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Sample records for hydrated fluid phase

  1. Coupled mass transfer through a fluid phase and volume preservation during the hydration of granulite: An example from the Bergen Arcs, Norway

    NASA Astrophysics Data System (ADS)

    Centrella, Stephen; Austrheim, Håkon; Putnis, Andrew

    2015-11-01

    The Precambrian granulite facies rocks of Lindås Nappe, Bergen Arcs, Caledonides of W. Norway are partially hydrated at amphibolite and eclogite facies conditions. The Lindås Nappe outcrops over an area of ca. 1000 km2 where relict granulite facies lenses make up only ca. 10%. At Hillandsvatnet, garnetite displays sharp hydration fronts across which the granulite facies assemblage composed of garnet (55%) and clinopyroxene (45%) is replaced by an amphibolite facies mineralogy defined by chlorite, epidote and amphibole. The major element bulk composition does not change significantly across the hydration front, apart from the volatile components (loss on ignition, LOI) that increases from 0.17 wt.% in the granulite to 2.43 wt.% in the amphibolite. However the replacements of garnet and of clinopyroxene are pseudomorphic so that the grain shapes of the garnet and clinopyroxene are preserved even when they are completely replaced. The textural evolution during the replacement of garnet by pargasite, epidote and chlorite and of pyroxene by hornblende and quartz in our rock sample conforms to that expected by a coupled dissolution-precipitation mechanism. SEM and electron microprobe analysis coupled with the software XMapTools V 1.06.1 were used to quantify the local mass transfer required during the replacement processes. The element losses and gains in replacing the garnet are approximately balanced by the opposite gains and losses associated with the replacement of clinopyroxene. The coupling between dissolution and precipitation on both the grain and whole rock spatial scale preserves the volume of the rock throughout the hydration process. However, the hydration involves reduction of rock density and mass balance calculations, together with volume preservation (isovolumetric reaction) require a significant loss of the mass of the rock to the fluid phase. This suggests a mechanism for coupling between the local stress generated by hydration reactions and mass

  2. Hydration forces at solid and fluid biointerfaces.

    PubMed

    Shrestha, Buddha Ratna; Banquy, Xavier

    2016-03-01

    The authors review the different molecular mechanisms giving rise to the repulsive hydration force between biologically relevant surfaces such as lipid bilayers and bioceramics. As the authors will show, the hydration force manifests itself in very different and subtle ways depending on the substrates. Soft, mobile surfaces such as lipid bilayers tend to exhibit monotonic, decaying hydration force, originated from the entropic constriction of the lipid head groups. Solid surfaces, on the other hand, tend to exhibit a periodic oscillatory hydration force, originated from the surface induced polarization of water molecules. In this review, the authors will describe both subtle faces of this important interaction by first describing the early experiments performed on solid surfaces and their interpretation by recent simulation studies. Then, the authors will describe the hydration force between fluid interfaces such as bilayers and explain how experimentally researchers have unraveled the dominant role of the lipid head groups' conformation. PMID:26795057

  3. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    2003-01-01

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

  4. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    1999-01-01

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

  5. New insight into probe-location dependent polarity and hydration at lipid/water interfaces: comparison between gel- and fluid-phases of lipid bilayers.

    PubMed

    Singh, Moirangthem Kiran; Shweta, Him; Khan, Mohammad Firoz; Sen, Sobhan

    2016-09-21

    Environment polarity and hydration at lipid/water interfaces play important roles in membrane biology, which are investigated here using a new homologous series of 4-aminophthalimide-based fluorescent molecules (4AP-Cn; n = 2-10, 12) having different lipophilicities (octanol/water partition coefficient - log P). We show that 4AP-Cn molecules probe a peculiar stepwise polarity (E) profile at the lipid/water interface of the gel-phase (Lβ') DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) bilayer at room temperature, which was not anticipated in earlier studies. However, the same molecules probe only a subtle but continuous polarity change at the interface of water and the fluid-phase (Lα) DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine) bilayer at room temperature. Fluorescence quenching experiments indicate that solutes with different log P values adsorb at different depths across DPPC/water and DOPC/water interfaces, which correlate with the polarity profiles observed at the interfaces. Molecular dynamics simulations performed on eight probe-lipid systems (four in each of the DPPC and DOPC bilayers - a total run of 2.6 μs) support experimental results, providing further information on the relative position and angle distributions as well as hydration of probes at the interfaces. Simulation results indicate that besides positions, probe orientations also play an important role in defining the local dielectric environment by controlling the probes' exposure to water at the interfaces especially of the gel-phase DPPC bilayer. The results suggest that 4AP-Cn probes are well suited for studying solvation properties at lipid/water interfaces of gel- and fluid-phases simultaneously. PMID:27147404

  6. New insight into probe-location dependent polarity and hydration at lipid/water interfaces: comparison between gel- and fluid-phases of lipid bilayers.

    PubMed

    Singh, Moirangthem Kiran; Shweta, Him; Khan, Mohammad Firoz; Sen, Sobhan

    2016-09-21

    Environment polarity and hydration at lipid/water interfaces play important roles in membrane biology, which are investigated here using a new homologous series of 4-aminophthalimide-based fluorescent molecules (4AP-Cn; n = 2-10, 12) having different lipophilicities (octanol/water partition coefficient - log P). We show that 4AP-Cn molecules probe a peculiar stepwise polarity (E) profile at the lipid/water interface of the gel-phase (Lβ') DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) bilayer at room temperature, which was not anticipated in earlier studies. However, the same molecules probe only a subtle but continuous polarity change at the interface of water and the fluid-phase (Lα) DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine) bilayer at room temperature. Fluorescence quenching experiments indicate that solutes with different log P values adsorb at different depths across DPPC/water and DOPC/water interfaces, which correlate with the polarity profiles observed at the interfaces. Molecular dynamics simulations performed on eight probe-lipid systems (four in each of the DPPC and DOPC bilayers - a total run of 2.6 μs) support experimental results, providing further information on the relative position and angle distributions as well as hydration of probes at the interfaces. Simulation results indicate that besides positions, probe orientations also play an important role in defining the local dielectric environment by controlling the probes' exposure to water at the interfaces especially of the gel-phase DPPC bilayer. The results suggest that 4AP-Cn probes are well suited for studying solvation properties at lipid/water interfaces of gel- and fluid-phases simultaneously.

  7. Impact of Compound Hydrate Dynamics on Phase Boundary Changes

    NASA Astrophysics Data System (ADS)

    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

  8. Fluids and hydration in prolonged endurance performance.

    PubMed

    Von Duvillard, Serge P; Braun, William A; Markofski, Melissa; Beneke, Ralph; Leithäuser, Renate

    2004-01-01

    Numerous studies have confirmed that performance can be impaired when athletes are dehydrated. Endurance athletes should drink beverages containing carbohydrate and electrolyte during and after training or competition. Carbohydrates (sugars) favor consumption and Na(+) favors retention of water. Drinking during competition is desirable compared with fluid ingestion after or before training or competition only. Athletes seldom replace fluids fully due to sweat loss. Proper hydration during training or competition will enhance performance, avoid ensuing thermal stress, maintain plasma volume, delay fatigue, and prevent injuries associated with dehydration and sweat loss. In contrast, hyperhydration or overdrinking before, during, and after endurance events may cause Na(+) depletion and may lead to hyponatremia. It is imperative that endurance athletes replace sweat loss via fluid intake containing about 4% to 8% of carbohydrate solution and electrolytes during training or competition. It is recommended that athletes drink about 500 mL of fluid solution 1 to 2 h before an event and continue to consume cool or cold drinks in regular intervals to replace fluid loss due to sweat. For intense prolonged exercise lasting longer than 1 h, athletes should consume between 30 and 60 g/h and drink between 600 and 1200 mL/h of a solution containing carbohydrate and Na(+) (0.5 to 0.7 g/L of fluid). Maintaining proper hydration before, during, and after training and competition will help reduce fluid loss, maintain performance, lower submaximal exercise heart rate, maintain plasma volume, and reduce heat stress, heat exhaustion, and possibly heat stroke.

  9. Indications of shallow fluid recirculation on Hydrate Ridge

    NASA Astrophysics Data System (ADS)

    Gubsch, S.; Gust, G.; Linke, P.; Sommer, S.; Viergutz, T.; Wallmann, K.

    2003-04-01

    Hydrate Ridge is a region of near-surface gas hydrates with considerable methane-rich fluid release. The release rate of methane is estimated up to 10 mmol/m^2/d. Tidal flows and topography strongly mix the water column, yet depending on the inhomogeneous distribution of gas hydrates located below the surface a distinct horizontal zonation of biological activity exists. Bacterial mats of Beggiatoa sp and clam fields of the genus Calyptogena sp are biomarkers for near surface gas hydrates. These regions are assumed to provide an intense fluid-porewater exchange. Guided by the discharge data from Linke and Tryon from this site, a newly developed FLUFO chamber was used on cruise Sonne 165-1 to quantify 2-phase fluid exchange across the sea floor and to determine both driving force and the high-frequency end of its temporal and spatial pattern. Monitoring of bottom current and hydrostatic pressure provided the environmental conditions during deployments, revealing strong tidal flows up to 50 cm/s. The device performed well, and at 5 locations on Hydrate Ridge inflow and outflow events were recorded during deployments lasting up to 72 hours. Of these locations, three were grouped very close on the Southern Summit with an average distance of 50 m amongst each other. The fourth location (control) had a distance of 500 m to this group. The remaining deployment site was selected in the Eastern Basin at a distance of 67 km. The unexpected result was a fluid exchange across the sea floor which involved per tidal phase a water layer of < 28mm height. We observed mostly inflow at 2.5 and 5 ml/min at two sites, mostly outflow at 2 ml/min at one site and nearly-balanced inflow and outflow at one site per tidal cycle. Combining the venting/inflow directions and speeds with the tide signal confirms the relation between fluid flux and tide reported by Linke. Upon closer examination, tidal flow rather than tidal phase controlled the fluid exchange, which is very low and very shallow

  10. Thermodynamic properties of hydrate phases immersed in ice phase

    NASA Astrophysics Data System (ADS)

    Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

    2006-01-01

    Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

  11. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member and/or six member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone.

  12. Hydration states of AFm cement phases

    SciTech Connect

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

    2015-07-15

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

  13. Hydration biomarkers and dietary fluid consumption of women.

    PubMed

    Armstrong, Lawrence E; Johnson, Evan C; Munoz, Colleen X; Swokla, Brittany; Le Bellego, Laurent; Jimenez, Liliana; Casa, Douglas J; Maresh, Carl M

    2012-07-01

    Normative values and confidence intervals for the hydration indices of women do not exist. Also, few publications have precisely described the fluid types and volumes that women consume. This investigation computed seven numerical reference categories for widely used hydration biomarkers (eg, serum and urine osmolality) and the dietary fluid preferences of self-reported healthy, active women. Participants (n=32; age 20±1 years; body mass 59.6±8.5 kg; body mass index [calculated as kg/m(2)] 21.1±2.4) were counseled in the methods to record daily food and fluid intake on 2 consecutive days. To reduce day-to-day body water fluctuations, participants were tested only during the placebo phase of the oral contraceptive pill pack. Euhydration was represented by the following ranges: serum osmolality=293 to 294 mOsm/kg; mean 24-hour total fluid intake=2,109 to 2,506 mL/24 hours; mean 24-hour total beverage intake=1,300 to 1,831 mL/24 hours; urine volume=951 to 1,239 mL/24 hours; urine specific gravity=1.016 to 1.020; urine osmolality=549 to 705 mOsm/kg; and urine color=5. However, only 3% of women experienced a urine specific gravity <1.005, and only 6% exhibited a urine color of 1 or 2. Water (representing 45.3% and 47.9% of 24-hour total fluid intake), tea, milk, coffee, and fruit juice were consumed in largest volumes. In conclusion, these data provide objective normative values for hyperhydration, euhydration, and dehydration that can be used by registered dietitians and clinicians to counsel women about their hydration status.

  14. THE EFFECT OF GAS HYDRATES DISSOCIATION AND DRILLING FLUIDS INVASION UPON BOREHOLE STABILITY IN OCEANIC GAS HYDRATES-BEARING SEDIMENT

    NASA Astrophysics Data System (ADS)

    Ning, F.; Wu, N.; Jiang, G.; Zhang, L.

    2009-12-01

    Under the condition of over-pressure drilling, the solid-phase and liquid-phase in drilling fluids immediately penetrate into the oceanic gas hydrates-bearing sediment, which causes the water content surrounding the borehole to increase largely. At the same time, the hydrates surrounding borehole maybe quickly decompose into water and gas because of the rapid change of temperature and pressure. The drilling practices prove that this two factors may change the rock characteristics of wellbore, such as rock strength, pore pressure, resistivity, etc., and then affect the logging response and evaluation, wellbore stability and well safty. The invasion of filtrate can lower the angle of friction and weaken the cohesion of hydrates-bearing sediment,which is same to the effect of invading into conventional oil and gas formation on borehole mechnical properties. The difference is that temperature isn’t considered in the invasion process of conventional formations while in hydrates-bearing sediments, it is a factor that can not be ignored. Temperature changes can result in hydrates dissociating, which has a great effect on mechanical properties of borehole. With the application of numerical simulation method, we studied the changes of pore pressure and variation of water content in the gas hydrates-bearing sediment caused by drilling fluid invasion under pressure differential and gas hydrate dissociation under temperature differential and analyzed their influence on borehole stability.The result of simulation indicated that the temperature near borehole increased quickly and changed hardly any after 6 min later. About 1m away from the borehole, the temperature of formation wasn’t affected by the temperature change of borehole. At the place near borehole, as gas hydrate dissociated dramatically and drilling fluid invaded quickly, the pore pressure increased promptly. The degree of increase depends on the permeability and speed of temperature rise of formation around

  15. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  16. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.

    1995-07-11

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  17. Hydrated metal ions in the gas phase.

    PubMed

    Beyer, Martin K

    2007-01-01

    Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.

  18. Hydration and vascular fluid shifts during exercise in the heat

    SciTech Connect

    Sawka, M.N.; Francesconi, R.P.; Pimental, N.A.; Pandolf, K.B.

    1984-01-01

    The present study has the primary objective to determine the effects of hydration level on vascular fluid shifts during exercise in the heat. The effect of gender on these fluid shifts was also investigated. The subjects employed in the tests included six male and six female volunteers. It was found that hemoconcentration occurs when subjects are hypohydrated and are performing light intensity exercise in the heat. A decrease in total plasma protein was observed under these test conditions. Gender does not alter vascular fluid shifts during exercise in the heat when subjects are matched with respect to fitness level. It is concluded that hydration level alters vascular fluid shifts during exercise in a hot environment.

  19. Phase behavior and hydration of silk fibroin.

    PubMed

    Sohn, Sungkyun; Strey, Helmut H; Gido, Samuel P

    2004-01-01

    The osmotic stress method was applied to study the thermodynamics of supramolecular self-assembly phenomena in crystallizable segments of Bombyx mori silkworm silk fibroin. By controlling compositions and phases of silk fibroin solution, the method provided a means for the direct investigation of microscopic and thermodynamic details of these intermolecular interactions in aqueous media. It is apparent that as osmotic pressure increases, silk fibroin molecules are crowded together to form silk I structure and then with further increase in osmotic pressure become an antiparallel beta-sheet structure, silk II. A partial ternary phase diagram of water-silk fibroin-LiBr was constructed based on the results. The results provide quantitative evidence that the silk I structure must contain water of hydration. The enhanced control over structure and phase behavior using osmotic stress, as embodied in the phase diagram, could potentially be utilized to design a new route for water-based wet spinning of regenerated silk fibroin.

  20. Gas hydrate, fluid flow and free gas: Formation of the bottom-simulating reflector

    NASA Astrophysics Data System (ADS)

    Haacke, R. Ross; Westbrook, Graham K.; Hyndman, Roy D.

    2007-09-01

    Gas hydrate in continental margins is commonly indicated by a prominent bottom-simulating seismic reflector (BSR) that occurs a few hundred metres below the seabed. The BSR marks the boundary between sediments containing gas hydrate above and free gas below. Most of the reflection amplitude is caused by the underlying free gas. Gas hydrate can occur without a BSR, however, and the controls on its formation are not well understood. Here we describe two complementary mechanisms for free gas accumulation beneath the gas hydrate stability zone (GHSZ). The first is the well-recognised hydrate recycling mechanism that generates gas from dissociating hydrate when the base of the GHSZ moves upward relative to hydrate-bearing sediment. The second is a recently identified mechanism in which the relationship between the advection and diffusion of dissolved gas with the local solubility curve allows the liquid phase to become saturated in a thick layer beneath the GHSZ when hydrate is present near its base. This mechanism for gas production (called the solubility-curvature mechanism) is possible in systems where the influence of diffusion becomes important relative to the influence of advection and where the gas-water solubility decreases to a minimum several hundred metres below the GHSZ. We investigate a number of areas in which gas hydrate occurs to determine where gas formation is dominated by the solubility-curvature mechanism and where it is dominated by hydrate recycling. We show that the former is dominant in areas with low rates of upward fluid flow (such as old, rifted continental margins), low rates of seafloor uplift, and high geothermal gradient and/or pressure. Conversely, free-gas formation is dominated by hydrate recycling where there are rapid rates of upward fluid flow and seabed uplift (such as in subduction zone accretionary wedges). Using these two mechanisms to investigate the formation of free gas beneath gas hydrate in continental margins, we are able

  1. Soft hydrated sliding interfaces as complex fluids.

    PubMed

    Kim, Jiho; Dunn, Alison C

    2016-08-21

    Hydrogel surfaces are biomimics for sensing and mobility systems in the body such as the eyes and large joints due to their important characteristics of flexibility, permeability, and integrated aqueous component. Recent studies have shown polymer concentration gradients resulting in a less dense region in the top micrometers of the surface. Under shear, this gradient is hypothesized to drive lubrication behavior due to its rheological similarity to a semi-dilute polymer solution. In this work we map 3 distinct lubricating regimes between a polyacrylamide surface and an aluminum annulus using stepped-velocity tribo-rheometry over 5 decades of sliding speed in increasing and decreasing steps. These regimes, characterized by weakly or strongly time-dependent response and thixotropy-like hysteresis, provide the skeleton of a lubrication curve for hydrogel-against-hard material interfaces and support hypotheses of polymer mechanics-driven lubrication. Tribo-rheometry is particularly suited to uncover the lubrication mechanisms of complex interfaces such as are formed with hydrated hydrogel surfaces and biological surfaces. PMID:27425448

  2. Hydration and endocrine responses to intravenous fluid and oral glycerol.

    PubMed

    van Rosendal, S P; Strobel, N A; Osborne, M A; Fassett, R G; Coombes, J S

    2015-06-01

    Athletes use intravenous (IV) saline in an attempt to maximize rehydration. The diuresis from IV rehydration may be circumvented through the concomitant use of oral glycerol. We examined the effects of rehydrating with differing regimes of oral and IV fluid, with or without oral glycerol, on hydration, urine, and endocrine indices. Nine endurance-trained men were dehydrated by 4% bodyweight, then rehydrated with 150% of the fluid lost via four protocols: (a) oral = oral fluid only; (b) oral glycerol = oral fluid with added glycerol (1.5 g/kg); (c) IV = 50% IV fluid, 50% oral fluid; and (d) IV with oral glycerol = 50% IV fluid, 50% oral fluid with added glycerol (1.5 g/kg), using a randomized, crossover design. They then completed a cycling performance test. Plasma volume restoration was highest in IV with oral glycerol > IV > oral glycerol  > oral. Urine volume was reduced in both IV trials compared with oral. IV and IV with oral glycerol resulted in lower aldosterone levels during rehydration and performance, and lower cortisol levels during rehydration. IV with oral glycerol resulted in the greatest fluid retention. In summary, the IV conditions resulted in greater fluid retention compared with oral and lower levels of fluid regulatory and stress hormones compared with both oral conditions.

  3. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.; Christiansen, R.L.; Lederhos, J.P.; Long, J.P.; Panchalingam, V.; Du, Y.; Sum, A.K.W.

    1997-06-17

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hindrance and/or charge repulsion. Also, polymers having an amide on which a C{sub 1}-C{sub 4} group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

  4. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle Dendy; Christiansen, Richard Lee; Lederhos, Joseph P.; Long, Jin Ping; Panchalingam, Vaithilingam; Du, Yahe; Sum, Amadeu Kun Wan

    1997-01-01

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hinderance and/or charge repulsion. Also, polymers having an amide on which a C.sub.1 -C.sub.4 group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

  5. Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  6. Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

    USGS Publications Warehouse

    Waite, William F.; Spangenberg, E.K.

    2013-01-01

    Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

  7. Pore Scale Mechanistic Study of the Preferential Mode of Hydrate Formation in Sediments: Fluid Flow Aspects

    NASA Astrophysics Data System (ADS)

    Behseresht, J.; Prodanović, M.; Bryant, S. L.

    2007-12-01

    A spectrum of behavior is encountered in ocean sediments bearing methane hydrates, ranging from essentially static accumulations where hydrate and brine co-exist, to active cold seeps where hydrate and a methane gas phase co-exist in the hydrate stability zone (HSZ). In this and a companion paper (Jain and Juanes) we describe methods to test the following hypothesis: the coupling between drainage and fracturing, both induced by pore pressure, determines whether methane gas entering the HSZ is converted completely to hydrate. Here we describe a novel implementation of the level set method (LSM) to determine the capillarity-controlled displacement of brine by gas from sediment and from fractures within the sediment. Predictions of fluid configurations in infinite-acting model sediments indicate that the brine in drained sediment (after invasion by methane gas) is better connected than previously believed. This increases the availability of water and the rate of counter-diffusion of salinity ions, thus relaxing the limit on hydrate build-up within gas- invaded grain matrix. Simulated drainage of a fracture in sediment shows that points of contact between fracture faces are crucial. They allow residual water saturation to remain within an otherwise gas-filled fracture. Simulations of imbibition, which can occur for example after drainage into surrounding sediment reduces gas phase pressure in the fracture, indicate that the gas/water interfaces at contact points significantly shifts the threshold pressures for withdrawal of gas. During both drainage and imbibition, the contact points greatly increase water availability for hydrate formation within the fracture. We discuss coupling this capillarity-controlled displacement model with a discrete element model for grain-scale mechanics. The coupled model provides a basis for evaluating the macroscopic conditions (thickness of gas accumulation below the hydrate stability zone; average sediment grain size; principal earth

  8. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

    PubMed

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K

    2010-05-01

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.

  9. Numerical investigations of the fluid flows at deep oceanic and arctic permafrost-associated gas hydrate deposits

    NASA Astrophysics Data System (ADS)

    Frederick, Jennifer Mary

    , allows us a unique opportunity to study the response of methane hydrate deposits to warming. Gas hydrate stability in the Arctic and the permeability of the shelf sediments to gas migration is thought to be closely linked with relict submarine permafrost. Submarine permafrost extent depends on several environmental factors, such as the shelf lithology, sea level variations, mean annual air temperature, ocean bottom water temperature, geothermal heat flux, groundwater hydrology, and the salinity of the pore water. Effects of submarine groundwater discharge, which introduces fresh terrestrial groundwater off-shore, can freshen deep marine sediments and is an important control on the freezing point depression of ice and methane hydrate. While several thermal modeling studies suggest the permafrost layer should still be largely intact near-shore, many recent field studies have reported elevated methane levels in Arctic coastal waters. The permafrost layer is thought to create an impermeable barrier to fluid and gas flow, however, talik formation (unfrozen regions within otherwise continuous permafrost) below paleo-river channels can create permeable pathways for gas migration from depth. This is the first study of its kind to make predictions of the methane gas flux to the water column from the Arctic shelf sediments using a 2D multi-phase fluid flow model. Model results show that the dissociation of methane hydrate deposits through taliks can supersaturate the overlying water column at present-day relative to equilibrium with the atmosphere when taliks are large (> 1 km width) or hydrate saturation is high within hydrate layers (> 50% pore volume). Supersaturated waters likely drive a net flux of methane into the atmosphere, a potent greenhouse gas. Effects of anthropogenic global warming will certainly increase gas venting rates if ocean bottom water temperatures increase, but likely won't have immediately observable impacts due to the long response times.

  10. Hydration-Induced Phase Transitions in Surfactant and Lipid Films.

    PubMed

    Björklund, Sebastian; Kocherbitov, Vitaly

    2016-05-31

    For several surfactant and lipid systems, it is crucial to understand how hydration influences the physical and chemical properties. When humidity changes, it affects the degree of hydration by adding or removing water molecules. In many cases, this process induces transitions between liquid crystalline phases. This phenomenon is of general interest for numerous applications simply because of the fact that humidity variations are ubiquitous. Of particular interest are hydration-induced phase transitions in amphiphilic films, which in many cases appear as the frontier toward a vapor phase with changing humidity. Considering this, it is important to characterize the film thickness needed for the formation of 3D liquid crystalline phases and the lyotropic phase behavior of this kind of film. In this work, we study this issue by employing a recently developed method based on the humidity scanning quartz crystal microbalance with dissipation monitoring (HS QCM-D), which enables continuous scanning of the film hydration. We investigate five surfactants films (DDAO, DTAC, CTAC, SDS, and n-octylβ-d-glucoside) and one lipid film (monoolein) and show that HS QCM-D enables the fast characterization of hydration-induced phase transitions with small samples. Film thicknesses range from tens to hundreds of nanometers, and clear phase transitions are observed in all cases. It is shown that phase transitions in films occur at the same water activities as for corresponding bulk samples. This allows us to conclude that surfactant and lipid films, with a thickness of as low as 50 nm, are in fact assembled as 3D-structured liquid crystalline phases. Furthermore, liquid crystalline phases of surfactant films show liquidlike behavior, which decreases the accuracy of the absorbed water mass measurement. On the other hand, the monoolein lipid forms more rigid liquid crystalline films, allowing for an accurate determination of the water sorption isotherm, which is also true for the

  11. Venting of carbon dioxide-rich fluid and hydrate formation in mid-okinawa trough backarc basin.

    PubMed

    Sakai, H; Gamo, T; Kim, E S; Tsutsumi, M; Tanaka, T; Ishibashi, J; Wakita, H; Yamano, M; Oomori, T

    1990-06-01

    Carbon dioxide-rich fluid bubbles, containing approximately 86 percent CO(2), 3 percent H(2)S, and 11 percent residual gas (CH(4) + H(2)), were observed to emerge from the sea floor at 1335- to 1550-m depth in the JADE hydrothermal field, mid-Okinawa Trough. Upon contact with seawater at 3.8 degrees C, gas hydrate immediately formed on the surface of the bubbles and these hydrates coalesced to form pipes standing on the sediments. Chemical composition and carbon, sulfur, and helium isotopic ratios indicate that the CO(2)-rich fluid was derived from the same magmatic source as dissolved gases in 320 degrees C hydrothermal solution emitted from a nearby black smoker chimney. The CO(2)-rich fluid phase may be separated by subsurface boiling of hydrothermal solutions or by leaching of CO(2)-rich fluid inclusion during posteruption interaction between pore water and volcanogenic sediments.

  12. Artificial Nutrition (Food) and Hydration (Fluids) at the End of Life

    MedlinePlus

    Artificial Nutrition (Food) and Hydration (Fluids) at the End of Life It is very common for doctors to provide fluids and food to people who are very sick ... to understand how the body processes food and fluids. The information below explains the medical facts about ...

  13. Abnormal fluid pressures at ODP Site 1251: Implications for fluid flow and hydrate concentration

    NASA Astrophysics Data System (ADS)

    Weinberger, J. L.; Brown, K. M.

    2005-12-01

    Consolidation test results from whole round samples collected at Ocean Drilling Program (ODP) Site 1251 were combined with geophysical logging-while-drilling (LWD) data to create a continuous down-hole record of fluid pressure in the slope basin to the east of Hydrate Ridge, OR. Underconsolidation of the sediment is documented in the void ratio vs. effective stress relationships from the consolidation studies in the upper 140 mbsf of the section. This interval corresponds with a zone of consistently elevated fluid pressure that reaches ~90% of the lithostatic overburden stress. Models of one dimensional sedimentation and consolidation show that the observed degree of overpressuring can be accounted for by the combined effect of rapid sedimentation (60 to 160 cm/k.y.) and low permeability (1x10-16 to 1x10-17 m2). Between 140 and 300 mbsf the fluid pressure varies from 90% of lithostatic to sub-hydrostatic in 5 distinct horizons. This variation may be linked to mechanical consolidation of the sediment related to pore fluid drainage along more permeable horizons, or changes in sedimentation rate related to either glacial/ interglacial cycles or the uplift history of the ridge. The derived pressure gradient and permeability measurements predict Darcy flow rates on the order of 1 mm/yr at this site, but a lack of laterally continuous permeable conduits likely prevents the flow generated by basin overpressures in the interval from 0 to 140 mbsf from contributing to flow at the crest of the ridge. Using an average methane concentration of 100 mM and the determined flow rate, the methane flux through the system is calculated to be ~5 x 10-11 kg s-1 m-2. These data can be used to examine the maximum theoretical percentage of the pore space that can be filled with hydrate given the time of deposition in the basin. At a depth of 50 mbsf, we find that the maximum concentration of hydrate in the pore space is expected to be 0.1 to 0.3%, agreeing with the lack of concentrated

  14. X-ray computed tomography observations of phase distribution during methane hydrate formation and dissociation process in a sediment sample

    NASA Astrophysics Data System (ADS)

    Ahn, Taewoong; Lee, Jaehyoung; Lee, Joo Yong; Kim, Se-Joon; Seo, Young-ju

    2016-04-01

    The recovery schemes for natural gas caged in the solid state have not been commercialized. Depressurization has been known as a promising method due to its economic feasibility according to previous lab-scale experiments and simulation studies. However, the results of few field tests showed that the production characteristics of real field differed from that of predicted results. To reliably predict the production performance of real fields, it is necessary to understand quantitative changes of phase distribution and fluid flow in sediments in response to hydrate dissociation by depressurization. In this study, we observed and analyzed the phase distribution and flow behavior during methane hydrate formation and dissociation using X-ray computed tomography which provides high-resolution density distribution. Artificial particles having similar grain size distribution of sandy layers found in real hydrate field were packed into X-ray transparent aluminum vessel. Information on pore distribution within a sediment sample was achieved by comparing CT images between dry condition and fully water-saturated condition. Dynamic changes of phase saturation were observed during gas flooding, through which potential flow pathway was estimated. Hydrate formation and dissociation significantly affected phase distribution and flow pathway. Hydrate distribution was extremely heterogeneous in every tests of hydrate formation repeated with same amount of water. It was inferred that water saturation prior to hydrate formation was not directly correlated to the hydrate distribution. There were definite differences of hydrate dissociation behavior between gas-saturated and water-saturated hydrate-bearing sample. The production of gas and water lasted quite a while even after the production pressure reached the target level of depressurization.

  15. Three-dimensional seismic imaging and fluid flow analysis of a gas hydrate province

    NASA Astrophysics Data System (ADS)

    Hornbach, Matthew J.

    Methane hydrate, an ice-like substance that consists of methane and water, forms at high pressures and low temperatures, and abounds below every continental margin on earth. The amount of carbon trapped in methane hydrate remains highly speculative: although Kvenvolden (1993) suggests two-thirds of all the carbon on earth may be trapped in methane hydrate, more recent estimates by Milkov et. al. (2003) conclude that hydrates make up perhaps only one-forth of the global carbon reservoir. Regardless of which is more accurate, both estimates suggest methane hydrate is the largest source of carbon on the planet, and because of this, methane hydrate reservoirs may be a future potential energy resource as well as a significant cause of past and future global warming, since methane is a potent greenhouse gas. Recent studies by Kennett et al. (2000) and Dickens et. al. (2003) suggest that methane release from methane hydrate dissociation can explain past global warming events. Nonetheless, such conclusion are only valid if (1) the statistical estimates of hydrate quantities are accurate, and (2) a well understood mechanism for hydrate dissociation and methane gas release is recognized. The goal of this work, therefore, is to create high-resolution 3D seismic images to quantify the amount of hydrate that exists in a known hydrate province, the Blake Ridge, and to determine how fluid migration, hydrate dissociation and gas escape may occur in the region. My results demonstrate that concentrated zones of methane hydrate can be directly detected within the 3D image, and that approximately two-thirds of all methane trapped below the Blake Ridge is located in concentrated zones of hydrate and free-gas. The images reveal that strata and sequence boundaries act as gas traps. Furthermore, critically thick free-gas zones exist below much of the Blake Ridge, and any changes in pressure or temperature in the region could result in significant gas escape. The analysis reveals that

  16. From Black Hole to Hydrate Hole: Gas hydrates, authigenic carbonates and vent biota as indicators of fluid migration at pockmark sites of the Northern Congo Fan

    NASA Astrophysics Data System (ADS)

    Kasten, S.; Schneider, R.; Spiess, V.; Cruise Participants Of M56b

    2003-04-01

    A recent high-resolution seismic, echosounder and video survey combined with detailed geological and geochemical sampling of pockmark sites on the Northern Congo Fan was carried out with RV Meteor in November/December 2002 in the frame of the project "CONGO" (BMBF/BEO "Geotechnologien"). These investigations revealed the extensive occurrence of surface and sub-surface gas hydrates as well as characteristic features of fluid venting such as clams (Calyptogena), tube worms (Pogonophera) and huge amounts of authigenic carbonates. In a first approach the patchyness in the occurrence of these features was mapped in relation to pockmark structure and seismic reflectors. Detailed sampling of three pockmarks by gravity corer showed that gas hydrates are present at and close to the sediment surface and often occur as several distinct layers and/or veins intercalated with hemipelagic muds. The depth of the upper boundary of these hydrate-bearing sediments increases from the center towards the edge of the pockmark structures. Pore water concentration profiles of sulfate and methane document the process of anaerobic methane oxidation above the hydrate-bearing layers. For those cores which contained several gas hydrate layers preliminary pore water profiles suggest the occurrence of more than one zone of anaerobic methane oxidation. Authigenic carbonates are found in high abundance, irregularly distributed within the pockmarks close to the sediment surface. These carbonates occur in a wide variety with respect to size, shape, structure and mineralogy. Their formation is associated with high amounts of bicarbonate released by the process of anaerobic methane oxidation. In the gravity cores authigenic carbonates are always present above hydrate-bearing sections. However, the quantities and characteristics of these authigenic minerals in relation to venting and microbial activity as well as to gas hydrate dissociation are not clear yet. Unraveling this relationship will be a major

  17. Computational phase diagrams of noble gas hydrates under pressure.

    PubMed

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems. PMID:26493915

  18. Computational phase diagrams of noble gas hydrates under pressure

    SciTech Connect

    Teeratchanan, Pattanasak Hermann, Andreas

    2015-10-21

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

  19. Effects of Fluid Saturation on Gas Recovery from Class-3 Hydrate Accumulations Using Depressurization: Case Study of Yuan-An Ridge Site in Southwestern Offshore Taiwan

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    Gas hydrates are crystalline compounds in which guest gas molecules are trapped in host lattices of ice crystals. In Taiwan, the significant efforts have recently begun to evaluate the reserves of hydrate because the vast accumulations of gas hydrates had been recognized in southwestern offshore Taiwan. Class-3 type hydrate accumulations are referred to an isolated hydrate layer without an underlying zone of mobile fluids, and the entire hydrate layer may be well within the hydrate stability zone. The depressurization method is a useful dissociation method for gas production from Class-3 hydrate accumulations. The dissociation efficiency is controlled by the responses of hydrate to the propagating pressure disturbance, and the pressure propagation is relating to the amount (or saturation) of the mobile fluid in pore space of the hydrate layer. The purpose of this study is to study the effects of fluid saturation on the gas recovery from a class-3 hydrate accumulation using depressurization method. The case of a class-3 hydrate deposit of Yuan-An Ridge in southwestern offshore Taiwan is studied. The numerical method was used in this study. The reservoir simulator we used to study the dissociation of hydrate and the production of gas was the STARS simulator developed by CMG, which coupled heat transfer, geo-chemical, geo-mechanical, and multiphase fluid flow mechanisms. The study case of Yuan-An Ridge is located in southwestern offshore Taiwan. The hydrate deposit was found by the bottom simulating reflectors (BSRs). The geological structure of the studied hydrate deposit was digitized to build the geological model (grids) of the case. The formation parameters, phase behavior data, rock and fluid properties, and formation's initial conditions were assigned sequentially to grid blocks, and the completion and operation conditions were designed to wellbore blocks to finish the numerical model. The changes of reservoir pressure, temperature, saturation due to the hydrate

  20. CO2-rich fluid inclusions in greenschists, migmatites, granulites, and hydrated granulites

    NASA Technical Reports Server (NTRS)

    Hollister, L. S.

    1988-01-01

    Data was discussed from several different terrains in which CO2-rich fluid inclusions occur despite parageneses that predict the presence of H2O-rich fluids. CO2-rich fluid inclusions, some having densities appropriate for peak-metamorphic conditions, were found in greenschists, amphibolites, migmatites, and hydrated granulites. The author suggested that there may be a common process that leads to CO2-rich secondary inclusions in metamorphic rocks.

  1. Comparing the mechanical properties of the porcine knee meniscus when hydrated in saline versus synovial fluid.

    PubMed

    Lakes, Emily H; Kline, Courtney L; McFetridge, Peter S; Allen, Kyle D

    2015-12-16

    As research progresses to find a suitable knee meniscus replacement, accurate in vitro testing becomes critical for feasibility and comparison studies of mechanical integrity. Within the knee, the meniscus is bathed in synovial fluid, yet the most common hydration fluid in laboratory testing is phosphate buffered saline (PBS). PBS is a relatively simple salt solution, while synovial fluid is a complex non-Newtonian fluid with multiple lubricating factors. As such, PBS may interact with meniscal tissue differently than synovial fluid, and thus, the hydration fluid may be an important factor in obtaining accurate results during in vitro testing. To evaluate these effects, medial porcine menisci were used to evaluate tissue mechanics in tension (n=11) and compression (n=15). In all tests, two samples from the same meniscus were taken, where one sample was hydrated in PBS and the other was hydrated in synovial fluid. Statistical analysis revealed no significant differences between the mean mechanical properties of samples tested in PBS compared to synovial fluid; however, compressive testing revealed the variability between samples was significantly reduced if samples were tested in synovial fluid. For example, the compressive Young׳s Modulus was 12.69±7.49MPa in PBS versus 12.34±4.27MPa in synovial fluid. These results indicate testing meniscal tissue in PBS will largely not affect the mean value of the mechanical properties, but performing compression testing in synovial fluid may provide more consistent results between samples and assist in reducing sample numbers in some experiments.

  2. Comparing the mechanical properties of the porcine knee meniscus when hydrated in saline versus synovial fluid.

    PubMed

    Lakes, Emily H; Kline, Courtney L; McFetridge, Peter S; Allen, Kyle D

    2015-12-16

    As research progresses to find a suitable knee meniscus replacement, accurate in vitro testing becomes critical for feasibility and comparison studies of mechanical integrity. Within the knee, the meniscus is bathed in synovial fluid, yet the most common hydration fluid in laboratory testing is phosphate buffered saline (PBS). PBS is a relatively simple salt solution, while synovial fluid is a complex non-Newtonian fluid with multiple lubricating factors. As such, PBS may interact with meniscal tissue differently than synovial fluid, and thus, the hydration fluid may be an important factor in obtaining accurate results during in vitro testing. To evaluate these effects, medial porcine menisci were used to evaluate tissue mechanics in tension (n=11) and compression (n=15). In all tests, two samples from the same meniscus were taken, where one sample was hydrated in PBS and the other was hydrated in synovial fluid. Statistical analysis revealed no significant differences between the mean mechanical properties of samples tested in PBS compared to synovial fluid; however, compressive testing revealed the variability between samples was significantly reduced if samples were tested in synovial fluid. For example, the compressive Young׳s Modulus was 12.69±7.49MPa in PBS versus 12.34±4.27MPa in synovial fluid. These results indicate testing meniscal tissue in PBS will largely not affect the mean value of the mechanical properties, but performing compression testing in synovial fluid may provide more consistent results between samples and assist in reducing sample numbers in some experiments. PMID:26592438

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

    PubMed Central

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

    2015-01-01

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

  4. Evaluation of phase envelope on natural gas, condensate and gas hydrate

    NASA Astrophysics Data System (ADS)

    Promkotra, S.; Kangsadan, T.

    2015-03-01

    The experimentally gas hydrate are generated by condensate and natural gas. Natural gas and condensate samples are collected from a gas processing plant where is situated in the northeastern part of Thailand. Physical properties of the API gravity and density of condensate are presented in the range of 55-60° and 0.71-0.76 g/cm3. The chemical compositions of petroleum-field water are analyzed to evaluate the genesis of gas hydrate by experimental procedure. The hydrochemical compositions of petroleum-field waters are mostly the Na-Cl facies. This condition can estimate how the hydrate forms. Phase envelope of condensate is found only one phase which is liquid phase. The liquid fraction is 100% at 15°C and 101.327 kPa, with the critical pressure and temperature of 2,326 kPa and 611.5 K. However, natural gas can be separated in three phases which are vapor, liquid and solid phase with the pressure and temperature at 100 kPa and 274.2 K. The hydrate curves explicit both hydrate zone and nonhydrate zone. Phase envelope of gas hydrate from the phase diagram indicates the hydrate formation. The experimental results of hydrate form can correlate to the hydrate curve. Besides, the important factor of hydrate formation depends on impurity in the petroleum system.

  5. Isotopic fractionation of methane and ethane hydrates between gas and hydrate phases

    NASA Astrophysics Data System (ADS)

    Hachikubo, Akihiro; Kosaka, Tomoko; Kida, Masato; Krylov, Alexey; Sakagami, Hirotoshi; Minami, Hirotsugu; Takahashi, Nobuo; Shoji, Hitoshi

    2007-11-01

    Isotopic fractionation of carbon and hydrogen in methane and ethane during the formation of gas hydrates was investigated. The gas hydrate samples were experimentally prepared in a pressure cell and isotopic compositions of both residual and hydrate-bound gases were measured. δD of hydrate-bound molecules of methane and ethane hydrates was several per mil lower than that of residual gas molecules in the formation processes, while there was no difference in the case of δ 13C. These isotopic differences in δD are enough small for discussing the source types of hydrate-bound gases using the δ 13C-δD diagram of Whiticar et al. [1986]. These results may provide useful insight into the formation process of gas hydrates.

  6. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    SciTech Connect

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

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).

  7. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates.

    PubMed

    Miskowiec, Andrew; Kirkegaard, Marie C; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W; Trowbridge, Lee; Rondinone, Adam; Anderson, Brian

    2015-12-10

    We report a novel production method for uranium oxyfluoride [(UO2)7F14(H2O)7]·4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl fluoride, UO2F2, through the gas phase at ambient temperatures followed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7]·4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous structure), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielastic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform restricted motion on a length scale commensurate with the O-H bond (r = 0.92 Å). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps(-1)) than their hydrogen-bonded partners (Dr = 28.7 ps(-1)). PMID:26575434

  8. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    DOE PAGES

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

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previousmore » measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).« less

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

    SciTech Connect

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin

    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.

  10. Hexosome and hexagonal phases mediated by hydration and polymeric stabilizer.

    PubMed

    Amar-Yuli, Idit; Wachtel, Ellen; Shoshan, Einav Ben; Danino, Dganit; Aserin, Abraham; Garti, Nissim

    2007-03-27

    In this research, we studied the factors that control formation of GMO/tricaprylin/water hexosomes and affect their inner structure. As a stabilizer of the soft particles dispersed in the aqueous phase, we used the hydrophilic nonionic triblock polymer Pluronic 127. We demonstrate how properties of the hexosomes, such as size, structure, and stability, can be tuned by their internal composition, polymer concentration, and processing conditions. The morphology and inner structure of the hexosomes were characterized by small-angle X-ray scattering, cryo-transmission electron microscope, and dynamic light scattering. The physical stability (to creaming, aggregation, and coalescence) of the hexosomes was further examined by the LUMiFuge technique. Two competing processes are presumed to take place during the formation of hexosomes: penetration of water from the continuous phase during dispersion, resulting in enhanced hydration of the head groups, and incorporation of the polymer chains into the hexosome structure while providing a stabilizing surface coating for the dispersed particles. Hydration is an essential stage in lyotropic liquid crystal (LLC) formation. The polymer, on the other hand, dehydrates the lipid heads, thereby introducing disorder into the LLC and reducing the domain size. Yet, a critical minimum polymer concentration is necessary in order to form stable nanosized hexosomes. These competing effects require the attention of those preparing hexosomes. The competition between these two processes can be controlled. At relatively high polymer concentrations (1-1.6 wt % of the total formulation of the soft particles), the hydration process seems to occur more rapidly than polymer adsorption. As a result, smaller and more stable soft particles with high symmetry were formed. On the other hand, when the polymer concentration is fixed at lower levels (<1.0 wt %), the homogenization process encourages only partial polymer adsorption during the dispersion

  11. Fluid Flow Patterns During Production from Gas Hydrates in the Laboratory compared to Field Settings: LARS vs. Mallik

    NASA Astrophysics Data System (ADS)

    Strauch, B.; Heeschen, K. U.; Priegnitz, M.; Abendroth, S.; Spangenberg, E.; Thaler, J.; Schicks, J. M.

    2015-12-01

    The GFZ's LArge Reservoir Simulator LARS allows for the simulation of the 2008 Mallik gas hydrate production test and the comparison of fluid flow patterns and their driving forces. Do we see the gas flow pattern described for Mallik [Uddin, M. et al., J. Can. Petrol Tech, 50, 70-89, 2011] in a pilot scale test? If so, what are the driving forces? LARS has a network of temperature sensors and an electric resistivity tomography (ERT) enabling a good spatial resolution of gas hydrate occurrences, water and gas distribution, and changes in temperature in the sample. A gas flow meter and a water trap record fluid flow patterns and a backpressure valve has controlled the depressurization equivalent to the three pressure stages (7.0 - 5.0 - 4.2 MPa) applied in the Mallik field test. The environmental temperature (284 K) and confining pressure (13 MPa) have been constant. The depressurization induced immediate endothermic gas hydrate dissociation until re-establishment of the stability conditions by a consequent temperature decrease. Slight gas hydrate dissociation continued at the top and upper lateral border due to the constant heat input from the environment. Here transport pathways were short and permeability higher due to lower gas hydrate saturation. At pressures of 7.0 and 5.0 MPa the LARS tests showed high water flow rates and short irregular spikes of gas production. The gas flow patterns at 4.2 MPa and 3.0MPa resembled those of the Mallik test. In LARS the initial gas surges overlap with times of hydrate instability while water content and lengths of pathways had increased. Water production was at a minimum. A rapidly formed continuous gas phase caused the initial gas surges and only after gas hydrate dissociation decreased to a minimum the single gas bubbles get trapped before slowly coalescing again. In LARS, where pathways were short and no additional water was added, a transport of microbubbles is unlikely to cause a gas surge as suggested for Mallik.

  12. The impact of fluid advection on gas hydrate stability: Investigations at sites of methane seepage offshore Costa Rica

    NASA Astrophysics Data System (ADS)

    Crutchley, G. J.; Klaeschen, D.; Planert, L.; Bialas, J.; Berndt, C.; Papenberg, C.; Hensen, C.; Hornbach, M. J.; Krastel, S.; Brueckmann, W.

    2014-09-01

    Fluid flow through marine sediments drives a wide range of processes, from gas hydrate formation and dissociation, to seafloor methane seepage including the development of chemosynthetic ecosystems, and ocean acidification. Here, we present new seismic data that reveal the 3D nature of focused fluid flow beneath two mound structures on the seafloor offshore Costa Rica. These mounds have formed as a result of ongoing seepage of methane-rich fluids. We show the spatial impact of advective heat flow on gas hydrate stability due to the channelled ascent of warm fluids towards the seafloor. The base of gas hydrate stability (BGHS) imaged in the seismic data constrains peak heat flow values to ∼60 mW m and ∼70 mW m beneath two separate seep sites known as Mound 11 and Mound 12, respectively. The initiation of pronounced fluid flow towards these structures was likely controlled by fault networks that acted as efficient pathways for warm fluids ascending from depth. Through the gas hydrate stability zone, fluid flow has been focused through vertical conduits that we suggest developed as migrating fluids generated their own secondary permeability by fracturing strata as they forced their way upwards towards the seafloor. We show that Mound 11 and Mound 12 (about 1 km apart on the seafloor) are sustained by independent fluid flow systems through the hydrate system, and that fluid flow rates across the BGHS are probably similar beneath both mounds. 2D seismic data suggest that these two flow systems might merge at approximately 1 km depth, i.e. much deeper than the BGHS. This study provides a new level of detail and understanding of how channelled, anomalously-high fluid flow towards the seafloor influences gas hydrate stability. Thus, gas hydrate systems have good potential for quantifying the upward flow of subduction system fluids to seafloor seep sites, since the fluids have to interact with and leave their mark on the hydrate system before reaching the seafloor.

  13. Pore fluid geochemistry from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    USGS Publications Warehouse

    Torres, M.E.; Collett, T.S.; Rose, K.K.; Sample, J.C.; Agena, W.F.; Rosenbaum, E.J.

    2011-01-01

    The BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well was drilled and cored from 606.5 to 760.1. m on the North Slope of Alaska, to evaluate the occurrence, distribution and formation of gas hydrate in sediments below the base of the ice-bearing permafrost. Both the dissolved chloride and the isotopic composition of the water co-vary in the gas hydrate-bearing zones, consistent with gas hydrate dissociation during core recovery, and they provide independent indicators to constrain the zone of gas hydrate occurrence. Analyses of chloride and water isotope data indicate that an observed increase in salinity towards the top of the cored section reflects the presence of residual fluids from ion exclusion during ice formation at the base of the permafrost layer. These salinity changes are the main factor controlling major and minor ion distributions in the Mount Elbert Well. The resulting background chloride can be simulated with a one-dimensional diffusion model, and the results suggest that the ion exclusion at the top of the cored section reflects deepening of the permafrost layer following the last glaciation (???100 kyr), consistent with published thermal models. Gas hydrate saturation values estimated from dissolved chloride agree with estimates based on logging data when the gas hydrate occupies more than 20% of the pore space; the correlation is less robust at lower saturation values. The highest gas hydrate concentrations at the Mount Elbert Well are clearly associated with coarse-grained sedimentary sections, as expected from theoretical calculations and field observations in marine and other arctic sediment cores. ?? 2009 Elsevier Ltd.

  14. Elasticity of methane hydrate phases at high pressure.

    PubMed

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-21

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment. PMID:27389226

  15. Pressure induced reactions amongst calcium aluminate hydrate phases

    SciTech Connect

    Moon, Ju-hyuk; Oh, Jae Eun; Balonis, Magdalena; Glasser, Fredrik P.; Clark, Simon M.; Monteiro, Paulo J.M.

    2011-06-15

    The compressibilities of two AFm phases (straetlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies.

  16. Elasticity of methane hydrate phases at high pressure

    NASA Astrophysics Data System (ADS)

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-01

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

  17. North Cascadia heat flux and fluid flow from gas hydrates: Modeling 3-D topographic effects

    NASA Astrophysics Data System (ADS)

    Li, Hong-lin; He, Tao; Spence, George D.

    2014-01-01

    The bottom-simulating reflector (BSR) of gas hydrate is well imaged from two perpendicular seismic grids in the region of a large carbonate mound, informally called Cucumber Ridge off Vancouver Island. We use a new method to calculate 3-D heat flow map from the BSR depths, in which we incorporate 3-D topographic corrections after calibrated by the drilling results from nearby (Integrated) Ocean Drilling Program Site 889 and Site U1327. We then estimate the associated fluid flow by relating it to the topographically corrected heat flux anomalies. In the midslope region, a heat flux anomaly of 1 mW/m2 can be associated with an approximate focused fluid flow rate of 0.09 mm/yr. Around Cucumber Ridge, high rates of focused fluid flow were observed at steep slopes with values more than double the average regional diffusive fluid discharge rate of 0.56 mm/yr. As well, in some areas of relatively flat seafloor, the focused fluid flow rates still exceeded 0.5 mm/yr. On the seismic lines the regions of focused fluid flow were commonly associated with seismic blanking zones above the BSR and sometimes with strong reflectors below the BSR, indicating that the faults/fractures provide high-permeability pathways for fluids to carry methane from BSR depths to the seafloor. These high fluid flow regions cover mostly the western portion of our area with gas hydrate concentration estimations of ~6% based on empirical correlations from Hydrate Ridge in south off Oregon, significantly higher than previously recognized values of ~2.5% in the eastern portion determined from Site U1327.

  18. Phase I (CATTS Theory), Phase II (Milne Point), Phase III (Hydrate Ridge)

    SciTech Connect

    None, None

    2009-10-31

    This study introduces a new type of cumulative seismic attribute (CATT) which quantifies gas hydrates resources in Hydrate Ridge offshore Oregon. CATT is base on case-specific transforms that portray hydrated reservoir properties. In this study we used a theoretical rock physics model to correct measured velocity log data.

  19. Fluid and salt supplementation effect on body hydration and electrolyte homeostasis during bed rest and ambulation

    NASA Astrophysics Data System (ADS)

    Zorbas, Yan G.; Kakurin, Vassily J.; Kuznetsov, Nikolai A.; Yarullin, Vladimir L.

    2002-06-01

    Bed rest (BR) induces significant urinary and blood electrolyte changes, but little is known about the effect of fluid and salt supplements (FSS) on catabolism, hydration and electrolytes. The aim was to measure the effect of FSS on catabolism, body hydration and electrolytes during BR. Studies were done during 7 days of a pre-bed rest period and during 30 days of a rigorous bed rest period. Thirty male athletes aged, 24.6±7.6 years were chosen as subjects. They were divided into three groups: unsupplemented ambulatory control subjects (UACS), unsupplemented bed rested subjects (UBRS) and supplemented bed rested subjects (SBRS). The UBRS and SBRS groups were kept under a rigorous bed rest regime for 30 days. The SBRS daily took 30 ml water per kg body weight and 0.1 sodium chloride per kg body weight. Plasma sodium (Na), potassium (K), calcium (Ca) and magnesium (Mg) levels, urinary Na, K, Ca and Mg excretion, plasma osmolality, plasma protein level, whole blood hemoglobin (Hb) and hematocrit (Hct) level increased significantly ( p≤0.05), while plasma volume (PV), body weight, body fat, peak oxygen uptake, food and fluid intake decreased significantly ( p≤0.05) in the UBRS group when compared with the SBRS and UACS groups. In contrast, plasma and urinary electrolytes, osmolality, protein level, whole blood Hct and Hb level decreased significantly ( p≤0.05), while PV, fluid intake, body weight and peak oxygen uptake increased significantly ( p≤0.05) in the SBRS group when compared with the UBRS group. The measured parameters did not change significantly in the UACS group when compared with their baseline control values. The data indicate that FSS stabilizes electrolytes and body hydration during BR, while BR alone induces significant changes in electrolytes and body hydration. We conclude that FSS may be used to prevent catabolism and normalize body hydration status and electrolyte values during BR.

  20. Hydration Status and Fluid Balance of Elite European Youth Soccer Players during Consecutive Training Sessions

    PubMed Central

    Phillips, Saun M.; Sykes, Dave; Gibson, Neil

    2014-01-01

    The objective of the study was to investigate the hydration status and fluid balance of elite European youth soccer players during three consecutive training sessions. Fourteen males (age 16.9 ± 0.8 years, height 1.79 ± 0.06 m, body mass (BM) 70.6 ± 5.0 kg) had their hydration status assessed from first morning urine samples (baseline) and pre- and post-training using urine specific gravity (USG) measures, and their fluid balance calculated from pre- to post-training BM change, corrected for fluid intake and urine output. Most participants were hypohydrated upon waking (USG >1.020; 77% on days 1 and 3, and 62% on day 2). There was no significant difference between first morning and pre-training USG (p = 0.11) and no influence of training session (p = 0.34) or time (pre- vs. post-training; p = 0.16) on USG. Significant BM loss occurred in sessions 1-3 (0.69 ± 0.22, 0.42 ± 0.25, and 0.38 ± 0.30 kg respectively, p < 0.05). Mean fluid intake in sessions 1-3 was 425 ± 185, 355 ± 161, and 247 ± 157 ml, respectively (p < 0.05). Participants replaced on average 71.3 ± 64.1% (range 0-363.6%) of fluid losses across the three sessions. Body mass loss, fluid intake, and USG measures showed large inter-individual variation. Elite young European soccer players likely wake and present for training hypohydrated, when a USG threshold of 1.020 is applied. When training in a cool environment with ad libitum access to fluid, replacing ~71% of sweat losses results in minimal hypohydration (<1% BM). Consumption of fluid ad libitum throughout training appears to prevent excessive (≥2% BM) dehydration, as advised by current fluid intake guidelines. Current fluid intake guidelines appear applicable for elite European youth soccer players training in a cool environment. Key Points The paper demonstrates a notable inter-participant variation in first morning, pre- and post-training hydration status and fluid balance of elite young European soccer players. On average, elite young

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

    SciTech Connect

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

    2011-02-11

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

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

    PubMed

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

    2016-08-01

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

  3. TOUGH-Fx/Hydrate

    SciTech Connect

    Moridis, George Julius

    2005-02-01

    TOUGH-Fx/HYORATL can model the non-isothermal gas release. phase behavior and flow of fluids and heat in complex geologic media. The code can simulate production from natural gas hydrate deposits in the subsurtace (i.e., in the permafrost and in deep ocean sediments), as well as laboratory experiments of hydrate dissociation/formation in porous/fractured media. T006H-Fx/HYDRATE vi .0 includes both an equilibrium and a kinetic model of hydrate Ibmiation and dissociation. The model accounts for heat and 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.

  4. TOUGH-Fx/Hydrate

    2005-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

    NASA Astrophysics Data System (ADS)

    Park, T.; Kyung, D.; Lee, W.

    2013-12-01

    Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

  7. Fluid Migration Patterns in Gas Hydrate System of Four-Way-Closure Ridge Offshore Southwestern Taiwan

    NASA Astrophysics Data System (ADS)

    Chen, Liwen; Chi, Wu-Cheng; Lin, Yu-Hsieh; Berndt, Christian; Lin, Saulwood

    2016-04-01

    Four-Way-Closure (4WC) Ridge shows great potential as a hydrate prospect from collected multitude of marine geophysical datasets offshore southwestern Taiwan. The aim of my study is to better understand the fluid migration patterns and the possible source locations of the methane at this site. It is a cold seep site with an elongated NW-SE trending anticlinal ridge, which is formed by fault-related folds in the frontal segment of the lower slope domain of the Taiwan accretionary prism along its convergent boundary. So I detail recognized the regional feature structures of the 4WC Ridge, including the thrust faulting and a seismic chimney beneath the seepage sites. I plan to study the temperature perturbation at the 4WC Ridge to better understand gas hydrate system there. To quantify the amount of temperature perturbation near the fault zone, we need to correct the temperature field data for other geological processes. One important correction we want to make concerns the topographic effects on the shallow crust temperature field. So we used 3D finite element method to quantify how much temperature perturbation can be attributed to the local bathymetry at the 4WC Ridge. This model will give us a temperature field based on pure thermal conduction. Then, we can compare the model temperature field with the temperature field derived from thousands of BSRs from the seismic cube, and interpret any resulting temperature discrepancy. As our previous study, we known several geological processes can cause such a discrepancy, including advective fluid migration. If the fault zone fluid migration hypothesis is correct and gas hydrate system reacts to the deep warm fluids from below it, we expect that the BSR will become shallower near the fluid pathways, and the BSR-based temperature field might be a few degrees Celsius higher than in the 3D thermal conductive temperature field. Otherwise, the two temperature fields should be similar. This study is important for hydrate

  8. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    DOE PAGES

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

    2015-05-21

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

  9. Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

    PubMed

    Park, Taehyung; Kyung, Daeseung; Lee, Woojin

    2014-06-17

    In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

  10. Phase boundary of hot dense fluid hydrogen

    PubMed Central

    Ohta, Kenji; Ichimaru, Kota; Einaga, Mari; Kawaguchi, Sho; Shimizu, Katsuya; Matsuoka, Takahiro; Hirao, Naohisa; Ohishi, Yasuo

    2015-01-01

    We investigated the phase transformation of hot dense fluid hydrogen using static high-pressure laser-heating experiments in a laser-heated diamond anvil cell. The results show anomalies in the heating efficiency that are likely to be attributed to the phase transition from a diatomic to monoatomic fluid hydrogen (plasma phase transition) in the pressure range between 82 and 106 GPa. This study imposes tighter constraints on the location of the hydrogen plasma phase transition boundary and suggests higher critical point than that predicted by the theoretical calculations. PMID:26548442

  11. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

    SciTech Connect

    Michalis, Vasileios K.; Costandy, Joseph; Economou, Ioannis G.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal–isobaric ensemble in order to determine the coexistence temperature (T{sub 3}) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T{sub 3}, is treated with long simulations in the range of 1000–4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T{sub 3} predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T{sub 3} of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  12. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

    NASA Astrophysics Data System (ADS)

    Michalis, Vasileios K.; Costandy, Joseph; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.

    2015-01-01

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  13. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology.

    PubMed

    Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models. PMID:25637989

  14. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology.

    PubMed

    Michalis, Vasileios K; Costandy, Joseph; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal-isobaric ensemble in order to determine the coexistence temperature (T3) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T3, is treated with long simulations in the range of 1000-4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T3 predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T3 of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  15. Dynamic phase equilibrium during formation and dissociation of marine gas hydrate

    NASA Astrophysics Data System (ADS)

    Xu, W.; Lowell, R. P.; Germanovich, L.

    2002-12-01

    Methane gas hydrate (MGH) is stable under relatively high pressure and low temperature conditions such as those in the marine sediments near continental margins. Much attention has been focused on related issues of MGH as a potential energy resource, a possible role in submarine sediment failure, and an agent in global climate change. Particularly, there has been controversy over whether and how methane released from dissociating marine gas hydrate makes its way to the ocean and the atmosphere. Despite its apparent importance, a comprehensive understanding of how a marine MGH system dynamically adjusts itself in a changing environment is still absent. A robust theory describing phase balance and dynamic equilibrium is a necessary step toward a better understanding of the dynamic behaviors of MGH systems. We have developed a method to determine the balance and equilibrium of a three-component (water, methane, salt) four-phase (liquid, gas, hydrate, halite) gas hydrate system. Analysis shows that there are dynamic feedbacks between MGH formation/dissociation and changes in pressure, temperature and salinity. A few important observations of this study are: 1) formation of brine with gas hydrate, 2) development of water-limited situation in certain circumstances, 3) broad region of coexisting three phases of hydrate, liquid and free gas, and 4) significant over pressurization due to MGH dissociation. It is also found that 1) free gas is able to migrate through gas hydrate stability zone, 2) a layer of coexisting hydrate, liquid and free gas can resides below the BSR, and 3) significant excess pore pressure can be built up within the three-phase zone resulting from either continuous sedimentation, seafloor temperature increase, or sea level drop. We will discuss their implications to marine gas hydrate systems. The meanings of BSR and BHSZ (base of hydrate stability zone) in the context of these new findings will be discussed.

  16. Controlled-source electromagnetic and seismic delineation of subseafloor fluid flow structures in a gas hydrate province, offshore Norway

    NASA Astrophysics Data System (ADS)

    Attias, Eric; Weitemeyer, Karen; Minshull, Tim A.; Best, Angus I.; Sinha, Martin; Jegen-Kulcsar, Marion; Hölz, Sebastian; Berndt, Christian

    2016-08-01

    Deep sea pockmarks underlain by chimney-like or pipe structures that contain methane hydrate are abundant along the Norwegian continental margin. In such hydrate provinces the interaction between hydrate formation and fluid flow has significance for benthic ecosystems and possibly climate change. The Nyegga region, situated on the western Norwegian continental slope, is characterized by an extensive pockmark field known to accommodate substantial methane gas hydrate deposits. The aim of this study is to detect and delineate both the gas hydrate and free gas reservoirs at one of Nyegga's pockmarks. In 2012, a marine controlled-source electromagnetic (CSEM) survey was performed at a pockmark in this region, where high-resolution 3-D seismic data were previously collected in 2006. 2-D CSEM inversions were computed using the data acquired by ocean bottom electrical field receivers. Our results, derived from unconstrained and seismically constrained CSEM inversions, suggest the presence of two distinctive resistivity anomalies beneath the pockmark: a shallow vertical anomaly at the underlying pipe structure, likely due to gas hydrate accumulation, and a laterally extensive anomaly attributed to a free gas zone below the base of the gas hydrate stability zone. This work contributes to a robust characterization of gas hydrate deposits within subseafloor fluid flow pipe structures.

  17. A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

    USGS Publications Warehouse

    Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

    1996-01-01

    A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

  18. Calcium-aluminum-silicate-hydrate "cement" phases and rare Ca-zeolite association at Colle Fabbri, Central Italy

    NASA Astrophysics Data System (ADS)

    Stoppa, F.; Scordari, F.; Mesto, E.; Sharygin, V. V.; Bortolozzi, G.

    2010-06-01

    Very high temperature, Ca-rich alkaline magma intruded an argillite formation at Colle Fabbri, Central Italy, producing cordierite-tridymite metamorphism in the country rocks. An intense Ba-rich sulphate-carbonate-alkaline hydrothermal plume produced a zone of mineralization several meters thick around the igneous body. Reaction of hydrothermal fluids with country rocks formed calcium-silicate-hydrate (CSH), i.e., tobermorite-afwillite-jennite; calcium-aluminum-silicate-hydrate (CASH) — "cement" phases - i.e., thaumasite, strätlingite and an ettringite-like phase and several different species of zeolites: chabazite-Ca, willhendersonite, gismon-dine, three phases bearing Ca with the same or perhaps lower symmetry of phillipsite-Ca, levyne-Ca and the Ca-rich analogue of merlinoite. In addition, apophyllite-(KF) and/or apophyllite-(KOH), Ca-Ba-carbonates, portlandite and sulphates were present. A new polymorph from the pyrrhotite group, containing three layers of sphalerite-type structure in the unit cell, is reported for the first time. Such a complex association is unique. Most of these minerals are specifically related to hydration processes of: (1) pyrometamorphic metacarbonate/metapelitic rocks (natural analogues of cement clinkers); (2) mineralization between intrusive stocks and slates; and (3) high-calcium, alkaline igneous rocks such as melilitites and foidites as well as carbonatites. The Colle Fabbri outcrop offers an opportunity to study in situ complex crystalline overgrowth and specific crystal chemistry in mineral phases formed in igneous to hydrothermal conditions.

  19. Effect of fluid and salt supplementation on body hydration of athletes during prolonged hypokinesia

    NASA Astrophysics Data System (ADS)

    Zorbas, Yan G.; Petrov, Kirill L.; Yarullin, Vladimir L.; Kakurin, Vassily J.; Popov, Vladimir K.; Deogeneov, Viktor A.

    Body hydration decreases significantly during hypokinesia (HK) (diminished movement), but little is known about the effect of fluid and salt supplements (FSS) on body hydration during HK. The aim of this study was to measure the effect of FSS on body hydration during HK. Studies were done during 30 days pre HK period and 364 days HK period. Thirty male athletes aged 24.5±6.6 yr were chosen as subjects. They were equally divided into three groups: unsupplemented ambulatory control subjects (UACS), unsupplemented hypokinetic subjects (UHKS) and supplemented hypokinetic subjects (SHKS). Hypokinetic subjects were limited to an average walking distance of 0.7 km day -1. The SHKS group took daily 30 ml of water/kg body weight and 0.1 g of sodium chloride (NaCl)/kg body weight. Control subjects experienced no changes in their professional training and routine daily activities. Plasma volume (PV), urinary and plasma sodium (Na) and potassium (K), plasma osmolality, plasma protein, whole blood hemoglobin (Hb) and hematocrit (Hct), plasma renin activity (PRA) plasma aldosterone (PA) levels, physical characteristics, food and fluid intakes were measured. Plasma osmolality, plasma protein, urinary and plasma Na and K, whole blood Hct and Hb, PRA and PA levels decreased significantly ( p⩽0.01), while PV and body weight increased significantly ( p⩽0.01) in the SHKS group when compared with the UHKS group and did not change when compared with the UACS group. Plasma osmolality, plasma protein, urinary and plasma Na and K, PRA and PA, whole blood Hb and Hct levels increased significantly ( p⩽0.01), while PV body weight, food and fluid intakes decreased significantly ( p⩽0.01) in UHKS group when compared with the SHKS and UACS groups. The measured parameters did not change in the UACS group when compared with their baseline control values. It was shown that during HK body hydration decreased significantly, while during HK and FSS body hydration increased significantly. It

  20. Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

    PubMed

    Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

    2009-04-23

    In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

  1. Hydration-Responsive Folding and Unfolding in Graphene Oxide Liquid Crystal Phases

    PubMed Central

    Guo, Fei; Kim, Franklin; Han, Tae Hee; Shenoy, Vivek B.; Huang, Jiaxing; Hurt, Robert H.

    2011-01-01

    Graphene oxide is promising as a plate-like giant molecular building block for the assembly of new carbon materials. Its water dispersibility, liquid crystallinity, and ease of reduction offer advantages over other carbon precursors if its fundamental assembly rules can be identified. This article shows that graphene oxide sheets of known lateral dimension form nematic liquid crystal phases with transition points in agreement with the Onsager hard-plate theory. The liquid crystal phases can be systematic ordered into defined supramolecular patterns using surface anchoring, complex fluid flow, and micro-confinement. Graphene oxide is seen to exhibit homeotropic surface anchoring at interfaces driven by excluded volume entropy and by adsorption enthalpy associated with its partially hydrophobic basal planes. Surprisingly, some of the surface-ordered graphene oxide phases dry into graphene oxide solids that undergo a dramatic anisotropic swelling upon rehydration to recover their initial size and shape. This behavior is shown to be a unique hydration-responsive folding and unfolding transition. During drying, surface tension forces acting parallel to the layer planes cause a buckling instability that stores elastic energy in accordion-folded structures in the dry solid. Subsequent water infiltration reduces interlayer frictional forces and triggers release of the stored elastic energy in the form of dramatic unidirectional expansion. We explain the folding/unfolding phenomena by quantitative nanomechanics, and introduce the potential of liquid crystal-derived graphene oxide phases as new stimuli-response materials. PMID:21877716

  2. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    USGS Publications Warehouse

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

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  3. Hydration biomarkers in free-living adults with different levels of habitual fluid consumption.

    PubMed

    Perrier, Erica; Vergne, Sébastien; Klein, Alexis; Poupin, Marie; Rondeau, Pascale; Le Bellego, Laurent; Armstrong, Lawrence E; Lang, Florian; Stookey, Jodi; Tack, Ivan

    2013-05-01

    Little is known about the impact of habitual fluid intake on physiology. Specifically, biomarkers of hydration status and body water regulation have not been adequately explored in adults who consume different fluid volumes in everyday conditions, without prolonged exercise or environmental exposure. The purpose of the present study was to compare adults with habitually different fluid intakes with respect to biomarkers implicated in the assessment of hydration status, the regulation of total body water and the risk of kidney pathologies. In the present cross-sectional study, seventy-one adults (thirty-two men, thirty-nine women, age 25–40 years) were classified according to daily fluid intake: thirty-nine low drinkers (LD; ≤ 1·2 litres/d) and thirty-two high drinkers (HD; 2–4 litres/d). During four consecutive days, urinary parameters (first morning urine (FMU) on day 1 and subsequent 24 h urine (24hU) collections), blood parameters, and food and beverage intake were assessed. ANOVA and non-parametric comparisons revealed significant differences between the LD and HD groups in 24hU volume (1·0 (se 0·1) v. 2·4 (se 0·1) litres), specific gravity (median 1·023 v. 1·010), osmolality (767 (se 27) v. 371 (se 33) mOsm/kg) and colour (3·1 (se 0·2) v. 1·8 (se 0·2)). Similarly, in the FMU, the LD group produced a smaller amount of more concentrated urine. Plasma cortisol, creatinine and arginine vasopressin concentrations were significantly higher among the LD. Plasma osmolality was similar between the groups, suggesting physiological adaptations to preserve plasma osmolality despite low fluid intake. The long-term impact of adaptations to preserve plasma osmolality must be examined, particularly in the context of renal health. PMID:22935250

  4. X-ray structure determination of fully hydrated L alpha phase dipalmitoylphosphatidylcholine bilayers.

    PubMed Central

    Nagle, J F; Zhang, R; Tristram-Nagle, S; Sun, W; Petrache, H I; Suter, R M

    1996-01-01

    Bilayer form factors obtained from x-ray scattering data taken with high instrumental resolution are reported for multilamellar vesicles of L alpha phase lipid bilayers of dipalmitoylphosphatidylcholine at 50 degrees C under varying osmotic pressure. Artifacts in the magnitudes of the form factors due to liquid crystalline fluctuations have been eliminated by using modified Caillé theory. The Caillé fluctuation parameter eta 1 increases systematically with increasing lamellar D spacing and this explains why some higher order peaks are unobservable for the larger D spacings. The corrected form factors fall on one smooth continuous transform F(q); this shows that the bilayer does not change shape as D decreases from 67.2 A (fully hydrated) to 60.9 A. The distance between headgroup peaks is obtained from Fourier reconstruction of samples with four orders of diffraction and from electron density models that use 38 independent form factors. By combining these results with previous gel phase results, area AF per lipid molecule and other structural quantities are obtained for the fluid L alpha phase. Comparison with results that we derived from previous neutron diffraction data is excellent, and we conclude from diffraction studies that AF = 62.9 +/- 1.3 A2, which is in excellent agreement with a previous estimate from NMR data. PMID:8785298

  5. Anti-Adhesive Behaviors between Solid Hydrate and Liquid Aqueous Phase Induced by Hydrophobic Silica Nanoparticles.

    PubMed

    Min, Juwon; Baek, Seungjun; Somasundaran, P; Lee, Jae W

    2016-09-20

    This study introduces an "anti-adhesive force" at the interface of solid hydrate and liquid solution phases. The force was induced by the presence of hydrophobic silica nanoparticles or one of the common anti-agglomerants (AAs), sorbitan monolaurate (Span 20), at the interface. The anti-adhesive force, which is defined as the maximum pushing force that does not induce the formation of a capillary bridge between the cyclopentane (CP) hydrate particle and the aqueous solution, was measured using a microbalance. Both hydrophobic silica nanoparticles and Span 20 can inhibit adhesion between the CP hydrate probe and the aqueous phase because silica nanoparticles have an aggregative property at the interface, and Span 20 enables the hydrate surface to be wetted with oil. Adding water-soluble sodium dodecyl sulfate (SDS) to the nanoparticle system cannot affect the aggregative property or the distribution of silica nanoparticles at the interface and, thus, cannot change the anti-adhesive effect. However, the combined system of Span 20 and SDS dramatically reduces the interfacial tension: emulsion drops were formed at the interface without any energy input and were adsorbed on the CP hydrate surface, which can cause the growth of hydrate particles. Silica nanoparticles have a good anti-adhesive performance with a relatively smaller dosage and are less influenced by the presence of molecular surfactants; consequently, these nanoparticles may have a good potential for hydrate inhibition as AAs. PMID:27564571

  6. New ordered metastable phases between the gel and subgel phases in hydrated phospholipids.

    PubMed Central

    Tenchov, B; Koynova, R; Rapp, G

    2001-01-01

    Formation of low-temperature ordered gel phases in several fully hydrated phosphatidylethanolamines (PEs) and phosphatidylcholines (PCs) with saturated chains as well as in dipalmitoylphosphatidylglycerol (DPPG) was observed by synchrotron x-ray diffraction, microcalorimetry, and densitometry. The diffraction patterns recorded during slow cooling show that the gel-phase chain reflection cooperatively splits into two reflections, signaling a transformation of the usual gel phase into a more ordered phase, with an orthorhombic chain packing (the Y-transition). This transition is associated with a small decrease (2-4 microl/g) or inflection of the partial specific volume. It is fully reversible with the temperature and displays in heating direction as a small (0.1-0.7 kcal/mol) endothermic event. We recorded a Y-transition in distearoyl PE, dipalmitoyl PE (DPPE), mono and dimethylated DPPE, distearoyl PC, dipalmitoyl PC, diC(15)PC, and DPPG. No such transition exists in dimyristoyl PE and dilauroyl PE where the gel L(beta) phase transforms directly into subgel L(c) phase, as well as in the unsaturated dielaidoyl PE. The PE and PC low-temperature phases denoted L(R1) and SGII, respectively, have different hydrocarbon chain packing. The SGII phase is with tilted chains, arranged in an orthorhombic lattice of two-nearest-neighbor type. Except for the PCs, it was also registered in ionized DPPG. In the L(R1) phase, the chains are perpendicular to the bilayer plane and arranged in an orthorhombic lattice of four-nearest-neighbor type. It was observed in PEs and in protonated DPPG. The L(R1) and SGII phases are metastable phases, which may only be formed by cooling the respective gel L(beta) and L(beta') phases, and not by heating the subgel L(c) phase. Whenever present, they appear to represent an indispensable intermediate step in the formation of the latter phase. PMID:11259300

  7. Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

    SciTech Connect

    Chavda, Mehul A.; Bernal, Susan A.; Apperley, David C.; Kinoshita, Hajime; Provis, John L.

    2015-04-15

    The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

  8. Unexpected phase assemblages in inclusions with ternary H2O-salt fluids at low temperatures

    NASA Astrophysics Data System (ADS)

    Bakker, Ronald J.; Baumgartner, Miriam

    2012-06-01

    Phase assemblages and temperatures of phase changes provide important information about the bulk properties of fluid inclusions, and are typically obtained by microthermometry. Inclusions are synthesized in natural quartz containing an aqueous fluid with a composition in the ternary systems of H2O-NaCl2-CaCl2, H2O-NaCl-MgCl2, and H2O-CaCl2-MgCl2. This study reveals that these fluid inclusions may behave highly unpredictably at low temperatures due to the formation of metastable phase assemblages. Eutectic temperatures cannot be detected in most of the fluid inclusions containing these ternary systems. Nucleation of a variety of solid ice and salt-hydrate phases in single fluid inclusions is often partly inhibited. Raman spectroscopy at low temperatures provides an important tool for interpreting and understanding microthermometric experiments, and visualizing stable and metastable phase assemblages. Final dissolution temperatures of ice, salt-hydrates, and salt must be treated with care, as they can only be interpreted by purely empirical or thermodynamic models at stable conditions.

  9. The nature of carbon-bearing phases in hydrated interplanetary dust particles. [Abstract only

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Thomas, K. L.; Mckay, D. S.

    1994-01-01

    We have been quantitatively measuring C abundances in hydrated interplanetary dust particles for the past few years, but in general, we have had to infer the distribution and nature of the C-bearing materials within these particles because of the complex microtextures of hydrated IDPs. Aside from rare carbonate grains, other C-bearing phases are difficult to distinguish from the fine-grained, poorly crystalline phyllosilicates that comprise the bulk of these particles. We know that carbonates alone cannot account for the high C abundances observed in most hydrated IDPs and that additional C-bearing phases must be present. We have recently applied the technique of electron energy-loss spectroscopy (EELS) in the transmission electron microscope (TEM) to identify and form the distribution of C-bearing phases in hydrated IDPs. These preliminary data show that several C-rich hydrated IDPs contain a mixture of two major forms of C, Mg-Fe carbonate and amorphous C. The near-edge structure in the C k-edges from these IDPs shows no evidence for the development of graphite or even poorly graphitized C. We conclude that the 'elemental' C in these IDPs is either very poorly ordered or is exceedingly fine-grained (we refer to this C as 'amorphous C'). The amorphous C is intimately intergrown with the fine-grained phyllosilicates and is evenly distributed within three of the four IDPs analyzed (only G1 contains discrete 'hot spots' of amorphous C). Not all hydrated IDPs contain carbonates.

  10. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  11. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  12. Nucleation of the CO2 hydrate from three-phase contact lines.

    PubMed

    Bai, Dongsheng; Chen, Guangjin; Zhang, Xianren; Wang, Wenchuan

    2012-05-22

    Using molecular dynamics simulations on the microsecond time scale, we investigate the nucleation and growth mechanisms of CO(2) hydrates in a water/CO(2)/silica three-phase system. Our simulation results indicate that the CO(2) hydrate nucleates near the three-phase contact line rather than at the two-phase interfaces and then grows along the contact line to form an amorphous crystal. In the nucleation stage, the hydroxylated silica surface can be understand as a stabilizer to prolong the lifetime of adsorbed hydrate cages that interact with the silica surface by hydrogen bonding, and the adsorbed cages behave as the nucleation sites for the formation of an amorphous CO(2) hydrate. After nucleation, the nucleus grows along the three-phase contact line and prefers to develop toward the CO(2) phase as a result of the hydrophilic nature of the modified solid surface and the easy availability of CO(2) molecules. During the growth process, the population of sI cages in the formed amorphous crystal is found to increase much faster than that of sII cages, being in agreement with the fact that only the sI hydrate can be formed in nature for CO(2) molecules.

  13. Phase change fluids for solar thermal systems

    SciTech Connect

    Sama, D.A.; Sladek, K.J.

    1981-01-01

    This study explores the use, for storage of solar energy, of phase change materials which are suspended or emulsified in an immiscible carrier fluid. Emulsions of up to 50 weight % paraffin wax in water were found to be very fluid, highly stable, and quite flame resistant. Such easily pumped emulsions allow for an increase in stored energy density while avoiding the severe heat transfer rate problems normally encountered with phase change storage. Since the suspended phase change materials can be used both to collect and store solar energy, a heat transfer step is eliminated and the energy may be stored at a higher average temperature. This in turn results in a higher thermodynamic availability which is shown to be particularly advantageous in the storage of solar energy for refrigeration or heat pump systems. 6 refs.

  14. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals.

  15. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals. PMID:26745181

  16. 2-Phase Fluid Flow & Heat Transport

    1993-03-13

    GEOTHER is a three-dimensional, geothermal reservoir simulation code. The model describes heat transport and flow of a single component, two-phase fluid in porous media. It is based on the continuity equations for steam and water, which are reduced to two nonlinear partial differential equations in which the dependent variables are fluid pressure and enthalpy. GEOTHER can be used to simulate the fluid-thermal interaction in rock that can be approximated by a porous media representation. Itmore » can simulate heat transport and the flow of compressed water, two-phase mixtures, and superheated steam in porous media over a temperature range of 10 to 300 degrees C. In addition, it can treat the conversion from single to two-phase flow, and vice versa. It can be used for evaluation of a near repository spatial scale and a time scale of a few years to thousands of years. The model can be used to investigate temperature and fluid pressure changes in response to thermal loading by waste materials.« less

  17. Role of in situ organic matter degradation and fluid flow in the global gas hydrate distribution: application of general functions

    NASA Astrophysics Data System (ADS)

    Pinero, E.; Hensen, C.; Marquardt, M.; Haeckel, M.; Wallmann, K. J.

    2010-12-01

    During the last decades several estimates of the global gas hydrate budget have been published. The published results range by several orders of magnitude and thus, the total gas hydrate inventory is still poorly known. In order to elucidate the global gas hydrate amount we applied a recently published transfer function that calculates the amount of gas hydrate produced by in situ generated methane through organic matter degradation (Marquardt et al., accepted). The transfer function was derived from a large set of systematic runs of a numerical diagenetic model (Wallmann et al., 2006) covering a wide range of environmental conditions that are typical for the continental margins. The transfer function only includes two variables: the accumulation rate of particulate organic carbon and the thickness of the gas hydrate stability zone. We tested various approaches to calculate both parameters on the global scale. The global grids used include seafloor bathymetry, TOC input, organic rain rate, bottom water temperature, geothermal gradient estimated from heat flow, sediment thickness, and age of the oceanic crust. The results obtained lead to the conclusion that only minor amounts of gas hydrates (<10 Gt of C) are formed by in situ methane production. An extended function considering fluid flow was developed applying the same transport-reaction model. The resulting global distribution map gives a total inventory of gas hydrate ranging from 400 to 2500 Gt of C. So far, some of our calculations are slightly lower than previously published results (e.g. Archer et al., 2009) and suggest that only <2 % of the global gas hydrate budget forms from an autochthonous source of methane. The results presented here suggest that where gas does not migrate into the gas hydrate stability zone only minor negligible concentrations of gas hydrate accumulate. References: Wallmann, K., Aloisi, G. Haeckel, M., Obzhirov, A., Pavlova, G., Tishchenko, P.: Kinetics of organic matter degradation

  18. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid

    NASA Astrophysics Data System (ADS)

    Buzano, C.; de Stefanis, E.; Pretti, M.

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the “Mercedes Benz” type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster.

  19. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid.

    PubMed

    Buzano, C; De Stefanis, E; Pretti, M

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster.

  20. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid.

    PubMed

    Buzano, C; De Stefanis, E; Pretti, M

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster. PMID:16089537

  1. Dynamic fluid flow and chemical fluxes associated with a seafloor gas hydrate deposit on the northern Gulf of Mexico slope

    NASA Astrophysics Data System (ADS)

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

    2008-06-01

    Gas hydrates outcrop on the seafloor at the Bush Hill hydrocarbon seep site in the northern Gulf of Mexico. Four newly designed fluid flux meters/chemical samplers, called the MOSQUITO, were deployed for 430 days at Bush Hill to determine how dynamic subsurface fluid flow influences gas hydrate stability and to quantify the associated methane fluxes into the ocean. Three of the flux meters were deployed adjacent to an outcropping gas hydrate mound, while the fourth monitored background conditions. The flux meter measurements reveal that the subsurface hydrology in the vicinity of the mound is complex and variable with frequent changes from downward to upward flow ranging from - 161 to 273 cm/yr, and with temporal variations in the horizontal component of flow. The continuous record of fluid chemistry indicates that gas hydrate actively formed in the sediments. We propose that long periods of downward flow of seawater adjacent to gas vents (up to 4 months) are driven by local sub-pressure resulting from gas ebullition through faults and fractures due to overpressure at depth. High frequency variations in flow rates (days to weeks) are likely due to temporal changes in sediment permeability and the 3-D fluid flow field as a result of active gas hydrate and authigenic carbonate precipitation, as well as the presence of free gas. Gas hydrate formation occurred as a result of long-term emanation of CH4 at focused gas vents followed by a more diffuse intergranular methane flux. The estimated CH4 flux to the water column from focused gas vents across the Bush Hill seep is ~ 5•106 mol/yr. This significant flux suggests that Bush Hill and similar hydrocarbon seeps in the northwestern Gulf of Mexico may be important natural sources of methane to the ocean and possibly the atmosphere.

  2. Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems.

    PubMed

    Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A; Alavi, Saman; Ripmeester, John A

    2012-09-11

    There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods.

  3. Direct Measurement of the Fluid Phase Diagram.

    PubMed

    Bao, Bo; Riordon, Jason; Xu, Yi; Li, Huawei; Sinton, David

    2016-07-19

    The thermodynamic phase of a fluid (liquid, vapor or supercritical) is fundamental to all chemical processes, and the critical point is particularly important for supercritical chemical extraction. Conventional phase measurement methods require hours to obtain a single datum on the pressure and temperature diagram. Here, we present the direct measurement of the full pressure-temperature phase diagram, with 10 000 microwells. Orthogonal, linear, pressure and temperature gradients are obtained with 100 parallel microchannels (spanning the pressure range), each with 100 microwells (spanning the temperature range). The phase-mapping approach is demonstrated with both a pure substance (CO2) and a mixture (95% CO2 + 5% N2). Liquid, vapor, and supercritical regions are clearly differentiated, and the critical pressure is measured at 1.2% error with respect to the NIST standard. This approach provides over 100-fold improvement in measurement speed over conventional methods. PMID:27331613

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

    PubMed

    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.

  5. Phase behavior of an amphiphilic fluid

    NASA Astrophysics Data System (ADS)

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H. L.

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995), 10.1103/PhysRevE.52.1915]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  6. Phase behavior of an amphiphilic fluid.

    PubMed

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H L

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995)]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed. PMID:24580230

  7. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases.

    PubMed

    Dureckova, Hana; Woo, Tom K; Alavi, Saman

    2016-01-28

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br2 and Cl2 in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water-oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br2 and Cl2 clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br2 and Cl2 guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br2 and Cl2 guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase. PMID:26827220

  8. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases.

    PubMed

    Dureckova, Hana; Woo, Tom K; Alavi, Saman

    2016-01-28

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br2 and Cl2 in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water-oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br2 and Cl2 clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br2 and Cl2 guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br2 and Cl2 guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  9. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

    NASA Astrophysics Data System (ADS)

    Dureckova, Hana; Woo, Tom K.; Alavi, Saman

    2016-01-01

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br2 and Cl2 in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water-oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br2 and Cl2 clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br2 and Cl2 guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br2 and Cl2 guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  10. Pathways through equilibrated states with coexisting phases for gas hydrate formation

    DOE PAGES

    Malolepsza, Edyta; Keyes, Tom

    2015-12-01

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less

  11. Pathways through equilibrated states with coexisting phases for gas hydrate formation

    SciTech Connect

    Malolepsza, Edyta; Keyes, Tom

    2015-12-01

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces the initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.

  12. Pathways through Equilibrated States with Coexisting Phases for Gas Hydrate Formation.

    PubMed

    Małolepsza, Edyta; Keyes, Tom

    2015-12-31

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces the initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation. PMID:26624929

  13. The void in using urine concentration to assess population fluid intake adequacy or hydration status.

    PubMed

    Cheuvront, Samuel N; Muñoz, Colleen X; Kenefick, Robert W

    2016-09-01

    Urine concentration can be used to assess fluid intake adequacy or to diagnose dehydration. However, too often urine concentration is used inappropriately to draw dubious conclusions that could have harmful health and economic consequences. Inappropriate uses of urine concentration relate primarily to convenience sampling (timing) and problems related to convenience sampling (misapplication of thresholds), but a conceptual problem also exists with using urine concentration in isolation. The purpose of this Perspective article is to briefly explain the problematic nature of current practices and to offer a possible solution to improve practice with minimal added complication. When urine is used exclusively to assess fluid intake adequacy and hydration status in adults, we propose that only when urine concentration is high (>850 mmol/kg) and urine excretion rate is low (<850 mL/24 h) should suspicion of inadequate drinking or impending dehydration be considered. Prospective tests of the 850 × 850 thresholds will provide supporting evidence and/or help refine the best thresholds for men and women, young and old. PMID:27465376

  14. Methane hydrate formation in partially water-saturated Ottawa sand

    USGS Publications Warehouse

    Waite, W.F.; Winters, W.J.; Mason, D.H.

    2004-01-01

    Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

  15. Calcium silicate hydrates: Solid and liquid phase composition

    SciTech Connect

    Lothenbach, Barbara; Nonat, André

    2015-12-15

    This paper presents a review on the relationship between the composition, the structure and the solution in which calcium silicate hydrate (C–S–H) is equilibrated. The silica chain length in C–S–H increases with the silicon concentration and the calcium content in the interlayer space with the calcium concentrations. Sodium and potassium are taken up in the interlayer space, preferentially at low calcium concentrations and thus by low Ca/Si C–S–H. Aluminium uptake in C–S–H increases strongly at higher aluminium concentrations in the solution. At low Ca/Si, aluminium substitutes silica in the bridging position, at Ca/Si > 1 aluminium is bound in TAH. Recently developed thermodynamic models are closely related to the structure of C–S–H and tobermorite, and able to model not only the solubility and the chemical composition of the C–S–H, but also to predict the mean silica chain length and the uptake of aluminium.

  16. Interfacial phase transitions in conducting fluids.

    PubMed

    Freyland, Werner

    2008-02-21

    We present a review, largely based on recent experimental work of our group, on phase transitions at interfaces of fluid metals, alloys and ionic liquids. After a brief analysis of possible experimental errors and limitations of surface sensitive methods, we first deal with first-order wetting transitions at the liquid/vapour and liquid/wall interface in systems such as Ga-based alloys, K-KCl melts, and fluid Hg. The following chapter refers to surface freezing or surface induced crystallization in different metal alloys. The respective surface phase diagrams are discussed in comparison with their bulk counterpart. In the last part we present very recent investigations of ionic liquid interfaces, including order-disorder transitions at the liquid/vapour interface and examples of two-dimensional phase transitions at the electrified ionic liquid/metal interface. Finally, a simple electrowetting experiment with an ionic liquid droplet under vacuum is described which gives new insight into the contact angle saturation problem. The article ends up with a few perspective remarks on open problems and potential impact of interfacial phenomena on applied research. PMID:18259631

  17. Feasibility of using phase change materials to control the heat of hydration in massive concrete structures.

    PubMed

    Choi, Won-Chang; Khil, Bae-Soo; Chae, Young-Seok; Liang, Qi-Bo; Yun, Hyun-Do

    2014-01-01

    This paper presents experimental results that can be applied to select a possible phase change material (PCM), such as a latent heat material (LHM), to control the hydration heat in mass concrete structures. Five experimental tests (microconduction, simplified adiabatic temperature rise, heat, and compressive strength tests) were conducted to select the most desirable LHM out of seven types of inorganic PCM used in cement mortar and to determine the most suitable mix design. The results of these experimental tests were used to assess the feasibility of using PCM to reduce hydration heat in mass concrete that was examined. The experimental results show that cement mortar containing barium- [Ba(OH)2 · 8H2O] based PCM has the lowest amount of total hydration heat of the cement pastes. The barium-based PCM provides good latent heat properties that help to prevent volume change and microcracks caused by thermal stress in mass concrete.

  18. Ecological and climatic consequences of phase instability of gas hydrates on the ocean bed

    NASA Astrophysics Data System (ADS)

    Balanyuk, I.; Dmitrievsky, A.; Akivis, T.; Chaikina, O.

    2009-04-01

    energy and gas that leads to explosion. Methane is the main natural source for power engineering specialists. It is transported by pipelines, and gas hydrate is dangerous in this case too. It can block the gas pipeline system forming the so-called "trombus" of "thermal ice". After that the pipes have to be opened. The mess of this strange ice discovered melts immediately releasing methane and water vapor. The trombus formation can be prevented by the temperature increase or the pressure decrease. Both methods are very uncomfortable under the conditions the pipelines work. The better method is thorough drying up of the gas because gas hydrate obviously cannot be formed without water. Gas hydrates attract attention not only as a fuel and chemical stuff but in relation to a serious anxiety of strong ecological and climatic problems that can occur as a result of methane release to the atmosphere due to both gas hydrate deposits development and minor changes in thermodynamic conditions in the vicinity of a threshold of gas hydrate phase stability. One of the most probable causes is the global warming of the Earth due to the hothouse effect because the specific absorption of the Earth heat radiation by methane (radiation effectivity) is 21 times higher than its absorption by carbonic gas. Analysis of the air trapped by polar ice show that contemporary increase of methane concentration in the atmosphere is unexampled for the last 160 thousands of years. The sources of this increase are not clear. Observer and latent methane bursts during natural gas hydrates decomposition can be considered as a probable source. Amount of methane hided in natural gas hydrates is 3000 times higher its amount in the atmosphere. Release of this hothouse potential would have terrible consequences for the humanity. The warming can cause further gas hydrates decomposition and released methane will cause the following warming. Thus, self-accelerating process can start. The most vulnerable for the

  19. A New Approach to Modeling Densities and Equilibria of Ice and Gas Hydrate Phases

    NASA Astrophysics Data System (ADS)

    Zyvoloski, G.; Lucia, A.; Lewis, K. C.

    2011-12-01

    The Gibbs-Helmholtz Constrained (GHC) equation is a new cubic equation of state that was recently derived by Lucia (2010) and Lucia et al. (2011) by constraining the energy parameter in the Soave form of the Redlich-Kwong equation to satisfy the Gibbs-Helmholtz equation. The key attributes of the GHC equation are: 1) It is a multi-scale equation because it uses the internal energy of departure, UD, as a natural bridge between the molecular and bulk phase length scales. 2) It does not require acentric factors, volume translation, regression of parameters to experimental data, binary (kij) interaction parameters, or other forms of empirical correlations. 3) It is a predictive equation of state because it uses a database of values of UD determined from NTP Monte Carlo simulations. 4) It can readily account for differences in molecular size and shape. 5) It has been successfully applied to non-electrolyte mixtures as well as weak and strong aqueous electrolyte mixtures over wide ranges of temperature, pressure and composition to predict liquid density and phase equilibrium with up to four phases. 6) It has been extensively validated with experimental data. 7) The AAD% error between predicted and experimental liquid density is 1% while the AAD% error in phase equilibrium predictions is 2.5%. 8) It has been used successfully within the subsurface flow simulation program FEHM. In this work we describe recent extensions of the multi-scale predictive GHC equation to modeling the phase densities and equilibrium behavior of hexagonal ice and gas hydrates. In particular, we show that radial distribution functions, which can be determined by NTP Monte Carlo simulations, can be used to establish correct standard state fugacities of 1h ice and gas hydrates. From this, it is straightforward to determine both the phase density of ice or gas hydrates as well as any equilibrium involving ice and/or hydrate phases. A number of numerical results for mixtures of N2, O2, CH4, CO2, water

  20. Non-equilibrium Simulation of CO­2-hydrate Phase Transitions from Mixtures of CO2 and N2 Gases

    NASA Astrophysics Data System (ADS)

    Qorbani Nashaqi, K.

    2015-12-01

    Storage of CO2 in aquifers is one of several options for reducing the emissions of CO2 to the atmosphere. Generally this option requires sealing integrity through layers of clay or shale. Many reservoirs have regions of temperature and pressure inside hydrate formation conditions. Whether hydrate formation can provide long term extra sealing still remains unverified in view of all co-existing phases that affect hydrate stability. Yet another storage option for CO2 is in the form of hydrate through exchange of in situ CH4 hydrate. Injection of CO2 into hydrate filled sediments is challenging due to the partial filling of pores with hydrate which results in low porosity and low permeability. Formation of new hydrate from injected CO2 will enhance these problems, Mixing N2 gas with the CO2 will increase permeability and will reduce driving forces for formation of new hydrate from pore water and injection gas. Hydrate can generally not reach thermodynamic equilibrium due to Gibbs' phase rule and the combined first and second laws of thermodynamics. These thermodynamic constraints on distribution of masses over co-existing phases are dynamically coupled to local mass- and heat-transport. Reservoir simulations are one possible method for investigation of possible scenarios related to injection of CO2 with N2 into aquifers containing CH4 hydrate. In this work we have developed prevoiusly modified RetrasoCodeBrite (RCB) simulator to handle injection of CO2/N2 gas mixtures. Hydrate formation and dissociation were determined by investigating Gibbs free energy differences between hydrate and hydrate formers. Gibbs free energy differences were calculated from changes in chemical potentials, which were obtained using non-equilibrium thermodynamic approach. Further extension of RCB has been implemented in this work through adding on-the-fly thermodynamic calculations. Correspondingly, hydrate phase transitions are calculated directly inside the code as a result of super

  1. Controls on mound formation and effects of fluid ascent on the gas hydrate system of mound structures offshore Costa Rica

    NASA Astrophysics Data System (ADS)

    Planert, L.; Klaeschen, D.; Berndt, C.; Hensen, C.; Brueckmann, W.

    2010-12-01

    Our analysis of 2D MCS seismic data from the Middle America margin provides an insight into the buildup and formation mechanisms of mound structures and the effects of fluid ascent on the gas hydrate system observed on the continental slope offshore Costa Rica. Our targets, Mounds 11&12, are the sites of IODP drilling proposal 633-Full2, which aims to enhance the general understanding of complex forearc dewatering processes of the erosive subduction system off Costa Rica. Major sites of dewatering planned for drilling are mounds, related to mud diapirism/volcanism and precipitation of authigenic carbonates, and large-scale slides related to the subduction of seamounts. Geochemical analysis of methane hydrate and chloride anomalies as well as heat flow modeling of the mounds indicate deeply sourced fluids discharged by clay dehydration at the decollement. Hence, the hydrogeological system at this margin appears to be dominated by the fracture porosity of faults which extend through the overriding plate and provide the paths for fluids liberated by early dehydration reactions from the plate boundary. In order to test the hypothesis of deeply sourced and fault-controlled dewatering sites and to better understand the interactions between gas hydrate formation and dissociation with the fluid ascent from the deep sources, new pre-site survey seismic profiles were acquired using the 36-gun, four-string linear gun array of R/V Marcus Langseth, and a 240 channel streamer with 3000 m of active length. The seismic lines were prestack depth migrated, in which the velocity model is iteratively improved using depth focusing analysis and residual moveout correction on common image point gathers. Improvement of the deep imaging involved multiple attenuation and detailed velocity analysis of the lower sedimentary portions and beneath the basement down to the plate boundary. Our results reveal an upward bending of the bottom simulating reflection (BSR) directly beneath the mounds

  2. Phase equilibria for complex fluid mixtures

    SciTech Connect

    Prausnitz, J.M.

    1983-04-01

    After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.

  3. Note: A simple correlation to locate the three phase coexistence line in methane-hydrate simulations

    NASA Astrophysics Data System (ADS)

    Conde, M. M.; Vega, C.

    2013-02-01

    In this Note, the three phases coexistence (hydrate-water-methane) temperature is determined by using direct coexistence simulations for a force field in which methane is described by a single Lennard-Jones site, and water is described by either SPC or SPC/E models. Results were obtained for two pressures: 100 and 400 bars. The results of this note along with those obtained in our previous work [M. M. Conde and C. Vega, J. Chem. Phys. 133, 064507 (2010)], 10.1063/1.3466751 allow to present the three phases coexistence line for a number of water models: SPC, SPC/E, TIP4P, TIP4P/2005, and TIP4P/Ice. A correlation between the three phases coexistence temperature T3 of the methane hydrate and the melting point of ice at normal pressure Tm of the water model is found. Models with a good prediction of the melting temperature of ice Ih, have also good predictions of the three phases coexistence line. Models with a bad prediction of the melting temperature of ice Ih, provide poor estimates of T3. As a rule of thumb, the three phase coexistence line of the methane hydrate at 100 bars for a water-methane force field is located approximately at about 15(7) K above the melting temperature of ice Ih of the considered water model. In summary, when modeling the methane-hydrate, if you are looking for a three phases coexistence line in good agreement with experiment, you need first a water model that describes accurately the melting temperature of ice Ih.

  4. Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

    USGS Publications Warehouse

    Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

    2001-01-01

    A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

  5. Stable isotopic (O, H) evidence for hydration of the central Colorado Plateau lithospheric mantle by slab-derived fluids

    NASA Astrophysics Data System (ADS)

    Marshall, E. W.; Barnes, J.; Lassiter, J. C.

    2013-12-01

    The Colorado Plateau is a tectonically stable, relatively undeformed Proterozoic lithospheric province in the North America Cordillera. Although the stability of the Colorado Plateau suggests that it is rheologically strong, evidence from xenoliths show that the lithospheric mantle is extensively hydrated (e.g., presence of hydrous minerals, 'high' water contents in nominally anhydrous minerals), and therefore weakened. In addition, LREE enrichments in clinopyroxene (cpx) imply that the lithospheric mantle has been metasomatized ([1],[2]). Here we analyze mineral separates from spinel and garnet peridotite xenoliths from the Navajo Volcanic Field (NVF), located in the center of the Plateau, for their oxygen and hydrogen isotope compositions. These compositions are compared to those of xenoliths at the margins of the Plateau: spinel peridotites from the Grand Canyon Volcanic Field (GCVF) in the west and Zuni-Bandera Volcanic Field (ZBVF) in the east. NVF xenoliths are significantly more hydrous than the xenoliths on the margins of the Colorado Plateau based on modal abundances of hydrous minerals and structural water in olivine (e.g. [3]). All hydrous phases have high δD values (antigorite = -71 to -46‰ (n = 6 xenoliths); chlorite = -49 to -31‰ (n=3); amphibole = -47‰ (n=1)) compared to normal mantle (~-80‰), suggesting the addition of a fluid that is enriched in D compared to typical mantle. δ18O values for the same hydrous minerals range from 6.0 to 6.6‰ (n=6). δ18O values of olivine from NVF spinel peridotites have a narrow range, 5.0 to 5.4‰ (n = 4), near mantle olivine values (~5.2‰). Olivines from spinel peridotites from the GCVF and ZBVF also have mantle-like δ18O values (5.1 to 5.2‰ (n=3) and 5.1 to 5.4‰ (n=7), respectively). However, olivines and orthopyroxenes (opx) from NVF garnet peridotites have a slightly larger range and some record 18O enrichment (olivine = 5.1 to 5.6‰ (n = 3); opx = 5.9‰ (n=1)). The high δ18O values of

  6. Effects of vitrified and nonvitrified sugars on phosphatidylcholine fluid-to-gel phase transitions.

    PubMed Central

    Koster, K L; Lei, Y P; Anderson, M; Martin, S; Bryant, G

    2000-01-01

    DSC was used to study the ability of glass-forming sugars to affect the gel-to-fluid phase transition temperature, T(m), of several phosphatidylcholines during dehydration. In the absence of sugars, T(m) increased as the lipid dried. Sugars diminished this increase, an effect we explain using the osmotic and volumetric properties of sugars. Sugars vitrifying around fluid phase lipids lowered T(m) below the transition temperature of the fully hydrated lipid, T(o). The extent to which T(m) was lowered below T(o) ranged from 12 degrees to 57 degrees, depending on the lipids' acyl chain composition. Sugars vitrifying around gel phase lipids raised T(m) during the first heating scan in the calorimeter, then lowered it below T(o) in subsequent scans of the sample. Ultrasound measurements of the mechanical properties of a typical sugar-glass indicate that it is sufficiently rigid to hinder the lipid gel-to-fluid transition. The effects of vitrification on T(m) are explained using the two-dimensional Clausius-Clapeyron equation to model the mechanical stress in the lipid bilayer imposed by the glassy matrix. Dextran and polyvinylpyrrolidone (PVP) also vitrified but did not depress T(m) during drying. Hydration data suggest that the large molecular volumes of these polymers caused their exclusion from the interbilayer space during drying. PMID:10733972

  7. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    SciTech Connect

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

    2015-05-21

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

  8. Phase changes of filled ice Ih methane hydrate under low temperature and high pressure.

    PubMed

    Tanaka, Takehiko; Hirai, Hisako; Matsuoka, Takahiro; Ohishi, Yasuo; Yagi, Takehiko; Ohtake, Michika; Yamamoto, Yoshitaka; Nakano, Satoshi; Irifune, Tetsuo

    2013-09-14

    Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under 2.0-77.0 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ X-ray diffractometry revealed distinct changes in the compressibility of the axial ratios of the host framework with pressure. Raman spectroscopy showed a split in the C-H vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the compressibility change. The results indicate the following: (i) the orientational ordering of the guest methane molecules from an orientationally disordered state occurred at high pressures and low temperatures; and (ii) this guest ordering led to anisotropic contraction in the host framework. Such guest orientational ordering and subsequent anisotropic contraction of the host framework were similar to that reported previously for filled ice Ic hydrogen hydrate. Since phases with different guest-ordering manners were regarded as different phases, existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray study. In addition, above the pressure of the guest-ordered phase, another high-pressure phase developed in the low-temperature region. The deuterated-water host samples were also examined, and the influence of isotopic effects on guest ordering and phase transformation was observed.

  9. Phase behavior and 13C NMR spectroscopic analysis of the mixed methane + ethane + propane hydrates in mesoporous silica gels.

    PubMed

    Lee, Seungmin; Cha, Inuk; Seo, Yongwon

    2010-11-25

    In this study, the phase behavior and quantitative determination of hydrate composition and cage occupancy for the mixed CH(4) + C(2)H(6) + C(3)H(8) hydrates were closely investigated through the experimental measurement of three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria and (13)C NMR spectra. To examine the effect of pore size and salinity, we measured hydrate phase equilibria for the quaternary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + water mixtures in silica gel pores of nominal diameters of 6.0, 15.0, and 30.0 nm and for the quinary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt %) in silica gel pores of a nominal 30.0 nm diameter. The value of hydrate-water interfacial tension for the CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) hydrate was found to be 47 ± 4 mJ/m(2) from the relation of the dissociation temperature depression with the pore size of silica gels at a given pressure. At a specified temperature, three-phase H-L(W)-V equilibrium curves of pore hydrates were shifted to higher pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent (13)C NMR chemical shifts of enclathrated guest molecules, the mixed CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) gas hydrate was confirmed to be structure II. The cage occupancies of each guest molecule and the hydration number of the mixed gas hydrates were also estimated from the (13)C NMR spectra.

  10. A comparison of hydration effect on body fluid and temperature regulation between Malaysian and Japanese males exercising at mild dehydration in humid heat

    PubMed Central

    2014-01-01

    Background This study investigated the effect of hydration differences on body fluid and temperature regulation between tropical and temperate indigenes exercising in the heat. Methods Ten Japanese and ten Malaysian males with matched physical characteristics (height, body weight, and peak oxygen consumption) participated in this study. Participants performed exercise for 60 min at 55% peak oxygen uptake followed by a 30-min recovery at 32°C and 70% relative air humidity with hydration (4 times each, 3 mL per kg body weight, 37°C) or without hydration. Rectal temperature, skin temperature, heart rate, skin blood flow, and blood pressure were measured continuously. The percentage of body weight loss and total sweat loss were calculated from body weight measurements. The percentage change in plasma volume was estimated from hemoglobin concentration and hematocrit. Results Malaysian participants had a significantly lower rectal temperature, a smaller reduction in plasma volume, and a lower heart rate in the hydrated condition than in the non-hydrated condition at the end of exercise (P <0.05), whereas Japanese participants showed no difference between the two hydration conditions. Hydration induced a greater total sweat loss in both groups (P <0.05), and the percentage of body weight loss in hydrated Malaysians was significantly less than in hydrated Japanese (P <0.05). A significant interaction between groups and hydration conditions was observed for the percentage of mean cutaneous vascular conductance during exercise relative to baseline (P <0.05). Conclusions The smaller reduction in plasma volume and percentage body weight loss in hydrated Malaysians indicated an advantage in body fluid regulation. This may enable Malaysians to reserve more blood for circulation and heat dissipation and thereby maintain lower rectal temperatures in a hydrated condition. PMID:24490869

  11. Changes in hydration status of elite Olympic class sailors in different climates and the effects of different fluid replacement beverages

    PubMed Central

    2013-01-01

    Background Olympic class sailing poses physiological challenges similar to other endurance sports such as cycling or running, with sport specific challenges of limited access to nutrition and hydration during competition. As changes in hydration status can impair sports performance, examining fluid consumption patterns and fluid/electrolyte requirements of Olympic class sailors is necessary to develop specific recommendations for these elite athletes. The purpose of this study was to examine if Olympic class sailors could maintain hydration status with self-regulated fluid consumption in cold conditions and the effect of fixed fluid intake on hydration status in warm conditions. Methods In our cold condition study (CCS), 11 elite Olympic class sailors were provided ad libitum access to three different drinks. Crystal Light (control, C); Gatorade (experimental control, G); and customized sailing-specific Infinit (experimental, IN) (1.0:0.22 CHO:PRO), were provided on three separate training days in cold 7.1°C [4.2 – 11.3]. Our warm condition study (WCS) examined the effect of fixed fluid intake (11.5 mL.kg.-1.h-1) of C, G and heat-specific experimental Infinit (INW)(1.0:0.074 CHO:PRO) on the hydration status of eight elite Olympic Laser class sailors in 19.5°C [17.0 - 23.3]. Both studies used a completely random design. Results In CCS, participants consumed 802 ± 91, 924 ± 137 and 707 ± 152 mL of fluid in each group respectively. This did not change urine specific gravity, but did lead to a main effect for time for body mass (p < 0.001), blood sodium, potassium and chloride with all groups lower post-training (p < 0.05). In WCS, fixed fluid intake increased participant’s body mass post-training in all groups (p < 0.01) and decreased urine specific gravity post-training (p < 0.01). There was a main effect for time for blood sodium, potassium and chloride concentration, with lower values observed post-training (p < 0.05). C

  12. Hydration status and fluid and sodium balance in elite Canadian junior women's soccer players in a cool environment.

    PubMed

    Gibson, Jennifer C; Stuart-Hill, Lynneth A; Pethick, Wendy; Gaul, Catherine A

    2012-10-01

    Dehydration can impair mental and on-field performance in soccer athletes; however, there is little data available from the female adolescent player. There is a lack of research investigating fluid and electrolyte losses in cool temperatures. Therefore, the purpose of this study was to investigate the pretraining hydration status, fluid balance, and sweat sodium loss in 34 female Canadian junior elite soccer athletes (mean age ± SD, 15.7 ± 0.7 years) in a cool environment. Data were collected during two 90 min on-field training sessions (9.8 ± 3.3 °C, 63% ± 12% relative humidity). Prepractice urine specific gravity (USG), sweat loss (pre- and post-training body mass), and sweat sodium concentration (regional sweat patch method) were measured at each session. Paired t tests were used to identify significant differences between training sessions and Pearson's product moment correlation analysis was used to assess any relationships between selected variables (p ≤ 0.05). We found that 45% of players presented to practice in a hypohydrated state (USG > 1.020). Mean percent body mass loss was 0.84% ± 0.07% and sweat loss was 0.69 ± 0.54 L. Although available during each training session, fluid intake was low (63.6% of players consumed <250 mL). Mean sweat sodium concentration was 48 ± 12 mmol·L⁻¹. Despite low sweat and moderate sodium losses, players did not drink enough to avoid mild fluid and sodium deficits during training. The findings from this study highlights the individual variations that occur in hydration management in athletes and thus the need for personalized hydration guidelines.

  13. The infrared spectrum of ammonia hydrate - Explanation for a reported ammonia phase

    NASA Technical Reports Server (NTRS)

    Still, G.; Fink, U.; Ferraro, J. R.

    1981-01-01

    A number of anomalous spectra of solid NH3 deposited from the vapor phase have appeared in the literature. These spectra have been ascribed to a new phase of NH3. In the experiment reported here these anomalous spectra were reproduced by depositing a thin film from a mixture of gaseous NH3 and H2O and annealing this film at a temperature of 162 K. The thin film spectra showed excellent agreement with recent data on NH3.H2O. The anomalous 'NH3' spectra are, therefore, seen to be caused by H2O contamination of solid NH3 with formation of NH3 hydrate.

  14. Phase transitions in fluids and biological systems

    NASA Astrophysics Data System (ADS)

    Sipos, Maksim

    In this thesis, I consider systems from two seemingly different fields: fluid dynamics and microbial ecology. In these systems, the unifying features are the existences of global non-equilibrium steady states. I consider generic and statistical models for transitions between these global states, and I relate the model results with experimental data. A theme of this thesis is that these rather simple, minimal models are able to capture a lot of functional detail about complex dynamical systems. In Part I, I consider the transition between laminar and turbulent flow. I find that quantitative and qualitative features of pipe flow experiments, the superexponential lifetime and the splitting of turbulent puffs, and the growth rate of turbulent slugs, can all be explained by a coarse-grained, phenomenological model in the directed percolation universality class. To relate this critical phenomena approach closer to the fluid dynamics, I consider the transition to turbulence in the Burgers equation, a simplified model for Navier-Stokes equations. Via a transformation to a model of directed polymers in a random medium, I find that the transition to Burgers turbulence may also be in the directed percolation universality class. This evidence implies that the turbulent-to-laminar transition is statistical in nature and does not depend on details of the Navier-Stokes equations describing the fluid flow. In Part II, I consider the disparate subject of microbial ecology where the complex interactions within microbial ecosystems produce observable patterns in microbe abundance, diversity and genotype. In order to be able to study these patterns, I develop a bioinformatics pipeline to multiply align and quickly cluster large microbial metagenomics datasets. I also develop a novel metric that quantifies the degree of interactions underlying the assembly of a microbial ecosystem, particularly the transition between neutral (random) and niche (deterministic) assembly. I apply this

  15. Controlled-source electromagnetic and seismic delineation of sub-seafloor fluid flow structures in a gas hydrate province, offshore Norway

    NASA Astrophysics Data System (ADS)

    Attias, Eric; Weitemeyer, Karen; Minshull, Tim A.; Best, Angus I.; Sinha, Martin; Jegen-Kulcsar, Marion; Hölz, Sebastian; Berndt, Christian

    2016-05-01

    Deep sea pockmarks underlain by chimney-like or pipe structures that contain methane hydrate are abundant along the Norwegian continental margin. In such hydrate provinces the interaction between hydrate formation and fluid flow has significance for benthic ecosystems and possibly climate change. The Nyegga region, situated on the western Norwegian continental slope, is characterized by an extensive pockmark field known to accommodate substantial methane gas hydrate deposits. The aim of this study is to detect and delineate both the gas hydrate and free gas reservoirs at one of Nyegga's pockmarks. In 2012, a marine controlled-source electromagnetic (CSEM) survey was performed at a pockmark in this region, where high-resolution three-dimensional seismic data were previously collected in 2006. Two-dimensional CSEM inversions were computed using the data acquired by ocean bottom electrical field receivers. Our results, derived from unconstrained and seismically constrained CSEM inversions, suggest the presence of two distinctive resistivity anomalies beneath the pockmark: a shallow vertical anomaly at the underlying pipe structure, likely due to gas hydrate accumulation, and a laterally extensive anomaly attributed to a free gas zone below the base of the gas hydrate stability zone. This work contributes to a robust characterization of gas hydrate deposits within sub-seafloor fluid flow pipe structures.

  16. Multiscale approach to CO2 hydrate formation in aqueous solution: phase field theory and molecular dynamics. Nucleation and growth.

    PubMed

    Tegze, György; Pusztai, Tamás; Tóth, Gyula; Gránásy, László; Svandal, Atle; Buanes, Trygve; Kuznetsova, Tatyana; Kvamme, Bjorn

    2006-06-21

    A phase field theory with model parameters evaluated from atomistic simulations/experiments is applied to predict the nucleation and growth rates of solid CO(2) hydrate in aqueous solutions under conditions typical to underwater natural gas hydrate reservoirs. It is shown that under practical conditions a homogeneous nucleation of the hydrate phase can be ruled out. The growth rate of CO(2) hydrate dendrites has been determined from phase field simulations as a function of composition while using a physical interface thickness (0.85+/-0.07 nm) evaluated from molecular dynamics simulations. The growth rate extrapolated to realistic supersaturations is about three orders of magnitude larger than the respective experimental observation. A possible origin of the discrepancy is discussed. It is suggested that a kinetic barrier reflecting the difficulties in building the complex crystal structure is the most probable source of the deviations.

  17. Evidence of focused fluid flow associated to the gas hydrate wedge on the angolan margin

    NASA Astrophysics Data System (ADS)

    Casenave, Viviane; Imbert, Patrice; Gay, Aurélien

    2013-04-01

    , in present-day water depth ranging from 750 to 850 m. These buried depressions cover a stripe in that depth range all over the area covered by the 3D seismic data. These two observations, made both on the seafloor and on it subsurface, seem to correspond to the same phenomenon of fluid expulsion, for the views of the seismic morphology similarities, but in different periods. It is interpreted as a result of a downward migration of the BSR, because of the last sea-level rise, which would have meant an upslope migration of the intersection of the BSR with the seafloor. Based on the evidence of gas hydrate dissociation phenomenon in the Lower Congo Basin, the pinch-out of the BSR may be considered as a natural laboratory for investigating a possible massive greenhouse gas release due to global warming.

  18. Prediction of phase equilibrium and hydration free energy of carboxylic acids by Monte Carlo simulations.

    PubMed

    Ferrando, Nicolas; Gedik, Ibrahim; Lachet, Véronique; Pigeon, Laurent; Lugo, Rafael

    2013-06-13

    In this work, a new transferable united-atom force field has been developed to predict phase equilibrium and hydration free energy of carboxylic acids. To take advantage of the transferability of the AUA4 force field, all Lennard-Jones parameters of groups involved in the carboxylic acid chemical function are reused from previous parametrizations of this force field. Only a unique set of partial electrostatic charges is proposed to reproduce the experimental gas phase dipole moment, saturated liquid densities and vapor pressures. Phase equilibrium properties of various pure carboxylic acids (acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid) and one diacid (1,5-pentanedioic) are studied through Monte Carlo simulations in the Gibbs ensemble. A good accuracy is obtained for pure compound saturated liquid densities and vapor pressures (average deviation of 2% and 6%, respectively), as well as for critical points. The vaporization enthalpy is, however, poorly predicted for short acids, probably due to a limitation of the force field to correctly describe the significant dimerization in the vapor phase. Pressure-composition diagrams for two binary mixtures (acetic acid + n-butane and propanoic acid + pentanoic acid) are also computed with a good accuracy, showing the transferability of the proposed force field to mixtures. Hydration free energies are calculated for three carboxylic acids using thermodynamic integration. A systematic overestimation of around 10 kJ/mol is observed compared to experimental data. This new force field parametrized only on saturated equilibrium properties appears insufficient to reach an acceptable precision for this property, and only relative hydration free energies between two carboxylic acids can be correctly predicted. This highlights the limitation of the transferability feature of force fields to properties not included in the parametrization database.

  19. Prediction of phase equilibrium and hydration free energy of carboxylic acids by Monte Carlo simulations.

    PubMed

    Ferrando, Nicolas; Gedik, Ibrahim; Lachet, Véronique; Pigeon, Laurent; Lugo, Rafael

    2013-06-13

    In this work, a new transferable united-atom force field has been developed to predict phase equilibrium and hydration free energy of carboxylic acids. To take advantage of the transferability of the AUA4 force field, all Lennard-Jones parameters of groups involved in the carboxylic acid chemical function are reused from previous parametrizations of this force field. Only a unique set of partial electrostatic charges is proposed to reproduce the experimental gas phase dipole moment, saturated liquid densities and vapor pressures. Phase equilibrium properties of various pure carboxylic acids (acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid) and one diacid (1,5-pentanedioic) are studied through Monte Carlo simulations in the Gibbs ensemble. A good accuracy is obtained for pure compound saturated liquid densities and vapor pressures (average deviation of 2% and 6%, respectively), as well as for critical points. The vaporization enthalpy is, however, poorly predicted for short acids, probably due to a limitation of the force field to correctly describe the significant dimerization in the vapor phase. Pressure-composition diagrams for two binary mixtures (acetic acid + n-butane and propanoic acid + pentanoic acid) are also computed with a good accuracy, showing the transferability of the proposed force field to mixtures. Hydration free energies are calculated for three carboxylic acids using thermodynamic integration. A systematic overestimation of around 10 kJ/mol is observed compared to experimental data. This new force field parametrized only on saturated equilibrium properties appears insufficient to reach an acceptable precision for this property, and only relative hydration free energies between two carboxylic acids can be correctly predicted. This highlights the limitation of the transferability feature of force fields to properties not included in the parametrization database. PMID:23697338

  20. Evidence for phase separation during the crystallization of hyperquenched glassy clathrate hydrate forming solutions

    NASA Astrophysics Data System (ADS)

    Tulk, C. A.; Ba, Y.; Klug, D. D.; McLaurin, G.; Ripmeester, J. A.

    1999-04-01

    Tetrahydrofuran, a water-soluble cyclic ether molecule, is well known for its ability to form clathrate hydrates (cubic structure II, melting point 277.5 K). An aqueous solution of THF (17:1 molecular ratio) was hyperquenched (cooled at a rate of 106Ks-1) to 77 K to give recoverable samples of ˜1 g of metastable amorphous material. The crystallization process was studied on three complementary length scales by x-ray powder diffraction, quadrupole echo double resonance (QEDOR) NMR spectroscopy, and Raman spectroscopy as the amorphous material was annealed at temperatures between 80 and 190 K. Results show that phase separation of the two components occurred predominantly during the annealing process, resulting in clusters of crystalline THF and ice Ic before clathrate hydrate crystallization was initiated. During the hyperquenching process, the decreasing molecular mobility of water molecules between room temperature and the fictive temperature (the temperature below which the solution becomes structurally immobilized upon hyperquenching) inhibits growth of the crystal nuclei that normally would result in crystalline clathrate hydrate formation. Annealing the samples between 110-140 K showed that the local hydrogen bonded O-H--O structure of the water molecules changed toward the arrangement characteristic of crystalline ice Ic. We propose that this process forces the THF out of the glassy solution, thus increasing the THF cluster size in the deposit so that these become visible to diffraction. Further annealing, above 150-160 K caused large-scale growth of crystalline clathrate hydrate material, which then could be associated with a reduction in the THF cluster size, and ice Ic.

  1. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces. Copyright 2009 by the American Geophysical Union.

  2. Application of the cell potential method to predict phase equilibria of multicomponent gas hydrate systems.

    PubMed

    Anderson, Brian J; Bazant, Martin Z; Tester, Jefferson W; Trout, Bernhardt L

    2005-04-28

    We present the application of a mathematical method reported earlier by which the van der Waals-Platteeuw statistical mechanical model with the Lennard-Jones and Devonshire approximation can be posed as an integral equation with the unknown function being the intermolecular potential between the guest molecules and the host molecules. This method allows us to solve for the potential directly for hydrates for which the Langmuir constants are computed, either from experimental data or from ab initio data. Given the assumptions made in the van der Waals-Platteeuw model with the spherical-cell approximation, there are an infinite number of solutions; however, the only solution without cusps is a unique central-well solution in which the potential is at a finite minimum at the center to the cage. From this central-well solution, we have found the potential well depths and volumes of negative energy for 16 single-component hydrate systems: ethane (C2H6), cyclopropane (C3H6), methane (CH4), argon (Ar), and chlorodifluoromethane (R-22) in structure I; and ethane (C2H6), cyclopropane (C3H6), propane (C3H8), isobutane (C4H10), methane (CH4), argon (Ar), trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), bromotrifluoromethane (R-13B1), chloroform (CHCl3), and 1,1,1,2-tetrafluoroethane (R-134a) in structure II. This method and the calculated cell potentials were validated by predicting existing mixed hydrate phase equilibrium data without any fitting parameters and calculating mixture phase diagrams for methane, ethane, isobutane, and cyclopropane mixtures. Several structural transitions that have been determined experimentally as well as some structural transitions that have not been examined experimentally were also predicted. In the methane-cyclopropane hydrate system, a structural transition from structure I to structure II and back to structure I is predicted to occur outside of the known structure II range for the cyclopropane hydrate. Quintuple (L

  3. Entropic description of gas hydrate ice/liquid equilibrium via enhanced sampling of coexisting phases

    SciTech Connect

    Malolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-04-28

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid/liquid equilibrium is of interest. However, aqueous crystal/liquid transitions are very difficult to simulate. A new MD algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. Furthermore, with replicas spanning the range between β ice and liquid water we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  4. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

    NASA Astrophysics Data System (ADS)

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized N P T ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  5. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases.

    PubMed

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions. PMID:25978217

  6. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  7. Measurement of the density of a two-phase fluid

    SciTech Connect

    Sreepada, S.R.; Rippel, R.R.

    1992-05-05

    This patent describes an apparatus for measuring the average density of an essentially transparent, dispersed two-phase fluid having a dispersed phase made up of essentially transparent bubbles, droplets, or particles that have smooth, rounded surfaces. It comprises: a source which produces a collimated beam that has a diameter no larger than 1% of the diameter of the bubbles, droplets, or particles of the dispersed phase; a diffraction grating, to which the collimated beam is directed; means for isolating a single-order component of the diffracted beam and directing it through the dispersed two-phase fluid; containing means for the dispersed two-phase fluid that allows the single-order component of the diffracted beam to pass through, and measuring means for determining the refraction of the beam by the dispersed two-phase fluid.

  8. Fluid, electrolyte, and renal indices of hydration during 11 days of controlled caffeine consumption.

    PubMed

    Armstrong, Lawrence E; Pumerantz, Amy C; Roti, Melissa W; Judelson, Daniel A; Watson, Greig; Dias, Joao C; Sokmen, Bulent; Casa, Douglas J; Maresh, Carl M; Lieberman, Harris; Kellogg, Mark

    2005-06-01

    This investigation determined if 3 levels of controlled caffeine consumption affected fluid-electrolyte balance and renal function differently. Healthy males (mean +/- standard deviation; age, 21.6 +/- 3.3 y) consumed 3 mg caffeine . kg(-1) . d(-1). on days 1 to 6 (equilibration phase). On days 7 to 11 (treatment phase), subjects consumed either 0 mg (C0; placebo; n= 20), 3 mg (C3; n = 20), or 6 mg (C6; n = 19) caffeine . kg(-1) . d(-1) in capsules, with no other dietary caffeine intake. The following variables were unaffected (P > 0.05) by different caffeine doses on days 1, 3, 6, 9, and 11 and were within normal clinical ranges: body mass, urine osmolality, urine specific gravity, urine color, 24-h urine volume, 24-h Na+ and K+ excretion, 24-h creatinine, blood urea nitrogen, serum Na+ and K+, serum osmolality, hematocrit, and total plasma protein. Therefore, C0, C3, and C6 exhibited no evidence of hypohydration. These findings question the widely accepted notion that caffeine consumption acts chronically as a diuretic. PMID:16131696

  9. Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

    PubMed

    Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2016-09-14

    Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined. PMID:27507133

  10. Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

    PubMed

    Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2016-09-14

    Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined.

  11. Concentration selective hydration and phase states of hydroxyethyl cellulose (HEC) in aqueous solutions.

    PubMed

    Arfin, Najmul; Bohidar, H B

    2012-04-01

    Solution behaviour of hydroxyethyl cellulose (HEC) is reported in the polymer concentration range spanning over two decades (c=0.002-5% (w/v)). The results conclude the following: (i) dilute solution regime prevailed for c<0.2% (w/v), flexible HEC fibres of typical length ≈ 1 μm and persistence length ≈ 10 nm were found here, (ii) for 0.2phase comprising soluble aggregates of hydrated HEC fibrils were observed with the material exhibiting viscoelastic behaviour and (iii) when 1hydration of HEC fibres in the aforesaid concentration regimes. Cole-Cole plots revealed phase homogeneity and miscibility was limited to concentrations less than ~2% (w/v). For higher polymer concentrations, strong fibre-fibre interactions prevailed and samples became heterogeneous.

  12. The reaction of CF2Cl2 with gas-phase hydrated electrons.

    PubMed

    Lengyel, Jozef; van der Linde, Christian; Fárník, Michal; Beyer, Martin K

    2016-09-14

    The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)n(-) (n = 30-86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF2Cl2, forming (H2O)mCl(-) with a rate constant of (8.6 ± 2.2) × 10(-10) cm(3) s(-1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔHr(CF2Cl2, 298 K) = -208 ± 41 kJ mol(-1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C-Cl bond dissociation enthalpy (BDE) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.

  13. The reaction of CF2Cl2 with gas-phase hydrated electrons.

    PubMed

    Lengyel, Jozef; van der Linde, Christian; Fárník, Michal; Beyer, Martin K

    2016-09-14

    The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)n(-) (n = 30-86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF2Cl2, forming (H2O)mCl(-) with a rate constant of (8.6 ± 2.2) × 10(-10) cm(3) s(-1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔHr(CF2Cl2, 298 K) = -208 ± 41 kJ mol(-1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C-Cl bond dissociation enthalpy (BDE) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs. PMID:27523883

  14. Phase equilibria of carbon dioxide hydrate system in the presence of sucrose, glucose, and fructose

    SciTech Connect

    Chun, M.K.; Lee, H.

    1999-09-01

    The three-phase (H-L{sub w}-V) equilibria of the carbon dioxide hydrate formation system in aqueous solutions containing sucrose, glucose, and fructose were experimentally determined at pressures ranging from 1.580 to 4.355 MPa and at temperatures between 273.6 and 281.7 K. The upper quadruple points (H-L{sub w}-L{sub CO{sub 2}}-V) were also measured at concentrations of 10, 20, and 30 mass % sucrose, glucose, and fructose. The addition of carbohydrates exhibited a similar inhibition effect as that observed for electrolytes and alcohols. A thermodynamic model predicting the three- and four-phase hydrate equilibria while accounting for the inhibition effect of carbohydrates was developed on the basis of the van der Waals-Platteeuw model and the Redlich-Kwong-Soave equation of state with a modified version of the Huron-Vidal mixing rule. The calculated results were found to be in good agreement with the experimental data.

  15. Full quantitative phase analysis of hydrated lime using the Rietveld method

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2012-09-15

    Full quantitative phase analysis (FQPA) using X-ray powder diffraction and Rietveld refinements is a well-established method for the characterization of various hydraulic binders such as Portland cement and hydraulic limes. In this paper, the Rietveld method is applied to hydrated lime, a non-hydraulic traditional binder. The potential presence of an amorphous phase in this material is generally ignored. Both synchrotron radiation and a conventional X-ray source were used for data collection. The applicability of the developed control file for the Rietveld refinements was investigated using samples spiked with glass. The results were cross-checked by other independent methods such as thermal and chemical analyses. The sample microstructure was observed by transmission electron microscopy. It was found that the consistency between the different methods was satisfactory, supporting the validity of FQPA for this material. For the samples studied in this work, the amount of amorphous material was in the range 2-15 wt.%.

  16. Natural Methane and Carbon Dioxide Hydrates in the Earth System

    NASA Astrophysics Data System (ADS)

    Research Team; Milkereit, B.

    2004-05-01

    Both CH4 and CO2 are abundant volatiles in the earth's crust. Methane hydrates occur in permafrost regions and continental slopes of oceans. It is currently estimated that the energy stored in CH4 hydrate reserves totals more than twice the global reserves of all conventional oil, gas, and coal deposits combined. This means that methane hydrate could prove to be a very important source of energy in the future. Pressure versus temperature phase diagrams for methane and carbon dioxide define characteristic stability fields for gas, fluid and hydrates states. Sequestration of carbon dioxide in the earths crust and production of methane hydrate reservoirs are critically dependent on knowledge of the in situ elastic moduli of natural hydrates. The physical properties of simple methane and carbon dioxide hydrates are similar [1]. Our compilation of experimental data confirms high compressional wave velocities and elastic moduli for CH4 and CO2 hydrates and low compressional wave velocities for the fluid and gas phases. As methane and carbon dioxide hydrates are stable over similar pressure-temperature ranges, the two types of hydrates form in similar settings in the earth's crust. For example, temperature and pressure conditions in deepwater marine environments require both CO2 and CH4 to be in hydrate phase. However, not much is known about the origin, distribution and total volume of natural carbon dioxide hydrates stored in the earth's crust. For a number of tectonic/geological settings, CO2-rich fluids from deep crustal reservoirs must be considered: rifted margins, volcanic arcs, deepwater vents [2], mud volcanoes and mud diapirs [3]. Both methane and carbon dioxide hydrates work to cement sea floors in similar ways. Slope failure, a phenomenon usually taken as a hallmark of the presence of methane hydrate, could also be attributed to the existence of carbon dioxide hydrates. Perhaps most critically, many of the estimations of the amounts of methane hydrates are

  17. Phase behaviour and thermoelastic properties of ammonia hydrate and ice polymorphs from 0 - 2 GPa

    NASA Astrophysics Data System (ADS)

    Fortes, A. D.; Wood, I. G.; Vocadlo, L.

    2008-12-01

    Ammonia remains amongst the most plausible planetary "antifreeze" agents, and its physical properties in hydrate compounds under the appropriate conditions (roughly 0 - 5 GPa, 100 - 300 K) must be known in order for it to be accommodated in planetary models. The pressure melting curve, and the expected polymorphism of the stoichiometric ammonia hydrates have implications for the internal structure of large icy moons like Titan, leading to phase layering and the possible persistence of deep subsurface oceans, the latter being sites of high astrobiological potential. Aqueous ammonia is also a candidate substance involved in cryomagmatism on Titan, and again the melting behaviour, and densities of liquids and solids, in the ammonia-water system must be known to model properly the partial melting and propagation of magma. We describe the results of a series of powder neutron diffraction experiments over the range 0 - 2.0 GPa, 150 - 280 K which were carried out with the objective of determining the phase behaviour and thermoelastic properties of ammonia dihydrate. In addition to the low-pressure cubic crystalline phase, ADH I, we have identified two closely related monoclinic polymorphs of ammonia dihydrate (ADH IIa and IIb) in the range 0.45 - 0.60 GPa (at 175 K), and have determined that this phase dissociates to a mixture of ammonia monohydrate phase II and ice II when warmed to ~190 K, which in turn melts at a binary eutectic at ~196 K; AMH II has a large (Z = 16) orthorhombic unit cell. Above 0.60 GPa, an orthorhombic polymorph of ammonia dihydrate, which we have referred to previously as ADH IV, persists to pressures > 3 GPa, and appears to be the liquidus phase over this whole pressure range. We have observed this phase co- existing with both ice II and ice VI. Here we describe the most plausible synthesis of the high-pressure phase diagram which explains our observations, and provide measurements of the densities, thermal expansion, bulk moduli, and crystal

  18. Thermodynamics of aqueous solutes at high temperatures and pressures: Application of the hydration theory and implications for fluid-mediated mass transfer

    NASA Astrophysics Data System (ADS)

    Sulak, M.; Dolejs, D.

    2012-04-01

    Magmatic activity and prograde devolatilization of subducting or underplating lithologies release large quantities of aqueous fluids that act as mass and heat transfer agents in the planetary interiors. Understanding of mineral-melt-fluid interactions is essential for evaluating the effects of fluid-mediated mass transport in subduction zones, collisional orogens as well as in igneous provinces. The thermodynamic properties of aqueous species were frequently described by the Helgeson-Kirkham-Flowers equation of state [1] but its utility is limited by inavailability of the solvent dielectric properties at high pressures and temperatures, and by decoupling of species-solvent mechanical and electrostatic interactions that cannot be separated within the Born theory. Systematic description of the hydration process in a Born-Haber cycle leads to the following thermochemical contributions: (i) thermodynamic properties of an unhydrated species, (ii) the pressure-volume work required to create a cavity within the solvent to accommodate the species, described by the scaled particle theory, (iii) entropic contribution related to changes in the solute's and the solvent's kinetic degrees of freedom, and (iv) contribution from the solute-solvent molecular interactions and corresponding rearrangement of the solvent molecules to form the hydration shell. Application of the spatial correlation functions [2, 3] results in apparent Gibbs energy of aqueous species, ΔaGi = a + bT + cTlnT + dP + eTlnρ + fTρlnρ, where athrough f represent constants related to standard thermodynamic properties of aqueous species (ΔfH, S, V, cP) and to solvent volumetric properties at 298.15 K and 1 bar (ρ, α, β etc.). In phase equilibrium calculations, the number of required parameters often reduces to four (c = f = 0) while noting that H2O density as the only solvent-related property is accurately known to extreme temperatures and pressures. The equation of state parameters were calibrated for 30

  19. The impact of transitions between two-fluid and three-fluid phases on fluid configuration and fluid-fluid interfacial area in porous media

    NASA Astrophysics Data System (ADS)

    Carroll, Kenneth C.; McDonald, Kieran; Marble, Justin; Russo, Ann E.; Brusseau, Mark L.

    2015-09-01

    Multiphase-fluid distribution and flow is inherent in numerous areas of hydrology. Yet pore-scale characterization of transitions between two and three immiscible fluids is limited. The objective of this study was to examine the impact of such transitions on the pore-scale configuration of organic liquid in a multifluid system comprising natural porous media. Three-dimensional images of an organic liquid (trichloroethene) in two-phase (organic-liquid/water) and three-phase (air/organic-liquid/water) systems were obtained using X-ray microtomography before and after drainage and imbibition. Upon transition from a two-phase to a three-phase system, a significant portion of the organic liquid (intermediate wetting fluid) was observed to exist as lenses and films in contact with air (nonwetting fluid). In these cases, the air was either encased by or contiguous to the organic liquid. The presence of air resulted in an increase in the surface-area-to-volume ratios for the organic-liquid blobs. Upon imbibition, the air was displaced downgradient, and concomitantly, the morphology of the organic-liquid blobs no longer in contact with air reverted to that characteristic of a two-phase distribution (i.e., more spherical blobs and ganglia). This change in morphology resulted in a reduction in the surface-area-to-volume ratio. These results illustrate the impact of transitions between two-phase and three-phase conditions on fluid configuration, and they demonstrate the malleable nature of fluid configuration under dynamic, multiphase-flow conditions. The results have implications for characterizing and modeling pore-scale flow and mass transfer processes.

  20. Determining the three-phase coexistence line in methane hydrates using computer simulations

    NASA Astrophysics Data System (ADS)

    Conde, M. M.; Vega, C.

    2010-08-01

    Molecular dynamics simulations have been performed to estimate the three-phase (solid hydrate-liquid water-gaseous methane) coexistence line for the water-methane binary mixture. The temperature at which the three phases are in equilibrium was determined for three different pressures, namely, 40, 100, and 400 bar by using direct coexistence simulations. In the simulations water was described by using either TIP4P, TIP4P/2005, or TIP4P/Ice models and methane was described as simple Lennard-Jones interaction site. Lorentz-Berthelot combining rules were used to obtain the parameters of the cross interactions. For the TIP4P/2005 model positive deviations from the energetic Lorentz-Berthelot rule were also considered to indirectly account for the polarization of methane when introduced in liquid water. To locate the three-phase coexistence point, two different global compositions were used, which yielded (to within statistical uncertainty) the same predictions for the three-phase coexistence temperatures, although with a somewhat different time evolution. The three-phase coexistence temperatures obtained at different pressures when using the TIP4P/Ice model of water were in agreement with the experimental results. The main reason for this is that the TIP4P/Ice model reproduces the melting point of ice Ih.

  1. Wettability of Freon hydrates in crude oil/brine emulsions.

    PubMed

    Høiland, S; Askvik, K M; Fotland, P; Alagic, E; Barth, T; Fadnes, F

    2005-07-01

    The surface energy of petroleum hydrates is believed to be a key parameter with regard to hydrate morphology and plugging tendency in petroleum production. As of today, the surface energy of natural gas hydrates is unknown, but will depend on the fluids in which they grow. In this work, the wettability of Freon hydrates is evaluated from their behavior in crude oil emulsions. For emulsions stabilized by colloidal particles, the particle wettability is a governing parameter for the emulsion behavior. The transition between continuous and dispersed phases as a function of brine volume in crude oil-brine emulsions containing Freon hydrates has been determined for 12 crude oils. Silica particles are used for comparison. The results show that phase inversion is highly dependent on crude oil properties. Based on the measured points of phase inversion, the wettability of the Freon hydrates generated in each system is evaluated as being oil-wet, intermediate-wet, or water-wet. Generation of oil-wet hydrates correlates with low hydrate plugging tendency. The formation of oil-wet hydrates will prevent agglomeration into large hydrate aggregates and plugs. Hence, it is believed that the method is applicable for differentiating oils with regard to hydrate morphology. PMID:15914170

  2. The Association of Hydration Status with Physical Signs, Symptoms and Survival in Advanced Cancer—The Use of Bioelectrical Impedance Vector Analysis (BIVA) Technology to Evaluate Fluid Volume in Palliative Care: An Observational Study

    PubMed Central

    Mayland, Catriona R.; Mason, Stephen; Cox, Trevor F.; Varro, Andrea; Ellershaw, John

    2016-01-01

    Background Hydration in advanced cancer is a controversial area; however, current hydration assessments methods are poorly developed. Bioelectrical impedance vector analysis (BIVA) is an accurate hydration tool; however its application in advanced cancer has not been explored. This study used BIVA to evaluate hydration status in advanced cancer to examine the association of fluid status with symptoms, physical signs, renal biochemical measures and survival. Materials and methods An observational study of 90 adults with advanced cancer receiving care in a UK specialist palliative care inpatient unit was conducted. Hydration status was assessed using BIVA in addition to assessments of symptoms, physical signs, performance status, renal biochemical measures, oral fluid intake and medications. The association of clinical variables with hydration was evaluated using regression analysis. A survival analysis was conducted to examine the influence of hydration status and renal failure. Results The hydration status of participants was normal in 43 (47.8%), 'more hydrated' in 37 (41.1%) and 'less hydrated' in 10 (11.1%). Lower hydration was associated with increased symptom intensity (Beta = -0.29, p = 0.04) and higher scores for physical signs associated with dehydration (Beta = 10.94, p = 0.02). Higher hydration was associated with oedema (Beta = 2.55, p<0.001). Median survival was statistically significantly shorter in 'less hydrated' patients (44 vs. 68 days; p = 0.049) and in pre-renal failure (44 vs. 100 days; p = 0.003). Conclusions In advanced cancer, hydration status was associated with clinical signs and symptoms. Hydration status and pre-renal failure were independent predictors of survival. Further studies can establish the utility of BIVA as a standardised hydration assessment tool and explore its potential research application, in order to inform the clinical management of fluid balance in patients with advanced cancer. PMID:27673684

  3. Cell sorting is analogous to phase ordering in fluids

    NASA Astrophysics Data System (ADS)

    Beysens, D. A.; Forgacs, G.; Glazier, J. A.

    2000-08-01

    Morphogenetic processes, like sorting or spreading of tissues, characterize early embryonic development. An analogy between viscoelastic fluids and certain properties of embryonic tissues helps interpret these phenomena. The values of tissue-specific surface tensions are consistent with the equilibrium configurations that the Differential Adhesion Hypothesis predicts such tissues reach after sorting and spreading. Here we extend the fluid analogy to cellular kinetics. The same formalism applies to recent experiments on the kinetics of phase ordering in two-phase fluids. Our results provide biologically relevant information on the strength of binding between cell adhesion molecules under near-physiological conditions.

  4. Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

    SciTech Connect

    Manohara, G.V.; Vishnu Kamath, P.; Milius, Wolfgang

    2012-12-15

    Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueous exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.

  5. Comparative Assessment of Advanced Gay Hydrate Production Methods

    SciTech Connect

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

    2009-06-30

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

  6. Thermodynamic and kinetic stability of zwitterionic histidine: Effects of gas phase hydration

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Sik; Kim, Ju-Young; Han, Yuna; Shim, Hyun-Jin; Lee, Sungyul

    2015-09-01

    We present calculations for histidine-(H2O)n (n = 0-6) to examine the effects of micro-hydrating water molecules on the relative stability of the zwitterionic vs. canonical forms of histidine. We calculate the structures and Gibbs free energies of the conformers at wB97XD/6-311++G(d,p) level of theory. We find that six water molecules are required to produce the thermodynamically stable histidine zwitterion. By calculating the barriers of canonical ↔ zwitterionic transformation, we predict that both the most stable canonical and zwitterionic forms of histidine-(H2O)6 may be observed in low temperature gas phase environment.

  7. Integral equation theory description of phase equilibria in classical fluids

    NASA Astrophysics Data System (ADS)

    Caccamo, C.

    1996-09-01

    We review the present status of applications of integral equation theories (IETs) for the radial distribution function g( r), to the determination of phase diagrams and stability conditions of simple and charged classical fluids. After having recalled some basic concepts and definitions in the structural description of fluid systems, a number of IETs are examined by reporting the constituting equations and solution procedures; these last are discussed also in relationship with the actual calculation of coexistence lines and description of the critical behavior of each envisaged theory. In this context, the crucial role played by the fulfilment of thermodynamic consistency in the improvement of the performances of the various approximations, is highlighted. Then, a number of results of phase diagram determinations, phase stability investigations, and estimates of critical exponents, are reported for several neutral and charged model fluids (and their mixtures) such as the hard sphere fluid, the square-well fluid, the hard-core Yukawa fluid, the Lennard-Jones fluid, and charged hard spheres in different regimes of density, sizes and charges. Calculations of the phase diagram of a rigid molecule model of C 60 are also reported. Besides their theoretical interest, these models are investigated by many authors also because they can reasonably mimic real systems like rare gas liquids, electrolyte solutions, molten salts, neutral and charged micellar systems, and colloidal solutions. The related experimental evidence is therefore frequently referred, and comparison with experimental results is also performed in some case. Theoretical results are usually presented in parallel with the available computer simulation data, which are extensively quoted both with the aim of a systematic assessment of the theories, and in order to offer a more complete scenario of phase behavior calculations in classical fluids. Perspectives and advantages of future extensions and applications

  8. Optimization of crystal nucleation close to a metastable fluid-fluid phase transition

    PubMed Central

    Wedekind, Jan; Xu, Limei; Buldyrev, Sergey V.; Stanley, H. Eugene; Reguera, David; Franzese, Giancarlo

    2015-01-01

    The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments PMID:26095898

  9. Phase behavior of coal fluids: Data for correlation development

    SciTech Connect

    Robinson, R.L. Jr.

    1990-02-06

    The effective design and operation of processes for conversion of coal to fluid fuels requires accurate knowledge of the phase behavior of the fluid mixtures encountered in the conversion process. Multiple phases are present in essentially all stages of feed preparation, conversion reactions and product separation; thus, knowledge of the behavior of these multiple phases is important in each step. The overall objective of the author's work is to develop accurate predictive methods for representation of vapor-liquid equilibria in systems encountered in coal conversion processes. 59 refs., 6 figs., 7 tabs.

  10. Lattice Boltzmann methods for viscous fluid flows and for two-phase fluid flows

    NASA Astrophysics Data System (ADS)

    Inamuro, Takaji

    2006-09-01

    Lattice Boltzmann methods (LBMs) for viscous fluid flows and for two-phase fluid flows are presented. First, the LBMs for incompressible viscous fluid flows and for temperature fields are described. Then, we derive a lattice kinetic scheme (LKS) which is an improved scheme of the LBM. The LKS does not require any velocity distribution functions and is more stable than the LBMs. In addition, the LBM for two-phase fluid flows is presented. The method can simulate flows with the density ratio up to 1000. Numerical examples of unsteady flows in a three-dimensional porous structure, binary droplet collision and rising bubbles in a square duct are illustrated. It is expected that the LBMs (and LKS) will become promising numerical schemes for simulating complex fluid flows.

  11. Pharmacological attenuation of Paramecium fluid-phase endocytosis.

    PubMed

    Wiejak, Jolanta; Surmacz, Liliana; Wyroba, Elzbieta

    2007-01-01

    Spectrophotometric quantification of fluid phase endocytosis in the presence of different pharmacological compounds was performed in the model unicellular eukaryote Paramecium. The kinetics of Lucifer Yellow Carbohydrazide (LY) uptake in cells exposed to forskolin and isoproterenol--known to stimulate phagocytosis in this cell--was analyzed. Reduction in both the rate of endocytosis and total accumulation of fluid phase marker was observed following the treatment. Forskolin diminished total LY accumulation by 11% and 21% after 5 min and 25 min of incubation, respectively, whereas the rate of uptake was lowered by 21% in comparison to control cells. The inhibitory effect ofisoproterenol was less pronounced than that of forskolin. The total accumulation of LY was decreased by 11% in 5 min as compared to the untreated cells and this effect was persistent upon further exposition to this reagent up to 25 min. To better understand these observations, the effect of inhibitors of PKA and cAMP phosphodiesterase on fluid phase uptake was tested. 3-isobutyl-1-methyl xanthine (IBMX) caused 12% decrease in LY accumulation after 5 min of incubation. In combination with isoproterenol or forskolin, IBMX enhanced their inhibitory effect on fluid endocytosis, which was lowered by 25% and 29%, respectively. The strongest inhibitory effect on fluid endocytosis was exerted by the 10 microM PKA inhibitor, which diminished endocytosis by 35% in 5 min. These results suggest that Paramecium fluid phase uptake may be regulated through activation of PKA, although the precise mechanism of this process has not yet been elucidated.

  12. Metastable ripple phase of fully hydrated dipalmitoylphosphatidylcholine as studied by small angle x-ray scattering

    PubMed Central

    Yao, Haruhiko; Matuoka, Sinzi; Tenchov, Boris; Hatta, Ichiro

    1991-01-01

    Fully hydrated dipalmitoylphosphatidylcholine (DPPC) undergoes liquid crystalline to metastable Pβ, phase transition in cooling. A small angle x-ray scattering study has been performed for obtaining further evidence about the structure of this phase. From a high-resolution observation of x-ray diffraction profiles, a distinct multipeak pattern has become obvious. Among them the (01) reflection in the secondary ripple structure is identified clearly. There are peaks assigned straightforwardly to (10) and (20) reflections in the primary ripple structure and peaks assigned to (10) and (20) reflections in the secondary ripple structure. Therefore the multipeak pattern is due to superposition of the reflections cause by the primary and secondary ripple structures. The lattice parameters are estimated as follows: for the primary ripple structure a = 7.09 nm, b = 13.64 nm, and γ = 95°, and for the secondary ripple structure a = 8.2 nm, b = 26.6 nm, and γ = 90°. The lattice parameters thus obtained for the secondary ripple structure are not conclusive, however. The hydrocarbon chains in the primary ripple structure have been reported as being tilted against the bilayer plane and, on the other hand, the hydrocarbon chains in the secondary ripple structure are likely to be perpendicular to the bilayer plane. This fact seems to be related to a sequential mechanism of phase transitions. On heating from the Lβ, phase where the hydrocarbon chains are tilted the primary ripple structure having tilted hydrocarbon chains takes place and on cooling from the Lα phase where the hydrocarbon chains are not tilted the secondary ripple structure with untilted chains tends to be stabilized. It appears that the truly metastable ripple phase is expressed by the second ripple structure although in the course of the actual cooling transition both the secondary and primary ripple structures form and coexist. PMID:19431787

  13. Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

    SciTech Connect

    Khan, I. John; Murthy, N. Sanjeeva; Kohn, Joachim

    2015-10-30

    Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

  14. Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

    PubMed Central

    Khan, I. John; Murthy, N. Sanjeeva; Kohn, Joachim

    2012-01-01

    Voclosporin is a highly potent, new cyclosporine-A derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. We therefore selected it as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin. PMID:24955746

  15. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates.

    PubMed

    Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice. PMID:26342376

  16. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates.

    PubMed

    Costandy, Joseph; Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.

  17. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates

    NASA Astrophysics Data System (ADS)

    Costandy, Joseph; Michalis, Vasileios K.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.

  18. Gyroid phase of fluids with spherically symmetric competing interactions.

    PubMed

    Edelmann, Markus; Roth, Roland

    2016-06-01

    We study the phase diagram of a fluid with spherically symmetric competing pair interactions that consist of a short-ranged attraction and a longer-ranged repulsion in addition to a hard core. To this end we perform free minimizations of three-dimensional triple periodic structures within the framework of classical density functional theory. We compare our results to those from Landau theory. Our main finding is that the double gyroid phase can exist as a thermodynamically stable phase. PMID:27415247

  19. Gyroid phase of fluids with spherically symmetric competing interactions

    NASA Astrophysics Data System (ADS)

    Edelmann, Markus; Roth, Roland

    2016-06-01

    We study the phase diagram of a fluid with spherically symmetric competing pair interactions that consist of a short-ranged attraction and a longer-ranged repulsion in addition to a hard core. To this end we perform free minimizations of three-dimensional triple periodic structures within the framework of classical density functional theory. We compare our results to those from Landau theory. Our main finding is that the double gyroid phase can exist as a thermodynamically stable phase.

  20. Packed column supercritical fluid chromatography using deactivated stationary phases

    SciTech Connect

    Ashraf-Khorassani, M.; Taylor, L.T.; Henry, R.A.

    1988-08-01

    A new cross-linked cyanopropyl bonded phase silica (Delta-bond) has been studied as a stationary phase for packed column supercritical fluid chromatography of basic nitrogen-containing compounds. The bonded phase impedes access to uncapped silanol sites, thereby giving rise to better peak shapes and more rapid elution without the necessity of a polar modifier in the mobile phase. Experiments both at elevated temperature and in the presence of a methanol modifier revealed that there is no short- or long-term deleterious effect on the column as opposed to the conventional cyanopropyl phase.

  1. A multi-phase, micro-dispersion reactor for the continuous production of methane gas hydrate

    SciTech Connect

    Taboada Serrano, Patricia L; Ulrich, Shannon M; Szymcek, Phillip; McCallum, Scott; Phelps, Tommy Joe; Palumbo, Anthony Vito; Tsouris, Costas

    2009-01-01

    A continuous-jet hydrate reactor originally developed to generate a CO2 hydrate stream has been modified to continuously produce CH4 hydrate. The reactor has been tested in the Seafloor Process Simulator (SPS), a 72-L pressure vessel available at Oak Ridge National Laboratory. During experiments, the reactor was submerged in water inside the SPS and received water from the surrounding through a submersible pump and CH4 externally through a gas booster pump. Thermodynamic conditions in the hydrate stability regime were employed in the experiments. The reactor produced a continuous stream of CH4 hydrate, and based on pressure values and amount of gas injected, the conversion of gas to hydrate was estimated. A conversion of up to 70% was achieved using this reactor.

  2. Molecular dynamics investigation of the structure of a fully hydrated gel-phase dipalmitoylphosphatidylcholine bilayer.

    PubMed Central

    Tu, K; Tobias, D J; Blasie, J K; Klein, M L

    1996-01-01

    We report the results of a constant pressure and temperature molecular dynamics simulation of a gel-phase dipalmitoylphosphatidylcholine bilayer with nw = 11.8 water molecules/lipid at 19 degrees C. The results of the simulation were compared in detail with a variety of x-ray and neutron diffraction data. The average positions of specific carbon atoms along the bilayer normal and the interlamellar spacing and electron density profile were in very good agreement with neutron and x-ray diffraction results. The area per lipid and the details of the in-plane hydrocarbon chain structure were in excellent agreement with wide-angle x-ray diffraction results. The only significant deviation is that the chains met in a pleated arrangement at the bilayer center, although they should be parallel. Novel discoveries made in the present work include the observation of a bimodal headgroup orientational distribution. Furthermore, we found that there are a significant number of gauche conformations near the ends of the hydrocarbon chains and, in addition to verifying a previous suggestion that there is partial rotational ordering in the hydrocarbon chains, that the two chains in a given molecule are inequivalent with respect to rotations. Finally, we have investigated the lipid/water interface and found that the water penetrates beneath the headgroups, but not as far as the carbonyl groups, that the phosphates are strongly hydrated almost exclusively at the nonesterified oxygen atoms, and that the hydration of the ammonium groups is more diffuse, with some water molecules concentrated in the grooves between the methyl groups. Images FIGURE 2 FIGURE 7 FIGURE 8 FIGURE 12 FIGURE 16 PMID:8789079

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  4. Microgravity experiments on phase change of self-rewetting fluids.

    PubMed

    Abe, Yoshiyuki; Iwasaki, Akira; Tanaka, Kotaro

    2004-11-01

    A series of microgravity experiments on self-rewetting fluids has been conducted at the 10-second drop shaft of the Japan Microgravity Center (JAMIC). In all the experiments, 1.5 wt% of 1-butanol aqueous solution were employed as a self-rewetting fluid. The objective of the first experiment was to observe the boiling behavior of two-dimensional adjacent dual vapor bubbles with the aid of a two-wavelength interferometer and tracer particles. A significant difference was observed between a self-rewetting fluid and a normal fluid (CFC-113 in this experiment) in bubble interaction and flow developed along vapor/bubble interface. The second experiment focused on the flow at the bubble/heater contact area and around the three-phase interline, visualized with tracer particles. Differing behavior among three fluids, 1-butanol aqueous solution, CFC-113, and ethanol aqueous solution, was observed. The last microgravity experiment was a demonstration of wickless heat pipes containing three different fluids as a working fluid, 1-butanol aqueous solution, water, and ethanol aqueous solution. The temperature variation of working fluid in the heat pipe was monitored, and the liquid flow returning from the condensation region to the evaporation region was visualized by tracer particles. In addition to microgravity experiments, the performance of conventional heat pipes with 1-butanol aqueous solution was evaluated on the ground, and compared with water heat pipes. Our preliminary results are presented.

  5. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the

  6. Stability evaluation of hydrate-bearing sediments during thermally-driven hydrate dissociation

    NASA Astrophysics Data System (ADS)

    Kwon, T.; Cho, G.; Santamarina, J.; Kim, H.; Lee, J.

    2009-12-01

    Hydrate-bearing sediments may destabilize spontaneously as part of geological processes, unavoidably during petroleum drilling/production operations, or intentionally as part of gas extraction from the hydrate itself. In all cases, high pore fluid pressure generation is anticipated during hydrate dissociation. This study examined how thermal changes destabilize gas hydrate-bearing sediments. First, an analytical formulation was derived for predicting fluid pressure evolution in hydrate-bearing sediments subjected to thermal stimulation without mass transfer. The formulation captures the self-preservation behavior, calculates the hydrate and free gas quantities during dissociation, considering effective stress-controlled sediment compressibility and gas solubility in aqueous phase. Pore fluid pressure generation is proportional to the initial hydrate fraction and the sediment bulk stiffness; is inversely proportional to the initial gas fraction and gas solubility; and is limited by changes in effective stress that cause the failure of the sediment. Second, the analytical formulation for hydrate dissociation was incorporated as a user-defined function into a verified finite difference code (FLAC2D). The underlying physical processes of hydrate-bearing sediments, including hydrate dissociation, self-preservation, pore pressure evolution, gas dissolution, and sediment volume expansion, were coupled with the thermal conduction, pore fluid flow, and mechanical response of sediments. We conducted the simulations for a duration of 20 years, assuming a constant-temperature wellbore transferred heat to the surrounding hydrate-bearing sediments, resulting in dissociation of methane hydrate in the well vicinity. The model predicted dissociation-induced excess pore fluid pressures which resulted in a large volume expansion and plastic deformation of the sediments. Furthermore, when the critical stress was reached, localized shear failure of the sediment around the borehole was

  7. NATURAL GAS HYDRATES STORAGE PROJECT PHASE II. CONCEPTUAL DESIGN AND ECONOMIC STUDY

    SciTech Connect

    R.E. Rogers

    1999-09-27

    DOE Contract DE-AC26-97FT33203 studied feasibility of utilizing the natural-gas storage property of gas hydrates, so abundantly demonstrated in nature, as an economical industrial process to allow expanded use of the clean-burning fuel in power plants. The laboratory work achieved breakthroughs: (1) Gas hydrates were found to form orders of magnitude faster in an unstirred system with surfactant-water micellar solutions. (2) Hydrate particles were found to self-pack by adsorption on cold metal surfaces from the micellar solutions. (3) Interstitial micellar-water of the packed particles were found to continue forming hydrates. (4) Aluminum surfaces were found to most actively collect the hydrate particles. These laboratory developments were the bases of a conceptual design for a large-scale process where simplification enhances economy. In the design, hydrates form, store, and decompose in the same tank in which gas is pressurized to 550 psi above unstirred micellar solution, chilled by a brine circulating through a bank of aluminum tubing in the tank employing gas-fired refrigeration. Hydrates form on aluminum plates suspended in the chilled micellar solution. A low-grade heat source, such as 110 F water of a power plant, circulates through the tubing bank to release stored gas. The design allows a formation/storage/decomposition cycle in a 24-hour period of 2,254,000 scf of natural gas; the capability of multiple cycles is an advantage of the process. The development costs and the user costs of storing natural gas in a scaled hydrate process were estimated to be competitive with conventional storage means if multiple cycles of hydrate storage were used. If more than 54 cycles/year were used, hydrate development costs per Mscf would be better than development costs of depleted reservoir storage; above 125 cycles/year, hydrate user costs would be lower than user costs of depleted reservoir storage.

  8. Long-Term Continuous Monitoring of Fluid Chemistry and Flux at the Bush Hill Gas Hydrate Field, Gulf of Mexico Using a New Flow Meter, The MOSQUITO

    NASA Astrophysics Data System (ADS)

    Solomon, E.; Kastner, M.; Jannasch, H.; Weinstein, Y.; Robertson, G.; Aubrey, A.

    2004-12-01

    Long-term monitoring of fluid, solute, and methane fluxes that influence marine gas hydrate formation and dissociation has important implications for the seafloor biochemical environment, ocean chemistry, and potentially the atmosphere. Four newly designed flux meters called the MOSQUITO (Multiple Orifice Sampler and Quantitative Injection Tracer Observer) and two temperature loggers were deployed adjacent to the Bush Hill hydrate mound in the northern Gulf of Mexico (GC185) in order to understand how chemistry, physics, biology, and subsurface hydrology dynamically influence the growth and dissociation of the hydrate mound. The MOSQUITO contains a network of osmotic samplers and a tracer injection device, each connected to a titanium capillary tube that penetrates the sediment. The tracer is injected as a point source, and fluid chemistry and tracer concentrations are continuously sampled simultaneously at multiple depths below the seafloor in a three dimensional array with respect to the tracer injection point. Bottom water chemistry is also sampled continuously. Vertical and horizontal flow rates as low as 1 cm/yr are determined by modeling the variability in tracer concentration at each depth over time. MOSQUITOs can be deployed at passive margins, ridge crests, ridge flanks, subduction zones, and lakes. MOSQUITOs were deployed over a period of 430 days from June 2002 to August 2003 and were sampled at weekly resolution. The temperature loggers were attached to the MOSQUITOs and recorded seafloor temperature every 40 minutes. Three MOSQUITOs were deployed within 3 m of the hydrate mound and ˜ 5 m apart, adjacent to transient methane seeps; in a mussel field, in a bacterial mat, and in a tubeworm field. The fourth MOSQUITO was placed ˜150 m southwest of the hydrate mound to monitor background fluid flow, geochemistry, and temperature. The average bottom water temperature over the 430-day deployment period was 7.94° C, with minimum temperatures occurring every

  9. Acyl chain composition and coexisting fluid phases in lipid bilayers

    NASA Astrophysics Data System (ADS)

    Gu, Yongwen; Bradley, Miranda; Mitchell, Drake

    2011-10-01

    At room temperature phospholipid bilayers enriched in sphingolipids and cholesterol may form a solid phase as well as two coexisting fluid phases. These are the standard fluid phase, or the liquid-disordered phase, ld, and the liquid-ordered phase, lo, which is commonly associated with lipid rafts. Ternary mixtures of palmitoyl-oleoyl-phosphocholine (POPC; 16:0,18:1 PC), sphingomyelin (SPM), and cholesterol (Chol) form coexisting lo, ld and solid phases over a wide range of molar ratios. We are examining the ability of two fluorescent probes to detect these 2 phases: NBD linked to di-16:0 PE which partitions strongly into the lo phase and NBD linked to di-18:1 PE which partitions strongly into the ld phase. We are also examining the effect of the highly polyunsaturated phospholipid stearoyl-docosahexanoyl-phosphocholine (SDPC; 18:0, 22:6 PC) on the ternary phase diagram of POPC/SPM/Chol with particular focus on the functionally important lo/ld coexistence region. We report on the fluorescence lifetime and anisotropy decay dynamics of these two fluorescent probes.

  10. Incorporation of surface tension into molecular dynamics simulation of an interface: a fluid phase lipid bilayer membrane.

    PubMed Central

    Chiu, S W; Clark, M; Balaji, V; Subramaniam, S; Scott, H L; Jakobsson, E

    1995-01-01

    In this paper we report on the molecular dynamics simulation of a fluid phase hydrated dimyristoylphosphatidylcholine bilayer. The initial configuration of the lipid was the x-ray crystal structure. A distinctive feature of this simulation is that, upon heating the system, the fluid phase emerged from parameters, initial conditions, and boundary conditions determined independently of the collective properties of the fluid phase. The initial conditions did not include chain disorder characteristic of the fluid phase. The partial charges on the lipids were determined by ab initio self-consistent field calculations and required no adjustment to produce a fluid phase. The boundary conditions were constant pressure and temperature. Thus the membrane was not explicitly required to assume an area/phospholipid molecule thought to be characteristic of the fluid phase, as is the case in constant volume simulations. Normal to the membrane plane, the pressure was 1 atmosphere, corresponding to the normal laboratory situation. Parallel to the membrane plane a negative pressure of -100 atmospheres was applied, derived from the measured surface tension of a monolayer at an air-water interface. The measured features of the computed membrane are generally in close agreement with experiment. Our results confirm the concept that, for appropriately matched temperature and surface pressure, a monolayer is a close approximation to one-half of a bilayer. Our results suggest that the surface area per phospholipid molecule for fluid phosphatidylcholine bilayer membranes is smaller than has generally been assumed in computational studies at constant volume. Our results confirm that the basis of the measured dipole potential is primarily water orientations and also suggest the presence of potential barriers for the movement of positive charges across the water-headgroup interfacial region of the phospholipid. Images FIGURE 2 PMID:8534794

  11. Voluntary fluid intake, hydration status, and aerobic performance of adolescent athletes in the heat.

    PubMed

    Wilk, Boguslaw; Timmons, Brian W; Bar-Or, Oded

    2010-12-01

    We determined whether beverage flavoring and composition would stimulate voluntary drink intake, prevent dehydration, and maintain exercise performance in heat-acclimated adolescent males running in the heat. Eight adolescent (age, 13.7 ± 1.1 years) runners (peak oxygen uptake, 59.5 ± 4.0 mL·kg-1·min-1) underwent at least four 80-min exercise heat-acclimation sessions before completing 3 experimental sessions. All sessions were performed at 30 °C and 60%-65% relative humidity. Each experimental session consisted of five 15-min treadmill runs at a speed eliciting 65% peak oxygen uptake, with a 5 min rest prior to each run. Ten minutes after the final run, a time to exhaustion test was performed at a speed eliciting 90% peak oxygen uptake. Counterbalanced experimental sessions were identical, except for fluid intake, which consisted of tap water (W), flavored water (FW), and FW with 6% carbohydrate and 18 mmol·L-1 NaCl (CNa) consumed ad libitum. Fluid intake and body weight were monitored to calculate dehydration. Voluntary fluid intake was similar to fluid losses in W (1032 ± 130 vs. 1340 ± 246 g), FW (1086 ± 86 vs. 1451 ± 253 g), and CNa (1259 ± 119 vs. 1358 ± 234 g). As a result, significant dehydration was avoided in all trials (-0.45% ± 0.68% body weight in W, -0.66% ± 0.50% body weight in FW, and -0.13% ± 0.71% body weight in CNa). Core temperature increased by ~1 °C during exercise, but was not different between trials. Time to exhaustion was not different between trials and averaged 8.8 ± 1.7 min. Under exercise conditions more closely reflecting real-life situations, heat-acclimatized adolescent male runners can appropriately gauge fluid intake regardless of the type of beverage made available, resulting in consistency in exercise performance. PMID:21164555

  12. Studies of Phase Transitions and Critical Phenomena: I. Origin of Broken Particle-Hole Symmetry in Critical Fluids. I. Phase Transitions of Interacting Membranes.

    NASA Astrophysics Data System (ADS)

    Goldstein, Raymond Ethan

    The longstanding problem of the precise correspondence between critical phenomena in fluids and ferromagnets is resolved in Part I through a synthesis of mean field theory, exact results for lattice models, field-theoretic techniques, and by extensive quantitative comparison with experiment. Emphasis is placed on the origin of broken particle-hole symmetry in fluids as reflected in the form of the critical point scaling fields and in systematic variations in certain nonuniversal critical amplitudes with molecular polarizability. Those trends and the degree to which the scaling axes are linearly mixed versions of the bare "thermal" and "magnetic" fields in particle-hole symmetric systems are shown both for lattice models and real fluids to be intimately related to the presence of many-body interactions of the Axilrod-Teller type. A quantitatively accurate microscopic expression for the field-mixing operator of fluids is derived on the basis of an exact Hubbard-Stratonovich transformation relating the fluid Hamiltonian to that of a Landau-Ginzburg-Wilson model. A phenomenological theory of the phase behavior of multilamellar liquid crystals of hydrated phospholipid bilayers is developed in Part II, and its predictions tested by extensive comparison with experiment. A Ginzburg-Landau free energy functional based on the elastic properties of two coupled monolayers is proposed to describe intrabilayer ordering, and the phenomenon of structural phase transitions driven by membrane interactions is described by incorporating in addition the attractive dispersion interactions and repulsive "hydration" forces acting between membranes. The theory indicates and experiments support a connection between the pseudocriticality of the bilayer transitions and the large susceptibility of the in-plane order to membrane interactions. The pseudocriticality in turn is suggested to arise from the analog of a capillary critical point accessible by finite-size effects. Theoretical phase

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

    PubMed

    Tanaka, Fumihiko; Koga, Tsuyoshi; Kaneda, Isamu; Winnik, Françoise M

    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 σ 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.

  14. Constant pressure and temperature molecular dynamics simulation of a fully hydrated liquid crystal phase dipalmitoylphosphatidylcholine bilayer.

    PubMed Central

    Tu, K; Tobias, D J; Klein, M L

    1995-01-01

    We report a constant pressure and temperature molecular dynamics simulation of a fully hydrated liquid crystal (L alpha) phase bilayer of dipalmitoylphosphatidylcholine at 50 degrees C and 28 water molecules/lipid. We have shown that the bilayer is stable throughout the 1550-ps simulation and have demonstrated convergence of the system dimensions. Several important aspects of the bilayer structure have been investigated and compared favorably with experimental results. For example, the average positions of specific carbon atoms along the bilayer normal agree well with neutron diffraction data, and the electron density profile is in accord with x-ray diffraction results. The hydrocarbon chain deuterium order parameters agree reasonably well with NMR results for the middles of the chains, but the simulation predicts too much order at the chain ends. In spite of the deviations in the order parameters, the hydrocarbon chain packing density appears to be essentially correct, inasmuch as the area/lipid and bilayer thickness are in agreement with the most refined experimental estimates. The deuterium order parameters for the glycerol and choline groups, as well as the phosphorus chemical shift anisotropy, are in qualitative agreement with those extracted from NMR measurements. PMID:8599662

  15. Multiple episodes of fluid flow in the SW Barents Sea (Loppa High) evidenced by gas flares, pockmarks and gas hydrate accumulation

    NASA Astrophysics Data System (ADS)

    Chand, S.; Thorsnes, T.; Rise, L.; Brunstad, H.; Stoddart, D.; Bøe, R.; Lågstad, P.; Svolsbru, T.

    2012-05-01

    Gas and gas hydrates have gained considerable attention in the last 20 yr due to their possible impact on global climate change from methane escalations. Our study area, the SW Barents Sea, is unique in its evolution due to the effect of glaciations which removed thick layers of sediment from the seabed. Unloading due to erosion and deglaciation resulted in opening of pre-existing faults and creation of new ones, facilitating fluid migration and eventually escape into the water from the subsurface. Expressions of hydrocarbon gas accumulation and fluid flow such as gas hydrates and pockmarks are widely distributed in the Barents Sea. Several gas flares, some of them 200 m high in echograms, occur along a segment of the Ringvassøy Loppa Fault Complex, indicating open fractures and active fluid flow. Observation of gas flares along regional fault complexes outside pockmark regions indicates that present gas escape occurs along faults only. The pockmark formation and gas flares belong to different episodes of fluid flow. The pockmarks are absent outside soft sediment depocentres indicating that their existence is related to the presence of recording medium. The thin sediment cover in pockmarks and their penetration down into glaciomarine sediments indicate that they formed after deposition of these sediments and that fluid escape was active to the very recent past. Methane hydrate stability zone (MHSZ) modelling shows that after the last glacial maximum 18 000-20 000 14C years ago, the MHSZ has thinned from 600 m to zero in most parts of the SW Barents Sea. The fluid expulsion probably happened after retreat of the glaciers causing release of methane from dissociation of methane hydrates through fluid escape processes which lasted until recently. Bottom simulating reflectors (BSR) observed are probably due to structure II hydrates formed from gas containing higher order hydrocarbon components such as ethane, propane, etc. along with methane. The study area falls close

  16. Hydration of gelatin molecules in glycerol-water solvent and phase diagram of gelatin organogels.

    PubMed

    Sanwlani, Shilpa; Kumar, Pradip; Bohidar, H B

    2011-06-01

    We present a systematic investigation of hydration and gelation of the polypeptide gelatin in water-glycerol mixed solvent (glycerol solutions). Raman spectroscopy results indicated enhancement in water structure in glycerol solutions and the depletion of glycerol density close to hydration sheath of the protein molecule. Gelation concentration (c(g)) was observed to decrease from 1.92 to 1.15% (w/v) while the gelation temperature (T(g)) was observed to increase from 31.4 to 40.7 °C with increase in glycerol concentration. Data on hand established the formation of organogels having interconnected networks, and the universal gelation mechanism could be described through an anomalous percolation model. The viscosity of sol diverged as η ∼ (1 - c(g)/c)(-k) as c(g) was approached from below (c < c(g)), while the elastic storage modulus grew as G' ∼ (c/c(g) - 1)(t) (for c > c(g)). It is important to note that values determined for critical exponents k and t were universal; that is, they did not depend on the microscopic details. The measured values were k = 0.38 ± 0.10 and t = 0.92 ± 0.17 whereas the percolation model predicts k = 0.7-1.3 and t = 1.9. Isothermal frequency sweep studies showed power-law dependence of gel storage modulus (G') and loss modulus (G'') on oscillation frequency ω given as G'(ω) ∼ ω(n') and G''(ω) ∼ ω(n''), and consistent with percolation model prediction it was found that n' ≈ n'' ≈ δ ≈ 0.73 close to gelation concentration. We propose a unique 3D phase diagram for the gelatin organogels. Circular dichroism data revealed that the gelatin molecules retained their biological activity in these solvents. Thus, it is shown that the thermomechanical properties of these organogels could be systematically tuned and customized as per application requirement.

  17. Rayleigh-Taylor instability of viscous fluids with phase change.

    PubMed

    Kim, Byoung Jae; Kim, Kyung Doo

    2016-04-01

    Film boiling on a horizontal surface is a typical example of the Rayleigh-Taylor instability. During the film boiling, phase changes take place at the interface, and thus heat and mass transfer must be taken into consideration in the stability analysis. Moreover, since the vapor layer is not quite thick, a viscous flow must be analyzed. Existing studies assumed equal kinematic viscosities of two fluids, and/or considered thin viscous fluids. The purpose of this study is to derive the analytical dispersion relation of the Rayleigh-Taylor instability for more general conditions. The two fluids have different properties. The thickness of the vapor layer is finite, but the liquid layer is thick enough to be nearly semi-infinite in view of perturbation. Initially, the vapor is in equilibrium with the liquid at the interface, and the direction of heat transfer is from the vapor side to the liquid side. In this case, the phase change has a stabilizing effect on the growth rate of the interface. When the vapor layer is thin, there is a coupled effect of the vapor viscosity, phase change, and vapor thickness on the critical wave number. For the other limit of a thick vapor, both the liquid and vapor viscosities influence the critical wave number. Finally, the most unstable wavelength is investigated. When the vapor layer is thin, the most unstable wavelength is not affected by phase change. When the vapor layer is thick, however, it increases with the increasing rate of phase change. PMID:27176406

  18. Rayleigh-Taylor instability of viscous fluids with phase change

    NASA Astrophysics Data System (ADS)

    Kim, Byoung Jae; Kim, Kyung Doo

    2016-04-01

    Film boiling on a horizontal surface is a typical example of the Rayleigh-Taylor instability. During the film boiling, phase changes take place at the interface, and thus heat and mass transfer must be taken into consideration in the stability analysis. Moreover, since the vapor layer is not quite thick, a viscous flow must be analyzed. Existing studies assumed equal kinematic viscosities of two fluids, and/or considered thin viscous fluids. The purpose of this study is to derive the analytical dispersion relation of the Rayleigh-Taylor instability for more general conditions. The two fluids have different properties. The thickness of the vapor layer is finite, but the liquid layer is thick enough to be nearly semi-infinite in view of perturbation. Initially, the vapor is in equilibrium with the liquid at the interface, and the direction of heat transfer is from the vapor side to the liquid side. In this case, the phase change has a stabilizing effect on the growth rate of the interface. When the vapor layer is thin, there is a coupled effect of the vapor viscosity, phase change, and vapor thickness on the critical wave number. For the other limit of a thick vapor, both the liquid and vapor viscosities influence the critical wave number. Finally, the most unstable wavelength is investigated. When the vapor layer is thin, the most unstable wavelength is not affected by phase change. When the vapor layer is thick, however, it increases with the increasing rate of phase change.

  19. Ternary phase behaviour and vesicle formation of a sodium N-lauroylsarcosinate hydrate/1-decanol/water system

    NASA Astrophysics Data System (ADS)

    Akter, Nasima; Radiman, Shahidan; Mohamed, Faizal; Rahman, Irman Abdul; Reza, Mohammad Imam Hasan

    2011-08-01

    The phase behaviour of a system composed of amino acid-based surfactant (sodium N-lauroylsarcosinate hydrate), 1-decanol and deionised water was investigated for vesicle formation. Changing the molar ratio of the amphiphiles, two important aggregate structures were observed in the aqueous corner of the phase diagram. Two different sizes of microemulsions were found at two amphiphile-water boundaries. A stable single vesicle lobe was found for 1∶2 molar ratios in 92 wt% water with vesicles approximately 100 nm in size and with high zeta potential value. Structural variation arises due to the reduction of electrostatic repulsions among the ionic headgroups of the surfactants and the hydration forces due to adsorbed water onto monolayer's. The balance of these two forces determines the aggregate structures. Analysis was followed by the molecular geometrical structure. These findings may have implications for the development of drug delivery systems for cancer treatments, as well as cosmetic and food formulations.

  20. Fluid structure interaction solver coupled with volume of fluid method for two-phase flow simulations

    NASA Astrophysics Data System (ADS)

    Cerroni, D.; Fancellu, L.; Manservisi, S.; Menghini, F.

    2016-06-01

    In this work we propose to study the behavior of a solid elastic object that interacts with a multiphase flow. Fluid structure interaction and multiphase problems are of great interest in engineering and science because of many potential applications. The study of this interaction by coupling a fluid structure interaction (FSI) solver with a multiphase problem could open a large range of possibilities in the investigation of realistic problems. We use a FSI solver based on a monolithic approach, while the two-phase interface advection and reconstruction is computed in the framework of a Volume of Fluid method which is one of the more popular algorithms for two-phase flow problems. The coupling between the FSI and VOF algorithm is efficiently handled with the use of MEDMEM libraries implemented in the computational platform Salome. The numerical results of a dam break problem over a deformable solid are reported in order to show the robustness and stability of this numerical approach.

  1. Hydration kinetics and 10-km outdoor running performance following 75% versus 150% between bout fluid replacement.

    PubMed

    Davis, Brett Alan; Thigpen, Lauren Kellet; Hornsby, Jared Heath; Green, James Matthew; Coates, Thomas Elliot; O'Neal, Eric Kyle

    2014-01-01

    Current American College of Sports Medicine (ACSM) guidelines recommend replacing 150% of sweat losses between training bouts separated by ≤12 hours, but little evidence exists concerning the implications of this strategy for runners. Participants (n = 13) in this study replaced 75% (1637 ± 372 mL) or 150% (3099 ± 850 mL) of sweat losses following an outdoor evening run (∼75 minutes; Wet-bulb-globe temperature (WBGT) = ∼27°C) and consumed a standardised evening meal and breakfast before completing an outdoor (WBGT = ∼23°C) 10-km time-trial the following morning. Urine was collected between runs and urine specific gravity (USG) was assessed pre-run. Significant differences were found in pre-run body mass (75% = 69.6 ± 9.2; 150% = 70.1 ± 9.3 kg; P = 0.02) and USG (75% = 1.026 ± 0.005; 150% = 1.014 ± 0.007; P < 0.001). Heart rate during 10-km run (168 ± 14 versus 168 ± 12 beats min(-1)) and post-run intestinal temperature (39.08 ± 0.52 versus 39.00 ± 0.70 °C) did not differ for 75% and 150%, respectively, despite an ∼3% performance improvement (75% = 47.28 ± 6.64; 150% = 45.93 ± 6.04 minutes; P = 0.001) due to a faster pace in the second half of the run with 150% replacement. Session rate of perceived exertion (RPE) was lower (P = 0.02) during 150% (7.5 ± 1.3) versus 75% (8.4 ± 0.9). Reluctant drinkers potentially hinder training quality between evening and morning runs in the heat, but copious urine production and difficulty in consuming recommended fluid volumes suggest fluid replacement <150% may be more ideal.

  2. Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

    USGS Publications Warehouse

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

    1997-01-01

    Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

  3. Hydrate Control for Gas Storage Operations

    SciTech Connect

    Jeffrey Savidge

    2008-10-31

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

  4. High-Resolution Scanning Tunneling Microscopy of Fully Hydrated Ripple-Phase Bilayers

    PubMed Central

    Woodward IV, J. T.; Zasadzinski, J. A.

    1997-01-01

    A modified freeze-fracture replication technique for use with the scanning tunneling microscope (STM) has provided a quantitative, high-resolution description of the waveform and amplitude of rippled bilayers in the Pβ, phase of dimyristoylphosphatidylcholine (DMPC) in excess water. The ripples are uniaxial and asymmetrical, with a temperature-dependent amplitude of 2.4 nm near the chain melting temperature that decreases to zero at the chain crystallization temperature. The wavelength of 11 nm does not change with temperature. The observed ripple shape and the temperature-induced structural changes are not predicted by any current theory. Calibration and reproducibility of the STM/replica technique were tested with replicas of well-characterized bilayers of cadmium arachidate on mica that provide regular 5.5-nm steps. STM images were analyzed using a cross-correlation averaging program to eliminate the effects of noise and the finite size and shapes of the metal grains that make up the replica. The correlation averaging allowed us to develop a composite ripple profile averaged over hundreds of individual ripples measured on different samples with different STM tips. The STM/replica technique avoids many of the previous artifacts of biological STM imaging and can be used to examine a variety of periodic hydrated lipid and protein samples at a lateral resolution of about 1 nm and a vertical resolution of about 0.3 nm. This resolution is superior to conventional and tapping mode AFM of soft biological materials; the technique is substrate-free, and the conductive and chemically uniform replicas make image interpretation simple and direct. ImagesFIGURE 1FIGURE 2FIGURE 3FIGURE 5 PMID:9017222

  5. Fluid hydrogen at high density - The plasma phase transition

    NASA Technical Reports Server (NTRS)

    Saumon, D.; Chabrier, G.

    1989-01-01

    A new model equation of state is applied, based on realistic interparticle potentials and a self-consistent treatment of the internal levels, to fluid hydrogen at high density. This model shows a strong connection between molecular dissociation and pressure ionization. The possibility of a first-order plasma phase transition is considered, and for which both the evolution in temperature and the critical point is given.

  6. A Phase-Field Method for Simulating Fluid-Structure Interactions in Multi-Phase Flow

    NASA Astrophysics Data System (ADS)

    Zheng, Xiaoning; Karniadakis, George

    2015-11-01

    We investigate two-phase flow instabilities by numerical simulations of fluid structure interactions in two-phase flow. The first case is a flexible pipe conveying two fluids, which exhibits self-sustained oscillations at high Reynolds number and tension related parameter. Well-defined two-phase flow patterns, i.e., slug flow and bubbly flow, are observed. The second case is external two-phase cross flow past a circular cylinder, which induces a Kelvin-Helmholtz instability due to density stratification. We solve the Navier-Stokes equation coupled with the Cahn-Hilliard equation and the structure equation in an arbitrary Lagrangian Eulerian (ALE) framework. For the fluid solver, a spectral/hp element method is employed for spatial discretization and backward differentiation for time discretization. For the structure solver, a Galerkin method is used in Lagrangian coordinates for spatial discretization and the Newmark- β scheme for time discretization.

  7. Phase equilibria and plate-fluid interfacial tensions for associating hard sphere fluids confined in slit pores.

    PubMed

    Fu, Dong; Li, Xiao-Sen

    2006-08-28

    The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.

  8. Geometry-induced phase transition in fluids: capillary prewetting.

    PubMed

    Yatsyshin, Petr; Savva, Nikos; Kalliadasis, Serafim

    2013-02-01

    We report a new first-order phase transition preceding capillary condensation and corresponding to the discontinuous formation of a curved liquid meniscus. Using a mean-field microscopic approach based on the density functional theory we compute the complete phase diagram of a prototypical two-dimensional system exhibiting capillary condensation, namely that of a fluid with long-ranged dispersion intermolecular forces which is spatially confined by a substrate forming a semi-infinite rectangular pore exerting long-ranged dispersion forces on the fluid. In the T-μ plane the phase line of the new transition is tangential to the capillary condensation line at the capillary wetting temperature T(cw). The surface phase behavior of the system maps to planar wetting with the phase line of the new transition, termed capillary prewetting, mapping to the planar prewetting line. If capillary condensation is approached isothermally with T>T(cw), the meniscus forms at the capping wall and unbinds continuously, making capillary condensation a second-order phenomenon. We compute the corresponding critical exponent for the divergence of adsorption.

  9. Membrane Elasticity in Giant Vesicles with Fluid Phase Coexistence

    PubMed Central

    Baumgart, T.; Das, S.; Webb, W. W.; Jenkins, J. T.

    2005-01-01

    Biological membranes are known to contain compositional heterogeneities, often termed rafts, with distinguishable composition and function, and these heterogeneities participate in vigorous transport processes. Membrane lipid phase coexistence is expected to modulate these processes through the differing mechanical properties of the bulk domains and line tension at phase boundaries. In this contribution, we compare the predictions from a shape theory derived for vesicles with fluid phase coexistence to the geometry of giant unilamellar vesicles with coexisting liquid-disordered (Ld) and liquid-ordered (Lo) phases. We find a bending modulus for the Lo phase higher than that of the Ld phase and a saddle-splay (Gauss) modulus difference with the Gauss modulus of the Lo phase being more negative than the Ld phase. The Gauss modulus critically influences membrane processes that change topology, such as vesicle fission or fusion, and could therefore be of significant biological relevance in heterogeneous membranes. Our observations of experimental vesicle geometries being modulated by Gaussian curvature moduli differences confirm the prediction by the theory of Juelicher and Lipowsky. PMID:15894634

  10. Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

    NASA Astrophysics Data System (ADS)

    Manohara, G. V.; Vishnu Kamath, P.; Milius, Wolfgang

    2012-12-01

    Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueous exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 μm.

  11. Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Seo, Jung Hun; Zajacz, Zoltán

    2016-06-01

    Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

  12. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  13. An immersed boundary method for two-phase fluids and gels and the swimming of Caenorhabditis elegans through viscoelastic fluids

    NASA Astrophysics Data System (ADS)

    Lee, Pilhwa; Wolgemuth, Charles W.

    2016-01-01

    The swimming of microorganisms typically involves the undulation or rotation of thin, filamentary objects in a fluid or other medium. Swimming in Newtonian fluids has been examined extensively, and only recently have investigations into microorganism swimming through non-Newtonian fluids and gels been explored. The equations that govern these more complex media are often nonlinear and require computational algorithms to study moderate to large amplitude motions of the swimmer. Here, we develop an immersed boundary method for handling fluid-structure interactions in a general two-phase medium, where one phase is a Newtonian fluid and the other phase is viscoelastic (e.g., a polymer melt or network). We use this algorithm to investigate the swimming of an undulating, filamentary swimmer in 2D (i.e., a sheet). A novel aspect of our method is that it allows one to specify how forces produced by the swimmer are distributed between the two phases of the fluid. The algorithm is validated by comparing theoretical predictions for small amplitude swimming in gels and viscoelastic fluids. We show how the swimming velocity depends on material parameters of the fluid and the interaction between the fluid and swimmer. In addition, we simulate the swimming of Caenorhabditis elegans in viscoelastic fluids and find good agreement between the swimming speeds and fluid flows in our simulations and previous experimental measurements. These results suggest that our methodology provides an accurate means for exploring the physics of swimming through non-Newtonian fluids and gels.

  14. Phase behavior of coal fluids: Data for correlation development

    SciTech Connect

    Robinson, R.J. Jr.; Gasem, K.A.M.; Shaver, R.D.

    1990-01-01

    The effective design and operation of processes for conversion of coal to fluid fuels requires accurate knowledge of the phase behavior of the fluid mixtures encountered in the conversion process. The overall objective of the author's work is to develop accurate predictive methods for representation of vapor-liquid equilibria in systems encountered in coal conversion processes. The objectives of the present project include: (1) measurements of binary vapor-liquid phase behavior data for selected solute gases (e.g. CO{sub 2} and C{sub 2}H{sub 6}) in a series of heavy hydrocarbon solvents to permit evaluation of interaction parameters in models for phase behavior, (2) measurements on ternary systems in which high-melting-point solvents are dissolved in more volatile aromatics to provide mixed solvents, (3) evaluation of existing equations-of-state and other models for representation of phase behavior in systems of the type studied experimentally; development of new correlation frameworks as needed, and (4) generalization of the interaction parameters for the solutes studied to a wide spectrum of heavy solvents; presentations of final results in formats useful in the design/optimization of coal liquefaction processes. This quarter, our framework for correlating saturation properties using a scaled-variable-reduced-coordinate'' approach was further developed to provide for generalized vapor pressure predictions. 59 refs., 6 figs., 8 tabs.

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

    SciTech Connect

    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.

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

    PubMed

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

    2015-05-21

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

  17. Elevating salinity and temperature with hydrate formation at deepwater Gulf of Mexico vents

    NASA Astrophysics Data System (ADS)

    Smith, Andrew J.; Flemings, Peter B.; Liu, Xiaoli

    2013-04-01

    We study the Ursa vent in ~1070 meters water depth at lease blocks MC852/853 in the northern Gulf of Mexico. Elevated salinities and temperatures at the vent shift the base of the hydrate stability zone (HSZ) to the seafloor (Paull et al., 2005; Ruppel et al., 2005). We model the coexistence of high salinities, high temperatures, and an uplifted hydrate phase boundary with a one-dimensional, multicomponent, multiphase, fluid- and heat-flow model of hydrate formation. In this model, free gas supplied from depth migrates vertically through a high-permeability conduit to the regional hydrate stability zone (RHSZ). Once reaching the base of the RHSZ, gas combines with water to form hydrate, salt is excluded, and heat is released. Hydrate formation continues until water is too warm and saline for further hydrate formation. This process self generates three-phase (gas, liquid, hydrate) equilibrium through the RHSZ and allows gas to vent from the base of the RHSZ to the seafloor. Once the reaction front breaches the seafloor, a pseudo steady state is reached in which a continuous salt flux diffuses from the seafloor, and further hydrate formation occurs at a rate necessary to replace the diffuse salt loss. This continued hydrate formation has the potential to produce large, steady fluxes of salt and heat from the seafloor. Such gas-hydrate and fluid-flow systems are important because they are especially sensitive to global ocean warming due to the large concentrations of hydrate that exist at three-phase equilibrium near the seafloor. References: Paull, C., Ussler, W., Lorenson, T., Winters, W., Dougherty, J., 2005. Geochemical constraints on the distribution of gas hydrates in the Gulf of Mexico. Geo-Marine Letters 25, 273-280. Ruppel, C., Dickens, G.R., Castellini, D.G., Gilhooly, W., Lizarralde, D., 2005. Heat and salt inhibition of gas hydrate formation in the northern Gulf of Mexico. Geophys. Res. Lett. 32, L04605.

  18. A phase diagram for fluid-driven sediment trasport

    NASA Astrophysics Data System (ADS)

    Clark, Abe

    When a fluid flows laterally over a granular bed, grains may be transported with the flow. This process shapes much of the natural world. The boundary between states with and without grain motion has been studied for decades. However, this boundary is not well understood, since the process whereby grains are transported involves the coupling of several complex phenomena: turbulent fluid flow near a rough boundary, Darcy flow through the pore structure of the granular bed, the yield strength of granular beds comprised of frictional grains with irregular shape, and inertial effects of grains that become entrained in the flow. In order to clarify the essential physics that governs the onset of granular motion, we study this process computationally by including only the minimal features and then adding complexities one by one. We start with a simple numerical model that includes only gravity, grain-grain interactions that are repulsive and frictionless, and a purely horizontal viscous fluid flow. By varying the fluid flow rate and the effective viscosity, we find behavior that is qualitatively consistent with a large collection of experimental data known as the Shields curve. Thus, our results suggest that the main features of this curve result from a competition between grain inertia and viscous damping. We find this phase diagram to be qualitatively insensitive to secondary effects, such as friction, irregular grain shape, and restitution losses. Funded by U.S. Army Research Office under Grant No. W911NF-14-1-0005.

  19. TEM and NanoSIMS Study of Hydrated/Anhydrous Phase Mixed IDPs: Cometary or Asteroidal Origin?

    NASA Technical Reports Server (NTRS)

    Nakamura, K.; Messenger, S.; Keller, L. P.

    2005-01-01

    Chondritic interplanetary dust particles (IDPs) are subdivided into (1) particles that form highly porous aggregates (chondritic porous "CP" IDPs), and (2) smooth particles ("CS" IDPs). Infrared (IR) spectroscopy has been a valuable tool for non-destructively determining the bulk mineralogy of IDPs. Most IDPs fall within three distinct IR groups: (1) olivine-rich particles, (2) pyroxene-rich particles, and (3) phyllosilicate-rich particles. From the IR studies, IDPs dominated by anhydrous minerals tend to be fine grained (CP), while phyllosilicate-rich IDPs are mostly CS. CP IDPs have been linked to cometary sources based on their compositions, spectral properties, and atmospheric entry velocities. Since no spectral signatures of hydrated minerals have been detected in comets, CS IDPs are thought to derive from primitive asteroids. Transmission electron microscopy (TEM) studies have revealed that the mineralogical distinctions between CP and CS IDPs are not always clear. Previous investigators have reported trace amounts of hydrous minerals in dominantly anhydrous particles. A better understanding of these particles will help to elucidate whether there is a genetic relationship between anhydrous and hydrated IDPs, provide insight into the earliest stages of aqueous alteration of primitive materials, and may help to determine whether comets have experienced any aqueous processing. Here we report a combined TEM and isotopic imaging study of an unusual anhydrous IDP with hydrated phases. Additional information is included in the original extended abstract.

  20. Microgravity fluid management in two-phase thermal systems

    NASA Technical Reports Server (NTRS)

    Parish, Richard C.

    1987-01-01

    Initial studies have indicated that in comparison to an all liquid single phase system, a two-phase liquid/vapor thermal control system requires significantly lower pumping power, demonstrates more isothermal control characteristics, and allows greater operational flexibility in heat load placement. As a function of JSC's Work Package responsibility for thermal management of space station equipment external to the pressurized modules, prototype development programs were initiated on the Two-Phase Thermal Bus System (TBS) and the Space Erectable Radiator System (SERS). JSC currently has several programs underway to enhance the understanding of two-phase fluid flow characteristics. The objective of one of these programs (sponsored by the Microgravity Science and Applications Division at NASA-Headquarters) is to design, fabricate, and fly a two-phase flow regime mapping experiment in the Shuttle vehicle mid-deck. Another program, sponsored by OAST, involves the testing of a two-phase thermal transport loop aboard the KC-135 reduced gravity aircraft to identify system implications of pressure drop variation as a function of the flow quality and flow regime present in a representative thermal system.

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

    NASA Astrophysics Data System (ADS)

    Odukoya, A.; Naterer, G. F.

    2015-07-01

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

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

    USGS Publications Warehouse

    Lee, Myung W.; Waite, William F.

    2008-01-01

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

  3. Dynamic Studies of Lung Fluid Clearance with Phase Contrast Imaging

    SciTech Connect

    Kitchen, Marcus J.; Williams, Ivan; Irvine, Sarah C.; Morgan, Michael J.; Paganin, David M.; Lewis, Rob A.; Pavlov, Konstantin; Hooper, Stuart B.; Wallace, Megan J.; Siu, Karen K. W.; Yagi, Naoto; Uesugi, Kentaro

    2007-01-19

    Clearance of liquid from the airways at birth is a poorly understood process, partly due to the difficulties of observing and measuring the distribution of air within the lung. Imaging dynamic processes within the lung in vivo with high contrast and spatial resolution is therefore a major challenge. However, phase contrast X-ray imaging is able to exploit inhaled air as a contrast agent, rendering the lungs of small animals visible due to the large changes in the refractive index at air/tissue interfaces. In concert with the high spatial resolution afforded by X-ray imaging systems (<100 {mu}m), propagation-based phase contrast imaging is ideal for studying lung development. To this end we have utilized intense, monochromatic synchrotron radiation, together with a fast readout CCD camera, to study fluid clearance from the lungs of rabbit pups at birth. Local rates of fluid clearance have been measured from the dynamic sequences using a single image phase retrieval algorithm.

  4. Comparison of the effects of oral hydration and intravenous fluid replacement in adult patients with non-shock dengue hemorrhagic fever in Taiwan.

    PubMed

    Lee, Ing-Kit; Lee, Wen-Huei; Yang, Kuender D; Liu, Jien-Wei

    2010-08-01

    The level of plasma leakage is mild to moderate in patients with non-shock dengue hemorrhagic fever (DHF grade I and grade II), and the necessity of intravenous fluid replacement for these patients remains controversial. We conducted an observational study in adult patients (>18 years) with non-shock DHF admitted to a medical centre in southern Taiwan comparing the effects of oral hydration [group 1 (n=19); age (mean+/-SD) 54.6+/-15.5 years] and intravenous fluid replacement, with a volume of >40ml/kg/day in the first 72h of hospitalization [group 2 (n=30); age 55.9+/-11.6 years]. No significant difference was found in demographics, clinical manifestations, and mean peak level of hematocrit between the two groups. Patients in group 2 had a significantly longer hospital stay compared to those in group 1 (P=0.007), and there was a trend suggesting patients in group 2 were prone to develop pleural effusion and/or pulmonary edema. No difference was found in daily mean pulse pressure, mean hematocrit level, and mean platelet count between the groups for the duration of the 7 days in hospital. All 49 patients survived. Our data suggest that oral hydration may be as effective as intravenous fluid replacement for adults with non-shock DHF and this warrants investigation in a larger series of patients.

  5. Density and Phase State of a Confined Nonpolar Fluid

    NASA Astrophysics Data System (ADS)

    Kienle, Daniel F.; Kuhl, Tonya L.

    2016-07-01

    Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers.

  6. Architectural remodeling of the tonoplast during fluid-phase endocytosis.

    PubMed

    Etxeberria, Ed; Gonzalez, Pedro; Pozueta-Romero, Javier

    2013-07-01

    During fluid phase endocytosis (FPE) in plant storage cells, the vacuole receives a considerable amount of membrane and fluid contents. If allowed to accumulate over a period of time, the enlarging tonoplast and increase in fluids would invariably disrupt the structural equilibrium of the mature cells. Therefore, a membrane retrieval process must exist that will guarantee membrane homeostasis in light of tonoplast expansion by membrane addition during FPE. We examined the morphological changes to the vacuolar structure during endocytosis in red beet hypocotyl tissue using scanning laser confocal microscopy and immunohistochemistry. The heavily pigmented storage vacuole allowed us to visualize all architectural transformations during treatment. When red beet tissue was incubated in 200 mM sucrose, a portion of the sucrose accumulated entered the cell by means of FPE. The accumulation process was accompanied by the development of vacuole-derived vesicles which transiently counterbalanced the addition of surplus endocytic membrane during rapid rates of endocytosis. Topographic fluorescent confocal micrographs showed an ensuing reduction in the size of the vacuole-derived vesicles and further suggest their reincorporation into the vacuole to maintain vacuolar unity and solute concentration. PMID:23656870

  7. Density and Phase State of a Confined Nonpolar Fluid.

    PubMed

    Kienle, Daniel F; Kuhl, Tonya L

    2016-07-15

    Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers. PMID:27472123

  8. Elastic-wave velocity in marine sediments with gas hydrates: Effective medium modeling

    USGS Publications Warehouse

    Helgerud, M.B.; Dvorkin, J.; Nur, A.; Sakai, A.; Collett, T.

    1999-01-01

    We offer a first-principle-based effective medium model for elastic-wave velocity in unconsolidated, high porosity, ocean bottom sediments containing gas hydrate. The dry sediment frame elastic constants depend on porosity, elastic moduli of the solid phase, and effective pressure. Elastic moduli of saturated sediment are calculated from those of the dry frame using Gassmann's equation. To model the effect of gas hydrate on sediment elastic moduli we use two separate assumptions: (a) hydrate modifies the pore fluid elastic properties without affecting the frame; (b) hydrate becomes a component of the solid phase, modifying the elasticity of the frame. The goal of the modeling is to predict the amount of hydrate in sediments from sonic or seismic velocity data. We apply the model to sonic and VSP data from ODP Hole 995 and obtain hydrate concentration estimates from assumption (b) consistent with estimates obtained from resistivity, chlorinity and evolved gas data. Copyright 1999 by the American Geophysical Union.

  9. Experimental Dissociation of Methane Hydrates Through Depressurization

    NASA Astrophysics Data System (ADS)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  10. Ternary phase behaviour and vesicle formation of a sodium N-lauroylsarcosinate hydrate/1-decanol/water system

    PubMed Central

    Akter, Nasima; Radiman, Shahidan; Mohamed, Faizal; Rahman, Irman Abdul; Reza, Mohammad Imam Hasan

    2011-01-01

    The phase behaviour of a system composed of amino acid-based surfactant (sodium N-lauroylsarcosinate hydrate), 1-decanol and deionised water was investigated for vesicle formation. Changing the molar ratio of the amphiphiles, two important aggregate structures were observed in the aqueous corner of the phase diagram. Two different sizes of microemulsions were found at two amphiphile-water boundaries. A stable single vesicle lobe was found for 1∶2 molar ratios in 92 wt% water with vesicles approximately 100 nm in size and with high zeta potential value. Structural variation arises due to the reduction of electrostatic repulsions among the ionic headgroups of the surfactants and the hydration forces due to adsorbed water onto monolayer's. The balance of these two forces determines the aggregate structures. Analysis was followed by the molecular geometrical structure. These findings may have implications for the development of drug delivery systems for cancer treatments, as well as cosmetic and food formulations. PMID:22355590

  11. Thermochemistry of the Reaction of SF6 with Gas-Phase Hydrated Electrons: A Benchmark for Nanocalorimetry.

    PubMed

    Akhgarnusch, Amou; Höckendorf, Robert F; Beyer, Martin K

    2015-10-01

    The reaction of sulfur hexafluoride with gas-phase hydrated electrons (H2O)n(-), n ≈ 60-130, is investigated at temperatures T = 140-300 K by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. SF6 reacts with a temperature-independent rate of 3.0 ± 1.0 × 10(-10) cm(3) s(-1) via exclusive formation of the hydrated F(-) anion and the SF5(•) radical, which evaporates from the cluster. Nanocalorimetry yields a reaction enthalpy of ΔHR,298K = 234 ± 24 kJ mol(-1). Combined with literature thermochemical data from bulk aqueous solution, these result in an F5S-F bond dissociation enthalpy of ΔH298K = 455 ± 24 kJ mol(-1), in excellent agreement with all high-level quantum chemical calculations in the literature. A combination with gas-phase literature thermochemistry also yields an experimental value for the electron affinity of SF5(•), EA(SF5(•)) = 4.27 ± 0.25 eV. PMID:26356833

  12. Hydrate detection

    SciTech Connect

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

    1992-06-01

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

  13. Hydrate detection

    SciTech Connect

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

    1992-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

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

    USGS Publications Warehouse

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

    2010-01-01

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

  16. The impact of increased sedimentation rates associated with the decay of the Fennoscandian ice-sheet on gas hydrate stability and focused fluid flow at the Nyegga pockmark field, offshore mid-Norway

    NASA Astrophysics Data System (ADS)

    Karstens, Jens; Haflidason, Haflidi; Becker, Lukas; Petter Sejrup, Hans; Berndt, Christian; Planke, Sverre; Dahlgreen, Torbjørn

    2016-04-01

    Climatic changes since the Last Glacial Maximum (LGM) have affected the stability of gas hydrate systems on glaciated margins by sea-level changes, bottom water temperature changes, isostatic uplift or subsidence and variability in sedimentation rates. While subsidence and sea-level rise stabilize gas hydrate deposits, bottom water temperature warming, uplift and enhanced sedimentation have the opposite effect. The response of gas hydrate systems to post-glaciation warming is therefore a complex phenomenon and highly depends on the timing and magnitude of each of these processes. While the impact of bottom water warming on the dissociation of gas hydrates have been addressed in numerous studies, the potential of methane release due to basal gas hydrate dissociation during periods of warming has received less attention. Here, we present results from numerical simulations which show that rapid sedimentation associated with the decay of the Fennoscandian ice-sheet was capable of causing significant basal gas hydrate dissociation. The modeling is constrained by a high-resolution three-dimensional sedimentation rate reconstruction of the Nyegga pockmark field, offshore mid-Norway, obtained by integrating chrono-stratigraphic information derived from sediments cores and a seismo-stratigraphic framework. The model run covers the period between 28,000 and 15,000 calendar years before present and predict that the maximum sedimentation rate-related gas hydrate dissociation coincides temporally and spatially with enhanced focused fluid flow activity in the study area. Basal gas hydrate dissociation due to rapid sedimentation may have occurred as well in other glaciated continental margins after the LGM and may have caused the release of significant amounts of methane to the hydrosphere and atmosphere. The major post glaciation deposition centers are the location of some of the largest known submarine slide complexes. The release of free gas due to basal gas hydrate

  17. Defining Condensed Phase Reactive Force Fields from ab Initio Molecular Dynamics Simulations: The Case of the Hydrated Excess Proton.

    PubMed

    Knight, Chris; Maupin, C Mark; Izvekov, Sergei; Voth, Gregory A

    2010-10-12

    In this report, a general methodology is presented for the parametrization of a reactive force field using data from a condensed phase ab initio molecular dynamics (AIMD) simulation. This algorithm allows for the creation of an empirical reactive force field that accurately reproduces the underlying ab initio reactive surface while providing the ability to achieve long-time statistical sampling for large systems not possible with AIMD alone. In this work, a model for the hydrated excess proton is constructed where the hydronium cation and proton hopping portions of the model are statistically force-matched to the results of Car-Parrinello Molecular Dynamics (CPMD) simulations. The flexible nature of the algorithm also allows for the use of the more accurate classical simple point-charge flexible water (SPC/Fw) model to describe the water-water interactions while utilizing the ab initio data to create an overall multistate molecular dynamics (MS-MD) reactive model of the hydrated excess proton in water. The resulting empirical model for the system qualitatively reproduces thermodynamic and dynamic properties calculated from the ab initio simulation while being in good agreement with experimental results and previously developed multistate empirical valence bond (MS-EVB) models. The present methodology, therefore, bridges the AIMD technique with the MS-MD modeling of reactive events, while incorporating key strengths of both. PMID:26616784

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

    USGS Publications Warehouse

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

    2012-01-01

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

  19. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

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

  20. Exploitation of subsea gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  1. Inverted hexagonal and cubic phases induced by alpha-tocopherol in fully hydrated dispersions of dilauroylphosphatidylethanolamine.

    PubMed

    Wang, X; Quinn, P J

    1999-08-01

    The effect of alpha-tocopherol on the thermotropic phase behaviour and structure of aqueous dispersions of 1,2-di-lauryl-sn-glycero-3-phosphoethanolamine was examined by synchrotron X-ray diffraction. The pure phospholipid exhibited a lamellar gel to liquid-crystal phase transition at 30 degrees C on heating at 3 degrees C min(-1) between 10 degrees C and 90 degrees C. The transition was reversible with a temperature hysteresis of 0.3 degrees C on cooling. At temperatures less than 10 degrees C only lamellar gel phase of the pure phospholipid was seen in co-dispersions of up to 20 mol % alpha-tocopherol. The presence of 2.5 mol % alpha-tocopherol caused the appearance of inverted hexagonal phase at temperatures just below the main phase transition temperature that co-existed with the lamellar gel phase. The intensity of scattering from the hexagonal-II phase increased with increasing proportion of alpha-tocopherol in the mixture and in proportions greater than 10 mol % it persisted at temperatures above the main transition and co-existed with the lamellar liquid-crystal phase of the pure phospholipid. At higher temperatures all co-dispersions containing up to 15 mol % alpha-tocopherol showed the presence of cubic phases. These phases indexed a Pn3m or Pn3 space grouping. When the proportion of alpha-tocopherol was increased to 20 mol % the only non-lamellar phase observed was inverted hexagonal phase. This phase co-existed with lamellar gel and liquid-crystal phases of the pure phospholipid, but was the only phase present at temperatures >60 degrees C. The X-ray diffraction data were used to construct a partial phase diagram of the lipid mixture in excess water between 10 degrees and 90 degrees C and up to 20 mol % alpha-tocopherol in phospholipid. PMID:17030321

  2. The dependence of phase change enthalpy on the pore structure and interfacial groups in hydrated salts/silica composites via sol-gel.

    PubMed

    Wu, Yuping; Wang, Tao

    2015-06-15

    It was found that the procedures for incorporating hydrated salts into silica, including mixing with sol in an instant (S1 procedure), mixing with sol via drop by drop (S2 procedure) and mixing until the sol forming the gel (S3 procedure), had pronounced effects on the phase change enthalpy of hydrated salts/silica composite via sol-gel process. The discrepancy of phase change enthalpies of the composites with the same content of hydrated salts can be as high as 40 kJ/kg. To unveil the mechanism behind, the pore structure of silica matrix and interfacial functional groups were investigated extensively. It was revealed that different incorporation procedures resulted in distinct pore structure of silica matrix and different intensities of interfacial Si-OH groups. The S3 procedure was beneficial to induce the silica matrix with bigger pore size and fewer Si-OH groups. Consequently, the phase change enthalpy of the hydrated salts/silica composite prepared by this procedure was the highest because of its lower size confinement effects and weaker adsorption by Si-OH groups. This study will provide insight into the preparation of shape-stabilized phase change materials for thermal energy storage applications.

  3. CONDENSED MATTER: STRUCTURAL, MECHANICAL, AND THERMAL PROPERTIES: Gas-Fluid and Fluid-Solid Phase Instability for Restricted Primitive Model

    NASA Astrophysics Data System (ADS)

    Guo, Yuan-Yuan; Chen, Xiao-Song

    2009-08-01

    By considering the fluctuation of grand potential Ω around equilibrium with respect to small one-particle density fluctuations δρα(vec r), the phase instability of restricted primitive model (RPM) of ionic systems is investigated. We use the integral equation theory to calculate the direct correlation functions in the reference hypernetted chain approximation and obtain the spinodal line of RPM. Our analysis explicitly indicates that the gas-fluid phase instability is induced by k = 0 fluctuation mode, while the fluid-solid phase instability is related to k ≠ 0 fluctuation modes. The spinodal line is qualitatively consistent with the result of computer simulations by others.

  4. Are seafloor pockmarks on the Chatham Rise, New Zealand, linked to CO2 hydrates? Gas hydrate stability considerations.

    NASA Astrophysics Data System (ADS)

    Pecher, I. A.; Davy, B. W.; Rose, P. S.; Coffin, R. B.

    2015-12-01

    Vast areas of the Chatham Rise east of New Zealand are covered by seafloor pockmarks. Pockmark occurrence appears to be bathymetrically controlled with a band of smaller pockmarks covering areas between 500 and 700 m and large seafloor depressions beneath 800 m water depth. The current depth of the top of methane gas hydrate stability in the ocean is about 500 m and thus, we had proposed that pockmark formation may be linked to methane gas hydrate dissociation during sealevel lowering. However, while seismic profiles show strong indications of fluid flow, geochemical analyses of piston cores do not show any evidence for current or past methane flux. The discovery of Dawsonite, indicative of significant CO2 flux, in a recent petroleum exploration well, together with other circumstantial evidence, has led us to propose that instead of methane hydrate, CO2 hydrate may be linked to pockmark formation. We here present results from CO2 hydrate stability calculations. Assuming water temperature profiles remain unchanged, we predict the upper limit of pockmark occurrence to coincide with the top of CO2 gas hydrate stability during glacial-stage sealevel lowstands. CO2 hydrates may therefore have dissociated during sealevel lowering leading to gas escape and pockmark formation. In contrast to our previous model linking methane hydrate dissociation to pockmark formation, gas hydrates would dissociate beneath a shallow base of CO2 hydrate stability, rather than on the seafloor following upward "grazing" of the top of methane hydrate stability. Intriguingly, at the water depths of the larger seafloor depressions, the base of gas hydrate stability delineates the phase boundary between CO2 hydrates and super-saturated CO2. We caution that because of the high solubility of CO2, dissociation from hydrate to free gas or super-saturated CO2 would imply high concentrations of CO2 and speculate that pockmark formation may be linked to CO2 hydrate dissolution rather than dissociation

  5. Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

    USGS Publications Warehouse

    Lu, W.; Chou, I.-Ming; Burruss, R.C.

    2008-01-01

    Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

  6. Particles at fluid-fluid interfaces: A new Navier-Stokes-Cahn-Hilliard surface- phase-field-crystal model

    NASA Astrophysics Data System (ADS)

    Aland, Sebastian; Lowengrub, John; Voigt, Axel

    2012-10-01

    Colloid particles that are partially wetted by two immiscible fluids can become confined to fluid-fluid interfaces. At sufficiently high volume fractions, the colloids may jam and the interface may crystallize. The fluids together with the interfacial colloids form an emulsion with interesting material properties and offer an important route to new soft materials. A promising approach to simulate these emulsions was presented in Aland [Phys. FluidsPHFLE61070-663110.1063/1.3584815 23, 062103 (2011)], where a Navier-Stokes-Cahn-Hilliard model for the macroscopic two-phase fluid system was combined with a surface phase-field-crystal model for the microscopic colloidal particles along the interface. Unfortunately this model leads to spurious velocities which require very fine spatial and temporal resolutions to accurately and stably simulate. In this paper we develop an improved Navier-Stokes-Cahn-Hilliard-surface phase-field-crystal model based on the principles of mass conservation and thermodynamic consistency. To validate our approach, we derive a sharp interface model and show agreement with the improved diffuse interface model. Using simple flow configurations, we show that the new model has much better properties and does not lead to spurious velocities. Finally, we demonstrate the solid-like behavior of the crystallized interface by simulating the fall of a solid ball through a colloid-laden multiphase fluid.

  7. Particles at fluid-fluid interfaces: A new Navier-Stokes-Cahn-Hilliard surface- phase-field-crystal model.

    PubMed

    Aland, Sebastian; Lowengrub, John; Voigt, Axel

    2012-10-01

    Colloid particles that are partially wetted by two immiscible fluids can become confined to fluid-fluid interfaces. At sufficiently high volume fractions, the colloids may jam and the interface may crystallize. The fluids together with the interfacial colloids form an emulsion with interesting material properties and offer an important route to new soft materials. A promising approach to simulate these emulsions was presented in Aland et al. [Phys. Fluids 23, 062103 (2011)], where a Navier-Stokes-Cahn-Hilliard model for the macroscopic two-phase fluid system was combined with a surface phase-field-crystal model for the microscopic colloidal particles along the interface. Unfortunately this model leads to spurious velocities which require very fine spatial and temporal resolutions to accurately and stably simulate. In this paper we develop an improved Navier-Stokes-Cahn-Hilliard-surface phase-field-crystal model based on the principles of mass conservation and thermodynamic consistency. To validate our approach, we derive a sharp interface model and show agreement with the improved diffuse interface model. Using simple flow configurations, we show that the new model has much better properties and does not lead to spurious velocities. Finally, we demonstrate the solid-like behavior of the crystallized interface by simulating the fall of a solid ball through a colloid-laden multiphase fluid. PMID:23214691

  8. Particles at fluid-fluid interfaces: A new Navier-Stokes-Cahn-Hilliard surface-phase-field-crystal model

    PubMed Central

    Aland, Sebastian; Lowengrub, John; Voigt, Axel

    2013-01-01

    Colloid particles that are partially wetted by two immiscible fluids can become confined to fluid-fluid interfaces. At sufficiently high volume fractions, the colloids may jam and the interface may crystallize. The fluids together with the interfacial colloids form an emulsion with interesting material properties and offer an important route to new soft materials. A promising approach to simulate these emulsions was presented in Aland et al. [Phys. Fluids 23, 062103 (2011)], where a Navier-Stokes-Cahn-Hilliard model for the macroscopic two-phase fluid system was combined with a surface phase-field-crystal model for the microscopic colloidal particles along the interface. Unfortunately this model leads to spurious velocities which require very fine spatial and temporal resolutions to accurately and stably simulate. In this paper we develop an improved Navier-Stokes-Cahn-Hilliard-surface phase-field-crystal model based on the principles of mass conservation and thermodynamic consistency. To validate our approach, we derive a sharp interface model and show agreement with the improved diffuse interface model. Using simple flow configurations, we show that the new model has much better properties and does not lead to spurious velocities. Finally, we demonstrate the solid-like behavior of the crystallized interface by simulating the fall of a solid ball through a colloid-laden multiphase fluid. PMID:23214691

  9. COMPARING SIMULATED AND EXPERIMENTAL HYSTERETIC TWO- PHASE TRANSIENT FLUID FLOW PHENOMENA

    EPA Science Inventory

    A hysteretic model for two-phase permeability (k)-saturation (S)-pressure (P) relations is outlined that accounts for effects of nonwetting fluid entrapment. The model can be employed in unsaturated fluid flow computer codes to predict temporal and spatial fluid distributions. Co...

  10. Major occurrences and reservoir concepts of marine clathrate hydrates: implications of field evidence

    USGS Publications Warehouse

    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.

  11. Optimizing fluid management in patients with acute decompensated heart failure (ADHF): the emerging role of combined measurement of body hydration status and brain natriuretic peptide (BNP) levels.

    PubMed

    Valle, Roberto; Aspromonte, Nadia; Milani, Loredano; Peacock, Frank W; Maisel, Alan S; Santini, Massimo; Ronco, Claudio

    2011-11-01

    The study tests the hypothesis that in patients admitted with acutely decompensated heart failure (ADHF), achievement of adequate body hydration status with intensive medical therapy, modulated by combined bioelectrical vectorial impedance analysis (BIVA) and B-type natriuretic peptide (BNP) measurement, may contribute to optimize the timing of patient's discharge and to improve clinical outcomes. Three hundred patients admitted for ADHF underwent serial BIVA and BNP measurement. Therapy was titrated to reach a BNP value of <250 pg/ml, whenever possible. Patients were categorized as early responders (rapid BNP fall below 250 pg/ml); late responders (slow BNP fall below 250 pg/ml, after aggressive therapy); and non-responders (BNP persistently >250 pg/ml). Worsening of renal function (WRF) was evaluated during hospitalization. Death and rehospitalization were monitored with a 6-month follow-up. BNP value on discharge of ≤250 pg/ml led to a 25% event rate within 6 months (Group A: 17.4%; Group B: 21%, Chi2; n.s.), whereas a value >250 pg/ml (Group C) was associated with a far higher percentage (37%). At discharge, body hydration was 73.8 ± 3.2% in the total population and 73.2 ± 2.1, 73.5 ± 2.8, 74.1 ± 3.6% in the three groups, respectively. WRF was observed in 22.3% of the total. WRF occurred in 22% in Group A, 32% in Group B, and 20% in Group C (P = n.s.). Our study confirms the hypothesis that combined BNP/BIVA sequential measurements help to achieve adequate fluid balance status in patients with ADHF and can be used to drive a "tailored therapy," allowing clinicians to identify high-risk patients and possibly to reduce the incidence of complications secondary to fluid management strategies.

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

    SciTech Connect

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

    2015-01-14

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

  13. Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

    NASA Technical Reports Server (NTRS)

    Peters, Bruce; Wingo, Dennis; Bower, Mark; Amborski, Robert; Blount, Laura; Daniel, Alan; Hagood, Bob; Handley, James; Hediger, Donald; Jimmerson, Lisa

    1990-01-01

    The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

  14. Kinetics of the main phase transition of hydrated lecithin monitored by real-time X-ray diffraction.

    PubMed Central

    Caffrey, M; Bilderback, D H

    1984-01-01

    A method is described for observing and recording in real-time x-ray diffraction from an unoriented hydrated membrane lipid, dipalmitoylphosphatidylcholine (DPPC), through its thermotropic gel/liquid crystal phase transition. Synchrotron radiation from the Cornell High Energy Synchrotron Source (Ithaca, New York) was used as an x-ray source of extremely high brilliance and the dynamic display of the diffraction image was effected using a three-stage image intensifier tube coupled to an external fluorescent screen. The image on the output phosphor was sufficiently intense to be recorded cinematographically and to be displayed on a television monitor using a vidicon camera at 30 frames X s1. These measurements set an upper limit of 2 s on the DPPC gel----liquid crystal phase transition and indicate that the transition is a two-state process. The real-time method couples the power of x-ray diffraction as a structural probe with the ability to follow kinetics of structural changes. The method does not require an exogenous probe, is relatively nonperturbing, and can be used with membranes in a variety of physical states and with unstable samples. The method has the additional advantage over its static measurement counterpart in that it is more likely to detect transiently stable intermediates if present. Images FIGURE 2 PMID:6546888

  15. Mechanisms of deep slab hydration: numerical modeling and implications

    NASA Astrophysics Data System (ADS)

    Faccenda, M.; Gerya, T.; Burlini, L.

    2009-12-01

    Water is a fundamental component of the Earth, affecting its internal structures and dynamics. Sea-water enters the subduction factory via slab hydration that occurs mainly at the trench and is subsequently released in the upper mantle wedge because of slab warming and de-hydration. In the last decades, the scientific research has focused mainly on geophysical processes related to the de-hydration of the slab. However, not much is known on how and to which extent the subducting oceanic plate get hydrated. In order to investigate hydration of the slab, we performed 2D numerical models of a spontaneously bending oceanic plate using I2ELVIS code that account for visco-elasto-plastic rheologies and where fluid flow is regulated by Darci’s law. At the outer rise, bending-related slab faulting occurs, providing a pathway for water percolation in the slab. Faults generally deep trenchward, but antithetic faults are also common. Downward deep fluid flow establishes during brittle extensional deformation at the trench outer rise producing strong variation of the tectonic pressure and causing sub-hydrostatic or even negative pressure gradients along bending related normal faults through which fluids are pumped. The results of the numerical experiment indicate that water can be transported down and stored in the bending area via serpentinization of the normal faults. Deep slab hydration has important implications for the rheological structure, seismicity and seismic anisotropy of the upper mantle because: 1) more water can be stored in the slab producing more enhanced weakening of the mantle wedge, 2) intermediate and deep intra-slab earthquakes can be triggered by slab de-hydration, 3) DHMS phases, able to bring fluids down to the transition zone and lower mantle, could form in the cold core of the slab, 4) the slab could acquire a strong anisotropic fabric responsible for the anisotropic patterns observed at subduction zones.

  16. Influence of phase connectivity on the relationship among capillary pressure, fluid saturation, and interfacial area in two-fluid-phase porous medium systems

    DOE PAGES

    McClure, James E.; Berrill, Mark A.; Gray, William G.; Miller, Cass T.

    2016-09-02

    Here, multiphase flow in porous medium systems is typically modeled using continuum mechanical representations at the macroscale in terms of averaged quantities. These models require closure relations to produce solvable forms. One of these required closure relations is an expression relating fluid pressures, fluid saturations, and, in some cases, the interfacial area between the fluid phases, and the Euler characteristic. An unresolved question is whether the inclusion of these additional morphological and topological measures can lead to a non-hysteretic closure relation compared to the hysteretic forms that are used in traditional models, which typically do not include interfacial areas, ormore » the Euler characteristic. We develop a lattice-Boltzmann (LB) simulation approach to investigate the equilibrium states of a two-fluid-phase porous medium system, which include disconnected now- wetting phase features. The proposed approach is applied to a synthetic medium consisting of 1,964 spheres arranged in a random, non-overlapping, close-packed manner, yielding a total of 42,908 different equilibrium points. This information is evaluated using a generalized additive modeling approach to determine if a unique function from this family exists, which can explain the data. The variance of various model estimates is computed, and we conclude that, except for the limiting behavior close to a single fluid regime, capillary pressure can be expressed as a deterministic and non-hysteretic function of fluid saturation, interfacial area between the fluid phases, and the Euler characteristic. This work is unique in the methods employed, the size of the data set, the resolution in space and time, the true equilibrium nature of the data, the parameterizations investigated, and the broad set of functions examined. The conclusion of essentially non-hysteretic behavior provides support for an evolving class of two-fluid-phase flow in porous medium systems models.« less

  17. X-Ray Microspectroscopic Investigations of Remote Aerosol Composition and Changes in Aerosol Microstructure and Phase State upon Hydration

    NASA Astrophysics Data System (ADS)

    Andreae, M. O.; Artaxo, P.; Bechtel, M.; Förster, J. D.; Kilcoyne, A. L. D.; Krüger, M. L.; Pöhlker, C.; Saturno, J.; Weigand, M.; Wiedemann, K. T.

    2014-12-01

    Atmospheric aerosols play a crucial role in the Earth's climate system and hydrological cycle by scattering and absorbing sunlight and affecting the formation and development of clouds and precipitation. Our research focuses on aerosols in remote regions, in order to characterize the properties and sources of natural aerosol particles and the extent of human perturbations of the aerosol burden. The phase and mixing state of atmospheric aerosols, and particularly their hygroscopic response to relative humidity (RH) variations, is a central determinant of their atmospheric life cycle and impacts. We present an investigation using X-ray microspectroscopy on submicrometer aerosols under variable RH conditions, showing in situ changes in morphology, microstructure, and phase state upon humidity cycling. We applied Scanning Transmission X-ray Microscopy with Near-Edge X-ray Absorption Fine Structure spectroscopy (STXM-NEXAFS) under variable RH conditions to standard aerosols for a validation of the experimental approach and to internally mixed aerosol particles from the Amazonian rain forest collected during periods with anthropogenic pollution. The measurements were conducted at X-ray microscopes at the synchrotron facilities Advanced Light Source (ALS) in Berkeley, USA, and BESSY II in Berlin, Germany. Upon hydration, we observed substantial and reproducible changes in microstructure of the Amazonian particles (internal mixture of secondary organic material, ammoniated sulfate, and soot), which appear as mainly driven by efflorescence and recrystallization of sulfate salts. Multiple solid and liquid phases were found to coexist, especially in intermediate humidity regimes (60-80% RH). This shows that X-ray microspectroscopy under variable RH is a valuable technique to analyze the hygroscopic response of individual ambient aerosol particles. Our initial results underline that RH changes can trigger strong particle restructuring, in agreement with previous studies on

  18. Transformations in methane hydrates

    USGS Publications Warehouse

    Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

    2000-01-01

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

  19. Aqueous Fluids in Carbon Nanotubes: Fluid Motion, Phase Change and Wetting at the Nanoscale

    NASA Astrophysics Data System (ADS)

    Yazicioglu, Almila; Megaridis, Constantine; Gogotsi, Yury

    2003-11-01

    Since multiwall carbon nanotubes are excellent candidates for use in micro- and nano-fluidic devices, it is important to investigate experimentally the dynamic behavior of fluids contained in nanotubes. We have used hydrothermally synthesized closed carbon nanotubes to test the behavior of multiphase fluids at the nanoscale. These nanotubes, with lengths varying from 1 to 10 microns and diameters 20-100 nm, have their hollow interiors filled with an aqueous fluid. The fluid, which, at equilibrium, consists of about 85manipulated thermally via the high-energy beam of a transmission electron microscope (TEM). The multiphase fluid motion in the nanotube interior can be visualized with the TEM, because the thin nanotube walls (10-25 nm) are almost transparent to the electron beam. The nanotubes are leak tight, as they encapsulate the fluids at pressures of about 30 MPa, even in the high vacuum environment of the TEM. Processes such as evaporation and condensation, evaporative transport, and reversible liquid volume expansion and contraction are observed in real time by expanding and contracting the electron beam. The superior wettability of the inner tube walls by the aqueous fluid is demonstrated with nanoscale resolution. The current study provides an experimental database for the development of theoretical models describing fluid behavior in nanosize channels.

  20. Rapid gas hydrate formation process

    DOEpatents

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

    2013-01-15

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

  1. Working fluid selection for space-based two-phase heat transport systems

    NASA Technical Reports Server (NTRS)

    Mclinden, Mark O.

    1988-01-01

    The working fluid for externally-mounted, space-based two-phase heat transport systems is considered. A sequence of screening criteria involving freezing and critical point temperatures and latent heat of vaporization and vapor density are applied to a data base of 860 fluids. The thermal performance of the 52 fluids which pass this preliminary screening are then ranked according to their impact on the weight of a reference system. Upon considering other nonthermal criteria (flammability, toxicity, and chemical stability) a final set of 10 preferred fluids is obtained. The effects of variations in system parameters is investigated for these 10 fluids by means of a factorial design.

  2. Interstitial Pressure in Pancreatic Ductal Adenocarcinoma Is Dominated by a Gel-Fluid Phase.

    PubMed

    DuFort, Christopher C; DelGiorno, Kathleen E; Carlson, Markus A; Osgood, Ryan J; Zhao, Chunmei; Huang, Zhongdong; Thompson, Curtis B; Connor, Robert J; Thanos, Christopher D; Scott Brockenbrough, J; Provenzano, Paolo P; Frost, Gregory I; Michael Shepard, H; Hingorani, Sunil R

    2016-05-10

    Elevated interstitial fluid pressure can present a substantial barrier to drug delivery in solid tumors. This is particularly true of pancreatic ductal adenocarcinoma, a highly lethal disease characterized by a robust fibroinflammatory response, widespread vascular collapse, and hypoperfusion that together serve as primary mechanisms of treatment resistance. Free-fluid pressures, however, are relatively low in pancreatic ductal adenocarcinoma and cannot account for the vascular collapse. Indeed, we have shown that the overexpression and deposition in the interstitium of high-molecular-weight hyaluronan (HA) is principally responsible for generating pressures that can reach 100 mmHg through the creation of a large gel-fluid phase. By interrogating a variety of tissues, tumor types, and experimental model systems, we show that an HA-dependent fluid phase contributes substantially to pressures in many solid tumors and has been largely unappreciated heretofore. We investigated the relative contributions of both freely mobile fluid and gel fluid to interstitial fluid pressure by performing simultaneous, real-time fluid-pressure measurements with both the classical wick-in-needle method (to estimate free-fluid pressure) and a piezoelectric pressure catheter transducer (which is capable of capturing pressures associated with either phase). We demonstrate further that systemic treatment with pegylated recombinant hyaluronidase (PEGPH20) depletes interstitial HA and eliminates the gel-fluid phase. This significantly reduces interstitial pressures and leaves primarily free fluid behind, relieving the barrier to drug delivery. These findings argue that quantifying the contributions of free- and gel-fluid phases to hydraulically transmitted pressures in a given cancer will be essential to designing the most appropriate and effective strategies to overcome this important and frequently underestimated resistance mechanism. PMID:27166818

  3. HYDRATE CORE DRILLING TESTS

    SciTech Connect

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

    2002-11-01

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

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

    NASA Astrophysics Data System (ADS)

    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

  5. Self-Gravitating Relativistic Fluids: The Formation of a Free Phase Boundary in the Phase Transition from Hard to Soft

    NASA Astrophysics Data System (ADS)

    Christodoulou, Demetrios; Lisibach, André

    2016-11-01

    In the 1990s Christodoulou introduced an idealized fluid model intended to capture some of the features of the gravitational collapse of a massive star to form a neutron star or a black hole. This was the two-phase model introduced in `Self-gravitating relativistic fluids: a two phase model' (Demeterios, Arch Ration Mech Anal 130:343-400, 1995). The present work deals with the formation of a free phase boundary in the phase transition from hard to soft in this model. In this case the phase boundary has corners at the null points; the points which separate the timelike and spacelike components of the interface between the two phases. We prove the existence and uniqueness of a free phase boundary. Also the local form of the shock near the null point is established.

  6. Self-Gravitating Relativistic Fluids: The Formation of a Free Phase Boundary in the Phase Transition from Hard to Soft

    NASA Astrophysics Data System (ADS)

    Christodoulou, Demetrios; Lisibach, André

    2016-06-01

    In the 1990s Christodoulou introduced an idealized fluid model intended to capture some of the features of the gravitational collapse of a massive star to form a neutron star or a black hole. This was the two-phase model introduced in `Self-gravitating relativistic fluids: a two phase model' (Demeterios, Arch Ration Mech Anal 130:343-400, 1995). The present work deals with the formation of a free phase boundary in the phase transition from hard to soft in this model. In this case the phase boundary has corners at the null points; the points which separate the timelike and spacelike components of the interface between the two phases. We prove the existence and uniqueness of a free phase boundary. Also the local form of the shock near the null point is established.

  7. Experimental Study of Gas Hydrate Dynamics

    NASA Astrophysics Data System (ADS)

    Fandino, O.; Ruffine, L.

    2011-12-01

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

  8. The effect of acute fluid consumption following exercise-induced fluid loss on hydration status, percent body fat, and minimum wrestling weight in wrestlers.

    PubMed

    Cutrufello, Paul T; Dixon, Curt B

    2014-07-01

    Acute fluid consumption (approximately 1 L) has been shown to reduce urine specific gravity (Usg) among subjects after an overnight fast, yet it is unknown if Usg may be reduced among subjects who have experienced exercise-induced fluid loss. The purpose of this study was to examine the effect of acute fluid consumption on Usg, body mass, percent body fat (%BF), and minimum wrestling weight (MWW) following an exercise-induced fluid loss protocol. National Collegiate Athletic Association coaches' perceptions of the weight certification program (WCP) were also evaluated. Twelve men wrestlers (19.8 ± 1.14 years) were tested prepractice (PRE), postpractice (POST), and 1 hour after consuming 1 L of water (PFC). Percent body fat was measured by skinfolds (SF), air displacement plethysmography (ADP), and multifrequency and leg-to-leg bioelectrical impedance analysis to calculate MWW. Urine specific gravity measurements significantly increased above PRE (1.013 ± 0.006) at the POST (1.019 ± 0.007; p = 0.017) and PFC (1.022 ± 0.008; p = 0.025) assessments; however, POST and PFC were not significantly different (p = 0.978) from one another. The %BF values were similar (p > 0.05) at each assessment point when using SF and ADP. When compared with PRE, MWW significantly reduced at the POST assessment when using SF (67.2 ± 8.4 vs. 65.7 ± 8.2 kg; p < 0.001) and ADP (66.6 ± 9.1 vs. 64.8 ± 9.0 kg; p = 0.001), reflecting the reduction in body mass observed after exercise. Forty-seven National Collegiate Athletic Association coaches completed the questionnaire and 2 central themes emerged: (a) concerns with the 1.5% weight loss plan and (b) wrestlers using strategies in an attempt to circumvent the WCP. Exercise-induced fluid loss followed by acute fluid consumption equal to 1 L was ineffective in reducing Usg.

  9. Horse heart cytochrome c entrapped into the hydrated liquid-crystalline phases of phytantriol: X-ray diffraction and Raman spectroscopic characterization.

    PubMed

    Misiūnas, Audrius; Niaura, Gediminas; Barauskas, Justas; Meškys, Rolandas; Rutkienė, Rasa; Razumas, Valdemaras; Nylander, Tommy

    2012-07-15

    Small angle X-ray diffraction (SAXD), resonance Raman (RR) spectroscopy with 413 nm excitation, and non-resonance Raman technique with 785 nm excitation were used to probe the influence of entrapped cytochrome c (Cyt c) on the structure of hydrated phytantriol (Phyt) liquid-crystalline phases as well as conformational changes of heme group and secondary structure of the protein. SAXD measurements indicated that incorporation of Cyt c affects both nanostructure dimensions and type of liquid-crystalline phases of hydrated Phyt. The unit cell dimensions decrease with increasing Cyt c concentration for all phases. In addition, protein perturbs the nanostructure of Q(230) and Q(224) liquid-crystalline phases of hydrated Phyt to such an extent that they transform into the Q(229) phase with the Im3m space group. RR data revealed that entrapment of oxidized Cyt c into the Q(230) phase at 1 wt.% content results in near complete reduction of central iron ion of the heme group, while its low-spin state and six-ligand coordination configuration are preserved. Based on the analysis of heme out-of-plane folding vibration near 568 cm(-1) (γ(21)) and ν(48) mode at 633 cm(-1), it was demonstrated that the protein matrix tension on the heme group is relaxed upon incorporation of protein into Q(230) phase. Non-resonant Raman bands of difference spectra showed the preservation of α-helix secondary structure of Cyt c in the liquid-crystalline phase at relatively high (5 wt.%) content. The Cyt c induced spectroscopic changes of Phyt bands were found to be similar as decrease in temperature.

  10. Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

    PubMed

    Rout, Alok; Binnemans, Koen

    2014-02-28

    The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

  11. Influence of phase connectivity on the relationship among capillary pressure, fluid saturation, and interfacial area in two-fluid-phase porous medium systems

    NASA Astrophysics Data System (ADS)

    McClure, James E.; Berrill, Mark A.; Gray, William G.; Miller, Cass T.

    2016-09-01

    Multiphase flows in porous medium systems are typically modeled at the macroscale by applying the principles of continuum mechanics to develop models that describe the behavior of averaged quantities, such as fluid pressure and saturation. These models require closure relations to produce solvable forms. One of these required closure relations is an expression relating the capillary pressure to fluid saturation and, in some cases, other topological invariants such as interfacial area and the Euler characteristic (or average Gaussian curvature). The forms that are used in traditional models, which typically consider only the relationship between capillary pressure and saturation, are hysteretic. An unresolved question is whether the inclusion of additional morphological and topological measures can lead to a nonhysteretic closure relation. Relying on the lattice Boltzmann (LB) method, we develop an approach to investigate equilibrium states for a two-fluid-phase porous medium system, which includes disconnected nonwetting phase features. A set of simulations are performed within a random close pack of 1964 spheres to produce a total of 42 908 distinct equilibrium configurations. This information is evaluated using generalized additive models to quantitatively assess the degree to which functional relationships can explain the behavior of the equilibrium data. The variance of various model estimates is computed, and we conclude that, except for the limiting behavior close to a single fluid regime, capillary pressure can be expressed as a deterministic and nonhysteretic function of fluid saturation, interfacial area between the fluid phases, and the Euler characteristic. To our knowledge, this work is unique in the methods employed, the size of the data set, the resolution in space and time, the true equilibrium nature of the data, the parametrizations investigated, and the broad set of functions examined. The conclusion of essentially nonhysteretic behavior provides

  12. Effects of porosity and mixed convection on MHD two phase fluid flow in an inclined channel.

    PubMed

    Hasnain, Jafar; Abbas, Zaheer; Sajid, Muhammad

    2015-01-01

    The present study deals with the flow and heat transfer analysis of two immiscible fluids in an inclined channel embedded in a porous medium. The channel is divided in two phases such that a third grade fluid occupies the phase I and a viscous fluid occupies the phase II. Both viscous and third grade fluids are electrically conducting. A constant magnetic field is imposed perpendicular to the channel walls. The mathematical model is developed by using Darcy's and modified Darcy's laws for viscous and third grade fluids respectively. The transformed ordinary differential equations are solved numerically using a shooting method. The obtained results are presented graphically and influence of emerging parameters is discussed in detail. PMID:25803360

  13. Effects of porosity and mixed convection on MHD two phase fluid flow in an inclined channel.

    PubMed

    Hasnain, Jafar; Abbas, Zaheer; Sajid, Muhammad

    2015-01-01

    The present study deals with the flow and heat transfer analysis of two immiscible fluids in an inclined channel embedded in a porous medium. The channel is divided in two phases such that a third grade fluid occupies the phase I and a viscous fluid occupies the phase II. Both viscous and third grade fluids are electrically conducting. A constant magnetic field is imposed perpendicular to the channel walls. The mathematical model is developed by using Darcy's and modified Darcy's laws for viscous and third grade fluids respectively. The transformed ordinary differential equations are solved numerically using a shooting method. The obtained results are presented graphically and influence of emerging parameters is discussed in detail.

  14. Effects of Porosity and Mixed Convection on MHD Two Phase Fluid Flow in an Inclined Channel

    PubMed Central

    Hasnain, Jafar; Abbas, Zaheer; Sajid, Muhammad

    2015-01-01

    The present study deals with the flow and heat transfer analysis of two immiscible fluids in an inclined channel embedded in a porous medium. The channel is divided in two phases such that a third grade fluid occupies the phase I and a viscous fluid occupies the phase II. Both viscous and third grade fluids are electrically conducting. A constant magnetic field is imposed perpendicular to the channel walls. The mathematical model is developed by using Darcy's and modified Darcy's laws for viscous and third grade fluids respectively. The transformed ordinary differential equations are solved numerically using a shooting method. The obtained results are presented graphically and influence of emerging parameters is discussed in detail. PMID:25803360

  15. A New n = 4 Layered Ruddlesden-Popper Phase K(2.5)Bi(2.5)Ti4O13 Showing Stoichiometric Hydration.

    PubMed

    Liu, Samuel; Avdeev, Maxim; Liu, Yun; Johnson, Mark R; Ling, Chris D

    2016-02-15

    A new bismuth-containing layered perovskite of the Ruddlesden-Popper type, K(2.5)Bi(2.5)Ti4O13, has been prepared by solid-state synthesis. It has been shown to hydrate to form stoichiometric K(2.5)Bi(2.5)Ti4O13·H2O. Diffraction data show that the structure consists of a quadruple-stacked (n = 4) perovskite layer, with potassium ions occupying the rock salt layer and its next-nearest A site. The hydrated sample was shown to remove the offset between stacked perovskite layers relative to the dehydrated sample. Computational methods show that the hydrated phase consists of intact H2O molecules in a vertical "pillared" arrangement bridging across the interlayer space. Rotations of H2O molecules about the c axis were evident in molecular dynamic calculations, which increased in rotation angle with increasing temperature. In situ diffraction data for the dehydrated phase point to a broad structural phase transition from orthorhombic to tetragonal at ∼600 °C. The relative bismuth-rich composition in the perovskite block results in a higher transition temperature compared to related perovskite structures. Water makes a significant contribution to the dielectric constant, which disappears after dehydration.

  16. Two-phase dusty fluid flow along a cone with variable properties

    NASA Astrophysics Data System (ADS)

    Siddiqa, Sadia; Begum, Naheed; Hossain, Md. Anwar; Mustafa, Naeem; Gorla, Rama Subba Reddy

    2016-09-01

    In this paper numerical solutions of a two-phase natural convection dusty fluid flow are presented. The two-phase particulate suspension is investigated along a vertical cone by keeping variable viscosity and thermal conductivity of the carrier phase. Comprehensive flow formations of the gas and particle phases are given with the aim to predict the behavior of heat transport across the heated cone. The influence of (1) air with particles, (2) water with particles and (3) oil with particles are shown on shear stress coefficient and heat transfer coefficient. It is recorded that sufficient increment in heat transport rate can be achieved by loading the dust particles in the air. Further, distribution of velocity and temperature of both the carrier phase and the particle phase are shown graphically for the pure fluid (air, water) as well as for the fluid with particles (air-metal and water-metal particle mixture).

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  18. Frequency scaling of seismic attenuation in rocks saturated with two fluid phases

    NASA Astrophysics Data System (ADS)

    Chapman, Samuel; Quintal, Beatriz; Tisato, Nicola; Holliger, Klaus

    2016-10-01

    Seismic wave attenuation is frequency dependent in rocks saturated by two fluid phases and the corresponding scaling behavior is controlled primarily by the spatial fluid distribution. We experimentally investigate the frequency scaling of seismic attenuation in Berea sandstone saturated with two fluid phases: a liquid phase, water, and a gas phase, air, carbon dioxide or nitrogen. By changing from a heterogeneous distribution of mesoscopic gas patches to a homogeneous distribution of pore scale gas bubbles, we observe a significant steepening of the high-frequency asymptote of the attenuation. A transition from one dominant attenuation mechanism to another, from mesoscopic wave-induced fluid flow (WIFF) to wave-induced gas exsolution dissolution (WIGED), may explain this change in scaling. We observe that the high-frequency asymptote, for a homogenous pore scale gas bubble distribution, scales in accord with WIGED.

  19. Extraordinary phase separation and segregation in vent fluids from the southern East Pacific Rise

    USGS Publications Warehouse

    Von Damm, K. L.; Lilley, M.D.; Shanks, Wayne C.; Brockington, M.; Bray, A.M.; O'Grady, K. M.; Olson, E.; Graham, A.; Proskurowski, G.

    2003-01-01

    The discovery of Brandon vent on the southern East Pacific Rise is providing new insights into the controls on midocean ridge hydrothermal vent fluid chemistry. The physical conditions at the time ofsampling (287 bar and 405??C) place the Brandon fluids very close to the critical point of seawater (298 bar and 407??C). This permits in situ study of the effects of near criticalphenomena, which are interpreted to be the primary cause of enhanced transition metal transport in these fluids. Of the five orifices on Brandon sampled, three were venting fluids with less than seawater chlorinity, and two were venting fluids with greater than seawater chlorinity. The liquid phase orifices contain 1.6-1.9 times the chloride content of the vapors. Most other elements, excluding the gases, have this same ratio demonstrating the conservative nature of phase separation and the lack of subsequent water-rock interaction. The vapor and liquid phases vent at the same time from orifices within meters of each other on the Brandon structure. Variations in fluid compositions occur on a time scale of minutes. Our interpretation is that phase separation and segregation must be occurring 'real time' within the sulfide structure itself. Fluids from Brandon therefore provide an unique opportunity to understand in situ phase separation without the overprinting of continued water-rock interaction with the oceanic crust, as well as critical phenomena. ?? 2002 Elsevier Science B.V. All rights reserved.

  20. Constraining the origin of the Messinian gypsum deposits using coupled measurement of δ^{18}O$/δD in gypsum hydration water and salinity of fluid inclusions

    NASA Astrophysics Data System (ADS)

    Evans, Nicholas P.; Gázquez, Fernando; McKenzie, Judith A.; Chapman, Hazel J.; Hodell, David A.

    2016-04-01

    We used oxygen and hydrogen isotopes of gypsum hydration water (GHW) coupled with salinity deduced from ice melting temperatures of primary fluid inclusions in the same samples (in tandem with 87Sr/86Sr, δ34S and other isotopic measurements) to determine the composition of the mother fluids that formed the gypsum deposits of the Messinian Salinity Crisis from shallow and intermediate-depth basins. Using this method, we constrain the origin of the Messinian Primary Lower Gypsum (PLG) of the Sorbas basin (Betic foreland) and both the Upper Gypsum (UG) and the Lower Gypsum of the Sicilian basin. We then compare these results to measurements made on UG recovered from the deep Ionian and Balearic basins drilled during DSDP Leg 42A. The evolution of GHW δ18O/δD vs. salinity is controlled by mixing processes between fresh and seawater, coupled with the degree of evaporation. Evaporation and subsequent precipitation of gypsum from fluids dominated by freshwater will result in a depressed 87Sr/86Sr values and different trajectory in δ18O/δD vs. salinity space compared to fluids dominated by seawater. The slopes of these regression equations help to define the end-members from which the fluid originated. For example, salinity estimates from PLG cycle 6 in the Sorbas basin range from 18 to 51ppt, and after correction for fractionation factors, estimated δ18O and δD values of the mother water are low (-2.6 < δ18O < 2.7‰ ; -16.2 < δD < 15.8‰). The intercepts of the regression equations (i.e. at zero salinity) are within error of the average isotope composition of the modern precipitation and groundwater in this region of SE Spain. This indicates there was a significant contribution of meteoric water during gypsum deposition, while 87Sr/86Sr (0.708942 < 87Sr/86Sr < 0.708971) indicate the ions originated from the dissolution of previously marine evaporites. Gypsum from cycle 2 displays similar mother water values (-2.4 < δ18O < 2.4‰ ; -13.2 < δD < 17.0‰) to

  1. Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 1. Electromagnetic properties

    USGS Publications Warehouse

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

    2010-01-01

    The marked decrease in bulk electrical conductivity of sediments in the presence of gas hydrates has been used to interpret borehole electrical resistivity logs and, to a lesser extent, the results of controlled source electromagnetic surveys to constrain the spatial distribution and predicted concentration of gas hydrate in natural settings. Until now, an exhaustive laboratory data set that could be used to assess the impact of gas hydrate on the electromagnetic properties of different soils (sand, silt, and clay) at different effective stress and with different saturations of hydrate has been lacking. The laboratory results reported here are obtained using a standard geotechnical cell and the hydrate-formed tetrahydrofuran (THF), a liquid that is fully miscible in water and able to produce closely controlled saturations of hydrate from dissolved phase. Both permittivity and electrical conductivity are good indicators of the volume fraction of free water in the sediment, which is in turn dependent on hydrate saturation. Permittivity in the microwave frequency range is particularly predictive of free water content since it is barely affected by ionic concentration, pore structure, and surface conduction. Electrical conductivity (or resistivity) is less reliable for constraining water content or hydrate saturation: In addition to fluid-filled porosity, other factors, such as the ionic concentration of the pore fluid and possibly other conduction effects (e.g., surface conduction in high specific surface soils having low conductivity pore fluid), also influence electrical conductivity.

  2. Method and turbine for extracting kinetic energy from a stream of two-phase fluid

    NASA Technical Reports Server (NTRS)

    Elliott, D. G. (Inventor)

    1979-01-01

    An axial flow separator turbine is described which includes a number of nozzles for delivering streams of a two-phase fluid along linear paths. A phase separator which responsively separates the vapor and liquid is characterized by concentrically related annuli supported for rotation within the paths. The separator has endless channels for confining the liquid under the influence of centrifugal forces. A vapor turbine fan extracts kinetic energy from the liquid. Angular momentum of both the liquid phase and the vapor phase of the fluid is converted to torque.

  3. Molecular theory for the phase equilibria and cluster distribution of associating fluids with small bond angles.

    PubMed

    Marshall, Bennett D; Chapman, Walter G

    2013-08-01

    We develop a new theory for associating fluids with multiple association sites. The theory accounts for small bond angle effects such as steric hindrance, ring formation, and double bonding. The theory is validated against Monte Carlo simulations for the case of a fluid of patchy colloid particles with three patches and is found to be very accurate. Once validated, the theory is applied to study the phase diagram of a fluid composed of three patch colloids. It is found that bond angle has a significant effect on the phase diagram and the very existence of a liquid-vapor transition.

  4. Computational study of trimer self-assembly and fluid phase behavior

    SciTech Connect

    Hatch, Harold W. Shen, Vincent K.; Mittal, Jeetain

    2015-04-28

    The fluid phase diagram of trimer particles composed of one central attractive bead and two repulsive beads was determined as a function of simple geometric parameters using flat-histogram Monte Carlo methods. A variety of self-assembled structures were obtained including spherical micelle-like clusters, elongated clusters, and densely packed cylinders, depending on both the state conditions and shape of the trimer. Advanced simulation techniques were employed to determine transitions between self-assembled structures and macroscopic phases using thermodynamic and structural definitions. Simple changes in particle geometry yield dramatic changes in phase behavior, ranging from macroscopic fluid phase separation to molecular-scale self-assembly. In special cases, both self-assembled, elongated clusters and bulk fluid phase separation occur simultaneously. Our work suggests that tuning particle shape and interactions can yield superstructures with controlled architecture.

  5. The role of hydration in enzyme activity and stability: 2. Alcohol dehydrogenase activity and stability in a continuous gas phase reactor.

    PubMed

    Yang, F; Russell, A J

    1996-03-20

    The degree of enzyme hydration is the one of the most important factors which can affect enzyme activity and stability in water-limited environments. Alcohol dehydrogenase from baker's yeast (YADH) has been used as a model enzyme to study the effects of hydration on activity, stability, and cofactor stability with gas phase substrates. In all cases, the enzyme is essentially inactive until a temperature-independent degree of surface coverage by water molecules has been reached. The critical water content corresponds to 40-50% of a single monolayer. Careful control of the degree of hydration, by adjustments to gas humidity and temperature, enables the enzyme to be stabilized for periods exceeding 1 month, whereas in water the half-life of the enzyme is 30 min. The reaction with gas phase substrates follows a pseudo-first-order mechanism with an activation energy of 7.5 +/- kcal/mol, which is almost half of that in aqueous solution. (c) 1996 John Wiley & Sons, Inc.

  6. Quantitative analysis of ripasudil hydrochloride hydrate and its impurities by reversed-phase high-performance liquid chromatography after precolumn derivatization: Identification of four impurities.

    PubMed

    Hui, Wenkai; Sun, Lili; Zhang, Hui; Zou, Liang; Zou, Qiaogen; Ouyang, Pingkai

    2016-09-01

    We report the development and validation of a stability-indicating reversed-phase high-performance liquid chromatography method with precolumn derivatization for the separation and identification of the impurities of ripasudil hydrochloride hydrate, a novel protein kinase inhibitor. 2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl isothiocyanate was chosen as the derivatizing reagent and triethylamine was added as catalyst. 200 μL sample solution (1 mg/mL), 600 μL derivatizing reagent (1 mg/mL), and 200 μL triethylamine solution (1%, v/v) were mixed and reacted at 40°C for 30 min. The separation was achieved on an Inertsil C18 ODS-3 (250 mm × 4.6 mm, 5 μm) column using mobile phases including 10 mmol monopotassium phosphate buffer (pH 3.0) and methanol in gradient mode. The column temperature was adjusted at 25°C and the flow rate at 1 mL/min. The detection was carried out at 220 nm. Different precolumn derivatization conditions as well as the high-performance liquid chromatography conditions were optimized. Ripasudil hydrochloride hydrate and its four impurities were detected and quantitated, among which two new compounds were characterized. The proposed method was validated and proven to be selective, accurate, and precise and suitable for the quantitative analysis of ripasudil hydrochloride hydrate. PMID:27390135

  7. Experimental investigation of gas hydrate formation, plugging and transportability in partially dispersed and water continuous systems

    NASA Astrophysics Data System (ADS)

    Vijayamohan, Prithvi

    As oil/gas subsea fields mature, the amount of water produced increases significantly due to the production methods employed to enhance the recovery of oil. This is true especially in the case of oil reservoirs. This increase in the water hold up increases the risk of hydrate plug formation in the pipelines, thereby resulting in higher inhibition cost strategies. A major industry concern is to reduce the severe safety risks associated with hydrate plug formation, and significantly extending subsea tieback distances by providing a cost effective flow assurance management/safety tool for mature fields. Developing fundamental understanding of the key mechanistic steps towards hydrate plug formation for different multiphase flow conditions is a key challenge to the flow assurance community. Such understanding can ultimately provide new insight and hydrate management guidelines to diminish the safety risks due to hydrate formation and accumulation in deepwater flowlines and facilities. The transportability of hydrates in pipelines is a function of the operating parameters, such as temperature, pressure, fluid mixture velocity, liquid loading, and fluid system characteristics. Specifically, the hydrate formation rate and plugging onset characteristics can be significantly different for water continuous, oil continuous, and partially dispersed systems. The latter is defined as a system containing oil/gas/water, where the water is present both as a free phase and partially dispersed in the oil phase (i.e., entrained water in the oil). Since hydrate formation from oil dispersed in water systems and partially dispersed water systems is an area which is poorly understood, this thesis aims to address some key questions in these systems. Selected experiments have been performed at the University of Tulsa flowloop to study the hydrate formation and plugging characteristics for the partially dispersed water/oil/gas systems as well as systems where the oil is completely dispersed

  8. Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea

    USGS Publications Warehouse

    Wang, X.; Hutchinson, D.R.; Wu, S.; Yang, S.; Guo, Y.

    2011-01-01

    Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190-221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone. Copyright 2011 by the American Geophysical Union.

  9. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and

  10. Phase equilibrium data for development of correlations for coal fluids

    SciTech Connect

    Robinson, R.L. Jr.; Gasem, K.A.M.; Darwish, N.A.; Raff, A.M.

    1991-02-01

    The overall objective of the authors' work is to develop accurate predictive methods for representations of vapor-liquid equilibria in systems encountered in coal-conversion processes. The objectives pursued in the present project include: (1) Measurements of binary vapor-liquid phase behavior data for selected solute gases (e.g., C{sub 2}H{sub 6}, CH{sub 4}) in a series of paraffinic, naphthenic, and aromatic hydrocarbon solvents to permit evaluations of interaction parameters in models for phase behavior. Solubilities of the gases in the liquid phase have been determined. (2) Evaluation of existing equations of state and other models for representations of phase behavior in systems of the type studied experimentally; development of new correlation frameworks as needed. (3) Generalization of the interaction parameters for the solutes studied to a wide spectrum of heavy solvents; presentation of final results in formats useful in the design/optimization of coal liquefaction processes.

  11. Gas hydrate dynamics in heterogeneous media - challenges for numerical modeling

    NASA Astrophysics Data System (ADS)

    Burwicz, Ewa; Ruepke, Lars; Wallmann, Klaus

    2013-04-01

    Gas hydrates are ice-like crystalline cage structures containing various greenhouse gases, such as methane or CO2, which are locked within their spatial structure. Gas hydrate distribution in oceanic settings is mainly controlled by three factors: 1) low temperature regimes, 2) high pressure regimes, and 3) presence of biodegradable organic matter. Due to their composition, hydrates are vulnerable to temperature, pressure, and, to a smaller degree, salinity changes. The occurrence of gas hydrates in marine sediments was discovered mainly along continental margins (slope and rise) where water depths exceed 400 m and the bottom water temperatures are small enough to sustain their presence. The amount of gas hydrates present in marine sediments on a global scale is still under debate. Several numerical models of a different complexity have been developed to estimate the potential amount of clathrates locked world-wide within marine sediments. The range of estimates starts from 500 Gt up to 57,000 Gt of methane carbon which implies a variation of several orders of magnitude. It has been already established that current climate changes are triggering some of the methane releases around the world. Prominent gas hydrate occurrence zones, such as Blake Ridge, can provide important information of the scale of potential hazards and help to predict a future impact of such events. Blake Ridge is a well investigated gas hydrate province containing a large amount of a locked methane gas. With the new numerical multiphase model we have been investigating 1) the potential risk of gas hydrate destabilization caused by several environmental factors (e.g. bottom water temperature rise, sea-level variations), 2) the effect of changing sedimentation regimes to the total amount of gas hydrate, 3) dynamics of hydrate formation in heterogeneous sediment layers, and 4) the impact of dynamic compaction on fluid and gas flow regimes. The model contains four phases (solid porous matrix, pore

  12. Research provides clues to hydrate formation and drilling-hazard solutions

    SciTech Connect

    Szczepanski, R.; Edmonds, B.; Brown, N.; Hamilton, T.

    1998-03-09

    Hydrate formation is a growing safety concern for offshore drilling programs, but, despite extensive laboratory research, pragmatic information is still lacking. Formation of hydrates in drilling fluids during a shut-in is the most likely hydrate-associated hazard in deep-water drilling, although the number of documented incidents is small. In addition to the known naturally forming hydrates, laboratory experiments have also identified heavier hydrocarbons found in oil and gas condensate systems and a new hydrate structure. These two factors may increase the range from which hydrate formation can occur. The paper discusses safety concerns, hydrate structures, modeling hydrates, hydrate stability, naturally occurring hydrates, techniques for drilling hydrates, hydrate formation while drilling, drilling fluids and hydrates, and completion fluids.

  13. 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

    NASA Astrophysics Data System (ADS)

    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

  14. Characterization of five chemistries and three particle sizes of stationary phases used in supercritical fluid chromatography.

    PubMed

    Khater, S; West, C; Lesellier, E

    2013-12-01

    Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercritical fluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEHEthyl-pyridine, X Select CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercritical fluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs).The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids,this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength.These changes could modify the retention and the selectivity of compounds in the case of method trans-fer, by using different particle sizes, from 5 down to 1.7 m. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid. PMID

  15. A model for wave propagation in a porous solid saturated by a three-phase fluid.

    PubMed

    Santos, Juan E; Savioli, Gabriela B

    2016-02-01

    This paper presents a model to describe the propagation of waves in a poroelastic medium saturated by a three-phase viscous, compressible fluid. Two capillary relations between the three fluid phases are included in the model by introducing Lagrange multipliers in the principle of virtual complementary work. This approach generalizes that of Biot for single-phase fluids and allows to determine the strain energy density, identify the generalized strains and stresses, and derive the constitutive relations of the system. The kinetic and dissipative energy density functions are obtained assuming that the relative flow within the pore space is of laminar type and obeys Darcy's law for three-phase flow in porous media. After deriving the equations of motion, a plane wave analysis predicts the existence of four compressional waves, denoted as type I, II, III, and IV waves, and one shear wave. Numerical examples showing the behavior of all waves as function of saturation and frequency are presented.

  16. A model for wave propagation in a porous solid saturated by a three-phase fluid.

    PubMed

    Santos, Juan E; Savioli, Gabriela B

    2016-02-01

    This paper presents a model to describe the propagation of waves in a poroelastic medium saturated by a three-phase viscous, compressible fluid. Two capillary relations between the three fluid phases are included in the model by introducing Lagrange multipliers in the principle of virtual complementary work. This approach generalizes that of Biot for single-phase fluids and allows to determine the strain energy density, identify the generalized strains and stresses, and derive the constitutive relations of the system. The kinetic and dissipative energy density functions are obtained assuming that the relative flow within the pore space is of laminar type and obeys Darcy's law for three-phase flow in porous media. After deriving the equations of motion, a plane wave analysis predicts the existence of four compressional waves, denoted as type I, II, III, and IV waves, and one shear wave. Numerical examples showing the behavior of all waves as function of saturation and frequency are presented. PMID:26936553

  17. Enthalpy and Phase Relations in Saline Geothermal Fluids to "Supercritical" Conditions

    NASA Astrophysics Data System (ADS)

    Driesner, T.

    2013-12-01

    Some of the world's largest geothermal systems contain saline fluids (e.g., Salton Sea), and 'supercritical' geothermal resources are targeted for the IDDP-2 well at saline system at Reykjanes, Iceland. Saline aqueous fluids have, however, phase relations of steam and liquid (+/- solid salt) that are much more complex than those for pure water (Fig. 1). These phase relations affect both the multiphase flow behavior in the system (impacting rock alteration) and the enthalpy of fluids that can be produced. This contribution introduces the phase diagram of H2O-NaCl in enthalpy-pressure-composition space. Various isobaric sections illustrate the phase states and enthalpies that can be expected in the deeper ('supercritical') parts of high-enthalpy, saline geothermal systems.

  18. Online quantitative phase imaging of vascular endothelial cells under fluid shear stress utilizing digital holographic microscopy

    NASA Astrophysics Data System (ADS)

    Odenthal-Schnittler, Maria; Schnittler, Hans Joachim; Kemper, Björn

    2016-03-01

    We have explored the utilization of quantitative phase imaging with digital holographic microscopy (DHM) as a novel tool for quantifying the dynamics of morphologic parameters (morphodynamics) of confluent endothelial cell layers under fluid shear stress conditions. Human umbilical vein endothelial cells (HUVECs) were exposed to fluid shear stress in a transparent cone/plate flow device (BioTech-Flow-System) and imaged with a modular setup for quantitative DHM phase imaging for up to 48 h. The resulting series of quantitative phase image sequences were analyzed for the average surface roughness of the cell layers and cell alignment. Our results demonstrate that quantitative phase imaging is a powerful and reliable tool to quantify the dynamics of morphological adaptation of endothelial cells to fluid shear stress.

  19. Transport processes in boiling and two-phase systems, including near-critical fluids

    NASA Technical Reports Server (NTRS)

    Hsu, Y.-Y.; Graham, R. W.

    1976-01-01

    Aspects of pool boiling are considered, taking into account nucleate boiling, the nucleate boiling mechanism, film boiling, and the transition between nucleate and film boiling. The characteristics of two-phase flow are also investigated, giving attention to two-phase flow parameters and equations, the flow pattern in two-phase flow, the pressure drop in two-phase flow, heat transfer in two-phase flow, two-phase flow dynamics, the boiling crisis in two-phase flow, the critical flow rate, the propagation of the pressure pulse and the sonic velocity in two-phase media, instrumentation for two-phase flow, and geometry and field effects on boiling and two-phase flow. Near-critical fluids are also considered.

  20. GH-3PAD - a new numerical solver for multiphase transport in porous media - new insights on gas hydrate and free gas co-existence

    NASA Astrophysics Data System (ADS)

    Burwicz, E.; Rupke, L.; Wallmann, K.

    2013-12-01

    Gas Hydrate-3 Phase Advanced Dynamics (GH-3PAD) code has been developed to study the geophysical and biochemical processes associated with gas hydrate as well as free methane gas formation and dissolution in marine sediments. Biochemical processes influencing in-situ organic carbon decay and, therefore, gas hydrate formation, such as Anaerobic Oxidation of Methane (AOM), sulfate reduction, and methanogenesis have been considered. The new model assumes a Lagrangian reference frame that is attached to the deposited sedimentary layers, which compact according to their individual lithological properties. Differential motion of the pore fluids and free gas is modeled as Darcy flow. Gas hydrate and free gas formation is either controlled by 1) instant gas hydrate crystallization assuming local thermodynamical equilibrium or by a 2) kinetically controlled rate of gas hydrate growth. The thermal evolution is computed from an energy equation that includes contributions from all phases present in the model (sediment grains, saline pore fluids, gas hydrate, and free gas). A first application of the GH-3PAD model has been the Blake Ridge Site, offshore South Carolina. Here seismic and well data points to the out-of-equilibrium co-existence of gas hydrate and free gas. It has been reported that these two distinct phases appear within sediment column with a gaseous phase tending to migrate upwards throughout the Gas Hydrate Stability Zone (GHSZ) until it reaches the seafloor despite relatively low gas hydrate content (4 - 7 vol. % after Paull et al., 1996). With the GH-3PAD model we quantify the complex transport- reaction processes that control three phase (gas hydrate, free gas, and dissolved CH4) out-of-equilibrium state. References: Paull C. K., Matsumoto R., Wallace P. J., 1996. 9. Site 997, Shipboard Scientific Party. Proceeding of the Ocean Drilling Program, Initial Reports, Vol. 164.

  1. Vapour-liquid phase diagram for an ionic fluid in a random porous medium.

    PubMed

    Holovko, M F; Patsahan, O; Patsahan, T

    2016-10-19

    We study the vapour-liquid phase behaviour of an ionic fluid confined in a random porous matrix formed by uncharged hard sphere particles. The ionic fluid is modelled as an equimolar binary mixture of oppositely charged equisized hard spheres, the so-called restricted primitive model (RPM). Considering the matrix-fluid system as a partly-quenched model, we develop a theoretical approach which combines the method of collective variables with the extension of the scaled-particle theory (SPT) for a hard-sphere fluid confined in a disordered hard-sphere matrix. The approach allows us to formulate the perturbation theory using the SPT for the description of the thermodynamics of the reference system. The phase diagrams of the RPM in matrices of different porosities and for different size ratios of matrix and fluid particles are calculated in the random-phase approximation and also when the effects of higher-order correlations between ions are taken into account. Both approximations correctly reproduce the basic effects of porous media on the vapour-liquid phase diagram, i.e. with a decrease of porosity the critical point shifts towards lower fluid densities and lower temperatures and the coexistence region gets narrower. For the fixed matrix porosity, both the critical temperature and the critical density increase with an increase of size of matrix particles and tend to the critical values of the bulk RPM. PMID:27548356

  2. Vapour-liquid phase diagram for an ionic fluid in a random porous medium

    NASA Astrophysics Data System (ADS)

    Holovko, M. F.; Patsahan, O.; Patsahan, T.

    2016-10-01

    We study the vapour-liquid phase behaviour of an ionic fluid confined in a random porous matrix formed by uncharged hard sphere particles. The ionic fluid is modelled as an equimolar binary mixture of oppositely charged equisized hard spheres, the so-called restricted primitive model (RPM). Considering the matrix-fluid system as a partly-quenched model, we develop a theoretical approach which combines the method of collective variables with the extension of the scaled-particle theory (SPT) for a hard-sphere fluid confined in a disordered hard-sphere matrix. The approach allows us to formulate the perturbation theory using the SPT for the description of the thermodynamics of the reference system. The phase diagrams of the RPM in matrices of different porosities and for different size ratios of matrix and fluid particles are calculated in the random-phase approximation and also when the effects of higher-order correlations between ions are taken into account. Both approximations correctly reproduce the basic effects of porous media on the vapour-liquid phase diagram, i.e. with a decrease of porosity the critical point shifts towards lower fluid densities and lower temperatures and the coexistence region gets narrower. For the fixed matrix porosity, both the critical temperature and the critical density increase with an increase of size of matrix particles and tend to the critical values of the bulk RPM.

  3. Phase behavior of coal fluids: Data for correlation development

    SciTech Connect

    Robinson, R.L. Jr.; Gasem, K.A.M.; Shaver, R.D.

    1989-10-15

    During the present report period, our framework for correlating saturation properties using the scaled-variable-reduced coordinate approach was used to develop a correlation for saturated liquid densities of pure fluids at temperatures from the triple point to the critical point. The new correlation results in precise representation of liquid densities of diverse chemical species with average errors of 0.12% when two adjustable parameters are used to characterize each substance. In addition, the proposed model compares favorably with the modified Rackett and the Hankinson-Thomson correlations with the added advantages of covering the full saturation range and obeying scaling-law behavior in the near-critical region. Although the approach is essentially empirical, the results obtained suggest an underlying physical significance for the model parameters and show an excellent potential for generalized predictions. This is demonstrated by the results given here for saturated liquid densities where fully generalized predictions yield average errors of less than 1.0%.

  4. Phase portrait methods for verifying fluid dynamic simulations

    SciTech Connect

    Stewart, H.B.

    1989-01-01

    As computing resources become more powerful and accessible, engineers more frequently face the difficult and challenging engineering problem of accurately simulating nonlinear dynamic phenomena. Although mathematical models are usually available, in the form of initial value problems for differential equations, the behavior of the solutions of nonlinear models is often poorly understood. A notable example is fluid dynamics: while the Navier-Stokes equations are believed to correctly describe turbulent flow, no exact mathematical solution of these equations in the turbulent regime is known. Differential equations can of course be solved numerically, but how are we to assess numerical solutions of complex phenomena without some understanding of the mathematical problem and its solutions to guide us

  5. MOLECULAR SIMULATION OF PHASE EQUILIBRIA FOR COMPLEX FLUIDS

    SciTech Connect

    Athanassios Z. Panagiotopoulos

    2009-09-09

    The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.

  6. Microgravity two-phase fluid flow pattern modeling

    NASA Technical Reports Server (NTRS)

    Lee, Doojeong; Best, Frederick R.

    1988-01-01

    When gas and liquid mixtures flow in a pipe, the distribution of the two phases may take many forms. A flow pattern, or flow regime, is the characteristic spatial distribution of the phases of flow in a pipe. Because heat transfer and pressure drop are dependent on the characteristic distribution of phases, it is necessary to describe flow patterns in an appropriate manner so that a hydrodynamic or heat transfer theory applicable to that can be chosen. A theoretical two phase flow regime transition map under a microgravity environment was developed on physical concepts. These transitions use four basic flow patterns: dispersed flow, slug flow, stratified flow, and annular flow. The forces considered are body force, surface tension force, inertial force, friction, and the force from eddy turbulent fluctuation. Three dimensionless parameters were developed. Because these transition boundaries were developed based on physical concepts, they should be applicable to flow regimes occurring in various design conditions. Because the flow pattern data from KC-135 experiments are insufficient to verify these theoretical transition lines completely, an adiabatic experiment for flow regime analysis is recommended.

  7. Tension induced phase transitions in biomimetic fluid membranes

    NASA Astrophysics Data System (ADS)

    Shapiro, Marc; Vlahovska, Petia

    2012-11-01

    Membranes in eukaryotic cells are mixtures of hundreds of lipid species. The lipid diversity enables membranes to phase separate and form domains, called rafts, which play a critical role in cell functions such as signaling and trafficking. The phase transitions underlying raft formation have been extensively studied as a function of temperature and composition. However, the third dimension of the phase diagram, i.e., the tension (2D pressure), is still unexplored because membrane tension is difficult to control and quantify. To overcome this challenge, we develop two approaches, capillary micromechanics and electrodeformation, in which the tension is regulated by the area dilation accompanying deformation of a vesicle (a closed membrane). The first technique consists of forcing an initially quasi-spherical vesicle through a tapered glass microcapillary, while the second method utilizes uniform electric fields to deform the vesicle into an ellipsoid. Domains are visualized using a fluorescent dye, which preferentially partitions in one of the phases. The experimental results suggest that the miscibility temperature (at which domains form in an initially homogeneous membrane) increases with applied tension. Domain motions and coarsening are also investigated.

  8. Application of Phase Shifted, Laser Feedback Interferometry to Fluid Physics

    NASA Technical Reports Server (NTRS)

    Ovryn, Ben; Eppell, Steven J.; Andrews, James H.; Khaydarov, John

    1996-01-01

    We have combined the principles of phase-shifting interferometry (PSI) and laser-feedback interferometry (LFI) to produce a new instrument that can measure both optical path length (OPL) changes and discern sample reflectivity variations. In LFI, coherent feedback of the incident light either reflected directly from a surface or reflected after transmission through a region of interest will modulate the output intensity of the laser. LFI can yield a high signal-to-noise ratio even for low reflectivity samples. By combining PSI and LFI, we have produced a robust instrument, based upon a HeNe laser, with high dynamic range that can be used to measure either static (dc) or oscillatory changes along the optical path. As with other forms of interferometry, large changes in OPL require phase unwrapping. Conversely, small phase changes are limited by the fraction of a fringe that can be measured. We introduce the phase shifts with an electro-optic modulator (EOM) and use either the Carre or Hariharan algorithms to determine the phase and visibility. We have determined the accuracy and precision of our technique by measuring both the bending of a cantilevered piezoelectric bimorph and linear ramps to the EOM. Using PSI, sub-nanometer displacements can be measured. We have combined our interferometer with a commercial microscope and scanning piezoelectric stage and have measured the variation in OPL and visibility for drops of PDMS (silicone oil) on coated single crystal silicon. Our measurement of the static contact angle agrees with the value of 68 deg stated in the literature.

  9. Structure of the calcium pyrophosphate monohydrate phase (Ca2P2O7·H2O): towards understanding the dehydration process in calcium pyrophosphate hydrates.

    PubMed

    Gras, Pierre; Ratel-Ramond, Nicolas; Teychéné, Sébastien; Rey, Christian; Elkaim, Erik; Biscans, Béatrice; Sarda, Stéphanie; Combes, Christèle

    2014-09-01

    Calcium pyrophosphate hydrate (CPP, Ca(2)P(2)O(7) · nH2O) and calcium orthophosphate compounds (including apatite, octacalcium phosphate etc.) are among the most prevalent pathological calcifications in joints. Even though only two dihydrated forms of CPP (CPPD) have been detected in vivo (monoclinic and triclinic CPPD), investigations of other hydrated forms such as tetrahydrated or amorphous CPP are relevant to a further understanding of the physicochemistry of those phases of biological interest. The synthesis of single crystals of calcium pyrophosphate monohydrate (CPPM; Ca(2)P(2)O(7) · H2O) by diffusion in silica gel at ambient temperature and the structural analysis of this phase are reported in this paper. Complementarily, data from synchrotron X-ray diffraction on a CPPM powder sample have been fitted to the crystal parameters. Finally, the relationship between the resolved structure for the CPPM phase and the structure of the tetrahydrated calcium pyrophosphate β phase (CPPT-β) is discussed.

  10. Site Selection for DOE/JIP Gas Hydrate Drilling in the Northern Gulf of Mexico

    SciTech Connect

    Hutchinson, D.R.; Shelander, D.; Dai, J.; McConnell, D.; Shedd, W.; Frye, M.; Ruppel, C.; Boswell, R.; Jones, E.; Collett, T.S.; Rose, K.; Dugan, B.; Wood, W.; Latham, T.

    2008-07-01

    In the late spring of 2008, the Chevron-led Gulf of Mexico Gas Hydrate Joint Industry Project (JIP) expects to conduct an exploratory drilling and logging campaign to better understand gas hydrate-bearing sands in the deepwater Gulf of Mexico. The JIP Site Selection team selected three areas to test alternative geological models and geophysical interpretations supporting the existence of potential high gas hydrate saturations in reservoir-quality sands. The three sites are near existing drill holes which provide geological and geophysical constraints in Alaminos Canyon (AC) lease block 818, Green Canyon (GC) 955, and Walker Ridge (WR) 313. At the AC818 site, gas hydrate is interpreted to occur within the Oligocene Frio volcaniclastic sand at the crest of a fold that is shallow enough to be in the hydrate stability zone. Drilling at GC955 will sample a faulted, buried Pleistocene channel-levee system in an area characterized by seafloor fluid expulsion features, structural closure associated with uplifted salt, and abundant seismic evidence for upward migration of fluids and gas into the sand-rich parts of the sedimentary section. Drilling at WR313 targets ponded sheet sands and associated channel/levee deposits within a minibasin, making this a non-structural play. The potential for gas hydrate occurrence at WR313 is supported by shingled phase reversals consistent with the transition from gas-charged sand to overlying gas-hydrate saturated sand. Drilling locations have been selected at each site to 1) test geological methods and models used to infer the occurrence of gas hydrate in sand reservoirs in different settings in the northern Gulf of Mexico; 2) calibrate geophysical models used to detect gas hydrate sands, map reservoir thicknesses, and estimate the degree of gas hydrate saturation; and 3) delineate potential locations for subsequent JIP drilling and coring operations that will collect samples for comprehensive physical property, geochemical and other

  11. The simplest model for non-congruent fluid-fluid phase transition in Coulomb system

    NASA Astrophysics Data System (ADS)

    Stroev, N. E.; Iosilevskiy, I. L.

    2015-11-01

    The simplest model for non-congruent phase transition of gas-liquid type was developed in frames of modified model with no associations of a binary ionic mixture (BIM) on a homogeneous compressible ideal background (or non-ideal) electron gas /BIM(˜)/. The analytical approximation for equation of state equation of state of Potekhin and Chabrier of fully ionized electron-ionic plasma was used for description of the ion-ion correlations (Coulomb non-ideality) in combination with “linear mixture” (LM) approximation. Phase equilibrium for the charged species was calculated according to the Gibbs-Guggenheim conditions. The presently considered BIM(˜) model allows to calculate full set of parameters for phase boundaries of non-congruent variant of phase equilibrium and to study all features for this non-congruent phase transition realization in Coulomb system in comparison with the simpler (standard) forced-congruent evaporation mode. In particular, in BIM(˜) there were reproduced two-dimensional remarkable (“banana-like”) structure of two-phase region P — T diagram and the characteristic non-monotonic shape of caloric phase enthalpy-temperature diagram, similar to the non-congruent evaporation of reactive plasma products in high-temperature heating with the uranium-oxygen system. The parameters of critical points (CP) line were calculated on the entire range of proportions of ions 0 < X < 1, including two reference values, when CP coincides with a point of extreme temperature and extreme pressure, XT and Xp. Finally, it is clearly demonstrated the low-temperature property of non-congruent gas-liquid transition — “distillation”, which is weak in chemically reactive plasmas.

  12. Polarization-phase tomography of biological fluids polycrystalline structure

    NASA Astrophysics Data System (ADS)

    Dubolazov, A. V.; Vanchuliak, O. Ya.; Garazdiuk, M.; Sidor, M. I.; Motrich, A. V.; Kostiuk, S. V.

    2013-12-01

    Our research is aimed at designing an experimental method of Fourier's laser polarization phasometry of the layers of human effusion for an express diagnostics during surgery and a differentiation of the degree of severity (acute - gangrenous) appendectomy by means of statistical, correlation and fractal analysis of the coherent scattered field. A model of generalized optical anisotropy of polycrystal networks of albumin and globulin of the effusion of appendicitis has been suggested and the method of Fourier's phasometry of linear (a phase shift between the orthogonal components of the laser wave amplitude) and circular (the angle of rotation of the polarization plane) birefringence with a spatial-frequency selection of the coordinate distributions for the differentiation of acute and gangrenous conditions have been analytically substantiated. Comparative studies of the efficacy of the methods of direct mapping of phase distributions and Fourier's phasometry of a laser radiation field transformed by the dendritic and spherolitic networks of albumin and globulin of the layers of effusion of appendicitis on the basis of complex statistical, correlation and fractal analysis of the structure of phase maps.

  13. Development of a Numerical Simulator for Analyzing the Geomechanical Performance of Hydrate-Bearing Sediments

    SciTech Connect

    Rutqvist, Jonny; Rutqvist, J.; Moridis, G.J.

    2008-06-01

    In this paper, we describe the development and application of a numerical simulator that analyzes the geomechanical performance of hydrate-bearing sediments, which may become an important future energy supply. The simulator is developed by coupling a robust numerical simulator of coupled fluid flow, hydrate thermodynamics, and phase behavior in geologic media (TOUGH+HYDRATE) with an established geomechanical code (FLAC3D). We demonstrate the current simulator capabilities and applicability for two examples of geomechanical responses of hydrate bearing sediments during production-induced hydrate dissociation. In these applications, the coupled geomechanical behavior within hydrate-bearing seducements are considered through a Mohr-Coulomb constitutive model, corrected for changes in pore-filling hydrate and ice content, based on laboratory data. The results demonstrate how depressurization-based gas production from oceanic hydrate deposits may lead to severe geomechanical problems unless care is taken in designing the production scheme. We conclude that the coupled simulator can be used to design production strategies for optimizing production, while avoiding damaging geomechanical problems.

  14. Two-Phase Working Fluids for the Temperature Range 50 to 350 C

    NASA Technical Reports Server (NTRS)

    Saaski, E. W.; Owzarski, P. C.

    1977-01-01

    The decomposition and corrosion of two-phase heat transfer liquids and metal envelopes have been investigated on the basis of molecular bond strengths and chemical thermodynamics. Potentially stable heat transfer fluids for the temperature range 100 C to 350 C have been identified, and reflux heat pipes tests initiated with 10 fluids and carbon steel and aluminum envelopes to experimentally establish corrosion behavior and noncondensable gas generation rates.

  15. Surface tension and vapor-liquid phase coexistence of confined square-well fluid.

    PubMed

    Singh, Jayant K; Kwak, Sang Kyu

    2007-01-14

    Phase equilibria of a square-well fluid in planar slit pores with varying slit width are investigated by applying the grand-canonical transition-matrix Monte Carlo (GC-TMMC) with the histogram-reweighting method. The wall-fluid interaction strength was varied from repulsive to attractive such that it is greater than the fluid-fluid interaction strength. The nature of the phase coexistence envelope is in agreement with that given in literature. The surface tension of the vapor-liquid interface is calculated via molecular dynamics simulations. GC-TMMC with finite size scaling is also used to calculate the surface tension. The results from molecular dynamics and GC-TMMC methods are in very good mutual agreement. The vapor-liquid surface tension, under confinement, was found to be lower than the bulk surface tension. However, with the increase of the slit width the surface tension increases. For the case of a square-well fluid in an attractive planar slit pore, the vapor-liquid surface tension exhibits a maximum with respect to wall-fluid interaction energy. We also report estimates of critical properties of confined fluids via the rectilinear diameter approach.

  16. Numerical schemes for anomalous diffusion of single-phase fluids in porous media

    NASA Astrophysics Data System (ADS)

    Awotunde, Abeeb A.; Ghanam, Ryad A.; Al-Homidan, Suliman S.; Tatar, Nasser-eddine

    2016-10-01

    Simulation of fluid flow in porous media is an indispensable part of oil and gas reservoir management. Accurate prediction of reservoir performance and profitability of investment rely on our ability to model the flow behavior of reservoir fluids. Over the years, numerical reservoir simulation models have been based mainly on solutions to the normal diffusion of fluids in the porous reservoir. Recently, however, it has been documented that fluid flow in porous media does not always follow strictly the normal diffusion process. Small deviations from normal diffusion, called anomalous diffusion, have been reported in some experimental studies. Such deviations can be caused by different factors such as the viscous state of the fluid, the fractal nature of the porous media and the pressure pulse in the system. In this work, we present explicit and implicit numerical solutions to the anomalous diffusion of single-phase fluids in heterogeneous reservoirs. An analytical solution is used to validate the numerical solution to the simple homogeneous case. The conventional wellbore flow model is modified to account for anomalous behavior. Example applications are used to show the behavior of wellbore and wellblock pressures during the single-phase anomalous flow of fluids in the reservoirs considered.

  17. Single-crystal equation of state of phase D to lower mantle pressures and the effect of hydration on the buoyancy of deep subducted slabs

    NASA Astrophysics Data System (ADS)

    Rosa, A. D.; Mezouar, M.; Garbarino, G.; Bouvier, P.; Ghosh, S.; Rohrbach, A.; Sanchez-Valle, C.

    2013-12-01

    An understanding of the physical properties of the hydrous magnesium silicate phase D is important for the interpretation of the seismic anomalies observed in subducted slabs and to evaluate the effect of hydration on slab dynamics. Here we report the equation of state of phase D (Mg1.1Si1.8H2.5O6) up to 65 GPa obtained from high-precision single-crystal X-ray diffraction. A single-crystal of phase D was loaded in a diamond anvil cell using helium as pressure transmitting medium to ensure quasi-hydrostatic conditions during the entire data collection. The volume of phase D decreases smoothly over the entire pressure range, without the anomalies in the compressibility reported at 40 GPa in previous powder diffraction studies. If existing in phase D, a hydrogen bond symmetrization transition as predicted by first-principles calculation is therefore not associated with anomalies in the volume compression behavior. The isothermal bulk modulus KT and its pressure derivative K'T obtained from the fitting of the unit cell volumes using a third-order Birch-Murnaghan equation of state are KT = 151.4 ± 1.2 GPa and K'T = 4.89 ±0.08, respectively. This bulk modulus is in good agreement with a recent single-crystal Brillouin scattering experiment. The presence of 16 vol. % of phase D in hydrous peridotite lithologies reduces the density by up to 2.6% at upper most lower mantle pressure-temperature conditions (1273 K and 30 GPa), phase D is thus a potential candidate to influence the buoyancy of hydrated stagnant slabs below the transition zone.

  18. Measurement of average density and relative volumes in a dispersed two-phase fluid

    SciTech Connect

    Sreepada, S.R.; Rippel, R.R.

    1990-12-19

    An apparatus and a method are disclosed for measuring the average density and relative volumes in an essentially transparent, dispersed two-phase fluid. A laser beam with a diameter no greater than 1% of the diameter of the bubbles, droplets, or particles of the dispersed phase is directed onto a diffraction grating. A single-order component of the diffracted beam is directed through the two-phase fluid and its refraction is measured. Preferably, the refracted beam exiting the fluid is incident upon a optical filter with linearly varying optical density and the intensity of the filtered beam is measured. The invention can be combined with other laser-based measurement systems, e.g., laser doppler anemometry.

  19. Measurement of average density and relative volumes in a dispersed two-phase fluid

    SciTech Connect

    Sreepada, S.R.; Rippel, R.R.

    1992-05-05

    An apparatus and a method are disclosed for measuring the average density and relative volumes in an essentially transparent, dispersed two-phase fluid. A laser beam with a diameter no greater than 1% of the diameter of the bubbles, droplets, or particles of the dispersed phase is directed onto a diffraction grating. A single-order component of the diffracted beam is directed through the two-phase fluid and its refraction is measured. Preferably, the refracted beam exiting the fluid is incident upon a optical filter with linearly varying optical density and the intensity of the filtered beam is measured. The invention can be combined with other laser-based measurement systems, e.g., laser doppler anemometry. 3 figs.

  20. Measurement of average density and relative volumes in a dispersed two-phase fluid

    DOEpatents

    Sreepada, Sastry R.; Rippel, Robert R.

    1992-01-01

    An apparatus and a method are disclosed for measuring the average density and relative volumes in an essentially transparent, dispersed two-phase fluid. A laser beam with a diameter no greater than 1% of the diameter of the bubbles, droplets, or particles of the dispersed phase is directed onto a diffraction grating. A single-order component of the diffracted beam is directed through the two-phase fluid and its refraction is measured. Preferably, the refracted beam exiting the fluid is incident upon a optical filter with linearly varing optical density and the intensity of the filtered beam is measured. The invention can be combined with other laser-based measurement systems, e.g., laser doppler anemometry.

  1. Natural solutal convection in magnetic fluids: First-order phase transition aspect

    NASA Astrophysics Data System (ADS)

    Ivanov, Aleksey S.

    2016-10-01

    Concentration stratification of magnetic fluids under the action of external magnetic field can disturb mechanical equilibrium in the system and cause intensive solutal convection. The current paper is devoted to the study of free solutal convection in magnetic fluids undergoing first-order phase transition. Simulation of solutal convection in OpenFOAM package makes it possible to compare numeric results with physical experiment observations. The numeric simulation of convective hydrodynamic flows was carried out in the framework of several theories of first-order phase transition in ferrocolloids. The numerical results are compared with experimental observations in order to choose the theory which predicts most accurately the concentration stratification in magnetic fluids undergoing magneto-controllable first-order phase transition.

  2. A two-phase solid/fluid model for dense granular flows including dilatancy effects

    NASA Astrophysics Data System (ADS)

    Mangeney, Anne; Bouchut, Francois; Fernandez-Nieto, Enrique; Koné, El-Hadj; Narbona-Reina, Gladys

    2016-04-01

    Describing grain/fluid interaction in debris flows models is still an open and challenging issue with key impact on hazard assessment [{Iverson et al.}, 2010]. We present here a two-phase two-thin-layer model for fluidized debris flows that takes into account dilatancy effects. It describes the velocity of both the solid and the fluid phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure [{Bouchut et al.}, 2016]. The model is derived from a 3D two-phase model proposed by {Jackson} [2000] based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work [{Bouchut et al.}, 2015]. In particular, {Pitman and Le} [2005] replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's model by closing the mixture equations by a weak compressibility relation following {Roux and Radjai} [1998]. This relation implies that the occurrence of dilation or contraction of the granular material in the model depends on whether the solid volume fraction is respectively higher or lower than a critical value. When dilation occurs, the fluid is sucked into the granular material, the pore pressure decreases and the friction force on the granular phase increases. On the contrary, in the case of contraction, the fluid is expelled from the mixture, the pore pressure increases and the friction force diminishes. To

  3. Conceptual design of two-phase fluid mechanics and heat transfer facility for spacelab

    NASA Technical Reports Server (NTRS)

    North, B. F.; Hill, M. E.

    1980-01-01

    Five specific experiments were analyzed to provide definition of experiments designed to evaluate two phase fluid behavior in low gravity. The conceptual design represents a fluid mechanics and heat transfer facility for a double rack in Spacelab. The five experiments are two phase flow patterns and pressure drop, flow boiling, liquid reorientation, and interface bubble dynamics. Hardware was sized, instrumentation and data recording requirements defined, and the five experiments were installed as an integrated experimental package. Applicable available hardware was selected in the experiment design and total experiment program costs were defined.

  4. Phase-Shifting Liquid Crystal Interferometers for Microgravity Fluid Physics

    NASA Technical Reports Server (NTRS)

    Griffin, DeVon W.; Marshall, Keneth L.

    2002-01-01

    The initial focus of this project was to eliminate both of these problems in the Liquid Crystal Point-Diffraction Interferometer (LCPDI). Progress toward that goal will be described, along with the demonstration of a phase shifting Liquid Crystal Shearing Interferometer (LCSI) that was developed as part of this work. The latest LCPDI, other than a lens to focus the light from a test section onto a diffracting microsphere within the interferometer and a collimated laser for illumination, the pink region contained within the glass plates on the rod-mounted platform is the complete interferometer. The total width is approximately 1.5 inches with 0.25 inches on each side for bonding the electrical leads. It is 1 inch high and there are only four diffracting microspheres within the interferometer. As a result, it is very easy to align, achieving the first goal. The liquid crystal electro-optical response time is a function of layer thickness, with thinner devices switching faster due to a reduction in long-range viscoelastic forces between the LC molecules. The LCPDI has a liquid crystal layer thickness of 10 microns, which is controlled by plastic or glass microspheres embedded in epoxy 'pads' at the corners of the device. The diffracting spheres are composed of polystyrene/divinyl benzene polymer with an initial diameter of 15 microns. The spheres deform slightly when the interferometer is assembled to conform to the spacing produced by the microsphere-filled epoxy spacer pads. While the speed of this interferometer has not yet been tested, previous LCPDIs fabricated at the Laboratory for Laser Energetics switched at a rate of approximately 3.3 Hz, a factor of 10 slower than desired. We anticipate better performance when the speed of these interferometers is tested since they are approximately three times thinner. Phase shifting in these devices is a function of the AC voltage level applied to the liquid crystal. As the voltage increases, the dye in the liquid crystal

  5. Single and two-phase flow fluid dynamics in parallel helical coils

    NASA Astrophysics Data System (ADS)

    De Salve, M.; Orio, M.; Panella, B.

    2014-04-01

    The design of helical coiled steam generators requires the knowledge of the single and two-phase fluid dynamics. The present work reports the results of an experimental campaign on single-phase and two phase pressure drops and void fraction in three parallel helicoidal pipes, in which the total water flow rate is splitted by means of a branch. With this test configuration the distribution of the water flow rate in the helicoidal pipes and the phenomena of the instability of the two-phase flow have been experimentally investigated.

  6. Phenomena at the QCD phase transition in nonequilibrium chiral fluid dynamics (Nχ FD)

    NASA Astrophysics Data System (ADS)

    Nahrgang, Marlene; Herold, Christoph

    2016-08-01

    Heavy-ion collisions performed in the beam energy range accessible by the NICA collider facility are expected to produce systems of extreme net-baryon densities and can thus reach yet unexplored regions of the QCD phase diagram. Here, one expects the phase transition between the plasma of deconfined quarks and gluons and the hadronic matter to be of first order. A discovery of the first-order phase transition would as well prove the existence of the QCD critical point, a landmark in the phase diagram. In order to understand possible signals of the first-order phase transition in heavy-ion collision experiments it is very important to develop dynamical models of the phase transition. Here, we discuss the opportunities of studying dynamical effects at the QCD first-order phase transition within our model of nonequilibrium chiral fluid dynamics.

  7. Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

    PubMed

    Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

    2016-09-14

    The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime.

  8. Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

    PubMed

    Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

    2016-09-14

    The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime. PMID:27498686

  9. Impact of the Condensed-Phase Environment on the Translation-Rotation Eigenstates and Spectra of a Hydrogen Molecule in Clathrate Hydrates.

    PubMed

    Powers, Anna; Marsalek, Ondrej; Xu, Minzhong; Ulivi, Lorenzo; Colognesi, Daniele; Tuckerman, Mark E; Bačić, Zlatko

    2016-01-21

    We systematically investigate the manifestations of the condensed-phase environment of the structure II clathrate hydrate in the translation-rotation (TR) dynamics and the inelastic neutron scattering (INS) spectra of an H2 molecule confined in the small dodecahedral cage of the hydrate. The aim is to elucidate the extent to which these properties are affected by the clathrate water molecules beyond the confining cage and the proton disorder of the water framework. For this purpose, quantum calculations of the TR eigenstates and INS spectra are performed for H2 inside spherical clathrate domains of gradually increasing radius and the number of water molecules ranging from 20 for the isolated small cage to more than 1800. For each domain size, several hundred distinct hydrogen-bonding topologies are constructed in order to simulate the effects of the proton disorder. Our study reveals that the clathrate-induced splittings of the j = 1 rotational level and the translational fundamental of the guest H2 are influenced by the condensed-phase environment to a dramatically different degree, the former very strongly and the latter only weakly. PMID:26727217

  10. LIPID RAFTS, FLUID/FLUID PHASE SEPARATION, AND THEIR RELEVANCE TO PLASMA MEMBRANE STRUCTURE AND FUNCTION

    PubMed Central

    Sengupta, Prabuddha; Baird, Barbara; Holowka, David

    2007-01-01

    Novel biophysical approaches combined with modeling and new biochemical data have helped to recharge the lipid raft field and have contributed to the generation of a refined model of plasma membrane organization. In this review, we summarize new information in the context of previous literature to provide new insights into the spatial organization and dynamics of lipids and proteins in the plasma membrane of live cells. Recent findings of large-scale separation of liquid-ordered and liquid-disordered phases in plasma membrane vesicles demonstrate this capacity within the complex milieu of plasma membrane proteins and lipids. Roles for membrane heterogeneity and reorganization in immune cell activation are discussed in light of this new information. PMID:17764993

  11. Fluid phase separation inside a static periodic field: an effectively two-dimensional critical phenomenon.

    PubMed

    Vink, Richard L C; Neuhaus, Tim; Löwen, Hartmut

    2011-05-28

    When a fluid with a bulk liquid-vapor critical point is placed inside a static external field with spatial periodic oscillations in one direction, a new phase arises. This new phase-the so-called "zebra" phase-is characterized by an average density roughly between that of the liquid and vapor phases. The presence of the zebra phase gives rise to two new phase transitions: one from the vapor to the zebra phase, and one from the zebra to the liquid phase. At appropriate values of the temperature and chemical potential, the latter two transitions become critical. This phenomenon is called laser-induced condensation [I. O. Götze, J. M. Brader, M. Schmidt, and H. Löwen, Mol. Phys. 101, 1651 (2003)]. The purpose of this paper is to elucidate the nature of the critical points, using density functional theory and computer simulation of a colloid-polymer mixture. The main finding is that critical correlations develop in two-dimensional sheets perpendicular to the field direction, but not in the direction along the field: the critical correlations are thus effectively two-dimensional. Hence, static periodic fields provide a means to confine a fluid to effectively two dimensions. Away from criticality, the vapor-zebra and liquid-zebra transitions become first-order, but the associated surface tensions are extremely small. The consequences of the extremely small surface tensions on the nature of the two-phase coexistence regions are analyzed in detail.

  12. [Hydration in clinical practice].

    PubMed

    Maristany, Cleofé Pérez-Portabella; Segurola Gurruchaga, Hegoi

    2011-01-01

    Water is an essential foundation for life, having both a regulatory and structural function. The former results from active and passive participation in all metabolic reactions, and its role in conserving and maintaining body temperature. Structurally speaking it is the major contributer to tissue mass, accounting for 60% of the basis of blood plasma, intracellular and intersticial fluid. Water is also part of the primary structures of life such as genetic material or proteins. Therefore, it is necessary that the nurse makes an early assessment of patients water needs to detect if there are signs of electrolyte imbalance. Dehydration can be a very serious problem, especially in children and the elderly. Dehydrations treatment with oral rehydration solution decreases the risk of developing hydration disorders, but even so, it is recommended to follow preventive measures to reduce the incidence and severity of dehydration. The key to having a proper hydration is prevention. Artificial nutrition encompasses the need for precise calculation of water needs in enteral nutrition as parenteral, so the nurse should be part of this process and use the tools for calculating the patient's requirements. All this helps to ensure an optimal nutritional status in patients at risk. Ethical dilemmas are becoming increasingly common in clinical practice. On the subject of artificial nutrition and hydration, there isn't yet any unanimous agreement regarding hydration as a basic care. It is necessary to take decisions in consensus with the health team, always thinking of the best interests of the patient.

  13. Hydrogen Bonding, Hydration of Species, Ion Pairing and Clusterization in H2O-NaCl-CaCl2-CO2-NaHCO3-Na2CO3 Fluids: Molecular Dynamics Simulation of the Effects of Temperature, Pressure and Composition

    NASA Astrophysics Data System (ADS)

    Kalinichev, A. G.; Kirkpatrick, R. J.; Wang, J.

    2004-12-01

    Molecular computer simulation is an especially valuable tool to study the structural and dynamic properties of carbon-bearing aqueous fluids on the fundamental atomic time- and length- scale because these fluids are not readily studied experimentally using conventional X-ray or EXAFS methods. In this case, experimental methods can produce ambiguous results, because the carbon and oxygen atoms of the solute species are not easily distinguishable from the oxygen atoms of solvent water. Systematic molecular dynamics (MD) computer simulation studies of several fluid compositions - H2O-CO2, H2O-CO2-NaCl, H2O-NaHCO3, and H2O-Na2CO3 - were performed to study the effects of temperature, pressure (fluid density) and concentration on the structural, energetic, spectroscopic and dynamic properties of these solutions characterized on the atomic scale via the statistical parameters of individual hydrogen bonds and H-bonding networks, local hydration structures of dissolved species, and ion pair formation. Similar molecular-level characteristics of pure water and H2O-NaCl and H2O-CaCl2 solutions are calculated and used for comparison with the properties of carbon-bearing fluids. H2O-rich and CO2-rich compositions of the ternary H2O-CO2-NaCl system demonstrate strikingly different structural and dynamic behavior at about the same average density. In dense CO2-rich fluids, dissolved H2O molecules exhibit a high degree of hydrogen bonding and form relatively stable H-bonded clusters structurally similar to those observed in supercritical water at a much lower density. In contrast, CO2 molecules dissolved in water-rich fluids occur in clathrate-like cages formed by surrounding H-bonded water molecules. The hydration shells of carbonate and bicarbonate ions both contain approximately 10 water molecules, but the water structure around the carbonate ion is much more pronounced due to the higher anion charge. This also leads to the formation of very stable ion pairs and larger ionic

  14. Study of Two-Phase Heat Transfer in Nano-fluids for Nuclear Applications

    SciTech Connect

    Kim, S.J.; Truong, B.; Buongiorno, J.; Hu, L.W.; Bang, I.C.

    2006-07-01

    Nano-fluids are engineered colloidal suspensions of nano-particles in a base fluid. We are investigating the two-phase heat transfer behavior of water-based nano-fluids, to evaluate their potential use in nuclear applications, including the PWR primary coolant and PWR and BWR safety systems. A simple pool boiling wire experiment shows that a significant increase in Critical Heat Flux (CHF) can be achieved at modest nano-particle concentrations. For example, the CHF increases by 50% in nano-fluids with alumina nano-particles at 0.001%v concentration. The CHF enhancement appears to correlate with the presence of a layer of nano-particles that builds up on the heated surface during nucleate boiling. A review of the prevalent Departure from Nucleate Boiling (DNB) theories suggests that an alteration of the nucleation site density (brought about by the nano-particle layer) could plausibly explain the CHF enhancement. (authors)

  15. Multinuclear NMR microscopy of two-phase fluid systems in porous rock.

    PubMed

    Doughty, D A; Tomutsa, L

    1996-01-01

    The high-field magnetic resonance (MR) characteristics of fluids in porous reservoir rock exhibit short T2 relaxation times and broad natural line widths. These characteristics severely restrict which MR imaging (MRI) methodology can be used to obtain high-resolution porescale images of fluids in porous rock. An MR microscopy protocol based on 3D backprojection using strong imaging gradients was developed to overcome many of these constraints. To improve the image quality of two-phase systems, multinuclear MRI using proton MR to image the brine phase and 19F MR of a fluorinated hydrocarbon to image the oil phase was used. Resolution as high as 25 microns per pixel has been obtained for fluid systems in Bentheim and Fontainebleau sandstones. Separate proton and 19F images of brine and oil phases show good agreement with total saturation images. Software has been developed to perform 3D erosion/dilations and to extract the pore size distribution from binarized 3D images of fluid filled porosity. Results from pore size measurements show significant differences in the nature of the pore network in Fontainebleau and Bentheim sandstones. PMID:8970097

  16. Mathematical study of hydrocyclone dispersed phase separation in clearing viscoplastic drilling fluids

    NASA Astrophysics Data System (ADS)

    Matvienko, O. V.; Evtyushkin, E. V.

    2011-03-01

    On the basis of rheodynamic equations, a numerical investigation of the flow structure of a viscoplastic fluid and dispersed phase separation in a hydrocyclone has been carried out. The proposed mathematical model will make it possible to calculate the separation indices and the velocity, pressure, and particle density fields in the apparatus.

  17. RELAP5 two-phase fluid model and numerical scheme for economic LWR system simulation

    SciTech Connect

    Ransom, V.H.; Wagner, R.J.; Trapp, J.A.

    1981-01-01

    The RELAP5 two-phase fluid model and the associated numerical scheme are summarized. The experience accrued in development of a fast running light water reactor system transient analysis code is reviewed and example of the code application are given.

  18. Nanoscopic dynamics of phospholipid in unilamellar vesicles: Effect of gel to fluid phase transition

    DOE PAGES

    Sharma, V. K.; Mamontov, E.; Anunciado, D. B.; O’Neill, H.; Urban, V.

    2015-03-04

    Dynamics of phospholipids in unilamellar vesicles (ULV) is of interest in biology, medical, and food sciences since these molecules are widely used as biocompatible agents and a mimic of cell membrane systems. We have investigated the nanoscopic dynamics of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) phospholipid in ULV as a function of temperature using elastic and quasielastic neutron scattering (QENS). The dependence of the signal on the scattering momentum transfer, which is a critical advantage of neutron scattering techniques, allows the detailed analysis of the lipid motions that cannot be carried out by other means. In agreement with a differential scanning calorimetry measurement, amore » sharp rise in the elastic scattering intensity below ca. 296 K indicates a phase transition from the high-temperature fluid phase to the low-temperature solid gel phase. The microscopic lipid dynamics exhibits qualitative differences between the solid gel phase (in a measurement at 280 K) and the fluid phase (in a measurement at a physiological temperature of 310 K). The data analysis invariably shows the presence of two distinct motions: the whole lipid molecule motion within a monolayer, or lateral diffusion, and the relatively faster internal motion of the DMPC molecule. The lateral diffusion of the whole lipid molecule is found to be Fickian in character, whereas the internal lipid motions are of localized character, consistent with the structure of the vesicles. The lateral motion slows down by an order of magnitude in the solid gel phase, whereas for the internal motion not only the time scale, but also the character of the motion changes upon the phase transition. In the solid gel phase, the lipids are more ordered and undergo uniaxial rotational motion. However, in the fluid phase, the hydrogen atoms of the lipid tails undergo confined translation diffusion rather than uniaxial rotational diffusion. The localized translational diffusion of the hydrogen

  19. Nanoscopic dynamics of phospholipid in unilamellar vesicles: Effect of gel to fluid phase transition

    SciTech Connect

    Sharma, V. K.; Mamontov, E.; Anunciado, D. B.; O’Neill, H.; Urban, V.

    2015-03-04

    Dynamics of phospholipids in unilamellar vesicles (ULV) is of interest in biology, medical, and food sciences since these molecules are widely used as biocompatible agents and a mimic of cell membrane systems. We have investigated the nanoscopic dynamics of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) phospholipid in ULV as a function of temperature using elastic and quasielastic neutron scattering (QENS). The dependence of the signal on the scattering momentum transfer, which is a critical advantage of neutron scattering techniques, allows the detailed analysis of the lipid motions that cannot be carried out by other means. In agreement with a differential scanning calorimetry measurement, a sharp rise in the elastic scattering intensity below ca. 296 K indicates a phase transition from the high-temperature fluid phase to the low-temperature solid gel phase. The microscopic lipid dynamics exhibits qualitative differences between the solid gel phase (in a measurement at 280 K) and the fluid phase (in a measurement at a physiological temperature of 310 K). The data analysis invariably shows the presence of two distinct motions: the whole lipid molecule motion within a monolayer, or lateral diffusion, and the relatively faster internal motion of the DMPC molecule. The lateral diffusion of the whole lipid molecule is found to be Fickian in character, whereas the internal lipid motions are of localized character, consistent with the structure of the vesicles. The lateral motion slows down by an order of magnitude in the solid gel phase, whereas for the internal motion not only the time scale, but also the character of the motion changes upon the phase transition. In the solid gel phase, the lipids are more ordered and undergo uniaxial rotational motion. However, in the fluid phase, the hydrogen atoms of the lipid tails undergo confined translation diffusion rather than uniaxial rotational diffusion. The localized translational diffusion of the hydrogen atoms of

  20. Coupled measurement of δ18O/δD in gypsum hydration water and salinity of fluid inclusions in gypsum: A novel tool for reconstructing parent water chemistry and depositional environment

    NASA Astrophysics Data System (ADS)

    Evans, Nick; Gázquez, Fernando; Turchyn, Alexandra; Chapman, Hazel; Hodell, David

    2015-04-01

    The measurement of oxygen and hydrogen isotopes in gypsum hydration water (CaSO4•2H2O) is a powerful tool to determine the isotopic composition of the parent fluid from which gypsum precipitated. To be useful, however, the hydration water must retain its original isotope signal and not have undergone postdepositional exchange. We developed a novel method to ascertain whether hydration waters have secondarily exchanged by coupling oxygen and hydrogen isotopes of gypsum hydration water with the salinities of fluid inclusions. Salinity is obtained through microthermometric analysis of the same gypsum crystals measured for hydration water by freezing the sample and then measuring the melting point of the fluid inclusions. We apply the method to Messinian gypsum deposits of Cycle 6 within the Yesares Member, Río de Aguas section, Sorbas Basin (SE Spain). After correction of oxygen and hydrogen isotopes of gypsum hydration water for fractionation factors, the estimated range of the mother water is -1.8o to 2.8o for δ18O and -12.5o to 16.3o for δD. In the same samples, estimated salinity of primary fluid inclusions range from 18 to 51ppt. Salinity is highly correlated with δ18O and δD, yielding an r2 of 0.88 and 0.87, respectively. The intercepts of the regression equations (i.e., at zero salinity) define the isotope composition of the freshwater endmember, and average -4.4±1.3o for δ18O and -28.9±8.7o for δD. These values are within error of the average isotope composition of precipitation and groundwater data from the local region of Almería today (-4.3o and -22.2o for δ18O and δD, respectively). This agreement provides strong evidence that the gypsum hydration water has retained its isotope composition and has not undergone postdepositional exchange. Furthermore, the isotope and salinity values indicate a significant contribution of meteoric water during gypsum deposition. This observation contrasts with sulfur and oxygen isotopes in sulfate (21.9 > δ34S

  1. The effect of hydrate saturation on water retention curves in hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Mahabadi, Nariman; Zheng, Xianglei; Jang, Jaewon

    2016-05-01

    The experimental measurement of water retention curve in hydrate-bearing sediments is critically important to understand the behavior of hydrate dissociation and gas production. In this study, tetrahydrofuran (THF) is selected as hydrate former. The pore habit of THF hydrates is investigated by visual observation in a transparent micromodel. It is confirmed that THF hydrates are not wetting phase on the quartz surface of the micromodel and occupy either an entire pore or part of pore space resulting in change in pore size distribution. And the measurement of water retention curves in THF hydrate-bearing sediments with hydrate saturation ranging from Sh = 0 to Sh = 0.7 is conducted for excess water condition. The experimental results show that the gas entry pressure and the capillary pressure increase with increasing hydrate saturation. Based on the experimental results, fitting parameters for van Genuchten equation are suggested for different hydrate saturation conditions.

  2. Device and method for measuring multi-phase fluid flow and density of fluid in a conduit having a gradual bend

    DOEpatents

    Ortiz, Marcos German; Boucher, Timothy J.

    1998-01-01

    A system for measuring fluid flow in a conduit having a gradual bend or arc, and a straight section. The system includes pressure transducers, one or more disposed in the conduit on the outside of the arc, and one disposed in the conduit in a straight section thereof. The pressure transducers measure the pressure of fluid in the conduit at the locations of the pressure transducers and this information is used by a computational device to calculate fluid flow rate in the conduit. For multi-phase fluid, the density of the fluid is measured by another pair of pressure transducers, one of which is located in the conduit elevationally above the other. The computation device then uses the density measurement along with the fluid pressure measurements, to calculate fluid flow.

  3. Device and method for measuring multi-phase fluid flow and density of fluid in a conduit having a gradual bend

    DOEpatents

    Ortiz, M.G.; Boucher, T.J.

    1998-10-27

    A system is described for measuring fluid flow in a conduit having a gradual bend or arc, and a straight section. The system includes pressure transducers, one or more disposed in the conduit on the outside of the arc, and one disposed in the conduit in a straight section thereof. The pressure transducers measure the pressure of fluid in the conduit at the locations of the pressure transducers and this information is used by a computational device to calculate fluid flow rate in the conduit. For multi-phase fluid, the density of the fluid is measured by another pair of pressure transducers, one of which is located in the conduit elevationally above the other. The computation device then uses the density measurement along with the fluid pressure measurements, to calculate fluid flow. 1 fig.

  4. Implicitly solving phase appearance and disappearance problems using two-fluid six-equation model

    DOE PAGES

    Zou, Ling; Zhao, Haihua; Zhang, Hongbin

    2016-01-25

    Phase appearance and disappearance issue presents serious numerical challenges in two-phase flow simulations using the two-fluid six-equation model. Numerical challenges arise from the singular equation system when one phase is absent, as well as from the discontinuity in the solution space when one phase appears or disappears. In this work, a high-resolution spatial discretization scheme on staggered grids and fully implicit methods were applied for the simulation of two-phase flow problems using the two-fluid six-equation model. A Jacobian-free Newton-Krylov (JFNK) method was used to solve the discretized nonlinear problem. An improved numerical treatment was proposed and proved to be effectivemore » to handle the numerical challenges. The treatment scheme is conceptually simple, easy to implement, and does not require explicit truncations on solutions, which is essential to conserve mass and energy. Various types of phase appearance and disappearance problems relevant to thermal-hydraulics analysis have been investigated, including a sedimentation problem, an oscillating manometer problem, a non-condensable gas injection problem, a single-phase flow with heat addition problem and a subcooled flow boiling problem. Successful simulations of these problems demonstrate the capability and robustness of the proposed numerical methods and numerical treatments. As a result, volume fraction of the absent phase can be calculated effectively as zero.« less

  5. Ultrasound Microbubble Treatment Enhances Clathrin-Mediated Endocytosis and Fluid-Phase Uptake through Distinct Mechanisms.

    PubMed

    Fekri, Farnaz; Delos Santos, Ralph Christian; Karshafian, Raffi; Antonescu, Costin N

    2016-01-01

    Drug delivery to tumors is limited by several factors, including drug permeability of the target cell plasma membrane. Ultrasound in combination with microbubbles (USMB) is a promising strategy to overcome these limitations. USMB treatment elicits enhanced cellular uptake of materials such as drugs, in part as a result of sheer stress and formation of transient membrane pores. Pores formed upon USMB treatment are rapidly resealed, suggesting that other processes such as enhanced endocytosis may contribute to the enhanced material uptake by cells upon USMB treatment. How USMB regulates endocytic processes remains incompletely understood. Cells constitutively utilize several distinct mechanisms of endocytosis, including clathrin-mediated endocytosis (CME) for the internalization of receptor-bound macromolecules such as Transferrin Receptor (TfR), and distinct mechanism(s) that mediate the majority of fluid-phase endocytosis. Tracking the abundance of TfR on the cell surface and the internalization of its ligand transferrin revealed that USMB acutely enhances the rate of CME. Total internal reflection fluorescence microscopy experiments revealed that USMB treatment altered the assembly of clathrin-coated pits, the basic structural units of CME. In addition, the rate of fluid-phase endocytosis was enhanced, but with delayed onset upon USMB treatment relative to the enhancement of CME, suggesting that the two processes are distinctly regulated by USMB. Indeed, vacuolin-1 or desipramine treatment prevented the enhancement of CME but not of fluid phase endocytosis upon USMB, suggesting that lysosome exocytosis and acid sphingomyelinase, respectively, are required for the regulation of CME but not fluid phase endocytosis upon USMB treatment. These results indicate that USMB enhances both CME and fluid phase endocytosis through distinct signaling mechanisms, and suggest that strategies for potentiating the enhancement of endocytosis upon USMB treatment may improve targeted

  6. Ultrasound Microbubble Treatment Enhances Clathrin-Mediated Endocytosis and Fluid-Phase Uptake through Distinct Mechanisms

    PubMed Central

    Fekri, Farnaz; Delos Santos, Ralph Christian; Karshafian, Raffi

    2016-01-01

    Drug delivery to tumors is limited by several factors, including drug permeability of the target cell plasma membrane. Ultrasound in combination with microbubbles (USMB) is a promising strategy to overcome these limitations. USMB treatment elicits enhanced cellular uptake of materials such as drugs, in part as a result of sheer stress and formation of transient membrane pores. Pores formed upon USMB treatment are rapidly resealed, suggesting that other processes such as enhanced endocytosis may contribute to the enhanced material uptake by cells upon USMB treatment. How USMB regulates endocytic processes remains incompletely understood. Cells constitutively utilize several distinct mechanisms of endocytosis, including clathrin-mediated endocytosis (CME) for the internalization of receptor-bound macromolecules such as Transferrin Receptor (TfR), and distinct mechanism(s) that mediate the majority of fluid-phase endocytosis. Tracking the abundance of TfR on the cell surface and the internalization of its ligand transferrin revealed that USMB acutely enhances the rate of CME. Total internal reflection fluorescence microscopy experiments revealed that USMB treatment altered the assembly of clathrin-coated pits, the basic structural units of CME. In addition, the rate of fluid-phase endocytosis was enhanced, but with delayed onset upon USMB treatment relative to the enhancement of CME, suggesting that the two processes are distinctly regulated by USMB. Indeed, vacuolin-1 or desipramine treatment prevented the enhancement of CME but not of fluid phase endocytosis upon USMB, suggesting that lysosome exocytosis and acid sphingomyelinase, respectively, are required for the regulation of CME but not fluid phase endocytosis upon USMB treatment. These results indicate that USMB enhances both CME and fluid phase endocytosis through distinct signaling mechanisms, and suggest that strategies for potentiating the enhancement of endocytosis upon USMB treatment may improve targeted

  7. Computational fluid dynamics analysis of SSME phase 2 and phase 2+ preburner injector element hydrogen flow paths

    NASA Technical Reports Server (NTRS)

    Ruf, Joseph H.

    1992-01-01

    Phase 2+ Space Shuttle Main Engine powerheads, E0209 and E0215 degraded their main combustion chamber (MCC) liners at a faster rate than is normal for phase 2 powerheads. One possible cause of the accelerated degradation was a reduction of coolant flow through the MCC. Hardware changes were made to the preburner fuel leg which may have reduced the resistance and, therefore, pulled some of the hydrogen from the MCC coolant leg. A computational fluid dynamics (CFD) analysis was performed to determine hydrogen flow path resistances of the phase 2+ fuel preburner injector elements relative to the phase 2 element. FDNS was implemented on axisymmetric grids with the hydrogen assumed to be incompressible. The analysis was performed in two steps: the first isolated the effect of the different inlet areas and the second modeled the entire injector element hydrogen flow path.

  8. Wax and hydrate control with electrical power

    SciTech Connect

    1997-08-01

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

  9. A fluid biopsy as investigating technology for the fluid phase of solid tumors

    NASA Astrophysics Data System (ADS)

    Kuhn, Peter; Bethel, Kelly

    2012-02-01

    , which has shown predictive utility in several cancer types—the blurry outlines of things to come began to coalesce. The field of CTC research is in its adolescence; enumeration and characterization research effort is methodologically varied, vigorously individuated and rich in innovation. The high definition CTC (HD-CTC) assay described herein and applied to several currently relevant research questions about cancer spread represents a new measure of an internal biologic process that will hopefully lead to great advancements in cancer medicine. First, the paper entitled 'Fluid biopsy in patients with metastatic prostate, pancreatic and breast cancers' by Marrinucci et al, represents the initial technical and clinical validation of an enrichment-free assay and demonstrates our ability to identify significant numbers of HD-CTCs in a majority of patients with prostate, breast and pancreatic cancers. It demonstrates very high rates of detection (>50%) in breast, prostate and pancreatic cancer patients with no CTCs found in normal control subjects. The assay detects significantly higher numbers of CTCs than the FDA-approved Cellsearch® assay and shows the presence of clusters of CTCs in many patients. The nature of the clusters is further evaluated in 'Characterization of circulating tumor cell aggregates identified in patients with epithelial tumors' by Cho et al, wherein CTC aggregates are identified in 43% of 86 patient samples. The fraction of CTC aggregation was investigated in blood draws from 24 breast, 14 non-small cell lung (NSCLC), 18 pancreatic, 15 prostate stage IV cancer patients and 15 normal blood donors (NBD). Cells contained in CTC aggregates had less area and length, on average, than single CTCs. The nuclear to cytoplasmic (N/C) ratio between single CTCs and CTC aggregates was similar. To assist with translating into patients the substantial cell biology work done using cell line cells instead of human tumor tissue, the paper entitled 'Cytometric

  10. Quantum chemical approach for condensed-phase thermochemistry (III): Accurate evaluation of proton hydration energy and standard hydrogen electrode potential

    NASA Astrophysics Data System (ADS)

    Ishikawa, Atsushi; Nakai, Hiromi

    2016-04-01

    Gibbs free energy of hydration of a proton and standard hydrogen electrode potential were evaluated using high-level quantum chemical calculations. The solvent effect was included using the cluster-continuum model, which treated short-range effects by quantum chemical calculations of proton-water complexes, and the long-range effects by a conductor-like polarizable continuum model. The harmonic solvation model (HSM) was employed to estimate enthalpy and entropy contributions due to nuclear motions of the clusters by including the cavity-cluster interactions. Compared to the commonly used ideal gas model, HSM treatment significantly improved the contribution of entropy, showing a systematic convergence toward the experimental data.

  11. Ductile flow of methane hydrate

    USGS Publications Warehouse

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

    2003-01-01

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

  12. Evaluation of an amide-based stationary phase for supercritical fluid chromatography.

    PubMed

    Borges-Muñoz, Amaris C; Colón, Luis A

    2016-09-01

    J. Sep. Sci. 2016, 39, 3469-3476 A stationary phase containing an amide group embedded in a hydrophobic backbone (i.e., C18-amide) attached to silica particles was characterized by means of the linear solvation energy relationship model, which relates the chromatographic retention factor to specific solute interactions. The evaluationwas conducted under supercritical fluid chromatographic conditions using a mobile phase composition of carbon dioxide and methanol as co-solvent. The stationary phase showed to provide an alternate separation selectivity that is attractive to separate drug-like polar compounds in a relatively fast analysis time. PMID:27598573

  13. Device for measuring the fluid density of a two-phase mixture

    DOEpatents

    Cole, Jack H.

    1980-01-01

    A device for measuring the fluid density of a two-phase mixture flowing through a tubular member. A rotor assembly is rotatively supported within the tubular member so that it can also move axially within the tubular member. The rotor assembly is balanced against a pair of springs which exert an axial force in the opposite direction upon the rotor assembly. As a two-phase mixture flows through the tubular member it contacts the rotor assembly causing it to rotate about its axis. The rotor assembly is forced against and partially compresses the springs. Means are provided to measure the rotational speed of the rotor assembly and the linear displacement of the rotor assembly. From these measurements the fluid density of the two-phase mixture is calculated.

  14. Research on one-dimensional two-phase flow. Theory on hydrodynamic balance in two fluid model and its application

    NASA Astrophysics Data System (ADS)

    Adachi, H.

    1986-08-01

    In the Part I, the author describes the fundamental form of the hydraulic basic equations for a one-dimensional two-phase flow (two fluid model). Most of the discussions are concentrated on the treatment of phase change inertial force terms in the equations of motion, and the author's equations of motion have a strong uniqueness on the following three points in comparison with conventional equations of motion: (1) To express force balance of unit mass two-phase fluid instead of that of unit volume two-phase fluid; (2) To pick up the unit existing mass and the unit flowing mass as the unit mass of two-phase fluid; and (3) To apply the kinetic energy principle instead of the momentum low in the evaluation of stational inertia force term. In these three, the item: (1) is for excluding a part of momentum change or kinetic energy change due to mass change of the elementary part of fluid, which is independent of force; (2) is not to introduce a phenomenological physical model into the evaluation of phase change inertial force term; and (3) is for correctly applying the momentum law taking into account the difference of representative velocities between the main flow fluid (vapor phase or liquid phase) and the phase change part of fluid. In the Part II, characteristics of various kinds of high speed two-phase flow are clarified theoretically by using the basic equations derived in the Part I.

  15. Shock waves and phase changes in a large-heat-capacity fluid emerging from a tube

    NASA Astrophysics Data System (ADS)

    Thompson, P. A.; Kim, Y.-G.; Carofano, G. C.

    1986-05-01

    The emergence of a shockwave from the open end of a shock tube is studied, with special emphasis on test fluids of high molar heat capacity, i.e. retrograde fluids. A variety of wavelike vapour-liquid phase changes are observed in such fluids, including the liquefaction shock, mixture-evaporation shock, condensation waves associated with shock splitting and liquid-evaporation waves (these phenomena have analogues in the polymorphic phase changes of solids; only the first two are treated in this paper). The open end of the shock-tube test section discharges into an observation chamber where photographs of the emerging flow are taken. Calculations were performed with the Benedict-Webb-Rubin, van der Waals and other equations of state. Numerical (finite-difference) predictions of the flow were made for single-phase and two-phase flows: solutions were tested against the experimental shock diffraction and vortex data of Skews. The phase-change properties of the test fluid can be quantified by the 'retrogradicity' r(T), measuring the difference in slope between the P, T isentrope and the vapour-pressure curve, and the 'kink' k(T), measuring the difference between the single-phase and mixture sound speeds. Mixture-evaporation (i.e. rerefaction) shocks appear to have a sonic-sonic or double Chapman-Jouguet structure and show agreement with amplitude predictions based on k(T). Liquefaction shocks are found to show a reproducible transition from regular, smooth shock fronts to irregular, chaotic shock fronts with increasing shock Mach number. This transition can be correlated with published stability limits.

  16. Bacterial migration and motion in a fluid phase and near a solid surface

    SciTech Connect

    Frymier, P.D. Jr.

    1995-01-01

    An understanding of the migration and motion of bacteria in a fluid phase and near solid surfaces is necessary to characterize processes such as the bioremediation of hazardous waste, the pathogenesis of infection, industrial biofouling and wastewater treatment, among others. This study addresses three questions concerning the prediction of the distribution of a population of bacteria in a fluid phase and the motion of bacteria near a solid surface: Under what conditions does a one-dimensional phenomenological model for the density of a population of chemotactic bacteria yield an adequate representation of the migration of bacteria subject to a one-dimensional attractant gradient? How are the values of transport coefficients obtained from experimental data affected by the use of the one-dimensional phenomenological model and also by the use of different descriptions of bacterial swimming behavior in a mathematically rigorous balance equation? How is the characteristic motion of bacteria swimming in a fluid affected by the presence of a solid phase? A computer simulation that rigorously models the movement of a large population of individual chemotactic bacteria in three dimensions is developed to test the validity of a one-dimensional phenomenological model for bacterial migration in a fluid.

  17. Chloral hydrate

    Integrated Risk Information System (IRIS)

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

  18. Gas Phase Hydration of Model Peptide Chains: Far/mid Infrared Signature of Water Intermolecular Motions in the Monohydrate

    NASA Astrophysics Data System (ADS)

    Cirtog, M.; Loquais, Y.; Brenner, V.; Tardivel, B.; Mons, M.; Gloaguen, E.; Rijs, A. M.

    2012-06-01

    The far/mid infrared region (100 - 800 cm-1) of two hydrated conformations of the model peptide chain N-acetyl-phenylalanine-amide (Ac-Phe-NH_2) have been investigated in a supersonic jet expansion by conformational selective double-resonance IR/UV spectroscopy, using the free electron laser FELIX for the far IR tunability. The two folded conformations (identified in a previous work share the same H-bonding network, with the water molecule bridging the peptide ends as a donor and acceptor but differ by the orientation of the free hydrogen. By comparison with the isolated peptide, hydration gives rise to new spectroscopic features locate in three different spectral regions namely around 160, 400 and 600 cm-1. The analysis of a series of quantum chemical harmonic frequency calculations using various approaches (DFT and DFT-D) suggests that this spectral region constitutes a real challenge to the theory. As expected, the low frequency modes present a strong anharmonicity and sensitivity to the position of the water molecule. It has nevertheless allowed us to assign the new experimental signatures to a direct excitation of normal modes widely involving intermolecular libration and wagging motions of the water molecule in the complex, and revealed an extended coupling with the peptide backbone deformation motions. H.S. Biswal, Y. Loquais, B. Tardivel, E. Gloaguen and M. Mons, J. Am. Chem. Soc. 133, 3931 (2011). S. Jaeqx, M. Schmit, W.J. van der Zande, and A.M. Rijs, manuscript in preparation

  19. Effects of confinement on anomalies and phase transitions of core-softened fluids

    SciTech Connect

    Krott, Leandro B. Barbosa, Marcia C.; Bordin, José Rafael

    2015-04-07

    We use molecular dynamics simulations to study how the confinement affects the dynamic, thermodynamic, and structural properties of a confined anomalous fluid. The fluid is modeled using an effective pair potential derived from the ST4 atomistic model for water. This system exhibits density, structural, and dynamical anomalies, and the vapor-liquid and liquid-liquid critical points similar to the quantities observed in bulk water. The confinement is modeled both by smooth and structured walls. The temperatures of extreme density and diffusion for the confined fluid show a shift to lower values while the pressures move to higher amounts for both smooth and structured confinements. In the case of smooth walls, the critical points and the limit between fluid and amorphous phases show a non-monotonic change in the temperatures and pressures when the nanopore size is increase. In the case of structured walls, the pressures and temperatures of the critical points varies monotonically with the pore size. Our results are explained on basis of the competition between the different length scales of the fluid and the wall-fluid interaction.

  20. Phase diagram of the two-fluid Lipkin model: A "butterfly" catastrophe

    NASA Astrophysics Data System (ADS)

    García-Ramos, J. E.; Pérez-Fernández, P.; Arias, J. M.; Freire, E.

    2016-03-01

    Background: In the past few decades quantum phase transitions have been of great interest in nuclear physics. In this context, two-fluid algebraic models are ideal systems to study how the concept of quantum phase transition evolves when moving into more complex systems, but the number of publications along this line has been scarce up to now. Purpose: We intend to determine the phase diagram of a two-fluid Lipkin model that resembles the nuclear proton-neutron interacting boson model Hamiltonian using both numerical results and analytic tools, i.e., catastrophe theory, and compare the mean-field results with exact diagonalizations for large systems. Method: The mean-field energy surface of a consistent-Q -like two-fluid Lipkin Hamiltonian is studied and compared with exact results coming from a direct diagonalization. The mean-field results are analyzed using the framework of catastrophe theory. Results: The phase diagram of the model is obtained and the order of the different phase-transition lines and surfaces is determined using a catastrophe theory analysis. Conclusions: There are two first-order surfaces in the phase diagram, one separating the spherical and the deformed shapes, while the other separates two different deformed phases. A second-order line, where the later surfaces merge, is found. This line finishes in a transition point with a divergence in the second-order derivative of the energy that corresponds to a tricritical point in the language of the Ginzburg-Landau theory for phase transitions.

  1. Phase separation of fluids in porous media: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Ahmad, Shaista; Puri, Sanjay; Das, Subir K.

    2014-10-01

    We present comprehensive molecular dynamics results for phase-separation kinetics of fluids in a porous medium. This system is modeled by a symmetric Lennard-Jones fluid mixture with a quenched random field. The presence of disorder slows down domain growth from power-law to a logarithmic form. It also modifies the correlation functions and structure factors which characterize the morphology. In particular, the structure-factor tail shows a non-Porod behavior, which is the consequence of scattering from rough interfaces.

  2. Incompressible two-phase flows with an inextensible Newtonian fluid interface

    NASA Astrophysics Data System (ADS)

    Reuther, Sebastian; Voigt, Axel

    2016-10-01

    We introduce a diffuse interface approximation for an incompressible two-phase flow problem with an inextensible Newtonian fluid interface. This approach allows to model lipid membranes as viscous fluids. In the present setting the membranes are assumed to be stationary. We validate the model and the numerical approach, which is based on a stream function formulation for the surface flow problem, an operator splitting approach and a semi-implicit adaptive finite element discretization, against observed flow patterns in vesicles, which are adhered to a solid surface and are subjected to shear flow. The influence of the Gaussian curvature on the surface flow pattern is discussed.

  3. On the transition between two-phase and single-phase interface dynamics in multicomponent fluids at supercritical pressures

    NASA Astrophysics Data System (ADS)

    Dahms, Rainer N.; Oefelein, Joseph C.

    2013-09-01

    A theory that explains the operating pressures where liquid injection processes transition from exhibiting classical two-phase spray atomization phenomena to single-phase diffusion-dominated mixing is presented. Imaging from a variety of experiments have long shown that under certain conditions, typically when the pressure of the working fluid exceeds the thermodynamic critical pressure of the liquid phase, the presence of discrete two-phase flow processes become diminished. Instead, the classical gas-liquid interface is replaced by diffusion-dominated mixing. When and how this transition occurs, however, is not well understood. Modern theory still lacks a physically based model to quantify this transition and the precise mechanisms that lead to it. In this paper, we derive a new model that explains how the transition occurs in multicomponent fluids and present a detailed analysis to quantify it. The model applies a detailed property evaluation scheme based on a modified 32-term Benedict-Webb-Rubin equation of state that accounts for the relevant real-fluid thermodynamic and transport properties of the multicomponent system. This framework is combined with Linear Gradient Theory, which describes the detailed molecular structure of the vapor-liquid interface region. Our analysis reveals that the two-phase interface breaks down not necessarily due to vanishing surface tension forces, but due to thickened interfaces at high subcritical temperatures coupled with an inherent reduction of the mean free molecular path. At a certain point, the combination of reduced surface tension, the thicker interface, and reduced mean free molecular path enter the continuum length scale regime. When this occurs, inter-molecular forces approach that of the multicomponent continuum where transport processes dominate across the interfacial region. This leads to a continuous phase transition from compressed liquid to supercritical mixture states. Based on this theory, a regime diagram for

  4. Bulk fluid phase behaviour of colloidal platelet-sphere and platelet-polymer mixtures.

    PubMed

    de las Heras, Daniel; Schmidt, Matthias

    2013-04-13

    Using a geometry-based fundamental measure density functional theory, we calculate bulk fluid phase diagrams of colloidal mixtures of vanishingly thin hard circular platelets and hard spheres. We find isotropic-nematic phase separation, with strong broadening of the biphasic region, upon increasing the pressure. In mixtures with large size ratio of platelet and sphere diameters, there is also demixing between two nematic phases with differing platelet concentrations. We formulate a fundamental measure density functional for mixtures of colloidal platelets and freely overlapping spheres, which represent ideal polymers, and use it to obtain phase diagrams. We find that, for low platelet-polymer size ratio, in addition to isotropic-nematic and nematic-nematic phase coexistence, platelet-polymer mixtures also display isotropic-isotropic demixing. By contrast, we do not find isotropic-isotropic demixing in hard-core platelet-sphere mixtures for the size ratios considered.

  5. Coupled measurements of δ18O and δD of hydration water and salinity of fluid inclusions in gypsum from the Messinian Yesares Member, Sorbas Basin (SE Spain)

    NASA Astrophysics Data System (ADS)

    Evans, Nicholas P.; Turchyn, Alexandra V.; Gázquez, Fernando; Bontognali, Tomaso R. R.; Chapman, Hazel J.; Hodell, David A.

    2015-11-01

    We studied one cycle (Cycle 6) of gypsum-marl deposition from the Messinian Yesares Member in Sorbas Basin, Spain. The objective was to reconstruct the changing environment of deposition and its relation to astronomically-forced climate change. The δ18O and δD of gypsum hydration water (CaSO4 • 2H2O) and salinity of fluid inclusions were measured in the same samples to test if they record the composition of the mother fluid from which gypsum was precipitated. Water isotopes are highly correlated with fluid inclusion salinity suggesting the hydration water has not exchanged after formation. The relatively low water isotope values and fluid inclusion salinities indicate a significant influence of meteoric water, whereas δ34S, δ18OSO4 and 87Sr/86Sr support a dominant marine origin for the gypsum deposits. The discrepancy between water and elemental isotope signatures can be reconciled if meteoric water dissolved previously deposited marine sulfates supplying calcium and sulfate ions to the basin which maintained gypsum saturation. This recycling process accounts for the marine δ34S, δ18OSO4 and 87Sr/86Sr signatures, whereas the low δ18O and δD values of gypsum hydration water and fluid inclusion salinities reflect the influence of freshwater. The cyclic deposition of gypsum and marl in the Yesares Member has previously been interpreted to reflect changing climate related to Earth's precession cycle. We demonstrate that the δ18O, δD and salinity of the parent brine increased from low values at the base of the cycle to a maximum in the massive gypsum palisade, and decreased again to lower values in the supercones at the top of the cycle. This pattern, together with changes in mineralogy (calcite-dolomite-gypsum), is consistent with a precession-driven change in climate with wettest conditions (summer insolation maxima) associated with the base of the calcium carbonate marls and driest conditions (summer insolation minima) during formation of the gypsum

  6. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, T.S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The "standard" and "quick look" Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in all of the gas hydrate accumulations assessed in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  7. Suppression of turbulent energy cascade due to phase separation in homogenous binary mixture fluid

    NASA Astrophysics Data System (ADS)

    Takagi, Youhei; Okamoto, Sachiya

    2015-11-01

    When a multi-component fluid mixture becomes themophysically unstable state by quenching from well-melting condition, phase separation due to spinodal decomposition occurs, and a self-organized structure is formed. During phase separation, free energy is consumed for the structure formation. In our previous report, the phase separation in homogenous turbulence was numerically simulated and the coarsening process of phase separation was discussed. In this study, we extended our numerical model to a high Schmidt number fluid corresponding to actual polymer solution. The governing equations were continuity, Navier-Stokes, and Chan-Hiliard equations as same as our previous report. The flow filed was an isotropic homogenous turbulence, and the dimensionless parameters in the Chan-Hilliard equation were estimated based on the thermophysical condition of binary mixture. From the numerical results, it was found that turbulent energy cascade was drastically suppressed in the inertial subrange by phase separation for the high Schmidt number flow. By using the identification of turbulent and phase separation structure, we discussed the relation between total energy balance and the structures formation processes. This study is financially supported by the Grand-in-Aid for Young Scientists (B) (No. T26820045) from the Ministry of Education, Cul-ture, Sports, Science and Technology of Japan.

  8. A Computational Study of Systemic Hydration in Vocal Fold Collision

    PubMed Central

    Bhattacharya, Pinaki; Siegmund, Thomas

    2013-01-01

    Mechanical stresses develop within vocal fold (VF) soft tissues, due to phonation-associated vibration and collision. These stresses in turn affect the hydration of VF tissue and thus influence voice health. In this paper, high-fidelty numerical computations are described taking into account fully three-dimensional geometry, realistic tissue and air properties, and high-amplitude vibration and collision. A segregated solver approach is employed, using sophisticated commercial solvers for both the VF tissue and glottal airflow domains. The tissue viscoelastic properties were derived from a biphasic formulation. Two cases were considered, whereby the tissue viscoelastic properties corresponded to two different volume fractions of the fluid phase of the VF tissue. For each case, hydrostatic stresses occurring as a result of vibration and collision were investigated. Assuming the VF tissue to be poroelastic, interstitial fluid movement within VF tissue was estimated from the hydrostatic stress gradient. Computed measures of overall VF dynamics (peak air-flow velocity, magnitude of VF deformation, frequency of vibration and contact pressure) were well within the range of experimentally observed values. The VF motion leading to mechanical stresses within the VFs and their effect on the interstitial fluid flux is detailed. It is found that average deformation and vibration of VFs tends to increase the state of hydration of the VF tissue whereas VF collision works to reduce hydration. PMID:23531170

  9. Hydrate problems in pipelines: A study from Norwegian continental waters

    SciTech Connect

    Lysne, D.; Larsen, R.; Lund, A.; Thomsen, A.K.

    1995-12-31

    This study was undertaken by the Norwegian Petroleum Directorate and SINTEF to identify hydrate problems occurring in pipelines on the Norwegian continental shelf. A brief review of hydrate dissociation theory is given. Three major techniques for hydrate removal are discussed, as well as hazards related to hydrate plug removal. Questionnaire answers from 15 companies operating in Norwegian waters show three specific occurrences of hydrate plugs in the North Sea. Problems from other geographical areas are also discussed. Hydrate problems are reported for a wide variety of pipe lengths, diameters, profiles, insulations characteristics and fluids. Most problems occur during normal operation.

  10. A Two-Phase Solid/Fluid Model for Dense Granular Flows Including Dilatancy Effects

    NASA Astrophysics Data System (ADS)

    Mangeney, Anne; Bouchut, Francois; Fernandez-Nieto, Enrique; Narbona-Reina, Gladys

    2015-04-01

    We propose a thin layer depth-averaged two-phase model to describe solid-fluid mixtures such as debris flows. It describes the velocity of the two phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure, that itself modifies the friction within the granular phase (Iverson et al., 2010). The model is derived from a 3D two-phase model proposed by Jackson (2000) based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work (Bouchut et al., 2014). In particular, Pitman and Le replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's equations. We close the mixture equations by a weak compressibility relation involving a critical density, or equivalently a critical pressure. Moreover, we relax one boundary condition, making it possible for the fluid to escape the granular media when compression of the granular mass occurs. Furthermore, we introduce second order terms in the equations making it possible to describe the evolution of the pore fluid pressure in response to the compression/dilatation of the granular mass without prescribing an extra ad-hoc equation for the pore pressure. We prove that the energy balance associated with this Jackson closure is dissipative, as well as its thin layer associated model. We present several numerical tests for the 1D case that are compared to the

  11. A Two-Phase Solid/Fluid Model for Dense Granular Flows Including Dilatancy Effects

    NASA Astrophysics Data System (ADS)

    Mangeney, A.; Bouchut, F.; Fernández-Nieto, E. D.; Narbona-Reina, G.; Kone, E. H.

    2014-12-01

    We propose a thin layer depth-averaged two-phase model to describe solid-fluid mixtures such as debris flows. It describes the velocity of the two phases, the compression/dilatation of the granular media and its interaction with the pore fluid pressure, that itself modifies the friction within the granular phase (Iverson et al., 2010). The model is derived from a 3D two-phase model proposed by Jackson (2000) based on the 4 equations of mass and momentum conservation within the two phases. This system has 5 unknowns: the solid and fluid velocities, the solid and fluid pressures and the solid volume fraction. As a result, an additional equation inside the mixture is necessary to close the system. Surprisingly, this issue is inadequately accounted for in the models that have been developed on the basis of Jackson's work (Bouchut et al., 2014). In particular, Pitman and Le replaced this closure simply by imposing an extra boundary condition at the surface of the flow. When making a shallow expansion, this condition can be considered as a closure condition. However, the corresponding model cannot account for a dissipative energy balance. We propose here an approach to correctly deal with the thermodynamics of Jackson's equations. We close the mixture equations by a weak compressibility relation involving a critical density, or equivalently a critical pressure. Moreover, we relax one boundary condition, making it possible for the fluid to escape the granular media when compression of the granular mass occurs. Furthermore, we introduce second order terms in the equations making it possible to describe the evolution of the pore fluid pressure in response to the compression/dilatation of the granular mass without prescribing an extra ad-hoc equation for the pore pressure. We prove that the energy balance associated with this Jackson closure is dissipative, as well as its thin layer associated model. We present several numerical tests for the 1D case that are compared to the

  12. Fluid-solid coexistence from two-phase simulations: binary colloidal mixtures and square well systems.

    PubMed

    Méndez-Maldonado, G Arlette; Chapela, Gustavo A; Martínez-González, José Adrián; Moreno, José Antonio; Díaz-Herrera, Enrique; Alejandre, José

    2015-02-01

    Molecular dynamics simulations are performed to clarify the reasons for the disagreement found in a previous publication [G. A. Chapela, F. del Río, and J. Alejandre, J. Chem. Phys. 138(5), 054507 (2013)] regarding the metastability of liquid-vapor coexistence on equimolar charged binary mixtures of fluids interacting with a soft Yukawa potential with κσ = 6. The fluid-solid separation obtained with the two-phase simulation method is found to be in agreement with previous works based on free energy calculations [A. Fortini, A.-P. Hynninen, and M. Dijkstra, J. Chem. Phys. 125, 094502 (2006)] only when the CsCl structure of the solid is used. It is shown that when pressure is increased at constant temperature, the solids are amorphous having different structures, densities, and the diagonal components of the pressure tensor are not equal. A stable low density fluid-solid phase separation is not observed for temperatures above the liquid-vapor critical point. In addition, Monte Carlo and discontinuous molecular dynamics simulations are performed on the square well model of range 1.15σ. A stable fluid-solid transition is observed above the vapor-liquid critical temperature only when the solid has a face centered cubic crystalline structure.

  13. Well log characterization of natural gas hydrates

    USGS Publications Warehouse

    Collett, Timothy S.; Lee, Myung W.

    2011-01-01

    In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed 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 controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate

  14. A Generalized Multi-Phase Framework for Modeling Cavitation in Cryogenic Fluids

    NASA Technical Reports Server (NTRS)

    Dorney, Dan (Technical Monitor); Hosangadi, Ashvin; Ahuja, Vineet

    2003-01-01

    A generalized multi-phase formulation for cavitation in fluids operating at temperatures elevated relative to their critical temperatures is presented. The thermal effects and the accompanying property variations due to phase change are modeled rigorously. Thermal equilibrium is assumed and fluid thermodynamic properties are specified along the saturation line using the NIST-12 databank. Fundamental changes in the physical characteristics of the cavity when thermal effects become pronounced are identified; the cavity becomes more porous, the interface less distinct, and has increased entrainment when temperature variations are present. Quantitative estimates of temperature and pressure depressions in both liquid nitrogen and liquid hydrogen were computed and compared with experimental data of Hord for hydrofoils. Excellent estimates of the leading edge temperature and pressure depression were obtained while the comparisons in the cavity closure region were reasonable. Liquid nitrogen cavities were consistently found to be in thermal equilibrium while liquid hydrogen cavities exhibited small, but distinct, non-equilibrium effects.

  15. Performance of WPA Conductivity Sensor during Two-Phase Fluid Flow in Microgravity

    NASA Technical Reports Server (NTRS)

    Carter, Layne; O'Connor, Edward W.; Snowdon, Doug

    2003-01-01

    The Conductivity Sensor designed for use in the Node 3 Water Processor Assembly (WPA) was based on the existing Space Shuttle application for the fuel cell water system. However, engineering analysis has determined that this sensor design is potentially sensitive to two-phase fluid flow (gadliquid) in microgravity. The source for this sensitivity is the fact that gas bubbles will become lodged between the sensor probe and the wall of the housing without the aid of buoyancy in l-g. Once gas becomes lodged in the housing, the measured conductivity will be offset based on the volume of occluded gas. A development conductivity sensor was flown on the NASA Microgravity Plan to measure the offset, which was determined to range between 0 and 50%. Based on these findings, a development program was initiated at the sensor s manufacturer to develop a sensor design fully compatible with two-phase fluid flow in microgravity.

  16. Using Image Processing Techniques for Cluster Analysis, and Droplet Formation in Phase Separating Fluids

    NASA Astrophysics Data System (ADS)

    Smith, Gregory; Oprisan, Ana; Hegseth, John; Oprisan, Sorinel; Lecoutre, Carole; Garrabos, Yves; Beysens, Daniel

    2009-03-01

    A series of experiments were performed using the Alice II apparatus in microgravity to study phase separation near critical temperature. Using image analysis techniques, we were able to obtain quantitative information regarding the morphology of gas-liquid interface near critical point of pure SF6 fluid in microgravity. Growth laws for liquid and gas clusters were extracted based on image segmentation both with thresholding and k-means clustering. By measuring the image features we analyzed the formation of spherical droplets during late stage of phase separation for a series of full view images. The growth of a wetting layer around the border of the cell containing the fluid was also investigated using image processing techniques.

  17. Surface tension and phase coexistence for fluids of molecules with extended dipoles.

    PubMed

    Sánchez-Arellano, Enrique; Benavides, A L; Alejandre, José

    2012-09-21

    Molecular dynamics simulations of fluids of molecules with extended dipoles were performed, with increasing distance between point charges but with a constant dipole moment, to obtain thermodynamic properties. It was found that the effect of varying the dipole length on the dielectric constant in the liquid phase, the vapor-liquid equilibria, and the surface tension was negligible for dipolar lengths up to half the particle diameter. By comparing thermodynamic properties of the predictions of the extended dipole model with those for the Stockmayer fluid of point dipoles, it was found that extended dipoles are equivalent to point dipoles over a wide range of dipole lengths, and not only near the point dipole limit, when the separation length is very small compared with the mean distance between particles. Finally, phase equilibrium results of extended dipoles were compared to those obtained from the discrete perturbation theory for a Stockmayer potential.

  18. Handbook of gas hydrate properties and occurrence

    SciTech Connect

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

    1983-12-01

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

  19. Immiscibility of Fluid Phases at Magmatic-hydrothermal Transition: Formation of Various PGE-sulfide Mineralization for Layered Basic Intrusions

    NASA Astrophysics Data System (ADS)

    Zhitova, L.; Borisenko, A.; Morgunov, K.; Zhukova, I.

    2007-12-01

    Fluid inclusions in quartz of the Merensky Reef (Bushveld Complex, South Africa) and the Chineisky Pluton (Transbaikal Region, Russia) were studied using cryometry, microthermometry, Raman-spectroscopy, LA ICP- MS, scanning electronic microscopy, gas-chromatography and isotopic methods. This allowed us to document some examples of fluid phase separation resulting in formation of different types of PGE-sulfide mineralization for layered basic intrusions. The results obtained show at least three generations of fluid separated from boiling residual alumosilicate intercumulus liquid of the Merensky Reef. The earliest fluid phase composed of homogenous high-dense methane and nitrogen gas mixture was identified in primary gas and co-existing anomalous fluid inclusions from symplectitic quartz. The next generation, heterophase fluid, composed of brines containing a free low-dense (mostly of carbon dioxide) gas phase, was observed in primary multiphase and coexisting gas-rich inclusions of miarolitic quartz crystals. The latest generation was also a heterophase fluid (low salinity water-salt solution and free low-dense methane gas phase) found in primary water-salt and syngenetic gas inclusions from peripheral zones of miarolitic quartz crystals. For the Chineisky Pluton reduced endocontact magmatogene fluids changed to oxidized low salinity hydrothermal fluids in exocontact zone. This resulted in formation of sulfide-PGE enrichment marginal zones of intrusion. The results obtained give us a possibility to suggest that: 1) Fluid phase separation is a typical feature of magmatogene fluids for layered basic intrusions. 2) Reduced fluids can extract and transport substantial PGE and sulfide concentrations. 3) Oxidation of reduced fluids is one of the most important geochemical barriers causing abundant PGE minerals and sulfides precipitation. This in turn results in both formation of PGE reefs or enriched contact zones of layered basic intrusions. This work was supported by

  20. Fluid inclusion study of diagenetic mineral phases, Upper Jurassic Smackover Formation, southwest Arkansas and northeast Texas

    SciTech Connect

    O'Hearn, T.C.; Moore, C.H.

    1985-02-01

    Homogenization and final melting temperature data from primary and secondary two-phase fluid inclusions within carbonate and sulfate mineral phases reflect the physical re-equilibration of pre-burial calcites and the precipitation of late diagenetic mineral phases during the burial of the upper Smackover (Upper Jurassic, Oxfordian) lime-grainstones in southwestern Arkansas and northeastern Texas. Homogenization temperatures range from 83.0/sup 0/C to 153.8/sup 0/C (uncorrected for excess ambient formation pressures at time of trapping). Final melting points range from -33.4/sup 0/C to -13.5/sup 0/C. Statistically distinct temperature populations reveal the re-equilibration of pre-burial bladed calcite cements and parallel the subsequent paragenesis during burial of nonfabric-selective dolomite, zoned equant mosaic calcite, anhydrite, celestite, unzoned poikilitic calcite cement, and baroque dolomite cement under conditions of increasing temperature and salinity. Re-equilibration/precipitation began after a minimum depth of burial in the range of 0.95 to 1.75 km. Re-equilibration/precipitation resulted, in part, in response to the original connate meteoric to marine pore water system being mixed with, and subsequently replaced by, basinal brines that migrated into the upper Smackover grainstones from the Louann Salt. Melting temperature data indicate that fluids trapped within the two-phase fluid inclusions are highly saline, varying from 17 to 27 wt. % NaCl. Melting temperature data also indicate that the fluids are CaCl/sub 2/-rich brines with NaCl and probably MgCl/sub 2/ and FeCl/sub 2/ as additional chloride components.

  1. Numerical Modeling on Two phase Fluid flow in a Coupled Fracture-Skin-Matrix System

    NASA Astrophysics Data System (ADS)

    Valsala Kumari, R.; G, S. K.

    2015-12-01

    Multiphase flow modeling studies below the ground surface is very essential for designing suitable remediation strategies for contaminated aquifers and for the development of petroleum and geothermal reservoirs. Presence of fractured bedrock beneath the ground surface will make multiphase flow process more complex due to its highly heterogeneous nature. A major challenge in modeling flow within a fractured rock is to capture the interaction between the high permeability fracture and the low permeability rock-matrix. In some instances, weathering and mineral depositions will lead to formation of an additional layer named fracture-skin at the fracture-matrix interface. Porosity and permeability of fracture-skin may significantly vary from the adjacent rock matrix and this variation will result in different flow and transport behavior within the fracture-skin. In the present study, an attempt has been made to model simultaneous flow of two immiscible phases (water and LNAPL) in a saturated coupled fracture-skin-matrix system. A fully-implicit finite difference model has been developed to simulate the variation of pressure and saturation of fluid phases along the fracture and within the rock-matrix. Sensitivity studies have been done to analyze the effect of change of various fracture-skin parameters such as porosity, diffusion coefficient and thickness on pressure and saturation distribution of both wetting and non-wetting fluid phases. It can be concluded from the study that the presence of fracture-skin is significantly affecting the fluid flow at the fracture-matrix interface and it can also be seen from the study that the flow behavior of both fluid phases is sensitive to fracture-skin parameters.

  2. Substellar fragmentation in self-gravitating fluids with a major phase transition

    NASA Astrophysics Data System (ADS)

    Füglistaler, A.; Pfenniger, D.

    2015-06-01

    Context. The observation of various ices in cold molecular clouds, the existence of ubiquitous substellar, cold H2 globules in planetary nebulae and supernova remnants, or the mere existence of comets suggest that the physics of very cold interstellar gas might be much richer than usually envisioned. At the extreme of low temperatures (≲10 K), H2 itself is subject to a phase transition crossing the entire cosmic gas density scale. Aims: This well-known, laboratory-based fact motivates us to study the ideal case of a cold neutral gaseous medium in interstellar conditions for which the bulk of the mass, instead of trace elements, is subject to a gas-liquid or gas-solid phase transition. Methods: On the one hand, the equilibrium of general non-ideal fluids is studied using the virial theorem and linear stability analysis. On the other hand, the non-linear dynamics is studied using computer simulations to characterize the expected formation of solid bodies analogous to comets. The simulations are run with a state-of-the-art molecular dynamics code (LAMMPS) using the Lennard-Jones inter-molecular potential. The long-range gravitational forces can be taken into account together with short-range molecular forces with finite limited computational resources, using super-molecules, provided the right scaling is followed. Results: The concept of super-molecule, where the phase transition conditions are preserved by the proper choice of the particle parameters, is tested with computer simulations, allowing us to correctly satisfy the Jeans instability criterion for one-phase fluids. The simulations show that fluids presenting a phase transition are gravitationally unstable as well, independent of the strength of the gravitational potential, producing two distinct kinds of substellar bodies, those dominated by gravity (planetoids) and those dominated by molecular attractive force (comets). Conclusions: Observations, formal analysis, and computer simulations suggest the

  3. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

  4. Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

    NASA Technical Reports Server (NTRS)

    Freund, Friedemann

    1991-01-01

    Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

  5. Predicting phase behavior of mixtures of reservoir fluids with carbon dioxide

    SciTech Connect

    Grigg, R.B.; Lingane, P.J.

    1983-01-01

    The use of an equation of state to predict phase behavior during carbon dioxide flooding is well established. The characterization of the C/sub 7/ fraction and the selection of interaction parameters are the most important variables. Single-contact phase behavior is presented for mixtures of Ford Geraldine (Delaware), Maljamar (Grayburg), West Sussex (Shannon), and Reservoir D reservoir fluids, and of a synthetic oil with carbon dioxide. The phase behavior of these mixtures can be reproduced using 3 to 5 pseudo components and common interaction parameters. The critical properties of the pseudo components are calculated from detailed oil characterizations. Because the parameters are not further adjusted, this approach reduces the empiricism in fitting phase data and may result in a more accurate representation of the system as the composition of the oil changes during the approach to miscibility. 21 references.

  6. Spacelab experiment definition study on phase transition and critical phenomena in fluids: Interim report on experimental justification

    NASA Technical Reports Server (NTRS)

    Moldover, M. R.; Hocken, M. R.; Gammon, R. W.; Sengers, J. V.

    1976-01-01

    Pure fluids and fluid mixtures near critical points are identified and are related to the progress of several disciplines. Consideration is given to thermodynamic properties, transport properties, and the complex nonlinear phenomena which occur when fluids undergo phase transitions in the critical region. The distinction is made between practical limits which may be extended by advances in technology and intrinsic ones which arise from the modification of fluid properties by the earth's gravitational field. The kinds of experiments near critical points which could best exploit the low gravity environment of an orbiting laboratory are identified. These include studies of the index of refraction, constant volume specific heat, and phase separation.

  7. Fluid flow, gas accumulations, and gas hydrate formation in Kumano forearc basin determined by seismic reflection interpretation and well data correlation

    NASA Astrophysics Data System (ADS)

    Barnes, Jessica L.

    A marine three dimensional (3-D) seismic reflection data set reveals a gas hydrate related bottom simulating reflector (BSR) within Kumano forearc basin, offshore Japan. Well data collected from Site C0002 within the surveyed area provides information on the physical and chemical properties of basin sediments and allows for correlation with the dipping sedimentary layers imaged in the dataset. Calculation of gas saturations in these horizons based on Archie's Law shows preferential concentrations within sandier horizons. Structural controls such as faults and channels affect the gas distribution and illuminate migration pathways for gas to the BSR. Correlation of the strength of the BSR amplitude with the physical and chemical properties of the dipping stratigraphic horizons that are intersected by the BSR, determined by well log and core data, reveals the applicability of BSR amplitude maps in determining locations of elevated gas hydrate and free gas concentrations away from the wellbore.

  8. Educational strategies used in increasing fluid intake and enhancing hydration status in field hockey players preparing for competition in a hot and humid environment: a case study.

    PubMed

    Dabinett, J A; Reid, K; James, N

    2001-09-01

    The purpose of the present study was to develop a hydration strategy for use by female English field hockey players at the 1998 Commonwealth Games in Malaysia. An additional aim was to initiate the process of acclimation. Fifteen elite players, mean age (+/-SEM) 24.1 +/- 1.19 years, height 1.67 +/- 0.01 m, and body mass 62.8 +/- 1.76 kg, took part in a 5-day training camp immediately prior to departure for the Games. In order to develop the hydration strategy, training took place under similar environmental conditions to those to be experienced in Malaysia (i.e., 32 degrees C, 80% humidity). Acclimation training consisted of 30-50 min of either continuous, low intensity cycling or high intensity intermittent cycling, which more closely replicated the pattern of activity in field hockey. Body mass measures taken each morning, and pre and post training, together with urine color measures, were used to assess hydration status. Pre-loading with up to 1 L of a 3% carbohydrate-electrolyte solution or water immediately prior to acclimation training, as well as regular drinks throughout, ensured that players avoided significant dehydration, with percent body mass changes ranging from -0.34% to +4.24% post training. Furthermore, the protocol used was sufficient to initiate the process of acclimation as demonstrated by a significant reduction in exercising heart rate and core temperature at all time points by days 4 and 5. In conclusion, although labor intensive and time consuming, the camp was successful in developing a hydration strategy that players were able to utilize once at the Games.

  9. Preferential accumulation of gas hydrate in the Andaman accretionary wedge and relationship to anomalous porosity preservation

    NASA Astrophysics Data System (ADS)

    Rose, K.; Torres, M. E.; Johnson, J. E.; Hong, W.; Giosan, L.; Solomon, E. A.; Kastner, M.; Cawthern, T.; Long, P.; Schaef, T.

    2015-12-01

    In the marine environment, sediments in the gas hydrate stability zone often correspond to slope and basin settings. These settings are dominantly composed of fine-grained silt and clay lithofacies with typically low vertical permeability, and pore fluids frequently under-saturated with respect to methane. As a result, the pressure-temperature conditions requisite for a GHSZ to be present occur widely worldwide across marine settings, however, the distribution of gas hydrate in these settings is neither ubiquitous nor uniform. This study uses sediment core and borehole related data recovered by drilling at Site 17 in the Andaman Sea during the Indian National Gas Hydrate Program Expedition 1 in 2006, to investigate reservoir-scale controls on gas hydrate distribution. In particular, this study finds that conditions beyond reservoir pressure, temperature, salinity, and gas concentration, appear to influence the concentration of gas hydrate in host sediments. Using field-generated datasets along with newly acquired sedimentology, physical property, imaging and geochemical data with mineral saturation and ion activity products of key mineral phases such as amorphous silica and calcite, we document the presence and nature of secondary precipitates that contributed to anomalous porosity preservation at Site 17 in the Andaman Sea. This study demonstrates the importance of grain-scale subsurface heterogeneities in controlling the occurrence and distribution of concentrated gas hydrate accumulations in marine sediments, and document the importance that increased permeability and enhanced porosity play in supporting gas concentrations sufficient to support gas hydrate formation. This illustrates the complex balance and lithology-driven controls on hydrate accumulations of higher concentrations and offers insights into what may control the occurrence and distribution of gas hydrate in other sedimentary settings.

  10. Using Fluid Inclusions to Bring Phase Diagrams to Life in a Guided Inquiry Instructional Setting

    NASA Astrophysics Data System (ADS)

    Farver, J. R.; Onasch, C.

    2011-12-01

    A fundamental concept in mineralogy, petrology, and geochemistry is the generation and interpretation of phase diagrams for various systems. We have developed an exercise to strengthen student's familiarity with and confidence in employing phase diagrams by using fluid inclusions. The activity follows the 5Es (Engagement, Exploration, Explanation, Extension, Evaluation) guided inquiry instructional model in order to best facilitate student learning. The exercise follows an activity adapted from Brady (1992) wherein students collect data to generate the phase diagram for the Ice-Water-NaCl system. The engagement activity involves using a USGS-type fluid inclusion heating-cooling stage with a camera and projection system. We typically employ either a doubly-polished quartz sample or a cleaved section of fluorite and select a typical two phase (L + V) aqueous inclusion. Students first observe the inclusion at room temperature and pressure and are asked to predict what would happen if the sample is heated. Students then watch as the sample is heated to its homogenization temperature (Th) and are asked to explain what they see. The sample is then cooled until completely frozen and then slowly warmed until the first ice melting (at the eutectic, Te) and then until all ice melts (Tm). Again, students are asked to explain what they see and, if necessary, they are guided to remember the earlier phase diagram activity. The process is then repeated while students follow along the appropriate phase diagrams. In this fashion, students literally see the changes in phases present and their relative abundances as they move through the phase diagram. The engagement activity generates student interest in the exercise to insure minds-on as well as hands-on exploration. The exploration activities involve students observing and describing a wide range of fluid inclusion types (e.g., CO2, daughter crystals, multiple inclusion trails, etc) and hands-on collection of Th and Tm data for a

  11. Laboratory experiment on poroelastic behavior of Berea sandstone under two-phase fluid flow condition

    NASA Astrophysics Data System (ADS)

    Goto, H.; Aichi, M.; Tokunaga, T.; Yamamoto, H.; Ogawa, T.; Aoki, T.

    2013-12-01

    Coupled two-phase fluid flow and deformation of Berea sandstone was discussed through laboratory experiments and numerical simulation. In the experiment, a triaxial compression apparatus with flow pipes to pass fluids through a rock sample was used. The experimental procedures were as follows. Firstly, external stresses close to hydrostatic condition were applied to a water saturated cylindrical Berea sandstone sample. Then, compressed air was infiltrated from the bottom of the sample. During the experiment, both axial and circumferential strains at half the height of the sample and volumetric discharge of water at the outlet were measured. Both strains showed sudden extensions after a few seconds, and monotonically extended thereafter. The volumetric discharge of water showed that air breakthrough occurred in around 100 seconds after the commencement of the air injection. Numerical simulations based on thermodynamically consistent constitutive equations were conducted in order to quantitatively analyze the experimental results. In a simulation in which the material was assumed to be homogeneous isotropic, the axial strain at half the height of the sample and the volumetric discharge of water at the outlet were reproduced well by using reasonable parameters, while that was not the case with the circumferential strain at half the height of the sample. On the other hand, in a simulation in which anisotropy of the material was introduced, all experimental data were reproduced well by using reasonable parameters. This result is reasonable because Berea sandstone is well known to be anisotropic under such Terzaghi effective stress condition as used in our experiment, i.e., 3.0 MPa (Hart and Wang, 1999; Hart, 2000). Our results indicate that the theory of poroelasticity for two-phase fluid system can explain the strain behavior of porous media for two-phase fluid flow observed in laboratory experiments.

  12. Seismoelectric couplings in a poroelastic material containing two immiscible fluid phases

    NASA Astrophysics Data System (ADS)

    Jardani, A.; Revil, A.

    2015-08-01

    A new approach of seismoelectric imaging has been recently proposed to detect saturation fronts in which seismic waves are focused in the subsurface to scan its heterogeneous nature and determine saturation fronts. Such type of imaging requires however a complete modelling of the seismoelectric properties of porous media saturated by two immiscible fluid phases, one being usually electrically insulating (for instance water and oil). We combine an extension of Biot dynamic theory, valid for porous media containing two immiscible Newtonian fluids, with an extension of the electrokinetic theory based on the notion of effective volumetric charge densities dragged by the flow of each fluid phase. These effective charge densities can be related directly to the permeability and saturation of each fluid phase. The coupled partial differential equations are solved with the finite element method. We also derive analytically the transfer function connecting the macroscopic electrical field to the acceleration of the fast P wave (coseismic electrical field) and we study the influence of the water content on this coupling. We observe that the amplitude of the co-seismic electrical disturbance is very sensitive to the water content with an increase in amplitude with water saturation. We also investigate the seismoelectric conversions (interface effect) occurring at the water table. We show that the conversion response at the water table can be identifiable only when the saturation contrasts between the vadose and saturated zones are sharp enough. A relatively dry vadose zone represents the best condition to identify the water table through seismoelectric measurements. Indeed, in this case, the coseismic electrical disturbances are vanishingly small compared to the seismoelectric interface response.

  13. Experimental Modeling of Mantle-Crust Interaction: the Influence of Fluid on Melting, Phase Composition and Critical Relationship Between Melt and Fluid

    NASA Astrophysics Data System (ADS)

    Gorbachev, Nikolay; Nekrasov, Alexey; Kostyuk, Anastasia; Sultanov, Dilshod

    2014-05-01

    Geophysical and geochemical data indicate for large-scale exchange of matter between crust and mantle. The most important exchange mechanism is the subduction of oceanic slab, leading to formation of volatile-enriched mantle reservoirs with protoliths subducted slab. To determine peculiarity of magma generation processes from such source and effect of fluids (H2O, H2O + CO2, H2O + HCl) on melting, phase composition and critical relationship between melt and fluid system peridotite- basalt -(Na, K)2CO3 were studied experimentally at 4GPa, 1400°C. Experiments were carried out in anvil-with-hole apparatus by quenching technique with Pt-Pt-peridotite ampoules. Products experiments - polished quench samples, were analyzed by electron microprobe. Type of fluids directly influences on phase relations and composition melts, formed by partial melting of initial sample. Pyroxenization and phlogopitization of peridotite, origin of K-containing (up to 1.5 wt. % K2O) clinopyroxene, formation of SiO2-rich melts normal alkalinity at H2O + CO2, H2O + HCl fluid types, or elevated alkalinity melts at dry, without fluid, are closely connected with fluid composition. The critical relations between partial silicates melt and H2O - containing fluid are observed. Intergranular silicate glass is not formed at supercritical P-T after quenching. Its absence leads to destruction of quenching samples. The supercritical fluid-melt interacts with Ol, Opx, ± Ca-Cpx restite of peridotite to form K-containing clinopyroxene, phlogopite and carbonate. Globules of Al-Si glass during quenching are formed. Solubility of minerals peridotite, reactionary relation between relict and neogenic reactionary mineral are testified about high reactionary ability supercritical phase. The revealed effects explain local development phase and chemical heterogeneity of the upper mantle and the mantle magmas. Supporting by grant RFBR 12-05-00777a

  14. Well log evaluation of gas hydrate saturations

    USGS Publications Warehouse

    Collett, Timothy S.

    1998-01-01

    The amount of gas sequestered in gas hydrates is probably enormous, but estimates are highly speculative due to the lack of previous quantitative studies. Gas volumes that may be attributed to a gas hydrate accumulation within a given geologic setting are dependent on a number of reservoir parameters; one of which, gas-hydrate saturation, can be assessed with data obtained from downhole well logging devices. The primary objective of this study was to develop quantitative well-log evaluation techniques which will permit the calculation of gas-hydrate saturations in gas-hydrate-bearing sedimentary units. The `standard' and `quick look' Archie relations (resistivity log data) yielded accurate gas-hydrate and free-gas saturations within all of the gas hydrate accumulations assessed in the field verification phase of the study. Compressional wave acoustic log data have been used along with the Timur, modified Wood, and the Lee weighted average acoustic equations to calculate accurate gas-hydrate saturations in this study. The well log derived gas-hydrate saturations calculated in the field verification phase of this study, which range from as low as 2% to as high as 97%, confirm that gas hydrates represent a potentially important source of natural gas.

  15. Fluid Phase Separation (FPS) experiment for flight on the shuttle in a Get Away Special (GAS) canister: Design and fabrication

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid that will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The phase separation experiment is totally self-contained, with three levels of containment on all fluids, and provides all necessary electrical power and control. The controller regulates the temperature of the fluid and controls data logging and sampling. An astronaut-activated switch will initiate the experiment and an unmaskable interrupt is provided for shutdown. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS 42 in April 1991. Presented here are the design and the production of a fluid phase separation experiment for rapid implementation at low cost.

  16. Water, Hydration and Health

    PubMed Central

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

    2010-01-01

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

  17. Prediction of fluid phase equilibria and interfacial tension of triangle-well fluids using transition matrix Monte Carlo

    NASA Astrophysics Data System (ADS)

    Sengupta, Angan; Adhikari, Jhumpa

    2016-05-01

    The triangle-well (TW) potential is a simple model which is able to capture the essence of the intermolecular attraction in real molecules. Transition matrix Monte Carlo simulations in the grand canonical ensemble (GC-TMMC) are performed to investigate the role of the range of attraction on the features of fluid phase equilibria. As the TW potential range increases, the vapour-liquid coexistence curves shift towards a higher temperature range with the critical temperature and pressure increasing, and the critical density values decreasing. These GC-TMMC results are in excellent agreement with the predictions of Gibbs ensemble Monte Carlo and replica exchange Monte Carlo (REMC) simulations reported in literature. Using the GC-TMMC method, the vapour pressures are also computed directly from the particle number probability distributions (PNPDs). It has been noted in literature that the surface tension values are computationally more expensive and difficult to determine than other coexistence properties using molecular simulations. The PNPDs from GC-TMMC simulations along with Binder's formalism allow for the calculation of the interfacial tension with relative ease. Also, our simulation generated results for the interfacial tension are in good agreement with the literature data obtained using REMC (via the virial route) and the plots of our interfacial tension values as a function of temperature are smooth unlike the literature data.

  18. Microtomography and pore-scale modeling of two-phase Fluid Distribution

    SciTech Connect

    Silin, D.; Tomutsa, L.; Benson, S.; Patzek, T.

    2010-10-19

    Synchrotron-based X-ray microtomography (micro CT) at the Advanced Light Source (ALS) line 8.3.2 at the Lawrence Berkeley National Laboratory produces three-dimensional micron-scale-resolution digital images of the pore space of the reservoir rock along with the spacial distribution of the fluids. Pore-scale visualization of carbon dioxide flooding experiments performed at a reservoir pressure demonstrates that the injected gas fills some pores and pore clusters, and entirely bypasses the others. Using 3D digital images of the pore space as input data, the method of maximal inscribed spheres (MIS) predicts two-phase fluid distribution in capillary equilibrium. Verification against the tomography images shows a good agreement between the computed fluid distribution in the pores and the experimental data. The model-predicted capillary pressure curves and tomography-based porosimetry distributions compared favorably with the mercury injection data. Thus, micro CT in combination with modeling based on the MIS is a viable approach to study the pore-scale mechanisms of CO{sub 2} injection into an aquifer, as well as more general multi-phase flows.

  19. Extended lattice Boltzmann method for numerical simulation of thermal phase change in two-phase fluid flow.

    PubMed

    Safari, Hesameddin; Rahimian, Mohammad Hassan; Krafczyk, Manfred

    2013-07-01

    In this article, a method based on the multiphase lattice Boltzmann framework is presented which is applicable to liquid-vapor phase-change phenomena. Both liquid and vapor phases are assumed to be incompressible. For phase changes occurring at the phase interface, the divergence-free condition of the velocity field is no longer satisfied due to the gas volume generated by vaporization or fluid volume generated by condensation. Thus, we extend a previous model by a suitable equation to account for the finite divergence of the velocity field within the interface region. Furthermore, the convective Cahn-Hilliard equation is extended to take into account vaporization effects. In a first step, a D1Q3 LB model is constructed and validated against the analytical solution of a one-dimensional Stefan problem for different density ratios. Finally the model is extended to two dimensions (D2Q9) to simulate droplet evaporation. We demonstrate that the results obtained by this approach are in good agreement with theory. PMID:23944580

  20. Extended lattice Boltzmann method for numerical simulation of thermal phase change in two-phase fluid flow

    NASA Astrophysics Data System (ADS)

    Safari, Hesameddin; Rahimian, Mohammad Hassan; Krafczyk, Manfred

    2013-07-01

    In this article, a method based on the multiphase lattice Boltzmann framework is presented which is applicable to liquid-vapor phase-change phenomena. Both liquid and vapor phases are assumed to be incompressible. For phase changes occurring at the phase interface, the divergence-free condition of the velocity field is no longer satisfied due to the gas volume generated by vaporization or fluid volume generated by condensation. Thus, we extend a previous model by a suitable equation to account for the finite divergence of the velocity field within the interface region. Furthermore, the convective Cahn-Hilliard equation is extended to take into account vaporization effects. In a first step, a D1Q3 LB model is constructed and validated against the analytical solution of a one-dimensional Stefan problem for different density ratios. Finally the model is extended to two dimensions (D2Q9) to simulate droplet evaporation. We demonstrate that the results obtained by this approach are in good agreement with theory.

  1. Evidence of a Pre-eruptive Fluid Phase for the Millennium Eruption, Paektu Volcano, North Korea

    NASA Astrophysics Data System (ADS)

    Iacovino, K.; Sisson, T. W.; Lowenstern, J. B.

    2014-12-01

    We present initial results of a study of comenditic to trachytic melt inclusions from the Millennium Eruption (ME) of Paektu volcano (AD 946; VEI≥7; 25 km3 DRE). Paektu volcano (aka Changbaishan) is a remote and poorly studied intraplate stratovolcano whose 37 km2 caldera is bisected by the political border between North Korea and China, limiting studies of its proximal deposits. ME magmas are predominantly phenocryst-poor (≤3 vol%) comendites plus a volumetrically minor late-stage, more phenocryst-rich (10-20 vol%) trachyte. Sizeable (100-500 µm diameter) glassy but bubble-bearing melt inclusions are widespread in anorthoclase and hedenbergite phenocrysts, as well as in rarer quartz and fayalite phenocrysts. Comparing the relative enrichments of incompatible volatile and non-volatile elements in melt inclusions along a liquid line of descent shows decreasing volatile/Zr ratios suggesting the partitioning of volatiles into a fluid phase. This suggests that current gas-yield estimates (Horn & Schminke, 2000) for the ME, based on the petrologic method (difference in volatiles between melt inclusions and matrix glass), could be severe underestimates. Establishing the composition and quantity of a pre-eruptive fluid phase is the primary goal of this study and has implications for eruption triggering and for modeling the climatic effects of one of the largest eruptions in the last 10,000 years. Including results from Horne and Schminke (2000), melt inclusions from within a single pumice fall unit show a wide range in dissolved volatile contents and magma chemistries. Concentrations of H2O are moderate (2-3.5 wt% via FTIR), with Cl and F ranging from 500-4600 ppm and 1100-4700 ppm (via EPMA). CO2 is below the detection limit of 2 ppm (FTIR with N2 purge) in bubble-bearing melt inclusions, but is detectable (≤56 ppm) in melt inclusions homogenized at 100 MPa and 850-900 °C for ~30 min (conditions also leading to reduction of dissolved H2O to 0.6-2 wt

  2. Thermohydrodynamic analysis of cryogenic liquid turbulent flow fluid film bearings, phase 2

    NASA Technical Reports Server (NTRS)

    Sanandres, Luis

    1994-01-01

    The Phase 2 (1994) Annual Progress Report presents two major report sections describing the thermal analysis of tilting- and flexure-pad hybrid bearings, and the unsteady flow and transient response of a point mass rotor supported on fluid film bearings. A literature review on the subject of two-phase flow in fluid film bearings and part of the proposed work for 1995 are also included. The programs delivered at the end of 1994 are named hydroflext and hydrotran. Both codes are fully compatible with the hydrosealt (1993) program. The new programs retain the same calculating options of hydrosealt plus the added bearing geometries, and unsteady flow and transient forced response. Refer to the hydroflext & hydrotran User's Manual and Tutorial for basic information on the analysis and instructions to run the programs. The Examples Handbook contains the test bearing cases along with comparisons with experimental data or published analytical values. The following major tasks were completed in 1994 (Phase 2): (1) extension of the thermohydrodynamic analysis and development of computer program hydroflext to model various bearing geometries, namely, tilting-pad hydrodynamic journal bearings, flexure-pad cylindrical bearings (hydrostatic and hydrodynamic), and cylindrical pad bearings with a simple elastic matrix (ideal foil bearings); (2) improved thermal model including radial heat transfer through the bearing stator; (3) calculation of the unsteady bulk-flow field in fluid film bearings and the transient response of a point mass rotor supported on bearings; and (4) a literature review on the subject of two-phase flows and homogeneous-mixture flows in thin-film geometries.

  3. Thermohydrodynamic analysis of cryogenic liquid turbulent flow fluid film bearings, phase 2

    NASA Astrophysics Data System (ADS)

    Sanandres, Luis

    1994-12-01

    The Phase 2 (1994) Annual Progress Report presents two major report sections describing the thermal analysis of tilting- and flexure-pad hybrid bearings, and the unsteady flow and transient response of a point mass rotor supported on fluid film bearings. A literature review on the subject of two-phase flow in fluid film bearings and part of the proposed work for 1995 are also included. The programs delivered at the end of 1994 are named hydroflext and hydrotran. Both codes are fully compatible with the hydrosealt (1993) program. The new programs retain the same calculating options of hydrosealt plus the added bearing geometries, and unsteady flow and transient forced response. Refer to the hydroflext & hydrotran User's Manual and Tutorial for basic information on the analysis and instructions to run the programs. The Examples Handbook contains the test bearing cases along with comparisons with experimental data or published analytical values. The following major tasks were completed in 1994 (Phase 2): (1) extension of the thermohydrodynamic analysis and development of computer program hydroflext to model various bearing geometries, namely, tilting-pad hydrodynamic journal bearings, flexure-pad cylindrical bearings (hydrostatic and hydrodynamic), and cylindrical pad bearings with a simple elastic matrix (ideal foil bearings); (2) improved thermal model including radial heat transfer through the bearing stator; (3) calculation of the unsteady bulk-flow field in fluid film bearings and the transient response of a point mass rotor supported on bearings; and (4) a literature review on the subject of two-phase flows and homogeneous-mixture flows in thin-film geometries.

  4. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

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

  5. An attempt to estimate ionic interactions with phenyl and pentafluorophenyl stationary phases in supercritical fluid chromatography.

    PubMed

    West, Caroline; Lemasson, Elise; Khater, Syame; Lesellier, Eric

    2015-09-18

    Pentafluorophenyl-bonded silica (PFP) phases employed in high-performance liquid chromatography (HPLC) often provide very different results depending on the column manufacturer. PFP phases also provide significantly different selectivity from non-fluorinated aromatic phases. As all HPLC columns can also be employed with carbon dioxide-based mobile phases, PFP phases can also be useful to supercritical fluid chromatography (SFC). However, whether they provide adequate retention and selectivity in SFC conditions is necessary for them to find applicability with this technique. In our laboratory, a column classification for packed column SFC was designed, based on the solvation parameter model, which currently comprises data for about eighty different columns. In this paper, we present the characterization of eleven PFP phases provided by different manufacturers used with carbon dioxide-methanol mobile phases. The columns are compared to fifteen other non-fluorinated phenyl and diphenyl phases in terms of their retention and separation characteristics assessed by the solvation parameter model with five Abraham descriptors. The latter is insufficient for an accurate description of retention mechanisms on the PFP phases, thus two extra terms accounting for ionic interactions with anions and cations (D(-) and D(+)), previously developed for HPLC in hydrophilic interaction mode (HILIC), are introduced. While some approximations are necessary regarding the true pH and pKa values in CO2-based mobile phases, the retention models are significantly improved by this addition, allowing to integrate ionizable analytes in the test set for evaluation of ionic interactions in the chromatographic systems. PMID:26278356

  6. Nematic spin fluid in the tetragonal phase of BaFe{<_2}As{<_2}.

    SciTech Connect

    Harriger, L. W.; Luo, H. Q.; Liu, M. S.; Frost, C.; Hu, J. P.; Norman, M. R.; Dai, P.

    2011-08-24

    We use inelastic neutron scattering to study spin waves below and above T{sub N} in iron-arsenide BaFe{sub 2}As{sub 2}. In the low-temperature orthorhombic phase, we find highly anisotropic spin waves with a large damping along the antiferromagnetic a-axis direction. On warming the system to the paramagnetic tetragonal phase, the low-energy spin waves evolve into quasi-elastic excitations, while the anisotropic spin excitations near the zone boundary persist. These results strongly suggest the presence of a spin nematic fluid in the tetragonal phase of BaFe{sub 2}As{sub 2}, which may cause the electronic and orbital anisotropy observed in these materials.

  7. Numerical Modeling of Three-Dimensional Fluid Flow with Phase Change

    NASA Technical Reports Server (NTRS)

    Esmaeeli, Asghar; Arpaci, Vedat

    1999-01-01

    We present a numerical method to compute phase change dynamics of three-dimensional deformable bubbles. The full Navier-Stokes and energy equations are solved for both phases by a front tracking/finite difference technique. The fluid boundary is explicitly tracked by discrete points that are connected by triangular elements to form a front that is used to keep the stratification of material properties sharp and to calculate the interfacial source terms. Two simulations are presented to show robustness of the method in handling complex phase boundaries. In the first case, growth of a vapor bubble in zero gravity is studied where large volume increase of the bubble is managed by adaptively increasing the front resolution. In the second case, growth of a bubble under high gravity is studied where indentation at the rear of the bubble results in a region of large curvature which challenges the front tracking in three dimensions.

  8. Halide based shock-wave treatment of fluid-rich natural phases

    NASA Astrophysics Data System (ADS)

    Schlothauer, T.; Schimpf, C.; Brendler, E.; Keller, K.; Kroke, E.; Heide, G.

    2015-11-01

    For the synthesis of high pressure phases from natural minerals and the shock wave treatment of fluid bearing phases a halide based method was developed. The experiments were performed in the pressure range between 25 and 162 GPa with a success rate for the new method of 100% for the new method. Based on the Impedance Corrected Sample Recovery Capsule under avoiding the adiabatic decompression a direct comparison between different loading paths and sample holder geometries is possible. The recovered samples show neither indications of melting in the case of kaolinite and very limited degassing in the case of carbonates. The recovery of amorphous water bearing Al-Si-phases with Aluminum in four-, five- and six-fold coordination was possible. The samples were analyzed with scanning electron microscopy, x-ray diffraction, nuclear-magnetic-resonance- and infra-red-spectroscopy and the results were directly compared.

  9. Computer simulation of two-phase fluid motion in unsaturated complex fractures using a volume of fluid method

    SciTech Connect

    Hai Huang; Paul Meakin

    2005-12-01

    Complex fluid behavior in unsaturated fracture and fracture networks, such as film flow, the migration, fragmentation, and coalescence of droplets, and rivulet flow with or without meandering or pulsation, has been widely observed in laboratory experiments. In this study, a modified two-dimensional volume of fluid (VOF) method was used to simulate liquid motion in partially saturated fracture apertures under a variety of flow conditions. This modeling approach systematically incorporates the effects of inertial forces, viscosity, gravity acting on the fluid densities, fracture wall wetting, and the pressure drop across curved fluid-fluid interfaces due to surface tension. This allows us to obtain a better understanding of the fundamental physics governing unsaturated fluid flow in fracture apertures. The VOF method is able to handle the complex dynamics of fluid-fluid interfaces and free surfaces in unsaturated fractures by using a fixed Eulerian grid. Fragmentation and coalescence of the fluids are automatically handled without resorting to complex adaptive mesh refinement or interface repairing algorithms. The wetting of fracture walls was modeled by imposing contact angles near the contact lines (contact points in two-dimensional simulations), and different contact angles were automatically chosen depending on whether the liquid interface is advancing, receding, or essentially stationary. The qualitative agreements between the numerical simulations and complex multiphase fluid dynamics reported in laboratory experiments clearly demonstrate the potential value of the VOF method for the mechanistically based modeling of immiscible liquid motion in unsaturated fracture networks.

  10. Fracture Genesis and Fracture Filling In Hydrate Systems

    NASA Astrophysics Data System (ADS)

    Daigle, H.; Dugan, B.

    2009-12-01

    Steady-state models of coupled flow through fractures and porous media predict that millions of years are required to accumulate the very high hydrate saturation (>50%) necessary to form hydraulic fractures by fluid pressure buildup; however, once a fracture system is formed, it will fill with hydrate in roughly 15 kyr. This modeling is a first step towards understanding heterogeneous, fracture-hosted methane hydrate deposits that have been observed in marine hydrate systems worldwide. In fine-grained sediments, methane hydrate is frequently observed in pores as well as in veins and fractures. One possible explanation is hydrate forms in pores and fluid pressure increases until fractures form. Fluid then flows through the fractures and forms hydrate-filled fractures. To study this, we ran 1-D numerical simulations with a prescribed flow rate of methane-charged fluid through a porous medium. As hydrate forms, pores are occluded and permeability is reduced, causing an increase in fluid pressure to maintain the constant flow rate. We assume that hydraulic fractures form when the fluid pressure reaches 90% of the overburden stress. Simulations of Blake Ridge (offshore South Carolina) indicate that fractures occur after 7.4 million years with a hydrate saturation (Sh) of 95% at the base of the methane hydrate stability zone (MHSZ). Simulations of Keathley Canyon (Gulf of Mexico) achieve the fracture criterion after 7.9 million years with Sh = 54% at the base of the MHSZ. Once fractures are formed they fill with hydrate after 15,000 years. Our results indicate that the time scale of pressure buildup assuming present-day fluxes is very long, and that lower-permeability sediments require lower hydrate saturations to reach the fracture criterion. However, once fractures form, they are filled with hydrate rapidly. This suggests that fractures may provide short-term migration pathways between higher-permeability layers, but also that additional research is needed to constrain

  11. Device and method for measuring multi-phase fluid flow in a conduit having an abrupt gradual bend

    DOEpatents

    Ortiz, Marcos German

    1998-01-01

    A system for measuring fluid flow in a conduit having an abrupt bend. The system includes pressure transducers, one disposed in the conduit at the inside of the bend and one or more disposed in the conduit at the outside of the bend but spaced a distance therefrom. The pressure transducers measure the pressure of fluid in the conduit at the locations of the pressure transducers and this information is used by a computational device to calculate fluid flow rate in the conduit. For multi-phase fluid, the density of the fluid is measured by another pair of pressure transducers, one of which is located in the conduit elevationally above the other. The computation device then uses the density measurement along with the fluid pressure measurements, to calculate fluid flow.

  12. Device and method for measuring multi-phase fluid flow in a conduit having an abrupt gradual bend

    DOEpatents

    Ortiz, M.G.

    1998-02-10

    A system is described for measuring fluid flow in a conduit having an abrupt bend. The system includes pressure transducers, one disposed in the conduit at the inside of the bend and one or more disposed in the conduit at the outside of the bend but spaced a distance therefrom. The pressure transducers measure the pressure of fluid in the conduit at the locations of the pressure transducers and this information is used by a computational device to calculate fluid flow rate in the conduit. For multi-phase fluid, the density of the fluid is measured by another pair of pressure transducers, one of which is located in the conduit elevationally above the other. The computation device then uses the density measurement along with the fluid pressure measurements, to calculate fluid flow. 1 fig.

  13. Process for inhibiting hydrates while producing moist CO/sub 2/ from subterranean reservoirs

    SciTech Connect

    Diaz, Z.

    1986-07-01

    A CO/sub 2/-producing process is described in which moist CO/sub 2/ is produced at high pressure from a subterranean well, is mixed with a hydrate inhibitor and is piped to a facility for drying CO/sub 2/ and subsequently supplying it for use at high pressure. An improvement is described here for avoiding the need for producing and piping the CO/sub 2/ at pressures and temperatures maintaining a single phase state which consists of: conducting the producing and piping of moist CO/sub 2/ at pressure and temperature conditions of at least about 500 psia but less than critical conditions and the ambient temperature near the wellhead apt to convert the fluid being piped to a fluid containing both an aqueous liquid-phase and a CO/sub 2/-rich liquid-phase having a volume which is many times greater than that of the aqueous liquid-phase; mixing the so produced moist CO/sub 2/ with sufficient hydrate inhibitor to cause the concentration remaining in the aqueous phase to be sufficient to prevent hydrate formation in spite of the amount of inhibitor which will be partitioned into the CO/sub 2/-phase; and using as the hydrate inhibitor a polyhydric alcohol hydrate inhibitor having a solubility in CO/sub 2/ at the conditions in the pipe which is low relative to the solubility of methanol in that CO/sub 2/, so that, while simplifying the producing and piping operations, both the contamination of CO/sub 2/ and loss of inhibitor are minimized.

  14. Prediction of Parameters Distribution of Upward Boiling Two-Phase Flow With Two-Fluid Models

    SciTech Connect

    Yao, Wei; Morel, Christophe

    2002-07-01

    In this paper, a multidimensional two-fluid model with additional turbulence k - {epsilon} equations is used to predict the two-phase parameters distribution in freon R12 boiling flow. The 3D module of the CATHARE code is used for numerical calculation. The DEBORA experiment has been chosen to evaluate our models. The radial profiles of the outlet parameters were measured by means of an optical probe. The comparison of the radial profiles of void fraction, liquid temperature, gas velocity and volumetric interfacial area at the end of the heated section shows that the multidimensional two-fluid model with proper constitutive relations can yield reasonably predicted results in boiling conditions. Sensitivity tests show that the turbulent dispersion force, which involves the void fraction gradient, plays an important role in determining the void fraction distribution; and the turbulence eddy viscosity is a significant factor to influence the liquid temperature distribution. (authors)

  15. Thermodynamics, compressibility, and phase diagram: shock compression of supercritical fluid xenon.

    PubMed

    Zheng, J; Chen, Q F; Gu, Y J; Chen, Z Y; Li, C J

    2014-09-28

    Supercritical fluids have intriguing behaviors at extreme pressure and temperature conditions, prompting the need for thermodynamic properties of supercritical fluid xenon (SCF) under shock compression. Double-shock experimental data on SCF xenon in the 140 GPa pressure range were directly measured by means of a multi-channel pyrometer and a Doppler-pins-system. It entered the so-called warm dense region. We found that the shock compressed SCF Xe had higher dynamic compression and higher number density than that of liquid Xe at same shock pressure. The larger compressibility of SCF Xe in our experiments could be explained that the increase of electronic excitations and ionizations leaded to a large drop of thermal pressure and a softening of Hugoniot. The high pressure phase diagram of xenon was depicted with the aid of the degeneracy, coupling parameter, and current available experiments on the pressure-temperature plane. PMID:25273430

  16. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Yun, T. S.; Santamarina, J. C.; Ruppel, C.

    2007-06-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  17. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    USGS Publications Warehouse

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

    2007-01-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  18. Induced compositional layering in a convecting fluid layer by an endothermic phase transition

    NASA Astrophysics Data System (ADS)

    Weinstein, Stuart A.

    1992-09-01

    An endothermic phase change in the presence of chemical heterogeneities can act as an efficient filter, such that heavy material is sequestered below the phase change and light material is trapped above the phase change. Due to the fact that the endothermic phase change damps thermal convection, it can act as a "trap door" for chemical heterogeneities. Ascending flows which are chemically dense will need more thermal buoyancy to rise through the transition than ascending flows whose composition is closer to the background composition. Likewise, descending flows which are chemically light need more thermal buoyancy to sink through the transition. The results of a suite of numerical calculations of two-dimensional, double diffusive convection in a fluid layer with an endothermic phase change suggests that, if the 670 km seismic discontinuity has a steep enough Clapeyron slope, compositional layering may be induced and dynamically maintained by the transition. Furthermore, these calculations also show that the phase change and compositional boundaries will approximately coincide.

  19. Study of Phase Equilibria of Petrochemical Fluids using Gibbs Ensemble Monte Carlo Methods

    NASA Astrophysics Data System (ADS)

    Nath, Shyamal

    2001-03-01

    Knowledge of phase behavior of hydrocarbons and related compounds are highly of interest to chemical and petrochemical industries. For example, design of processes such as supercritical fluid extraction, petroleum refining, enhanced oil recovery, gas treatment, and fractionation of wax products. A precise knowledge of the phase equilibria of alkanes, alkenes and related compounds and their mixtures are required for efficient design of these processes. Experimental studies to understand the related phase equilibria often become unsuitable for various reasons. With the advancement of simulation technology, molecular simulations could provide a useful complement and alternative in the study and description of phase behavior of these systems. In this work we study vapor-liquid phase equilibria of pure hydrocarbons and their mixtures using Gibbs ensemble simulation. Insertion of long and articulated chain molecules are facilitated in our simulations by means of configurational bias and expanded ensemble methods. We use the newly developed NERD force field in our simulation. In this work NERD force field is extended to provide coverage for hydrocarbons with any arbitrary architecture. Our simulation results provide excellent quantitative agreement with available experimental phase equilibria data for both the pure components and mixtures.

  20. Solvent-free model for self-assembling fluid bilayer membranes: Stabilization of the fluid phase based on broad attractive tail potentials

    NASA Astrophysics Data System (ADS)

    Cooke, Ira R.; Deserno, Markus

    2005-12-01

    We present a simple and highly adaptable method for simulating coarse-grained lipid membranes without explicit solvent. Lipids are represented by one head bead and two tail beads, with the interaction between tails being of key importance in stabilizing the fluid phase. Two such tail-tail potentials were tested, with the important feature in both cases being a variable range of attraction. We examined phase diagrams of this range versus temperature for both functional forms of the tail-tail attraction and found that a certain threshold attractive width was required to stabilize the fluid phase. Within the fluid-phase region we find that material properties such as area per lipid, orientational order, diffusion constant, interleaflet flip-flop rate, and bilayer stiffness all depend strongly and monotonically on the attractive width. For three particular values of the potential width we investigate the transition between gel and fluid phases via heating or cooling and find that this transition is discontinuous with considerable hysteresis. We also investigated the stretching of a bilayer to eventually form a pore and found excellent agreement with recent analytic theory.

  1. Origin of the Director Tilt in the Lyotropic Smectic C* Analog Phase: Hydration Interactions and Solvent Variations.

    PubMed

    Bruckner, Johanna R; Knecht, Friederike; Giesselmann, Frank

    2016-01-01

    The origin and long-range correlation of the director tilt in the recently discovered Lα'* phase, which is the lyotropic analog of the thermotropic smectic C* (SmC*) liquid crystalline phase, are investigated. Polarized micro-Raman spectroscopy reveals that the director tilt in the Lα'* phase originates from a tilting of the aromatic 2-phenylpyrimidine cores of the surfactant molecules. Optical measurements of the tilt angle show that its magnitude decreases with increasing solvent concentration, suggesting that the long-range inter-lamellar correlation of the tilt directions is reduced at increasing thickness of the solvent layers. The phase diagrams with four different solvents (water, formamide, N-methylformamide, N,N-dimethylformamide) are investigated, showing that the Lα'* phase is only formed with those solvents that exhibit a dense network of hydrogen bonds. This observation suggests that these hydrogen bond networks play an essential role in the long-range correlation of the director tilt between adjacent surfactant layers. To verify this assumption, mixtures with deuterated solvents are investigated, showing that the tilt angle in the Lα'* phase is indeed reduced by this modification of the solvent's hydrogen bond network.

  2. Simulation of plasma discharge in liquids: A detailed two-phase fluid approach

    NASA Astrophysics Data System (ADS)

    Charchi Aghdam, Ali; Farouk, Tanvir; Reacting Systems; Advanced Energy Research Laboratory Team

    2015-09-01

    Plasma discharge in liquids has gained great attention recently due to its applications in biomedical engineering, fuel processing, and water treatment and so on. Despite the tremendous interest, a comprehensive understanding of the underlying physics still remains limited. In the current work, an attempt is made to present a mathematical multi-physics model to describe the discharge of plasma in liquids. An in-house modeling platform is developed for simulating plasma formation in multiphase fluids. The model resolves a detailed two-phase fluid including viscous effects, surface tension, gravitational forces and electrical body force. All the governing equations are solved for gas and liquid phases. Electric field and charged species equations along with the plasma reaction kinetics are solved to get the charge distribution in the different phases as well as at the gas-liquid interface to obtain the electric body force acting at the interface. By coupling the above sub-models, a comprehensive multi-physics model for plasma discharge in liquids is constructed which is able to capture several physical aspects of the phenomena especially the role of the bubble, its motion and distortion on plasma characteristics.

  3. Reentrant radio-frequency resonator for automated phase-equilibria and dielectric measurements in fluids

    SciTech Connect

    Goodwin, A.R.; Mehl, J.B.; Moldover, M.R.

    1996-12-01

    A reentrant rf cavity resonator has been developed for automated detection of phase separation of fluid mixtures contained within the cavity. Successful operation was demonstrated by redetermining the phase boundaries of a CO{sub 2}+C{sub 2}H{sub 6} mixture in the vicinity of its critical point. We developed an accurate electrical model for the resonator and used helium to determine the deformation of the resonator under pressure. With the model and pressure compensation, the resonator was capable of very accurate dielectric measurements. We confirmed this by remeasuring the molar dielectric polarizability {ital A}{sub {epsilon}} of argon and obtained the result {ital A}{sub {epsilon}}=(4.140{plus_minus}0.006) cm{sup 3}/mol (standard uncertainty) in excellent agreement with published values. We exploited the capability for accurate dielectric measurements to determine the densities of the CO{sub 2}+C{sub 2}H{sub 6} mixture at the phase boundaries and to determine the dipole moment of 1,1,1,2,3,3-hexafluoropropane, a candidate replacement refrigerant. Near the operating frequency of 375 MHz the capacitor in the resonator has an impedance near 14 {Omega}. This low impedance is more tolerant of electrical conductivity within the test fluid and in parallel paths in the support structures than comparable capacitors operating at audio frequencies. This will be an advantage for operation at high temperatures where some conductivity must be expected in all fluids. Of further value for high-temperature applications, the present rf resonator has only two metal{endash}insulator joints. These joints seal coaxial cables; neither joint is subjected to large mechanical stresses and neither joint is required to maintain precise dimensional tolerances. The resonator is rugged and may be operated with inexpensive electronics.

  4. Seismoelectric Coupling in a Poroelastic Material Containing Two Immiscible Fluid Phases

    NASA Astrophysics Data System (ADS)

    Jardani, A.; Revil, A.

    2014-12-01

    Recently, a new approach of seismoelectric imaging has been proposed in which seismic waves are focused in the subsurface to scan its heterogeneous nature and determine saturation fronts. Such type of imaging requires a complete modeling of the seismoelectric properties of porous media saturated by two fluid phases, one being the wetting phase for the solid grains and one being the non-wetting phase (for instance water and oil). We combine an extension of the poroelastic modeling to two-phase flow conditions with an extension of the electrokinetic theory based on the notion of an effective charge per unit pore volume that can be dragged by the flow of each fluid phase. These effective charge densities can be related directly to the permeability. We used finite element approach to simulate the seismoelectric signals in the partially saturated condition to formulate a transfer equation connecting the macroscopic electrical field to the acceleration of the fast P-wave and to study the influence of the water content on the amplitude of the co-seismic waves. The amplitude of the co-seismic wave is very sensitive to the water content with an increase in the amplitude of the electro-coseismic wave with water saturation. We also investigate the seismoelectric conversions occurring at the water table and the absence of conversion below the irreducible water saturation. We show that the conversion response at the water table can be identifiable only when the saturation contrasts between the vadose and saturated zones is sharp. Then a relatively dry vadose zone represents the best condition to identify the ground water level through seismoelectric measurements especially because in this case, the co-seismic signal is very small compared to the seismoelectric conversion response.

  5. Phosphatidylinositol induces fluid phase formation and packing defects in phosphatidylcholine model membranes.

    PubMed

    Peng, Aaron; Pisal, Dipak S; Doty, Amy; Balu-Iyer, Sathy V

    2012-01-01

    Liposomes consisted of phosphatidylinositol (PI) and phosphatidylcholine (PC) have been utilized as delivery vehicle for drugs and proteins. In the present work, we studied the effect of soy PI on physical properties of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) liposomes such as phase state of lipid bilayer, lipid packing and phase properties using multiple orthogonal biophysical techniques. The 6-dodecanoyl-2-dimethylamino naphthalene (Laurdan) fluorescence studies showed that presence of PI induces the formation of fluid phases in DMPC. Differential scanning calorimetry (DSC), temperature dependent fluorescence anisotropy measurements, and generalized polarization values for Laurdan showed that the presence of as low as 10mol% of PI induces substantial broadening and shift to lower temperature of phase transition of DMPC. The fluorescence emission intensity of DPH labeled, PI containing DMPC lipid bilayer decreased possibly due to deeper penetration of water molecules in lipid bilayer. In order to further delineate the effect of PI on the physico chemical properties of DMPC is due to either significant hydrophobic mismatch between the acyl chains of the DMPC and that of soy PI or due to the inositol head group, we systematically replaced soy PI with PC species of similar acyl chain composition (DPPC and 18:2 (Cis) PC) or with diacylglycerol (DAG), respectively. The anisotropy of PC membrane containing soy PI showed largest fluidity change compared to other compositions. The data suggests that addition of PI alters structure and dynamics of DMPC bilayer in that it promotes deeper water penetration in the bilayer, induces fluid phase characteristics and causes lipid packing defects that involve its inositol head group.

  6. Measurements of viscosity and permeability of two phase miscible fluid flow in rock cores.

    PubMed

    Williams, J L; Taylor, D G

    1994-01-01

    This paper describes the application of 1H magnetic resonance imaging (MRI) to the measurement of fluid viscosity and rock core plug permeability during two phase miscible displacements in certain rock types. The core plug permeability was determined by monitoring glycerol solutions displacing D2O. Simple physical principles were used to calculate the core permeability from the measured displacement angle for a set of Lochaline sandstone core plugs. In a further experiment the viscosity of polyacrylamide solution 1500 ppm was determined in the core plug. The permeability and viscosity results compared well to conventional core analysis methods.

  7. Phase behavior and structure of a fluid confined between competing (solvophobic and solvophilic) walls.

    PubMed

    Stewart, M C; Evans, R

    2012-09-01

    We consider a model fluid with long-range r(-6) (dispersion) interparticle potentials confined between competing parallel walls. One wall is solvophilic and would be completely wet at bulk liquid-gas coexistence μ(co)(-), whereas the other is solvophobic and would be completely dry at μ=μ(co)(+). When the wall separation L is large and the system is below the bulk critical temperature T(C) and close to bulk liquid-gas coexistence, a delocalized interface or soft-mode phase forms with a liquid-gas interface near the center of the slit; this interacts with the walls via the power-law tails of the interparticle potentials. We use a coarse-grained effective Hamiltonian approach to derive explicit scaling expressions for the Gibbs adsorption Γ, the surface tension γ, the solvation force f(s), and the total susceptibility χ. These quantities depend on the dimensionless scaling variable (L/σ)(3)βδμ, where β=(k(B)T)(-1), σ is the diameter of the fluid particles and δμ=μ-μ(co) is the chemical potential deviation from bulk coexistence. Using a nonlocal density functional theory, we calculate density profiles for the asymmetrically confined fluid at different chemical potentials and for sufficiently large L confirm the scaling predictions for the four thermodynamic quantities. Since the upper critical dimension for complete wetting with power-law potentials is less than 3, we argue that our (mean-field) scaling predictions should remain valid in treatments that incorporate the effects of interfacial fluctuations. As the wall separation L is decreased at μ(co), we predict a capillary evaporation transition from the delocalized interface phase to a dilute gas state with just a thin adsorbed film of liquidlike density next to the solvophilic wall. This transition is closely connected to the first-order prewetting transition that occurs at the solvophilic wall in the semi-infinite system. We compare the phase diagram for the competing walls system with the phase

  8. Prominin-2 expression increases protrusions, decreases caveolae and inhibits Cdc42 dependent fluid phase endocytosis

    SciTech Connect

    Singh, Raman Deep Schroeder, Andreas S.; Scheffer, Luana; Holicky, Eileen L.; Wheatley, Christine L.; Marks, David L. Pagano, Richard E.

    2013-05-10

    Highlights: •Prominin-2 expression induced protrusions that co-localized with lipid raft markers. •Prominin-2 expression decreased caveolae, caveolar endocytosis and increased pCav1. •Prominin-2 expression inhibited fluid phase endocytosis by inactivation of Cdc42. •These endocytic effects can be reversed by adding exogenous cholesterol. •Caveolin1 knockdown restored fluid phase endocytosis in Prominin2 expressing cells. -- Abstract: Background: Membrane protrusions play important roles in biological processes such as cell adhesion, wound healing, migration, and sensing of the external environment. Cell protrusions are a subtype of membrane microdomains composed of cholesterol and sphingolipids, and can be disrupted by cholesterol depletion. Prominins are pentaspan membrane proteins that bind cholesterol and localize to plasma membrane (PM) protrusions. Prominin-1 is of great interest as a marker for stem and cancer cells, while Prominin-2 (Prom2) is reportedly restricted to epithelial cells. Aim: To characterize the effects of Prom-2 expression on PM microdomain organization. Methods: Prom2-fluorescent protein was transfected in human skin fibroblasts (HSF) and Chinese hamster ovary (CHO) cells for PM raft and endocytic studies. Caveolae at PM were visualized using transmission electron microscopy. Cdc42 activation was measured and caveolin-1 knockdown was performed using siRNAs. Results: Prom2 expression in HSF and CHO cells caused extensive Prom2-positive protrusions that co-localized with lipid raft markers. Prom2 expression significantly decreased caveolae at the PM, reduced caveolar endocytosis and increased caveolin-1 phosphorylation. Prom2 expression also inhibited Cdc42-dependent fluid phase endocytosis via decreased Cdc42 activation. Effects on endocytosis were reversed by addition of cholesterol. Knockdown of caveolin-1 by siRNA restored Cdc42 dependent fluid phase endocytosis in Prom2-expressing cells. Conclusions: Prom2 protrusions primarily

  9. Parametric numerical investigaion of natural convection in a heat-generating fluid with phase transitions

    SciTech Connect

    Aksenova, A.E.; Chudanov, V.V.; Strizhov, V.F.; Vabishchevich, P.N.

    1995-09-01

    Unsteady natural convection of a heat-generating fluid with phase transitions in the enclosures of a square section with isothermal rigid walls is investigated numerically for a wide range of dimensionless parameters. The quasisteady state solutions of conjugate heat and mass transfer problem are compared with available experimental results. Correlation relations for heat flux distributions at the domain boundaries depending on Rayleigh and Ostrogradskii numbers are obtained. It is shown that generally heat transfer is governed both by natural circulation and crust formation phenomena. Results of this paper may be used for analysis of experiments with prototypic core materials.

  10. On the challenges of measuring interfacial characteristics of three-phase fluid flow with x-ray microtomography.

    PubMed

    Brown, K; Schlüter, S; Sheppard, A; Wildenschild, D

    2014-03-01

    Synchrotron-based x-ray computed microtomography contributes high-resolution, three-dimensional observations to investigations of multiphase fluid transport in porous media. Pore-scale observations are valuable to the development and validation of new theory, as well as numerical models. Computed microtomography has been used previously to measure fluid content and interfacial areas in systems containing two fluids (air-water, oil-water) and to a limited extent to measure fluid content and entrapped fluid morphology in systems containing three fluids (air-oil-water). This study addresses challenges that arise when imaging three-phase flow in spreading systems. The first challenge is related to wettability alteration. Observations reported herein suggest that the wettability of solid surfaces changed over the course of a three-fluid phase flow experiment, a phenomenon that has not been observed in similar, previously conducted two-fluid phase experiments. Follow-up experiments showed that wettability alteration is significant when oil-solid contact is combined with x-ray exposure, and is not reversed with a conventional cleaning procedure. The second challenge arises in segmenting three-phase images, and thereby obtaining data from which various measures can be quantified with sufficient accuracy. Partial volume effects and blur often cause the grey-scale values of different fluids to overlap and appropriate steps must be taken to avoid ambiguity at phase boundaries. A comparison of images collected at standard resolution (10.6 microns voxel(-1) ) to those collected at a higher resolution (5.3 microns voxel(-1) ) showed that saturation measurements are within 5% of each other, but interfacial areas for three-phase systems may be underestimated at standard resolution by as much as 25%.

  11. Thermodynamic properties of methane hydrate in quartz powder.

    PubMed

    Voronov, Vitaly P; Gorodetskii, Evgeny E; Safonov, Sergey S

    2007-10-01

    Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.

  12. Lipid bilayers in the gel phase become saturated by triton X-100 at lower surfactant concentrations than those in the fluid phase.

    PubMed

    Ahyayauch, Hasna; Collado, M Isabel; Alonso, Alicia; Goñi, Felix M

    2012-06-01

    It has been repeatedly observed that lipid bilayers in the gel phase are solubilized by lower concentrations of Triton X-100, at least within certain temperature ranges, or other nonionic detergents than bilayers in the fluid phase. In a previous study, we showed that detergent partition coefficients into the lipid bilayer were the same for the gel and the fluid phases. In this contribution, turbidity, calorimetry, and 31P-NMR concur in showing that bilayers in the gel state (at least down to 13-20°C below the gel-fluid transition temperature) become saturated with detergent at lower detergent concentrations than those in the fluid state, irrespective of temperature. The different saturation may explain the observed differences in solubilization. PMID:22713566

  13. Lipid Bilayers in the Gel Phase Become Saturated by Triton X-100 at Lower Surfactant Concentrations Than Those in the Fluid Phase

    PubMed Central

    Ahyayauch, Hasna; Collado, M. Isabel; Alonso, Alicia; Goñi, Felix M.

    2012-01-01

    It has been repeatedly observed that lipid bilayers in the gel phase are solubilized by lower concentrations of Triton X-100, at least within certain temperature ranges, or other nonionic detergents than bilayers in the fluid phase. In a previous study, we showed that detergent partition coefficients into the lipid bilayer were the same for the gel and the fluid phases. In this contribution, turbidity, calorimetry, and 31P-NMR concur in showing that bilayers in the gel state (at least down to 13–20°C below the gel-fluid transition temperature) become saturated with detergent at lower detergent concentrations than those in the fluid state, irrespective of temperature. The different saturation may explain the observed differences in solubilization. PMID:22713566

  14. Fluid migration in the subduction zone: a coupled fluid flow approach

    NASA Astrophysics Data System (ADS)

    Wang, Hongliang; Huismans, Ritske; Rondenay, Stéphane

    2016-04-01

    Subduction zone are the main entry point of water into earth's mantle and play an important role in the global water cycle. The progressive release of water by metamorphic dehydration induce important physical-chemical process in the subduction zone, such as hydrous melting, hydration and weakening of the mantle wedge, creation of pore fluid pressures that may weaken the subduction interface and induce earthquakes. Most previous studies on the role of fluids in subduction zones assume vertical migration or migration according to the dynamic pressure in the solid matrix without considering the pore fluid pressure effect on the deformation of the solid matrix. Here we investigate this interaction by explicitly modeling two-phase coupled poro-plastic flow during subduction. In this approach, the fluid migrates by compaction and decompaction of the solid matrix and affects the subduction dynamics through pore fluid pressure dependent frictional-plastic yield. Our preliminary results indicate that: 1) the rate of fluid migration depends strongly on the permeability and the bulk viscosity of the solid matrix, 2) fluid transfer occurs preferentially along the slab and then propagates into the mantle wedge by viscous compaction driven fluid flow, 3) fluid transport from the surface to depth is a prerequisite for producing high fluid pore pressures and associated hydration induced weakening of the subduction zone interface.

  15. [Effect of space flight factors on hydration homeostasis in monkeys].

    PubMed

    Zhidkov, V V; Abrosimov, S V; Endeka, D K; Borisov, G I; Lobachik, V I

    1987-01-01

    Using nuclear physics methods, hydration homeostasis of three monkeys flown on Cosmos-1514 and Cosmos-1667 was investigated. Measurements were made before flight 1.5 hours after touchdown and during the recovery period. Total water content, extracellular and tissue fluid volumes were measured and intracellular and interstitial fluid volumes were calculated. Postflight, all the animals showed hydration status changes of similar sign: total water content, intracellular and extracellular fluid volumes decreased. Most significant changes occurred in tissue and interstitial fluid volumes. Hydration status responses to space flight factors were variable and the above changes disappeared in the course of the recovery period. The variations recorded were viewed as adaptive.

  16. A parametric analysis of waves propagating in a porous solid saturated by a three-phase fluid.

    PubMed

    Santos, Juan E; Savioli, Gabriela B

    2015-11-01

    This paper presents an analysis of a model for the propagation of waves in a poroelastic solid saturated by a three-phase viscous, compressible fluid. The constitutive relations and the equations of motion are stated first. Then a plane wave analysis determines the phase velocities and attenuation coefficients of the four compressional waves and one shear wave that propagate in this type of medium. A procedure to compute the elastic constants in the constitutive relations is defined next. Assuming the knowledge of the shear modulus of the dry matrix, the other elastic constants in the stress-strain relations are determined by employing ideal gedanken experiments generalizing those of Biot's theory for single-phase fluids. These experiments yield expressions for the elastic constants in terms of the properties of the individual solid and fluids phases. Finally the phase velocities and attenuation coefficients of all waves are computed for a sample of Berea sandstone saturated by oil, gas, and water.

  17. Complex admixtures of clathrate hydrates in a water desalination method

    DOEpatents

    Simmons, Blake A.; Bradshaw, Robert W.; Dedrick, Daniel E.; Anderson, David W.

    2009-07-14

    Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

  18. Liquid phase fluid dynamic (methanol) run in the LaPorte alternative fuels development unit

    SciTech Connect

    Bharat L. Bhatt

    1997-05-01

    A fluid dynamic study was successfully completed in a bubble column at DOE's Alternative Fuels Development Unit (AFDU) in LaPorte, Texas. Significant fluid dynamic information was gathered at pilot scale during three weeks of Liquid Phase Methanol (LPMEOJP) operations in June 1995. In addition to the usual nuclear density and temperature measurements, unique differential pressure data were collected using Sandia's high-speed data acquisition system to gain insight on flow regime characteristics and bubble size distribution. Statistical analysis of the fluctuations in the pressure data suggests that the column was being operated in the churn turbulent regime at most of the velocities considered. Dynamic gas disengagement experiments showed a different behavior than seen in low-pressure, cold-flow work. Operation with a superficial gas velocity of 1.2 ft/sec was achieved during this run, with stable fluid dynamics and catalyst performance. Improvements included for catalyst activation in the design of the Clean Coal III LPMEOH{trademark} plant at Kingsport, Tennessee, were also confirmed. In addition, an alternate catalyst was demonstrated for LPMEOH{trademark}.

  19. Workshop on Two-Phase Fluid Behavior in a Space Environment

    NASA Technical Reports Server (NTRS)

    Swanson, Theodore D. (Editor); Juhasz, AL (Editor); Long, W. Russ (Editor); Ottenstein, Laura (Editor)

    1989-01-01

    The Workshop was successful in achieving its main objective of identifying a large number of technical issues relating to the design of two-phase systems for space applications. The principal concern expressed was the need for verified analytical tools that will allow an engineer to confidently design a system to a known degree of accuracy. New and improved materials, for such applications as thermal storage and as heat transfer fluids, were also identified as major needs. In addition to these research efforts, a number of specific hardware needs were identified which will require development. These include heat pumps, low weight radiators, advanced heat pipes, stability enhancement devices, high heat flux evaporators, and liquid/vapor separators. Also identified was the need for a centralized source of reliable, up-to-date information on two-phase flow in a space environment.

  20. Molecular dynamics study of phase separation in fluids with chemical reactions

    NASA Astrophysics Data System (ADS)

    Krishnan, Raishma; Puri, Sanjay

    2015-11-01

    We present results from the first d =3 molecular dynamics (MD) study of phase-separating fluid mixtures (AB) with simple chemical reactions (A ⇌B ). We focus on the case where the rates of forward and backward reactions are equal. The chemical reactions compete with segregation, and the coarsening system settles into a steady-state mesoscale morphology. However, hydrodynamic effects destroy the lamellar morphology which characterizes the diffusive case. This has important consequences for the phase-separating structure, which we study in detail. In particular, the equilibrium length scale (ℓeq) in the steady state suggests a power-law dependence on the reaction rate ɛ :ℓeq˜ɛ-θ with θ ≃1.0 .

  1. Molecular dynamics study of phase separation in fluids with chemical reactions.

    PubMed

    Krishnan, Raishma; Puri, Sanjay

    2015-11-01

    We present results from the first d=3 molecular dynamics (MD) study of phase-separating fluid mixtures (AB) with simple chemical reactions (A⇌B). We focus on the case where the rates of forward and backward reactions are equal. The chemical reactions compete with segregation, and the coarsening system settles into a steady-state mesoscale morphology. However, hydrodynamic effects destroy the lamellar morphology which characterizes the diffusive case. This has important consequences for the phase-separating structure, which we study in detail. In particular, the equilibrium length scale (ℓ(eq)) in the steady state suggests a power-law dependence on the reaction rate ε:ℓ(eq)∼ε(-θ) with θ≃1.0.

  2. Connecting Pore Scale Dynamics to Macroscopic Models for Two-Fluid Phase Flow

    NASA Astrophysics Data System (ADS)

    McClure, J. E.; Dye, A. L.; Miller, C. T.; Gray, W. G.

    2015-12-01

    Imaging technologies such as computed micro-tomography (CMT) provide high resolution three-dimensional images of real porous medium systems that reveal the true geometric structure of fluid and solid phases. Simulation and analysis tools are essential to extract knowledge from this raw data, and can be applied in tandem to provide information that is otherwise inaccessible. Guidance from multi-scale averaging theory is used to develop a multi-scale analysis framework to determine phase connectivity and extract interfacial areas, curvatures, common line length, contact angle and the velocities of the interface and common curve. The approach is applied to analyze pore-scale dynamics based on a multiphase lattice Boltzmann method. Dense sets of simulations are performed to evaluate the equilibrium relationship between capillary pressure, saturation and interfacial area for several experimentally imaged porous media. The approach is also used study the evolution of macroscopic quantities under dynamic conditions, which is compared to the equilibrium data.

  3. Effect of partial charge parametrization on the fluid phase behavior of hydrogen sulfide.

    PubMed

    Kamath, Ganesh; Lubna, Nusrat; Potoff, Jeffrey J

    2005-09-22

    The effect of partial charge parametrization on the fluid phase behavior of hydrogen sulfide is investigated with grand canonical histogram reweighting Monte Carlo simulations. Four potential models, based on a Lennard-Jones + point charge functional form, are developed. It is shown that Lennard-Jones parameters can be tuned such that partial charges for the sulfur atom in the range -0.40 < q(s) < -0.252 will lead to an accurate reproduction of experimental vapor-liquid equilibria. Each of the parameter sets developed in this work are used to predict the pressure composition behavior H2S-n-pentane at 377.6 K. While the mixture calculation provides a means of reducing the number of candidate parameter sets, multiple parameter sets were found to yield an excellent reproduction of both the pure component and mixture phase behavior.

  4. Using Hydrated Salt Phase Change Materials for Residential Air Conditioning Peak Demand Reduction and Energy Conservation in Coastal and Transitional Climates in the State of California

    NASA Astrophysics Data System (ADS)

    Lee, Kyoung Ok

    The recent rapid economic and population growth in the State of California have led to a significant increase in air conditioning use, especially in areas of the State with coastal and transitional climates. This fact makes that the electric peak demand be dominated by air conditioning use of residential buildings in the summer time. This extra peak demand caused by the use of air conditioning equipment lasts only a few days out of the year. As a result, unavoidable power outages have occurred when electric supply could not keep up with such electric demand. This thesis proposed a possible solution to this problem by using building thermal mass via phase change materials to reduce peak air conditioning demand loads. This proposed solution was tested via a new wall called Phase Change Frame Wall (PCFW). The PCFW is a typical residential frame wall in which Phase Change Materials (PCMs) were integrated to add thermal mass. The thermal performance of the PCFWs was first evaluated, experimentally, in two test houses, built for this purpose, located in Lawrence, KS and then via computer simulations of residential buildings located in coastal and transitional climates in California. In this thesis, a hydrated salt PCM was used, which was added in concentrations of 10% and 20% by weight of the interior sheathing of the walls. Based on the experimental results, under Lawrence, KS weather, the PCFWs at 10% and 20% of PCM concentrations reduced the peak heat transfer rates by 27.0% and 27.3%, on average, of all four walls, respectively. Simulated results using California climate data indicated that PCFWs would reduce peak heat transfer rates by 8% and 19% at 10% PCM concentration and 12.2% and 27% at 20% PCM concentration for the coastal and transitional climates, respectively. Furthermore, the PCFWs, at 10% PCM concentration, would reduce the space cooling load and the annual energy consumption by 10.4% and 7.2%, on average in both climates, respectively.

  5. Phase separation of critical binary fluids under microgravity: Comparison with matched-density conditions

    SciTech Connect

    Beysens, D.; Guenoun, P.; Perrot, F.

    1988-10-15

    A number of phase-separation mechanisms in fluids are hidden in earth-bound experiments due to the influence of gravitationally induced flow. Solutions to this problem can be found by using strictly matched-density systems, such as the partially deuterated cyclohexane and methanol system (C/sup */C-M), or by performing experiments in space so as to benefit from the microgravity environment. Both types of studies have been performed here to determine quantitatively to what extent such matched-density systems could recreate, on earth, microgravity conditions; they were restricted to the neighborhood of the liquid-liquid critical point. A 6-min microgravity environment has been provided in the sounding rockets of the TEXUS program: Two experiments have been performed, one (T11) using the nonmatched-density system of fully deuterated cyclohexane and methanol (C/sup */-M), and one (T13) using the matched-density system C/sup */C-M. In experiment T13 the phase separation was seen to be characterized by a high-contrast, periodiclike pattern, so that the observations could be performed by a simple optical method. In order to analyze quantitatively the possible differences with the earth-based experiments, the origin of the detected images had to be carefully analyzed. It appeared that they are connected to the interface pattern of the phase-separating fluid. Therefore, after digitization and statistical treatment, it was possible to check the important scaling properties of the phase separation: structure factor, reduced moments, typical wavelength pattern. Experiment T11 was qualitatively different from the earth-bound experiment and can be understood only by an unexpected extreme sensitivity of the growth mechanism to the volume fraction.

  6. The interaction of calcium nitrate and a Class C fly ash during hydration

    SciTech Connect

    Hill, R.; Daugherty, K.

    1996-07-01

    Different analytical techniques were used to study the hydration of a Class C fly ash in the presence of various concentrations of calcium nitrate. Calcium nitrate was found to accelerate the hydration of calcium aluminate phases in relationship to dosage. Hydration mechanisms were modified resulting in altered products. The new products consisted of calcium aluminate hydrate and nitrate. Evidence suggested that the modified nitrate-hydrates competed with or inhibited the formation of calcium aluminate sulfates hydrates.

  7. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

  8. Optical Measurement of Mass Flow of a Two-Phase Fluid

    NASA Technical Reports Server (NTRS)

    Wiley, John; Pedersen, Kevin; Koman, Valentin; Gregory, Don

    2008-01-01

    An optoelectronic system utilizes wavelength-dependent scattering of light for measuring the density and mass flow of a two-phase fluid in a pipe. The apparatus was invented for original use in measuring the mass flow of a two-phase cryogenic fluid (e.g., liquid hydrogen containing bubbles of hydrogen gas), but underlying principles of operation can readily be adapted to non-cryogenic two-phase fluids. The system (see figure) includes a laser module, which contains two or more laser diodes, each operating at a different wavelength. The laser module also contains beam splitters that combine the beams at the various wavelengths so as to produce two output beams, each containing all of the wavelengths. One of the multiwavelength output beams is sent, via a multimode fiberoptic cable, to a transmitting optical coupler. The other multiwavelength output beam is sent, via another multimode fiber-optic cable, to a reference detector module, wherein fiber-optic splitters split the light into several multiwavelength beams, each going to a photodiode having a spectral response that is known and that differs from the spectral responses of the other photodiodes. The outputs of these photodiodes are digitized and fed to a processor, which executes an algorithm that utilizes the known spectral responses to convert the photodiode outputs to obtain reference laser-power levels for the various wavelengths. The transmitting optical coupler is mounted in (and sealed to) a hole in the pipe and is oriented at a slant with respect to the axis of the pipe. The transmitting optical coupler contains a collimating lens and a cylindrical lens that form the light emerging from the end of the fiber-optic cable into a fan-shaped beam in a meridional plane of the pipe. Receiving optical couplers similar to the transmitting optical couplers are mounted in the same meridional plane at various longitudinal positions on the opposite side of the pipe, approximately facing the transmitting optical

  9. A Pore Network Model Evaluation of the Types of Fluid/Fluid Interfacial Area Measured by Static and Dynamic Water-Phase Tracer Methods

    NASA Astrophysics Data System (ADS)

    Kibbey, T. C.; Chen, L.

    2010-12-01

    Tracer methods have gained acceptance for measuring fluid/fluid interfacial areas in porous media, and have been applied in both laboratory and field settings. Tracer methods make use of chemicals (typically surfactants or other surface-active chemicals) which adsorb to fluid/fluid interfaces, leading to changes (retardation of transport, depletion of solution concentration, or mobilization of fluid) which can be used to calculate the amount of interfacial area. Advantages of tracer methods include that they are inexpensive to use, don’t require specialized equipment, and can potentially be applied in field settings. The primary disadvantages include uncertainty about the types of interfacial area measured, and questions about whether the tracers themselves produce interfacial area changes. Interfacial areas in porous media containing multiple fluids are often categorized as capillary area (area corresponding to fluids held by capillary forces) and film area (area corresponding to molecular films of the wetting phase on porous medium surfaces). Total area is a measure of area that includes both capillary and film area. The focus of this work was on examining the types of interfacial area measured by both static and dynamic water-phase advective transport tracer methods. Static advective transport methods were introduced in the late 1990s (e.g., Kim et al., Water Resour. Res., 1997, 33, 2705-2711), and involve measuring the retardation of a tracer passed through a porous medium maintained at a preset degree of saturation (interfaces are presumed to be static). Dynamic advective transport methods were introduced in 2006 (Chen and Kibbey, Langmuir, 2006, 22, 6874-6880), and involve measuring depletion of tracer during drainage from a specially-constructed low volume soil cell. As new interfacial area is formed during drainage, tracer adsorbs to the interface, depleting the bulk solution; mass balance calculations are used to determine interfacial area as a function

  10. Mass transfer and trace element redistribution during hydration of granulites in the Bergen Arcs, Norway

    NASA Astrophysics Data System (ADS)

    Centrella, Stephen; Austrheim, Håkon; Putnis, Andrew

    2016-10-01

    The Bergen Arcs, located on the western coast of Norway, are characterized by Precambrian granulite facies rocks partially hydrated at amphibolite and eclogite facies conditions. At Hilland Radöy, granulite displays sharp hydration fronts across which the granulite facies assemblage composed of garnet (55%) and clinopyroxene (45%) is replaced by an amphibolite facies mineralogy defined by chlorite, epidote, and amphibole. The replacement of both phases is pseudomorphic and the overall reaction is isovolumetric. In the present study, LA ICPMS has been used to determine the trace element redistribution during the hydration. Although the bulk concentrations of the trace elements do not change, the LILE, HFSE, and REE losses and gains in replacing the garnet are qualitatively balanced by the opposite gains and losses associated with the replacement of clinopyroxene. From the REE compositions of the parent granulite and the product amphibolite, measured in μg/cm3, we conclude that the mass of rock lost to the fluid phase during the hydration is approximately 20%. This suggests a mechanism for coupling between the local stress generated by hydration reactions and mass transfer, dependent on the spatial scale over which the system is open.

  11. A Multi-Phase Based Fluid-Structure-Microfluidic interaction sensor for Aerodynamic Shear Stress

    NASA Astrophysics Data System (ADS)

    Hughes, Christopher; Dutta, Diganta; Bashirzadeh, Yashar; Ahmed, Kareem; Qian, Shizhi

    2014-11-01

    A novel innovative microfluidic shear stress sensor is developed for measuring shear stress through multi-phase fluid-structure-microfluidic interaction. The device is composed of a microfluidic cavity filled with an electrolyte liquid. Inside the cavity, two electrodes make electrochemical velocimetry measurements of the induced convection. The cavity is sealed with a flexible superhydrophobic membrane. The membrane will dynamically stretch and flex as a result of direct shear cross-flow interaction with the seal structure, forming instability wave modes and inducing fluid motion within the microfluidic cavity. The shear stress on the membrane is measured by sensing the induced convection generated by membrane deflections. The advantages of the sensor over current MEMS based shear stress sensor technology are: a simplified design with no moving parts, optimum relationship between size and sensitivity, no gaps such as those created by micromachining sensors in MEMS processes. We present the findings of a feasibility study of the proposed sensor including wind-tunnel tests, microPIV measurements, electrochemical velocimetry, and simulation data results. The study investigates the sensor in the supersonic and subsonic flow regimes. Supported by a NASA SBIR phase 1 contract.

  12. Monte Carlo cluster algorithm for fluid phase transitions in highly size-asymmetrical binary mixtures.

    PubMed

    Ashton, Douglas J; Liu, Jiwen; Luijten, Erik; Wilding, Nigel B

    2010-11-21

    Highly size-asymmetrical fluid mixtures arise in a variety of physical contexts, notably in suspensions of colloidal particles to which much smaller particles have been added in the form of polymers or nanoparticles. Conventional schemes for simulating models of such systems are hamstrung by the difficulty of relaxing the large species in the presence of the small one. Here we describe how the rejection-free geometrical cluster algorithm of Liu and Luijten [J. Liu and E. Luijten, Phys. Rev. Lett. 92, 035504 (2004)] can be embedded within a restricted Gibbs ensemble to facilitate efficient and accurate studies of fluid phase behavior of highly size-asymmetrical mixtures. After providing a detailed description of the algorithm, we summarize the bespoke analysis techniques of [Ashton et al., J. Chem. Phys. 132, 074111 (2010)] that permit accurate estimates of coexisting densities and critical-point parameters. We apply our methods to study the liquid-vapor phase diagram of a particular mixture of Lennard-Jones particles having a 10:1 size ratio. As the reservoir volume fraction of small particles is increased in the range of 0%-5%, the critical temperature decreases by approximately 50%, while the critical density drops by some 30%. These trends imply that in our system, adding small particles decreases the net attraction between large particles, a situation that contrasts with hard-sphere mixtures where an attractive depletion force occurs.

  13. A Two-length Scale Turbulence Model for Single-phase Multi-fluid Mixing

    SciTech Connect

    Schwarzkopf, J. D.; Livescu, D.; Baltzer, J. R.; Gore, R. A.; Ristorcelli, J. R.

    2015-09-08

    A two-length scale, second moment turbulence model (Reynolds averaged Navier-Stokes, RANS) is proposed to capture a wide variety of single-phase flows, spanning from incompressible flows with single fluids and mixtures of different density fluids (variable density flows) to flows over shock waves. The two-length scale model was developed to address an inconsistency present in the single-length scale models, e.g. the inability to match both variable density homogeneous Rayleigh-Taylor turbulence and Rayleigh-Taylor induced turbulence, as well as the inability to match both homogeneous shear and free shear flows. The two-length scale model focuses on separating the decay and transport length scales, as the two physical processes are generally different in inhomogeneous turbulence. This allows reasonable comparisons with statistics and spreading rates over such a wide range of turbulent flows using a common set of model coefficients. The specific canonical flows considered for calibrating the model include homogeneous shear, single-phase incompressible shear driven turbulence, variable density homogeneous Rayleigh-Taylor turbulence, Rayleigh-Taylor induced turbulence, and shocked isotropic turbulence. The second moment model shows to compare reasonably well with direct numerical simulations (DNS), experiments, and theory in most cases. The model was then applied to variable density shear layer and shock tube data and shows to be in reasonable agreement with DNS and experiments. Additionally, the importance of using DNS to calibrate and assess RANS type turbulence models is highlighted.

  14. Reservoir condition pore-scale imaging of multiple fluid phases using X-ray microtomography.

    PubMed

    Andrew, Matthew; Bijeljic, Branko; Blunt, Martin

    2015-02-25

    X-ray microtomography was used to image, at a resolution of 6.6 µm, the pore-scale arrangement of residual carbon dioxide ganglia in the pore-space of a carbonate rock at pressures and temperatures representative of typical formations used for CO2 storage. Chemical equilibrium between the CO2, brine and rock phases was maintained using a high pressure high temperature reactor, replicating conditions far away from the injection site. Fluid flow was controlled using high pressure high temperature syringe pumps. To maintain representative in-situ conditions within the micro-CT scanner a carbon fiber high pressure micro-CT coreholder was used. Diffusive CO2 exchange across the confining sleeve from the pore-space of the rock to the confining fluid was prevented by surrounding the core with a triple wrap of aluminum foil. Reconstructed brine contrast was modeled using a polychromatic x-ray source, and brine composition was chosen to maximize the three phase contrast between the two fluids and the rock. Flexible flow lines were used to reduce forces on the sample during image acquisition, potentially causing unwanted sample motion, a major shortcoming in previous techniques. An internal thermocouple, placed directly adjacent to the rock core, coupled with an external flexible heating wrap and a PID controller was used to maintain a constant temperature within the flow cell. Substantial amounts of CO2 were trapped, with a residual saturation of 0.203±0.013, and the sizes of larger volume ganglia obey power law distributions, consistent with percolation theory.

  15. Reservoir Condition Pore-scale Imaging of Multiple Fluid Phases Using X-ray Microtomography

    PubMed Central

    Andrew, Matthew; Bijeljic, Branko; Blunt, Martin

    2015-01-01

    X-ray microtomography was used to image, at a resolution of 6.6 µm, the pore-scale arrangement of residual carbon dioxide ganglia in the pore-space of a carbonate rock at pressures and temperatures representative of typical formations used for CO2 storage. Chemical equilibrium between the CO2, brine and rock phases was maintained using a high pressure high temperature reactor, replicating conditions far away from the injection site. Fluid flow was controlled using high pressure high temperature syringe pumps. To maintain representative in-situ conditions within the micro-CT scanner a carbon fiber high pressure micro-CT coreholder was used. Diffusive CO2 exchange across the confining sleeve from the pore-space of the rock to the confining fluid was prevented by surrounding the core with a triple wrap of aluminum foil. Reconstructed brine contrast was modeled using a polychromatic x-ray source, and brine composition was chosen to maximize the three phase contrast between the two fluids and the rock. Flexible flow lines were used to reduce forces on the sample during image acquisition, potentially causing unwanted sample motion, a major shortcoming in previous techniques. An internal thermocouple, placed directly adjacent to the rock core, coupled with an external flexible heating wrap and a PID controller was used to maintain a constant temperature within the flow cell. Substantial amounts of CO2 were trapped, with a residual saturation of 0.203 ± 0.013, and the sizes of larger volume ganglia obey power law distributions, consistent with percolation theory. PMID:25741751

  16. Reservoir condition pore-scale imaging of multiple fluid phases using X-ray microtomography.

    PubMed

    Andrew, Matthew; Bijeljic, Branko; Blunt, Martin

    2015-01-01

    X-ray microtomography was used to image, at a resolution of 6.6 µm, the pore-scale arrangement of residual carbon dioxide ganglia in the pore-space of a carbonate rock at pressures and temperatures representative of typical formations used for CO2 storage. Chemical equilibrium between the CO2, brine and rock phases was maintained using a high pressure high temperature reactor, replicating conditions far away from the injection site. Fluid flow was controlled using high pressure high temperature syringe pumps. To maintain representative in-situ conditions within the micro-CT scanner a carbon fiber high pressure micro-CT coreholder was used. Diffusive CO2 exchange across the confining sleeve from the pore-space of the rock to the confining fluid was prevented by surrounding the core with a triple wrap of aluminum foil. Reconstructed brine contrast was modeled using a polychromatic x-ray source, and brine composition was chosen to maximize the three phase contrast between the two fluids and the rock. Flexible flow lines were used to reduce forces on the sample during image acquisition, potentially causing unwanted sample motion, a major shortcoming in previous techniques. An internal thermocouple, placed directly adjacent to the rock core, coupled with an external flexible heating wrap and a PID controller was used to maintain a constant temperature within the flow cell. Substantial amounts of CO2 were trapped, with a residual saturation of 0.203±0.013, and the sizes of larger volume ganglia obey power law distributions, consistent with percolation theory. PMID:25741751

  17. Phase equilibria constraints on the chemistry of hot spring fluids at mid-ocean ridges

    SciTech Connect

    Seyfried, W.E. Jr.; Ding, K.; Berndt, M.E. )

    1991-12-01

    Recent advances in experimental and theoretical geochemistry have made it possible to assess both homogeneous and heterogeneous equilibria involving a wide range of aqueous species at temperatures and pressures appropriate to model hydrothermal alteration processes at mid-ocean ridges. The authors have combined selected aspects of the chemistry of hot spring fluids with constraints imposed by a geologically reasonable assemblage of minerals in the system Na{sub 2}O-K{sub 2}O-CaO-MgO-FeO-Fe{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-SiO{sub 2}-H{sub 2}O-HCl-H{sub 2}S to assess the effect of temperature on the composition of the aqueous phase and the activities of mineral components in plagioclase and epidote solid solutions. Assuming fO{sub 2(g)} and fS{sub 2(g)} controlled by pyrite-pyrrhotite-magnetite equilibria, a constant dissolved Ca concentration, and a dissolved Cl concentration equivalent to that of seawater, increasing temperature from 250 to 400C at 500 bars results in systematic changes in the composition of mineral phases, which in turn constrain pH and the distribution of aqueous species. The model predicts that dissolved concentrations of Fe, SiO{sub 2}, K, H{sub 2}S, and H{sub 2} increase, while Na and pH{sub (25C)} decrease with increasing temperature. That many hot springs vent fluids are characterized by variable degrees of conductive heat loss renders measured temperatures unreliable as indicators of the maximum temperature of subseafloor hydrothermal alteration processes. The implications of this are significant for hot spring fluids which reveal large Cl variations relative to seawater, since likely mechanisms to account for such variability typically require temperatures in excess of those inferred for subseafloor reaction zones by simply correcting measured temperatures for the effects of adiabatic cooling.

  18. Sum of ranking differences to rank stationary phases used in packed column supercritical fluid chromatography.

    PubMed

    West, Caroline; Khalikova, Maria A; Lesellier, Eric; Héberger, Károly

    2015-08-28

    The identification of a suitable stationary phase in supercritical fluid chromatography (SFC) is a major source of difficulty for those with little experience in this technique. Several protocols have been suggested for column classification in high-performance liquid chromatography (HPLC), gas chromatography (GC), and SFC. However, none of the proposed classification schemes received general acceptance. A fair way to compare columns was proposed with the sum of ranking differences (SRD). In this project, we used the retention data obtained for 86 test compounds with varied polarity and structure, analyzed on 71 different stationary phases encompassing the full range in polarity of commercial packed columns currently available to the SFC chromatographer, with a single set of mobile phase and operating conditions (carbon dioxide-methanol mobile phase, 25°C, 150bar outlet pressure, 3ml/min). First, a reference column was selected and the 70 remaining columns were ranked based on this reference column and the retention data obtained on the 86 analytes. As these analytes previously served for the calculation of linear solvation energy relationships (LSER) on the 71 columns, SRD ranks were compared to LSER methodology. Finally, an external comparison based on the analysis of 10 other analytes (UV filters) related the observed selectivity to SRD ranking. Comparison of elution orders of the UV filters to the SRD rankings is highly supportive of the adequacy of SRD methodology to select similar and dissimilar columns. PMID:26228853

  19. Packed column supercritical fluid chromatography using stainless steel particles and water as a stationary phase.

    PubMed

    Murakami, Jillian N; Thurbide, Kevin B

    2015-09-15

    Stainless steel (SS) particles were demonstrated as a novel useful support for a water stationary phase in packed column supercritical fluid chromatography using a CO2 mobile phase. Separations employed flame ionization detection, and the system was operated over a range of temperatures and pressures. Retention times reproduced well with RSD values of 2.6% or less. Compared to analogous separations employing a water stationary phase coated onto a SS capillary column, the packed column method provided separations that were about 10× faster, with nearly 8-fold larger analyte retention factors, while maintaining good peak shape and comparable column efficiency. Under normal operating conditions, the packed column contains about 131 ± 4 μL/m of water phase (around a 5% m/m coating), which is over 25× greater than the capillary column and also affords it a 20-fold larger sample capacity. Several applications of the packed column system are examined, and the results indicate that it is a useful alternative to the capillary column mode, particularly where analyte loads or sample matrix interference is a concern. Given its high sample capacity, this packed column method may also be useful to explore on a more preparative scale in the future.

  20. Sum of ranking differences to rank stationary phases used in packed column supercritical fluid chromatography.

    PubMed

    West, Caroline; Khalikova, Maria A; Lesellier, Eric; Héberger, Károly

    2015-08-28

    The identification of a suitable stationary phase in supercritical fluid chromatography (SFC) is a major source of difficulty for those with little experience in this technique. Several protocols have been suggested for column classification in high-performance liquid chromatography (HPLC), gas chromatography (GC), and SFC. However, none of the proposed classification schemes received general acceptance. A fair way to compare columns was proposed with the sum of ranking differences (SRD). In this project, we used the retention data obtained for 86 test compounds with varied polarity and structure, analyzed on 71 different stationary phases encompassing the full range in polarity of commercial packed columns currently available to the SFC chromatographer, with a single set of mobile phase and operating conditions (carbon dioxide-methanol mobile phase, 25°C, 150bar outlet pressure, 3ml/min). First, a reference column was selected and the 70 remaining columns were ranked based on this reference column and the retention data obtained on the 86 analytes. As these analytes previously served for the calculation of linear solvation energy relationships (LSER) on the 71 columns, SRD ranks were compared to LSER methodology. Finally, an external comparison based on the analysis of 10 other analytes (UV filters) related the observed selectivity to SRD ranking. Comparison of elution orders of the UV filters to the SRD rankings is highly supportive of the adequacy of SRD methodology to select similar and dissimilar columns.

  1. Application of capillary fluid management techniques to the design of a phase separating microgravity bioreactor

    NASA Technical Reports Server (NTRS)

    Finger, Barry W.; Neville, Gale E., Jr.; Sager, John C.

    1993-01-01

    Manned space missions require the development of compact, efficient, and reliable life support systems. A number of aqueous biological conversion processes are associated with bioregenerative life support systems. Vessels, or bioreactors, capable of supporting these processes in microgravity must be developed. An annular flow bioreactor has been conceived. It has the potential to incorporate containment, phase separation, gas exchange, and illumination into a single vessel. The bioreactor utilizes capillary fluid management techniques and is configured as a cylindrical tube in which a two-phase liquid-gas flow is maintained. Vanes placed around the inner perimeter enhance capillary forces and cause the liquid phase to attach and flow along the interior surface of the tube. No physical barrier is required to complete phase separation. It is shown analytically that liquid film thickness is limited only by vane geometry and that an annular flow bioreactor capable of managing 284 liters would occupy 0.7 cubic m, less than half the volume of a Spacelab experiment rack.

  2. Predicting phase behavior of mixtures of reservoir fluids with carbon dioxide

    SciTech Connect

    Grigg, R.B.; Lingane, P.J.

    1983-10-01

    The use of an equation of state to predict phase behavior during carbon dioxide flooding is well established. There is consensus that the characterization of the C fraction, the grouping of this fraction into ''pseudo components'', and the selection of interaction parameters are the most important variables. However, the literature is vague as to how to best select the pseudo components, especially when aiming for a few-component representation as for a field scale compositional simulation. Single-contact phase behavior is presented for mixtures of Ford Geraldine (Delaware), Maljamar (Grayburg), West Sussex (Shannon), and Reservoir D reservoir fluids, and of a synthetic oil C/C/C, with carbon dioxide. One can reproduce the phase behavior of these mixtures using 3-5 pseudo components and common interaction parameters. The critical properties of the pseudo components are calculated from detailed oil characterizations. Because the parameters are not further adjusted, this approach reduces the empiricism in fitting phase data and may result in a more accurate representation of the system as the composition of the oil changes during the approach to miscibility.

  3. Phase and chemical equilibria in multicomponent fluid systems with a chemical reaction

    NASA Astrophysics Data System (ADS)

    Toikka, A. M.; Samarov, A. A.; Toikka, M. A.

    2015-04-01

    Studies of the phase and chemical equilibria in the systems with chemical reaction cover a wide range of problems related to both experimental determination of physicochemical characteristics of these systems and various aspects of thermodynamic analysis of the phase and chemical processes occurring there. The main goal of this review consists in systematization and analysis of available experimental data concerning the vapour-liquid and liquid-liquid equilibria in multicomponent systems where chemical reactions