment similar to the field-test conditions of the production test in the Mallik gas hydrate field (Mallik 2L-38) in the Beaufort Mackenzie Delta of the Canadian Arctic. The aim of this experiment was to study the transport behavior of fluids in gas hydrate reservoirs during depressurization (see also Heeschen et al. and Priegnitz et al., this volume). The experimental results from LARS are used to provide details about processes inside the pressure vessel, to validate the models through history matching, and to feed back into the design of future experiments. In experiments in LARS the amount of methane produced from gas hydrates was much lower than expected. Previously published models predict a methane production rate higher than the one observed in experiments and field studies (Uddin et al. 2010; Wright et al. 2011). The authors of the aforementioned studies point out that the current modeling approach overestimates the gas production rate when modeling gas production by depressurization. They suggest that trapping of gas bubbles inside the porous medium is responsible for the reduced gas production rate. They point out that this behavior of multi-phase flow is not well explained by a "residual oil" model, but rather resembles a "foamy oil" model. Our study applies Uddin's (2010) "foamy oil" model and combines it with history matches of our experiments in LARS. Our results indicate a better agreement between experimental and model results when using the "foamy oil" model instead of conventional models of gas flow in water. References Uddin M., Wright J.F. and Coombe D

  20. Hydrate-based technology for CO2 capture from fossil fuel power plants

    International Nuclear Information System (INIS)

    Yang, Mingjun; Song, Yongchen; Jiang, Lanlan; Zhao, Yuechao; Ruan, Xuke; Zhang, Yi; Wang, Shanrong

    2014-01-01

    Graphical abstract: Application of hydrate based technology on carbon dioxide capture and storage (CCS). - Highlights: • Hydrate-based CO 2 –N 2 separation data was obtained for flow in porous media. • Tetrahydrofuran and sodium dodecyl sulphate are used as additives simultaneously. • Solution movement rarely occurs when residual solution saturations are low. • Bothe of pressure and temperature have remarkable impacts on gas compositions. • A suitable operation parameter choice is proposed for hydrate-based CO 2 capture. - Abstract: Hydrate-based CO 2 capture is a promising technology. To obtain fundamental data for a flowing system, we measured the distribution of pore solution to analyse hydrate formation/dissociation and gas separation properties. An orthogonal experiment was carried out to investigate the effects of glass beads, flow rates, pressures and temperatures on it. Magnetic resonance imaging (MRI) images were obtained using a spin echo multi-slice pulse sequence. Hydrate saturations were calculated quantitatively using an MRI mean intensity. The results show that hydrate blockages were frequently present. During the hydrate formation and dissociation process, the movement of the solution occurred in cycles. However, the solution movement rarely occurred for residual solution saturations obtained with a high backpressure. The solution concentrate phenomenon occurred mostly in BZ-04. The highest hydrate saturation was 30.2%, and the lowest was 0.70%. Unlike that in BZ-01, there was no stability present in BZ-02 and BZ-04. The different CO 2 concentrations for the three processes of each cycle verified hydrate formation during the gas flow process. The highest CO 2 concentration was 38.8%, and the lowest one was 11.4%. To obtain high hydrate saturation and good separation effects, the values of 5.00 MPa, 1.0 ml min −1 and 280.00 K were chosen. For the gas flow process, only the pressure had a significant impact on gas composition, and all

  1. Isotope separation by photoselective dissociative electron

    International Nuclear Information System (INIS)

    Stevens, C.G.

    1978-01-01

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule is described. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, 235 UF 6 is separated from a UF 6 mixture by selective excitation followed by dissociative electron capture into 235 UF 5 - and F

  2. Studies of neutron dissociation at Fermilab energies

    International Nuclear Information System (INIS)

    Ferbel, T.

    1975-01-01

    The latest results obtained in a continuing investigation of neutron dissociation in (pπ - ) systems in neutron--nucleus collisions between 50 and 300 GeV/c are summarized. The nuclear coherent dissociation data are discussed first; then new measurements of total cross sections of neutrons on nuclei in the Fermilab momentum range are presented; finally, neutron dissociation using a hydrogen target is considered, and the hydrogen data are compared with expectations from simple Deck models. A substantial correlation was observed between the mass and the t of the system produced. The spin structure of the pπ - amplitudes at low mass was described surprisingly well by the simple Deck mechanism. The t-channel helicity amplitudes contained comparable contributions from flip and nonflip terms, and the states produced were not restricted to those expected on the basis of the Morrison rule. (19 figures, 2 tables) (U.S.)

  3. 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.

  4. Three dimensions of dissociative amnesia.

    Science.gov (United States)

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders.

  5. A computational study on the energetics and mechanisms for the dissociative adsorption of SiH{sub x}(x = 1–4) on W(1 1 1) surface

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Y.H.; Raghunath, P.; Lin, M.C., E-mail: chemmcl@emory.edu

    2016-01-30

    Graphical abstract: - Highlights: • Behavior of the SiH{sub x} species on the W surface under cat-CVD conditions. • The adsorption and dissociation mechanisms of SiH{sub x}(x = 1–4) species on W(1 1 1) surface. • H-migration to its neighboring W atoms is more favorable compared to H{sub 2} elimination. - Abstract: The adsorption and dissociation mechanisms of SiH{sub x}(x = 1–4) species on W(1 1 1) surface have been investigated by using the periodic density functional theory with the projector-augmented wave approach. The adsorption of all the species on four surface sites: top (T), bridge (B), shallow (S), and deep (D) sites have been analyzed. For SiH{sub 4} on a top site, T-SiH{sub 4(a)}, it is more stable with an adsorption energy of 2.6 kcal/mol. For SiH{sub 3}, the 3-fold shallow site is most favorable with adsorption energy of 46.0 kcal/mol. For SiH{sub 2}, its adsorption on a bridge site is most stable with 73.0 kcal/mol binding energy, whereas for SiH and Si the most stable adsorption configurations are on 3-fold deep sites with very high adsorption energies, 111.8 and 134.7 kcal/mol, respectively. The potential energy surfaces for the dissociative adsorption of all SiH{sub x} species on the W(1 1 1) surface have been constructed using the CINEB method. The barriers for H-atom migration from SiH{sub x(a)} to its neighboring W atoms, preferentially on B-sites, were predicted to be 0.4, 1.0, 4.5 and, 8.0 kcal/mol, respectively, for x = 4, 3, 2, and 1, respectively. The adsorption energy of the H atom on a bridge site on the clean W(1 1 1) surface was predicted to be 65.9 kcal/mol, which was found to be slightly affected by the co-adsorption of SiH{sub x−1} within ± 1 kcal/mol.

  6. Childhood maltreatment and intimate partner violence in dissociative disorder patients.

    Science.gov (United States)

    Webermann, Aliya R; Brand, Bethany L; Chasson, Gregory S

    2014-01-01

    Childhood maltreatment (CM) is a risk factor for subsequent intimate partner violence (IPV) in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD) have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80-95% and severe dissociative symptoms. DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV) and childhood neglect were associated with emotional IPV. The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD.

  7. Childhood maltreatment and intimate partner violence in dissociative disorder patients

    Directory of Open Access Journals (Sweden)

    Aliya R. Webermann

    2014-09-01

    Full Text Available Background: Childhood maltreatment (CM is a risk factor for subsequent intimate partner violence (IPV in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. Objective: The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80–95% and severe dissociative symptoms. Methods: DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Results: Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV and childhood neglect were associated with emotional IPV. Conclusions: The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD.

  8. Dissociative features in posttraumatic stress disorder: A latent profile analysis.

    Science.gov (United States)

    Műllerová, Jana; Hansen, Maj; Contractor, Ateka A; Elhai, Jon D; Armour, Cherie

    2016-09-01

    The fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) characterizes the dissociative subtype of posttraumatic stress disorder (PTSD) in terms of the individual meeting the criteria for PTSD and additionally reporting symptoms of depersonalization and/or derealization. The current study aimed to examine whether a dissociative PTSD profile may include alternative features of dissociation and whether it could be differentiated from a nondissociative PTSD profile on certain psychopathologies and demographics. Data from 309 trauma-exposed participants, collected through Amazon Mechanical Turk, were subjected to latent profile analysis. Regression analyses were used to examine the predictors of latent classes. Three discrete profiles named Baseline, PTSD, and Dissociative profile were uncovered. All examined features of dissociation were significantly elevated in the Dissociative profile. Anxiety, male sex, being employed, and having a minority racial background significantly predicted the Dissociative profile relative to the PTSD profile. The study points to the importance of alternative symptoms of dissociation in the dissociative PTSD subtype beyond the symptoms of depersonalization and derealization. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

  9. Chemical alteration of cement hydrates by dissolution

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

    2000-01-01

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

  10. 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.

  11. Investigation of the Methane Hydrate Formation by Cavitation Jet

    Science.gov (United States)

    Morita, H.; Nagao, J.

    2015-12-01

    Methane hydrate (hereafter called "MH") is crystalline solid compound consisting of hydrogen-bonded water molecules forming cages and methane gas molecules enclosed in the cage. When using MH as an energy resource, MH is dissociated to methane gas and water and collect only the methane gas. The optimum MH production method was the "depressurization method". Here, the production of MH means dissociating MH in the geologic layers and collecting the resultant methane gas by production systems. In the production of MH by depressurization method, MH regeneration was consider to important problem for the flow assurance of MH production system. Therefore, it is necessary to clarify the effect of flow phenomena in the pipeline on hydrate regeneration. Cavitation is one of the flow phenomena which was considered a cause of MH regeneration. Large quantity of microbubbles are produced by cavitation in a moment, therefore, it is considered to promote MH formation. In order to verify the possible of MH regeneration by cavitation, it is necessary to detailed understanding the condition of MH formation by cavitation. As a part of a Japanese National hydrate research program (MH21, funded by METI), we performed a study on MH formation using by cavitation. The primary objective of this study is to demonstrate the formation MH by using cavitation in the various temperature and pressure condition, and to clarify the condition of MH formation by using observation results.

  12. Dissociation of acetaldehyde in intense laser field: Coulomb explosion or field-assisted dissociation?

    Science.gov (United States)

    Elshakre, Mohamed E.; Gao, Lirong; Tang, Xiaoping; Wang, Sufan; Shu, Yafei; Kong, Fanao

    2003-09-01

    Dissociation of acetaldehyde in moderate strong laser field of 1013-1014W/cm2 was investigated. Singly charged parent ion CH3CHO+ and fragmental ions CH3+, CHO+, C2H4+, O+, CH2CHO+, and H+ were produced by 800 nm laser of 100 fs pulse duration and recorded by time-of-flight mass spectrometer. The CH3+ fragment further dissociated to CH2+, CH+, and C+ ions at higher intensity. Ab initio calculated results show that the singly-, doubly-, and triply charged parent ions are stable. So, the dissociation mechanism was not due to Coulomb explosion of multicharged ion. A field-assisted dissociation (FAD) theory, which assumes that only one bond undergoes dissociation while the rest of the molecular geometry stays unchanged, was employed to treat the dissociation dynamics. Accordingly, the dressed potential energy surfaces of the ground state for the parent and the fragment ions were calculated. Corresponding quasiclassical trajectory calculations show that the bond ruptures take place in the order of C-C, C-O, and C-H, agreeing with the observation. The observed angular dependence and charge distribution of the product ions can also be interpreted by the FAD theory.

  13. Predictors of trait dissociation and peritraumatic dissociation induced via cold pressor.

    Science.gov (United States)

    Gómez-Pérez, Lydia; López-Martínez, Alicia Eva; Asmundson, Gordon John Glenn

    2013-11-30

    Understanding which factors predict individual dissociative response during stressful situations is important to clarify the nature of dissociation and the mechanisms associated to its use as a coping strategy. The present study examined (1) whether experiential avoidance (EA), anxiety sensitivity (AS), depressive symptoms, and state anxiety concurrently predicted trait dissociation (TD)-absorption, amnesia, depersonalization, and total TD scores-and laboratory induced dissociation (LID); and (2) whether TD and catastrophizing predicted LID. We also examined whether catastrophizing mediated the relationships between both AS and depressive symptoms and LID. A total of 101 female undergraduate students participated in a cold pressor task, which significantly induced dissociation. Results of hierarchical regression analyses showed that AS at Time 1 (9 months before the experimental session), as well as depressive symptoms and catastrophizing at the time of the experiment (Time 2), predicted LID at Time 2. Depressive symptoms at Time 2 predicted total TD, absorption, and amnesia scores. AS at Time 1 and depressive symptoms at Time 2 predicted depersonalization. AS, depressive symptoms, and catastrophizing seem to facilitate the use of dissociative strategies by healthy individuals, even in response to non-traumatic but discomforting stress. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  14. Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

    Energy Technology Data Exchange (ETDEWEB)

    Daigle, Hugh; Nole, Michael; Cook, Ann; Malinverno, Alberto

    2017-12-14

    In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability (~1 md in the absence of hydrate). Pore sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.

  15. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C{sub 3}S, {beta}-C{sub 2}S and their blends; Caracterizacion textural y mecanica de geles C-S-H formados en la hidratacion de muestras sinteticas T1-C{sub 3}S, {beta}-C{sub 2}S y sus mezclas

    Energy Technology Data Exchange (ETDEWEB)

    Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

    2011-07-01

    The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C{sub 3}S, {beta}-C{sub 2}S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of {beta}-C{sub 2}S and the 30-70 (T1-C{sub 3}S and {beta}-C{sub 2}S mixture) are higher than those from hydration of T1-C{sub 3}S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the {beta}-C{sub 2}S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from {sup 2}9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

  16. 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

  17. BSRs Elevated by Fluid Upwelling on the Upper Amazon Fan : Bottom-up Controls on Gas Hydrate Stability

    Science.gov (United States)

    Praeg, D.; Silva, C. G.; dos Reis, A. T.; Ketzer, J. M.; Unnithan, V.; Perovano Da Silva, R. J.; Cruz, A. M.; Gorini, C.

    2017-12-01

    The stability of natural gas hydrate accumulations on continental margins has mainly been considered in terms of changes in seawater pressures and temperatures driven from above by climate. We present evidence from the Amazon deep-sea fan for stability zone changes driven from below by fluid upwelling. A grid of 2D and 3D multichannel seismic data show the upper Amazon fan in water depths of 1200-2000 m to contain a discontinuous bottom-simulating seismic reflection (BSR) that forms `patches' 10-50 km wide and up to 140 km long, over a total area of at least 5000 km2. The elongate BSR patches coincide with anticlinal thrust-folds that record on-going gravitational collapse of the fan above décollements at depths of up to 10 km. The BSR lies within 100-300 m of seafloor, in places rising beneath features that seafloor imagery show to be pockmarks and mud volcanoes, some venting gas to the water column. The BSR patches are up to 500 m shallower than predicted for methane hydrate based on geothermal gradients as low as 17˚C/km measured within the upper fan, and inversion of the BSR to obtain temperatures at the phase boundary indicates gradients 2-5 times background levels. We interpret the strongly elevated BSR patches to record upwelling of warm gas-rich fluids through thrust-fault zones 101 km wide. We infer this process to favour gas hydrate occurrences that are concentrated in proportion to flux and locally pierced by vents, and that will be sensitive to temporal variations in the upward flux of heat and gas. Thus episodes of increased flux, e.g. during thrusting, could dissociate gas hydrates to trigger slope failures and/or enhanced gas venting to the ocean. Structurally-driven fluid flow episodes could account for evidence of recurrent large-scale failures from the compressive belt on the upper fan during its Neogene collapse, and provide a long-term alternative to sea level triggering. The proposed mechanism of upward flux links the distribution and

  18. 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

  19. 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.

  20. 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.)

  1. 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.

  2. 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.)

  3. On the hydration and conformation of cocaine in solution

    Science.gov (United States)

    Gillams, Richard J.; Lorenz, Christian D.; McLain, Sylvia E.

    2017-05-01

    In order to develop theories relating to the mechanism through which cocaine can diffuse across the blood-brain barrier, it is important to understand the interplay between the hydration of the molecule and the adopted conformation. Here key differences in the hydration of cocaine hydrochloride (CHC) and freebase cocaine (CFB) are highlighted on the atomic scale in solution, through the use of molecular dynamics simulations. By adopting different conformations, CHC and CFB experience differing hydration environments. The interplay between these two factors may account for the vast difference in solubility of these two molecules.

  4. Simulating the gas hydrate production test at Mallik using the pilot scale pressure reservoir LARS

    Science.gov (United States)

    Heeschen, Katja; Spangenberg, Erik; Schicks, Judith M.; Priegnitz, Mike; Giese, Ronny; Luzi-Helbing, Manja

    2014-05-01

    LARS, the LArge Reservoir Simulator, allows for one of the few pilot scale simulations of gas hydrate formation and dissociation under controlled conditions with a high resolution sensor network to enable the detection of spatial variations. It was designed and built within the German project SUGAR (submarine gas hydrate reservoirs) for sediment samples with a diameter of 0.45 m and a length of 1.3 m. During the project, LARS already served for a number of experiments simulating the production of gas from hydrate-bearing sediments using thermal stimulation and/or depressurization. The latest test simulated the methane production test from gas hydrate-bearing sediments at the Mallik test site, Canada, in 2008 (Uddin et al., 2011). Thus, the starting conditions of 11.5 MPa and 11°C and environmental parameters were set to fit the Mallik test site. The experimental gas hydrate saturation of 90% of the total pore volume (70 l) was slightly higher than volumes found in gas hydrate-bearing formations in the field (70 - 80%). However, the resulting permeability of a few millidarcy was comparable. The depressurization driven gas production at Mallik was conducted in three steps at 7.0 MPa - 5.0 MPa - 4.2 MPa all of which were used in the laboratory experiments. In the lab the pressure was controlled using a back pressure regulator while the confining pressure was stable. All but one of the 12 temperature sensors showed a rapid decrease in temperature throughout the sediment sample, which accompanied the pressure changes as a result of gas hydrate dissociation. During step 1 and 2 they continued up to the point where gas hydrate stability was regained. The pressure decreases and gas hydrate dissociation led to highly variable two phase fluid flow throughout the duration of the simulated production test. The flow rates were measured continuously (gas) and discontinuously (liquid), respectively. Next to being discussed here, both rates were used to verify a model of gas

  5. Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

    Energy Technology Data Exchange (ETDEWEB)

    Asiaee, Alireza; Raeissi, Sona [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of); Shariati, Alireza, E-mail: shariati@shirazu.ac.i [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of)

    2011-05-15

    Research highlights: A model is presented to predict dissociation pressures of gas hydrates at various temperatures. The present model is applicable on a wide range of equilibrium conditions. The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

  6. Thermodynamics of a post combustion hydrate-based carbon dioxide capture process

    International Nuclear Information System (INIS)

    Ben Attouche Sfaxi, I.

    2011-07-01

    Hydrates selectivity towards carbon dioxide is offering a promising route for carbon dioxide removal from flue gases. Hydrate-based CO 2 capture process could substitute amine facilities widely implemented in gas treatment plants but suffering from oxidative degradation problems and high energy demand. In the framework of this thesis, we focus on phase equilibria that are involved in such process. Experimental dissociation conditions for clathrate hydrates of carbon dioxide and nitrogen, in the presence of some promoting molecules (Tetrahydrofuran, Tetrabutyl ammonium bromide and Tetrabutyl ammonium Fluoride ) are reported in the experimental section of this work. The data generated in this work along with literature data are compared to the model predictions. The developed model is based on the Cubic Plus Association (CPA) equation of state (EoS) for fluid phases combined to the van der Waals and Platteeuw's theory for the hydrate phase. (author)

  7. Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

    International Nuclear Information System (INIS)

    Asiaee, Alireza; Raeissi, Sona; Shariati, Alireza

    2011-01-01

    Research highlights: → A model is presented to predict dissociation pressures of gas hydrates at various temperatures. → The present model is applicable on a wide range of equilibrium conditions. → The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

  8. 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)

  9. 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...

  10. Zirconium molybdate hydrate precipitates in spent nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Magnaldo, A.; Noire, M.H.; Esbelin, E.; Dancausse, J.P.; Picart, S.

    2004-01-01

    This paper presents through 2 posters a general overview studies realised by CEA teams on deposits observed in the La Hague plant dissolution facilities. Their main constituents are metallic debris bound together with zirconium molybdate hydrate. A comprehensive study of zirconium molybdate hydrate formation included nucleation and growth kinetics was developed. Fouling mechanisms were consequently explained as influenced by the operation conditions. Pu insertion was also overviewed. Its behaviour is important when curative and preventive chemical treatments are considered. (authors)

  11. 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.

  12. Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6- arene)(en)Cl]+ complexes: Density functional theory computational study

    Science.gov (United States)

    Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V.

    2011-01-01

    The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl2 (from the RAPTA family) and [Ru(arene)(en)Cl]+ (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP/6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt/Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal/mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

  13. Electron spin resonance study on γ-ray-induced ethyl radical in ethane hydrate

    International Nuclear Information System (INIS)

    Takeya, Kei; Nango, Kouhei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi; Ito, Hironori; Okada, Michio; Kasai, Toshio

    2007-01-01

    Electron spin resonance (ESR) studies have been performed to investigate radicals induced in ethane hydrate irradiated by γ-rays at 77K. Two ESR spectra are observed and identified as the induced ethyl radical (g=2.0031±0.0005, A α sub(perpendicular)=2.2±0.1mT, A α sub(parallel)=2.5±0.1mT, A β =2.7±0.1mT) and induced atomic hydrogen (g=2.0026±0.0005, A=50.5±0.1mT). From the results of ESR analysis and gas mass spectroscopy, it is concluded that the ethyl radical decays into butane by dimerization in the first-order reaction in the temperature region of 250-265K. The activation energy of the decay reaction is 73.1±6.3kJ/mol, which is near the dissociation enthalpy change of ethane hydrate to liquid water and gaseous ethane. This finding implies that ethane hydrate does not dissociate into ice but supercooled water in the present temperature region, similar to the dissociation of methane hydrate in our previous study. (author)

  14. Time lapse survey plan on the first offshore methane hydrate production test in 2013 around the eastern Nankai Trough area by multi-component OBC seismic tool

    Science.gov (United States)

    Inamori, T.; Hayashi, T.; Asakawa, E.; Takahashi, H.; Saeki, T.

    2011-12-01

    We are planning to conduct the multi-component ocean bottom cable (hereafter OBC) seismic survey to monitor the methane hydrate dissociation zone at the 1st offshore methane hydrate production test site in the eastern Nankai Trough, Japan, in 2013. We conducted the first OBC survey in the methane hydrate concentrated zone around the eastern Nankai Trough area in 2006 by RSCS which we developed. We obtained to the good image of methane hydrate bearing layer by P-P section as similar as the conventional surface seismic survey. However, we could not obtain the good image from P-S section compared with P-P section. On the other hand, we studied the sonic velocity distribution at the Mallik 2nd production test before and after in 2007, by the sonic tool data. We could clearly delineate the decrease of S-wave velocity, however, we could not detect the decrease of P-wave velocity because of the presence of the dissociated methane gas from methane hydrate. From these reason we guess the S-wave data is more proper to delineate the condition of the methane hydrate zone at the methane hydrate production tests than P-wave data. We are now developing the new OBC system, which we call Deep-sea Seismic System (hereafter DSS). The sensor of the DSS will install three accelerometers and one hydrophone. A feasibility study to detect the methane hydrate dissociation with the DSS was carried out and we found that the methane hydrate dissociation could be detected with the DSS depending on the zone of the dissociation. And the baseline survey will be held at the 1st offshore methane hydrate production test site in summer 2012. Two monitoring surveys are planned after the methane hydrate production test in 2013. We believe that we will get the good images to delineate the methane hydrate dissociated zone from this time lapse survey. The Authors would like to thank METI, MH21 consortium and JOGMEC for permissions to publish this paper.

  15. 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

  16. [Dissociative disorders and affective disorders].

    Science.gov (United States)

    Montant, J; Adida, M; Belzeaux, R; Cermolacce, M; Pringuey, D; Da Fonseca, D; Azorin, J-M

    2014-12-01

    The phenomenology of dissociative disorders may be complex and sometimes confusing. We describe here two cases who were initially misdiagnosed. The first case concerned a 61 year-old woman, who was initially diagnosed as an isolated dissociative fugue and was actually suffering from severe major depressive episode. The second case concerned a 55 year-old man, who was suffering from type I bipolar disorder and polyvascular disease, and was initially diagnosed as dissociative fugue in a mooddestabilization context, while it was finally a stroke. Yet dissociative disorders as affective disorder comorbidity are relatively unknown. We made a review on this topic. Dissociative disorders are often studied through psycho-trauma issues. Litterature is rare on affective illness comorbid with dissociative disorders, but highlight the link between bipolar and dissociative disorders. The later comorbidity often refers to an early onset subtype with also comorbid panic and depersonalization-derealization disorder. Besides, unipolar patients suffering from dissociative symptoms have more often cyclothymic affective temperament. Despite the limits of such studies dissociative symptoms-BD association seems to correspond to a clinical reality and further works on this topic may be warranted. Copyright © 2014 L’Encéphale. Published by Elsevier Masson SAS.. All rights reserved.

  17. Strong-field dissociation dynamics

    International Nuclear Information System (INIS)

    DiMauro, L.F.; Yang, Baorui.

    1993-01-01

    The strong-field dissociation behavior of diatomic molecules is examined under two distinctive physical scenarios. In the first scenario, the dissociation of the isolated hydrogen and deuterium molecular ions is discussed. The dynamics of above-threshold dissociation (ATD) are investigated over a wide range of green and infrared intensities and compared to a dressed-state model. The second situation arises when strong-field neutral dissociation is followed by ionization of the atomic fragments. The study results in a direct measure of the atomic fragment's ac-Stark shift by observing the intensity-dependent shifts in the electron or nuclear fragment kinetic energy. 8 figs., 14 refs

  18. BSR and methane hydrates: New challenges for geophysics and rock physics

    Energy Technology Data Exchange (ETDEWEB)

    Nur, A. [Stanford Univ., CA (United States). Dept. of Geophysics

    1996-12-31

    It is generally accepted that solid gas hydrates which form within the uppermost few hundred meters of the sea floor are responsible for so-called Bottom Simulating Reflectors (BSRs) at continental margins. Gas to solid volumetric ratio in recovered hydrate samples may be as large as 170. Consequently, huge amounts of compressed methane (more than twice all recoverable and nonrecoverable oil, gas, and coal on earth) may exist under earth`s oceans. These hydrates are a potential energy resource, they influence global warming and effect seafloor mechanical stability. It is possible, in principle, to obtain a quantitative estimate of the amount and state of existing hydrates by relating seismic velocity to the volume of gas hydrate in porous sediments. This can be done by linking the elastic properties of hydrated sediments to their internal structure. The authors approach this problem by examining two micromechanical models of hydrate deposition in the pore space: (1) the hydrate cements grain contacts and thus significantly stiffens the sediment; and (2) the hydrate is located away from grain contacts and only weakly affects the stiffness of the sediment frame. To discriminate between the two models the authors use the Amplitude Versus Offset (AVO) technique of seismic data processing. This approach allows them to estimate the amount of gas hydrates in the pore space, and also to tell whether the permeability of the hydrated sediment is high or low. The latter is important for determining whether free methane can be trapped underneath a BSR.

  19. Multi-property characterization chamber for geophysical-hydrological investigations of hydrate bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Yongkoo, E-mail: Yongkoo.Seol@netl.doe.gov; Choi, Jeong-Hoon; Dai, Sheng [National Energy Technology Laboratory, U.S. Department of Energy, Morgantown, West Virginia 26507 (United States)

    2014-08-01

    With the increase in the interest of producing natural gas from methane hydrates as well as potential risks of massive hydrate dissociation in the context of global warming, studies have recently shifted from pure hydrate crystals to hydrates in sediments. Such a research focus shift requires a series of innovative laboratory devices that are capable of investigating various properties of hydrate-bearing sediments (HBS). This study introduces a newly developed high pressure testing chamber, i.e., multi-property characterization chamber (MPCC), that allows simultaneous investigation of a series of fundamental properties of HBS, including small-strain stiffness (i.e., P- and S-waves), shear strength, large-strain deformation, stress-volume responses, and permeability. The peripheral coolant circulation system of the MPCC permits stable and accurate temperature control, while the core holder body, made of aluminum, enables X-ray computer tomography scanning to be easily employed for structural and morphological characterization of specimens. Samples of hydrate-bearing sediments are held within a rubber sleeve inside the chamber. The thick sleeve is more durable and versatile than thin membranes while also being much softer than oedometer-type chambers that are incapable of enabling flow tests. Bias introduced by the rubber sleeve during large deformation tests are also calibrated both theoretically and experimentally. This system provides insight into full characterization of hydrate-bearing sediments in the laboratory, as well as pressure core technology in the field.

  20. Hydrate studies of northern Cascadia margin off Vancouver Island : a reference source

    Energy Technology Data Exchange (ETDEWEB)

    Hyndman, R. [Natural Resources Canada, Sidney, BC (Canada). Geological Survey of Canada, Pacific Geoscience Centre]|[Victoria Univ., BC (Canada). School of Earth and Ocean Sciences; Riedel, M. [McGill Univ., Montreal, PQ (Canada). Dept. of Earth and Planetary Sciences; Spence, G.D. [Victoria Univ., BC (Canada). School of Earth and Ocean Sciences

    2008-07-01

    Extensive geophysical studies have been conducted to determine the occurrence, distribution, and concentration of gas hydrate in the Cascadia subduction zone off western Canada. In this paper, the authors compiled a comprehensive reference list of studies involving marine natural gas hydrate surveys and studies on the northern Cascadia margin. The reference categories included general reviews; regional tectonic framework for northern Cascadia hydrate; prism sediment thickening, fluid expulsion and hydrate formation; and, seismic surveys. This paper first addressed the local tectonics and the sedimentary accretionary prism in which the hydrate forms, followed by a description of the geophysical and geological surveys that have been conducted. The surveys included a wide range of seismic surveys such as multichannel, ocean-bottom, high-resolution single channel and very high resolution deep towed surveys. Heat flow, electrical sounding, seafloor compliance, sediment coring, and mapping gas plumes from the seafloor were among the other geophysical studies listed in this paper. The conclusions that have resulted from this work in terms of distribution, concentrations and amounts of hydrate were presented along with a discussion on the process of hydrate formation and dissociation. 96 refs., 3 figs.

  1. Multi-property characterization chamber for geophysical-hydrological investigations of hydrate bearing sediments

    International Nuclear Information System (INIS)

    Seol, Yongkoo; Choi, Jeong-Hoon; Dai, Sheng

    2014-01-01

    With the increase in the interest of producing natural gas from methane hydrates as well as potential risks of massive hydrate dissociation in the context of global warming, studies have recently shifted from pure hydrate crystals to hydrates in sediments. Such a research focus shift requires a series of innovative laboratory devices that are capable of investigating various properties of hydrate-bearing sediments (HBS). This study introduces a newly developed high pressure testing chamber, i.e., multi-property characterization chamber (MPCC), that allows simultaneous investigation of a series of fundamental properties of HBS, including small-strain stiffness (i.e., P- and S-waves), shear strength, large-strain deformation, stress-volume responses, and permeability. The peripheral coolant circulation system of the MPCC permits stable and accurate temperature control, while the core holder body, made of aluminum, enables X-ray computer tomography scanning to be easily employed for structural and morphological characterization of specimens. Samples of hydrate-bearing sediments are held within a rubber sleeve inside the chamber. The thick sleeve is more durable and versatile than thin membranes while also being much softer than oedometer-type chambers that are incapable of enabling flow tests. Bias introduced by the rubber sleeve during large deformation tests are also calibrated both theoretically and experimentally. This system provides insight into full characterization of hydrate-bearing sediments in the laboratory, as well as pressure core technology in the field

  2. Low temperature X-ray diffraction studies of natural gas hydrate samples from the Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Rawn, C.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Materials Science and Technology Div.; Sassen, R. [Texas A and M Univ., College Station, TX (United States). Geochemical and Environmental Research Group; Ulrich, S.M.; Phelps, T.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Biosciences Div.; Chakoumakos, B.C. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Neutron Scattering Science Div.; Payzant, E.A. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Center for Nanophase Materials Science

    2008-07-01

    Quantitative studies of natural clathrate hydrates are hampered by the difficulties associated with obtaining pristine samples for the sea floor without comprising their integrity. This paper discussed X-ray power diffraction studies conducted to measure natural gas hydrate samples obtained from the Green Canyon in the Gulf of Mexico. Data on the hydrate deposits were initially collected in 2002. The X-ray diffraction data were collected in order to examine the structure 2 (s2) gas hydrates as functions of temperature and time. A diffractometer with a theta-theta goniometer modified with a helium closed cycle refrigerator and temperature controller was used. Aragonite, quartz and halite phases were determined in the decomposed sample. Refined phase fractions for both the ice and the s2 hydrate were obtained as a function of temperature. Results of the study demonstrated that the amount of hydrates decreased with increasing temperatures and amounts of time. Large pieces of the hydrate showed heterogenous ice content. Dissociation rates were higher at lower temperatures. It was concluded that unusual trends observed for the smaller lattice parameter of the hydrates resulted from the formation of ice layers that acted as barriers to the released gases and caused increased isostatic pressures around the hydrate core. 9 refs., 6 figs.

  3. Dissociative State and Competence

    Directory of Open Access Journals (Sweden)

    Yu-Ju Lin

    2007-10-01

    Full Text Available This report presents the results of forensic evaluation of the civil competence of a case of alleged dissociative identity disorder (DID and discusses whether such dissociative states substantially jeopardize civil competence. A 40-year-old woman claimed that she had had many personalities since her college days. From the age of 37 to 40, she shopped excessively, which left her with millions of dollars of debt. She ascribed her shopping to a certain identity state, over which she had no control. (In this article, we use the term identity state to replace personality as an objective description of a mental state. She thus raised the petition of civil incompetence. During the forensic evaluation, it was found that the identity states were relatively stable and mutually aware of each other. The switch into another identity state was sometimes under voluntary control. The subject showed consistency and continuity in behavioral patterns across the different identity states, and no matter which identity state she was in, there was no evidence of impairment in her factual knowledge of social situations and her capacity for managing personal affairs. We hence concluded that she was civilly competent despite the claimed DID. Considering that the existence and diagnosis of DID are still under dispute and a diagnosis of DID alone is not sufficient to interdict a person's civil right, important clinical and forensic issues remain to be answered.

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

    Science.gov (United States)

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

    2009-01-01

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

  5. Scapulothoracic Dissociation: A Rare Variant: A Case Report

    Directory of Open Access Journals (Sweden)

    Rajat Jangir

    2014-07-01

    Full Text Available Scapulothoracic dissociation is a rare injury involving separation of scapula from the thorax along with the upper extremity. Majority of the patients have concomitant neurovascular injury and the prognosis is uniformly poor in such cases. We present a case of scapulothoracic dissociation with comminuted fracture of scapula and acromioclavicular joint disruption without neurovascular deficit. There were associated avulsion fractures of the spinous processes of vertebrae (T3-T5. Such presentation is rare in an already rare scapulothoracic dissociation injury. A discussion regarding the probable mechanism of injury, management and prognosis is presented.

  6. Electron Capture Dissociation of Weakly Bound Polypeptide Polycationic Complexes

    DEFF Research Database (Denmark)

    Haselmann, Kim F; Jørgensen, Thomas J D; Budnik, Bogdan A

    2002-01-01

    as well as specific complexes of modified glycopeptide antibiotics with their target peptide. The weak nature of bonding is substantiated by blackbody infrared dissociation, low-energy collisional excitation and force-field simulations. The results are consistent with a non-ergodic ECD cleavage mechanism.......We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non-specific peptide-peptide dimers...

  7. Acetaldehyde dissociates the PTP1B–E-cadherin–β-catenin complex in Caco-2 cell monolayers by a phosphorylation-dependent mechanism

    Science.gov (United States)

    Sheth, Parimal; Seth, Ankur; Atkinson, Katherine J.; Gheyi, Tarun; Kale, Gautam; Giorgianni, Francesco; Desiderio, Dominic M.; Li, Chunying; Naren, Anjaparavanda; Rao, Radhakrishna

    2006-01-01

    Interactions between E-cadherin, β-catenin and PTP1B (protein tyrosine phosphatase 1B) are crucial for the organization of AJs (adherens junctions) and epithelial cell–cell adhesion. In the present study, the effect of acetaldehyde on the AJs and on the interactions between E-cadherin, β-catenin and PTP1B was determined in Caco-2 cell monolayers. Treatment of cell monolayers with acetaldehyde induced redistribution of E-cadherin and β-catenin from the intercellular junctions by a tyrosine phosphorylation-dependent mechanism. The PTPase activity associated with E-cadherin and β-catenin was significantly reduced and the interaction of PTP1B with E-cadherin and β-catenin was attenuated by acetaldehyde. Acetaldehyde treatment resulted in phosphorylation of β-catenin on tyrosine residues, and abolished the interaction of β-catenin with E-cadherin by a tyrosine kinase-dependent mechanism. Protein binding studies showed that the treatment of cells with acetaldehyde reduced the binding of β-catenin to the C-terminal region of E-cadherin. Pairwise binding studies using purified proteins indicated that the direct interaction between E-cadherin and β-catenin was reduced by tyrosine phosphorylation of β-catenin, but was unaffected by tyrosine phosphorylation of E-cadherin-C. Treatment of cells with acetaldehyde also reduced the binding of E-cadherin to GST (glutathione S-transferase)–PTP1B. The pairwise binding study showed that GST–E-cadherin-C binds to recombinant PTP1B, but this binding was significantly reduced by tyrosine phosphorylation of E-cadherin. Acetaldehyde increased the phosphorylation of β-catenin on Tyr-331, Tyr-333, Tyr-654 and Tyr-670. These results show that acetaldehyde induces disruption of interactions between E-cadherin, β-catenin and PTP1B by a phosphorylation-dependent mechanism. PMID:17087658

  8. Chemical alteration of calcium silicate hydrates in saline groundwater. Mechanism of sorption of Na on C-S-H and effect of NaCl on leaching of Ca from C-S-H

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari

    2004-01-01

    In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In the presence of some reactive ions in a saline groundwater, the chemical properties of cement materials should be affected. In this study, the mechanism of sorption of sodium (Na) on C-S-H and the effect of sodium chloride (NaCl) concentration on dissolution of Calcium Silicate Hydrate (C-S-H) are discussed by measuring the sorption isotherm of sodium onto C-S-H gel (Ca/Si = 0.65-1.2). Based on the experimental results, it is showed that sodium sorbs by substitution for Ca in C-S-H phases and leaching of Ca from C-S-H is enhanced in NaCl solution ( -1 mol dm -3 ). The results of sorption experiments are reasonably well modelled by the ion-exchange model assuming some calcium sites with different ion-exchange log K values. It is also suggested that the dissolution of C-S-H can be modelled reasonably well by considering the effect of ionic strength on activity coefficients of aqueous species for high Ca/Si ratio of C-S-H, and the effect of exchange of sodium with calcium of C-S-H on leaching of Ca becomes obvious for lower Ca/Si ratio of C-S-H. (author)

  9. Hydrated electron: a destroyer of perfluorinated carboxylates?

    International Nuclear Information System (INIS)

    Huang Li; Dong Wenbo; Hou Huiqi

    2006-01-01

    showed that fluorine ion was generated in the mixed solution of K 4 Fe(CN) 6 and PFCAs after irradiation. This phenomenon also proved that hydrated electron could attach to PFCAs and followed by efficient dissociation of PFCAs via heterolytic cleavage of C-F bond. Considering that a majority of hydrated electron are generated in the course of radiation and non-thermal plasma, such technologies are believed to be capable of serving to PFCAs abatement. . (authors)

  10. Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

    Science.gov (United States)

    Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

    2015-08-03

    We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Dissociation: a developmental psychoneurobiological perspective

    African Journals Online (AJOL)

    Adele

    ... the stream of con- sciousness and memory.1 It is a frequent symptom of a range ... infant for long time spans in an extremely disturbed psycho- biological state that ... Advantage: Dissociation is adaptive in the short-term. Dissociation can be ...

  12. 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.

  13. Dissociative recombination of dications

    International Nuclear Information System (INIS)

    Seiersen, K.; Heber, O.; Jensen, M.J.; Safvan, C.P.; Andersen, L. H.

    2003-01-01

    Dissociative recombination (DR) of doubly-charged positive ions has been studied at the heavy ion storage ring ASTRID. Low-energy electrons were scattered on the dication of the N 2 molecule, and the absolute cross section was measured in the energy range of 10 -4 -50 eV. From the measured cross section, a thermal rate coefficient of 5.8x10 -7 cm 3 s -1 at 300 K was extracted. Furthermore, we present new results on the CO 2+ DR rate, and a summary and comparison of measured DR rate coefficients for both the singly and doubly-charged ions of CO, CO 2 , and N 2 is presented

  14. Quarkonium dissociation by anisotropy

    Science.gov (United States)

    Chernicoff, Mariano; Fernández, Daniel; Mateos, David; Trancanelli, Diego

    2013-01-01

    We compute the screening length for quarkonium mesons moving through an anisotropic, strongly coupled mathcal{N} = 4 super Yang-Mills plasma by means of its gravity dual. We present the results for arbitrary velocities and orientations of the mesons, as well as for arbitrary values of the anisotropy. The anisotropic screening length can be larger or smaller than the isotropic one, and this depends on whether the comparison is made at equal temperatures or at equal entropy densities. For generic motion we find that: (i) mesons dissociate above a certain critical value of the anisotropy, even at zero temperature; (ii) there is a limiting velocity for mesons in the plasma, even at zero temperature; (iii) in the ultra-relativistic limit the screening length scales as (1 - v 2)ɛ with ɛ = 1 /2, in contrast with the isotropic result ɛ = 1 /4.

  15. The N54-αs Mutant Has Decreased Affinity for βγ and Suggests a Mechanism for Coupling Heterotrimeric G Protein Nucleotide Exchange with Subunit Dissociation.

    Science.gov (United States)

    Cleator, John H; Wells, Christopher A; Dingus, Jane; Kurtz, David T; Hildebrandt, John D

    2018-05-01

    Ser54 of G s α binds guanine nucleotide and Mg 2+ as part of a conserved sequence motif in GTP binding proteins. Mutating the homologous residue in small and heterotrimeric G proteins generates dominant-negative proteins, but by protein-specific mechanisms. For α i/o , this results from persistent binding of α to βγ , whereas for small GTP binding proteins and α s this results from persistent binding to guanine nucleotide exchange factor or receptor. This work examined the role of βγ interactions in mediating the properties of the Ser54-like mutants of G α subunits. Unexpectedly, WT- α s or N54- α s coexpressed with α 1B -adrenergic receptor in human embryonic kidney 293 cells decreased receptor stimulation of IP3 production by a cAMP-independent mechanism, but WT- α s was more effective than the mutant. One explanation for this result would be that α s , like Ser47 α i/o , blocks receptor activation by sequestering βγ ; implying that N54- α S has reduced affinity for βγ since it was less effective at blocking IP3 production. This possibility was more directly supported by the observation that WT- α s was more effective than the mutant in inhibiting βγ activation of phospholipase C β 2. Further, in vitro synthesized N54- α s bound biotinylated- βγ with lower apparent affinity than did WT- α s The Cys54 mutation also decreased βγ binding but less effectively than N54- α s Substitution of the conserved Ser in α o with Cys or Asn increased βγ binding, with the Cys mutant being more effective. This suggests that Ser54 of α s is involved in coupling changes in nucleotide binding with altered subunit interactions, and has important implications for how receptors activate G proteins. Copyright © 2018 by The American Society for Pharmacology and Experimental Therapeutics.

  16. 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

  17. Dissociation - a preliminary contextual model

    Directory of Open Access Journals (Sweden)

    C Krüger

    2007-02-01

    Full Text Available Background. The Diagnostic and Statistical Manual of Mental Disorders (DSM system has certain limitations when applied to two South African examples of dissociation, because it is descriptive (non-explanatory and focuses on intrapsychic (non-communal processes. Even the existing Western explanatory models of dissociation fail to accommodate fully the communal aspects of dissociation in our South African context. Objectives and methods. The aim was to explore an expanded perspective on dissociation that does not limit it to an intrapsychic phenomenon, but that accounts for the interrelatedness of individuals within their social context. Auto-ethnography was used. In this article a collective, socially orientated, contextual hermeneutic was applied to two local examples of dissociation. Three existing Western models were expanded along multicontextual, collective lines, for them to be more useful in the pluralistic South African context. Results. This preliminary contextual model of dissociation includes a person’s interpersonal, socio-cultural, and spiritual contexts, in addition to the intrapsychic context. Dissociation is considered to be a normal information-processing tool that maintains balanced, coherent selves-in-society, i.e. individuals connected to each other. In the South African context dissociation appears mostly as a normal phenomenon and seldom as a sign of mental illness. Dissociation is pivotal for the normal construction of individual and communal identities in the face of conflicting sets of information from various contexts. Dissociation may help individuals or communities to survive in a world of conflicting messages, where conflict is often interpersonal/cultural/societal in nature, rather than primarily intrapsychic. Conclusions. This model should be developed and evaluated further. Such evaluation would require suitable new local terminology.

  18. Linear Discriminant Analysis for the in Silico Discovery of Mechanism-Based Reversible Covalent Inhibitors of a Serine Protease: Application of Hydration Thermodynamics Analysis and Semi-empirical Molecular Orbital Calculation.

    Science.gov (United States)

    Masuda, Yosuke; Yoshida, Tomoki; Yamaotsu, Noriyuki; Hirono, Shuichi

    2018-01-01

    We recently reported that the Gibbs free energy of hydrolytic water molecules (ΔG wat ) in acyl-trypsin intermediates calculated by hydration thermodynamics analysis could be a useful metric for estimating the catalytic rate constants (k cat ) of mechanism-based reversible covalent inhibitors. For thorough evaluation, the proposed method was tested with an increased number of covalent ligands that have no corresponding crystal structures. After modeling acyl-trypsin intermediate structures using flexible molecular superposition, ΔG wat values were calculated according to the proposed method. The orbital energies of antibonding π* molecular orbitals (MOs) of carbonyl C=O in covalently modified catalytic serine (E orb ) were also calculated by semi-empirical MO calculations. Then, linear discriminant analysis (LDA) was performed to build a model that can discriminate covalent inhibitor candidates from substrate-like ligands using ΔG wat and E orb . The model was built using a training set (10 compounds) and then validated by a test set (4 compounds). As a result, the training set and test set ligands were perfectly discriminated by the model. Hydrolysis was slower when (1) the hydrolytic water molecule has lower ΔG wat ; (2) the covalent ligand presents higher E orb (higher reaction barrier). Results also showed that the entropic term of hydrolytic water molecule (-TΔS wat ) could be used for estimating k cat and for covalent inhibitor optimization; when the rotational freedom of the hydrolytic water molecule is limited, the chance for favorable interaction with the electrophilic acyl group would also be limited. The method proposed in this study would be useful for screening and optimizing the mechanism-based reversible covalent inhibitors.

  19. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

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

  20. Risk factors of methane hydrate resource development in the concentrated zones distributed in the eastern Nankai Trough

    Science.gov (United States)

    Yamamoto, K.; Nagakubo, S.

    2009-04-01

    , low pressure. Deformation and subsidence of the sea floor may be unavoidable but does not cause serious concern on the safety. Some have argued that hydrate dissociations in wide area may cause landslide due to weakened formation by dissociation. To manage the concern, the test site should be chosen carefully and formation property alternation should be well known. One common misunderstanding widespread in public is that methane hydrate is "unstable material." Indeed, the hydrate is stable in the original temperature and pressure conditions, and the endothermic process of hydrate dissociation leads negative feedback to the formation conditions from the altered states by artificial depressurization. Also the hydrate dissociation in the sandy sediments is governed by relatively slow heat and fluid transport phenomena in porous media, so the process is gradual. Therefore, a catastrophic chain reaction which many people imagine is surely unlikely. As mentioned above, at present, risks of methane hydrate resource development in the concentrated zones distributed in the eastern Nankai trough are not significant, and comparable or less serious than conventional oil and gas production, we concluded. Of course, this evaluation should be verified with offshore production tests in the future, and new knowledge should be reflected to the safe and environmentally friendly production system designs. The nature of unconsolidated formation after the hydrate dissociation is key issue of such investigation. MH21 consortium has studied the issue in many aspects, and will continue the investigation.

  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. How thioredoxin dissociates its mixed disulfide.

    Directory of Open Access Journals (Sweden)

    Goedele Roos

    2009-08-01

    Full Text Available The dissociation mechanism of the thioredoxin (Trx mixed disulfide complexes is unknown and has been debated for more than twenty years. Specifically, opposing arguments for the activation of the nucleophilic cysteine as a thiolate during the dissociation of the complex have been put forward. As a key model, the complex between Trx and its endogenous substrate, arsenate reductase (ArsC, was used. In this structure, a Cys29(Trx-Cys89(ArsC intermediate disulfide is formed by the nucleophilic attack of Cys29(Trx on the exposed Cys82(ArsC-Cys89(ArsC in oxidized ArsC. With theoretical reactivity analysis, molecular dynamics simulations, and biochemical complex formation experiments with Cys-mutants, Trx mixed disulfide dissociation was studied. We observed that the conformational changes around the intermediate disulfide bring Cys32(Trx in contact with Cys29(Trx. Cys32(Trx is activated for its nucleophilic attack by hydrogen bonds, and Cys32(Trx is found to be more reactive than Cys82(ArsC. Additionally, Cys32(Trx directs its nucleophilic attack on the more susceptible Cys29(Trx and not on Cys89(ArsC. This multidisciplinary approach provides fresh insights into a universal thiol/disulfide exchange reaction mechanism that results in reduced substrate and oxidized Trx.

  3. Hydration Phase Diagram of Clay Particles from Molecular Simulations.

    Science.gov (United States)

    Honorio, Tulio; Brochard, Laurent; Vandamme, Matthieu

    2017-11-07

    Adsorption plays a fundamental role in the behavior of clays. Because of the confinement between solid clay layers on the nanoscale, adsorbed water is structured in layers, which can occupy a specific volume. The transition between these states is intimately related to key features of clay thermo-hydro-mechanical behavior. In this article, we consider the hydration states of clays as phases and the transition between these states as phase changes. The thermodynamic formulation supporting this idea is presented. Then, the results from grand canonical Monte Carlo simulations of sodium montmorillonite are used to derive hydration phase diagrams. The stability analysis presented here explains the coexistence of different hydration states at clay particle scale and improves our understanding of the irreversibilities of clay thermo-hydro-mechanical behavior. Our results provide insights into the mechanics of the elementary constituents of clays, which is crucial for a better understanding of the macroscopic behavior of clay-rich rocks and soils.

  4. Dissociative Excitation of Thymine by Electron Impact

    Science.gov (United States)

    McConkey, William; Tiessen, Collin; Hein, Jeffrey; Trocchi, Joshuah; Kedzierski, Wladek

    2014-05-01

    A crossed electron-gas beam system coupled to a VUV spectrometer has been used to investigate the dissociation of thymine (C5H6N2O2) into excited atomic fragments in the electron-impact energy range from threshold to 375 eV. A special stainless steel oven is used to vaporize the thymine and form it into a beam where it is intersected by a magnetically collimated electron beam, typical current 50 μA. The main features in the spectrum are the H Lyman series lines. The probability of extracting excited C or N atoms from the ring is shown to be very small. In addition to spectral data, excitation probability curves as a function of electron energy will be presented for the main emission features. Possible dissociation channels and excitation mechanisms in the parent molecule will be discussed. The authors thank NSERC (Canada) for financial support.

  5. Ion conduction mechanisms and thermal properties of hydrated and anhydrous phosphoric acids studied with 1H, 2H, and 31P NMR.

    Science.gov (United States)

    Aihara, Yuichi; Sonai, Atsuo; Hattori, Mineyuki; Hayamizu, Kikuko

    2006-12-14

    To understand the behaviors of phosphoric acids in fuel cells, the ion conduction mechanisms of phosphoric acids in condensed states without free water and in a monomer state with water were studied by measuring the ionic conductivity (sigma) using AC impedance, thermal properties, and self-diffusion coefficients (D) and spin-lattice relaxation times (T1) with multinuclear NMR. The self-diffusion coefficient of the protons (H+ or H3O+), H2O, and H located around the phosphate were always larger than the diffusion coefficients of the phosphates and the disparity increased with increasing phosphate concentration. The diffusion coefficients of the samples containing D2O paralleled those in the protonated samples. Since the 1H NMR T1 values exhibited a minimum with temperature, it was possible to determine the correlation times and they were found to be of nanosecond order for a distance of nanometer order for a flip. The agreement of the ionic conductivities measured directly and those calculated from the diffusion coefficients indicates that the ion conduction obeys the Nernst-Einstein equation in the condensed phosphoric acids. The proton diffusion plays a dominant role in the ion conduction, especially in the condensed phosphoric acids.

  6. Dynamics of dissociative adsorption of hydrogen on Ni(100)

    International Nuclear Information System (INIS)

    Hamza, A.V.; Madix, R.J.

    1985-01-01

    Nearly monoenergetic beams of hydrogen and deuterium were used to determine dissociative sticking probabilities for H 2 and D 2 on Ni(100) at various energies. Variation of the surface temperature between 90 and 300 K had no effect on the dissociative sticking probability of H 2 at 3.6 and 5.8 kJ/mol incident beam energy, indicating a direct mechanism of dissociation. A four fold increase in the initial dissociative sticking probability for H 2 from 0.2 to 0.8 was observed by increasing the translational kinetic energy from 0.7 to 7.0 kJ/mol. The initial dissociative sticking probability for D 2 was slightly lower, increasing from 0.15 to 0.75 with increasing translational kinetic energy from 1.3 to 10.5 kJ/mol. The form of the increase with kinetic energy was explained by tunnelling through a low activation barrier, accounting as well for the high dissociation probability at low kinetic energies. The dissociative sticking probability decreased with hydrogen or deuterium adatom coverage at all energies. The decline in sticking probability with hydrogen coverage was fit to a s(theta) = s 0 (1 - a theta)/sup n/ functional form. From this relationship it was deduced that hydrogen adatoms block only single sites and that four vacant sites are needed for dissociation. The dissociative sticking probability for H 2 declined precipitously from 0.77 to 0.16 with oxygen adatom coverage from 0 to 5% of a monolayer at a translational energy of 9.6 kJ.mol. 36 references, 8 figures

  7. Dissociative symptomatology in cancer patients

    Science.gov (United States)

    Civilotti, Cristina; Castelli, Lorys; Binaschi, Luca; Cussino, Martina; Tesio, Valentina; Di Fini, Giulia; Veglia, Fabio; Torta, Riccardo

    2015-01-01

    Introduction: The utilization of the post-traumatic stress disorder (PTSD) diagnostic spectrum is currently being debated to categorize psychological adjustment in cancer patients. The aims of this study were to: (1) evaluate the presence of cancer-related traumatic dissociative symptomatology in a sample of cancer patients; (2) examine the correlation of cancer-related dissociation and sociodemographic and medical variables, anxiety, depression, and post-traumatic stress symptomatology; (3) investigate the predictors of cancer-related dissociation. Methods: Ninety-two mixed cancer patients (mean age: 58.94, ds = 10.13) recruited from two hospitals in northern Italy were administered a questionnaire on sociodemographic and medical characteristics, the Karnofsky Scale to measure the level of patient activity and medical care requirements, the Hospital Anxiety and Depression Scale (HADS) to evaluate the presence of anxiety and depression, the Impact of Event Scale Revised (IES-R) to assess the severity of intrusion, avoidance, and hypervigilance, and the Peritraumatic Dissociative Experiences Questionnaire (PDEQ) to quantify the traumatic dissociative symptomatology. Results: 31.5% of participants report a PDEQ score above the cutoff. The results indicated that dissociative symptomatology was positively correlated with HADS scores (HADS-Anxiety: r = 0.476, p dissociative symptomatology. The results converged on a three predictor model revealing that IES-R-Intrusion, IES-R-Avoidance, and IES-R-Hyperarousal accounted for 53.9% of the explained variance. Conclusion: These findings allow us to hypothesize a specific psychological reaction which may be ascribed to the traumatic spectrum within the context of cancer, emphasizing the close relationship between the origin of dissociative constituents which, according to the scientific literature, compose the traumatic experience. Our results have implications for understanding dissociative symptomatology in a cancer

  8. A millimeter-wave reflectometer for whole-body hydration sensing

    Science.gov (United States)

    Zhang, W.-D.; Brown, E. R.

    2016-05-01

    This paper demonstrates a non-invasive method to determine the hydration level of human skin by measuring the reflectance of W-band (75-110 GHz) and Ka-band (26-40 GHz) radiation. Ka-band provides higher hydration accuracy ( 1 mm), thereby allowing access to the important dermis layer of skin. W-band provides less depth of penetration but finer spatial resolution (~2 mm). Both the hydration sensing concept and experimental results are presented here. The goal is to make a human hydration sensor that is 1% accurate or better, operable by mechanically scanning, and fast enough to measure large areas of the human body in seconds.

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

    KAUST Repository

    Kirchheim, A. P.; Dal Molin, Denise Carpena Coitinho; Fischer, Peter J.; Emwas, Abdul-Hamid M.; Provis, John L.; Monteiro, Paulo José Meleragno

    2011-01-01

    window, combined with solution analysis by 27Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C3A hydration during the early stages. There are differences in the hydration mechanism between

  10. Influence of surfactants on gas-hydrate formation' kinetics in water-oil emulsion

    Science.gov (United States)

    Zemenkov, Yu D.; Shirshova, A. V.; Arinstein, E. A.; Shuvaev, A. N.

    2018-05-01

    The kinetics of gas hydrate formation of propane in a water-oil emulsion is experimentally studied when three types of surfactants (SAA (surface acting agent)) - anionic type emulsifiers - are added to the aqueous phase. It is shown that all three types of surfactants decelerate the growth of the gas-hydrate in the emulsion and can be considered as anti-agglutinating and kinetic low-dose inhibitors. The most effective inhibitor of hydrate formation in water-oil emulsion of SV-102 surfactant was revealed. For comparison, experimental studies of gas-hydrate formation under the same conditions for bulk water have been carried out. It is shown that in bulk water, all the surfactants investigated act as promoters (accelerators) of hydrate formation. A qualitative explanation of the action mechanisms of emulsifiers in the process of gas-hydrate formation in water-oil emulsion is given.

  11. Hydration kinetics modeling of Portland cement considering the effects of curing temperature and applied pressure

    International Nuclear Information System (INIS)

    Lin Feng; Meyer, Christian

    2009-01-01

    A hydration kinetics model for Portland cement is formulated based on thermodynamics of multiphase porous media. The mechanism of cement hydration is discussed based on literature review. The model is then developed considering the effects of chemical composition and fineness of cement, water-cement ratio, curing temperature and applied pressure. The ultimate degree of hydration of Portland cement is also analyzed and a corresponding formula is established. The model is calibrated against the experimental data for eight different Portland cements. Simple relations between the model parameters and cement composition are obtained and used to predict hydration kinetics. The model is used to reproduce experimental results on hydration kinetics, adiabatic temperature rise, and chemical shrinkage of different cement pastes. The comparisons between the model reproductions and the different experimental results demonstrate the applicability of the proposed model, especially for cement hydration at elevated temperature and high pressure.

  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. Mapping the Fluid Pathways and Permeability Barriers of a Large Gas Hydrate Reservoir

    Science.gov (United States)

    Campbell, A.; Zhang, Y. L.; Sun, L. F.; Saleh, R.; Pun, W.; Bellefleur, G.; Milkereit, B.

    2012-12-01

    An understanding of the relationship between the physical properties of gas hydrate saturated sedimentary basins aids in the detection, exploration and monitoring one of the world's upcoming energy resources. A large gas hydrate reservoir is located in the MacKenzie Delta of the Canadian Arctic and geophysical logs from the Mallik test site are available for the gas hydrate stability zone (GHSZ) between depths of approximately 850 m to 1100 m. The geophysical data sets from two neighboring boreholes at the Mallik test site are analyzed. Commonly used porosity logs, as well as nuclear magnetic resonance, compressional and Stoneley wave velocity dispersion logs are used to map zones of elevated and severely reduced porosity and permeability respectively. The lateral continuity of horizontal permeability barriers can be further understood with the aid of surface seismic modeling studies. In this integrated study, the behavior of compressional and Stoneley wave velocity dispersion and surface seismic modeling studies are used to identify the fluid pathways and permeability barriers of the gas hydrate reservoir. The results are compared with known nuclear magnetic resonance-derived permeability values. The aim of investigating this heterogeneous medium is to map the fluid pathways and the associated permeability barriers throughout the gas hydrate stability zone. This provides a framework for an understanding of the long-term dissociation of gas hydrates along vertical and horizontal pathways, and will improve the knowledge pertaining to the production of such a promising energy source.

  14. Designing a reservoir flow rate experiment for the GOM hydrate JIP leg 2 LWD drilling

    Energy Technology Data Exchange (ETDEWEB)

    Gullapalli, I.; Silpngarmlert, S.; Reik, B.; Kamal, M.; Jones, E. [Chevron Energy Technology Co., San Ramon, CA (United States); Moridis, G. [Lawrence Berkeley National Laboratories, CA (United States); Collett, T. [United States Geological Survey, Reston, VA (United States)

    2008-07-01

    Studies have indicated that the Gulf of Mexico may contain large deep sea hydrate deposits. This paper provided details of short-term production profiles obtained from a geological model of hydrate deposits located in the Gulf area. A well test analysis tool was used to obtain the production parameters. Pressure transients from numerical simulations of various well test designs were used to provide estimates of important flow parameters. The aim of the study was to determine the type and duration of a well test capable of providing data to support the accurate modeling of gas hydrate deposits. Parameters studied in the test included the effects of permeability and hydrate saturation as a function of the duration of the flow test. Results indicated that production using a constant bottom hole pressure is an appropriate method of impacting hydrate dissociation by depressurization. However, changes in transient pressure plots could not be characterized in order to identify regions of varying saturation levels. Results suggested that the rate of effective water to effective gas was higher than rates obtained from relative permeability relations due to low gas saturation levels. Fluid saturation regions were in areas of low confidence in relative permeability curves. However, it was not possible to calculate absolute permeability of the reservoir for systems with short production periods. Further studies are needed to determine effective permeability using history matching and a hydrate simulator. 8 refs., 4 tabs., 27 figs.

  15. Dissociative absorption: An empirically unique, clinically relevant, dissociative factor.

    Science.gov (United States)

    Soffer-Dudek, Nirit; Lassri, Dana; Soffer-Dudek, Nir; Shahar, Golan

    2015-11-01

    Research of dissociative absorption has raised two questions: (a) Is absorption a unique dissociative factor within a three-factor structure, or a part of one general dissociative factor? Even when three factors are found, the specificity of the absorption factor is questionable. (b) Is absorption implicated in psychopathology? Although commonly viewed as "non-clinical" dissociation, absorption was recently hypothesized to be specifically associated with obsessive-compulsive symptoms. To address these questions, we conducted exploratory and confirmatory factor analyses on 679 undergraduates. Analyses supported the three-factor model, and a "purified" absorption scale was extracted from the original inclusive absorption factor. The purified scale predicted several psychopathology scales. As hypothesized, absorption was a stronger predictor of obsessive-compulsive symptoms than of general psychopathology. In addition, absorption was the only dissociative scale that longitudinally predicted obsessive-compulsive symptoms. We conclude that absorption is a unique and clinically relevant dissociative tendency that is particularly meaningful to obsessive-compulsive symptoms. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Hydration, phase separation and nonlinear rheology of temperature-sensitive water-soluble polymers

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Fumihiko; Koga, Tsuyoshi [Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510 (Japan); Kaneda, Isamu [Department of Food Science, Rakuno Gakuen University, Ebetsu, Hokkaido 069-8501 (Japan); Winnik, Francoise M, E-mail: ftanaka@phys.polym.kyoto-u.ac.jp [Department of Chemistry and Faculty of Pharmacy, University of Montreal, Montreal, H3C 3J7 (Canada)

    2011-07-20

    The collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating and the phase diagrams of aqueous PNIPAM solutions with a very flat lower critical solution temperature (LCST) phase separation line are theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes sharper with the cooperativity parameter {sigma} of hydration. The reentrant coil-globule-coil transition and cononsolvency in a mixed solvent of water and methanol are also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves (LCST cononsolvency) with the mol fraction of methanol due to the competition is calculated and compared with the experimental data. Aqueous solutions of hydrophobically modified PNIPAM carrying short alkyl chains at both chain ends (telechelic PNIPAM) are theoretically and experimentally studied. The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation), and separate from the coil-globule transition line. Associated structures in the solution, such as flower micelles, mesoglobules, and higher fractal assembly, are studied by ultra small-angle neutron scattering with theoretical modeling of the scattering function. Dynamic-mechanical modulus, nonlinear stationary viscosity, and stress build-up in start-up shear flows of the associated networks are studied on the basis of the affine and non-affine transient network theory. The molecular conditions for thickening, strain hardening, and stress overshoot are found in terms of the nonlinear amplitude A of the chain tension and the tension-dissociation coupling constant g.

  17. Enclathration of CO2 as a co-guest of structure H hydrates and its implications for CO2 capture and sequestration

    International Nuclear Information System (INIS)

    Lee, Yohan; Lee, Dongyoung; Lee, Jong-Won; Seo, Yongwon

    2016-01-01

    Highlights: • We examine sH hydrates with CO 2 + N 2 + neohexane for CO 2 capture and sequestration. • The structural transition occurs in the CO 2 (40%) + N 2 (60%) + neohexane system. • CO 2 molecules are enclathrated into sH hydrates in the N 2 -rich systems. • CO 2 selectivity in sH hydrates is slightly lower than that in sI hydrates. • ΔH d values provide information on the structural transition of sH to sI hydrates. - Abstract: In this study, the thermodynamic behaviors, cage-specific guest distributions, structural transition, and dissociation enthalpies of sH hydrates with CO 2 + N 2 gas mixtures were investigated for their potential applications to hydrate-based CO 2 capture and sequestration. The stability conditions of the CO 2 + N 2 + water systems and the CO 2 + N 2 + neohexane (2,2-dimethylbutane, NH) + water systems indicated that the gas mixtures in the range of flue gas compositions could form sH hydrates, thereby mitigating the pressure and temperature required for gas hydrate formation. Structure identification using powder X-ray diffraction (PXRD) revealed the coexistence of sI and sH hydrates in the CO 2 (40%) + N 2 (60%) + NH system and the hydrate structure transformed from sH into sI as the CO 2 concentration increased. In addition, the Raman analysis clearly demonstrated that CO 2 molecules were enclathrated into the cages of sH hydrates in the N 2 -rich systems. It was found from direct CO 2 composition measurements that CO 2 selectivity in the sH hydrate phase was slightly lower than that in the corresponding sI hydrate phase. Dissociation enthalpy (ΔH d ) measurements using a high-pressure micro-differential scanning calorimeter (HP μ-DSC) indicated that the ΔH d values could also provide valuable information on the structural transition of sH to sI hydrates with respect to the CO 2 concentration in the feed gas. This study provides a better understanding of the thermodynamic and physicochemical background for CO 2

  18. Numerical studies of gas production from several CH4 hydrate zones at the Mallik site, Mackenzie Delta, Canada

    Science.gov (United States)

    Moridis, G.J.; Collett, T.S.; Dallimore, S.R.; Satoh, T.; Hancock, S.; Weatherill, B.

    2004-01-01

    The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. A gas hydrate research well was drilled at the site in 1998. The objective of this study is the analysis of various gas production scenarios from five methane hydrate-bearing zones at the Mallik site. In Zone #1, numerical simulations using the EOSHYDR2 model indicated that gas production from hydrates at the Mallik site was possible by depressurizing a thin free gas zone at the base of the hydrate stability field. Horizontal wells appeared to have a slight advantage over vertical wells, while multiwell systems involving a combination of depressurization and thermal stimulation offered superior performance, especially when a hot noncondensible gas was injected. Zone #2, which involved a gas hydrate layer with an underlying aquifer, could yield significant amounts of gas originating entirely from gas hydrates, the volumes of which increased with the production rate. However, large amounts of water were also produced. Zones #3, #4 and #5 were lithologically isolated gas hydrate-bearing deposits with no underlying zones of mobile gas or water. In these zones, thermal stimulation by circulating hot water in the well was used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increased with the gas hydrate saturation, the initial formation temperature, the temperature of the circulating water in the well, and the formation thermal conductivity. Methane production appears to be less sensitive to the specific heat of the rock and of the hydrate, and to the permeability of the formation. ?? 2004 Published by Elsevier B.V.

  19. 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

  20. Dissociation Energies of Diatomic Molecules

    International Nuclear Information System (INIS)

    Qun-Chao, Fan; Wei-Guo, Sun

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7 LiD, 7 LiH, 6 LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy–Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies D e theory , which are in excellent agreement with the experimental dissociation energies D e expt . (atomic and molecular physics)

  1. Neural complexity, dissociation, and schizophrenia

    Czech Academy of Sciences Publication Activity Database

    Bob, P.; Šusta, M.; Chládek, Jan; Glaslová, K.; Fedor-Ferybergh, P.

    2007-01-01

    Roč. 13, č. 10 (2007), HY1-5 ISSN 1234-1010 Institutional research plan: CEZ:AV0Z20650511 Keywords : neural complexity * dissociation * schizophrenia Subject RIV: FH - Neurology Impact factor: 1.607, year: 2007

  2. Dissociative Tendencies and Traffic Incidents

    Directory of Open Access Journals (Sweden)

    Valle, Virginia

    2012-01-01

    Full Text Available This paper analyses the relationship between dissociative experiences and road traffic incidents (crashes and traffic tickets in drivers (n=295 from Mar del Plata (Argentina city. A self-report questionnaire was applied to assess traffic crash involvement and sociodemographic variables. Dissociative tendencies were assessed by a modified version of the DES scale. To examine differences in DES scores tests of the difference of means were applied. Drivers who reported to be previously involved in traffic incidents obtained higher puntuations in the dissociative experiences scale than drivers who did not report such events. This result is observed for the total scale and for the three sub-scales (absorption, amnesia and depersonalization. However, differences appeared mainly for minor damage collisions. Further studies are needed to evaluate the role of dissociative tendencies as a risk factor in road traffic safety.

  3. Dissociative disorders in DSM-5.

    Science.gov (United States)

    Spiegel, David; Lewis-Fernández, Roberto; Lanius, Ruth; Vermetten, Eric; Simeon, Daphne; Friedman, Matthew

    2013-01-01

    The rationale, research literature, and proposed changes to the dissociative disorders and conversion disorder in the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) are presented. Dissociative identity disorder will include reference to possession as well as identity fragmentation, to make the disorder more applicable to culturally diverse situations. Dissociative amnesia will include dissociative fugue as a subtype, since fugue is a rare disorder that always involves amnesia but does not always include confused wandering or loss of personality identity. Depersonalization disorder will include derealization as well, since the two often co-occur. A dissociative subtype of posttraumatic stress disorder (PTSD), defined by the presence of depersonalization or derealization in addition to other PTSD symptoms, is being recommended, based upon new epidemiological and neuroimaging evidence linking it to an early life history of adversity and a combination of frontal activation and limbic inhibition. Conversion disorder (functional neurological symptom disorder) will likely remain with the somatic symptom disorders, despite considerable dissociative comorbidity.

  4. Gas production potential of disperse low-saturation hydrate accumulations in oceanic sediments

    International Nuclear Information System (INIS)

    Moridis, George J.; Sloan, E. Dendy

    2007-01-01

    In this paper, we evaluate the gas production potential of disperse, low-saturation (S H H hydrate-bearing sediments subject to depressurization-induced dissociation over a 10-year production period. We investigate the sensitivity of items (a)-(c) to the following hydraulic properties, reservoir conditions, and operational parameters: intrinsic permeability, porosity, pressure, temperature, hydrate saturation, and constant pressure at which the production well is kept. The results of this study indicate that, despite wide variations in the aforementioned parameters (covering the entire spectrum of such deposits), gas production is very limited, never exceeding a few thousand cubic meters of gas during the 10-year production period. Such low production volumes are orders of magnitude below commonly accepted standards of economic viability, and are further burdened with very unfavorable gas-to-water ratios. The unequivocal conclusion from this study is that disperse, low-S H hydrate accumulations in oceanic sediments are not promising targets for gas production by means of depressurization-induced dissociation, and resources for early hydrate exploitation should be focused elsewhere

  5. Withholding hydration and nutrition in newborns.

    Science.gov (United States)

    Porta, Nicolas; Frader, Joel

    2007-01-01

    In the twenty-first century, decisions to withhold or withdraw life-supporting measures commonly precede death in the neonatal intensive care unit without major ethical controversy. However, caregivers often feel much greater turmoil with regard to stopping medical hydration and nutrition than they do when considering discontinuation of mechanical ventilation or circulatory support. Nevertheless, forgoing medical fluids and food represents a morally acceptable option as part of a carefully developed palliative care plan considering the infant's prognosis and the burdens of continued treatment. Decisions to stop any form of life support should focus on the clinical circumstances, not the means used to sustain life.

  6. 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.

  7. 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.

  8. Failure of cement hydrates: freeze-thaw and fracture

    Science.gov (United States)

    Ioannidou, Katerina; Del Gado, Emanuela; Ulm, Franz-Josef; Pellenq, Roland

    Mechanical and viscoelastic behavior of concrete crucially depends on cement hydrates, the ``glue'' of cement. Even more than the atomistic structure, the mesoscale amorphous texture of cement hydrates over hundreds of nanometers plays a crucial role for material properties. We use simulations that combine information of the nano-scale building units of cement hydrates and on their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles.Our mesoscale model was able to reconcile different experimental results ranging from small-angle neutron scattering, SEM, adsorption/desorption of N2, and water to nanoindentation and gain the new fundamental insights into the microscopic origin of the properties measured. Our results suggest that heterogeneities developed during the early stages of hydration persist in the structure of C-S-H, impacting the rheological and mechanical performance of the hardened cement paste. In this talk I discuss recent investigation on failure mechanism at the mesoscale of hardened cement paste such as freeze-thaw and fracture. Using correlations between local volume fractions and local stress we provide a link between structural and mechanical heterogeneities during the failure mechanisms.

  9. Class H cement hydration at 180 deg. C and high pressure in the presence of added silica

    International Nuclear Information System (INIS)

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

    2008-01-01

    Under deep oil-well conditions of elevated temperature and pressure, crystalline calcium silicate hydrates are formed during Portland cement hydration. The use of silica rich mineral additives leads to the formation of crystalline hydrates with better mechanical properties than those formed without the additive. The effects of silica flour, silica fume (amorphous silica), and a natural zeolite mixture on the hydration of Class H cement slurries at 180 deg. C under externally applied pressures of 7 and 52 MPa are examined in real time using in-situ synchrotron X-ray diffraction. For some compositions examined, but not all, pressure was found to have a large effect on the kinetics of crystalline hydrate formation. The use of silica fume delayed both C 3 S hydration and the formation of crystalline silicate hydrates compared to what was seen with other silica sources

  10. Pore Effect on the Occurrence and Formation of Gas Hydrate in Permafrost of Qilian Mountain, Qinghai-Tibet Plateau, China

    Science.gov (United States)

    Gao, H.; Lu, H.; Lu, Z.

    2014-12-01

    Gas hydrates were found in the permafrost of Qilian Mountain, Qinghai- Tibet Plateau, China in 2008. It has been found that gas hydrates occur in Jurassic sedimentary rocks, and the hydrated gases are mainly thermogenic. Different from the gas hydrates existing in loose sands in Mallik, Mackenzie Delta, Canada and North Slope, Alaska, USA, the gas hydrates in Qilian Mountain occurred in hard rocks. For understanding the occurrence and formation mechanism of gas hydrate in hard rcok, extensive experimental investigations have been conducted to study the pore features and hydrate formation in the rocks recovered from the hydrate layers in Qilian Mountain. The structures of sedimentary rock were observed by high-resolution X-ray CT, and pore size distribution of a rock specimen was measured with the mercury-injection method. Methane hydrate was synthesized in water-saturated rocks, and the saturations of hydrate in sedimentary rocks of various types were estimated from the amount of gas released from certain volume of rock. X-ray CT observation revealed that fractures were developed in the rocks associated with faults, while those away from faults were generally with massive structure. The mercury-injection analysis of pore features found that the porosities of the hydrate-existing rocks were generally less than 3%, and the pore sizes were generally smaller than 100 nm. The synthesizing experiments found that the saturation of methane hydrate were generally lower than 6% of pore space in rocks, but up to 16% when fractures developed. The low hydrate saturation in Qilian sedimentary rocks has been found mainly due to the small pore size of rock. The low hydrate saturation in the rocks might be the reason for the failure of regional seismic and logging detections of gas hydrates in Qilian Mountain.

  11. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  12. International Society of Nephrology-Hydration and Kidney Health Initiative - Expanding Research and Knowledge.

    Science.gov (United States)

    Moist, Louise M; Clark, William F; Segantini, Luca; Damster, Sandrine; Le Bellego, Laurent; Wong, Germaine; Tonelli, Marcello

    2016-01-01

    The purpose of this manuscript is to describe a collaborative research initiative to explore the role of hydration in kidney health. Our understanding of the effects of hydration in health and disease is surprisingly limited, particularly when we consider the vital role of hydration in basic human physiology. Recent initiatives and research outcomes have challenged the global medical community to expand our knowledge about hydration, including the differences between water, sugared beverages and other consumables. Identification of the potential mechanisms contributing to the benefits of hydration has stimulated the global nephrology community to advance research regarding hydration for kidney health. Hydration and kidney health has been a focus of research for several research centers with a rapidly expanding world literature and knowledge. The International Society of Nephrology has collaborated with Danone Nutricia Research to promote development of kidney research initiatives, which focus on the role of hydration in kidney health and the global translation of this new information. This initiative supports the use of existing data in different regions and countries to expand dialogue among experts in the field of hydration and health, and to increase scientific interaction and productivity with the ultimate goal of improving kidney health. © 2016 The Author(s) Published by S. Karger AG, Basel.

  13. Major occurrences and reservoir concepts of marine clathrate hydrates: Implications of field evidence

    Science.gov (United States)

    Booth, J.S.; Winters, W.J.; Dillon, William P.; Clennell, M.B.; Rowe, M.M.

    1998-01-01

    This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). Questions concerning clathrate hydrate as an energy resource, as a factor in modifying global climate and as a triggering mechanism for mass movements invite consideration of what factors promote hydrate concentration, and what the quintessential hydrate-rich sediment may be. Gas hydrate field data, although limited, provide a starting point for identifying the environments and processes that lead to more massive concentrations. Gas hydrate zones are up to 30 m thick and the vertical range of occurrence at a site may exceed 200 m. Zones typically occur more than 100m above the phase boundary. Thicker zones are overwhelmingly associated with structural features and tectonism, and often contain sand. It is unclear whether an apparent association between zone thickness and porosity represents a cause-and-effect relationship. The primary control on the thickness of a potential gas hydrate reservoir is the geological setting. Deep water and low geothermal gradients foster thick gas hydrate stability zones (GHSZs). The presence of faults, fractures, etc. can favour migration of gas-rich fluids. Geological processes, such as eustacy or subsidence, may alter the thickness of the GHSZ or affect hydrate concentratiion. Tectonic forces may promote injection of gas into the GHSZ. More porous and permeable sediment, as host sediment properties, increase storage capacity and fluid conductivity, and thus also enhance reservoir potential.

  14. The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

    Science.gov (United States)

    Zhang, Zhengcai; Guo, Guang-Jun

    2017-07-26

    Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

  15. 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...

  16. 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.

  17. Exciton-Dissociation and Charge-Recombination Processes in Pentacene/C 60 Solar Cells: Theoretical Insight into the Impact of Interface Geometry

    KAUST Repository

    Yi, Yuanping; Coropceanu, Veaceslav; Brédas, Jean-Luc

    2009-01-01

    The exciton-dissociation and charge-recombination processes in organic solar cells based on pentacene/C60 heterojunctions are investigated by means of quantum-mechanical calculations. The electronic couplings and the rates of exciton dissociation

  18. A laboratory study of anaerobic oxidation of methane in the presence of methane hydrate

    Science.gov (United States)

    Solem, R.; Bartlett, D.; Kastner, M.; Valentine, D.

    2003-12-01

    In order to mimic and study the process of anaerobic methane oxidation in methane hydrate regions we developed four high-pressure anaerobic bioreactors, designed to incubate environmental sediment samples, and enrich for populations of microbes associated with anaerobic methane oxidation (AMO). We obtained sediment inocula from a bacterial mat at the southern Hydrate Ridge, Cascadia, having cell counts approaching 1010 cells/cc. Ultimately, our goal is to produce an enriched culture of these microbes for characterization of the biochemical processes and chemical fluxes involved, as well as the unique adaptations required for, AMO. Molecular phylogenetic information along with results from fluorescent in situ hybridization indicate that consortia of Archaea and Bacteria are present which are related to those previously described for marine sediment AMO environments. Using a medium of enriched seawater and sediment in a 3:1 ratio, the system was incubated at 4° C under 43 atm of methane pressure; the temperature and pressure were kept constant. We have followed the reactions for seven months, particularly the vigorous consumption rates of dissolved sulfate and alkalinity production, as well as increases in HS-, and decreases in Ca concentrations. We also monitored the dissolved inorganic C (DIC) δ 13C values. The data were reproduced, and indicated that the process is extremely sensitive to changes in methane pressure. The rates of decrease in sulfate and increase in alkalinity concentrations were complimentary and showed considerable linearity with time. When the pressure in the reactor was decreased below the methane hydrate stability field, following the methane hydrate dissociation, sulfate reduction abruptly decreased. When the pressure was restored all the reactions returned to their previous rates. Much of the methane oxidation activity in the reactor is believed to occur in association with the methane hydrate. Upon the completion of one of the experiments

  19. Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process

    International Nuclear Information System (INIS)

    Babu, Ponnivalavan; Kumar, Rajnish; Linga, Praveen

    2013-01-01

    Hydrate based gas separation (HBGS) process with silica sand and silica gel as contact medium was employed to capture CO 2 from fuel gas mixture. Gas uptake measurement at three different pressures (7.5, 8.5 and 9.0 MPa) and 274.15 K were conducted for hydrate formation kinetics and overall conversion of water to hydrate, rate of hydrate formation were determined. Water conversion of up to 36% was achieved with silica sand bed compared to 13% conversion in the silica gel bed. Effect of driving force on the rate of hydrate formation and gas consumption was significant in silica sand bed whereas it was found to be insignificant in silica gel bed. Hydrate dissociation experiments by thermal stimulation (at constant pressure) alone and a combination of depressurization and thermal stimulation were carried out for complete recovery of the hydrated gas. A driving force of 23 K was found to be sufficient to recover all the hydrated gas within 1 h. This study indicates that silica sand can be an effective porous media for separation of CO 2 from fuel gas when compared to silica gel. - Highlights: ► The clathrate process for pre-combustion capture of carbon dioxide in a novel fixed bed reactor is presented. ► Performance of two contact media (silica gel and silica sand) was investigated. ► Water to hydrate conversion was higher in a silica sand column. ► A pressure reduction and thermal stimulation approach is presented for a complete recovery of the hydrated gas

  20. Childhood trauma and dissociation in first-episode psychosis, chronic schizophrenia and community controls.

    Science.gov (United States)

    Braehler, Christine; Valiquette, Luc; Holowka, Darren; Malla, Ashok K; Joober, Ridha; Ciampi, Antonio; Pawliuk, Nicole; King, Suzanne

    2013-11-30

    Increasing evidence supports the role of childhood trauma in the etiology of psychosis but underlying mechanisms are poorly understood. Early maltreatment has been linked to dissociative symptoms in psychosis patients. We explored associations between childhood trauma (Childhood Trauma Questionnaire) and dissociation (Dissociative Experiences Scale) in first-episode psychotic patients (n=62), chronic psychotic patients (n=43), and non-psychotic community controls (n=66). Multivariate analyses of covariance were used to test associations between childhood trauma and dissociation by group while controlling for sex. Chronic patients reported the highest level of dissociation. More severe childhood trauma was associated with greater dissociative symptoms in all groups although most strongly in chronic patients. Emotional abuse showed the strongest associations with dissociation, with these being strongest for chronic patients, followed by first-episode patients--and least for controls. Men showed a stronger association between physical neglect and dissociation than women, irrespective of group. There were no significant group by sex interactions. Our findings replicate the strong association between childhood trauma and dissociative symptoms in chronic and first-episode psychotic patients relative to non-psychotic control subjects. We also demonstrate the salience of emotional abuse in explaining variance in dissociation, especially in chronic patients. © 2013 Elsevier Ireland Ltd. All rights reserved.

  1. 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.

  2. Analytical investigation of high temperature 1 kW solid oxide fuel cell system feasibility in methane hydrate recovery and deep ocean power generation

    International Nuclear Information System (INIS)

    Azizi, Mohammad Ali; Brouwer, Jacob; Dunn-Rankin, Derek

    2016-01-01

    Highlights: • A dynamic Solid Oxide Fuel Cell (SOFC) model was developed. • Hydrate bed methane dissociation model was integrated with the SOFC model. • SOFC operated steadily for 120 days at high pressure deep ocean environment. • Burning some of the dissociated gas for SMR heat leads to more net methane produced. • Higher SOFC fuel utilization produces higher integrated system efficiency. - Abstract: Methane hydrates are potential valuable energy resources. However, finding an efficient method for methane gas recovery from hydrate sediments is still a challenge. New challenges arise from increasing environmental protection. This is due in part to the technical difficulties involved in the efficient dissociation of methane hydrates at high pressures. In this study, a new approach is proposed to produce valuable products of: 1. Net methane gas recovery from the methane hydrate sediment, and 2. Deep ocean power generation. We have taken the first steps toward utilization of a fuel cell system in methane gas recovery from deep ocean hydrate sediments. An integrated high pressure and high temperature solid oxide fuel cell (SOFC) and steam methane reformer (SMR) system is analyzed for this application and the recoverable amount of methane from deep ocean sediments is measured. System analysis is accomplished for two major cases regarding system performance: 1. Energy for SMR is provided by the burning part of the methane gas dissociated from the hydrate sediment. 2. Energy for SMR is provided through heat exchange with fuel cell effluent gases. We found that the total production of methane gas is higher in the first case compared to the second case. The net power generated by the fuel cell system is estimated for all cases. The primary goal of this study is to evaluate the feasibility of integrated electrochemical devices to accomplish energy efficient dissociation of methane hydrate gases in deep ocean sediments. Concepts for use of electrochemical devices

  3. Comparison of Physical Properties of Marine and Arctic Gas-Hydrate-Bearing Deposits

    Science.gov (United States)

    Winters, W. J.; Walker, M.; Collett, T. S.; Bryant, S. L.; Novosel, I.; Wilcox-Cline, R.; Bing, J.; Gomes, M. L.

    2009-12-01

    Gas hydrate (GH) occurs in both marine settings and in arctic environments within a wide variety of sediment types. Grain-size analyses from both environments indicate that intrinsic host-sediment properties have a strong influence on gas-hydrate distribution and morphologic characteristics. Depending on the amount formed or dissociated, gas hydrate can significantly change in situ sediment acoustic, mechanical, and hydraulic properties. The U.S. Geological Survey, in cooperation with the U.S. Dept. of Energy, BP Expl.-Alaska, Nat. GH Prog. of India, Canadian Geological Survey, Int. Ocean Drilling Program, Japan Oil Gas and Metals Nat. Corp., Japan Pet. Expl. Co., Int. Marine Past Global Changes Study (IMAGES) program, and Paleoceanography of the Atlantic and Geochemistry (PAGE) program, determined physical properties from marine and arctic sediments and their relation to the presence of GH. At two arctic sites, the Mount Elbert well on the Alaskan North Slope and the Mallik wells on the Mackenzie Delta, NWT, >10-m thick gas-hydrate-bearing (GHB) sandy deposits are capped by finer-grained sediments that may reduce gas migration. In the Mount Elbert well, average median grain sizes (MGS) for the two thickest GHB deposits are 65 and 60 µm. Finer-grained (average MGS of 9 and 28 µm) sediments have plug permeabilities that are 300 and 14 times smaller than underlying GHB sediment. Average MGS of GHB sediment from the Mallik 2L well is ~ 111 µm, compared to overlying sediment with an average MGS of ~ 32 µm. Gas hydrate morphology in the Gulf of Mexico (GOM) and offshore India is substantially more complex than in the arctic, and is related to pervasive, although not exclusive, finer-grained deposits. Massive, several-cm thick, GH layers were recovered in piston cores in the northern GOM, in sediment with little visible lithologic variability (average MGS ~ 0.8 µm). In wells off the east coast of India, GH was present in sand-rich, fractured clay, and reservoirs

  4. Squeezing out hydrated protons: low-frictional-energy triboelectric insulator charging on a microscopic scale

    Directory of Open Access Journals (Sweden)

    Nikolaus Knorr

    2011-06-01

    Full Text Available Though triboelectric charging of insulators is common, neither its mechanism nor the nature of the charge is well known. Most research has focused on the integral amount of charge transferred between two materials upon contact, establishing, e.g., a triboelectric series. Here, the charge distribution of tracks on insulating polymer films rubbed by polymer-covered pointed swabs is investigated in high resolution by Kelvin probe force microscopy. Pronounced bipolar charging was observed for all nine rubbing combinations of three different polymers, with absolute surface potentials of up to several volts distributed in streaks along the rubbing direction and varying in polarity on μm-length scales perpendicular to the rubbing direction. Charge densities increased considerably for rubbing in higher relative humidity, for higher rubbing loads, and for more hydrophilic polymers. The ends of rubbed tracks had positively charged rims. Surface potential decay with time was strongly accelerated in increased humidity, particularly for polymers with high water permeability. Based on these observations, a mechanism is proposed of triboelectrification by extrusions of prevalently hydrated protons, stemming from adsorbed and dissociated water, along pressure gradients on the surface by the mechanical action of the swab. The validity of this mechanism is supported by explanations given recently in the literature for positive streaming currents of water at polymer surfaces and by reports of negative charging of insulators tapped by accelerated water droplets and of potential built up between the front and the back of a rubbing piece, observations already made in the 19th century. For more brittle polymers, strongly negatively charged microscopic abrasive particles were frequently observed on the rubbed tracks. The negative charge of those particles is presumably due in part to triboemission of electrons by polymer chain scission, forming radicals and negatively

  5. Integrating Natural Gas Hydrates in the Global Carbon Cycle

    Energy Technology Data Exchange (ETDEWEB)

    David Archer; Bruce Buffett

    2011-12-31

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

  6. Role of interlayer hydration in lincomycin sorption by smectite clays.

    Science.gov (United States)

    Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

    2009-08-15

    Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

  7. [Prospects for Application of Gases and Gas Hydrates to Cryopreservation].

    Science.gov (United States)

    Shishova, N V; Fesenko, E E

    2015-01-01

    In the present review, we tried to evaluate the known properties of gas hydrates and gases participating in the formation of gas hydrates from the point of view of the mechanisms of cryoinjury and cryoprotection, to consider the papers on freezing biological materials in the presence of inert gases, and to analyze the perspectives for the development of this direction. For the purpose, we searched for the information on the physical properties of gases and gas hydrates, compared processes occured during the formation of gas hydrates and water ice, analyzed the influence of the formation and growth of gas hydrates on the structure of biological objects. We prepared a short review on the biological effects of xenon, krypton, argon, carbon dioxide, hydrogen sulfide, and carbon monoxide especially on hypothermal conditions and probable application of these properties in cryopreservation technologies. The description of the existing experiments on cryopreservation of biological objects with the use of gases was analyzed. On the basis of the information we found, the most perspective directions of work in the field of cryopreservation of biological objects with the use of gases were outlined. An attempt was made to forecast the potential problems in this field.

  8. WatAA: Atlas of Protein Hydration. Exploring synergies between data mining and ab initio calculations.

    Science.gov (United States)

    Černý, Jiří; Schneider, Bohdan; Biedermannová, Lada

    2017-07-14

    Water molecules represent an integral part of proteins and a key determinant of protein structure, dynamics and function. WatAA is a newly developed, web-based atlas of amino-acid hydration in proteins. The atlas provides information about the ordered first hydration shell of the most populated amino-acid conformers in proteins. The data presented in the atlas are drawn from two sources: experimental data and ab initio quantum-mechanics calculations. The experimental part is based on a data-mining study of a large set of high-resolution protein crystal structures. The crystal-derived data include 3D maps of water distribution around amino-acids and probability of occurrence of each of the identified hydration sites. The quantum mechanics calculations validate and extend this primary description by optimizing the water position for each hydration site, by providing hydrogen atom positions and by quantifying the interaction energy that stabilizes the water molecule at the particular hydration site position. The calculations show that the majority of experimentally derived hydration sites are positioned near local energy minima for water, and the calculated interaction energies help to assess the preference of water for the individual hydration sites. We propose that the atlas can be used to validate water placement in electron density maps in crystallographic refinement, to locate water molecules mediating protein-ligand interactions in drug design, and to prepare and evaluate molecular dynamics simulations. WatAA: Atlas of Protein Hydration is freely available without login at .

  9. The EPR paradox, the hydrated (solvated) electron, and the reactions of the hydrated electron (Preprint no. RC-02)

    International Nuclear Information System (INIS)

    Gopinathan, C.

    1991-01-01

    Einstein, Podolsky and Rosen pointed out in 1935 a serious flaw in the reasoning behind quantum mechanical modelling. It is shown in this work that this flaw applies to the interpretation of the hydrated electron and its reactions as well. (author). 3 refs

  10. Down the Rabbit Hole: toward appropriate discussion of methane release from gas hydrate systems during the Paleocene-Eocene thermal maximum and other past hyperthermal events

    Directory of Open Access Journals (Sweden)

    G. R. Dickens

    2011-08-01

    Full Text Available Enormous amounts of 13C-depleted carbon rapidly entered the exogenic carbon cycle during the onset of the Paleocene-Eocene thermal maximum (PETM, as attested to by a prominent negative carbon isotope (δ13C excursion and deep-sea carbonate dissolution. A widely cited explanation for this carbon input has been thermal dissociation of gas hydrate on continental slopes, followed by release of CH4 from the seafloor and its subsequent oxidation to CO2 in the ocean or atmosphere. Increasingly, papers have argued against this mechanism, but without fully considering existing ideas and available data. Moreover, other explanations have been presented as plausible alternatives, even though they conflict with geological observations, they raise major conceptual problems, or both. Methane release from gas hydrates remains a congruous explanation for the δ13C excursion across the PETM, although it requires an unconventional framework for global carbon and sulfur cycling, and it lacks proof. These issues are addressed here in the hope that they will prompt appropriate discussions regarding the extraordinary carbon injection at the start of the PETM and during other events in Earth's history.

  11. 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.

  12. 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

  13. 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.

  14. Growth of a Hydrate Mound in the Sea of Japan over 300 ka as Revealed by U-Th Ages of MDAC and by H2S Concentrations of Massive Hydrates

    Science.gov (United States)

    Matsumoto, R.; Snyder, G. T.; Hiruta, A.; Kakizaki, Y.; Huang, C. Y.; Shen, C. C.

    2017-12-01

    level fall, resulting in the dissociation of gas hydrates right above the BGHS and an enhancement of methane flux through the gas chimney. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI. Reference [1] Matsumoto et al. (2017), Fire in the Ice, 17, 1-6.

  15. [Dissociative identity disorder or schizophrenia?].

    Science.gov (United States)

    Tschöke, S; Steinert, T

    2010-01-01

    We present a case of dissociative identity disorder in which Schneiderian first rank symptoms were present besides of various states of consciousness. Thus the diagnosis of schizophrenia had to be considered. Formally, the symptoms met ICD-10 criteria for schizophrenia. However, taking into account the lack of formal thought disorder and of negative symptoms as well as a typical history of severe and prolonged traumatisation, we did not diagnose a co-morbid schizophrenic disorder. There is good evidence for the existence of psychotic symptoms among patients with dissociative disorders. However, in clinical practice this differential diagnosis is rarely considered.

  16. Diffraction dissociation at the LHC

    Energy Technology Data Exchange (ETDEWEB)

    Jenkovszky, Laszlo [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680, Ukraine and Wigner Research Centre for Physics, Hungarian Academy of Sciences 1525 Budapest, POB 49 (Hungary); Orava, Risto [Institute of Physics, Division of Elementary Particle Physics, P.O. Box 64 (Gustaf Haellstroeminkatu 2a), FI-00014 University of Helsinki, Finland and CERN, CH-1211 Geneva 23 (Switzerland); Salii, Andrii [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680 (Ukraine)

    2013-04-15

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  17. Diffraction dissociation at the LHC

    International Nuclear Information System (INIS)

    Jenkovszky, László; Orava, Risto; Salii, Andrii

    2013-01-01

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  18. Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment

    OpenAIRE

    Belli, Hasan

    2014-01-01

    Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative expe...

  19. Modelling of oceanic gas hydrate instability and methane release in response to climate change

    International Nuclear Information System (INIS)

    Reagan, M.T.; Moridis, G.J.

    2008-01-01

    Methane releases from oceanic hydrates are thought to have played a significant role in climatic changes that have occurred in the past. In this study, gas hydrate accumulations subjected to temperature changes were modelled in order to assess their potential for future methane releases into the ocean. Recent ocean and atmospheric chemistry studies were used to model 2 climate scenarios. Two types of hydrate accumulations were used to represent dispersed, low-saturation deposits. The 1-D multiphase thermodynamic-hydrological model considered the properties of benthic sediments; ocean depth; sea floor temperature; the saturation and distribution of the hydrates; and the effect of benthic biogeochemical activity. Results of the simulations showed that shallow deposits undergo rapid dissociation and are capable of producing methane fluxes of 2 to 13 mol m 3 per year over a period of decades. The fluxes exceed the ability of the anaerobic sea floor environment to sequester or consume the methane. A large proportion of the methane released in the scenarios emerged in the gas phase. Arctic hydrates may pose a threat to regional and global ecological systems. It was concluded that results of the study will be coupled with global climate models in order to assess the impact of the methane releases in relation to global climatic change. 39 refs., 5 figs

  20. Thermo physical and flow properties of CO{sub 2} hydrate slurry - Scientific paper

    Energy Technology Data Exchange (ETDEWEB)

    Sari, O.; Hu, J.; Eicher, S.; Egolf, P. W. [Institute of Thermal Engineering, University of Applied Sciences of Western Switzerland, Yverdon-les-Bains (Switzerland); Homsy, P. [Nestec, Vevey (Switzerland)

    2008-07-01

    The apparent viscosity and flow regime of CO{sub 2} hydrate slurry were investigated with a XL7-100 on-line resonant viscometer. Possible reasons for the viscosity changes before and after the nucleation of hydrates are discussed. In addition, super saturation of the CO{sub 2} solution under certain pressure and temperature conditions as well as its density and apparent viscosity were examined. The hydrate's solid fraction and the dissociation enthalpy were evaluated by an on-line Micro DSC system. Real-time coupled multi-electrode array sensor (CMAS) probes were applied to measure the maximal localized corrosion rate of three different materials subjected to CO{sub 2} hydrate slurry and saturated CO{sub 2} solution in the temperature range of 1 to 18 {sup o}C and pressure range of 25 to 30 bar. The density of CO{sub 2} hydrate slurry was also experimentally investigated and the relation between the density and the solid fraction has been established. (author)

  1. Sensitivity of the global submarine hydrate inventory to scenarios of future climate change

    Science.gov (United States)

    Hunter, S. J.; Goldobin, D. S.; Haywood, A. M.; Ridgwell, A.; Rees, J. G.

    2013-04-01

    The global submarine inventory of methane hydrate is thought to be considerable. The stability of marine hydrates is sensitive to changes in temperature and pressure and once destabilised, hydrates release methane into sediments and ocean and potentially into the atmosphere, creating a positive feedback with climate change. Here we present results from a multi-model study investigating how the methane hydrate inventory dynamically responds to different scenarios of future climate and sea level change. The results indicate that a warming-induced reduction is dominant even when assuming rather extreme rates of sea level rise (up to 20 mm yr-1) under moderate warming scenarios (RCP 4.5). Over the next century modelled hydrate dissociation is focussed in the top ˜100m of Arctic and Subarctic sediments beneath business-as-usual scenario (RCP 8.5), upper estimates of resulting global sea-floor methane fluxes could exceed estimates of natural global fluxes by 2100 (>30-50TgCH4yr-1), although subsequent oxidation in the water column could reduce peak atmospheric release rates to 0.75-1.4 Tg CH4 yr-1.

  2. [Dissociative disorders: from Janet to DSM-IV].

    Science.gov (United States)

    Nakatani, Y

    2000-01-01

    I reviewed the literature on dissociation and dissociative disorders from Pierre Janet to DSM-IV, and examined the current trends in research. Janet's theory on hysteria is multifaceted, and is based on three psychological models. Based on a hierarchical model, Janet related hysteric symptoms to the activities within the lower strata of mental hierarchy (automatisms psychologiques), which were demonstrably shown in somnambulism. A second model was based on the concept of a psychological system, which was hypothetically composed of ideas, images, feelings, sensations, and movements. According to this model, dissociation of psychological functions was fundamental to the mechanism of hysteria: loss of integration was thought to engender fixed ideas (ideas fixes) and to lead to the development of a system totally isolated from the whole personality system. Janet also attempted to explain various mental disorders using an economic model. He referred to a loss of equilibration between psychological force and psychological tension. Thus, an unexpected emotional experience was conceived to cause a consumption of reserved psychological force, which was in turn followed by exhaustion associated with hysteric symptoms. Whereas most current researchers regard Janet as the first to study psychological trauma as a principal cause of dissociation, I feel it is important to note that he also emphasized the role of stigmata, i.e., permanent traits of hysteric patients, which were represented as a suggestibility and a tendency toward a narrowing of the consciousness field. Discussion about dissociation and its relation to trauma all but disappeared after Janet. However, during the Second World War and post-war period, some psychiatrists began to pay attention to two emerging phenomena: a high incidence of dissociative symptoms such as fugue and amnesia among combatants, and traumatic neurosis frequently observed among ex-inmates of concentration camps. In the 1970s, interest in

  3. Dissociative symptoms and neuroendocrine dysregulation in depression.

    Science.gov (United States)

    Bob, Petr; Fedor-Freybergh, Peter; Jasova, Denisa; Bizik, Gustav; Susta, Marek; Pavlat, Josef; Zima, Tomas; Benakova, Hana; Raboch, Jiri

    2008-10-01

    Dissociative symptoms are traditionally attributed to psychological stressors that produce dissociated memories related to stressful life events. Dissociative disorders and dissociative symptoms including psychogenic amnesia, fugue, dissociative identity-disorder, depersonalization, derealization and other symptoms or syndromes have been reported as an epidemic psychiatric condition that may be coexistent with various psychiatric diagnoses such as depression, schizophrenia, borderline personality disorder or anxiety disorders. According to recent findings also the somatic components of dissociation may occur and influence brain, autonomic and neuroendocrine functions. At this time there are only few studies examining neuroendocrine response related to dissociative symptoms that suggest significant dysregulation of the hypothalamus-pituitary-adrenal (HPA) axis. The aim of the present study is to perform examination of HPA axis functioning indexed by basal cortisol and prolactin and test their relationship to psychic and somatoform dissociative symptoms. Basal cortisol and prolactin and psychic and somatoform dissociative symptoms were assessed in 40 consecutive inpatients with diagnosis of unipolar depression mean age 43.37 (SD=12.21). The results show that prolactin and cortisol as indices of HPA axis functioning manifest significant relationship to dissociative symptoms. Main results represent highly significant correlations obtained by simple regression between psychic dissociative symptoms (DES) and serum prolactin (R=0.55, p=0.00027), and between somatoform dissociation (SDQ-20) and serum cortisol (R=-0.38, p=0.015). These results indicate relationship between HPA-axis reactivity and dissociative symptoms in unipolar depressive patients that could reflect passive coping behavior and disengagement.

  4. The Dependence of Water Permeability in Quartz Sand on Gas Hydrate Saturation in the Pore Space

    Science.gov (United States)

    Kossel, E.; Deusner, C.; Bigalke, N.; Haeckel, M.

    2018-02-01

    Transport of fluids in gas hydrate bearing sediments is largely defined by the reduction of the permeability due to gas hydrate crystals in the pore space. Although the exact knowledge of the permeability behavior as a function of gas hydrate saturation is of crucial importance, state-of-the-art simulation codes for gas production scenarios use theoretically derived permeability equations that are hardly backed by experimental data. The reason for the insufficient validation of the model equations is the difficulty to create gas hydrate bearing sediments that have undergone formation mechanisms equivalent to the natural process and that have well-defined gas hydrate saturations. We formed methane hydrates in quartz sand from a methane-saturated aqueous solution and used magnetic resonance imaging to obtain time-resolved, three-dimensional maps of the gas hydrate saturation distribution. These maps were fed into 3-D finite element method simulations of the water flow. In our simulations, we tested the five most well-known permeability equations. All of the suitable permeability equations include the term (1-SH)n, where SH is the gas hydrate saturation and n is a parameter that needs to be constrained. The most basic equation describing the permeability behavior of water flow through gas hydrate bearing sand is k = k0 (1-SH)n. In our experiments, n was determined to be 11.4 (±0.3). Results from this study can be directly applied to bulk flow analysis under the assumption of homogeneous gas hydrate saturation and can be further used to derive effective permeability models for heterogeneous gas hydrate distributions at different scales.

  5. 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 hydro